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Part 1: The synthesis of optically active metryl ethyl N-butyl methane and a study of its optical properties. Part 2: A study of some replacement reactions of optically active αγ-dimethylallyl alcohol and some of its derivatives

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V arious attem p ts have been made from tim e to tim e to d isc o v e r .
' mm® r e la tio n s h ip he tween the chemical c o n s titu tio n o f an o p tic a lly ;..
. aetlw© ^compound and th e m g n ltu d e -o f i t s r o ta to r y powers $
the.,
d i f f i c u l t i e s of th e ta s k .are* however* m oraoua and th e ©uceess h ith e rto
achieved in i t s s o lu tio n i s n o t v ery isarked#
Much.of th e e a rly work in t h i s "fie ld was c a rrie d o u t w ith n a tu r a lly ,
o cc u rrin g o p tic a lly a c tiv e compounds and s tiff era from the follow ing
.drawbacks*
•
(1) .. The compounds, under in v e s tig a tio n a re com plicated ©*g* pinene#.
(it)
Ihey -are s o lid s and m utt he in v e s tig a te d in s o lu tio n e*g# Camphor#
( H i ) T hey-contain mom than one a s y a u e trle c e n tre ©#g# t a r t a r i c acid*
Insmny cases a substance un d er in v e s tig a tio n would s u ffe r f r o a a l l
th re e drawbacks.
Furtherm ore In th e m a jo rity of c a s ts the r o ta to r y power was
determ ined f o r one w ave-length o f l i g h t only*
In more re c a n t tim es advances have been made in two d i f f e r e n t
d ire c tio n s * .
•;• Du© m ainly to th e in v e s tig a tio n s o f howry and Ms c o lla b o ra to rs ; the r o ta to r y powers of a number■o f compounds f o r l i g h t o f a wide range
•:of Wave**lengths a re now known w ith a^-high degree o f accuracy#
On the ' o th e r hand Pickard and Kenyon and t h e i r ' co-workers have
determ ined the ro ta to ry powers of a la rg e number of liq u id compounds
of r e la ti v e l y sim ple chemical c o n s titu tio n and, fo r the most p a r t,
r e la te d to one an o th er as members.<afT homologous serie s#
..More r e c e n t l y - s t i l l , f 3*0 9 . 1924 onwards, Rule and h is stu d e n ts have
determ ined r o ta to r y powers of substances in a w ide.ra n g e ’ of so lv en ts mnd
have put forw ard c e r ta in em p irical re la tio n s h ip s between the n a tu re of
the so lv en t and i t s in flu e n c e on the r o ta to r y power of a solute#
r Bo sy stem atic in v e s tig a tio n has been made of the in flu e n c e o f
tem perature, on r o ta to r y power and although numerous d ata are recorded
in -tb s work o f Pickard and Kenyon and of P a tte rso n , i t appears very .
d i f f i c u l t to draw any u s e fu l deductions from them beyond those
con tain ed in th e follow ing paragraph#
.From a .s u rv e y .o f the accum ulated d ata bearin g on th e in flu e n c e of
tem perature on l iq u id o p tic a lly a c tiv e compounds in the homogeneous
s t a t e and of th e e f f e c t o f so lv e n ts on o p tic a lly a c tiv e compoundsiin
so lu tio n ^ th e fo llo w in g main g e n e ra lis a tio n s of a q u a lita tiv e c h a ra c te r
can be .drawn: (i)
For compounds of th e .same type ©#g* s a tu ra te d a lip h a tic alco h o ls
or e th e rs th e in flu e n c e of tem perature i s g re a te r th e ..smaller the
m olecular w eight.
C ii)
The presence of u n sa tu ra te d groups or o f arom atic r a d ic a ls
.
■■■ '
.
g e n e ra lly .in c r e a s e s , o fte n to a very marked degree, the in flu e n c e of
•'
'
.
tem perature on r o ta to r y power and r o ta to r y d is p e rs io n :
group g e n e ra lly e x e rts a s im ila r influence#
i
|
i
a carbalkoxyl
3.
( i i i ) . . The in flu e n c e of p o l a r . so lv e n ts I s .'g en erally r e la te d to t h e i r •
d ip o le moments •(as ■is . shewn by ..the . e x te n s ile measurements o f , i n t e r
a ll© * Rule and h is co -w o rk ers)*
{Xv). ' The in flu e n c e o f ;non-»polar ■solvents' on th e r o ta to r y power o f aany
types'- o f compounds i s o fte n irery considerable#
from t h e .fo reg o in g c o n sid e ra tio n s i t can be a p p re c ia te d th a t the
exam ination o f .•a .s a tu r a te d •a lip h a tic .hydrocarbon should o f f e r many, \
advantages sin c e in th e c a se -o f .such a .compound^Influences due to
a s s o c ia tio n and. to . th e presence, of.- u n d atu ra te d c e n tre s o r re a c tiv e
groups .are .reduced to a -minimum*..-.
: 4 number .of .hydrocarbons have .previously , been examined by v ario u s
i n v e s t ! g a t o r s b u t th e se a l l c o n ta in .a n arom atic nucleus' as shown by',
th e fo llo w in g form ulae*«•
(-H0gH^G.ca2.C!Ig < 3
OH'3
Klaf.es and .Sautter# Bar*, 1904#
37* 649
-fc-JF
ct - p h e n y l - y - E e t h y l - 2 , . p e r. t e m
1
{-BC2H59 - CHg,CH ■
)S o t> r o p / ^ ^ 3
Klages and Sautter, Ber•, 1905,
53, 2316#
^•a^hcnyl- y -methyl~n*-pantane
i - n c,
4 b
r< ~ >
f
Harrison, Kenyon and Shepherd,
J.C.S., 1920, 658.
£ - phenyl** n~ bu bane
(-} c gHs - c - Q
C%
and :, i+J 1
( - ) C ;3 % 7 •
■'&evene and Marker, 3* Biol#
■ Chesu, 1935, 103, ■40,9# j-
1
9 •
v il3
CEfe.CBg / — “ )
Levene and Harris, J# Did#
Chem# , "1956, -111, ■736.
^
V . Knm*
4*
o r were prep&asl fro® amyl a lco h o l which I f v e r y .d i f f i c u l t , t o : o b ta in
in a co n d itio n o f o p tic a l; p a r ity , . « * g ...
CgHg —— | ■—— 0s H7
;;;■ /
^
c%
■'■;■
Marckwald, B e r,, 1904, 87.1046,
;
■■
. I t was f i n a l l y decided th a t . j^»&ethyl n^feeptane ( m ethyl e th y l n«
b u ty l
th a n e ). would be a s u ita b le compound f o r stu d y , fo r as
enumerated above i t possessed th e m e rits o f being a s a tu ra te d a lip h a tic
hydrocarbon o f ..simple., chemical s tru c tu re which;on. g en e ral -grounds might
be expected, to ;p o s s e s s no- permanent d ip o le mmm% and could b e ' synthes­
ised . i n an o p tic a lly pur© co n d itio n w ith n o t too g r e a t .experim ental
d iffic u lty . ■
In connection w ith the. d ip o le moment o f J ^ a e th y l n -h ep tan e, alth o i#
t h i s has n o t been a c tu a lly determ ined, Smyth and Stoops-
1928Jj
60,.1883} f a i l e d . t o d e te c t any d ip o le moment in nine isom eric heptanes ,
and In; p a r ti c u l a r , in -m # th a n e -|i-h e x a n e ( I ) and |^® et& yl-n*he;*:tee ( I l j
. CH3 r CH - 04H0
1.
•
% H5 * f* m % %
; '^ V
XI.
■
% % ~ CH ^ C4H9
!
CHa
III.
which are s im ila r in e le c tr o n ic s tr u c tu r e toy*m ethyl«n*heptane (XII)* !
. I t was hoped a t th e commencement o f th e se experim ents to stu d y
j
th e In flu e n c e of temperate*#, m&rmt and tfm n m n tm tio n on cpttoaHy active Kmetey)
-n -h ep tan e I
J
5
; and -fwrther i t was imped to synthesis©-a se rie s of s te l la r o p tic a lly
• activ e hydrocarbons by means of a T&rtsi re a c tio n ' on o p tic a lly active
- P ~ 0thyl~n~hexyl. iodide which was obtained in -th e course of th is work*
-As to •the f i r s t point* the ©xtaaaIve work planned had severely to b©
c u rta ile d owing to the d if f ic u ltie s of preparing the o p tic a lly active
hydrocarbon (see experimental section) and the second point * th a t.o f
synthesising fu rth e r hydrocarbons - had to he abandoned as in the
^
mints- synthesis EX -f!if X~f2Ha
» H.~Hf4-2MaX
i t was found th a t th e re a c tio n 'proceeded p r e f e r e n tia l l y in favour of
the a lk y l io d id e co n tain in g th e fe w er.number of carbon atoms so
g iv in g an alm ost n e g lig ib le y ie ld of the d e s ire d hydrocarbon•R - It1,
The ^*m ethyl-n-hep t an© was prepared a n d /its ro ta to r y powers fo r
l i g h t o f' c a rio u s wavelengths In th e v i s i b le spectrum determ ined both
in th e homogeneous cord ltd on -at d if f e r e n t tem peratures and, in v ario u s
solve* t s a t room tem p erate® *
: Over a range o f 31°0 th e s p e c if ic r o ta to r y powers o f th e hydro*
carbon remained alm ost c o n sta n t (Table IX) supporting tirn view th a t
th e substance i s n o t a s s o c ia te d to any marked defetee and t h a t the
a l t e r a t i o n in observed r o ta to ry power fo llo w s .pari...passu th e
a l t e r a t i o n In d e n sity as th e tem perature changes#
On th e o th e r hand the s p e c if ic r o ta to r y powers o f th e hydro*
carbon miff©red co n sid erab le a l t e r a ti o n when th e y were determ ined In
m ethylene ch lo rid e* and th e Ben*polar so lv e n ts tem zem and carbon
a is u lp h ld e (Table
X)*
Even l a th e same so lv e n t
-
carbon d ts u l p h id e -
-j
6.
the s p e c ific rotatory. power underwent a 10$ a lte r a tio n ;lavvalu e' when
the eoneentrattoti o f too so lu te was changed from 4#4$ to 2*2$*
It
i s tin s e l early m tab! is,hod t h a t :under »oatvfavourable 'conditional for
the .svoidanoe of polar in flu en ces a solvent- d oes'n ot a ct as a-more ;
in e r t d ilu en t for - toe solute* :
: ; ?:
T*
flllSSTIf •
-THEO1I r T :'QF:SOLVTST BFFBOT 01 OHT CAL dO.TATCRY FOWISE* ;;.F
/I n te r e s t beganlfn be centerad on -th e . e f fe c t s o f .solven ts on o p tics!
r&tat©ry:'power about 35 years ago, when Walden;( Ber«, 1905* •SB* -345)
revtewed the a v a ila b le data 'end-.case to the conclusion t h a t . the :e ffe c t:
of, so lv en ts •on opt leal:.' r o ta to r y :power varied in ..the- same manner as the .
d la le e tr ie constant o f the solvent* - >'•. sin ce that tim e, however,- much'.
more '/-extensive 'in v e stig a tio n has revealed toany; anomalies' In th is' g en er a lisa tio n * - >■-.•■■...
■,.,; -
‘th e read ily obtainable ta r ta r ic acid d eriv a tiv es Were soon used in
Investigations- of-'Solvent e ffects?
e*g* liowry and Dickson (*I*0*.S*., 19LS|
10?, 1183} from s e r ie s o f observations with a t h y l - ta r tra te found that
I n 'oxygen-containing; so lv en ts the e s te r had a p o s itiv e ro ta tio n , wherea
in hfilogem ted hydrocarbons i t possessed .a negative .rotation* •.
:
*
■ ' the e f f e c t o f concentration o f the s o lu t e ‘In various solven ts
using glucose and m altose'd eriv a tiv es -showed th at •a lte r a tio n •o f „•
concentration a ff e c te d •only s lig h t ly the s p e c ific rotatory powers o f.th i
so lu te s {Hudson end. eo^worKers, -<1*A*0 .S*, ,1915*. 3?* 1265); sim ilar
r e s u lts were obtained w ith glucose' and mannose d eriv a tiv es .«*,. (£&vene.an4
Bencow its, J * •B io l# •Chest#,:1 9 3 7 , -Y3* 689)#
However, in cases o th e r
than sugar ' d e r iv a tiv e s, e.g# (+ k r-dlm ethy!aliyl .hydrogen phthal&te,; :
a lte r a tio n s "of concentration bring about pronounced va ria tio n s in .
rs
■ ’
i .. o
rotatory power:^/
;in carbon dlsulphide varies- fr©m..T* 10*3 ..to ••
Ui>qJbI
• 2 . 1° when o. changes f » a 10.0 to 5 .0 ( H ills , Kenyon and P h illip s ,
J .O .S ., 193S, 579) .
|
8.
\'Where eoapouttd-ftoraation-vbetraire^ii- solute m& solvent cm tmke piace#
then naturally* .co n cen tritlo a:;e ffe c ts w ill be considerable* e*g» w ith •
' a lte ra tio n of concentration of n ico tin e in agtieoua solution. I t wae
■found \fchti fo r the sp ecifie ro ta to ry powers a se rie s of maxima were
obtained which edaelded with the formation of n ico tin e hydrates m
shown by freezing point cafvee
Jepheott*
* .1019,1,15* 104)*
Other workers •* &owry and Xleyd# ;,<1#0#3** 1§2§# 1576 <* p refer to
in te rp re t the re s u lts as being due to the formation of a pseudo base
'r a th e r :than to simple fejdrat# formation# e*g* •
i
ch.
\
;
;
i
/
H
ch
,
■i -f-
ii
a>o.
~
ch
-
Influence o f .Dipole,.,Moment»
\
/
i
. choh
ffi
' ■■. .. ■
.■
•
■-. ■
:■■.
:
. : ■.■■.-.
■
.
.
A system atic attack on the g&otolm o f sol wont e ffe c ts mm begun
'by Kule e t s i . (J#0»S»*. 1951» 674* e t, sea*)
when i t was discovered
j
j
}
. th a t .j^m enfeyl.methyl naphthslate exhibited a large molecular ro ta to ry i
power fetch was .sensitive, towards solvents#
•ftiese workers found th a t I
...in the m ajority o f ' c a sts i-sao o th curve was obtained by p lo ttin g
|
molecular ro ta tio n against the dipole moment of -the solvent fo r this • j
p a rtic u la r ester*
For non-polar solvents also#large v a ria tio n s wore
observed! th is was a,scribed to fee p o lar interaction of a solvent
molecule with, the solute# although the fom er-considered a s ;& whole— j
■possesses no e le c tric dipole*
th is would be possible in fee case of
j
p-diehlorobensene where th e C-C& dipoles* sep a rated •by two carbon ■
"I
atoms# carl each s e p a ra te ly i n te r n e t w ith th e d ip o le o f the: s o lu te e s te r
m olecules- .
•■■■■' •
..... h s i m i l a r . s t a t e .o f a f f a i r s n ig h t e x i s t l a th© e a r ten d l sulphide;.
|
m olecule, c o n sid erin g ' th e two Q -S d ip o le s each ;t© he capable, of. , • .
j
*anchoring* a s o lu te molecule*
’Thus I t may be p o s s ib le ;.fo r a non-*
■j
p o la r s o lv e n t t o produce, e f f e c t s s im ila r .to those o f “p o la r solvents*
j
b a te r i t was found ( J*C*S** 1933, STS) when working w ith: .
d e r iv a tiv e s o f
- o c ty l and amyl a lc o h o ls t h a t# . in th e m ain, th e
r o ta to r y powers v a rie d a s th e d ip o le moment o f t h e . so lv en t, provided
th a t th e s o lv e n ts were ..m cnosubstltutad d e r iv a tiv e s o f the same ■■.■
hydrocarbon*.
However# In th e c a s e . o f fo u r compounds nam elyct-am yl •.
o»tolu& tef s e e -o c ty l c h lo rid e and brom ide, and d -amyl alcohol* th e -r o ta to r y power In creased w ith in c re a s e in th e dipole, moment, e f th e
solvent*
I tils le d the au th o rs to c l a s s i f y s o lu te s , from th e p o in t
o f view o f In flu e n c e on t h e i r o p tic s ! r o ta to r y powers,: i n t o ' th re e
groupss~
!
,
j
j
non-polsr# #*g*. hydrocarbons; weakly p o la r , ©*&*>•.o th ers
.and a l c o h o l s |.and s tr o n g ly p o la r s o lu te s , e*g* n itro * and fceto.
d e riv a tiv e s*
'
.
.
.
j
10 *
. From m in v e s tig a tio n o f t h e ' in flu e n c e o f arom atic so lv e n ts
(which were found to. .g iv e .more .eerrel&iee'fele r e s u l t s ) on th e o p tic a l
2 i4 d l n l tr o
r o ta to r y pow ers. of. j^m eath y l o^tfi troben&oate end
ben zo ate,. i t was, found, th a t .the a b s o rp tio n ' band., re sp o n sib le fo r' th e
'o p tic a l a c tiv ity * -a s given by A, i n ' Drude equati.ona o f th e type «
k2
k.
ch
moved towards the' re d
£%'■
-1
?*-x,
end. of. th e;sp ectru m
<v
as :t h e .p o la r i t y o f th e .
so lv e n t In c re a se d C lehein, 'J*C«3»-V 1934,"359)*
• Continuing the d ip o la r th e o ry o f so lv e n t in flu e n c e on o p tic a l "
..ro tato ry power, Melean (£«C*§«, 193$, 229) p o s tu la te s , in a d d itio n to .
th e d ip o la r fo rc e s th ich . had so f a r been in v o led to ex p lain so lv e n t
in flu en ce,, .feexa^polar a s s o c ia tio n between o p tic a lly a c tiv e e s t e r s end.,
a ro m a tic ■.so lv m ts* :■ . f h is re c e iv e s soma support from the m olecular
w eight d eterm in atio n s o f two e s t e r s ^ J ^ m e n th y l i^ n itro b e n z o a te and
X^mmthyl 3 |5 d ln itro b e n s c a ts - - i n &mz®m§ from which i t appeared th a t
a d d itio n compounds were form ed.between th e e s t e r s and bensene* whereas
no such addition^ compounds war# formed when the hy&rosrematie •c y c le hexane was used as a solvent*.
Ucl&m p o s tu la te s the fo llo w in g •
' form ulae fo r the two e s t e r s and. beaaenet* :
W
i
/V
N/y*
'V V ° ^
A
-/fo.
•n.
From a c o n s id e ra tio n o f those form ulae i t fo llo w s th a t i f a
p o la r s u fe s titu rn t e a te r s ' thB' bmism® 21 ng, th e e s te r s would n o t so
e a s ily be a b le 'to ''in flu en c e the p o la r is a tio n o f the- arom atic r in g and
sot they would fetire.loss in flu e n c e e w t the. a s s o c ia tio n o f so lv e n t and
solute# -. , Hence. co n sid erin g o n ly th e hex& pclar. in flu e a e a , th e low ering
o f o p tic a l ro ta to ry power ©hou^ decrease. w ith in crease. in p o la r ity o f *
th e mono s u b s titu te d arem bl© . s o l v e n t t h e r o ta to r y power would
,£ \
in cre ase- w ith in crease' t o :so lv e n t p o la rity # •: -However, th e normal
Ii
a ;
d ip o la r a s s o c ia tio n a f f e c t s the r o t a t o r y :power in e x a c tly the o p p o site
j
sen se, so th a t it.- is ..th e predominance o f e i t h e r hex®** or. d i^ p p la r
' j
fo rc e s whleh w ill determ ine th e change i n r o ta to r y power# '
' ;j
ACTIVE X dtO
I n re c e n t •years, prominence ha a been ‘g iv e n ' to th e in flu e n c e ' o f "
r e f r a c tiv e ' index on th e o p tic a l r o ta to r y power o f so lu tio n s# : flila has
''b e e n 's tim u la te d fey v ario u s formula® co n n e ctin g ' o p tic a l r o t a Id ry power'
and th e r e f r a c t i v e index o f th e medium# which.have been, suggested on ' .
4S&
th e o r e tic a l grounds#
put' ferarar&s«**■■
' f l m : fo llo w in g form ulae have a t v a rio u s tim es baca
■
, \
Born, Ihys* Zeit# 1916, 16, 251
dans, ton# Fhys#, 1 9 2 6 ,(4 ), %9.#533
B e y s ,.Proe# Roy#See#, 1934, ,4144,
681
Kufea, 2. Hftya. C hea., 1935, B30,
afl
Becteann and Cohan,
Cham* Phys#,
. .1936, 4 , 794 '
vwhere g k ' c o n s t a n t .
IS ». ■?©£**&©tiV6 , M W Of..
-
•:
£•. m . d i e l e c t r i c c o n sta n t of... so lv en t *
and
- In 1930 th e experim ental study o f ' th e e f f e c t o f r e f r a c tiv e index
-on o p tic a l r o ta to r y power began to tak e shape*'"' ; VoXkmann (S« Fhys*
Cheau* 1950, BIO, 161) stu d ie d the o p t i c a l 'r o t a t o r y power ofJL^
llasonene In v ario u s so lv en ts In r e la tio n , to th e r e f r a c tiv e index o f
the.- medium*
«*Llmonene was c h o s e n ,f o r n o t "only was I t r e a d ily
a c c e s s ib le , but In the a u th o rf s words (Ib id * , p* 173) I t'p o s s e s s e s
*&'. sm a lle st p o s s ib le moment, the- m olecules o f which a re the l e a s t ,
deform able and whose c h a r a c te r is tic a b so rp tio n w avelength in. v ario u s
so lv e n ts experiences th e l e a s t p o ssib le d isp la c e m e n t/1
He found
good agreement w ith 0 an st a formula 0 . ■kCrf"^^} ' ■tvrdL •limonene a t
v a rio u s 'c o n c e n tra tio n s -'in alco h o l and heptane fo r (V 6461*
However,
using. •carbon 't e t r a c h l o r i d e ;and carbon d isu lp h id e as -solvents,, the
experim ental fig u re s did "not ag ree w ith the above equation;-
th is .
i s a l l the more s u rp ris in g as from afesoption sp e c tra evidence th ese
l a t t e r two. so lv e n ts should behave- s im ila r ly to"heptane*.
Beckmann and Cohen,, (loo* c lt* )-fro m a th e o r e tic a l study o f solvent.
: e f f e c t s , ■deduce a r e la tio n , between, s p e c if ic ro ta tio n ,, r e f r a c ti v e index
and d i e l e c t r i c c o n sta n t ** namely*' f c Q '/ n 2+ 2
-
k /£ -X
—
j- B
fhey war# ab le to show, using th e experim ental r e s u l t s of Eul@
and McLean ( J .C .3 ., 1931, 674). f o r r o ta to r y pow ers o f 1-m enthyl methyl
BAphtbalat®, th a t th e above equation h eld good i f arom atic and
13*
a lip h a tic so lv e n t8 were..considered, separately*.
-From the r e la tio n s h ip o f .r e f r a e t l v l t y to r e f r a c tiv e index, these
au th o rs w ith th e c o n c ise n e ss-'ty p ic a l-o f 'Americans,, c h ris te n th e term
k 3
th e
nr o t i v l t y n of .the- ’compound (loc* ■c it* y p * 785)
. .. .. F or a, m olecule w ith l i t t l e o r no d ip o le moment, a plot- of
J L ~—! . should g iv e-a s t r i g h t
iL “h i
. T h i s was ;found to .he t h e .case .fo r.
Inane
**ro t'lv ib y tt ■a g a in s t the d i e l e c t r i c r a t i o
l in e - o f sero slope*
u sin g the experim ental r e s u l t s of Rule a n d .Chambers (N ature, 1934,
.133* 910)*..
. . :
,
.
. -
. h, A more re c e n t attem p t to . c o r r e la te o p tic a l r o ta to r y power w ith
the r e f r a c tiv e .ln d ie e s ,o f s o lu tio n s was. made, by Hul© and Chambers
(j*Q*S*,,1 9 3 7 , 145)• ,. They t r i e d to apply the e q u a tio n s ' o f Born, Cans '
.and Boys to s o lu tio n s offlC_~pinene^*pinane a n d ^ -lim c n e n e * .
For the
s a t u r a te d hydrocarbonfj^-pinane..It.w as found th a t except fo r p o la r
s o lv e n ts , Born1s e q u a t i o n . k(n?*f-2) ' f i t t e d the experim ental values*
However,' for.\-the two un.satura.tcd hydrocarbons th e re was no agreement
at, a l l ;
-t h i s - l e d Rule and Chambers to .th e sta te m e n t. th a t “ccn cen tra-
tio n e f f e c ts o f b o th ^ -p in en .e and
**lliaon@ne show t h a t th ey have the p ;
p ro p e rtie s, o f .a., p o la r compound* *
- |
■Using the ex p erim en tally determ ined values, o f th e s p e c ific . '
,
■
.
-
-
,
|
^
.
o p tic a l ro tato ry , power of ' (~B~ Jo-methyl n^-heptane, both homogeneous .:ui
and in so lv e n ts (fa b le s IX and-X) and th© r e f r a c tiv e in d ic e s of -those ;
s o lu tio n s , th© v alu es "of .the c o n sta n ts (k) in th e fiv e equ atio n s
q u o te d ‘above were d eterm in ed "(fab le XXX)V
From the In c o n sisten c y o f j
t h e i r V a lu e s, I t c a n ;be' re a d ily , seen t h a t none of the equations f i t s
th e experim ental fig u re s* those o f Kuhn and o f Boys shewing th e l e a s t
divergences* :
-;"'■
I t would th e re fo re seem .th a t-a s t i l l - f u r th e r attem p t w ill .be
necessary, to o b ta in an eq u ation .which w ill .a c c u ra te ly c o r r e la te
r o ta to r y power and th e r e f r a c ti v e index o f th e medium*
1 5
PRBPARATIOH OP OPTICALLY" ACTIVE |'»MBTfnT!>n«HEPTAKE.
mm
«*»<«*«* « * •» < •» < M « n « B w » . » « » « • « • « » * • • # a* *» <*»**«» a* «*»*•*»«»-*)■
Mr * * « •
■The K«*methyl. »*heptan«. o r methyl- e t h y l ; n -b u ty l methane i s
obtained"'from o p tic a lly a c tiv e
• e th y l n-hexano 1 v i a ' th e iodide*
However-, : the p ro d u ctio n o f' th e 'o p tic a lly .'a c tiv e e& rblnol proved to be
o f g r e a t . d i f f i c u l t y ; ^ i t w as' n o t found p o s s ib le •to re s o lv e the e& rbinol
by the'"usual method, namely com bination of an a c id e s te r .'o f th e earbi.no 1
w ith an a l k a lo id ,' and so recourse had to fee made to e th y l n~butyl- a c e tic
acid .;
-This was re so lv e d , converted in to i t s e th y l e s te r-a n d th e l a t t e r
reduced to f • e th y l n*h.exan©l* b u t a- y ie ld o f only 18$ o f o p tic a lly ©ilva
p ro d u c t,c o u ld be o b tain ed from th e e s te r# -- S everal methods war© t r i a d
and one whih gave a y i e l d
when working w ith d l m a te ria ls gave, on
usin g ' o p tic a lly a c tiv e m a te r ia ls , :a
e th y l i^hexanol o f very sm all
a c tiv ity .-
Ci£iHfc>ci.c0DE —— d
C'2H/<a."coo«2a 5 -— —
C4<
G4 h /
'
— V C2Hj ^
7
ch, ch oh
C4 h /
•
8
1
02b5.
^ ■J >CH.Ca* - 4r
: C4 % "
.
;
/ c a .C B e t
C45l9
•
:
. An attem p t was made to obtain, the ^ -m eth y l ^ h e p ta n e from
-
o p tic a lly a c tiv e fS-ebhyX n«hex$tnoJ,|" however attem p tsjw ere n o t atten d ed
i
o
b y -m u ch 'su cce ss,-"th e'v alu e'o b tain ed f o r i t being ✓V
- -0*11
j
46/
(^1,0*5) - only 5$ o f th e value o b tain ed by an I n d ir e c t method.
l a t t e r eons is ted i n f i r s t o x id isin g
This
e th y l n-hexyl alco h o l o r i t s
corresponding aldehyde follow ed by re s o lu tio n o f the r e s u ltin g e th y l
|v»butyl a c e tic a c id fy th e method o f Xeveno, Bothen and Meyer (J* Biol#
j
Che®*, 1936, 115. 413}—who, however, re so lv ed the a c id only In ­
c o m p letely —* and then subsequent re d u c tio n o f th e e th y l .©steer o f th e
o p tic a lly a c tiv e a d d to />-©tehyi tHhexanol#
>
!
■ I t i s a - s tr ik in g f a c t t h a t although a la rg o number o f . secondary ■ I
alcofeols have been re so lv e d in to t h e i r o p tic a lly pur© d~ and 1* ’
1
forma by th e f r a c t i o n a l c r y s t a l l i s a t i o n of the a lk a lo id s ! s a l t s of
th e i r hydrogen p h th a lle e s t e r s , y e t th i s method appears to f a i l in t h e ./
■case ;o f -prim ary a lc o h o ls which c o n ta in , a n . asym m etric. c e n tre <»
/£-m ethyl n -p ro p y l alco h o l ..is another ;example o f th is f a i l u r e , the
.a lk a lo id a l s a l t s , o f .- i t s hydrogen p h th a lle e s te r .y ie ld nixed c r y s ta ls
which system s tel e . f r a c tio n a l c r y s t a l l i s a t i o n f a i l s to se p a ra te cempSsteily#
, This d iffe re n c e in .b eh av io u r Might be a t tr ib u te d to the
asymmetric c e n tre -.present i n th e hydrogen p h th a lle estei^ being' more -.
remote \fro© th e o p tic a lly a c tiv e a lk a lo id .m olecule. i n case o f primary, |
a lc o h o ls th en -in secondary a lc o h o l$$ ■h u t this ex p lan a tio n s i s n o t ,.
e n t i r e l y adequate, fo r .the..follow ing reasons*
A c o n sid erab le number
o f attem p ts have been made in th e se la b o r a to r ie s .to re so lv e t e r t i a r y
j
a lc o h o ls o f th e g e n e ra l form ula •%%%C0H into, t h e i r o p tic a lly a c tiv e
:
■forms, b u t a ll- such, attem pts' have prowed f r u i t l e s s *
In th e se t e r t i a r y ’
i
a lc o h o ls . t h e .asymmetric c e n tre i s as .clo se to th e o p t ic a l l y a c tiv e
a lk a lo id as i t i s in the..corresponding aecond&ry. a lc o h o ls so th a t, m
■'
e x p la n a tio n based on r e l a t i v e d is ta n c e s o f the asymmetric c e n tre s
in th e s l k a l o i d a l ■s a l t s b reaks down#
.. j
;
R ecently m attem p t ,waa made t o . a y n th e sise (+ )~ K *«thyl n-heptane
by xween,arid., Kenyon;: (Bull* 3©e* CMm#, 1958, B9 1120) commencing with
n-propyl-8ec-*btttyl e a rb in o l (I)
:— >
caoa
-
CD
/
, CH.CHX
ch_
v
7
5
C,B*
''v e i . e . i
c s°* - - ’'
f "
Cli)
cem verti»g th is to th e io d id e (XI) and by re d u c tio n , o b ta in in g th e
re q u ire d hydrocarbon (XXX)#
However, t h i s method la dependent on the
complete r e s o lu tio n o f fcha o r ig in a l H rpropyl seo^b u ty l c a rb in e ! and
attem p ts to se p a ra te i t com pletely in to i t ^ g p t l c a l an tip o d es by
fre e to n a l c r y s t a l l i s a t i o n o f an a lk a lo id s ! s a l t o f i t s hydrogen p h th a lle
e s t e r were u n su c c e ssfu l, as proved by the low v a l u e ^
+ 0*59
o b tain ed fo r th e r e s u l t a n t hydrocarbon as compared w ith the value'
W j ) S~
$7° o r th e value
o b tain ed by th e method doscribed
■in the experim ental section*
; The in e ff e c tiv e n e s s o f the re s o lu tio n o f n~propyI se c -b u ty l
c&rbinol was obviously due to the c a rb in e ! c o n ta in in g two asymmetric
carbon atom s, and the method o f re s o lu tio n e ffe c te d only the se p a ra tio n
in to o p tic a l is o users of. th a t carbon atom, to which was a tta c h e d the •
hydroxyl group, and th e asymmetry of t h i s carbon atom was d estro y ed on
conversion to the hydrocarbon#
obtained by Levene ( J , B io l. Chem., 1936, 115, 413.J
.
.'
1 8
••
sim ilar, e x p la n a tio n /'is a p p lic a b le :to .th e . f a i l u r e o f thm nmm
workers .'(.lee* •©it* ) to xmolr® oorm X etelj:-ethyl
tn to :’its.ep tie& X antipodes*
-■.
■e&rMnol
, 8;
i
9
':
PREPARATION OP ETHXL n-BOTTO. ACETIC ACID AND ITS RESOLUTION,
«
« • w , -M <•* w* a # m» «*■ m
* m < t» «»► «»* * * « * *w «*» * »
'
m u t t * m u t u u m * « » * » • * K» # * m <**. ■»*««(.•■*•
j
» • ■ • ! . « ♦ » » Mt-w*. ***► « * < * •« » <w < *»*,«■ • a » « * w —
j
In order to overcome., the d if f ic u lt! es enumerated in .the previous
section, i t was decided to. oxidise
ethyl n^liexsnol (1) to ethyl
H -butyl; a c e tic acid (2) — a compound in which the asymmetric carbon
atom is . in the d ♦position to the carboxyli© group a n d ,th erefo re, by
analogy, more lik e ly to y ie ld aXkaleldal s a lts capable of separation
into ■th e ir diestereoisom eidt modi.fications by fra c tio n a l c ry s ta llis a tio n
' r
'
O/Ha'v v
■ * * CiUGS^OH
V W/
**
’- ;
2 5
(1)
.■
^
■
CA
^
* *> j ;
b2i 5 ^
cb * o o o i
{2}
I t would then be possible to reconvert an o p tic a lly active fo m
of ..(2) by the reduction, of i t s e s te r by su ita b le means Into the
corresponding o p tic a lly active fo ra o f •(1 )#
.Experiment proved .that on oxidation with alkaline permanganate,
-ethyl n-hexanel was smoothly converted Into ethyl n-butyl acetic
acid in good, yield*. fh© larger proportion of the ethyl n-butyl acetic
acid used In this investigation .was ■prepared, however, from commercial
jl -ethyl n*hexaldehyde. by oxidation with alkaline
permanganate*
$ho
resolution of:ethyl ’n«butyl acetie acid has.been described by levene,
Rothen and Mayer (J* Biol* Che©#, 193$, 116* 411} and the procedure
of•these workers was adopted In the present Investigation;
fractional
crystallisation of the quinine salt of the "dl«*sold from aqueous
acetone yielded after six crystallisations a salt of constant rotatory
|
power fro® which '{*}-e th y l ***butyX a c e tic a c id was ob tain ed by
decomposlti on w i t h ' d ilu te su lp h u ric ©eld*.
fh© mother liq u o rs
c e n ta lr in g th e m o re.so lu b le f r a c tio n s of th e quinine s a l t war© lik e w ise
decomposed and the- r e s u ltin g d e x tro ro ta to ry a c id combined w ith
einehonidln©*
The r e s u ltin g cinehonidlne. s a l t a f te r fo u r re c ry s ta llls H
i
!
a iie n s from aqueous ace ton© y ie ld e d , <©» decom position {-H-ethyl n~toutyl |
a c e tic a c id # th e d e x tro ro ta to ry power o f which was alm ost equal in
m agnitude, though o p p o site in sign* to th a t o f th e {**)- a c i d .obtained
from th e qu in in e s a lt*
The v alu es o f b o th th e ' C-fK a n d ' (-l-acid are
reco rd ed in fa b le s I and XX*
TOB CSSVE'iSIOK CP W - BTKTL n -BClVX ACCTIO ACID TO ( - H - ^ MRTOYUn.
...... The (44d is u b s tlb a te d a c e tic a c id was f i r s t converted into- i t s
e th y l e s t e r by th e yischess*Speier method*
i t s r o ta to r y powers are
reco rd ed In fa b le 1X1* ■ fh@ r o ta to r y powers of the corresponding e th y l
a cid
e s t e r of (~)-©thyl n»bntyl a c e tic ^ b o th i n th e homogeneous -state and in
so lv e n ts a r e ’reco rd ed in fa b le s X? &nd;V.. ■
■ Reduction o f th is (-H ester by f r i n 1s method (Hoc*' Trsw* Ohim, 1923
42* 1050) y ield ed
f t *^cthyl rwhexsnol;
i t s rotatory powers are
recorded in fa b le s ¥X and ¥XX#
The {'H-p• e th y l zwfrs&yl io d id e was p repared
{-B-alcohol*
from the eorrcapon&ln
i t s ro ta to ry powers a re recorded In th e ©xptriment&l
sectio n * : On re d u c tio n 'o f
~ e th y l n -h ex y l io d id e by means o f sin e and
a c e tic .acid,, (-fimethyl ©thyl n~butyl methane re su lte d * i t s r o ta to r y
powers a re reco rd ed In fa b le s ¥111f XI end X*
|
.1
■I t w ill be m m t h a t th e v alu es fo r th e o p tle a lly pur® a e id ,
,e s t e r , alcohol* io d id e m& hydrocarbon recorded iu the ta b le s e re
' co n sid erab le h ig h e r; than those given by kevene*;.Bother* and Meyer '
(loc# e i t # ) ,.
I
! 4 B O
S p e c ific Ro^ater*' Powers m d D e n sitie s of* (-f-)-snd {-)-Et.h 2 l i>Mt*
A eetie Acid at.. Various. T®merafcuree.
t°
<
g r
f c-J&ft
T
£*f
L
T t3 ; t c
t-[*Jss>
^fW(
+7,05" -+9*00° +-8,47° +10,67° +12,43° +18,19° ■ 1*7
f C
14
0,9112
20
0*9064 : 7,34
8.95
9.43
10,62
31
0,8975 i 7,38
8.89
9.37
10,50
48
0,8340 '; ' 7*43
8.78
9,22
63
0.8078
7.14
8,71
■mm
«*
**
90 0,8500 ’
#•
15 0, 9104
16
a ,e ) .
——
I f . 50
12,28
■17.58
10,33
** «,
16 *74
1 ,6
9,17 -
10*28
12.26
-------
mm
0.61
9.13
10*21
12.20
«*
8.92
9.43
10*64
12. S3
17.33
1 .6
-7 ,2 5
-0 .7 3
-9 .1 4
-10,32
-1 2 ,0 4
-1 7 .1 5
1,7
...
1,6
1 .7 -.-
m
om,
l>VTO8 . Rothen . and .Meysrs*f s Values (loc* C'1t )(*
*
Mifm
25 ' 0,9031 +’5*74
85-
-4,20
rtWWWinoi'i!
a f te r co o lin g .
•
VARIATIQN^QF
ROXAX1 QP<—QF.„.l+l~ ETH VL
n * BUXYU A C E X jC A c ID iWITH X£/V\P£RAXUR£_
-
20
-
TEMP. c
20
60
lOO
A
1 AB t E
'■
I .1,
_ ,;.
' ■■■;
r
Speciflo, Botatony Powers of, (•)—
Ethyl
im
ww'.wifcniii
In Various Solvents.*, (1*2)*
S o lv e n t.
0
c
Aeetlo Add (* feL
i*,
L- ■5
^-61 **10*
■■
.Ei-
IStoO
20
S'
L-W&5*008--8.59 •-4).08° --10*50* -1 2 .2 8 ' -14.87° -18.37°
CH2Cla
20
4*990 6.91
©.62
20
6.079
CS0X3
'
------------
4L~
Js&s
[*-'-4‘S'W0
9.12 ”
9.41
11.48
16.43
1 .7
7.88 ' 8.17
8,88
10.14
13.98
1*8
7.54
8 . 84
0.92
12.60
1*5
7.67 '■: 9.04 ■12.78
1 .7
6.94
3j4 BS&fcsn
21
"5.043 6.45
c o i4;
20
■5.087 6.29 ■1 .0 8 -7.27 '
19 ■ 5.075 ^m m 6.60
cv . 0oJL.
-5
o6i 5*ch3
/ ksh-u
1*5
11 *f
. * . s . 4S
1 .5
•7 .5 1
• 9.85
1 .6
7.00
10.0
1 .6
6.80
7.39
8.28
;.: 18
5.127 ‘*4«t9 -*•6.00 •aao
-6 .2 4
.' 19
4.994
8,11
4 . Cl ■ 5.01
5.41
*PAB£E ' X I X *
* » « » > » » **>m »i*»<w «»<w >»w m » < m < m
Observed
Kotatogy •Powers-of-th e
£chy{
Ethyl
E s te r of ; (d~Jn~Butffl
Acid* (1,23.' ■
'
t®
(L^
>
^SS^TS
J>a 7 > 5
^57So
^-5W
^«tS«P
—
17■■■■■'0.8841' *M2.16° ' +12*S3 ‘>14*42*; +23.75°
** «»«# w w
m um m m
m -m m m im m
m m m
OL^rai
/&-SW
1.7
A
eeti. o
2 5
;.f A b
",
a: V.
l
/.Vv-
Obser‘ved Hot a to ry Powers o f th e E th y l..I s t e r o f (* )Ethyl n-B utyl A cetic
Acid a t Various'Tetnpe ra tunes*. (2 ,2 5 .
to '
I? ; -9 .7 4
■
m
-12.28° •13.86*
-11*76
11.78
24
• «■
29.5
9.63 ■ 11.62
59
9.54 -
11.40
89'V
8.90
11.11
28*
9.86
11.76
«•
—
mm -m.
22,22
,
•:
^ScSL
^4-3Sf
-16.15"
-23.10°
16.03
1.7
m> mm-
mm mm
22.70 ‘ 1 .7
13.72 ' 16.01
mm
13.43
15.59 ■ 22.10
1 .6
11.88
13.03
15. 53
«■* mm
mm m
12.23
13.81
16.23
22.56
1 .6
•*
'
leven©* Bothen arid Meyer1s V alue,- (loc* c i t . )
25
-2 .9 0 ,(1*13. „ •
*a f t e r cooling
f i b 'm
.v,
S p e c ific R otatory Powers o f th e Ethyl Us t e r o f C
' /* L
5.047 —6*94
CSg
23 ; 5.025
C5% . ^
20
CH£oS
l0
L*
1
18
22
18
GBC13
20
6OI4*
CgHc CHS 22
20
^ H,
•
•
.
E tg° ; ■ 2 1 '
c
1
^
0?0
S o lv en t. ’ t °
11 ^«k s
A cetic
6.27 - 7.16
5.010- - 6. 49 6.79
5.027
5.041
m
mm
5 X5
.
. 6.66
6.45
M'
I -*s*Sb t r
W
LJj-w H '
-8. S3 -9.62* - 11. 20* -13.8°
*.36' 8.26
7.29 8.39
7.16
6.55
*■»
s.
l u
%
%
i
M
9.08
7.78; . 9.05
8.84
7.34
5.054 5.34 6*13 6.13 6.83
5.067
5.*92 6.61 7; 30
5*. 035 ~4**47 - 4 17 mmA mm
5.065 -3 .8 5 -4 .0 5 -4 .1 5 -4 .7 4
•»
9. 2 5 .
«tp
13.0
1 .4
. 1*6
mm mm
1.7
1.5
11.3
1 .6
10 8
8 . 61
8.0 0 11; 0 115
-5*86
8 34 ; 1*6
1.6
-5 .5 3 -7 .6 0
*
*
VARIATION
OF : 0 5 S E RVED IROTATION
■).- ETHVU. T t~ BuT V L
Z) OF ETHVU E.STE.I
KCETtC
AQtB „ ,
■20
X5056
■0^
io-
10
9o
110
TAB L E
•
• A w a in iiiia w M
¥ X*
iiia a a iw tiiH
Powers’.and' l)m $itles .of ;(*v-)7 ^ Bthyl n»Bexanol a t
7arlm is Tem perature 3 »
0
t ..
<
0^£,<tSS
<KsW
r
(3^r<?(s’o
■+7,10°
> 7 *53°.
+ 8.48*
r
19
0.8342
30'
0.8611 '
5*85
6*94 ■
7.87
8.20
9*68
37 ..
0,8205
5*68
6.89
7.17
8*09
9*46
44 ..-
0.8150
. 5*01
6.76 ■
7*09 ;
. 8,04-
94
0.7770
5.01
6.10
6.40
7.19
0.41
0.8334
' 5*80 '
7.12
7.56
B. 49 ;
9.84
■■■
2d*
+ 5*92°
; + 9.82°
9*54 ■
*
■a f t e r cooling*
s u
1 4
Solvents*.; (1 $ 2 }
.O
t
20
Eto0
ca0c i0 20
#a>
(&
CEC1*
u
lilt
CSg
19
19
23
'
IS
eo
c
1
.
"
M
V H
.
Solvent
r .i
ff- fT
n „
l j^ e
II JSf aU
LJfoft I JVJff
-/
5*069 + 3.46* +4*95° -5.92*'+0.51 ■ +6,91 +9 *97°
-
5.049
,
' «fr
«M
5.002' , 2 . 4 0
2.33
4*926
4.951- m mm
mm mm
4*975
m m
5*060
.
■
,3.47
,3.60
-3.05
;3*17
,5.42
2*57
4*26
3.16
4*80
5.15 ", 8.32
4*30 5.00 ’5*70
4*04 ' 4*24 6.6
3.76 ■- 4*16 ' : 6*96
3.62
4*52 ■ ,5.53
7.12
5.16 4.55
VARIATION
OF
OBS £ R V £ P
R O t/\T iQ N
;
_OF (+J
~~'7“ '~'ETHiYtr~tvrT"HEXano C V :
20
4b
loo
1 A J L I
111.
_ ¥ ____
<1*0.5)
Observed- Kot&toyy Powers of I-fTf**Methyl n~Heptane a t various tlfem^e^atrures.
tQ
tr
Vt-SSIS
+ 2 .m
V
18.. ':,
£5.5
34 .
49 :
+ 2.51
-f-2.81*
^ 5e<f&
-y-3.50°
*» «*
. a . ?6
3.27
’ 2 . SO . , 2.43
2.74
2.41 .
1.83 •
. ...
mm
.
«• m
19*/
2.2 9
. 2 .3 ?
' 2.64
2.37
2 . 46
2 .8 0
0^ 4.46
1.60
; 4.52
: i .8 3 '
3 .2 0
4.38 ■ ■ 1.60
■ '3.13
**■ M
r
mm
4.52
.
1.61
a f t e r cooling,
. T A B I» B.
W M M .W W m H W W W W * * * *
S p ecific' R otatory Powers; and 'P e n a ltie s of ■•(f-V»^«»Methyi n*»Heptene
t° ■
18
<
/£ „
7 f £ r
'0.7075 + 5.18° +6*70° ^7 .1 0 ° -^7.95*
12.9
7.87
9.32
7.00
7.89
9.21
12.6
■■- 6.71
6.94 ‘ 7.74
9.17
«* «*
■; 6.71
6.87
7.93
M
fc M
»
12.8
5.22
4» *.
34
0*6948"
m. m
' 6.62
"0.6827 ;
49; :
%
19 , ■ 0.7066 '
mm
mm
*
a f t e r co o lin g .
TZefra. ct/ve Xu elites^
/ 3f?o
& c»
-/xa.e*
«M
<
25.5 " ’ 0.7014 ‘
/?
tc .
+ 9 .S 3'
) <4-002
) <4-00*1
V
I 1<4>Z<{
.
.
'l
;• ..............
"
vTMRIATlOM
s pi
O F
4V -
EC IFIC
H E PT jA N E
If
RC> T A T < O N
0
C + > - Y * " f '1 E T H Y L
T£LM PEIR A TU R E
WlTt-
s
!
AU
...............................i-O
;
....
_
........
14_
o
o
4 3 5 ~ 8 > --------------
o
o
-- ..............: ........L Z
n
;
i
5ogb
...'g .....
.......
:
X;
—0 — -------:-----------o
—0 0
5"&Oi
7
-----------:— --------------©J
-------------------©--------------- —----------©------,--------------
....................................o -
o
00
- : .
r
C
-----... ----------
...........
:
...
..
_.|
i
■ - ................
:v - >
:
:
......
.........
.
------------------------- - g<s-
:
T E M P ° c
i
; Y
; ■;
i 5
.’
2si : ; :
;:
i
3 >:'
:
;
;.
a ■3
Figure
;
4
f to
1
30
<
. . .
&0-y l n~I“leptane in V arious
S p ed f i t 'R o ta to ry ;Fowera o f
Solvents# .
(I*-
Solvent
t°
1 ).
■C '
lx]
lwJl^S L-‘SS?3 «--v*?® 14
LJSW i JfiiSl, M
■V4*13
5*99° + 6*82' +8*05" + 1 2 .2 “
p. • U
%O
$t\° 5*38
11.3
7*82
'_**■ +r.M
5*59
GllgClg
' 23
4*842
C0H6 . CSg
18
4*470
19
' 4*359
a* **-
4*36 4*59'
5*51
0,43
«* 4*
C3„
20 .
2.179
”M
e H*
4*59 *» «»
5*05
5. 50
«* *»
**
A B It
.XI*
n-*Hentan© in S olvents a t Temperatures
■8f r a e tiv e In d ice s o f
and C oncentrations Id e n tic a l
juO
c
t
Solvent#
M'SflS
those or.f® M e X
Ws?gc
m --m
1*4116
1*4252
■1*4240
1*49S3 1.4903
1*4994
1*5037
1*5107
/a)
0
1* 8488
1.8758
CHpCl0 ■
23
4*842
© ®•.••.
CS0
**
lone
18
4*476
19:
4*359' 1*8119 1*6156
18
100
1*4002 •1*4009
mk m
1*4024
1.4042
1*4314
1# 4094
lo te s i
a
Values o f
f o r CSg s o lu tio n were n o t ex p erim en tally detexrolttSftii
fo r th e r e f r a c tiv e in d ic e s o f ' the prism o f the fu lfr lc h r e f r s e to m e ttr
and o f th e s o lu tio n were approxim ately equal*
ir
T herefor# values o f pure. CSo f o r (a) —
and
/f
a re
(b) —n ’w /
were used sine© no v alues o f nSogb s ad n *-3€S
reco rd ed in th e li te r a t u r e #
The above'quoted values a re c a lc u la te d
'/*> v
from n po
and h
i%
~v
^
«*»»•.
and 4fc given by Ttsm evm ns m.& M artin {J*
Chira* Physique# 1028, g5, 447)#
-Support fo r th e c a lc u la te d n ^
l i t r e s i s given by th e c a lc u la te d value o f n , r, . 1*67688, u sin g the
454-/
■/gr0
above d a ta j th is agrees w ith th e ex p erim en tally found ft
1*87665
<*/?4/
byvBrfthl (Z*; iPhys*'Chem*, 1899, 50, 1)* ■
f a b %> n
Lty o f give E q u atio n s:connec tin g ■Optical .R otatory
fe a t
n~i
Powers •and R e fra c t lire In d ic e s o f yn*Jf®
Born, 1915* -
2)
u
- kg(n * 2 )
0aus# 192S#
: !53 (a8 f 2 H a 2+ 5}
V’ 2
* kJn'''*- 2)
a
£
Boys, 1954*
IXuto, 1955* ‘
Bmkm&m 'and Oohea, 1936*
«
C alcu lated values' o f
k.
Wavelength Solvent
5893
CH2C12
OqH6
Mono
0*30.
, 1*5
0*1?
0.95 0*13
0.43
1*7 -0.24
kt
0*45
4*2
0*33 " 2*6
. 0.60
*> -
*.38
1 .5
0.21
0*53
1*9
0*30
.1*3
0.17
0.45
4.2
0 .2 2
1*0
0.13
0.35
2*8
0*25
0. 62
Mone
0.45
CB^OX
0.42
1 .?
0.24
0.60
2 .1
0.31
1 ,3
0.18
0.43
4 .4
tm
*»
m -m
**
C6H6
3461
k3
0.21
CH-Cic'
& &
S780
k
m -
■«*
0.50 ■ 2 .0
tm
tm
0.29
*w
0.70
(fa b le eo n td , on m x t page)
f
CLH
o o
soae
A B-X E -X tt*
0#so
2*0
0 43
' .1*8
#
0*2#
0*59
2 2
CJHL - :
« * ■
4558
flone
*
0*74
.
0*28
■
‘
0*23
0*71 ■
o
0*65
6 .1
0.43*
s .s *
&
K.
0 < j
1*#-
0*17
■
2*3
0*34
. 0*83.'
<m
' 1 .1
3*8
3*0 . 0*45
■ ..
4m >
j
0*64 -■2*7,. ■0*38
*
*
*
0*79
0.97 ■ ■9*2
*
*
3*1 : ■; 0*45 ■. 1*1
f h ts e w k f s a re o b tain ed u sin g ..calculated v alu es o f
(ss
,C
/
43 41
.
/■ p i a l e e t r i e c o n s ta n ts {£}. o f so lv e n ts a t 20
k '7
rid .U
'jr.
V
aken fro a «UC«T*
Ksro’CTior og th^1
asm,-ALCOHOL.
r3 op erm'i. a - s m
/ - :.tn acid i o JP»w®m. n*
;
-
■
■
■
’. ^co n sid erab le 'd if f ic u lty ' was encountered In m
& tm p t
to reduce an
e a te r ..of e th y l n^buteyl a c e tic a c id to 'ft* e th y l g^fcexyl a lc o h o l-In good
y ield # ' :' fh a stan d ard method o f reducing ea rb o x y lie e a te r s t o ’prim ary
alc o h o ls nam ely'B ouveault.and B lanc1a m ethod/ (fount* rend*, 1903,
1 3 6 .. 1676} produced y ie ld s ' o f only W $ to 31$#'
Therefor® various
m o d ificatio n s ou tlin ed b e lo w / which, have from time' to tim e, been
suggested,' were trfedUh-- Kupe and L&uger (Melv* CMm* -Actest*, 1920, 3 ,
2 7 2 )"reduced e s te r s o f camphollc a c id to the corresponding•alcoh ol
u sin g sodium and eth yl alcohol# • - U sing'the e th y l, i e ^ W t y l isc^amyl, p «naphthyl and phenyl e s t e r s , they o b tain ed y ie ld s of. 15$,' 22$, 25$,.
64$ and 95$ r e sp e c tiv e ly .of the carbinol .<* /the increasing y ie ld s being
presumably due to the In c re a sin g d i f f i c u l t y with which th e a s te r s could
be hydrolysed to th e a c id and so l o s t f o r re d u ctio n purposes*- • frin a
(Bee# Trav# CM©*, 1923, 42* .1050) c a r r ie d o u t th e re d u c tio n o f e s te r s I
of. a lip h a tic a c id s w ith s odium m d c o o tie a c id in th e p re s e m e o f
sodium a c e ta te , to o b ta in a 90$ y ie ld ©f o c ty l a lc o h o l from e th y l
eapryl&te, b u t only a 50$ y ie ld from phenyl a c e tic e ste r#
' Ford and Marvel (Org# 3ya#, 1030,.10," 62) reduced th e e th y l e s t e r ;
o f 'l a u r i e a c id w ith sodium and s p e c ia lly d rie d e th y l a le c h o l In th e
presence of to lu en e to y ie ld 70$ o f la u ry l a lc o h o l# .
Bleyberg and
U lrich {Bor#, 1951, 64, 2504) c a r r ie d carte th e reduction o f e s t e r s o f
h ig h er f a t t y ©ei&a In the presence o f lig h t petroleum to p r e c ip ita te
the' sodium e thoseide which i s produced during th e reaction* . w h ilst
Bevy CAnn# £him.*, 1958, x l t 9 ,5 ) reduced the iao^emyl a s t e r of oi •benzyl
i
oQ n<P>
j^-batyrXe a c id wit& .'sodium m d isoam yl a lc o h o l'to th® corresponding
alco h o l i n
■yield* - v ^ 'l
A ll o f th e above,mat hods were t r i e d on. e a te rs of e th y l n * te ty l
; a c e tic .a c id . I n .an attem p t to'.. e f f e c t I t s re d u c tio n t o f t <*e th y l j^hoxanolf
i n .addition th e re d u c tio n o f th®' e t h y l ' e a te r in .n * b u ty l and tso~amyX
a lc o h o ls and o f th e iwtoutyi e s t e r In n~butyl alco h o l were a ls o .c a rrie d
B o m m r , nonm o f th ese Methods le d to th e .production . o f ^ e t h y l
. out*
j*»h®xftncl in more than 39$ yield*
■".fhe y ie ld s o b tain ed by th e v ario u s methods are enumerated In
• fa b le
X X II*
' /* . ^ ^ >
C & rlA ' 4' ■<?-n.
7<7^7
*7
T A B L E
y ie ld s o f
X III*
Efchy1-n-hexsnol obtained by the ..action o f sodiim and
various- a lco h o ls on e s te r s of I th y l - n -butyX a c e tic acid*
E s te rs
Reagent used.- to g eth er w ith -S o d iu m * ...Ref.
Y ield .
E thyl
99$ Eton v;
a)
15-31$
L ight F© trolmm and d r i e d , BtOH:
(S)
Impure product:
23%
Dried BtOll ^ toluen© '-
23%
11 ■■'."’■* ■’■'>'benzene m
(->*
it
b - E m DH
:v
28-39$
b-B mOE
- giving- alm ost d l- c a r b in o l
60$
rf
iso-am yl alco h o l •(3)
18-1JlWj#
W M -V *
A cetic a c id and sodium a c e ta te
'tv-Butyl
n ^ b u ty l-a lc o h o l
Iso*Amyl
i s o - amyl alco h o l
(<0
30%
Phenyl
«
99$ EtQS
(2)
33%
(z)
38%
Bribed EtOH.
23%
........ ' ;
The iso-am yl and n-b u tyl. a lc o h o ls were d rie d and d i s t i l l e d from
uMiT ^ wffa
w
m e t*
V
M e ta llic calcium ;.' th e d r l e d ’e th y l alco h o l was d rie d by means of.
magnesium methoxid© {Org*. Syn#
7 , •57) ♦ ; ■
■' The' re fe re n c e s are* -' (1) Bouvesult and Blanc,. Oampt* -rend#.,'. 1903,136>,
1876* v- (2) Rupe and Xawger, Eelv* Chiau Acta*, 1920, ■3, 272* {3}
P rin s , Kee* Tmr* Chim., 1925, 42, 1050* {4} Ford and Marvel, Org*
Syru, ¥ol* 1 0 ,8 2 / (5) Bleyberg and U lric h , Bei%, 1931, 84, 2504.
(6) Levy, Am* Chlsru, 1933, x i , 9, 5*
R eduction fey d i r e c t h jd p o g eaatio n 'u sin g ' a *copper chromite® '•
e& taly at as suggested by Adkins and F e lk e rs ; (J*A.C* S*, 1981* 83# 1095)
proved a f a i l u r e , most p ro b a b ly ■because i t was not p o s sib le 'to a t t a i n a
s u f f i c ie n tl y h ig h p re ss u re 'a n d tem perature*
CThe p r a c t i c a b i l i t y of
the l a t t e r method o f reducing e& rboxylto"e s te r s ~to aleo h o is i s shown by
th e f a c t .th a t' b u s ie r : has p a te n te d (1?«S*F* 2 , 079# 414) a met te d f o r th e
pro d u ctio n < falco h o ls from th e e s te r s o f notM roatatlo (i#e# a lk y l o r
a r a lk y l) ael&s usin g ms c a ta ly s t copper o r sin e in th e presence o f
copper ©r sin e chrom ite a t a working p re ssu re o f f r e e 50 to 250
atm ospheres and a tem pers.tare o f 200° to 500°*,
More re c e n tly ©arsons (Oompb* fiend## 1937# 205* 682) has prepared
th e g ly e e rid c c o f phenyl s u b s titu te d a l ip h a t ic a c id s and reduced them
to good y ield # u s in g •sodium an d .amyl' alcohol# t o th e corresponding
phenyl s u b s titu te d a lip h a tic a lc o h o ls * .
However, ,th ls method was n o t
t r i e d in th e p re se n t Instance* '
th e b e s t m ethodIbr th e p re p a ra tio n o f the d l-o a rb in o l proved to- be
th a t o f red u cin g th e e th y l e s t e r w ith s odium and '**.b u ty l a lc o h o l|
©a sis a l l ru n s (M/20) gave y ie ld s o f frcaa 2 8 / to 39/*
th is
When# however#
th is method w asrrepeated on e th y l e s t e r o f (^5-ethyl n -b u ty l a c e tic a c id
( I I ) th e r e s u lta n t (*)-/* * e th y l t^h ex en el was produced to 6 0 / yield# b u t
had only 1 9 / o f t h e 'a c t i v i t y o f t h a t produced when F r i a s 1, method of
re d u c tio n was'used# - -th e re fo re # f o r th e p re p a ra tio n o f th e o p tic a lly
■active' alco h o l recourse, had to be made to F r ia s 1 m atted which unfortnn**
s t e l y •gave a y ie ld o f only 18/* •
\
8 9
"f h l s ex te n siv e r&cemia&tion suggests th a t'd u r in g ' th e r e d u c tio n '
o f carb o x y lic e s t e r s by means o f sodium and a lco h o l' th e follow ing
re a c tio n must occur to a co n sid erab le extent'**
B*OKa
‘CO^R
.Ola
^
N-OK
B»OH
Support fo r th is view wm provided by th e fo llo w in g experim ental
re s u lts ;—
A specimen o f th e eth y l e s te r of ( * ) - eth y l |**butyl a c e tic a c id .
j
w as.r©fluxed 3. hours w ith sodium ftutoxlde in n-*butyl a lc o h o l .when th e
j
r e su lta n t {-)- e th y l j£*butyX a c e tic a c id possessed only 20$ o f the
|
a c t iv it y o f th e o r ig in a l
i
etfa^i e s te r was made*
{
-
)
-
ethyl' n*b u ty l a c e tic a c id from which th e '
! M i f a c t i s in -agreement; w ith an actual reduc­
t io n ©f th e e th y l e s te r o f ( » ) - eth yl jWbutyl- a c e tic a c id when th e
. .j
r e s u ltin g («#)-y£f-ethyl ivh exsnol had only 18$ o f th e o p tic a l, 'rotatoryi
power' o f a s im ila r sample, o f th e (+)- e a rb ln o l made by re d u c tio n o f th e j
■
■
- ■
ii
W - e t h y l e s t e r u sin g frin s * method {see experim ental se c tio n ) - a
method u n lik e ly to cause ra c ami cation#
[
f h © ( - - e t h y l n-hexanol la reasonably o p tic a lly sta b le , as a
specimen w ithstood 3 hours r e fla tin g with- sodium butoxide in n-butyl
a lc o h o l, r e ta in in g 80$ o f i t e a o r ig in a l o p tic a l a c tiv ity *
.- I t thus appeared d esirab le t o e f f e c t the re d u c tio n o f the opt! call;
a c tiv e e s t e r in a n on-alkaiine medium and ac co rd in g ly P rtn s 1 method
of-.using sodium, and c o ld d i l u t e a c e tic a c id in the p resence o f sodium
a c e ta te was adopted* .
;
fhe preparation. o f the ethyl*. n~butyl* iso ~ amyl and phenyl. eaten,
o f ■'■,e th y l n«bmtyl,f*e@bio avid proceeded ■smoothly** the eaters being
obtained In good y ield s*
■
3beir- preparation and propanties* together
w ith-the attempts 'a t reduetlen to ft ~eth yl n^hex&mol are described
In"; the experimental seetloa.#' "
« » w» « * * * * » * * « *
4
....
'
t m lUOFMTSAflOlf OF ESffcRS OF^OFflOALLY AOfXW CAKBOXXLXC ACIDS 'IS
ri ^
TnV' S^C 2 OF •AhKAhl# '
'
V ^
';'
:
,Th© raeemlaatlon o f caters o f ..optically a c tiv e e&rboxylie acids
by a l k a l i ..la .a .w all estab lish ed .phen&menon* . .'. ..As.,early .as .1899 ,
•MeKensls observed that the barium .s a lb , o f JUpbenyl.. ethoxy.a c e tic acid
. obtained. by hydrolysing .the e t h y l. ester- had approximately only h a lf
1899* 75,
, the rotatory power .o f.=the ..op tically pur© barium, s a lt
.,759}. ;.. fhen McKenzie. a n d ,fhompson {j* 0*S# # 190S, 87,' 1019} noted •that
l^menthyl §+ or ly mandelat® r&cemised with great ease on hydrolysis
with alcohol!© a lk a li, but that the fro# d~ or 1* acids were imeh more
o p t i c a l l y .sta b le under the sm® conditions#
' ' ih e s e o b serv a tio n s were follow ed by th o se o f d&damer and Kants*
(Chem* f e l t # , 1910, 54,. 1094) w ho/discovered t h a t a lth o u g h ,th e e s t e r s
o f t r o p i c .a c id a r e .r e a d ily racem isod, .th e .f r e e a c id ia n o t racem lsed .
. in the., presence of ..hydroxyl ions*
Franklend (J*C*S*, 1913, 103, 725) m ggested an explanationcf the.
above fa c ts by postulating th a t the ionisation, o f the e ste rs is. .
preceded by a tautomeric change which- d e s tro y s 'th e :a symmetry o f . the
molecule, thus yielding a m o m ic product, e*g# in the case of. the
tro p ic esters?*
%%
->
EOCHrj
CCOR
■tr o p ic e s t e r ■
.
OH
C cC
HOCHg
N
OH
/ f b ls typ e o f .t&ntojserissa.i s only p o s s ib le i f th e re i s a hydrogenatom .attach ed to the^cerben atom o f th e g&rhoxylte e s te r s , which m n
■
m ig rate to th e k eto group, o f the carboxyl .group;.. . th e re fo re i f th e .e s te r
eon t a i n t no such hydrogen atom I t would n e t be ra e e m ise d :in ...the presence
o f aXeeholle ,a l k a l i ♦ " th is was found b y .McKenste and Wren,( £#C*S#, . 1920,
117, 080) to be..the ease f o r X^menthyl X ~afcrolactinat e which, on. hyd* .
ro ly s i s w ith excess a lc o h o lic a l k a l i d id not; give- the, In a c tiv e a c id ,
nor ;was th e e s te r, which remained a f te r , tre a tm e n t w ith itm if f l e i e a t •
a lk a li: ap p reciab ly .raeemlsed#
.. ': .
.
6 5 \
v
. ;;'
• -SO-,
■■
- C iX *
,
■
/
'
3
. .COOS , ;■■■■•
, a t r o i a e t i h i c a c id , .
.
She follo w in g a re f u r th e r examples o f carb o x y l!c a c/£-»# ls who§#, e s te r s
■■.•■■■
' 1-■■■•
■are raeemlaed' in th e •presence o f a lc o h o lic a lk a lis *
O'
CLH*
CH*C00H
V D |
. ;CHEC0C$E
CoH CH.CO0H ‘
5 |
■' C^IIg
..
.
•• Blok e l , ^.A.C#S*, X053,6O,927#
•'
see experim ental s e c ti o n *
ip * 76 ) .
0JBL CH»C00H ■
I
CELCOOH
■ 2
■
.
Wren and W illiam s, M * 8 m$
1916, 109, 579.
*”™ -
■
%H« CH.0OOH
I
'
McKenzie and W ddows/!
1915, 107, 713.
,
CrtScCJr,* CH.COOH
& &|
c^Hg.
Rap® sad gerfcoviits,' B w ,, 1912,45.
1398.
■
A ll the above example®' eaa be accommodated by f^ an k lsn d 1a
' h y p o th e sis..of ta u to m e ric .change* 4* /CEydroxf»/?«*pheayl. p ro p io n ic acid.
w as.obtained o p tic a lly .p u r e from h y d ro ly sis o f i t s methyl e a te r w ith
a lc o h o lic p o tash (leftenzt# and .M artin,
J*C*3«»
1913* 103# 112}*
. Iv ea
i f /th is .ester, d id e n o lis e , i t would n o t on th a t account 1b come, in activ e#
f o r rthe asymmetric carbon atom i s th e y^earbon atom and i s l e f t w ith
a l l . i t s ;four;bonds i n t a c t (a f a c t which th e a u th o rs f a i l e d to p o in t
cuiji-*'1
*
V-
06H5 CHtG% C00K
C6H5 CH * CH « C ^
Oil
’
'
. Oil
However# .■Frankland* s h y p o th esis w ill not account fo r the ;
. behaviour o f th e e th y l e s te r o f
^hydroxyyS -phenyl, propionic, acid*,
Although t h i s compound c o n ta in s th e re q u is ite ^ -h y d ro g e n atom I t
y ie ld s ' th e unraeeaiised mold on h y d ro ly sis w ith a lc o h o lic a lk a lis
and
th e : e s te r 9: on- treatm en t, w ith i n s u f f i c i e n t - a lk a li for.' eospXe te .
'h y d ro ly sis* can be re c o v e re d ,o p tic a lly -pure*. ' ( McKensie:end Wren*
"£Vfc*S** 1920* 117* €80}* :; t h i s must mean th a t th e hydrogen of ;th®A ^hydroxyl group i s f i r s t
re le a s e d as m proton, under' the a c tio n o f th e a l k a l i and t h i s p re v e n ts
:the •r e le a s e of th© hydrogen atom d i r e c t l y a tta c h e d to. th est •carb o n .
atoms**'’
■■: f*1t
’ CgHgCi^ C _ CQOEt
Icm
vU
"-— -/>
' H ' CaHfiC&> - 'C - CQQEfc
f7l
t ^^
jn
^
Q
¥ f » * v >* f-> T
p .
0i^XCAr'i T
IS ^pp'^p^^P J?£ (if 1”**
^ * , ’ “ K -*
Onro&ueing IM othyl ostia? o f othyl n-M tyl so©tit m M t o ^ <*
©thyl ^ m m m ^ l using-^cMlltiii and f ^ l l a i i j metiTO
«deobol#
i t waa-.obsorwed that,tho i||o*sto 3,t 'sM ohoi recovered tm m th is
■e ^r&nc&t was 'almost In m ttm * ; ' (See.'-e^parisicixtal sestion ♦ p# ?? )♦
*rhi$. :rsciemisati€ii o f ;aleohol&tos fey haai was f i r s t observed far
SO*#»■>*•vtwt
®Ui£^j?1 aleohoiate by JD0 Bel" (0cgs^?t*' r®nd## 1378, •67 * 8X3}/
,1
whsroas th© aXoohoX i t s t l f i s ©plioally.otabl® m% E&mh higher
tasaptratin^s#
' Similarly net!VO sf0*feutyl aloohoX ratssnlses on heating
with sodim {Alfereohb# i^hesis* itoieh# IDS?* 31)#
-
' As, i t was found tlml- aXoohoXs i l M ^ i tanpepaitttpos lose bfawagtti; ■.
foraing aldohydas 02* katoaas* «M that .the aXoohoXttos uo©^ :p^st at /./'..
lower temperatures .{about &OO0 ler cr) than the aXeohola
ten**
j
1901® 316*. 158)|, I t was'suggested by Wa^nsr^Jauregg (fpmtoifeerg1©
Steroofheml#* .1953® Si*!) tlmt tho raocnisatiari' e f aleoholates owsswdj
'through.the'©©aversion of few aleoholato. to in ald©hydo®'whieh thon
|
re&stod with further sleobol&t©* wttmiting in'en interchange of tha . "]
. '■
•■ .
■
• .
. . ■ • . • ■ .
alhfX, radicals ntU ’Chod
t o
th e
.-
-
’sat 'loss of. m iiw lfyr*
' *, : ^ 0 '
:
" .* *
'
.
•'
■
■ ■.
.' ■ -
"
> 0 ■
E - OSa = = ± . B » GC
n « G Z ' ... -f■■',■■ E
......................
■
fh in taeohanism r o o e lw t
■
alooholiO and' aldehydio gr<mp% with
-f-
. '
■■'✓■
-K * OSs
■
j
j
!
■■ ■■' I
from th© m $ k o f r ^rwato and . ■,.,.;
Schmidt {tel*®/ WBB$ M4» SSI) and o f VorXey {Bull* Soo# €him** .'1965® ■
rg?.» 637) who found that an interchange of aldehyde and'alcohol grcmps ;
©c^-'Tad in the presence of w&min&m alooholato tod osocss alcohol* e.&
4 5
ftCBO■+■'U em jM
Mi oEt)3
MaCHO
Sh«se workers suggested -th® use ' of sitnainjxsm eihoxtde as * method
o f-red u cin g an ’u n sa tu ra te d 'a ld e h y d e to th©. cor r e s pond ing unsa fu ra tod
a lc o h o l* v (X he'use o f "aluminium ethoxl&e f o r 't h i s p u rp o se ;.has-been:-,
superseded by alm siiiixm isoprbpbxidie* ; : '.fh# ;lm tie r .is- converted to th#
re a s o n a b ly '.v o la tile arid, easily'"condensable acetone ms' -compared.with; ....
mcetaldehyde-- which i s : too v o l a t i l e •to ‘be conveniently. handled ** th e
production, of acetone serv in g as an in d ic a to r o f-th e p ro g ress o f :th e
re d u c tio n * )
Pom dorf (Z* Angew* Chem** 1920* 39* 138) was ab le to show t h a t .
"the in terch an g e o f.g ro u p s took p la c e .in the presen ce o f sodium
alcokohCe^ e .g . anisal&ehy&e .'and b en zyl',a lco h o l i n th e presence o f
sodium' bensoxido y l e ld e d 'p*methoxy-bBnzyl a lco h o l and./toens&ldehyde*.^■b-Mckei and I&ab {Ber*# 1931#' 643# 2157) f a w u r a n o th e r
mechanism f o r the mcemt c a tio n •o f a lec h o la te a* • th e y found t h a t eis**
■**
mnafmurowi
^Vdefcalol ( I ) i s converted ms th© m loholate^to ta»s.na«» ^ * d e k a lo l { II)
' E2id /B lm ila rly a second tran s* o&»dck&lol
XI.
m.p# ’63
o
{III)
Isom erlsea in to II*
o ;0x p la l n. th ese 'r e s u lts . Etekel iM -la&b suggest th a t e*g* - th e
anoint®- of'- th® ■cis~ ^••dakalol (Ij f i r s t lose®, two ' atom s. o f hydrogen
one from th e a lc o h o lic c a rto n atom and th e second from the carton
.tom' dotm on to b o th rings**
Kao . : .S
laO
I
:::
:x ? \.;
CSL.;- ^ C - H !'! ;'C£U
| 2
|
| ^
-- ---- — >
*
Cllg ■;
yCMf. ^CH2 '
,0 H ^
m
.
:■
/ If*
■.
CEL :
,—
o '
1
yO~H
x 0So
■ ■ ■ ■': ;
'm 2
I "
yrCll2
^
'
I!2
*
xo%;
Y .'/■
V,;. :fh© sodium d e r iv a tiv e (V), and n o t th e -free aldehyde "a® in
WagneavJaurcgg*a h y p o th e sis, •then react® w ith f u r th e r amounts o f X?
to .g iy s th e transw Jt *dekaX®X (XX) * th® hydrogen adding to the
double head, o f ? i n the u su a l tra n s mmmvt**: . SaO
'.
'
' H ° >*■" :
4 7
; : ik-g i s
to
fch# r e a r r a n g e m e n t
e ^ p a a t e d ,' i t
th # hy& ro^ X grou p i s
in
a b o u t ' th # '' carbon-■afc6&;'c©»©»'-t© th#
talc# p l a c e * " " . " V ' ? . - :
th # ^ - p o s i t i o n
r in g
d o e s 'n o t'
.
4 8
prude Ecuafelons caleul&fce«l f o r th e o p tic a l r o ta to r y powers in th e
<W#Tiis» nii» i i ii'injiwU '•'t i |iiJTi,l»'>mi g. irrrir 11 mTumtjriuw^ri^yrrKfir r'tt tiwisii m r ■- ‘Tr-“ “‘-iT m.iynrnnVifii inr‘"h- 1—1
*r “ -'*t ‘l”f
»i»»n ■»■ t r
tomo^eneoue s t a t e o f :
,|. n ..|. - a j ^ . . >
■'■■■‘■’ »
, ,-.
■
"Roetl.o aeidfi the # th y l e s te r o f
e th y l' n~b u ty l a c e tic acid#; -■(-B/* * ethyl; n^hex&nol and^m eiftyi ri^heptane#
The f i r s t attem p t a t ex p ressin g o p tic a l
r o ta to r y powers
j
j
by means
o f m athem atical eq u atio n s was •mad# 1n 18X7 by Blob who.p ut forw ard th e
equations*
*7nz
k
*
■-
v; u.,I-./;.---,- ■-■■■:.;
when© k i s a constant^ and
i s th e w&w®~iength
j
' I
- j
: r, .
a t which the \
- r o t a t i o n ^ 1 ©measured*
. • ■. - ' ■]
However* t h i s was found n o t .to be s t r i c t l y tr u e , and I t was n o t
u n t i l 1000 th a t r e a l l y s a tis f a c to r y eq u atio n s were p u t forw ard by t&mde
t h e o r y o f Optica®* 1900) *
■V
Bis form ula was**
• ,X
where k * constant
w ave-length corresponding to a'; c h a r a c t e r is t i c wave-length*
©
and
• :"\1 * dispersion c o n sta n t
...
(2kmry and Dickson*"'Trans* Par# See#*
1914, 10, 9 6 .)
' \ Drude1s form ula h m not- been- d isp laced ms y e t* 'a n d was la r g e ly . .
used by Lowry and h is .co*workers#
Lowry and Dickson coined th e term
. nsim ple r o ta to r y dispersion® f o r o p tic a l r o t a t i o n s 1, which can bea c c u ra te ly expressed by a one*term JDrude' equation; ■end Rcomplex ;
r o ta to r y dispersion® ' f o r o p tic a l' -r o ta to r y powers which can only be
expressed by two o r more to m s of
a ©rude equation# ' ...:.
]
j
: Bxmde. 'equations f o r th e . o p tic a lly a c tiv e compounds used In t h i s
In v e s tig a tio n war# c a lc u la te d from th# ex p erim en tally observed
r o ta to r y powers and. d is p e rs io n curves by th e method o f Lowry and
Owen, (T rans. Far* Soer# 1930, j|@, 371)*
F o r.th e o p tic a l r o ta tio n s in the v is ib le region o f tf ) e th y l nb u ty l a c e tic ac id In th e homogeneous s t a t e , i t was found th a t a cue
te r n Prude eq u atio n having a c h a r a c te r is ti c wavelength ^
a c c u ra te ly e x p re s s e d . th e •experim ental fig u re s*
* 1516 4°
The o p tic a l
r o ta tio n s of th e (<*j-ethyi n -h n ty i a c e tic a c id in so lv e n ts wore also
n o t anom alous,. as h o m e ©lit by p lo ttin g •a ne h a r a e te r is tic diagram11
(Armstrong and % lk e r # Free*. Soy* See*, 1913, ASS, 38B) o f 'th e
o p tic a lly a c tiv e ©old in e ig h t s o lv e n ts , when a s e r ie s o f s tr a ig h t
lin e s were obiitald - th e expected behaviour f o r a compound p o ssessin g sim ple d isp ersio n #
.. .The d is p e rs io n eonsbant o f th e homogeneous a c id v a rie d from
/ a 't M
'*'***
m B r a tem perature range o f 34°, w h ils t the
d is p e rs io n c o n sta n t o f th® a c id measured In so lv e n ts a t room temper atm
v a rie d -o n ly from 1*5 to 1#?, (fa b le s X and IX)*
•''The aq uation f o r (v-) - e th y l n -b u ty l ace t i e a c id is*:
f
o°
+. 2 . 9 2 3
/ A I N—‘'T'17“nu‘"'rinn’,-,"”n1f1
•
>
/T *0,02300
x
A
.
0
a X51SA
' 0
Thus i t can be s ta te d t h a t the {+-}-e th y l sa-butyl a c e tic a c id
e x h ib its sim ple r o t a t o r y d is p e rs io n in -th e v is ib le re g io n .
. w ave-length
She
15164°) o f th# a b so rp tio n band c o n tro llin g th#
o p tic a l ro ta to r y power o f t h i s &1s u b s titu te d a c e tic sdd Is r a th e r
low when compared w ith Leven©1$ statem ent *th# r o ta to r y d is p e rs io n
o-
^J_ACEXi^AaX>
curves o f .d isu b s t i t u t e d .see-tlo ac id s ©an -be -e x p re s s e d ,: fo r a l l •members,
'
■,
\ . ...d.u ® » .
by a on® term m m formula having /) glSSOA *
{Oilman1s *Organic
.«* - 1938, 2 , 1316).
Chemistry*1
(
' © '
'' S im ila rly th e e th y l e s t e r o f {* Methyl. n*butyl a c e tic a c id e x h ib its
a$mpl* ro ta to ry -dispersion in the v is ib le region*
v a rie s fro® 1*7 to 1*6 o v e r.40
o
i t s d isp e r cion ' eonstei
range o f tem perature*
{Table 1?}*
The fo llo w in g eq u atio n a c c u ra te ly exp resses th e .sp e c ific r o ta to r y
powers' of the C~) e s te r in th e homogeneous sta te * *
£0
'1 \
y
■ - 2 ~ ™ ----------^ i -0.0273
,
. 1 « . A°
and' «a would tee expected, l t a d is p e rs io n ctirvs
p lo tte d a g a in s t X )
i s a . s t r a i g h t lin e*
■--.'The values o f th e d is p e rs io n c o n sta n ts of e th y l n~butyX. aeeti©
a c id and o f i t s e th y l e s t e r ~ 15161° and .16821° re s p e c tiv e ly «* show
th a t t h e i r o p tic a l r o ta tio n s a re n o t c o n tro lle d e x c lu siv e ly by the
*0 s 0
r a d ic a l o f the carboxyl group# f o r t h e ab so rp tio n band o f the
o
carboxyl group- shows a mmximm mt B100A (iow ry, *O p tical R ptatory
fower% 1935#.- p*288) o r approxim ately 20001° (Levene, Rethen and Meyer#
J* Biol* Chcm., 1934# 107* 556}*
Thee sp e c ific r o ta tio n s cfthe e th y l e s t e r o f {~V e th y l n -b u ty l
ace t i e a c id in nine, so lv e n ts a re recorded in fa b le ,
from which i t i s
seen th a t the d is p e rs io n c o n sta n t v a rie s '-from 1.4: to 1*7*
■A
11c h a ra c te r i s t i e diagram** ( Figure#) p lo tte d from th ese fig u re s g iv es th e
ty p ic a l s e r i e s 'o f s tr a ig h tu lin e s* ,
:OXATQRY
SPERSt.QN .QFL-_.ET.HXU._; ESTER,_.QF_YrH ETHtU
: :;Tt~ BuXVk ACfcTiC ACID 1 AT iT°C
A X 10
150
2bo
CHARACTERISTIC
DIAGRAM
T i* B u t y l
■O F
ETH^L
a c e t ic
ESTER
OF
(~ ) ~ E i H Y U
5
Th©" (~h}f **e th y l ja~hexanoX whose r o ta to r y powers a re recorded Ia
Table VI* displayed simple dispersion in t'm v is ib le region as sf own
by a 'normal straight line dispersion curve (Figure)) and th©
th a t its specific rotatory power m n b© .ae eu rately expressed by the one
'term, ,Drud© aquation, as follows;**
1.395
>\ -0.02X73
o
\
<
5 A * 14V4&
;"fhe (+) carbinol also exhibited normal behaviour in seven
solvents (fable VII}*
.-. fhe optical rotatory powers of { ^ m e t h y l ethyl n-butyl methane
at various temperatures are recorded in fables V III and XX, and It Is ,;
seen .that Its specific rotatory power remains fairly constant over a
©
temperature range of 21 , as does ©Iso its dispersion constant*
. I t Is a curious fact that the hydrocarbon molecule should not
exhibit simple rotatory dispersion* whereas the ethyl n*»butyl acetic
acid* i t s eth y l ester and /*•eth y l n-hexanol from which the hydrocarbon
Is derived ©re possessed of simple dispersion*
The evaluation o f Its
rotatory powers necessitate m Brad© equation of a sere complicated
type than
Lj I ^
ir
*
~f "2
thus su g g estin g tn a t
^ * >o KIts rotatory dispersion is controlled by several absorption bands
i— />
»
k-*’
and not predominantly by one band as in the-case of ethyl n-butyl a e e tl
acid and Its ethyl eater*
In this connection, it is interesting to
note Levene#s remark {op* © It*)
compounds of .the type
that the dispersion curves of
when•expressed as a one*tern Urud©
equation, give dispersion constants of ^ ^2^:1600 to 1VOO&0 *
His
R o ta to r y
d is p e r s io n
of
: (+ )- p - £ t h v l v
1875
1125
X X lo ‘
260
250
'3?o
h e lx a in o l
at
e a r l i e r remarks .{Leimnm and Hoth en ,
Org* Cham*f 1036, 1, 79) are
a ls o In a p p lic a b le in th® p ro sen t in s ta n c e , *the a n a ly s is of r o ta to r y
d isp e rsio n c u rv e s 'o f th s s e substances {hydrocarbons), in d ic a te s th e
p o s s i b i l i t y th a t the r o t a t i o n 'i n th# v is ib le region-.can he expressed
(1)
by .the sum o f two
c o n trib u tio n s o f -o p p o site sig n ,
by- a Drud©.
'
formula of two tennis w ith o p p o site signs*®
S ia& lafly Harrison*. Kenyon and Shepherd (loo* c lt* ) s t a t e th a t fo r
sec*b u ty l benzene a one term Bmde eq u atio n was in a p p lic a b le , end from, •
t h e i r p u b lish ed fig u re s o f o p tic a l r o ta to r y powers a so re com plicated.
Crude equation th&npLm
4-
i s n ecessary to compute
c o r r e c tly the s p e c if ic ro ta to ry powers o f th® hydrocarbon* .
.. && th e ..u ltra , v io l e t a b so rp tio n spectrum o f n e ith e r^ m e th y l nr
heptan© nor se e -b u ty l benzene Is .re c o rd e d in th® l i t e r a t u r e , th ere i s
no evidence forthcom ing from a b s o rp tio n •sp e c tra to sjupport o r c o n tra 'diet-- th© .statement th a t more :ih a a one' a b so rp tio n band c o n tro ls th©
o p tic a l r o ta to r y powers of both hydrocarbons as. in d ic a te d b y 'th® u
inadequacy o f one o r two term. l)rud@ eq u atio n s to compute t h e i r
o p tical.; r o ta to r y powers*
Th© s p e c if ic r o ta to r y powers o f ' (~H- y^m ethyl •n-heptane in. th re e
so lv en ts a re recorded in 'T ab le. X* No extended study o f th© e f f e c t of so lv en ts on th e o p tic a l
'ro ta to ry powers o f
mm u n d ertaken, owing to
th© poor o v e ra ll y ie ld o f hydrocarbon which r e s u l te d from-theo p tic a lly a c tiv e s ta r t i n g fa c to ria l — e th y l n -b u ty l a c e tic acid*
u_
9
T
m
m
-
xi?.
PoEti&e eous.ttcm® fo r ’s p e c ific ■yofcafropy powers o:
«bMt» iMl
acefcio a c id , e th y l e s te r of (- Methyl n -foutyl a c e tic a c td and
'n-hexanol.
n -tu ty l se e tie eeid
— — ■—
a t mi Tf t i i . . iiMMift'fl iiw n iiin iiT iii»-i m il
liquations< r*
X
r
Uj
v
>A
Oh&ermdfc];
»
2.923
*••0*02300
OslculstedfcSx
0
-
1)1£ferenc e .,
fe3oi>j. "~6iraU.
-0 .1 4 °
6438
■+ 7 • 34
■+ 7*47
5393
8*95
9.01
-0.06
5780
0.43
0.39
+
5461
10.62
10.63
—0 • 01
4358
17.60
17.51
\ - 0.01
0*04
W.thfl Fster_o£. ( - ) e th y l iv b n ty l s c e tie a etc
E quations-
A
»7'
Observed [o(L
-2 .1 7 3
^ -0.0273
C s X e u la te d
•5 .4 7
6433
Difference*
^o£s.~~ l9§<?a)<?_
o
■t- 0,17
»8WW—VCTL>MCWm«u*M>^ M
WM*W6-awW*iiW.iM*—«W
Wml
+ 0.01
+ 0.02
5780
7.10
5431
5086
43&B
8.02
8.02
* 0.00
9.34
13.37
9.58
'*.56
+C.C1
-0 .0 4
;
60
'
;; A ; ;i. ; 6433
'"*>
-
.
.
r ,y Q 0
Equation*- k f j \
0
. SkssszsM *
1 + 3 .5 6 °
1.295
A -0.C217S
£ a ls a M M 0 A
+-3.55°
JMEgssafift*.
*0,09°
5893 •
4.25
4.23
-0 .0 3
5780
4.51
4.47
-#-0.04
5461
: 5.08
5.04
+0.04
5033
5.38
8*83
*0,00
4358
8.89
8.29
*0.00
m ,m
m * » * * .* * * * < » « * «*«»■**
'
* * * * * * « * « • •» * * * » * * «* « •
'l
fcT
■g5* t V M
I*
V£"<I.#®41*4.jfciu#
a s K . ’ ' JED RESOiWff OM.OP/^-WSYL n-KTiXAHCL IOTO ITS
OPTICALLY ACTXVK CO »'?C5FK'i’S«
n~.hexan©l l a smoothly converted
In to
h ydrogen"phthalie e s t e r which r e a d ily f o r ma
Its
c r y s ta llin e
b r u c in e
s a lt s
’r e e ry s
t a l l ls a tio n s '' f r o ®
d il& te 'hydrochloric
phthmli© e s t e r ’ had }ot}s^w *1*73°
in
T he
a c e to n e was
a c i d w he n th © l i b e r a t e d
carbon d lsu lp h id e
hydrogen
s o lu t io n *
■
e s t e r w he n s a p „o n ifled w i t h sodium h y d r o x id e
■■■-,*■ ' 0
2v»hexand w i t h
.
— 0*11'" C l„ * 0 * 6 } *
I n a second
fe e b ly r o t a t o r y
y ie ld e d ^ * e th y l
e x p e r i m e n t .th e
but
w e ll d e fin e d
ein ch o n ld ln e’ and morphine*
w it h b r u c in e *
s a lt a fte r f iv e
decom posed w it h
This
b y th e u s u a l p ro c e d u re
In
b ru c in e . s a l t
case* th®
th is
In activ e*
.. In
w as
r e e r y s ta ll ls e d
lib e r a t e d h y d ro g e n p h t h a llc
e s t e r w as o p t i c a l l y
- .
lik e
m anner th e
elnchonidln©
s a lt
and
ware subm itted to f r a c tio n a l c r y s t a l l i s a t i o n
b o th ca se s
fr o m m e t h y l a c e t a t e
th e
lib e r a t e d
o p tic a l a c t iv it y *
h y d ro g e n p h t h a llc
• However* on f r a c tio n a l
t h e m o rp h in e ,
fro
s a lt
m a c e to n e b u t In
e s t e r w as
devoid o f
c r y s ta llis a tio n
o f the
e ln o h o n ld ln e"s a l t from an aeetone^chloroform f i x t u r e , th e lib e r a te d
h y d ro g e n p h t h a llc
was I t ' found
e s te r had
p o s s ib le
a lk a lo id a l
s a lt s
th ® l a t t e r
in to
f *1*7° in
c a rb o n
d lsulphide*
Bor
b y f r a c tio n a l r e c r y s t a l l i s a t i o n o f the
o f ’t h e •1-hydrogen -3 ~ n itro p h th a llc e s t e r to
o p tic a lly
a c tiv e
enantlem orphs •
s e p a r a te
Frepa.rat.ion of
*»Bthyl n»ffeHanyl, Hydrogen P hthslate* . A m ixture
o f ' r e d i s t i l l e d commercial/M ethyl n-hex&nol (b.p*,': 180-181°t ■65g*}
j
phthallc anhydride .{741*.}-: and. pyridine. .(40g*) was heated on -the steam
j
h a th fo r 2h h o u r s . .- fh e cooled re a c tio n m ixture was added to ic e and
!
d i lu t e . h y d ro ch lo ric -a c id and the. lib e r a te d hydrogen: p h th a llc : e s te r :
j
e x tra c te d .with ether j
j
i t (l40g*:); was o b tain ed as an o i l which
s o l i d if ie d when cooled to about "~B°C -and m elted a t 14^16° . -(Founds
■■
■
- ■
0,68#65; If, 8 *05* - ®i6%g®4 -s-.-requires 0,69*04; h H#7*97)4*
Found,, y
by t i t r a t i o n w ith N/lO KaOHf Jf*.W* 283$
C^^HggO^ re q u ire s
Brucine B alt o f /^ ~ Btfcyl n -Hexanyl Hydrogen Phthala&e*
|
i
,j
m*sr*' 278) .
B rucine (40g*)
was d isso lv ed in a warn s o lu tio n of the hydrogen ph th allc e s t e r (£8g*)
in acetone (50c*o*)
The brucine s a l t which sep a rated on. cooling, was \.
r e c r y s ta llis e d fiv e ' tim es fro© acetone when i t was obtained (17g#) w ith
®*p. '91*?-94°j
decom position with d i l u t e hydrochloric acid y ie ld e d
ethyl^n-hexanyl .hydrogen phthalate w ith
-1*75° .(£,4*919$
in
i
Carbon &isulphide solution*. In a s im ila r manner th e same amount o f brucine s a lt was prepared in methyl a c e ta te (ISOc.c*) s o lu tio n and r e c r y s ta llis e d -three tim esfrom- th© same’solvent*
. The hydrogen p h th a llc e s te r o b tain ed by
decomposition of., th is .-s a lt was o p tic a lly in activ e*
Olhohohldlne S a lt of (&**Ethyl n-»Hexanyl Hydrogen Bfathalate*.
j
4 '
s o lu tio n o f the hydrogen p h th a llc ester (28g*) and einchonidine (29g#)
in war® acetone {|LO0c*o.} gave a c r y s t a l l i n e crop o f the s a l t a f t e r
j
stan d in g -& few minutes*
1f h i s ;s a l t a f te r ; th re e r e e r y s t a l l ts a tl o n s
- from -acetone had a*p* ■128-*131° and; on decom position y ie ld e d o p tic a lly
In activ e-h y d ro g en phthallc. e ste r* - .The s a l t was then f u r th e r
■r e c r y s ta llia e d - tw ic e from, a-m ixture o f acetone and chloroform (2:1) :
on d e c o m p o sitio n .it y ie ld e d { +)-/&*e th y l
when i t s m*p# was. 154*135°;
~n~hexanyl hydrogen p h th a la te
1*7° (J3t 4*598;
1^2) in carbon
--d tsulphide, .'.solution# „
.
.;••;. A s o lu tio n o f dly hydro gen :p h th a llc e s t e r (28g*) and cinchonidine
.(29g*> i n warm methyl a c e ta te (l£5c*c*) ra p id ly d ep o sited the s a l t
in r o s e tte s o f needles*
' This a f to f fo u r r e c r y s t a l 11c a tio n s and
' subsequent decom position y ie ld e d a- hydrogen phthal ie e s t e r w i t h :
M & w ^-0*51^ {0,5*929;
%&%) In carbon d lsu lp h id e ;
a f t e r fcwib
f u r th e r - x e e r y s ta llls a tio n e th is s a l t on decom position y ie ld e d a '
h y d ro g en .p h th allc e s t e r which was o p tic a lly in a c tiv e #
’Morphine S a lt o f /6 ■»E th y l; ft»He»anylj-Hydrogen.,P h th alate * .; ;A s o lu tio n .
■o f th e' hydrogen"p h th a llc ; e s t e r ' (2Sg*} - and morphine •( 30g#) i n warn
a c e to n e --(lS0e«c#) a f t e r standing se v e ra l .days deposited-',
b
' c r y s t a ll i n e crop o f the..morphine - s a lt# ■ T h i s 'a f t e r th re e re « ."
c r y s ta llis a tio n s 'f r o m acetone-gave#-on decomposition# the dl»
. hydrogen phthallc'" e ste r#
• Hydroly-sls of (~ Y/3~35thyl.
-1#7S°) •
.
"
n -Hexsnyl Hydrogen P hthalate#
(
A c u rre n t o f steam was passed through a s o lu tio n o f . the ,
hydrogen p h th a llc e s te r (8g#) in. sodium hydroxide s o lu tio n (25c*c#
o f 511}*
E x tra c tio n o f th© steam d i s t i l l a t e w ith e th e r y ield ed
( ~ ) ^ « e th y l n«hexanol (5c*c«)'f b*p* 178~179^.... s.rvci
6 5
£<f~b{
■
*0# XX ,..... ^ (csss
0#27'
0*£>) *
l a t a attem pt' to p rep are a c r y s t a lli n e ac id e s t e r of. '&!*/<?*
ethyl'ti~hexanol th e fo llo w in g e s te r s were prepared by the combination
o f the a lc o h o l w ith the corresponding a c id anhydride In the presence
. of-p yrid in e:-h yd rogen -su ccin ic e s t e r , hydrogen d-camphoric e s t e r ,
hydrogen. ,4*nitrophthall.0: eater-none. however,, was. obtained in a s o l i d •
■**s
condition*.
But the l-Hydrogan 3«*IItrophtha.ilc Bater o f /f-*Ethyl
| #wn>rirt>*iiiiiw»M*»*
•
• *WK!» n n«w«n'*iMaiirf&mwmwiw M m i< im.»iiriOTi
n — «ninv*wM> *
n»Hexanol was o b tain ed In, a s o lid c o n d itio n as fo llo w s5
• M M iim ih i w i k m *
ethyl
.. n-hexanol. .(!* % * ), 3~nltrophthalie anhydride (l*9g#) and p y rid in e
• ' : (l»5g«) were heated, oa:the water hath f o r
hours* , ■A fter co o lin g ,
" a d d itio n -of d ilu te h y d ro ch lo ric a d d and e x tr a c tio n 'with e th e r the
hydrogen 5 -n lfro p .h th a lic e s te r was obtained*
On r e c r y s t a l l is a t i o n
from -ether, and .lig h t .petroleum, the. e ste r (l*4g* ) was d ep o sited as
o
n i
' '
g lis te n in g p la te s w ith m*.p# 108 *110 (Morgan, Hardy and P ro c te r,
1932, 61, 7 give a .p . 107-108°).
Both stry c h n in e end
morphine g&ye ’c r y s t a ll i n e a lk a lo id a l s a l t a ,.,the form er In methyl
' ' a lc o h o lic s o lu tio n sn-d th e l a t t e r in b o th acetone and meihyl a c e ta te
-s o lu tio n , b u t as w ith the hydrogen p h th a lie e s t e r - no s e p a ra tio n in to .'optica} -.isomers '0&ul& be e f fe c te d by re p eated f r a c tio n a l
■ c r y s t a llis a t io n 'o f -these sa lts*
'
•p*Xenyi Urethane of d l ^ * B thyl n -HexanoI* ' ‘p*Xenyl earbim ide (l#9g#)
and
hour#
e th y l n*hexanol {l*3g*) were heated -on •the steam b a th fo r §
fh e product was e x tra c te d w ith l i g h t petroleum (b*p* 60-80°*
10Qo«e«), f i l t e r e d and allowed, f a .,c r y s t a ll is e In r o s e tte s of fe a th e ry /
need les |3g*} w ith m*p#. 81-82°
g iv e
(Morgan, Hardy and P ro c te r loe* ..e l t *
80°)* . ■■■
- ■.
d ly ^ -S th y l n -Bexyl' 3s 5. P in !tro b en so a t
- cll-^ - e th y l n-h@xan.ol (l*3g*).
was added to; S$5 ''d in itro h en g oyi c h lo rid e (2#3g*,
(lg»)»
. 69°) I n p y rid in e
fh® m ixture 'was h eated 3 h o u rs 'on th e 'w a te r h a th ,.•cooled, and .
d ilu te.; h y d ro c h lo ric add added*
S h e product was e x tra c te d w ith e th e r ,
’washed- w ith rhodium carbonst® s o lu tio n , d rie d and :e x sic c a te d ' to give an
o
'o il,w h ic h r e a d i l y s o l i d if ie d on co o lin g m d M& itwp* 80-21 # ■ :Poundi
. -r
0,58*255 ;,H#a .3 1 f .
Ct55*52j ':H,0*23|*.
P rep aratio n , and H eaolution' o f -■B thyl n -B u ty l•A e e tic . Actd and i t s
•" ..Conversion to'' O p tic a lly A ctive
-
Meth y l n -Heptane» •
p re p a ra tio n o f &l«*B th y l:n-B u ty l A cetic Acid* .
(a)
: By O xidation:o f >d*jsthyl n~H#.xanol* . A, s o lu tio n of.,potassium
permanganate (340g.) in w ater {3000c #c*) was ra p id ly added to a w ell
s t i r r e d m ixture of th e a lco h o l ' {b*p« 180-181 ,
:1*4300, 130g») and
sodium hydroxide (30g»). d isso lv ed in w ater (250o#©*}*
A fte r 12 hours
s t i r r i n g the m ixture was .a c id ifie d w ith d i l u t e su lp h u ric a c id and the
m n '■‘rase, d io x id e mud d isso lv e d by .passing -a -current o f sulphur dioxide*
t h e 'l i b e r a t e d e th y l n-butyl a c e tic acid-..(10'7g*, y ie ld .74^). which was .-.'
©
o
e x tra c te d w ith .ether, h a d ’b*p» 119-121 '/liia*m *, b*p* 218 /ysOrn*®*,
18°
**
1*4255* (bevene, Rothen and-Mayor, J* B iel* Ghesu, 1938, .1,15*. 411
,
.
£5
.give’ b*p* -120 /X3m*m*#
&/Q
, 1*4289 and ,Tif f enesu., Ball* See*' Chin* #
1923, 33, 183 g iv es tup* 22D-224G/?yom*M# )*
.-If sodium carbonate la
used in p lace of sodiua'hydroxide in '-the fo re -g o in g experim ent the y lel4
o f'; eth y l n~butyl ace 11 e a c id f a l l s to 19^0, th e ' remainder of the alcohol
..being •recovered unchanged*
(b)
By O xidation .of
- Ethyl n- Hexanal* ; A s o lu tio n o f .potassium
permanganate (150g*) in w ater (25Q0e*e«) was added to a w ell s t i r r e d
m ixture -of th e aldehyde (.. a commercial sam ple,b*p* 158-60o $ 128g*)#
anhydrous sodium carbonate (85g♦) and w ater {SO0o»e*>* ■ A fter b ein g
s t i r r e d fo r ? hours the" re a c tio n m ixture .w a s.a c id ifie d with sulp h u r . ....
d io x id e* ' ' The lib e r a te d e th y l n -b utyl a c e tic a c id (113g# y ie ld 78$) '
t o d b . p . 119-1280A t o . » . . a f l . 4 3 4 3 .
,
( - ) E thyl n -Butyl il.eet:1c 'A e i d . q u in in e .'(324g*) was -d isso lv e d In a h o t
s o lu tio n o f :e th y l n -b u ty l a c e tic a c id (14%*.) in .aqueous., acetone
(1500c*c* o f - 5010# .-ifhe s a lt'w h ic h se p a ra te d o v ern ig h t was r e c r y s t- ..
a l l i s e d s ix tim es from aqueous acetone when i t weighed 140g# and had
m . p . 6 4 - 8 S ° s kQ sm
-270°
-1 1 2 .0 °;
(0,5.084}
-117.0°}
-1 3 5 .0 °;
l.,2 ) In e th y l a lc o h o lic sclitlen .
On
decomposition th is s a l t gave ..(•)-e th y l n -b u ty l a c e tic a c id b*p* 218-220*
ro ta to r y pow ers'recorded, in fa b le s I and IX* -.
.(t-)Ftbyl n*Butyl A cetic Acid*.' --.The more so lu b le f r a c tio n s o f th e
qu in in e s a l t were decomposed'with d i l u t e sulpbudL c and the r e s u ltin g
d e x tro ro ta to ry eth yl n-butyl a c e tic a c id (80g«) combined w ith
e
elnchontdine... {X61g«) .In aqueous; aee ten© so lu tio n *
•. fh& ©lnchonldin© •
s a l t : which; sep arated was r© c ry s ta llis e d fo u r ..times from aqueous u
acetone; ' i t (.13»5g#) had s«p« 6?-69° and
- S S .lj .
^
*74#8°j M
.<*160*5° ■■ {£, 4*6481 - 1,2}< l a ’e th y l -a lc o h o lic
so lu tio n * ■;' The ^ }- ethyl'"n-butyl; a c e tic a c id o b tain ed from ■th i s s a l t
o '
/
had b .p * ; 218-220 end : : (X ^ . .0*9064 its . ■r o t a t o r y . powers are given
in..''Table 1*;
■ :
v,;,.
•; Ethyl E s te r o f (-/-)-Ethyl n-B a ty l■Acetic, Held.
-A mixture of (-*-)-
e th y l n -b u ty l, a c e t ic eaeXd. (21g«3$ a b so lu te eth yl alco h o l (75g«) and'
sulphuric a c id ClOg*) was h eated under r e f lu x fo r 5 hours and the
excess ©f alco h o l subsequently removed 'on th e steam bath*"
Hie
eth y l ..eater thus -prepared (2lg*) .hat..b*p# 96-9? /35m.ir*.*, 'n^ ' .1*4185
and:d^o° 0*8641*
i t s r o ta to r y powers are given in Table XXX and
those' o f e th y l e s te r o f ( -) -e th 'y l n-butyl a c e tic acid in fa b le s
f S ’ ‘ IV.’and.V
;
(-+)-/g-l th y l n*Hexanol was prepared according $© F rin 's method; • th e
ethyl: e s t e r o f ■(+)e th y l n -im ty l a c e tic a c id {34g.} was d isso lv e d i n ■
e th e r "(lOOc.c*) :and a s a tu ra te d s o lu tio n o f ' so dium a c e ta te (2Sg»)
. in water (30c*c*)*' Sodium (25g*), c u t in to sm all p ie c e s , was added
.' from tim e .to'tim e;
th e re a c tio n m ixture was k ep t a t 0°C and.:
‘ ' ; m aintained s l i g h t l y . a c id by a d d itio n s o f 80^ aceti c acid*
. fh© ■
re a c tio n was completed in 5 days,
c a rrie d o u t
and
s e v e r a l' such reductions- were
th e combined pm duct-5 worked up;'
two main fr a c tio n s
were o b tain ed ;—(1 )a' a .liquid- {SOg*} to#p* 84->92°/18m*mv and (11). a
o
. yellow, coloured h lg v b o ilin g liq u id b*p# '117*157 /3m# m# ■(23g#) * •■
The' form er was r e f luxed T er ■two h ours w ith '.a lc o h o lic c a u s tic :coda \
s o lu tio n Cl50c#e#l'of "31} when"th e re was o b tain ed ' W ^ » e t h y l n* ?
f<J ■
‘jrf
Jf
o
hexsnoX (X5g#). with. b*p* 92*94 /82m#m#*
1*4325 and c<sfvz -**7*10*
+.8*48* ..(1,2) as recorded in Table f l *
By a c id ify in g th e ■
o
caustic-.soda, so lu tio n * (-*■}ethyl-"n-butyl a c e tic acid* b*p* 128 /18a.®#
C.52g#} was recovered with - o^SSfJ -/-15#82*
+ 50*49* (1 ,2 ;
o^s^so
18*30,
oC.<^JSS>
homogeneous) i*e* 9 7 / o f a c t i v i t y o f th e o r ig in a l (To­
othy X:»* b u ty l a c e tic - a d d * .
l + M ~E thyl n*Kexyl Io d id e *. - To \+ )j£ • e th y l' n*hexanol (13g#) was
added.su cc esalv ely re d phosphorus {l*3g*5 and io d in e (17#6g«) and the
m ixture heated f or. 3 h o trs a t 150°*; ' A fte r working -up in the u su a l
manner the r e s u ltin g /M e th y l :n*h©xyl io d id e {18g#) had b*p* 1 0 0 * 1 0 5 /
18m#m* *
1*4933 and-
3#13j,
*^3#27 {1,0* 5)«
25
tev en e , Rothen and Meyer."{lo o # ' e l t # ) g iv e f o r the (~ )-io d id e , up
1*4897 and
oC/^y *3*45" (1 * 1 )#
(-t)Methyl Bthyl n*Butyl Methane { ^V Methyt ■'n*H eptane)« ■.- 21nc d u st ■
(27g*) was added t o 'a s o lu tio n o f i-r} ^ * e th y l n*hexyl io d id e (18g*) i n
g la c ia l a c e tic a c id ; (150e.*e#) and til© m ixture h eated on th e steam, b a th
u n t i l th e sin e was alm ost com pletely d isso lv e d (7 hours)*
th e
7 0
reactio n '.m ix tu re was f i l t e r e d and e x tra c te d w ith others. ' tM a y ie ld e d
(+)-^ m e t h y l n-heptan© b*p* 115*122
v-1 #36|
■
■-*-1*25}
' cX^y^XtSlj
\l,0 * 2 5 )» ‘ '
’' f h i s : 'a f t e r heating, on th e .steam bath f o r 3 hours in the presence
o f, sodium had b*p* XlS*X130 {5g*} ri® ;1*4000, ■•(S m itte n te rg # Hoog and
■20 ■
Eehkes, <J*JL#0*S*, 1938, 60*. 18 g ive
1*3933, and Levene, <1*'Biol*
Chem*#;. 1928, 54.*'" 351 "gives n®® 1*3980) "and alm ost u n a lte re d ro ta to ry .,
powers —g iv e n ' i n ' fa b le s VX.XX and'IX*
(founds
0,84*305. H,18#78j.
0s H13 re q u ire # 0,84*82^': II# 15*?9^)*
;
F re e s ra tio n o f th e E s te rs •o f E thyl n~Butyl "Aeeti e Acid* •.
W M i i i i m m ^ w w u ' w n i r M B iM
i * m iim * i
■»« n * mj i;
• ;■<—
i k ■w
M 'f l f l w i w w t
1
f a t u „ j - n - f - ■ -, u n m m ,- , ,
- n i n * n — —1— r r . - 11 n c i r
f t h y l E s te r- o f B thyl n^B u tjl A cetic M id* ■
• E th y l n~bufcyl a c e tic a c id (30g«) was re flu x e d to g e th e r w ith 99$
e th y l alco h o l (lOOg*) and co n cen trated su lp h u ric a c id (l4g*) f o r 3
hours*
Most o f th e excess alcohol, w as. slow ly d i s t i l l e d o f f on th© ■
w ater..b a th , w ater was added and th© a c id n e u tr a lis e d w ith potassium /
■carbonate* - The e s t e r , a f t e r e th e re a l e x tra c tio n and d ry in g , was
©,
"
o- ■ .
d i s t il l e d * I t had b*p* 82 /X6m*m* and 185*186 /760m*m*
Y ield 32g* ....
(93$);
.1*4150* ' X evene,. Bo then and Meyer, Yf* Bi0l*Chem*, 1936,
115, 411 g iv e tup* 90o/28m*©# and
1*4123 w h ils t Levene and f a y lo r ,
ib id * , 1922, 54, 351 give tup* 189~12X0/?66m*m, end n | D° 1*4128*
7 i
>fhifcrl E a te r o f ft* ?1
HOid*
S th y i n°>hutjl a e e tin ’ m old:{50g#) * nv& utyI':alco h o l (25g#) and
c o n c e n tra te d ; su lp h u ric c e l l (% • ) w e re flu x c d f o r $ h o u rs# :..-. t o
cooling* w ater w®§ added ''together'w ith"potasstiiiB 1carbonate* ■th e e s te r*
a f t e r Q th M w m l''^ t^ m tto n a n d 'd ry !n g # Imd'h#p#
■o i
:
B ^ . 1.4SS5,
% S% 4^2
Y ieM K5g« (82*15,:- : (I'em a*
Ct 7 1 ,8 3 | . 8* l l . e S j
rsq ttlp sa C#71*90j•■■■H* lS # f0 5, ; --■ ;
■
: is o ~ r*"■"’1 ’' '•*•--•-• e f R tlw l iv»ftettsrl A,!'etin Aeifl*
E th y l n # h u t|l a c e tic ao id
:
.. . , '
; -- -
alcohol. <S2g
*2#?Ba (3-*%)] and e e n o ^ tf* st# d 'aiilf!M ^ i 0 a c id (6g«) were refluxoci.
f o r . 2 hours#
'"liar dark co lo ured product was d ilu te d w ith water*
p o ta ssiu m :c a rh o m t# added, and th e -ester a t t r a c te d w ith ether#
fh s
este*aG» o b tain ed had b*p*
120+131*/l$m9m*„ n|0 1#4247#
'" y ie ld 36g*
(SCt)#. ■ {Fomdi 0*72*78 J,
l*12*l@f ' < ^ 0 ^ 0 ^
0* 72*S0j
s* xa#24;S)« ■Ethyl u*hutyl a c e tic a cid
■•■
ra q p lre *
',.V‘.':
w&a placed in 2S0o*e*
. Olmlsea
flask * to one n m k o f which was. a ttach ed ;a r e flu x condenser* .
fh io n fl
Ohio rid® (68g«) i 5 slow ly added' d u rin g a p e rio d o f 2 hours from a tap
funnel, a tta c h e d to th e o th e r neck o f th e fla sh # ‘ She f i r - * and......
c o n te n ts were th en h ea te d on th e w ater h a th f o r 45 minutes# ..• th e
excess th le n y l c h lo rid e was restored ©a the' w ater *
? and f i n a l l y th e
a c id c h lo rid e was d i s t i l l e d * b*p* lf'5**lB20/76^#m * and on r e d i s t i l l i n g
i t .bad to,p. 173-173°, • -. m e l d t»*r.
(8?;fi5,
¥h.m j ! ' I s te r yo f Ethyl n^Butyl' Acetic-Acid*
<I *111ija ifcir. I>■ I
*rt»i..^ w«M^fr|milriigtw^ ^ iM.jiiiiiMi^ '.Mimi^ J w wabh.
s ip , m i
■iwwnwfti» u .i >'■i*www>I iiW i'
Bhenol; {36g*}•■was d is s o lv e d ;in p y rid in e (10Qg«) end .eth y l n«*butyl
a c e t y l c h l o r i d e (S2g,)' was slow ly added# ' "The m ixture warmed up
" slig h tly , w h ilst'p r e c ip ita tio n o f p y rid in e hydrochlojicde tooK place*
f le \ whole wan f i n a l l y h eated 3 hours on"the w ater hath-to . complete
the.■■r e a c t i o n * Water and d ilu te h y d ro c h lo ric a c id were then added
and' the. e s t e r ’extracted w ith ether*
the.. so lu tio n was washed’ •
su c c e ssiv e ly w ith -w a te r, c a u stic soda"solution'and w ate r, a n d .f in a lly ,
d rie d with .calcium ch lorid e,'
21
-
'
Op .1,4818*
014H20O2
;fh s ester.h ad b#p*.rl$3~l410/l2in#m##'*
if i e l d 59g*; (70$) *
re q u ire s 0»70#3O|
(Founds . C#76#TO}.. H#9,20*
;
S ,9*X $|).. ■
Reduction o f th e Bstera o f Ethyl h* Butyl, b e e tle Acid to ^ l.thyl;-- ■
n»Bexariel»
:
,
.
.th e follow ing' e ste r s of' eth yl n -h u ty l a c e tic a c id were reduced
to f t <*etb y l n-hexanol .in y arying y ie ld s I*
(1) .the e th y l .ester#
■ ^
■
-.
{11); the n -b u ty l e ste r# ' ( i l l ) the' I s o -amyl e ste r#
and; (iv ) the phenyl'ester*'1
■Reduction o f Ethyl 'Fster o f Ethyl n«»Butyl Acetic/ Acid# ■ /
.
Bouifean.lt and B lanc1s. .method*/ .' Sodium (7g*),w as p laced in a £5©o#e*
round bottomed f l a s h .to which was attached a. lotig u p rig h t e m denser#
E th y l: e s t e r o f eth y l n -b u ty l a c e tic a c id (8#6g*) d isso lv e d in 99$
e th y l alco h o l ■{30g#) ...was slow ly added* - a f t e r ; th e ■f i r s t f a ir ly 'v ig o r o u s
re a c tio n 'w a s .o v e r, th e f la s k and c o n ten ts were heated to d isso lv e th e .
l a s t .tra c e s o f th e sodium*- ., _Water w&a.-the».added' and th e soluttjon was .
tw ice e x tra c te d with, other*
t h i s s o lu tio n was; .dried w ith potassium *■
carbonate end d i s t i l l e d , tb e ^ -e th y X n-hexanol had b *p# 82 ./XSm*m#....
.and 178-180°/760s,m« and n^9 1.4325*
H e l d 2g. (31^).
However,
a- r e p e t it i o n on tw ice th e above .sc a le 'yielded.- only. 16$^ © t h y l n**
hexyl . alco h o l tu p , 179-181° and n |8 1,4430, ,v
F rin ys iiethod*.
,
,;. ■
E th y l e s t e r of e th y l n -b u ty l a c e tic a c id (I7g*) was
d is s o lv e d in e th e r (50c.c#) and a s o lu tio n o f sodium a c e ta te (I4g«)
In.. w ater (14e*e«) was' added*;.,. The whole was.: surrounded by an ic e acetone m ixture and . s o d i u m . w a s added in s m a ll:p ie c e s o v er a
p e rio d o f 2 days, . t h e . s d u t l on being k e p t s l i g h tl y a c id - to , litm u s by' .
the', a d d itio n o f '80$ a c e tic a c id from tim e .'to tim e * ..; . The lo w e r.la y e r '
o f .so dl um a c e ta te was-run o f f , s o l u t i o n washed w ith sodium carb o n ate,
w a te r ,' an d -d ried w ith potassium carb o n ate* ,. / The 'pm .duct 10g#V(80$) • .:
had"to.p. 8S-88°/20m.ia. and 18i-185o/760m ,a. : end n i7l*4200.
This ■be
.
■product however, on h y d ro ly sing with- c a u s tic soda, .was shown- to ^ la rg e ly
unchanged e s t e r ,' th e y i e l d ,o f - e t h y l n-hezanol th ereb y being reduced
to 20$* b
' ■; - '
Bleyberg and tllrie h * s method*
-.-
-
- .-■■■•■ - - ■ -
E thyl e s te r .of. e th y l "n-butyl a c e tic a c id
(r/g#) • d isso lv e d in 75c#e* o f 40-60
lig h t, petroleum ( d i s t i l l e d from ..'.,
sodium)' and sodium (37g*) c u t in to sm all p ie c e s,' were r ef Juxed on th e .
w ater b a th w ith a calcium c h lo rid e tube a tta c h e d t o th e condenser#
Absolut© e t h y l ' a lc o h o l, {*?3g*}, d rie d by magnesium mefchoxide. (Org* /.
Syn., 7, 37};. waa added over a p erio d Of an. hour*
, A fter, ro o m in g 5 h o u rs, the s o lu tio n became dark .red and sodium' •
othoxl’de vms p r e e ip ita te d i . / t h i s l a t t e r was 'd ie s o lv e d to g e th e r w ith a ;•
" l i t t l e unchanged sodium; -’by-. ad d in g ' j u s t 'm f f i c i e n t 96$ e th y l alco h o l/.
and': r® flu x in g ■'f o r 2 •.hours*11"' Water was added and th e p ro d u ct -th rice
e x tra c te d w ith e th e r and d rie d w ith 'p o tassiu m ' carbonate# .y:.$he pm d m t
o
however, was v ery impure b*p*..178-196
E th y l.|i~ butyl a c e tic a c id
'(2g) was reco v ered a f t e r a c id ify in g th e .aqueous la y e r fro m .e th e r • :
''ex tractio n *
••
Beduetlon in oresence o f toluene*- . (Ford and M arvel)•
m n .i t i n i." • n u i- if tT - n i.m m iir i n r . r i M ' r m n r r t n • n - y t
t • r u~ r i n i n v im
'm i i i r - n f f l r i n m i r t —
I ' l i m r ^ n r - ^ r - ' • ‘-f u m n n m t n w i r r r r w
Sodium (14g*) was h eated with, vigorous s t i r r i n g in 4Oe*e* to lu en e
(d rie d over sodium) in a th ree-n eck ed f l a s k u n t i l the m etal was;
o b tain ed in a f in e ly d iv id e d s ta te *
th en the to lu e n e had eoele&to
•about 60 , ■e th y l -e s te r o f ethyl n -b u ty l a c e tic a c id (l?*2g*.) 'i n dry
.'e th y l'a lc o h o l 300*6* (d rie d by magnesium met box id s) was q u ick ly added
v i a ' one -o f th e condensers a tta c h e d to- th e .fla sk * , . fh e re was v ig o ro u s '
; e ffe ry e s c e m e , and.. alm ost im m ediately a f u r th e r .100c#©# ■dry e th y l
alco h o l was added*
/'; 'A fter the r e a c tio n had su b sid e d ,■.the f la s k was h ea te d f o r an hour
to d is s o lv e the rem ainder o f th e sodium* . /As much as p o s s ib le o f th e
ethyl, alco h o l w as'■ distilled- o f f and a f t e r a d d itio n o f w a te r, th e
p ro d u ct was th r ic e e x tra c te d w ith ether* • A fter d rying w ith potassium
•y
> **.
*■ s
c arb o n ate, ■th e •pro due t , y£ » a th y l' n- hexanol >' Had h *p* 176*183° and n^/*3%Y ield ;3g* (83$)* ■';; 7g* e th y l n*butyl -acetic'; a c id were reco v ered .
R eduction' i n presence o f ben sens
,: $h@. same ap p aratu s was used ,as in \
prev io u s methodi •;sodium {9g*:) was warned in. 6pe«0*..'.bmsene { d i s t i l l e d |
from . sodium).. and e th y l: e s te r o f - e t h y l' n * b u ty l a c e tie a c id {8#6g*} l a
35g#- .dry.;e th y l alco h o l {d ried by means o f' magn@3itm:metfeoxide) was
q u ick ly .&dded ;and a f u r th e r 33g, dry e th y l a lc o h o l were, alm ost 1mm* ;
ediafcaly' added#" . . A f a i r l y .vigorous re a c tio n ,.ensued, which .w as, over in
an :h o u r* : , Water -was added ■and, product e x tra c te d w i th :e th e r , washed
s e v e ra l tim es w ith w ater and th e e th y l a lco h o l was removed by sM klng
with-.a s o lu tio n of. calcium c h lo rid e (IGOg#) i n w ater - {lSOo*e*)#
.A fter ag§&n washing filth w ater and drying w ith calcium ehlcal
•
; the
e th y l n«*hexan.ol- had b#p# 178*181°# .,. Y ield l#5g* (23^) *
. 5g*. e th y l n*butyl a c e tic a c id , a r i d ng from .the h y d ro ly sh o f th e
e s t e r ;by sodium eth o x id e, were recovered*
R ed actio n :wi th gQodium and n- b u ty l 'alco h o l » ~■ " (a)
Ethyl; e s te r o f '
e t h y l n - b u t y l • a c e tic a c id -(8#5g*) In n -b u ty l a lc o h o l: (30g#) was ‘added
to sodium -(7g*) in a round bottom ed'f l a s k , ' a -g e n tle ' r e a c tio n ensued
and a f u r th e r 35g. ■n -b u ty l alco h o l were added to d is s o lv e u p th® sodium
but©3d.de which c r y s t a ll i s e d out*
A fter "heating fo r 2§ h o u rs, a l l the
sodium had by now. re a c te d and w ater was-added to' hydrolyse the sodium- butoxide*
-
:' x
0n co o lin g ,' th e product was ■e x tra c te d with" e th e r , washed and d rie d f
7 0
o
w ith ,:p o tassiu m carb o n ate* ':' ' T h e e t h y l svhex&nolvhad: b*p* ■179-181 •
1
Wad ng0 1 *4300 (3#5g* )|' ■.’t h i s , a f t e r refluuting w ith e le o h o lie c a u s tic :
o
■■■soda s o lu tio n t o ’hydrolyse any rem aining e th y l e ste r# ■h a d .h*p*. 179-181and
1 .4 3 0 4 .
Y ield 2 .5 g . ( 3 9 ^) . -
‘
■(h)
■Ethyl.' e s te r o f ( - H th y l n -b u ty l; a c e t i c . a c id ■(151g« 5 w ith •
O
17
■
/^
o
•11 .7 6 i ": o t ' ^ - i e , 2 8 ° |
*13.86°}
" o C ^ ■—23,10 j
•
,-^s •'
j
fit
' (1,2}. was reduced as in (a)' w ith'sodium and n -b u ty l:al cohol •—. • '
■■■■The' (
t hyl n-Ziexyl alco h o l ($9g«t";i» e » : 60$ y ie ld ) had tup* .
o ■ ' '■■;■■■• S I
'7
o
/f
o
87—B9 ./iSm#&* , ■n._ 1*4314 and, "oCs■s,ef3 "*1*33|
■ ' ■■■
*—1 *42 p
o
n
a
oL
—1*61;
d~ ^ 3 f s
**3*88 (,1*3) r l* e . t h i s c a rb in e ! had
jQ
' enly.:19$'.0f th e o p tic a l activityV of' the (*/*) • carbine! produced in non' a lk a lin e "solution ^experimental, p..£?
. Th©' recovered e th y l n-butyl" a c e tic , a c id ( 9 § * ) was
!•'a c tiv e w ith
<*£ fS
.«■£„ - *3*-*,
only
- 0 - 3 ? (£,»■*).
■■,Reduction .w ith sodiitm and i s o - amyl a lc o h o l♦
..(a) . E thyl •e s te r .o f ...ethyl n -b u ty l a c e tic • a c id (8*8g*) d isso lv e d in
is o amyl a lc o h o l, (40g*) which had been d i s t i l l e d over calcium b*p#
128-130° end ol s t f 3 . -2*38°}
oi
-2.73°;
(1 ,2 j •• homogeneous), ■was added to sodium (7 g * )*••
'*+ ,**
- 4 . SO;
A r a th e r ' slu g g ish , -■
’ re a c tio n follow ed and a f t e r f u r th e r acldlfl on o f ' is o a myl a lco h o l <20g#)
■and. h e a tin g f o r 4 h o u r s , 'a l l the sodium had reacted* - Water w a s .a d d e d ■to th© ' h o t so lu tio n , to hydrolyse ‘ th© %odium amyloxide and
h e a tin g was continued fo r §• hour#
' . The product, a fte r extra©felon with eth er# 'washing with water m&
*
#4 il '***
drying with p o ta a ite i carbonate ■trnd b*p# 178*181V n^a 1*433$ and
.0
;
-
to o g ea m « )* " ■'••■yield i*4g*; {SfJ}*.
"Th© reeotrerad .:.
^ssamjl; s ie o b e l bad-been almost © o ^ le te ly rmcemlsed and now had
*s
O
©
/<r
• «© #
4Ljf&is ;*®*3S
|
<**42 |
ol
<L3*g
*0*63 .-t3Lf8j homogeneous) *
/■ ftile raeoEdamtloa had been trim* ht about by;, the ©©dim
:
oxide which was formed, fo r th# fso*»amfl alcoh ol l i s e l f i s o p tic a lly ■
©table to heat* rid© Fran&lan&;and .p r ic e ■(3*C*S«f 1S97* 71* .063} who
fbancl that a lcoh ol i t only p a r tia lly r&eeisis#& a t IfO0 during 7 hoars,
w h ilst sodium icorgro?! .oxide -i s com pletely raee&ised a t iOSd a fte r
th r s# _tears* .
.
; ■:
{b}^ ''.A /variation, o f .th© above method was t r i e d ,:nsmeiyt
o f eth yl n^bafcyl a c e tic acid .{8*©g«} -in |e^ u ayl alcoh ol
©thyl e sb tf
{IS G g # }
nas
•
brought.to the b o ilin g p o in t and-©odium {10s*} in small piece©,' was
added* '. ..AftW l i | hours, when all-th © ecdlim'bad rea cted , water m i '
added am! the. product extracted w ith ether #w a chocI w ith w ater and the
ethyl' a lc o h o l' rasOTOcS by a eoncentrated so lu tio n o f calcium chloride* .
The .solution wm dried with ealclm a ch lorid e and't t e y ^ methyl rw
liam nol obtained had b .p . OT-ISO0,
T ioldi
l*SgV (23,<),
'
fo ln cti^ n o f i>»r ^tyl- faster o f Ethyl n*Bat.yl Acetic'' Acid# ■
^ ticH ^ n ..rtnr..B!oana. of;sodium ant n-b u ty l alcohol* . < .
hj*Butyl' ea ter o f eth y l j^bufcyl a c e tic acid (log*) in f^ ta ty l alcoh ol
{68g*} was added to m ^ h m {%*}f
& mild reaction ©nauod and was
fin is h e d in 2 hours; ■. w ater was then added and the whole h eated fo r .
f houxv
A fte r -e x tr a c tio n w ith e th e r , washing with, w ater and drying
w ith .potassium carb o n ate th® ^*-ethyl n-hexanol had b * p .. 178-181° and
n j 3 1.4323.
X leld:
l.S g .
(23;<5,
c ic-id
’ Be d u etto n by-means o f ©odium' and i so*enrfl a lc o h o l»
JLso-'toyl e s t e r o f '.eth y l n -b u ty l aoetl© a c id (10* ?g*} d isso lv e d in
/f ;
is o - amyl alcohol, (100g*} d rie d over calcium ,;. "<X
-2*79 (l» £ f .
homogeneous) :was h e a te d ' to the boiling' point and sodium (7g* )""was ';
■added i n .p e r tic a s , th©:reaction being o v e r:in 1 ‘ hour * - - 'W ater.was
added,’to h ydrolyse th© sodium sayloxl&ej -"" the product was e x tra c te d w ith
e th e r , washed with, water,, d r ie d ' with -potassium /ca&bonate end d is t il l e d *
■The ^ - e t h y l n-hexyl a lco h o l h a d :b#p*: 178-184°*
fie ld * Eg# {30$) *
Reduction- of Phenyl E ste r-o f. E thyl .n- B utyl A cetic Acid*
Bouveanlt and'B lanche Method*
/
(a) . Phenyl e s te r of ethyl ,.n-butyl .
no©tie a c id (llg * ) in 99$ e th y l alco h o l (4.5g*) .was added .to ..sodium
(10g#) , th e d is s o lu tio n o f sodium being com pleted by 1~| hours heating*
l a t e r was th en added as u su a l and the- e th y l a lco h o l dlsU lie d , o f f on;
. the water, bath#- . A fter two e th e re a l e x tra c tio n s ,' washing w ith w ater
and drying w ith potassium carb o n ate, th e
U .p, 178-182°,
a*61.4338.
m e ld s , 2 , 5g.
e th y l n -b sx y l a lco h o l had
(Sag),'.
7 3
(b) '. f h© above was. re p eated using, e th y l a lc o h o l d rie d by magned urn
methoxl&e* in the .hope., of. minimising, the h y d ro ly tic a c tio n o f th e sodium •eth.oxide, .but ..th e. tame y ie ld
eth y l, fe*hexyl.' alco h o l .was
•obtained* namely .38$. $ 2g*' e th y l n -b u ty l a c e tic a c id wore also
recovered* '
.
'A etlo a’ of, sodium butoxlde on {
*
e t hyl xt^hex&nol» : To t e s t whether
ra cem isatlo n o ccu rred by th© a c tio n of: sodium hutoxi&e on the
o p tic a lly a c tiv e ■/£♦ e th y l n^hexanol.. during th© ..reduction o f th©
e th y l e s t e r o f . o p t i c a l l y a c tiv e e th y l nybutyl ace t i e a c id * ’ a ■specimen {
/f
o
■'
o f '■(*}^*© th.yl n-hexanol (2g) w ith
*1*35*
< *1*61* ;.. I
■ I
e
' oi +3S# •.~2*88
was r e f ttx e d w ith a. s o lu tio n o f sodium (3.5g*)
|
......
i n dry nybutyl alcohol. f43g«) fo r 3 hours*' ’ ih e product was h e a te d
’i
§ hour -w ith water , to e f f e c t hydrolysis*' smi th s re c o v e re d . ( • * et hyl 1
n -h e x an o l; (2g*)' b*p*".179*181
-0*52
O
had
oCs$?f3 *^* 13?
■ oL
■*0*17$- . |
9 /
(1*0*25}
l* e * '8 0 / £ o£ th e o r ig in a l a c t i v i t y o f:th o -
alco h o l was m ain tain ed * ,
-
■■•.>>
I
J
Action o f -sodium bmtoxlde on the e th y l eater, o f (~ ) e th y l n -b u ty l
ace t i c acid*. •' Sodium..’{5* 5g«) "'dissolved In dry nybutyl alco h o l ’( 45g*). j
was re flu x e d ' 3 hours w ith e th y l e s te r , o f (-} e th y l n -b u ty l a c e tic a c i d .:
■' ?
{4 *6g*) with
.
o is s fs
o'
-1*25|
J '*> , ..V
svtf
*1*44
*
■
■
■ •■
■
■~
'■
■■
(1#1) which had been
.
j
€3
derived from (*)ethyl 'n-butyl acetic acid w ith ■.ots&*sm§
*
, fhe resultant homogeneous liquid was refluxed i hour with water
■
,|
i
to hydrolyse any unchsnged-ethyl-es tor and also th© sodium butoxide* '
8 0
1
A fte r e x tra c tio n ’ and, drying*’ th e {«*}-e th y l n -b u ty l a c e ti e a c id {3g*)
' gv
O
so o b tain ed had b*p«127 /XSm*M* a
n
d
- 0, 19
{JL*0*5> ' i»e» only 20^ o f th e o p t i e a l i ^ e t i v i t y ’possessed,fey th e o r ig in a l
{*•}*e th y l'n - b u ty l a c e tic acid* . ...
Reduction of
11—H'
Iodide
n-H eoiane*
Ee,due,tl&& w ith Raney .Catalyjrt^ ^ ~ ith y l g.*hexyl io d id e (IS g .h w a a d l a solved in 96# e th y l a lco h o l (25c#e#) and potassium hydroxide (% *).
in water* (XOe* c*} was added to g e th e r w ith a l i t t l e Raney n ic k e l c a ta ly s t* ,
-She whole was -shaken, fo r .15 hours under 1 atmosphere
p re ssu re o f hydro geft* during .which tim e -1 l i t r e hydrogen was absorbed*
.Af t e r working u p t h e product and d i s t il l i n g * Y'-methyl n-heptane b*p*
123° (2g» ) was o b ta in e d ' to g e th e r w ith some ..recovered iodide* •
Reduction w ith zin c-co p p er couple*,' .lin e -c o p p e r c o u p le •{5g*): w as., ,
added:
e th y l n -hexyl io d id e (12g«) and a l i t t l e a c id u la te d water*
a f t e r re flu x in g a t 115° f o r 5 hours* th e m etal’was f i l t e r e d o f f . and
s o lu tio n washed w ith sodium carbonate s o lu tio n and f i n a l l y dried*
o
An.Impure p ro d u ct (4c*c*) b*p* 90-135 was obtained*
.■-th e above was .re p eated , but a methyl alco h o l - w ater m ixture ( 1 1 1 )
was used in s te a d of W ater#, : A fter working up* th© product (3e*c*) had j
,b,p . 113-126°,
;
Reduction w ith aluminium amalgam*. .
~ e th y l n-hexyl io d id e (X2g*) -in
■96$ also h o i s o lu tio n was added to aluminium -amalgam (4g*J m d .a- q u ite
vigorous r e a c tio n ensued#- ■
. Af t e r -standing a l l n ig h t however $ the
io d id e was recovered unchanged*
Reduction v ia th® Grignard complex* "/$ - e th y l n-hexyl io d id e (I2g«) wm
added to magnesium tu rn in g s {l*2g) covered w ith eth er* ,a l t e r " th e
magnesium had dissolved* ic e and d i lu te h y d ro ch lo ric meld were added:to
the cooled s o lu tio n * • On e th e re a l e x tra c tio n and drying however*, only
o
a, small amount o f y^-methyl n-heptane tup* 114-116 . {Xc#c*} w as-obtained,
Reduction .with sin e d u st and aeeti c fee-id*
A s o lu tio n o f /^ - e th y i n- .
hexyl io d id e (8g#j; In g la c ia l ac etic , ac id was h eated on th e w ate r hathf d r 8 hours ,w ith z l no d u st (12g* )*
A fte r coolihg* f i l t r a t i o n * and u
e th e re a l, e x tra c tio n o f th e upper la y e r o f ^’-m ethyl n -h e p ta n e, th e
' o' ' ' " ’ ’
14 ■
l a t t e r was oht a i nod "in .9 o;l y ie ld w ith b*p« 114-110 {2*5g«>
1*4031
and
/
d y 0*7053,
. wibs^t b#' Eoog* Longcdljk* Overhoff and Smittenberg*
Bee* trav* ehlss** 1930, -58* 329 g iv e
ci ¥
0*70584*
A
STOP? CP y ? ? R"'* ? r
ACTIVE ^
. DT-^SiY: 'T tt,
~ fp j,c-'r
1 OP OPTIQATXY
1 OF ITS
8. 3
•
■- Anlonotropy In fttree-g orben -gysterne*.^
-
;:
Although p ro to tro p ic changes had been reco g n ised and s t a l l e d in a
la rg e number o f cases*. anlonotroplo changes have been stu d ie d only I n
-.
mar© re c e n t years*
In p a r tic u la r * th e m io n o tro p ic changes undergone by th re e -c a rb o n
CaXlyl). systems appear to fc&ve'toem s tu d ie d f i r s t by a i l l e t {Bull* see*
ehim** Belg#* 1922, 31*
from m $ k on th e a d d itio n o f
halogens to conjugated systems* © n e s t e d th a t 1*4 a d d itio n o f #*g* .
bromine was preceded by 1*2 a d d itio n follow ed by m ig ratio n . t o the' 1*4 .
p o sitio n s *
He p o s tu la te d that*
*Xf in th e system
-0 » c - CX th e .
.ra d ic a ls a t 0^ are* as a whole* more n e g a tiv e than th o se a t 0 ^ i the
most .n eg ativ e r a d ic a l (X) a tta c h e d to 0^ w il l tend to m igrate to 0* *fS
However* t h i s view was n o t f u l l y te n a b le i n th e l i g h t o f l a t e r evidence
and O ille t* s theory-w as l a t e r m odified - b u t n o t to a w r y s a tis f a c to r y
e x te n t - by F r e w s t ( Oompt*yrend# *' 192?* 165» 133} and by ttelscm helsier „
(A im .,; 1927, 458, 13 3 ).
, "'-'a m ch Biore adequate theory was pat forw ard by Burton and in g o ld ,
( J . C # S ** 1 9 2 8 *
by a lly l
■of t h e
904 a n d 1 6 5 0 ) f o r th e a n i o n o t r o p i c m i g r a t i o n s undergone
systems*
F ro m
d e r iv a tiv e s c t o i
a -stu d y
-p h e n y l
Hi 011*011 * 0%
i
x .
^
■
o f th e
a lly l
an io n o tro p le in te r-c o n v e rsio n s
m l echol'
and
e ln m u n y l
alcohol*
m 0B = OH,€% 1
>
**
'6
'
-■
:
they war# a b le be co n clu d e. th a t three: main f a c to r s in flu e n c e d th e
;
^
\1
;
1
8 4
e q u ilib riu m between, th e isomers^
.
Sr.
(a) the- s tre n g th o f th e meld MX **
in c re a se d a c id i t y o f MX g t f e in c re a sin g m o b ility t o th e a n ic n e tro p ic
system#
(b) th e io n is in g power o f th e ©olvenb «* the-.higher tho
d i e l e c t r i c c o n sta n t o f th e solvent* th e c **&ter th e m o tility o f th©
>above s js te m ; in. th a t so l vent and fe), th e c a p a c ity o f . t h e <*«*s u b s titu e n t
{phenyl in., th e case quoted) to ..supply electron© ' to th e system *' thus
aiding, .the r e le a s e o f X as an anion and increasing* th@ s t a b i l i t y of th e
cation# , , fh e indu ctiv e; e&p&city of. v a rio u s groups m n -thus he
compared by observing th e m o b ility which th e y c o n fe r' m th e - th re e
carbon a l l y l system s in
•
‘
* ic h they a re s u b s titu e n ts #
'
-
. . . . . . . . . . . . . . . . . . . . . .
"
:.;
.
:.
. ....fhe m ig ratin g group* on le a v in g th eeU earb o n atom* cm c i t h e r
.
|
. r e tu r n -to. theot»carbon atom o f th e so a m olecule _o r can ml.g ra ta to th© . |:
^e& rfcon o f th© same m olecule o r to th©<** e c a r b o n atom, o f another!,1
molecule# ... fh© ...attachment to sn oC ^carbon atom would in v o lv e un io n ic
jj
mechanism* whereas m ig ra tio n . to a j/^ c a rb o n could -occur v ia a c y c lic
rearrangem ents
X— -> G8a
S&
• .- . >
V
CIUC
*£t
i
Evidence- t h a t . during th# fsigration $ . X might e x is t as a fr e e ©nim
'
^though' n e t 'sa©o©s s a r l l y :in ©very;cat#*'■m m 'fortheotaing ■from the ■- ■.:
observation. th a t ..when th e ’" conversion’o f :X»phonfl a lly l p -n it r cbonscate I;
t o . eis^amyl p-nltrcbcnsoat© was carried out in th@. presence o f ....
tetrsm othyi- amoniu® ..acetate* • the product contained' both citinamyX -pm ■
nltrobensoate and eimam yl acetst© ..(Burton#7£«C#S«*;. 19S8# •1650)#. •.
- Kenyon# farbrldg© and P h illip s (£»C«S«» 103?# 20?)- studied the rep*in,
■ -,/
Xecetscnt r e s e t Ions ©J* th© e s t e r s o f o p tic a lly a c tiv e <rt~ph@nyl
a lly ! 'alcohol*' whereby ",' <*-phttiyl </^methyl a l l y l hydrogen phfchalabecould, be concerted in to fm p h m y l (X^methylallyl^liydrogan phthalat© with ,
in version o f eon flgu ratim # hot mere p a r tic u la r ly with 70$ r e te n tio n o f
, o p tic a l; a c tiv ity # ; .fhey consider that the-m igration from<*-carbon
-
td ^ e a F t m cannot h o .wholly lo n ie but probably occurs v ia the- c y c l i c ' .
mechanism given above#
,
.,
•
• ■.
1 ~i the group %$ m igratin g'from th©'a liy l-sy ste m i s replaced,by
' another group Y? th en 5th © 'la tter -can:enter th© molecule e ith e r stea lta n e ou sly with* or- after* the elim in ation o f %* ■. Benee the p o s s i b i l i t y o f '
‘■mono- or b i - :molecular mechanisms- fo r th ese replacement reaction s i s ■
inferred#- " Emm evidence fo r th e 'occurrence o f ■■■both mono-; and b lmolecular replacement© in; d iffe r e n t media was .found with the in te r rea ctio n between-.elnnsmyl ch lorid e and potassium aeet&t© {Meisenheimer■ j
and Sautter# -Am* 1933* SOB# SB)#
.; fu rth er study o f © H ylic migration rea ctio n s with d e r iv a tiv e s o f
o p tic a lly active. y-methyl oc^?v*propyl' a l ly ! a lc o h o l, le d Arcus and.
E®nyon:(0#0*8## 1958* 19X2} to t h e ' view th a t the m ig ratio n re a c tio n s
occur m ainly v ia t h e 'io n i c mechanism le a d in g to r a e e s is a tie fi at: th e
cation# w hilst a s u b s id ia ry ^eohcniea-leads' to an' in v e rsio n of.
con fig u ra tio n ' with -some' r e ten tio n o f o p tica l' a c tiv ity *
/ M s lattes*
mechanism' may be e ith e r b im o leeular (n c n * slm lta n e o u s'ra p la e a m m t^
■or may ©ecus* by th e resetlin g anion p a r t l a l l y s h ie ld in g i t s sid e o f th e .
e& rbonitua'cation#
"
■
•V. '•..to interesting example of ndgmtion in ‘a tfereo carbon system-baa
v ery r e c e n t l y ■been observed*
■■'•9 : ■■"■.ir v-: - ^
<*
C.% OH.* 'C(He) V 0 ; (C*l)0O0Bt
■
...
■/ •■■
. ■r
: ■
^
■• • <* ■
01% 0H.*» 0( a) «\0lCf} CQm%
t h i s ; change# t h i c i i s ..the f i r s t reco rd ed example o f th e m ig ratio n
1^
llv j
group
In
a non^&reiimtie th ree^carb o n system#
is
constl~re&
to ;o c c u r.v ia ant in tra m o le c u la r c y c lic mechanism#- w hereto ■.th e
gtovLp a t t a o h e a 'I t s e l f 1to U e ^ c a r b o n s to ir w ith In v e rsio n o f th e a l l y !
g ro u p / ^ Inc® he rearrau g eB ^n t i t observed when th e ot»& llyl group i t
re p la c e d by methyl# H rpropyl ©r |W tmtyl* ■■(Cope and Hardy# J#A*C«S**
\
,
o 1%
v jl « I l f ! Ch V» **!de *
d*»if}*> <*^~®%m®thjt®l%jt aleo h o !
n le o lii w ith & :
p o s i t iv e s ig n o f ro ta tio n -a n d assum ed'*4* co n fig u ratio n * o b ta in e d . f rosa ;
th a'('..{-/-}'^hyd3?os®^- p h t h a l i e . e s te rJ is . e©nV©rb©& by ..phosphorus. t r ic h l o r i d e ■
.
x*thylalX yl ch lo rid e* ,-.._; f h ls . l a t t e r on
o r th ic n y l c h lo rid e i n t o .
h y d ro ly s is w ith wat#i* f i e l d s a ,{*)«o^vdiEietlsflaXlfl a lc o h o l.w ith a
n e g a tiv e . sig n of. ro ta tio n *
■From.
d
oasa^f n a tio n o f th a aboya i t ,-wouJ.d appear t h a t th©
b
{*>!*>■ a lc o h o l f i n a l l y o b tain ed rm*fc .ba. o f o p p o site c o n fig u ra tio n to th e ;
o r ig in a l
{/.)* aleo h o l and. so should b e w r itte n iss.
a lly l" alcohol#
dtaethyl** ■
Hcrev-r* t h i s alco h o l lias p ro p e rtie s which a r c . a© very
d is s im ila r from th o se or th© o r i g i m l §g»M** o r
a lc o h o ls obtained
from th e hydrogen p h th s lte e s te r s, t h a t doubt i s ' thrown on this. r
assu^fclon* .
- .. ;,
. ( Evidence f o r th e e o n flg u ra tie n o f th e t#>)«^*dl:mefchyl a l l y ! alcohol
p rep ared from th e (<*)- ^ » d im e th y la lly ! c h lo rid e ,i s : p re se n te d ©a.p#*2-*? ) :
ftenoe f o r the sale© o f .a c c u ra c y .and. c la r ity * tfcla {*)<* alcohol. I s designs
te d r ^ ( * ) w ^ d t e e t h y l a l l y l alcohols,,., th u s _s i i p l f f i n g t h a t i t . has been
,o b tain ed from ^ { ^ l ^ ^ d l s i e t h y l a l l y l a lc o h o l and has a. n e g a tiv e sig n
o f n o ta tio n *
; ■■ -
.
._
-
.■■■. , ■
■,-, -• '.
' ..lise &• C * )» ^ s» d te e th y !a lly !. a lco h o l .e x h ib its several- anom alies when
cc^. : ■ ■
compared w ith..th e d~ (^)w /'-dlm ethyX allyX .alcohol* .<..,;fh e
■mefchyX&Xlyl aleo h o l dees n o t undergo smt&rotatlen on sta n d in g , as dees
t tm ^ { t)« a le o fta o lj
I t can a ls o be converted in to i t s hydrogen p h th a lic f
|
■}
8 r8
,1
, t ^ n i i r e b ^ s o l o mid b m z o le .e s te r s # -but th e s e a r e a l l o b tain ed o p tic a lly }
■ inactive I n - c o n t r a ^ i s t i n c t l m . to t h e c o rresp o n d in g ■e s te r s o f te c
&»(v-}»&le0hol*
' ■ ;
.
j
To'over# th e ,:D »(^)^o^4l*»cth3rlallyl-alcohol can
reduced to .
., • i+y*mthz?l i^ p ro p y l c a rb ln cl* . and c m a ls o be converted to. ,{**)«•
.J
. dim ethyl a l l y ! a c e ta te # bo th .p ro d u e ta being o f low .o p tic a l p u r ity
t compared w ith th o se from th e
-j
^ • o ^ t ll r a e t h y l a l l y l a l c o h o l * . P o t h ■■. ..]
oq<**
.1
d lia e th y la llf l a lc o h o l have th e o p p o site sig n o f r o t a ti o n to t h e ';
|
. te e reduced a lc o h o l and. th® (**)«acctatc obtainod from
:• - corresponding p ro d u c ts o b tain ed from.^•{+)**«/^-*dixaethyl.allyl alcohol*' j
. •O n..this 'evidence I t would appear th a t t h e ' a n d
d*{v-}^alcohols a re
..'..o f o p p o site c o n fls u n itio a s# whereas H il ls # . Kenyon and
IM lX ip s
1938# '576J t e n ta tiv e ly suggest t e a t th e s e ,tro a lc o h o ls a re o f
.
th e same co n fig u ratio n *
.,
>.
..
Hence i t fo llo w s t h a t e i t h e r te e conversion o f th e
dim ethyl, a l l y l alcohol. In to . I t s {^J-eh lo rid e# o r te e h y d ro ly s is o f te i£
^
' c h lo rid e to
* d taathylftllyX a lc o h o l ferns proceeded w ith th e ....’•
occurence .of. a'W alden In version*.
1■-. From :th e w r it o f fCsnyon* P h illip s and c o lla b o ra to r s on th e .
1
'In v e rsio n re&c11one o f d e r iv a tiv e s - o f a s e r ie s o f secondary alcohols# j
. i t was co n sid ered Boat probable t e a t th e replacem ent o f an anion by , . j
& h a lI d a .I a n ms- aceo tv enied by a Walden Inversion*-
. This assum ption ;
. has re ceiv ed eonflrm ntion- from t h e .m m re c e n t' work o f Hughes and M i !
ee^wor&era {J .C .3 ,* 1933, 1528)
i b i d , ,1 9 3 6 * 1173J.
Ib id * , 1933, 209) I
-..................... ..u
.■
' v.
.
.. « n
n
89 ]
who showed .th at th e r a t# o f is o to p le exchange o f . a haltd® io n by a
.
I
ra d io - a c tiv e .Isotope, wan ®$uaX "to .th # r a t s o f r&eofalaabion o f th®
ton*
oogpoand. c o n ta in in g
■. / : ■'
'•■
,|
’
■-!
I n a ll- p r o b a U ility .th e re fo r® ,'■ihe.W iadon in v e rs io n occurs during
j
■■■-...
.
.
-j
th e conversion o f th®
alco h o l i n to t i n («*.)<*
' I
:
'
‘
.
1
1
-chloride and n o t d u rin g th e h y d ro ly s is o f - th # l a t t e r # ';1'A d d itio n al
j
evidence t*0 fring..on' t h i s p o in t i s 1r e i m l i d
,J
'
However# a f u r th e r ' p e c u lia r ity o f
slcehoij
a l i i o t to .th® w&lden in v a ra lo n Question# i s th® conversion o f t h i s
lM *)~aicG hol to {
«
#
■|
bhyl&XXyl c h lo rid e# in s te a d o f th® asp e eb ed ,
(■*•)-c h lo r id e (in v o lv in g an tiw e ra lc n b ;
th ia l a t t e r (« )* e h l 0 rld® r e a c ts ,
l a l l f 1 ®Le o to l which#' m
w ith w ater .t® f i e l d a p»( *•
re d u c tio n g iv e s an o p t i c a l ly In a c tiv e m ethyl |£*prepyl carb ln o l#
.
.. r * » f i r s t Q uestion ^ h ie h arid®® 1st . why i s th® < |(+ )*ty^li£thyl«»
m l l f i alco h o l eo n irtrted r i a th e c h lo rid e to a («*)«*alcohol o f o p p o site
sign# th an eas t h is produced .!M * )* ^ * d lM th y X a lly l alc o h o l i s
converted, v ia i t s c h lo rid e to {^)*^*M iim ethyX allyl -alcohol f
..this .imply I M
Does
no Walden in v e rs io n has occurred d u rii^ th e prod u ctio n :
o f -;fch® second c h lo rid e ? .
-
w........
; A gain. i t i s d i f f i c u l t to. u n d erstand, why th e
a l l y l . alcohol- o b tain ed v ia on# c h lo rid e ■sh o u ld f i e l d on re d u c tio n
|
an. o p t i c a l l y a c tiv e methyl. Ty*pv®pjX carfeinel# whereas th e
j
.d lm eth y ia lly l. alco h o l o b tain ed v i a two c h lo rid e s should g iv e in. e p tie *
a l l y In a c tiv e re d u c tio n product*,;.
S £ heme
. ..........._...... ^ .. 11,1061*161
x#
yy*-* a of Reactions of X>(<»
d«{-/-}^loohol
i>*{**)«*&1eohol
(m)mQW0 *£ 1©
-* {*}~cbioride'
(» }* a le o to l
J't'Z
{*)*&cet$ite- {^}~mcth$U-
j£J»hydrog©a .phthalate-
2^&ethyl*
&P&PS! •
■; o& rbinol
d l^p ^ n itro b en g o ait:
e a a ^ in o l
I t . i s ammimed..iii)th0. a‘b ow .41ae\ii^4i6E th a t th e 'fb rraa tlo h ;e&Kjr <* ■
dime tb y l.o lly l - te e imt e . from o^disie t h ^ s l l ^ l ■a l o o t e d
a c e tic mrJmiride and p|r£dtii@t proceeds
t^ r& ctien w ith
o?rA*rre&ce''.of a
WaMcm.lCTernieii^■i t i tl th at the c a t e r lf le c t io n o f an/alcpfe^jr^JW^S''-a c id ;snh^drlde fo llo w s a p a r a ll e l.course to ’the a 0 t^r,£ f l^ t X m : by SS^>.
acid #■'-.■■■■Tbis.-la tte r .r e a c tio n , has .been sh o rn by- n ^ i e f * Xngold mud
1
' ■:
r
.•
■
\
$
~
~
' ■' :
.-Ifas&erst&n (J#C#S#.t 1039*-£40).'.' [loi^rsaeiiiiaaU ©a a t an m s e e n t r
m d by Heberts and U rty {*r#A*.C#S** 193S*
£301). |uciisg-p*?-icotop@J •
.met to in volve. the breaking-.of'tUsS* fe- «* § bond l a th e alcohol- E.**. 0 **• E*
/.
.,, I t '. Ib .also ' a soured above th a t -tfcO^coftTOrsica ©f <^dln€thyX at l y l
m le e h e l. t o ^ d l m t t t y l u l l j l m ottute proceeds e i t h e r w ith o u t a n io n o tro p ie
m ig ra tio n /o f t h e . a c e t a t e . -Ion from ■■• <* 4*0‘-tO' the. ;> ^ p .a to m *sr i f , i t cio©%
t!m.t;, i t : ;. proceeds ** b - v ^ in v e r s io n .o f .c o n fig u ra tio n # .- ' Aa.:-p o in te d out.
ea rlier* th ea n lo n o tro p le m igration i s undetectable w in g to the.
sysmsetry o f th® rtj'-a ta eth y la lly l io a .
SeKiS sappei*t f o r t ’ c=o
9a
■]
, m m m p tim B may t o d eriv e d ' from experim ents on # ~r^tofcy3^allyl -alcohol ;
..(i^ b u ty l v in y l e a rM s o lJ i- t h i s a lc o h o l‘.can be converted w ith f e t e l e
:1
’
, acid, a t 100'. in to its .f o r m ic C3tef*.f3!0*a nhieh th e o r ig in a l a lc o h o l
e&n be recoveredw i t h n o .l o s t o f o p ti c a l r o ta to r y power o r e to sg e o f
s
i g
n
{
K
e
n
y
o
n
m
a
d
S
a
e
l
l
g
r
o
t
e
^
1
1 » 9 S S #
'
j
S
f
*
'
l
i
W
}
*
'
j y
n
y
s z
&
g
r &
t i o
’ o f th e f c r ^ t © io n would feavo le d to th e in a c tiv e h^^toutyl~«iXXyX
■■■■■■- *
. , ,
a lo o h o lt* 04% # |B Oil n 0%'
04^ 0 H v, OB*e%0II /
■
.
j
n
.1 -
■ !
In a c tiv e
i; :.. X% has h e m suggested th a t th^fepttoal. . a c t i v i t y ' o f th e
!
dim ethyl. ally l^ o lco fe o l i s .du^-not to £h* .ae y m e b rie c a rto n atom tout
. s o l e l y .to .Induced d is p s c e try t o th e double bond*-
i f t h i s l a fefee ease. ■
a more o r l e s s ,r a p i d rao«® daation migh^- h# ecspectsd. to occur* tout on
to e co n trary * th e
soatarotate- m d o a a . th e
alc o h o l dot® n o t even
alcohol#
i n ad d itio n #
i t , was to o m {Kenyon. and P a rtrid g e , J«C*S*# X0S6* IS M ) tin* to t h i s ... .
assume! Induced .d ia y m s try of;, to# double bond was- unable to d i r e c t an
asymmetric a d d itio n of tow sin# to th e double bond, .as was too uooo
\:
m jm e tv l® cartoon atom o f ' b o th d ^ |-t* |^ o ^ d to ath v l aXXf| alcohol, and t*-)*.'
f^phehyl-<x^m sthyl& llyl alcohol*
ilo o th o r.'p o s s ib ility wMc i t % L t be n m d to e x p la in .the d iffe r e n t .,!
b eh aviours o f d-C-c)** and.
alcohols,/is the
eeeurreo.ee' o f * ^om erlsm in one o f this two forms o f too. alcohol*
S t♦ acto re s I ana 11 (b e lo w ).a re .possible d egenerate t e s h f too
.
•j
.. ]
alcohol,. sin ce th ese would im & lm only the
en t o f an *ieetron.
, :, j;
rotmsi; the' 'Moloeule* ■ --Asw sing .the two sta?uete*re« to ./fee, of',
j
equal energy content*. the actual. s ta te o f : the (X/^aisetbyXaXXyl alcoh ol jj
.mleeule would .he Inteymediete het^eea X end XX* -,
i* ; '
. .
|;
■ xx*
: #
I n m a tte m p t fo .d is c o v e r any such dlffer#ne#6etw ee& th e
and z>»(«»)«» a lc o h o ls , pur#, specim ens.o f .th e dl*>. **c!lmatfcylallyl alcohols
corresponding to th e &*{*-}♦ and l> (* j* a le e h o l$ were obt& inod*, a n d . their.,
experim ental: h eat# o f - fo rm feio n .from s e p a ra te atoms determined* , fhese;
v a lu e s were o b tain ed from the experim ental, h e a ts ' of■••cesibasli on a t . ' " •/.c o n sta n t volume Cut# experim ental section}*
- $he h e a te o f form ation
thus o b tain ed were compared;with, th o se c a lc u la te d o n -a.•.th eo retical
b asis* . - .
v. . : •...
.... .
'j
.
'
■
'
. -i
A compound which e x i s t s in a. mesomeri© s t a t e l a more s ta b le th an !
e i t h e r o f i t s ’degenerate form##.: a© t h a t the experimental h e a t o f
•
fo rm atio n o f th e h y b rid imisb be g r e a te r than th e Value c a lc u la te d .f o r ' .1
the. h e a t o f .formation o f th e two can o n ical structures*
This method, .
has been used by Fauling and h is co-workers to in d ic a te the occurrence j
o f ^resonance11 o r ^mesomerlai# i n aroma t i e hydro carbons and in
isydrobarbon f r e e ra d ic al® , e* g# tsdphm ylm e th y l (F a ilin g andWholaiii* J« Chesa# fhy$«, 1033* .1 ^ 362)* and .in 'c o n ju g a te d system s
'(P auling sM Sheivasfi* ibid#* 1933, 1* 679)$
f u r th e r .examples a re
given by- Pauling, and sh an taa (ib id # , .1933, 1 / 606) and. a more .’"
re c e n t and f u l l e r a c c o u n t.1# given in fftie- Mature o f th e Ghenieal
£cni** 1059'by Pauling* ' fh e sh o rten in g ' o f in terato m ic- d is ta n c e s i s
a ls o c a lle d In evidence o f ■mesomerisia i n th e m olecules o f n itro u s
oxide* carbon d io x id e and the carbonate and n i t r a t e io n s, etc#'
(P a u lin g , Pro©#' Mat# Acad#. SoS#, 1932* ^9*. 295-and 498)#.
• However* i n th e ease o f th e tw o. ^
^-dimotfeylaXlyX a lc o h o ls , th e
d iffe re n c e between th e . ex p erim ental and. c a lc u la te d ^tu es f o r - th e ” •.
b o a ts o f .formation v a rie d frm- 0 *4 $ to I»2jS fo r th e one.'and"-frota
1 * 1 $ 'to 2 * i$ f o r t h e other* according t o . th e v alu es o f th e bond ' • '
s tr e n g th s which were taken ttm a c a lc u la tin g th e h e a ts o f .fosn& tien m
namely th o se given by Sidgwielc i n 1933 o r.b y P auling i n 1 9 5 2 'and
1939* ■
' /
'
.; T he-disoropaneies' between th e e x p e rim e n ta l' and th e o r e tic a l ■
v a lu e s f o r 't h e h e a ts •o f f cassation w e re ' to e 7in s ig n if ic a n t to support,
th e h y p o th esis th a t- o n e - o f ' th e forms o f o tf•d im e th y la liy l aleohol" ' :
m ig h t-e x is t in -a mesomerlo. s ta te # ;.
«pm*> tm**«»•<*-*>** w****
^t& rot& tion --of
*y
^DimettolaXXyl' Alcohol* "’ ■■■-
' "■!
■ ■. X%' was found ttin t *^*dteothyl& llyX - alcohol.' m ta r o t a ta d on
i
stan d in g a t -rocss tem perature • n o t to a raoesdo alcohol* b u t to an
'!
alco h o l which gava e*g* a hydrogen p h th a lic e s te r w ith about ©Ojl"
J
©f .the r o ta to r y power o f :th e o r ig in a l
;
0^ « > d in d th y la lly l''a le o h o l*
D iffe re n t sample a underwent isn ta ro ta tio n a t d i f f e r e n t r a te s and tills i
le d to th e b e l i e f t h a t th e m t a r o t a t l o n slig h t b e . due to th e presence i
o f a tr a c e o f m. im p u rity a c tin g m a. c a ta ly s t* o r t h a t th e o r ig in a l j
<*^«*dimethfXalXyX a lco h o l was undergoing a chem ical olmage* ©*g# slow,
ae n eal o x id a tio n * p o s s ib ly to a © arboxyltc a c id o r f i s s i o n o f th e . j
double bond co n tain ed in th e molecule* " l e t a t h i r d p o s s i b i l i t y i s . i
t h a t th e o r ig in a l rf^ d tm e th y la lly l alco h o l may on m t a r o t a t l o a te s s x '
s lo w ly ' iso m erise e ith e r to an o th er f o r a 'o f th e a lc o h o l o r to an o th er '
compound w ith an o p p o site sig n o f ro ta tio n , and w ith a high r o ta to r y
power compared to t h a t o f th e o r ig in a l ^ ^ d l m o t h y i a l i y l alcohol*
' '. .'■''XIm ©bow p o s s i b i l i t i e s a re d isc u sse d "in turn* '
•■.One .o f 'the f i r s t su g g estio n s t h a t was pu t-fo rw ard , to ■t r y ' and ■
.e x p la in ;th e im itaro ia tie n o f ^ • d l m e t b y l a l l y l a lc o h o l was t h a t .the
a lc o h o l slow ly a s s o c ia te d .on stan d in g to a polymer c o n ta in in g two
o r mom c a rb ln c l r e s id u e s '«* th e number p o s s ib ly in c re a s in g on keeping
f h i s rlew* howerer* i s seen to'-be u n ten ab le on g e n e ra l grounds ’
because i t I s d i f f i c u l t to see why a s s o c ia tio n does n o t occur
in sta n ta n e o u sly - when th e e& rbinol i s f i r s t prepared* ' Xn. a d d itio n /
th e p araeh o r o f th e f r e s h ly p re p a re d ' ^•dteethyX & X X yl a lc o h o l I s no |
•. different from th&toJV*
:.which tlma
. . ; . 4
;which ha a stood for. 6 months «•*.by
m t& rotatlen tins' taken place*
......
-second■poBslbilityii and ..one;:put forward by Hills* Kenyon and .
'Phillips.. floe# elb*Jf;it that•the o y ^ ^ . d t e e j X , alcohol.can.e^isb
-either-', as. the normal str a ig h t ehai n formula .{I}- or ■mo a. o f a lio
■
. iaomsrldc o f which. there mre.;: two .p c e sifc ijities (11 and 111) .due to
cls**tr&na -ieonorismt .
, ,
.......
■
; ,...
Me - ...
... H
■ 1M,a su g g estio n m ight homed, t o e x p la in th e anomalous ■r o t a t o r y , .
• d i v e r s i o n o f th e a lc o h o l f o r •both th e c y c lic isom ers eon ta in two
; c e n tre s o f - a a f m c t r f * .- '■However* t h © o ^ * d i « t t i f l a l l f l a lc o h o lf ■
■
f r e s h l y .is o la te d from i t s hydrogen phthali© e s te r* can be re co n v erted
to th e a c id e s t e r w ith m lo s s o f r o ta to r y power*
t h i s b e te v io u r
i s n o t to be expected from an a lc o h o l which co n tain ed any p ro p o rtio n j
o f th e c y c lic isosaer 11%§ f o r t h i s ' i a an i n t o t a l l y compensated
sfem ctore and would le a d to an o p tic a lly In& otivs'hydrogen p h tb a llo '
antes*. /
In a d d itio n th e observed va3u# o f th* niolecuXar r e f m o t i v t t y
{ [bJp m 2S»44). a g le ts w ith th e valu e c a lc u la te d ' f o r t h e open ch ain
form ula {26*35):: and i m f w ith t h a t 'o f th e 'e y o lie fo ra (25*21) ;
(A rcus■and Kenyon/:«T*C*$«#.' X§38/ S IS )* ■■■
:
.p o s s ib ilit y : o f the :.<x^*disaethylallyl' a lc o h o l under going •■.
eh em ieal; change_d u rin g m ita ro ta tio n . m s iiuroatigatcd* ; ^:i t was;/
found, th a t (+)-* ^ * d l n s t h y l a l I f 1- elcohol# f a » d in tho pros one#
o f anhydrous potassium e s rb o m ie or. stood' a t room tssgpsrature w ith
su lp h u ric acid* r e a d ily gave _(*)»dl^<x^wdim®thylallyl ether*
If
th e tf ^ d ltn e th y la lly l alco h o l d v r lvv * i t t .. s t a t i o n was .being
.
slow ly co n certed to th e d i ~ ^ ^ d i i a e t i y l a l l f l o th e r, t h i s would
afford'.'-a 'f e a s ib le ■e x p lan a tio n of. th e isu ta ro ta tio n phenomenon* ..for
tho r e q u i s i t e chango of. sign' {+} to ( * ) • occurs during th e conversion*
Bowaver/ s e v e ra l a ttem p ts t o . i s o l a t e any o f th e re q u ire d e th e r from long-*sttbn&Xng samples o f <?y^ •d im eth y ls! Xyl a lco h o l fa ile d #
. S im ila rly attem p ts to i s o l a t e m. o rg an ic a c id • p o s s ib ly
formed by a e r i a l o x id a tio n • a ls o y ie ld e d m p o s itiv e r e s u l t * .
2
I t was found th a t" 'specimens o f
••dimthyX&lXyX alcoh ol which
had;been stan d in g fo r .15$ 22 and. 33-months save a. red colour*
- d i s c a r d a b l e ,fcy mercuric ohlosi da ■so lu tio n , when shaken /;
•■:•■
/
with a so lu tio n containing fsrretid mmmt&tm sulphate and ■ . . .
stnsnonium tliioefmmt©|
a sample o f 'c * ^ d i» e tlijlil, I f 1 aleohol
which. had sto o d fo r only one month gave m ^k nch co lo u r re actio n *
j f M i conversion o f ferrous to f w r ld .ir o n was used fcy Kharaaeti
and Mayo# d*A*0#S## 1933# Jg|£# .£4iS# .as a .'te st fo r ;the presence
■of pero x id es i n t h e i r In v e s tig a tio n o f th e a d d itio n o f hydrogen.
"beside to a l l y ! derivatives to field ^norase!* .and-. %bnormaifl
p ro d u cts.)
v^ho above r e s e t s suggest th at the ^ • d i m e t h f l s l l f l '
a lc o h o l sa y fo ra a peroxide (across the douhl© bond) on standing#
"with a ' consequent a lte r a tio n . in rotatory power.
t h i s was
•In v e stig a te d Of o b serv in g th e laut&retsfclon'.of a sample o f (•■*•)—
«
*
p o rtio n s !
t hyl &l i yl a lc o h o l wM nkwas d iv id ed in to th re e
to one-was added, the pro^oxldant h m m j l peroxide#
to the second th e ant&»oxi<taftt diphenylas&ne#
and th e t h i r d
was allowed to xaatarotat* without the addition o f any adulterant
as a control.
the rotatory .powers wore observed era? a period
.of I4j Months* ":■' ■Pram a
data Cgraphs
comparison of the.-.- tm ia r o ta tio n
it is readily seen that th e -'th re e samples
OH,
r\
—
1
.0 .. 1
follow ed th e same . g en eral ;.tre n d i n t h e i r change o f o p tic a l -ro tato ry . ; j
power, 1*#* th e a d d itio n o f a pro* ©a? antl** r■oxid«at d id not-
I
s e n s ib ly a l t e r th e m t& r o ta tlo n 'd a ta compared w ith t h e neat.. -
..I
u n a d u lte ra te d {+)**■*r -dime thy MXXyl alcohol# ... Eemca i t fo llo w s -t h a t
j
)
th e formation o f a pero&ld* ©arnob ajo n o 'account fo r the sutarot& tion :;
9bene«eaoD.
.
;
-S..
;
|
As w ill t>$ r e a d ily Appreciated* th 9 « ^ -d lm e b h y la lly l slea h o l can
'
tind#Fge anion© tropie change w ith m ig ratio n of, th e hydroxyl group
frost th e <*• carbon atom to th e ^ e & rb o ii atom# - .... _
*
^=t0SU0H
*
CK«C8«CH*
.
■
l« ^ ■
# *—*■«£-V
- CEUCS
■u■
si
OH
oh
' Owing to the. symmetry o f th e n o le e u le * . th e f i n a l p roduct i s
■id e n tic a l. w ith ’th e o rig in a l# ' I f , however*' th e federation from • '
• od -c arb o n to 1^ -c a rb o n o ccurred w ith inversion- o f c o n fig u ra tio n oM .
r e te n tio n o f asymmetry, th® m io n o tm p l® change would r e s u l t i n a
^
©hang* o f •sig n for an the original and' final alcohols a re •chem ically
ate
i d e n t i c a l , / d ia s tereoisof& srldes w ith o p p o site c o n fig u ra tio n s would v...
.
. n e c e s s a r ily p o sse ss o p p o site s ig n s ' o f ro ta tio n #
■'
dho q u e stio n a r i s e s , ' can ta lo n o trc p y ' be steeomp&nled both by :
. r e te n tio n ©f asymmetry and I n v a s i o n o f e o n flg u ra tio n t
fh e work"
© n ^ d i s u b s t it u t o d 'a l ly ! alcohols' c a rrie d , o u t ' In th ese la b o r a to r ie s
by Kenyon and h i s co-w orkers has prowed co n clu siv ely t h a t the
anion© tropic' changes' undergone •by th e se a lc o h o ls and t h e i r d erivatives
■ ©an occur w ith , a t any -rats' p a r tia l, ro te n tio n c f asyymntry# :
10
r:
I n the p a r tic u la r - ms& o f th e a n lc n o tro p ic conversion of. {*»)«* o r p h a n jl |
^•phenylw # *®ethyiaXXyl aleoho1*.
> ^ » m © th y la liy l alcohol Into;
it was shorn- by Keaton*' farMdge $md' Phillips* .(^*.0*3** 103?#'£07)
th a t th e change occurred both with re te n tio n ..o f ..asysmtatry. end. inversion
of configuration* '
:
(
:- ;.. -
.On applying th e se c o n s id e ra tio n s to th e fe m ta ro ta tic n 'o f
<^*&im©thyXaXXyl alcohol* i t . i s seen t h a t ’ th e d e r iv a tiv e s o f the
tetaretated alcohol should he of o p p o site sign, to those o f th e
fre s h ly .p re p a re d
^disathyXaXXyX alcohol*
this* however* is not
Ch© ease* for th e mtarobatecl alcohol can ho converted into its
bcnscie- and hydrogen p h th a lie e s t e r s * ;whose sig n s of rotation are th e ■
B^p-o as th o se of th e e s te r s propared from the o r ig in a l fre s h ly -
p rep ared o c^ d tm eth y lirly X &Xcchl«: . S im ila rly th e t-f)** ^ ~ d im e th y la ily
sle o h o l freshly isolated from- its (*M*ydrogen-phtlmX&b#* and a ’sample
which has' m ataro tate d for IS months*' both f i e l d on raductiot*. with
hydrogen* th e (+)^methyl 'j^ p ro p y l carbihoX#-:
It I s 't r u e '. t h a t th e
e s te r s and th e re d u c tio n p ro d u ct o f the' m t& rc ta te d o^*.&imethyX&lXyX
a lc o h o l -a r e n o t o b tain ed o p tically '-'p u re '($$ V\93jT a c tiv e depending
on time of m utaroiablon o f th e a lc o h o l)* but i f t h i s l o s s ' of activity!
wore due'to- the partial•■■lnyefsien of c o n f ig u r a tio n 'o f the' alcohol*
/*■.Q
w ould-sot h e %so la r g d .a s ©*g# .^s^tf | ^ 2 i t o
Q ^ g )-.in 13 m a th s# •
i
; Hence i t fo llo w s tl s a t-th e m t& rob& tiea o f tf^dim ethylaX X yl
a lco h o l is sot accompanied by an in v e rsio n of c o n fig u ra tio n , although!
I
th e p o s s i b i l i t y of auX enotropic m ig ratio n Is sot ruled out*
'I
j
A .fu rth e r pQ%Bltd© m chM nim o f •the -mutarefcattoi* •* sad the most
probable * la that tha .^•■dliasthylaXlyl alcoh ol i s m dergoing slow
.j
conversion to an* as yet*., u n id en tified product- which possessed a high j
rotafeorf power and whose sig n o f/r o ta tio n i s opposite’ to th at o f the
o r ig in a l <^^dim#thylallyX alcohol*
5
■;A .1t& vf small proportion o f a
e e v ^ 'n d with a high rotatory power .would to s u f f i c ie n t to a l t e r th e :;
sig n i of rotation , o f th e o r ig in a l
*Miimeth y ia i i y l alcohol#
A p o ssib le* b u t r a th e r novel# suggestion f o r 't h e atrucfcuro o f
t h i s .’assumed p ro d u c t.o f im ta ro ta tto n # l a t h a t very slow conversion to
.-©ethyl .a l l y l ..carb in cl i s occurring#
eiI3CH W:0H CH«CJ% . ■ —
— ~±
_ ...
di g m Ci*CH2€H*C% ; ,
OH ; .
,'oa-.:'.
,
;
and th a t the. sig n of. r o ta tio n o f th e.m eth y l u t l j l e& rbinel I s
o p p o site . to t h a t o f tho'< ^W !lm ethylallyl .alcohol fro a .w h ieh i t I s
obtained*
fh© I s o la tio n -of th e form er would n o t bo. an easy m atter^
f o r i t s b o ilin g p o in t. ( H i 0 ) l i e s 'Close to. th a t.,o f'.th e l a t t e r : (h*p 111?
.• Hi© conversion could, occur by c ith e r; o f . two mechanlsmst.
(a)
th e hydroxyl group o f th e o ^ d lm o th y la lly l a lc o h o l i s p a r t i a l l y •
re le a s e d lead in g , a o&rbonium c a tio n (Complete r e le a s e from th e sphere j
o f in flu e n c e o f ' t h e ' m olecule is . n o t issplied# so- th a t th e remaining.
.j
c a tio n does n o t become e f f e c tiv e ly planar* w ith r e s u l t a n t p ro d u ctio n
o f a. racem ic alco h o l)*
A em ail p ro p o rtio n of. th e se p a r t i a l l y f r e e
•
'
’
/
•c a tio n s th en Isomer is # a s follow s* in flu e n c e d by.’th e •indue ti v e e f f e c t
o f th e <X^methyl group!
|
-
{
.n m m h t m t t m 'of th e hydroxyl group w i t h ' the \ 1 isomer!sad c a tio n
y ie ld s m e th y l.a l l y l c a r b in c l, w hile recom bination w ith th e l a r g e r
p ro p o rtio n o f , th e o r ig in a l ea&lea regenerates ^
alcohol*
♦dlaetdtyXaliyl
/,
(b} : it soeond p o s s ib le p ath d for the rearrangem ent is, that th e
(X^.dim eth^lall^X alco h o l e lim in a te s r a t e r between the h y d ro x y l' group
and t h e t h y 1 group o f th e same m oleeule (th e f a c i l e e lim in a tio n ”
o f .a -.molecule of w ater f r m two Bioleemles of the.a lc o h o l is shown by
■the guest readiness with which di~^^dtaethyX aX lyX ether l a .feinted •
from th e alcohol} f
en d ..t h a t . siTOl.tfm eoraly w ith , .o r immediately. .
n 'S
following, the liberation o f the,. ./] - *»penta&!en© (so,-that, at any
ra te ,- a sm all p ro p o rtio n . c f optical., a c ti v i ty , i s m aintained in th e ■
m olecule) recombination with the w ater takes p la c e ;* ' ;.';...
ft
OH
OH**OH
* OH*OH * CHo
M’ '
** f- HoO
<W
. t r a n s i e n t e x iste n c e •
recom bination w ith w ater can t h e o r e t i c a l l y .occur In s ix
Af' S
d i f f e r e n t ways*
C onsidering th e u • * p enta£iene a s a 4 » a u b s tin te d
A1/^
u •butadlen© , .th e w ater can r e a c t by 3 ;4 , Is 8 o r I s 4 a d d itio n and ■
1 o. 5 ,
th e re s.ra two p o a a i M i l t i e i i n each case* depending on ...whether th e
-f~
■—
-t~
--------
a d d itio n o o a w s m HO » H.. m H ** 0 1. ' E le c tro n ic th eo ry however*
p re d ic ts -that o n ly on®'of1 th e p o s s ib le mod#s o f a d d itio n i s
l i k e l y i n each o f th e th re e o ase a^ te give methyl a l l y l c a rb ln o l from
5 |4 a d d itio n and,o ^ d im e th y l a l l y l a lc o h o l from 'both h 2 to d I f 4
addition#.
ffae .three methods of. w ater a d d itio n w ill/b e co n sid ered in tu x n if o r th e 5*4 a d d itio n o f ...water* ...the m olecule can. be c o n sid e r# ! ■a s - a
m eth y l•v in y l'd is u h d tltu te d ethylene* .
■
,
CBU r CH - CH. ! Cl! s CH.,
. . o i
| .
.. *; .
I
.
I
: -
’
• ■
and .th e mode o f a d d itio n to tills d iru b s tib u te d ' e th y le n e w i l l "bo . .
governed by the. e le c tr o n ic in flu e n c e s e x e rte d by t t f . f e o s u b s titu e n ts #
•..How th e tr ^ h y l group feat'a sm all e le c tr o n repuM ve e f f e c t f l ) ••
compared: w ith hydrogen a s /standard* whereas th e v in y l group has m
l a r g o :e le c tr o s a t t r a c t i v e c a p a c ity ■{*■!) n e a rly ' equal to t h a t o f a .
phenyl group*
eons te n ts
. f h t s i a deduced from m .comparison o f the d is s o c ia tio n ;
o f s u b s titu te d a c e tic acids^ shown below* ■ (Values tmkam -
from. Watson* 1 Modemth e o rie s .of.'Organic Chemistry11* 1937*p # 3 6 * f 5 ) *
&
^
IQ a /c la s s .)
io it^thena.)
CH3*CHgC00H .
1.34
H.CiJgCCOH
.
1.75 .
H.CHgCGOH
>
1.8S
C^aCH. CHgCOOH
4,62
CfiHe.CSoCOOa
Vw -&
4,83
Jh no O' th e la r g e e le c tr o n attr&ofclirii c a p a c ity o f th e v in y l group
aid ed by th e sm all or e le c tr o n re p u ls io n o f th e m ethyl group w i l l .
^
ten d to b rin g about a j a
A3
i o l e ttr o n ie d r i f t i n th e c\ «*p©ntadlen#
r e s u ltin g i n a-sm a ll p o a i t l w charge, 'on t l it 4~ carbon atom*
the hydroxyl ion of the reacting water will combine with that carbon,
atom y ie ld in g methyl a l l y l aarbinoll* ': v .u
■
#
• ca^GH.eiic cat s-cs«
m ~ * m 5 ■CH*CH a 0Hg
~t~
HO I?
I
OS ^
la. I similar mamer fo r the l i d addition o f water*' the
4-p@ntadlenf can bo coneIdered a s a propeayl s&bsiltubed e ih y lm e i
CH3*0S * Si*and fro m
a
comparison o f
th e
■CS a CH-hH
induotive
e ffe c t
of
hydtogea (d isso e la tlo n eon stsn ts o f el ^pontsnole
a c id } *
it
fo llo w s
t h a t t h e 'a d d it io n
p re p e n y 1 w it h
a c id and
o f w a t e r w o u ld r e s u l t
a c e tic
in
th e
..regeneration o f ^ ♦ d im etb 3rl..allyl a lc o h o ls
*
s ©
entail * ss*
oh
«
oii#h
*
HO t H
0%OH * CH»0Ht€H3
Oil
' For a th e o r e tic a l c o n sid e ra tio n o f I f 4 a d d i ti o n , to ZT^pentM leM .
a 3
i t i s necessary to consider the molecule m a .mono methyl 0 <*-.
butadi ana
'
■
I
-
-,
'« ,! j o u GH.ea ■S ere' th e ' conjugated'system' would enhance the sm all •>-f- % e f f e c t
o f the m ethyl'group;r e su ltin g in a sm all p o s itiv e chcrge on the
•4~e&nben atom# thus yielding fcy 1*4
ttlcohoi# ' .:
(9
■
oombtmtien w ith water
V:::v-v-.:
-
;-"■.
chs -^ € 1 I m * m « .ca^ ,;— ——— — ^ ca3cs e H t C i t . 0%
-.
..
j
:
+-
'"
■ :.
ho.------- :— -—-ii
::; v ' ;'
■ ©a
=_' *-' :
|
I
'
.-
;J
j
.
.j
: ‘A- study of the o p ticalteh & irio w of oc <*a!lcyI //^ m e th y l '"ally 1 '
aleohols which has boon mdertalceii in these la b o ra to ries y ie ld s the
following d a ta f
\ '
;: ; ; ;
Me CH j* ei!*0H*M0
.. }
0
V ” 1
.;
.. ..Hoadlly m ta r e ta te s {ate- experimental)* 'V
■■
- ■ .
JteCB « 0h#0H#Et
1
: ■--■V OH;
'
'
.
la€II 9 ’GHiCH^PaMn*)
|
.
-
.-,.
,
•
yary slowly m tarot& tes (unputllshed) *'
- '.'■■■
.Does not m ta ro ta ta (Arena and Kenyon* .
. - ,1*0*8-.*. 1958, 313}*- .
.- .In order to decide whether the sy&metrle&l nature ■of the w le e u le :
{
mXXyl aleol^ilwms Um' e s s e n tia l' featu re fo r th# occurrence
of m tarot& tlon* a second ;0y»#ti*ieml a lebhol ^
aleohol-j
was synthesised and vm.Qtm&* ;. However* th is l a t t e r alcohol a fte r
standing fo r 9 months had not pats rotated# ' The ofiiiirwid ro ta to ry
"
powers of th is'rf^d lstfcy lally X aloohol# I n c o n tra d istin c tio n to those
* * 's
!
c
o f ^ ^ d lM e th y la lly l alcc-bol* wore r e la tiv e ly larg e * ®*g# <*5^,, **6#8X I
(itO , 6) so th a t any tendonoy towards sm tarotation would ho e a s ily
f
doteetablet
I
• E t * C B . - O i l ' n o t - s « i u t a r o t a t © Csee 03^paj?toenta!l>.■♦..■•■
■’ oh '
; Heao# th# s y m e tr lo a l a i t e
o f th e a lc o h o ls i s n o t alone..th#
d ecid in g f a c to r fop jsutarfctablon# .
From a study o f the. s t r u c tu r a l fo m ila © ofj^mno dl«*sufcatitutad
a l l y ! alcohols*.:i t :ap p eals '.th a t m ‘in c re a s e in also '.o f .t h e ' ^ ~& lkyl" '
■group suppresses" th* tendency. towards im t& retafetotu" ./..This f o o t decides
.a g a in st th e im ta ro ta tio n tieeh& nissi;( a ) ' above (p*
fo r .m thyi.*• ethyl*
\iso * p ro p y l and t e r t r b u t y l groups stan d i n ascen d in g o rd e r o f e le e tro n
. re p u ls io n .(Watson*
Am*
Eep**
.1938* 35^:213),
s o :.th a t replacem ent o f
i ethyl, by e th y l i n th e A p p o sitio n o f th e oi*&lkyl / m e t h y l -a lly l
.a lc o h o ls should in c re a s e th e ten d en cy . to ts e n e x d s a tie n {and foenea,.,'
im t& rot& tlon) by mechanism {&)*.whereas th e re v e rse I s found to occur .
experim entally*
. The in c re a s e i n e le c tr o n re p u ls io n w ith in c re a s e in th e sisse o f
th e
- a lk y l group, i s in agreement w ith mechanism <h)
’ . th e n
.,
th e oC- s u b s titu e n t I s a l a r g e r group than Cl!^t th e s u b s titu e n t can be
C onsidered a s CHjg*R-(the nen-aS»dor o f th e m olecule being xmctenged)
and in e r ease in th e le n g th o f .E would tend to . lo ad th e carbon atom o f
t h i s cHg group w ith electrons*, and so p re s e n t th e re le a s e I f a p ro to n
from th e ^ c a r b o n .for com bination w ith th e oil anion*
ste p i s h in d e re d ,. is o m e ria c tio n
also, prevented*
of
th e r e m in d e r
of
I f th is in itia l,,
the m olecule i s
th is
an- even ^
follows t h a t i f th e o( *m ibstltu@ nt had . ■
lies? ,+ t. e f f e c t t M I OH3 * e l t e i m t t m .of. If^O w ith, consequent;..
I s o r c r i s a b l e a •:Shout<jt oocu 3? m m mere rm & i l j *
S u b s titu tin g .H f o r
in'this formula g iv e a erotyl.-alcohol- Clf^OS 3 ®*0IIo | m
. -. ' ;■■■=■ .
.. . ,.
.- oh .
T O ia ro ts tle h i s "p o ssib le b ar a fen*-th e ' alco h o l eon ta in s no c e n tra o f
a» 3 ri^ t r ^ and-eannot ha -.rsaolved* -- ;;
However* ■evidence -b ea rin g on the kind o f t&utcmeriem p o s tu la te d
above for erotjl alc o h o l is provided by tbs follow ing*
M as toad and Kydon {^#0 *8 ## 1934# IQ§5) found- th a t on t r e a ti n g A <+■....
b u tan o l {1 } w ith phosphorus tribrom i& e and p y rid in e th a t th e norm al 7
3T
i:'A -b a te n y l bromide (XI) was formed* b u t whan co n v ersio n -to the
bromide was e ffe c te d by means o f a .su lp h u ric a c id soluH on o f ;
hydrotjroaio a c id th at* 4 ••'batenyl 'bi'osildd ( I I I ) was a ls o prodaeed.*
II.
CH„ s CH.CHoCHoOH
.if*
it*
A t
ii
-r cnaca
3-£ w-.i'*#v**oi
3
■ *■. I l l * :
I t th u s appeared' th a t an isomerle&fcion' o f e i t h e r A -b u ta n o l 02*
d - b u t e n j l bromide had o ccu rred in t3aa'second instance*
2
.10
(Xh# c o n s titu tio n Of th e hm ixidfa XX' fend'XXI-ms-'checked by. >
\ conversion, v ia th e G rlgnard r e a g t i t
phony! tuo&jmmt® to . ,
f
/S
knowi an tli& es o f . ^
^n~ pm tenelo acids* and a ls o v ia
I f - and
th e s z a lm lc . meld s y n th e s is ’ to
Z)^~]£"hexett0le fefeidsl .
■S m s i t appeared, a t f i r s t s ig h t th a t m ig ratio n o f a hydrogen and
n o t o f the', ex p ected teomino a t m had occurred i n th e th re e
carbon a l l y ! system*"- r
'
■■''
F u rth e r work on t h i s problem (iUmmn.Bnd. B y& oa/£«€♦$«* 1930,
■ £61)' showed' t h a t '-the p ro d u ctio n e f XXX was n o t ' due' to s ta p le hytW;
rogeh m igration*
fhfese w orkers p o s tu la te th a t th e 4 •b u te n o l '
i s f i r s t ' dehydrated ' to butadiene* follow ed by 1*4 a d d itio n ’ o f'
:
/i
H8t* to y ie ld th e Xl-but®ayX bromide#. :
•
" •
—
. «*>ho0.
c%* oh#ch2<^oh •"--; -■
". >.
" .
\
m
‘
-
ca*an^ o%
HB?
'
.
g
.
/
Clt^OH a CH.CHg Br
■■- A v ery mmh e a r l i e r ta t e c o n v e radon. o f prop any X sad a lly ! . ■
r a d ic a ls o ccu rrin g w ith o u t 'a a io n o tro p ic ’m ig ratio n was o b se rv e d . ,■■■:
e
i
. by F i t t # . (Be?**' 1891 # 24#' 82). who found th a t '.the
e f <*/i~
j
and ^ y w ra e a tu ra tsd a c id s' ware •l a t e r e c n v e rtib le in hot a lk a lin e
so lu tio n * e*g# ■
'
^ ■
■
■ -'■■
. . .
Cllg CH * CH.COO* ^ = = ;
|
j
» CH.CHgCOO-
M©re re c e n tly tau to m eric e q u ilib riu m has been observed
o(
.. •between ^fw&lphenyl** a - t a t m o l e a c id (XV) and /*fMlph«&yl<»
/^"b u ten o lo a e ld '(V ) w ith 'e q u i l i b r i a ' being reached whoa 83|C o f f
!
1
11
As p^essatt ( RiaXnlka? and larguncl, ■J» OnlT. .Bonfbay, 1939* '§*
’
.
Part'S, 184)*-,
■'Pbca , e « CH.eocu
S'
| .
Ph.
.
:
jjj
.v
■
,
• : j y - ’-.-
;|j
;|j
rise
» c,
j
gh0
cocar
' ' : : ' ' ■■■ ■■'"•Ph- : "v
::V
■
.
'
1
;jj
' :
'\iy.
■V* "" ■
" ■ij
These throe cases* sim ilarly to the conversion of
j;
dimethylallyl alcohol to methyl a lly l carbine! postulated above# ' p
. r e su lt1to' the isigrablon of a double bond from the penultimate "
■to-the terminal position to-the molecule*"
■ /
-it might be thought that these postulated changes in the
:
substituted a lly l alcohols would he influenced^ and so be , j;
detectable* by alkali, or mold reagents* '., However* th is la nob so*I;
fop Provost {ton* Cihim*#-l$2S# 10* 14f) found, and Hewnsan and
. Hymn Cloe* ei t * ) confirmed that d^buttenyX acetate i s hydrolysed ;
by alk ali without isomefisation* . toe two la tte r authors -also
%
.. ■ found the 'same to be true for./i **butenyl acetate; ...and- that
., I
j
A(S
and A ^butonols are recovered a lw a t unchanged a fter heating with.'
50^ caustic .poth$h f o r .43. hours at 100°* and in addition that
, acid catalysts fa ile d to -laomerise the two alcohols * '
■i
j
toe general •type of isomeriactions undergone by propenyl and. ,j|
a lly ! derlvattves e#g* totaroonveraion of methyl vinyl carbine! . I
end erotyl alcohol are usually postulated as occurring vie.
. ■, .
.
.
-v
.:anionic migration* ' However* in. the ease quoted#.. tha mum tm%
I
u
j;
r e s u l t 1a o b ta in e d -v ia r
$ b ). fp i IV1^ #■ so t h a t th e
|
c o n v e r s i o n m a y b e t a l c i n g p la e @ ' « t M l t a n e o a » l y v i a . b o t h p a t h s * t h e j
a n io n ic m ig rato ry meehnnt*n enedoiaim ttii^*
;vflie conversion o f
m ethyl .y ii^ l o arb in o X 'to c w t y l 'a lo o h o l'c a n occur' v ia m ech sn ltt
j|
{b)-&$ fo llo w s» '
1
f h e .- f ir s t .'stag e i s ' th e e lim in a tio n o f w ater-v
betw een. th e hy& rozjl g%*mip and th e ct
■transient 1*4 b u tad ien e m olecules*
' group t o s ty e a
"
^
-
i
* .-CSUCH S '0% ; vK % 0
/' f he lib e r a te d 'Is 4 b u tad ien e can now add w a te r i n t m ways : ;
(a) "by 1 |2 a d d itio n re g e n e ra tin g th ^ b r% in a l' © ethyl vinyl, e&rbinol;
and (b) by l t d a d d itio n to g tm oryfcyl alco h o ls*
CE. Oil# •CS * 0H{
O ■i
i
m «j3m « geuc&
• #3os
E eturning t o .t h e q u estio n o f -the m la r o ta tl o n
dXsubsfclfcufe&•a J l y l aiecfcola i t would appear from th e above
saeehanleta th a t a l l <rt ^m ethyl ^ a l p h a l b y l a l l y l a lc o h o ls ’ titoM
undergo m taret& fcica by v i r tu e o f t h e i r conversion to a l l y l
alphollcyl earblnols#.
However# owing to ■p r e p a r a t i v e 'd if f i o u lt i a a
th e only st ■*m eihyl y ^ a lp h a ik y l' a l l y ! -alcohol' which' has been
in v e s tig a te d tap to ’t he p re se n t i s th e a fj^ d iis o th y la lly l alcohol#
.fh is. p re d ic tio n r e l a t i n g . to '.th e m u ta ro ta tlo a phoaoisaM
a p p lie s ottly to
^~<aafcal%yi a l l y l alcohols* f o r as a i
■
•■
j
i
p o in ted o u t e a r lie r * th e replacem ent o f th e ex' *mefchyl group .by a
I
l a r r p r alliyX re sid u e w $ *& d .Xn.iiMt. tho i n i t i a l sto p - ( I # * # w ater
j
e lis d m tio n ) . i n t o i m t o o t a t i o n aecpeaoe* ■. ..this i s hom o c u t by
th e absence o f a n ta ro t& tle n observed i n t+)«j(dlethylaXIyl ■
•a lc o h o l
Csec experimental) * and in a l l other ^ • d is u b s t it u t e d a l l y l
'.
a lc o h o ls -{except irary s l i g h t m tw ro t& tio n o f y m ethyl ^-methyl**
a l l y ! alcohol} which haw* boon ozamiiiocl in t h i s laboratory*. ■;
p o s s i b i l i t y o f p ro to tro p io ehang# ©cmirrlng d u rin g th e
m fc a ro b a tic a .o f oL ^m dim cthjiallj 1 a lco h o l i s ru le d out* : sin c e th e
r e s u l t o f .p ro to tro p ic , ta u tc r.c rla tt would bo methyl. {^propyl ketone*#
m,t on# 0H - ch# cat* ■ > - = ^±. ■; ch^co"'chuceucsu- ■
/
.... OH ... :■■
I
' |
.■,■■■■■
t h i s Seaton# would n e c e s s a r ily be o p tic a lly in a c tiv e * s o .t h a t j
i t s cm tim w uM p ro d u c tio n from ^
^ d l m t h y l a l l y l . aleo h o l would
r e s u l t in an o p tic a lly -in a c tiv e product#
It'll a i s n o t observed ■
alcohol
when o p tic a lly a c tiv e y ^ d iiM th y la liy l^ is allow ed to' stand* even
over a p e rio d of' th re e years#
Attempted Sotrnration'-ef ;
{t }**V y ^Dlrnethylall.jX Alcohol' in to
T^O FOW3 by D is tilla tio n *
‘ ■■ "•"
Mi s K s '% tms
': -
.
V :V
:■ :
to se p a ra te &*{+)* <^*dimethylaXXyX'
j
a lc o h o l-in to two f o m s b y ;slew - d is t ill a ti o n o f th e
,j
■obtained from eXHalln* h y d ro ly sis Of th e (*)*hy3rogen p tsth a lie
'j
■-ester* ■■Ihe low b o ilin g freetlon'w & a .re& risd w ith potassium , ;. \' j
c a rb o n ate and ag&ln d i s til le d * ^ fh e re were th u s cbt&laod two
j
ftyaeWone {*} 1>*p« 113-1S3° *n<t ( t ) . ts-.p.
j
101*192°*
Thm® ta o f r a c tio n s wer# ailew dd to s e p a ra te ly m ts r o b a te o r
<. over n p e rio d .o f S f y eanr in d t h e i r r o ta to r y powers p e r io d ic a lly . :
fixe r o ta to r y p » e r s o f th e two f r a c tio n s c o rre c te d
o
*“
. to a tem perattire o f SO ' and isA* .are p lo tte d i n graphs
j
.
determined*
I t i s seen -th a t. although t h e ‘g ra p h s-fo llo w ,th e same gmar&X
.
tendency* th e r o ta to r y powers o f the lew b o ilin g f r a c tio n » r ©
' ra p id ly change t h e i r sig n o f r o t a t i o n and .m aintain them a t a
.
r e l a t i v e l y larger num erical m im e than th e f r a c tio n f f
di&ethylAlXyX a lc o h o l b*p»
,
■ th e low b o ilin g f r a c tio n
. a ls o g iv e s r i c e ‘t o m complex#. m t a r o t a t i o n f o r th e sequence o f .
m in e s f o r . X
Z°
,
•
Zo
ots ^ f
nd
it>
,
in v e r t thorns e l v e s '
j
a f t e r about XoO.^daya* whereas the h ig h e r b o ilin g f r a c tio n
.1
m ain tain s the sequence over a p e rio d of 9SS days* ■
i
fhtxs I t can be r e a d ily a p p re c ia te d , th a t u n le s s th e dy(**-}•
<Xf^di«tbylallyl alcohol is carefully distilled arid separated into I
'
!
■th e c o r r e c t boiling fraction,.several n ee d le ss anomalies will
j
;1 1 S
appeal-* in the m fcaretatlon data Of ’th^
;.
•dlaethyX&.llyi alcohol#
■ rorfcicns o f the high and low b o ilin g fr a ctio n s were* a fte r .
m tarotation * reconverted to fcordrcgsn'phtballe eaters* • ■
b o ilin g f r a c t i o n ftoXdod &,
lew
p h ttm lio e s t e r w ith.;
[ (*iS¥i{'t3{?c><’w h ils t the h i ^ b o ilin g f r a c ti o n gave an e a te r w ith
• ; . ^ s.
. Both epeetoens' o f . th o tf/^&imeth^X&Xlfl.
alco h o l had b^en d e riv e d from a (^ ^ h y d ro g e n phth&Xie e s t e r w ith
^
i 4 w f S0#0®*
V
OQ
tto to n lsm Of thm K eastlons o f OotlO&lly A ctive w *»tto® ttolg l l y l
11
0hl&flde»
i
■ j f c W W r i J M W B W MiWMfi"t*W«^
. .,
,
.. .......
..
|. !
■
■ (*,)«* (^»|}im©tii|laXlfX'eblci^lde obtained frcm (■/•)-'^**
’ !|
dlm ethylailyl 'a lc o h o l'-reacts v ig o ro u sly w ith ooM water to y ie ld . |i •
(•J^ ^^d im o th y ifiO ly X ' iacohol'# '.’1'- th is r e a c tio n , a p a r t ' » «
tfca
. ..]!:.
o p tic a l p ro p e rtie s o f th e p ro d u c t, In d ic a te s th e entoneed
. j! j
r e a c t i v i t y .e o n ferre d b y ' th e presence e f a double bond, 'f o r tb® ....... Ik
corresponding s a tu r a te d "c h lo rid e *^»ehloro~fi~p®nt&ne * needs t o t jr
c a u s tic soda s o lu tio n 1b •o f f a c t i t s h y d ro ly sis {Ayres, I nd* .Bag# ; . !|
Ctosi#V io so , gl* S9D)*'
;
fh@ {«*)*• ^^clim ethylallyl chloride reacts also with methyl ... j^j
alcohol, n^tmtyl alcohol and silirer acetate to give respectively
j
the' (*)*&»&thyl ether, the (*)~j^bubyl other and the (~)-&cet&te*
j|
I t i s net possible' to ascertain’''the' percentage'of retention
j
of optical a c tiv ity in the reactions of ^ ♦ d im eth y la lly l ,ehlorM%ij
for th is compound i t s e l f Is produced* with "the occurrence of m
: ;|
unknown amount of raeea&satlen * th is i s shown by the .Inconsistent i;j
r o ta to r y powers o f d if f e r e n t p re p a ra tio n s (see experim ental
|i
jii ■
■section)*''.'
■
Ii
"
lid
.
/
' !(i!
Sine® th® {-#-)*#^ » d i m e t h y l a l l y l a lc o h o l can he co n certed v ia f
th e (~}«ehlorid* t® ' th £ {*)*&ethyl e th e r , th a
e th e r
and to th® (*>)~&c#babe l#e« ti. d e r iv a tiv e s w ith th e same sig n o f
|
f;
r o ta tio n as th o se prep ared d i r e c t l y •from th e (-*•)<• 0^« d i& eth y iftlX y l f
a lco h o l b y methods i n which lal& en in v e rsio n s cannot ocour
1;
1 19
{Bills#..Kenyon; a n d J p , * «
t i t #)* - i t fo llo w s .th a t th e re
. h as b arn no -w m l t m t in v e rsio n when.-th©', conversion o f th e '--;
alco h o l v ia th e. ch lo rid e* to ' i t s e th er® 'an d 7e s t e r l a co n sid ered
a s a whole#- ■.However# :th i s dees.'net- i m p l f t h a t ' each re a c tio n hse
o ccu rred w ith o u t Inversion} -■' th e aame r e s u l ta n t e f f e c t :i s . obtained., wtmt b o th re a c tio n s are. accompanied fcy an' inversion#
/
■Etideno# has been ad d u c e d .th a t an in v e r s io n 'does ooeur in
th e ,co n version
a lc o h o l in to ^ •d im eth y l* *
"V a lly l-© h lo rld e (p # ,.£? ;■)* •■•>ln
I&i£hea and XngoM w ith :'
• th e ir , c o lla b o ra to r s C*f*0*S## 1937# 1052) from a study o f & la rg e
: ■ o u sster.o f^rep lacesaeat■r e a e tto n a ■o f b o th ,:4QE and **X C ^'fealogen)#
. p re s e n t a. g e n e ra l mechanism:- f o r th e replacem ent of^Q B h j «*%
ubI uq
phosphorus h a lid e s and e s y h u lid ss a n d 'a ls o tM o n y l h a l l dee#
■ftioy asmaae t!m t t h e . f i r a t sto p i n th e re a c tio n i s th e ■■■
:
f o w a tlo n o f . © atesvhalidee o#g#-f!#.0#'PC3U;end
■-H#0#S0C1 (th e *<•
pyri&inium complex 0rJ!Jf<0H) *0001 was i s o la te d t p m th e re a c tio n
_
.
. of. {•)-o y ^d im © th y lallyl a lc o h o l w ith th io B y l c h lo rid e i n th e - ■
presence o f pyridine ** es&etttftsntal p ./ 4-?%*
fhoae e s t e r '
h a lid e s can undai^o conversion to t o hali& a i n th re e ways, e#g*
fo r the thtonyl ch lorid e r e a c t io n * A : ; ' ■ ■ '
fk ** Cl -t- SOa
r
- c& o + cr
01 « S -f- SOo Is)
E eaetlea {%) Involves m intram olecular change w ith
re te n tio n of oenflgurafclenj
:
m m tlm {£) Involves the cation of., \
H#0*S0C1 in & bim olceular su b stitu tio n lead ing to m Inversieni
.;„j;
sad reactio n C3) involves the decomposition o f fUOSO to 1 • #
. j|
follow ed by rea ctio n w lth OlT to B*cl*
th e v e lo c ity o f rea ctio n j
(3) i s mainly determined by the deeom pesiiioa o f the B«O30
■
io n and so i s predes&nantly im ^ -M lecu la r# loading to seme
.
j
. ItI:
Inversion bat w ith ex ten sive raeeEdsation*:' th e p resem e o f a
.j
te r tia r y h ast e*g« pyridine# favours the io n is a tio n mechanisms
(0}"end {3) loading t o 1inversion# ■
■ a # re a g e n t f o r Mm p ro d u ctio n o f ctfm dimethyXa. 13,y l c h lo rid e ■' I
from th e ejco h o l w ith th e moslcMt p r o b a b ility o f in v e rsio n ■■
occurring# would th e re fo re he phosphorus t r ic h lo r i d e in th e
p resen ce c f p y rid in e*
Indeed# whether, th e r e a c tio n i s c a r r ie d
.
o u t u sin g th e l a t t e r reagent- o r tfolenyl c h lo rid e e i t h e r m a t o r.in |
th e p resen ce o f p y rid in e# th e r e s u l t C i#e*{«)«e^»difff:et!iylallyl' .
a lc o h o l t© {*f-)<*ehlori&e) i s always th e seme#
la m e i t can-be
.stated t h a t th e e c n v e rslon o f o ^ d iis o th y l a lly l alc o h o l I n to i t s /
c h lo rid e proceeds n o t v ia a monomloemlar mechanism# t o t v ia one.. I
o r both o f th e feim oleeular mechanisms (2) and (3} sh o w
involving;
an In v e rsio n -en d some r a e m ts a tlo a #
then **0!I la replaced by **! w ith the aid o f a halogen a d d
the product Is# I n the m ajority o f oases# raecmie* \
B it l££* e i t *)»
{Xngold, a t *
trhis was found to occur w ith ^ •d im e th y la lly l ;
alcohol* ■" u sin g l^clroc&Xofl©.'®oid gun in the presence.-of e ith e r
nine ehlorl&s © r.csleiu a carbonate#-:an .lmctiTOcy'*dlmethylftlXyl ' ;
ch lo rid e-was obtained#■■; / / : ; ;'
■
;
.
: p ^ e # - re tu rn in g "to th e q u e stio n o f in v e rsio n s Involved i n
co n v e rtin g at^dtoethyXaXXyX alcohol* v is i t s efiXoiid#* to i t s
r^ c h y l m b u t y l 'e t h e r s and a c e tic e s t e r # 'i t 'follow s from -the
,.|
tV 'W th a t t»fo' eo n seoutive in v e rs io n s a r e involved*' ' fh© f i r s t ■
*W«a*K**a*
'
o ccu rs. during Mi# preparation o f the'chloride^ and second during' '
th e r e a c tio n o f th e'ch lo rid e'w ith fhemlwyX aXeohoXs and s i l v e r ' .
acetate#'- fh # query a r ls e a r'-.d o th e ’ r e a c tio n s o f
* d im e th y la lly l
c h lo rid e fa llo w ' a mono* o r U * r oleeul& r course? . ' ,AS lias been
.stated#-bim oX eeular s ia b s tite tio n s In v a ria b ly are.m ot e m p tie d b j
an in v e rs io n '' {Hughes and lng©Xd*\ J #0*S**' 1935# 244}# ,
However i n t h e o o n s lie ra tio si o f a
mechanism* th e re
i s ' the. added c©* p l ic a tio n o f 'is o m e r ls a tic h o f th e c a tio n ' '
-g* o'* I g
# F v* i and Xngold t lyg*
d e a lin g w ith
's u b s titu tio n a t a 's i n g l e carbon'atom #.’su g g est th a t th e stere©-*
c h o s id c a l-re s u lt''d e p e n d s 'o n -th e 'life o f-th e c a tio n s " a -c a tio n w ith
a; lo ng life " '(lo « r’r e a c t i v i t y J ■lo a d s to a racem le product# w hile
a c c m p a ra tiv e ly 's h o rt liv e d c a tio n 'le a d s norm ally to In v e rsio n and
■paoeml'aiatl©n# b u t whore a p o s itiv e ly charged s u b s titu e n t e#g»
ion' i s p re se n t i n the' catio n # c o n sid e ra b le r e te n tio n o f " ;
22
1
s c o n fig u ra tio n i s probable (la@S.& et*
gX»,
lo g . c l t . ) .
: I f , bom v m , to e l i b e r a t e d c a rlo n uadergoea I s o s e r l s a t ic n
'
; I . e . m ig ra tio n frsoss C,t to cr# the o p t l e a l 'r e s u l t w ill aleo :'
depend o s w hether th e .m igration i t s e l f o c c u rs‘‘w ith o r w ith out
In v e rsio n o f c o n fig u ra tio n ' o r w ith raeesis& tieii*
:'■... ^JTlnworsioh in th e f e g m tio n re&eiicm s o f
■ m ethyl&Hyi a lc o h o l (Kenyon, f a r tr M g e .and P h i ll i p s , j*C*S*,
^
l i 37, 207} j
ra co aiisati on In th e aa ig ratio n y emotions o f
w
p ro p y l-^ m o fe y la lX y l &leol& .(Arcus and Eenyon, "JVC*S*,; 1930, i$ l£ j^
th e r e f o r e , d u rin g the re a c tio n s o f
w ife methyl o r
a lco h o ls,- if*
ch lorid e
is-snosfc lilc e ly # '"no” .
' >
\
Isomoxdssa o f t! © m s e ^ ^ i o c a tio n ISaCK * GS*e3Ma occurs*. then
th e re a c tio n s imxnt proceed v ia a bltaoloeulfii* p ath ' in v o lv in g ..inversion*
I f however, t h e 'o a tlo a d o es'i« o m e risa in ..the ”
~.;
a lc o h o lic s o lv e n ts , th e n th e replacem ent’’re a c tio n s proceed v ia a
m ono
0<* to
o r bi*m olecular iMch&nlsm, according a s th e m ig ratio n -fro©
i t s e l f In v o lv es an in v e rsio n o r not*
th e p o s tu la te d
; m ig ra tio n , l f . i t o ccu rs a t a l l in th ese oases," 'e s m c V re s i& t i n ...
a c a tio n pea cessin g a 'p la n a r c o n fig u ra tio n w ith consequent t o t a l
;
lo s s o f o p tic a l a c t i v i t y , f o r th e r e s u l t a n t e th e rs a rc n o t ''
o b tained i n a raoemio condition*
”
'
'
She in te r a c tio n o f (*>)** X /^ & ta e th y la lly l c h lo rid e w ith an ,.
e th e r e a l suspension o f . s i l v e r a c e ta te (experim ental p » /£ ?} to
y ie ld (♦}*<x^«dimethylalXyl a c e ta te i s ' a heterogeneous ' -'
■’ r e a c tio n , whereas th e /to te r& c tio n with, a lc o h o ls l&'' &h&mgmwma
ra s e tto s u
;; la g o ld .f tp
(lee# e l t * ) .p o s t u l a t e .a .In k r;g e n e o n a '
io n ia m tle a teeh&alssa. for.; su ch rejaetlpasj&f a lk y l I m li d ta w ith ..."■.
a llv e r ^ c s id e © ^ s o lu b le silver-, s a lts #
t o b e ak in to th # .
, T h lt. a^ e! c m i t a .la dhmm
j
hoRKjgeneeua h y d ro ly sis .o f. alley! •
j
chlorldes-l ■. Im t the'- h stm ^g m m m B m m tim m l a m l m in v a s io n - -with
tmve o f .lo t a.' feooibI sa t i c ^ # - ■t u "t h i .« oonnee tlon* Ucrgrrim;, ■{Itoiv#
( M i t .&efca«* I®57* f0« §97) su g g ests a ll. m e ta llic s a l t s e f /
dp m ,
o rg a n ic acl&a which^ r e a c t, w ith o p tio a llf^
filial- th e o ccu rren ce o f
« vv'
a inversion# ■; T his vl#s3L accords--
!
w ltii tha- e x p e rim e n ta l^ found In v e rsio n which occurs I n -the - ..... !p ro d u c tio n o f
X»)»eblori&en# ■■
\ '
'- - '. s d v ,
frc n -th e corresponding | '
:
r
".■■■ ---V-,
SS30;.production o f . .{ ♦ ^ c ^ ^ d iE je th /la lly l .alco h o l tv€m {«*}*»Q((f'«>
d t e e t l i y l a l l y l .c h lo rid e ^ h y d r o l y s i s w ith cold w a te r does, a c t
j
In volve m in v e rs io n at;©no cerfcoh atoi% sine© t h e '(«-)• c h lo rid e ... J
hap .been O b ta in e d . from .'the (+J*a!cob©X tw hich to co tio n . Involves.
!'
an in v e r s io n )*
]
..Slicrcfora^a .b im o lecu lar isoehanisa i s ruled: outf-
and a s has-boon shown by in g o ld and h is .©©^workers# .a- s o lv e n t -
Ji;
w ith n a M # v d i e l e c t r i c c o n s ta n t fh ig h io n is in g , power I ' f a v o u r s .-«, jj.
und^fsolecular m a g a in s t a fcl^m olecular E^chasdsj^
,.lh a .g re a te r, :J
io n is in g c a p a c ity o f . water* • es. eatspared w ith m ethyl o r f ^ b n ty l
If
alcohols* would ha. s u f f i c i e n t to allow o f th e predominance o f.
...!!:
th e [uxti*polom%a& mechanism*. th u s m aintaining, .th e ;o p tic a l' .' '
]]’
c o n fig u ra tio n round th e a e y M e trlc carbon a Zm*
s u p p o rt.fo r t h i s 1;
v i m i s forthcom ing from th e worh o f ,Arcus and. t i t h tJ«C*3*t I93C|I f 48} who found th a t th e h y d ro ly s is o f 4 v o c^ ^d iiseth y lally l
CllLOriclt i& fB$
at ®%.ia 'VaseatlaUy isoiiDBoieetilar^
k'Mtih&tm of tba reaetiont'of
»dia«atbylalXyl ehlorM#;
£ g ■a^pendadU'
"
*
I Q I I I I JL
Is*&Mon In v e rsio n Enaction* o f !<*{«• ]k<XK«*r
j|» C+
*** '
Via K;
dariv*
Iffl ChloFMt#
/A lsehoi
trla
&arlv«
£«*(**)** ©hio3?£da
BmOE
d»(~)*2seth9& tt&es*
J^OAOi
a th w
I
1 k5
oSKfSa6SOctieiUlsr
^i^i^-jSuSE^iSiBSSg®
aJSSKSg^a«^^Si'isSSS^^'^%^^A
^'S5Sctive
gsa^^.'SS^SS <*^]UmthYl&lXyl
«
■ ■
3 h m i th e /ochantmn o f a tie h ’, '
Xr,T!iffVf'*sionc cJ**rIn** th^SO
^^^v*)^^l^ ^ f ^^T^^fx^ w•^ ^ >^a^y^^w ^^^.^w ^^{^^rt«^^9^^ -^.^■«^•»»^«»^^^^fft■^■W
' “^W'^^<*«w»*»»*»»-^w^■a^lfcW<^^^^^lTl^ >,i.B#iynw»•* ^ i *^ »tr«>imat»ttj?w-«*»* ■■■*'*■rO'-iM
wiVinwa^vosw-
T~~?S£3srX%'
.'.■ Heol&eemtnt r e a c tio n s o f
&<«(+'}« * < X r l e l l y l
Hydrogen fh tfm lata
■■■^(+J**'<x^Bim@ii^iftiiji hydrogen phtftli© e s t e r i s convert&d^.. ■/.
^
"
hy th e 's e U e n a t rot*'* tei 3per».ture o f e i t h e r n e a t, f canalc a c id o r .: / ..
form ic a c id ' d ilu te d v i'th /e h lo ro fo ra * into- l ^ { ^ ) * ^ « d i ^ o t h f l a l l f 1 ., ;
'■
" f o m t i i ' ’ Sosa p a r t i a l l y ?ae&*!sed (-f)^hgrdrogm p h th a lle a s t e r .
, :.ia reco v ered in each c&aej . i n e d d ltle n p h th a lic a c id is"
.: ■■precipitated# :.
f h i s replacem ent re a c tio n w ith f& m te a c id i s
la d by J
a ' Walden \tn v ersio n * a s s t e m h f th e f o l i o /irg f&etss
{^)m<x^m ;../.
V . - d ia e ih y ia lly l 'a lc o h o l; f ie ld # a (f)*->hyd:fccon p h th a lic . e s t e r and .......
■; ■also * -b y th e n o tio n o f th e i s i » d .anhydride o f festal e .and a c e t i c .;
^
, acids* y ie ld s a
loe#
0l
t »)»
e s t e r (B ills * Kenyon a id P h illip s * ' ■.
Hence the;.(f-)^hydr© g« p h th a lic e a te r, and th e (*►)»
...; f o r n a te 'a r e o f .the same
;, of, th e
i
co n fig u ratio n * .so th a t t h e :eonverslox .'
hydrogel phthdl a te . in to (+-)«* otj?«« ■ ..
; d i m e t h ^ l l y l form ate m ist hanr© occurred w ith mi in v e rsio n of.
'config u ratio n *
• ihe- i n t e r a c t i o n .o f i+)«* ^
... ;. /.
«N$taethyli* Iy3 3hy i ?ogen ■p h th a la te -.
w ith g la c ia l.'a c e tic a c id p ro c e e d s'w ith a slow er re a c tio n v e lo c ity
. ' .• . than i j s ' the. ease w ith 'form ic aoxd* e*g* th e d**{-^}-hydrogen.
/
ft 2 1 ']
; p&th&iat* m stan d in g.a t
' a cid ■y ield ed
fo r a .s m th s w ith ■g la c ia l « eo tlo
l^ t f o y ie ily l a ceta te together w ith
■
# © 23® . •. j
■,' wooTOMd p a r tia lly r&cemieed ^ {^ J -h s’arogofi -phfchalate* ■■ Eoweirer*'
■; . ^ cm the rea ctio n w&a allowed- to' proceed at- wf* fo r 7*5. months*. j
the products wur©
^ d te e th ^ liilltl a c e ta te and phthalio mold*;';
' S io addition, of. a ce ta te ion© 'to' ther S olution taste»ed..;fhe ;
^
;, -■prodaotim 'of' :a d ^ a o tta to # sine© a 'to ln ticm o f
diiittlifX alX fl hydrogen phthalate in 'a c e t ic a cid containing ,6$ .
sodium acetate* "on;- steading ■i t -room t^ aperatw e fo r 17 mcmtta tad
;/.' . fccecmc p r a c tic a lly imaciiim* o resw a b ly ‘eont3&nin% dt* y * »
;■■
'; •.: d ia o th y la llfl . acetate# ■' ' t t e produetloa o f a £X«*aos ta te from the ::
C+|»hydregm' ‘i ^ tfca la te’w ith 'g la e ia l ■s o e tio mold in 7 * 8 months a t ,
o>
37" would M m c e r ta in ly reoiairM^msre than donhl© that, len gth
.
o f time to yield ' a £*«ae*tote‘ i f th e reaction were e ffe c te d
. a t room tcr^rrature* ■'■
■ • - ,'. '
■' 'Oii evidence sim ila r 'to th a t -preseated’fo r tte formic
^
...aeld/reaction* th c.co a y era io a -o f the ^{+)m<xf.*&,lmt$x^l&tfl .
. . Iijrdrogon phthaiat'e'into the 2u(^)»(^«dim ethylallyX . a ceta te
occur© with' am in version o f eoxtfigurafclon* ‘
..ThedyCw)** o^& ls& ethylallyl hydrogen p hthalaie r e a cts a lso ;.,
■‘'with am'athoweal: so lu tio n o f phenolf.. a fte r 14 day© a t room
temperaturef there was is o la te d |*>*p h B
e vnyl*oy^*dimethylallyl
‘ ' •' .: 'ether- to gettar. with' aosse r*XvW** i {t-J^hidrogem ptatmXmto* •
i t was m t p o ssib le to d e te r td a e ,if t h i s rea ctio n tad -oocw rod
’
with lOTorslon e t
IgoMt&on*' sins© attempts t o isolate th@
phonal other from the *otis to derivative of. <^*dXm®bh^&Xljl .
aXcohol and phewl. failed # .. , : ■
■
-
■ fh« r&ccmts&ttm Of
-hydrogen' .
pht&al&fce. In an ionisiag solimni waa,' demonstrated as follow s*
tf e r a t s f o r f pmrnw ,©f:..a solution of .&*{*).* fy" ~dir.ethfXsXlfX .
liX’Orogen phtlmlat# ■In methyl alcoh ol {0 *,0#. 33* 7) s?0isiinad mehargoi
on keeping te * 3 isontha. a t. 31% whore&a tlx® rat&tory. powers o f m
solution o f tli# f-0~t^di*os®2*. p h th elle e s te r In n itro i otnans. •.
10*0#. 30*4) ;f e ll steadily on aliowing to stand, a t 31% and the. .
a o lu tlo n t# g m to d e p o s it phth&ll© a c id a f t e r 3 weeks* '
A fte r
2 months a t 81°# th e re was 4s o l s t 1 p h th a lic mold- gM la r g e ly
r&oemlsed
hydrogen phtiml&te#
I t was
c a lc u la te d f e a t 20,1 o f th e o s d iiim l f^ l^ b y d rc ^ n p h th a ile m%m*
had deeoispoa@ii w ith •l i b e r a t io n ©f .phth&ll© m<i&# w hile, th e .
rem aining
p b tlm lie e s tu r was ©0$ rae«tfdsed#
^
r
■ ■
******
?r r 0 T T 0 T n o r £ m ( + \ m t
*
! * ( * } < » olk<*rdn<* t h y * * 1 1 1
■
•
.w<»^ ftfH
X* («*)*^ * B im etfefIslly l bonsoats r e s e ts " w ith anhydrous form ic
sold at 100°
field
with benzoic acid*
^disaethflallfl format# together
ihis r e a c tio n proceeds without In v e rsio n ©f <•
co-nflgnration# . sin c e l* C^)^o(^ «&te#thfl&XXf1. a lc o h o l is © enw rted
by rn.es.ss o f f o n a io a o s ti o anhydride to th e 2*»{*)~f©rtalc e s to r # and
FI 2 8
b j s e e n o f b e n m fl e h lo rtd e to- th# 3 U (^ J^ en so io e a te r* -b o th
■reactions-taking place ^ttfeout ©a inversion*
■Hence (+-)*»otf «* ■
dl?sethjlallyl- fo rm tc and (•J* o ^ ^ d ia c l^ y la ll^ l^ e n s o a t# .possess the
Bmm mn£lguratlon*
,
r
'
bmzo^te ma
th e Interaction-:© ^
•;'.
:m#thjX alco h o l a t '5X°' f o r t days* .:ih « rt was i s o l a t e ' ^ M ^ a e tb y l
*
>
t h y l a l l y l e th # r$ . benzoic sold* m ethyl bensoat® and'-
p§sof6f©d
' bensoste*
r e a c tio n a t m
0
■■'
■-f o r 80 hpxrs* tb s r e s u lt a n t
On carrying ©at the
o t t e r was- o p tic a lly .tn a c ttv a ana th e recovered benzoate was alm ost
■com pletely raceadaed*
:■'• •
•
.alcohol' la 'c o n v e r te d >by means o f
b en to y l.-ch lo rid e to
e t h y la ll y l benzoate* and v ia i t s
p o ta s s io ■d e r iv a tiv e .to
^ d im e th y la lly l o tte r*
It
fo llo w s t h a t the., abovef.conversion .of {+}<* b ^*dlm ® thylallyl
in to {
*
^ ^ d i me t h y l a l l y l .eth er has. been '-effected to g e th e r
with, an inversion© # -c o r f ifn im tlo n * .: •
y*oh**iam of- th an e/-H ep lsc^^ n t R eactions* ■•
.
.f te racem iaation-..occurring i n .a ll th e above replacem ent
■'reactions i s v e r y ' e&fconslvci . th e recovered s t a r t i n g m a te ria l i s
a l s o is o la te d o p tic a lly impure as shown by..' the•■following scheme***
'
d e te n tio n
o p t ic a l'■'■■'■■■'
.purity t o
product* ■
off**M se t h y l a l l y l :
■F orm te
< * v * * lO isa tta y ia lly l ^
Hydrogen■-— 1 ^
Phthalafce*
0M
^ ^ i t o e & y X a l l y l .'
powatO: -,•■■■,■■■■
'
P *B lrotb$hliyl
A cetate
oy^*Biiis t h y la lly l
off**EXijje thyl&l l.y1
Bonro&te
Eetenfciea o f
o p tic a l p u r i t y - t o ' '.'
re c o v e re d : ■•
o ri-in a l
eater#
F
o
r
m
a
t e
■”
■
<Y w itoetliylallyl:'
“fV4#ethyl sttae*
3TJC
* •
o*s|
1#2J
&
*8:#tJ/tj
■*<$■
}&
" ;' rfhe f a c t th at the products are obtained w ith the occurren ce'
.of such m tm & im w cem isatlon* rules. out b h rp o ssiM llty o f too
replacement rea ctio n s taking plaa© by a M^moleeuler mechnnism a t
one carbon atom*
sine# such' a hi*SGolecular mechanism would involve
■inversion i m i s observed in . th r e e 'o f'th e above rea ctio n s) but
almost complete reten tio n o f o p tic a l p u rity «* totleh i s not
ohsewed#
.
.
: *:owoifer* there# i s a n o th e r p o s s i b i l i t y which t o s t n o t be owi**
looked# namely th a t th e replacement r e a c tio n s may occur by
l i b e r a t i o n o f the bcnaoyl and p h th a lo y l ions# follow ed by
attachm ent o f th e a tta c k in g Ion n o t ;to th e same- <x »eaffeoa atom o f
th e 'mesomeric c a tio n t o t by attaoh^iaent to
vhon atom#
1 30
t t ' tkm 'm le n s # of; th e io n i&'m fch©
~eiirb©n atom i s follow ed
©.Most instanttB osualy by attiuft' a t the ^ c a r b o n atom* them the
rapineement■rea ctio n s w ould,W 'controlled by ft bl-molordltj?
mechanlOT*- : However* th is again ’would not &eo©unfc fo r the
ex ten siv e racemdsafcion'which occurs*"'
r
<*
H©-0E «* 01!*Cl#Mo
m
m
m
0H
*C
H
*M
O
1
I f th e re were ft v ery & m ll tiiso, la g between r e le a s e and atta c k *
s u f f i c i e n t only'.to- allow ©f th e mesosaerl© c a tio n assuming a p la n a r,
co n fig u ratio n * th en th e jesperlmmtal f a c te would b# accounted fo ri
and th e o rd e r o f th e re a c tio n would ten d towards a 'M ^ n e ie c u lw
mechanism#' :“ But if * as- i t nor© l i k e l y oa g e a e ra l grounds*' th e r a te ' d eterm in in g sto p o f
a r e a c tio n i t the' isomerism o f th e
l ib e r a te d ©mrbonim catio n * th en a tc n o ^ io le e m la r mechanl* *s would
predominate#
'
'
-
'
/. ,
■ Ih e replacem ent r e a c tio n s •o f <x^*>aimethyl&llyl e s t e r s most ;
■probably occur v ia a ia©no*»olesutlar mech&nism a t asm ( th e oc4sorbcri
atom* :' : th e feea^oyl o r p h tb a lo y l io n s a re l i b e r a t e d * . g e n e ra tin g a ',
carbcmltra e a t l e n |' ’ t h i s l a t t e r * . i s then a tta c h e d by th © .e* g * a c e ty l
ions# "" fh eae a tta c k s tak e p la c e on b o th s id e s o f th e catio n * b u t a
s l i g h t l y la r g e r number w i l l occur on' tha$ s id e o f th e c a tio n which.:
I s f a r t h e s t from th e reced in g m lm * f o r the. l a t t e r p a r tly s h ie ld s
i t s aid® o f th e catio n *
ftm s t k x
w ill bo a s l i g h t predominance
of substitu#*** o ccu rrin g wit^x Invwsicn- ows* those occurring' without
lOTerBioni so ttmt .th# result will he a largely raeemtsed produet v
w ith Inversion*
..
,
-h;.
\
h o o v e r* ti ll s ia - n e t th e whole, s to r y , f o r su c h ’a meehaalem;" b
would n o t a f f e c t .the. o p tie a l p w l tj r .o f .any. re c o v e re d '-sta rtin g
m terl& X* whereas r& eem laation does -occur# ■;- ■IM s ra c tm is a tlo ji :o f ."the
o r ig in a l is a te r ia l ;£« »©thing- Xiic# to oattenslvo. as -th a t o f th e product
(u-m Scheme p* /Z 1J* . ..^©re$r©# i t ■fo llo w s th a t l a th e ' rep lacem en t-■
r e a c tio n s of* e#g» <*#. ^dl,m#th7 l a l l |r l hydrogen ..phth&X&te,- th a t the,
llU eratied carteoniisn eaU on. £
5
u C H l _ffi!^5 '9 "is a tta c h e d n o t
exelitslireXy by th e ex cess i f ©#g« a c e ty l io n s p re s e n t i n the
so lu tio n * b u t a ls o by-. s « e o f th e lib e r a te d phffcaloyl l e n t '{the r e ? .
Emlndor o f th e p h th a lo y l io n s r e a c t w ith hydrogen io n s in s o lu tio n .
to y ie ld p h th a lie acid )#
t h iir view o f ' t o re a c tio n loads to th e
p ro d u ctio n o f a g re a te r o r lo s s p ro p o rtio n o f ^
^dim ethyl a l l y l
;
hydrogen p h th a la te e i t h e r w ith in v e rs io n o r jo&lnly r&csemie*- ■f h t
r e s u l t a n t e f f e c t would b e th e i s o l a t io n o f m o p tic a lly impure'
reco v ered hydrogen p h th a lio e s t e r «*• which i s found ex p e rim e n ta lly t o
bo the ease*' ;
: . i h i a isoMXXty o f th e ' a n io n 'la i l l u s t r a t e d by th e re a c tio n o f
•d im e th y la lly l . b#ne<mt# w ith m athyl m le r h o l r
. ' O' i s c a r r ie d o u t a t SI th e recovered tom&eftt* i e
'
when th e re a c tio n '
,
$ o p tic a lly
p u re , whereas .afte r r e a c tio n a t 60°. t h e . recovered bm itoata i*
■ p ra c tic a lly '■in&ebttre# ■
h ig h e r tem perature in c re a s e s the.,
m o b ility o f th e benzoyl .io n , lo ad in g to more e x te n siv e raeem isatSon#
■
I I w i l l be n o ted t h a t a l l o f th e above replacem ent r m o t l m s
o f xfm&lm®Ih y ia lly l 'e s te r s * expept one* occur ■id.th-Inversion* '
Ih a ^ c e p tio n i s th e im te r a o tim ’ o f
b#nsoat#
w ith form ic a c id to ’.'y ie ld .|i'C ^ )^ < ^ d im o th /io lly l f e r ^ t a * ■;
/ Ooasitoring f i r s t the ..mnmmtm o f *<f ~&l»t&y2aiiyX hydrogen
p h th a la t# iiiS t th e forsm t# o r a c e ta te with, th # occurrence o f :
In v e rsio n ^ h o t ’o n ly l a th e predominance o f a tta c k s by the" fo rs y l
o r acety l. lo s s on th e aid ® 'of th e d te a t h y ia H y l ’c a tio n f a r t h e s t
from th® 'reced in g 'phth& loyl to n duo to th e s h ie ld in g e f f e c t o f t h is
lo n #' b a t a m x h s ld ia ry 'fa c to r is., th e in flu & ie e o f th e in d u c tiv e ’e f f e c t {«*!) o f th e t o d i s e o c i a t e i c ^ r h o ^ l'g r o u p o f th e phtbaloyX
ion#.' ' i h i s l a t t e r ten d s t o 'a t t r a c t e le c tro n s to i t s e l f f t*m th e
ncsighhourlng oyoarbo^syiate ion* in c id e n ta lly a id in g th e re le a s e of
tfea p h th a lo y l anion from th e a^~&tm#tfeylaXiyi c a tio n {as shown by
t h e ’l a r g e r ’ r e te n tio n o f ' o p tic a l 'pw& t f o f th e reco v ered bssso& te
or-- ^ r e d w ith t h a t o f th e hydrogen p h th a llo e s te r* ’b o th from
I n te r a c tio n w ith f b m ie a c id ) » ■'"
h\
- ’.
•,
•j3»*-0«0C-»- ^
0
ii
■+ ;
HC08.
^
_
C3
toooo~j/As'
•+'.
BSOG
V
\ t h is a ttr a ctio n o f -electrons, to, the undissoel&ted carboxyl
group c re a te s ' an a d d itio n a l c e n tre o f eXeebrmI® e h irg o which
fir th e r re p e ls, th e a c e ty l o r form f1 anions to the o p p o site sid e o f
th e x^»dX»:ctftyle&iyX cation *• tlm s aiding the predcssinanoe■o f
II 3$
In v ersio n # . However* I n th e trnnmfX l e n t h i s e f f e c t i s absent*
so th a t thoi4# i s l e s s XlM itiood o f sitoii it la rg o proposition o f t h e . .
fo ~ y l io n s b ein g re p e lle d .to th e f a r si&e o f th e cation*. hence ill
..the conversion o f < x /^ d in eth p ialiy l ts n s o a te to th e fo rm ic . e s t e r
tfeoro i s m sm all r e te n tio n ©f c o n fig u ra tio n
th e
-In te ra c tio n o f methyl a lc o h o l .on - th e ^ •d in e th y l& lly l bsmtoafce : ■to .yield oy^d ime th y l& lly l m ethyl te th e r proceeds w ith in v e rsio n ;
t h i s i s th e more txast.’fo ris n to o le c u litr mechanisms and la .fa v o u re d
by th e sm all amount o f methostyl. io n s i n 's o lu tio n coshered w ith th e
. number o f form yl lo n e p re se n t i n the., form ic noid re a c tio n .above* . ■
.flio la rg e r, number o f ’forsayl le a s re d u c e s . t o
l i f e o f th e -fro #
. ©arbcnlnas c a tio n by reaso n o f ..their, g r e a te r r e a c t i v i t y and so
allow ing .o f s a s e jre ita tie ii
configuration---In th e product*
.■■■-..In, co n clu sio n I t can be s ta te d t h a t th e meobantea o f th e abcvs
..replacem ent r e a c tio n s ' eemXd be -4eter®dned w ith g r e a te r p re cisio n *
■
; i f i t was d e f in it e ly known. to,, which carbon atom { cx- ■ o r : ^ ca rb o n )
,,of.'the.m escaaerlo ion, Me*€M m €H*CII*Mo th e e n te rin g anions wore
.attach ed * X A-soXmtion m ight appear to be forthcom ing f mm a study
, p f ;fth e replacem ent reactions...©? tm s y s m e tric s lly •srubsfcltdnd o y ^ a lly l'1
.-e s t e r s * . where d i f f t r e a t products, wcmjd be o b tain ed from a tta c k a t
. th e ". X-«or ^ c a r b o n atoms*
<r
z37 *
IUCH «* m |H*H*
. . .
+■
E|H*CE * SHE*
•x B*€B ft CK»€8 Ef
Bat th e v ery f a s t of. s u b s titu tin g ' d i f f e r e n t groups" fB and R*).
m th e o(«* and ^woarbon atoms* would toad to u p s e t th e e le c tr o n ic
1 34
o f th e peeemorle c a tio n due to .the d if f e r in g In d u c tiv e
o f f s e ts o f th e groups B and- H*f
sp t h a t a n io n ic m ig ratio n would
'p rep o n d erate in .the r e a c tio n s ' o f e i t h e r EOH
Cl
or--;
H#OH Oil ^ CH E t ■r e l a t i v e 'to- th# Induct!*® e f f e c t s o f 1!* -and Efj
■1
T his has d e f in i t e l y been shown to T-bo th e oaso in th e follow ing*
■where th e ■In d n c tiv e e f f e c t s o f pfcca|l ftM m ethyl a re eempi.r#ds«*
.H iO ia *
011a
: ^ --Z .o.Z T t
I
;""; x
ftoCS * CH#CH»K*
I
.
x .■
■‘ ■. She balance l a alm ost e ^ d u c iv e ly on th e r i g h t hand aid e o f
th e eq u atio n (Kenyon*1C a rtrid g e and P h illip s * ^*0*3** 1037*' 007)#.. .
..
Thus tli# problem o f tkibmmin in g A e t h e r m ig ratio n occurs i n th e
oq^dim eth^-laX lil replacem ent r e a c tio n s - is In trln s lc a X ly hound-tap .;.
w ith th e sy m c trie a X n a tu re o f th® jRoleoulej
a s o lu tio n would seem
■to h e . forthcom ing only i f one. o f th e e&rben atoms C <**• o r/" * )
I
could he. la b e lle d ! e i t h e r 'by th e u se o f a radlcH -aetive is o to p e o r by!
a tta c h in g a hydrogen iaowjp* (deuterium ) to m e. o f th e carbon
|
.atoms .In question#
j
-
.
.
.
S C l :I I B JjL.
|«'^1,*.
p^saf^t■
»f
o f •&{•t*)}**1o i y '
*
*
J
h
t
h
s
l
i
o
"AX&ohoi '
1^0001
i#-.
Mfl«M*ti&
«’#
"*•*«<»£X
I fj.1
\| f £*®
il*»
&4
4*
#<
%
##
#
i»coon. .;,
:O0 S
J^CH'’-►methyl
'*’"'
. ©fchex* ■
& - H *8 yd?og«n P h ttel& ta
(SaLCQCHj
iyt
H.0 0 O2
{-f-H
(~ )~ phenil
e tte ?
tite tte * oi* no* am invarisim te a oeeuwad in.-tho eoOTeraiGn
of
th a
{ i-} m h y $ m g m p h t t e la t *
indefce:mln&lbl6 *
to tlw
(« }* p h e » $ l
ethar* i s -
1 30
•f-n I - i'tn s Value o f xy»PtEWthylRllyj. AMsfael*
':%% m m mentioned by Hills* ■K m jo n and Phillips t|ro» git*) that
a tte m p ts to deterais** th e iodine; value'o f <*y*dteeihyXally! alcoh ol
.gave- a low r e s u lt mud a/'wry'.ttndatiafactory end^poinfc#' :• t o /
":e&pl&nafcien of' th ese result® hat beirr supplied by Jtssatow (Itx$a««f«
. 0tiim* Appl## 1939 1 I S | 1387) who s tu d ie d , th e Iodine v alu es o f
o le ic acid* cyelohexen* and Iso ^ amylene*.
Ec. su g g ests th a t .th is
anomaly i t due. to the h y d ro ly sis o f th e . l a b i l e di^iodo compound
w ith watsa? to give* f i r s t a j ^ o * l t | fdro^y^ncH *iodo^d@ riim tiye.
•-' followed by a di^hydpsj^d^i^atiir# *-a^oh leading to ■lib e r a tio n
of hydrogen iodide 11dh upsets the starch on4*poiut off the
■ ' . ' 'reaction*
'
‘ >€ « ;C< +- :ln
*
I
.
- ^
. i
I
r ■■■-.
”
: '
11^0
^
'
>0 ~ C< ’ ' >
l
I
■■■■•■■ i ■ on ■
% 0
. ' ■
> c ’* :'c<
I
I
oa -o a
O p tic a lly Act i r e
HI
+ ■'
HI
.
M e th y l
•:; ; V fh e d ^ ^ d i e t h y l a l l y l - a lc o h o l was p repared i n 70$ y ie ld by
th e i n te r a c tio n
of
e th y l sncgneslim c h lo rid e 'a n d ot^pentenal#
■x^pontenal' was prep ared by in s e r tio n o f a
valeral& ehyde' by
m eans
double bond In %%*
o f h r u in a tlo n In the p resence o f m
s tro n g
lig h t* follow ed by e l l M m ti o n o f th e elem ents o f ■k y d re to e sie
. -I
']
,’ . j
|
aatd Itte aldabyd®
'
wus
! ^ b r y c i a oold*. rcouXtln:;
g,lgi.fiM timas i®cg«irg- *
:-
;
: 'i
or*tcm to
- iWtlioi ;o f :ISii!m aM G i^ to a a fit Star*, i ””7 f B ,
She ^oooibility of the
': "
jirstottoi by ao
?
■"■ ■
■
■
"
■
c j : 0c :v in r:r c : i ( c m n
"
o lir r iL o h lc n
in
c t tim mim m nt® of '
n n i ^ r / p e \h zt <putalni~ - h
v''' ‘ :
-
r
—
n
o
'
^ V
n
'
— ->
‘
' ■ : K ' ; : ''
r
■
’ " ■ ' ■ v' -
o ^ o t i « c n .r a t o s t i g .., ,,.
xzi3 l&vootisvfcod by the a t t e s t e d m p & m tlm or
^
hvdr>;cn pbthaloco ***., a, do IJU <U*rtvsittv& prepuixjd fron <x^pontonal ~
frvsno* tut fractional oryota llig a tio n failed to
it/to
e f f e c t * t- y o r o x j^ tJ U m * .
'® & a
aSsaira l l s l tls s ^ l i ^ L n ^ t i c a
of
V%z i n .
tb # iiuOtw coas*, proceeded v iio lly by e i t h e r to p pa o r rn*rT wli::Je:atlcm |
ta d .o n to n e rs 1 ^ ro ra d a * t r a r o
r t
It
e lim in a t io n
ir
th e nvsx
^ t .A t t ic *
e a r bs m fc X y s t a t e d t h a t t b s o y • d i e t b y l a l l y l a lc o h o l p r > -
* nnl fron too ^ ^rsant^al m § c e r ta in ly not a n ixhiro o f a** and
trans_ inonnrs*
....... ... .
■
*fho resolution or t-’O f V
.b y f r a o t l / m l c r y a t ia i*
c th y lu iX y l
e o K V .u
i . e f th e a tr y e h r in o
c & lb . of..
k ytm $ ® n p h t h a l n t c f r o a a s o t m e s o l u t i o n ,
oy'^&i"
"
o
i r m t l m after tAca roorpatolllootlrno y L ld o d , cm
C c ^ a v o ^ itlo n ,
■«iure
t i
*&lothylally 1 alcohol xna of foe tod
th e
(•*-)**. o ^ d i c t h y l n t X y l
iT jlr A o n
fh tn a X a te * .
.
.'.
th e
i’ ?o fraction# of. tte atryetznino ozlt yielded-si
. dlci?iylnllyl hydrate&.pfeth&late$ which after u*? reoryatalliseiloma
ir o n
X I r £ : t ^ f c r o X e u a , h a d r o t a t o r y p a v e r a X d o -n tic u X w i t h *
but o f
opposite $i n , to t un® of the W A yuto:pm phthaXio scterlfe]^
^ifhu^
end
in ohlor-fer i o ?lutio:-}* in o identity f
th e se r o ta to r y power# affo rd # f a l i y c e r ta in p ro o f th a t th e
o^vdi #thyXallyX' hf&vogm phth&X&t# had been f u l l y •resolved#
.
BIO :(+}- ^ w d ltth y la llf l.- a lc o h o l was o b tain ed by h y d ro ly sis o f
!
'!
th e (f-)•►hydrogen phth& lie e s te r w ith e i t h e r 51. a<pootis c a u s tic
j
soda o r a lc o h o lic 'p o ta s h .s o lu tio n s * -
i
■ ’
-th is h y d ro ly sis was .
'
■.
■
■
I
e f fe c te d w ith - p r s e tie a lly 'e o ^ p le te " re te n tio n o f o p tic a l p a r it y ,
|
w as.shorn by re co n v ersio n to th e (f )~hy&rog®h p h th a lie e s t e r
.;
possessing.
j
00$
. . fh e
o f t h # ■o p tic a l a c tiv ity * of* th e o r ig in a l C ) ♦ e ste r*
~&XethyXalXyX' a lc o h o l,.’ so ''obtained, had markedly .
d i f f e r e n t p ro p e rtie s from (*)•*<*</"*dlta& th r if tily X alco h o l fa te p*
- J
• The num erical m in e a o f th e r o ta to r y pow ers. o f ' C-/-}-o^ ^ d ie th y la lly l
■a lc o h o l were
lo ad in g to a m a i l e r p ercen tag e e r r o r i n -.their
- d e te n s in a tio n -«» compared w ith th o se o f th e dim ethyl homologae, ■
2.1
O
2.°
H/
\
. e*g*
■a n i
f-0*39‘ (both homogeneous and 3^0#5»)
' In a d d itio n ,, th e r o ta to r y powers o f ( *)«*<y*4iethy!a.!!yi a lco h o l
were very l i t t l e e f fe c te d by change o f to r^ e ra to re (fa b le
) f '... j
!
whereas {+)«* - ^ » d te e t b y l a l ly l a lc o h o l d isp lay ed a ste e p tem perature j
:
■
■
■
■
■
.
XV
•
■i
- -rotation curve. ( H i l l s , Kenyon and f h i l l t p s ,. I c e * p i t »)
fliese two f a c to r s , sm all observed r o ta to r y powers and th e
|
I
la rg e e f f e c t o f tem perature on th e se r o ta to r y powers, added to th e
experim ental d i f f i c u l t i e s o f working w ith <Xtf »dlm et& ylallyl a lc o h o l# !
Tim occurrence o f a n io n e tro p ic m ig ratio n i s , o f c o u rse , e q u a lly
d i f f i c u l t to d e te c t i s b o th o y « d im e th y la lly l and o ^ ^ d ie th y la lly l
j
!
a lc o h o ls , owing to t h e i r e y m e trie & l s tru c tu re #
But ^ ~ h »$€ sp
... I
' ■
■'
•
/
!
''.. d iffe re n c e between th o se two o p tic a lly a c tiv e a lc o h o ls ' i * tb© \. .\
,;
leg
'.
1
u n s is te k a b le m ta ro tm titm undergone by f-*-)* ^dim ethyiaH yX
'
a lc o h o l on sta n d in g , whereas (t-|~ oy^ **<HethyX®XXyl a lc o h o l e x h ib its
{aft'er ^ '
m
such' e ffe c t* \ m e x p lan a tio n o f : this :■
phenomenon %M e f t ©red on p* i°S.
;
'
I n a d d itio n * th a sp© ciflo ro ta to ry 'g n c i^ rs o f {-/-)-oy^-dtethyl*.
a l l y ! hydrogen phthalat© I n fir©
characteristic dlagrasi {Oraph
eoXrenta f a l l on a s in g le
?£> } § w hile those o f ' (-*-)•■
d im e th y la lly i hydrogen' p h th a llc e a te r f a l l on tw o■d i s t i n c t
c h a r a c t e r is t i c diagrams**
f b e s p e c if ic r o ta to r y powers o f the'
form er e a te r a re u n a lte re d by d ilu tio n in s o lr m ta except i n
carbon diatilp h id o s o lu tio n ( fa b le _fi7 )*
s im ila r ly th e s p e c if ic
r o ta to r y power* o f {+)« ^^dUtarc t h y l a l ly l hydrogen phth&X&te a re b u t
l i t t l e a l t e r e d by d ilu tio n in so lv e n ta # ' ex cep t f o r carbon;d isu lp h id e
s o lu tio n (H ills* Sonyon and FhlXli|>% I pOt e it« )»
[CHAgAGTIE-RiSTlO
fco
^ETHYuALHYL
xx
<Mh
D IA G R A M
HYDROGEN
OF
phth alate.
A*
«•>««****<»i»-«i«(«r»««i#
1 48
e.nd O s tie s l S e so to tte n o f
l y l Aleohol.
: *Eh© &1 * ocr *dt&ot>*ylal l y i . alco h o l was pr©oared I n 60»7s£
W
•» w w ^ w s» » «4(at <
U# f t i*W * g jw (^
>iaW ^
* a ^ ^
*
*
^
: y ie ld s fey th e I n t e r a c t i o n ' of. m ethyl m gnesium feresai&e and
CTOtcn&ldehyde (b*p# 101*103°) "fallow ed fey decom position w ith ic e
I t was found w orth w hile to n%®m d i s t i l
_and atntoonlum ch lo rid e*
th e aqueous Xnyoi8* a f t e r © thoroal ©attraction# to re c o v e r a f a r t h e r
amount o f ^ ~dim ethyiaIX yl alcohol' f o r i t i s so lu b le i n w ater to
..the e x te n t o f ab o u t 1 0 $
ffo# « ^ * d im e th y la lly l alcohol th u s
::
' ’ "•.
^ ■' © :. .. '■•
o b tain ed fond fe.#p* 119*221 «
'
dl* &y ~Vt?i »fcfeytallyl,frydropen .phthalata, was o b tain ed i n
CS> y ie ld fey h e a tin g S6 g*{l 1) dl*
X40g*) {1 II) phth&Xie aiifydrM e and
fooura on th e steam feath#
*dici@tliyM l y l a lc o h o l w ith
8 8 g*<l*iM)
p y rid in e f o r 1ft
ih© r e s u l t a n t 'o i l was poured in to lo o
'© o ld .d ilu te hydroehlorl© a c id and e x tra c te d w ith e th e r; - a f t e r ■■■■■.v
.■washing :w ith w afer# drying w ith calcium c h lo rid e and removal o f
,.the s o lv e n t th e feyditsgen p h th a lle . e s t e r m s o b tain ed .as a so lid * ■
On r e e r y s t a l X i s t ii c a •from c a r to n .b is u lp h id e o r e th e r and l i g h t /•.
p e t r o l e m . i t had .cup* 90^*
(tl* m i {
^
*
rn n _ i» -wflym irt
^
*
^1
)
*
■
'
l e l l yl hvdrer.en chth a i& te st-■
K T j i . y - i 'r — n r . t n TCii^ iracn' - i'i"
r - i r u r i ^ i m ~ir>»if ^ w iT iirrg v r 'T i-i'i r - ° '- — —
-
'" d 'f f
’‘'r "
•
«
■
'
-
^
dl^flCf « d laeth y ltiL ly l hydrcgen ..p h th alate ©Ofgi was d isso lv e d l a a .
h o t s o lu tio n o f aeetm e^obloroform {in p ro p o rtio n o f
2 ;1
fey
. volume) and to the. hot. s o lu tio n anhydrous feruein© (X370g«>) war®
added*
On stan d in g a femela© s a l t was d e p o site d '.and after* th re e
1 44
re cry sfc & llisat ion© fix*a &e«tori*»ohlcpt)fom inixfcur® f ie ld e d ICSOg*
o p tic a lly par® fcracla® s a l t o f t+)k o ^ * d lin e tli^ la il^ l hydrogen
g h t ^Iste* ' ' $ h is on decom position wit h ic® to d 'd ilu te h y d ro c h lo ric
aoici y ie ld e d BSOg* o p t i c a l ly pair®
phtbalat® w ith m*p# •
;(oV K O f-:
1 *2
hydrogen
- and - [°§s^ ( + 30,0° %n ch lo ro fo rm '
}* -V:
V
r
>-..:
; -'/By.working up- th® mother .' lit e r s * there'was" obtained a' w o p '1-*
o f . th® ■bruoin© :m t t o f .(«►)*
tiydrogen phtbalat®
i4i£cii on decom position gaimlS&rg'* {«)' hy^ogen. p h ttm lie e s t e r w ith
.. —20#2®.i n , chloroform {e# S * 2 |.
+
.'..'toother r e s o lu tio n * 'u s in g S8 ^ft*: <tl«»<y ~ d t e s th s l a l l y l hydrogen'
phthdat® ' and §8 %* anhydrous ,'bruala©*; f i«M #d
( t f *4 * *>0g m phthal&t®
2 1 ?g*
o p tic a lly pure
$ 0 *0 ® i n chloroform a n d .8 Bg#.o p t i c a l l y
'■'■pur®' (•)»hydrogeiv phthal&t®' [o(js^ f ^S 0 #0 ° ' in chloroform to g e th e r
'
w ith 138g* («J^hfdrogto p h th a la t# w ith •U\ ■*20*5® in ehloioform *
LJSyH
(-*-)«* and C«»)**<xy~p in*thyl^ 1 1 $ 1 f l c^hola
won® o b tain ed free* th e
{+)*» and U)«hydrog®& phthalafeos re g p e o tiire lj hi* 'h y d ro ly sis w ith
51* .cau stic soda s o lu tio n * ' .followed by s te s a i' d i s t i l l a t i o n #
fh a
'd i s t i l l a t e m t s a lte d o u t w ith potassium .carbonate# “e x tra c te d w ith
■o th e r ond
w ith potassium carbonate to "y ie ld th e re q u ire d
o p t i c a l l y .a c t i v e elaohols* ■;'■■ -'
\ fchen th u s s a l t i n g out th e <x^ ^ d im c th y la ljl' alco h o l i t . i s ' - ’.
• -...,.
-•■
-■
:
•- *
£ ■ ....
e s s e n tia l' to add the- -s o l i d ' po taaslum carhoha t® a f te r
*
I**
WWIW.V■*»*—■
the c a rb in e !
h as a l l • d i s t i l l e d oyer and w ith cooling* f o r on on® occasion th e
1 45
still'.w a rm d i s t i l l a t e was
lun.cwdbt© s o lid potassium , '
_
carb o n ate ** a l i t t l e h e a t was generated, and t h e .m i a p roduct was th en
'dl«* o ^ d i m tf c y la lly l.. ether* b*p* ■15*?°, . t^ y .1 *4310* _
and (*•}*oty'^dtaethyXsllyX a lc o h o ls had ste e p ;
tem peratw #^.rotsti< m eu w ea mud xButarptated on stan d in g a t rocsa
bempr'p&ture|.; furfcheiwr® ’,d i f f e r e n t samples' o f th e o p tic a lly s a t i r e
a lc o h o ls *mita ro t s t e d to .varying e x te n ts {see H i l l s *'.■Kenyon and
f k m i p s * ,' J « c# s* t .195d* S76)» . '■ ,
Conversion a,f O p tic a lly A ctive < x Bimethyla H y l Alcohol to
^
.......... -
■••• -**-••
- ... -taaft-
flr :
wywrrwaivw**. «r - •
"4“ .................. — ...<o*~............. —-
............... .......... ........... -
Bim s th y ia lly l -CM,orMa»
..4n Several methods of replacing the hydroxyl group of .ay<^&l~ ;
.methylallyl a lc o h o l by chloride ware •tried*
fii# most satisfactory
Botlioi for th e -production o f a^«dimethyl& l y ! •chloride possessing.,
the highest rotatory power was method".!' ct.)below «*’using phosphorus
trichloride in he presence o f pyridine# - the products of
.successive experiments possessed inconsistent rotatory powers*. :
thus sbowin^ t h a t ewet^thia method did not proceed without some
rfteeiaisatio n talcing plan##
{&)■■'. tfsl nab d ry .try
c h lorl de./.in. ..the p re s ence of s in e c h lo rld e i
Ery hydrogen c h lo rid e was j>a.§s#d In to .{*)*oy^dim cthylallyl alco h o l
**^
■ •B*78 C1*2} containing -a small
.amount-of .fused sine, c h lo rid e and surrounded with, lee* ' In a s h o rt
ti. mo' the liq u id reddened and separated into two layers; : after
standing* the u p p er layer was run o f f and distilled#
dlraefchylsliyl ehleri& e b#p#
f a s /opties& ly in a c tiv e #
{&•)■ $sini? dry'hyctottgen c t o M s in th e presence ®T m l ^ m
carbonate*
.
j
'
n
fh e pstmed&fe
o f testhod .-(&)"*&& follow ed t a t calcium
*
__
-w
carb o n ate m s a u ls ltitu te d f o r th e s i n e ' ch lo rid e#
<x^dim©tfe|dmXi^ c h lo rid e re su lte d *
I
*r
, ..
. |
A fe e b ly a c tiv e
,.(
||
.
j
(c)(1 ) tfafm t n g at ih te r T l efrlo rid ei ;(8 *tf%) ( • K ^ d i a a t h y l f t X X f l, .
.
alco h o l ^
ZV
^
<?
'
.. .
«» .■'
j 4~bf •FX#4y|
j
,ef"
^ <?ssg **3*ys C3t»S) was.
slow ly gldded through a f in e c a p illa r y to r e d i s t i l l e d th lo n y l
c h lo rid e ( 1 % *) coolS# i n a fre u s in g uslxtur®*
.|
' A fte r stan d in g a t
;
room te s ^ e ra ta r© , tto p ro d u o t m s d i s t i l l e d under reduced p re ssu re and
'{%#) had
*®«31#
tMonfX c h lo rld e l ■
QU^I and s t i l l C ontained aosae
I
-
. j
f h i s was re co n v erted to {+)™ot^*&ivwthflB,XXjl a lc o h o l fcy
shaking w ith an mqimoim suspension o f emloitim carb o n ate to y i e l d ’
|i
an alco h o l w ith b .p . 118-121° and p e £ , ' * p ,1 2 j . *JX ,'0,1® *(1,. 0.2S) ]j
■(c) a i ; tteinsf th lo n y l c h lo rid e in th e t>rasane# o f rmttfMrm* •
*
"
V
/
30*%*
n rn m n r n > t-irriT iianngSTi*i>wmiWwn»»iiin>w " n. ^■■■»*Tm^Tit«iWfiJi^ cwa>tin'i<w-niin<^.'ii- ii : il-j i iif_i,i>,rtf<ifr.fnMfr»^ p fairi«r : i>t*>Wpa ur iwirrii r a^ ^ l-jr rri^ i^' r ^ ^ ^ i^ i trrtTrt-'Tirirti^tBrT-^rhi r r '--*i' ■ n iT - r r ^ ' y i r.fr itrniiTiir n ^ i r ' m n i H ^ t r t m r r t w - ^ 'T - T '- T i ir -ii'f f -i r 'm ttl t r t f -
' .■■
t h i m jX c h lo rid e dissolved- in 35e*o# d ry ^ th tr'w a # slow ly
f/S /
added to S%*
!
,* J '
Vifl&l%$% eleofcol ■c*s+t,f » 0 * t 0 ~f .
;i
o
‘ i
•SU9 & 1
CJU‘S ) -d isso lv ed i n e-tdbcfcore # f
p y rid in e , eniw unded by m f r e
1 0 0 e«e«
d ry efche*' and fsd*8 g*
Ing CG&xtitre#
h;
A « s ? i e f .w h its n e e d le s •® em rated, which did n e t 'a l t e r i n ’
.;;;
i6pS?ecrsnce on ellow iiig th e ■w hole. t o ' a t t a i n roondTtate etn * tu ls wore f i l t e r e d o f f m &.
wt th dry etfconj
.they
.very h ffre s e o p io » a d ■in th e .s ir evolve su lp h u r•d io x id e ■■•.■ "
co p io u sly * ..
j
;
:
fh e y mgf tm the pyri&lniuta-' complex o f th e .h y p o th eticsi
. M l* •a c id o
1
>•>ule ©f sulphurous aoM
^
nj£
/*■
>
s o lid weighed S3 g*, iftaloulsted fo r %i%!! (Oil), 5001 I s S3*S g.
f t e e th e r e a l f i l t r a t e was evaporated to f i e l d 14 g, (*%
' x ^ d i m e t h y l a l l y l ch lo rid e- w ith b*p» E S ° /li m*»* «m&
*&1*3^$
(d)
^\S>*Y
y**-y *74° Ilf-S).*
tTsla g phosphorus .tr ic h lo r id e nr«d p y r ld ir n :
.
A m ist tart o f
1+)* o c ^ d im e th y ls lly l sle o h o i ( 3 t § i l ." < X ^s - n l* ll0%
■ <*-'^3SS *4#94° | l , a | and dry p y rid in e (8*6 §*.} * *
slow ly a* u la t e .r e d is t ille d phosphoxua tr ic h lo r id e (20 g , )
s iir r ^ nW> i f % f r t e s in g m ixture*
texp^x *u*ro f; o r
1
A fte r s ta n d in g -a t room
hour th e u ? tjo r la y e r m s removed end. die**
t i l l e d t o y i e l d ( ^ ) ^ ^ ^ « d t o s t h y l e l l y l e h lo rld e iZ Z s* l w ith
b ,p , s o o /ia iB.m,
- a ,a s 0;:
m&
<>d,
-ic » ? 4 ° U » 8 ).
A re p e a t experim ent u sin g 14 ,3 g* . |^ )* * ^ -* d im e th y la lly i
a lco h o l
( X ^ -~ 0 *?Q# (j^S) r e s u lte d In { ^ j ^ c ^ ^ d i ^ t h y l d l l y l
C hloride (17,5 &*) l>*p* S 0^/l3 m,a* and <x'* *i-3*06°*
•g
**ovS
* 1 * , +14.*5®*
^
+ 28.1<sC i,'s j.' ;
■'
A t h i r d ex p e rir c n t w ith S g* {*-}«*
itii
<X.‘i , ' ♦6.520*
.<*vt»
■*0 .C 1 ° ,
l a l l y 1 a lc o h o l
«gO ,
*1 . 1 0 ° ,
<*£, ‘*4.30° (Jt^S) t a t o i g, ■(-J -o y ^ -filire th y ia lls 'l shlorM ©
,p. 24-2S°/ia-20 n.K. with
'>l°*
o f Tj**{«*)*
o* I.-* (+}<* y^ ■%
LVr*"1a l ly t [Alegt>gi rtt
yjs - d t o t , ’ifX o ll^ l a lc o h o l io ua. a lc o h o l \ i t h a
necutivo alga v t rotation. derived from the dyM **a> * 1
{taioh. l a t t e r h'is # '.p o 3 itiT O :sl^ '-.o f-.ro t4 tte -.imd tlio ss ■
configuration la aaawad-to bn *M * ):vl4 ttm
u l l f t elllerSia*.
dy
:.... .■v -
*s!tothyl-
:;a .
! jig a re used to A m ote a&anixd e o r ^ ig ir a t ia a, (+}«*
•and (**}• to denote observes! signs of rotation#
.:;
. w
■
.;
CD*. <2C»w*H<*n In to ' &!«*•ocv**!*^ *M rtaliyl Tfyr*m^en Phth&late# ts
®
ts
r\
%**{+)«*
‘•e th y la lly l'; alco h o l with' oc^,^l*27. | 1•:"cx s ^ a , •?• l * Z2" $.-.
%s
0
ts
& * ' ' * ' '
'
(XSf£^/ -r 1 *4 6 . | ,, q l -f
■f’ S#&©, ; C i t 2 ) w a s c o n v e r t e d 'b y : th e u s u a l
j
j
j
i
procedure u sin g p y rid in e a t room te s ^ e ra to re In to 3*3g* o f th e
|
hy&m g m phtfefLlio e s te r nt*p# 82*04 *' , $fcis was reery st& lll& ed from.
.1
j
w&ra--'carbon & 1sulphide to y ie ld p u re c!l*<Xr* d its e th y la ily l hydrogen
phtfcslate. sup* 6 8 * 9 0 * th e f i l t r a t e was com pletely in a c tiv e
and on ev ap o ratio n to dryaepe gav® about
:.■ ;
-V
-
0
. ■:
.
2
$ o f dl*oor * d lm e th y la lly l
,
■
■■• ■■■; . .
■
•
hydro cn p h th a la te of sup* 81*83 * which when mixed w ith an
. ■' -.
- 0
■•■■' ■■='■■o ■' ;
^
a u th e n tic specimen o f tup* S9*f>0 * m e lte d -a t 83*S§ *
•
Since d *- dim. a^*dime t h y l a i l y l
:
!
.|
frogen phtfealate i s r e a d ily
j
■se p a ra te d by e&rban d lsu lp h id e s o lu tio n in to th e l e s s so lu b le <31*
e s te r and th e much more so lu b le
.ester* i t - I s obvious t h a t th e .
.above esterlfle& fcio n i s aeeonpflfttsd by com plete r a c c s ls a tlo r u
f h is i s confirmed by B ills * Eaayon and’JFhlllips
■
' ■'
,0
who converted iD*(^)^<^fi*dimethylallyl alco h o l o f, <Xsv*r
. Conversion in to
j
' j
.1953* 583) j
O
**1*48
'(!*£)' i n t o .a dlwhydregen phfchalle. e s te r* v.‘
(2 )
I
-u
Benzoate*
rE e a ls tillo c l' b en sey l e h lc rl& e s{£*&$*) was •slowly, run ih to a n 'Ie o
c o e ^ d s o lu tio n 'o f Sg.
.
cX-5' 9 i>®' ^.l*34 ' i
. ^ t h y l s l l y l a lc o h o l
^ 1*49 J
^
3SS’ * B#bo-
f w ^ l.S O ^
(
: d isso lv e d I n '3 g * ' dry pyridl& ei ■a w h ite ' s o lid s e p a ra te d ■
•d uring
th e re a c tio n #
:■
.:j
a f te r , st&nding overnight* th e whole was th o r c jg - ly J 1
shaken w ith sodium earboim t# s o lu tio n and th e e s t e r e x tra c te d w ith
;
1 50
e ih w i ..th e e th e r e a l' s o lu tio n w as.washed s u c c e ssiv e ly w ith d i l u te '
■hy&roehXerle A.oId imd w ith w ater and f in a lly - dried- w ith e&Xeium
ehXerl&e*.’• t t e e a te r was d i s t i l l e d under reduced pro a o w e b*p* ■,:
1360/I8m*m*. and r e d i s t i l l e d b #p* 140 /felm#25# to y ie ld 5#5g* o p tic a lly
■"'■ , ■
•'. ■
>
••
■ ': ■"■ pgr
'
In a c tiv e (Jj0 * 5 )
t h y l a i ly l ienaoat# w ith n^. / I *5075# ..,
{.3J - for ver s i on' •in t & dl* <*y**P4**-*th y la lly l' p« 11trotoensoa te»- ■
'rsl
,?
3*7£* p^nttrebensoyl chloride' w a? added to s n ;l e e •se e le d s o lu tio n •
o
o f l#7§* h * C + ^ ^ ^ d isietliy laX lfl alcohol t
pyri& tne ( f > )
** 1*46.1 1,2) -in'
The e s te r -.{4*$g#) , r e s u l t e d ' in alm ost q u a n tita tiv e ■ •
- y ie ld with.®#p* 58*»54°- a n d - Its s o lu tio n In ethyl, a lc o h o l' {0 *1 0 *0 $
1 ,8
)' was o p tic a lly in a c tiv e * ' f h # "e s t e r wm r e e r y s ta llia e d fro m ;
aqueous g&eehol t o ' y ie ld dlm^Cf' «*dim©thylallyl p » n ltr o t ©n&eate &»p#
©
©0
alone o r s iz e d w ith an a u th e n tic specimen*
(4) : Conversion o f l^ { t-)^ (K**Mmettylmllyl Alcohol Into •( *')«*<*>'<*'•• ■
D im ethyleliyi A cetate* ^
^
•• r-■■■'.
-
■
,:,. S g * \i^ { t)* ^ » d im e .th y X a ily X 'a le o h o i : / cX^j'- Vl^'So0! c
< o
.*
■ < - .
J
+ 1*49 |
■ oi
+• 8 * 5 5:{JjB}/ -were d is s o lv e d , in 3*% *-d ry
^
"'
5 S S
...pyridine and to th e s o lu tio n -was slow ly added 4#2g# pure a c e tic
anhyclridf*
fo r
2
■ Am so p e r c e p tib le re a c tio n had taken p la c e on s ta n d in g .
days [ r o t a t i o n o f the s c lu ti'cn r r a i n e d c o n sta n t a t <X^ +-0 * 6
(’2 k > £ ^ ) J ' 9
th e whole was h eated f o r
8
hours o n 'th e steam bath* ’ fh e
"e s t e r was '^worked up In the u s u a l ’mariner and d i s t i l l e d In vacuo.;
o
'
on r e d i s t i l l a t i o n ' a t o rd im ry p re ss u re b#p# X36~137 • th e (+*)*<>4 r«*
■
■
*•
,,
* ., + 0*31’;
d t e t h y l a l l y l a c e ta te |5e*e*) had <x +-0*29
<*:*■?*>'
i'Q»3 s >
■.
a i*3s*
+ 0 ,6 5 i (3^0,5) a n d : a T 1.4179 ( H i ll s ,
■ 2 0 'Kenyon and P h i l l i p s , f e e , e t t . g iv e it 1*4179), :
D
o f tmC+ymptf
, Cagbinoi«f
ft*?......
ropy!"
^ J « +1*50°?
tm th yla21j l A1 eohol in to (mj^ e t h r l
A specimen' o f JU{-f
<*1*
+i*6S°i
mleohol
,x'J3Si,+ 2 .9 ° (1, 2)1
ahsorhed
.the ca lcu la ted amount o f hydrogen w ithin 5 minutes u sin g Mama
catalyst# ■: The -re s u ltin g J*)*mettqrX' i^propyl earhteol had fc*pt -, _ :
, O
(8
' T 7*.S
IIS 'I,. -Uk
■ l# 4 0 il and;
0
'0 •
~0*1B (X^O^S)*
f ic k s r d and Eenycm
j f l
U .C ,S „ 1911, £ 9 , 49) g ive
+ 1 1 ,1 0 ° (1*1) f o r th e o p tic a lly
pure c a r t i n o l j . .hmc® th e ( • ) » m e th y i^ p r o p y l c a rb in e ! •o b ta in e d
above p o ssessed o n ly
'
■
s
'
o f the a c t iv it y o f tfcc&ore (*)«e&rblnol«
-
(d i :Sohversion o f &»(**)*J*rjct&ylallyl Alcohol Into (*)m oa'm
&meKhyl®XXjl Chloride* follow ed by reco n v ersio n to
-zlXyl
3
5
A
.tec>ol end reduction to d im e th y l »~?rot3yX Csrbtnol# • •
* » a !(» f l* m i*u<nfcy .^ ^ i^ .» ) » ty s f t * » » f l A i i 'i « i « n ^ ^
iw ni T r n i r i-iTirfffTTiirrfriir r , ~iin< ii n
.,. 4*¥5g*
■' o' .
■ /<f ■
«*2#S7. | . • ..
■■■
-irr-ir n m r r
- in
m i m (rrm fl
r
,<r
o
thyXaXtyl a lc o h o l / <Xs .f+3 **l#t5 « <2* ^ ,
© ■ \7
<*3#87 i2ut%n » s cotwerted v is th® pyridine
•phosph©:mii tr i c h l o r i d e method in to {*)** ^ * d l& e tfc y la lly l; c h lo rid e
b#p# s s
0
\
o
end
,C
,
)»
■", this («•}<*ch lorid e gave* oi^ibsklng with an aqueous suspension
'■
,
■
©
■;
H
.
I
o f calcium earfconate* I>{-»)^,.<^/A»diiacthylallfl alcohol b#p* 35
md
<*s^ 3 “-0#34°*'; ° ^s^r
?4W1
**0#c2D Cl#0*5}#
. Oil reduction asab ove* th i sC»}^ carb im l gave dl^mothyl j*»
j
propyl o& rtinel'b*p« XX8«*XX9° C1>0*5) which in turn gay®, a gt*
hydrogen phthaiate m*p# 65^
specimen #■
eaatiriat 4#
alo n e o r mixed with an authentic* ' •
***•■flV'ipinia
!
Mr «*»*«,
15 2
C proarlsott o f E zs« in en ta3 , and &®Xml a t e d Heat 3 c f Formation from
.Separate Ate?*s e f o c j^ B im t^ X a iir l 'Alcohol p re p a re d 'in T m Ways* '
. .,■; A 'Bpmlmm, o f jJIx oc^^di^thyX alX yl. alcohol w&ss propared. by
.';
hydrolysing §tk*Xf ^dlaotl3jrlallyl chloride withhold water ia th«.;-
prosonoo 'of calcium .carbonate#'- fk# p roduct hud b*p* 119*120^
19
■... ■
a a d t i ^ . 1*4549 and Is . r e f e r r e d - to as specimen A t o ■
"th e .atom#!*
■ A second s p e ite e n o f the. d^Ue a rb in o l was p rep ared by hydrolysing
. dl*<yk ^ d lm s th s la lly l -hydrogen phth&X&te .{ re e ry a ta llls e d from c&ffem.
-- e%
, d is u lp h id e , m*p* 86«*88 ) with SI*, c a u stic so d a . solu tion , to ..yield ■
Q
19
.^he g d * carb in cl w ith.b«p.. 119 .. and n^" 1*4380 - specimen B l i t .
’
tli© sequel*
i . . . >.
.,.-
• "; - ' -
v '
.-:4,
. : The h e a ts of. combustion a t m m sta n t volume c f b o th A and B were
k in d ly ' d o t# m in ed by tbftUead ihamiist o f M essrs, B rice*a Candle 0o#- .
. u sin g a bomb calorim eter# •., ,fhe experim entally found values wore
8702 c a ls /'. ^a* f o r A (average of" th re e d eterm in atio n s w ith a ’
maximum d ifferen ce o f 1*03,1), and 8514 eala/gra*, fo r B (average o f
^
■
two 'determination* tid-fch1'a d iffe r e n c e -o f -0*03^)* - "From th is t i ’
fo llo w s t h a t -th # x p e ris s e n ta l. limb- o f comhuetlon a t ' constant.volum e
f o r a was 748*3? & mX*f&&* m l* * m& f o r B wm 732*29 S csOu/gns* nol*
. th e method o f c a l c u l a t i o n o f th e experim ental h eat o f form ation
from, s e p a ra te atoms f o r d l^ ^ d iiio th jla iX f X a lc o h o l from th e h e a ts " ;
,
o f combustion a t c o n sta n t volume l a th a t g iv e n ;by Sidgwiek* *Hh&
Oev&Xent Link in ChOEtatrf11, ^1933, p *105*-' '
■-
" " .-■■-
fh e h e a ts o f com bustion w ere•d eterm in ed .a t c o n sta n t volume*’ tft
■h as to be c o rre c te d to- co n stan t p ressu re?
2
th e re i s an in c re a s e o f
volumes on th e complete''.'-combustion o f one m olecule o f oty'-dlmethyi-
153
a l l y l .alcohols
^ MO*
-f- ' • m o
*
2 '
. 10 to ll# .
Increase o f 2 trois s £ 7 ; * . n Ef
*
a X 0*00199 se '{8731*20)
'
*
l i l S 'E #alS*/gsi* M l# a t S0° C
V 'C o rre e tio a to fee &&&#& to tho o ^ e r t o o a t a l l f found t e a t s 'o f
combustion i s 1*18 K eals#
■Thoro i* a ls o a oorraotion iba .tlio la te n t t e a t {L} o f oty'-dl*
i&at&ylaXXyX alootel *
t a t ea n b o
1*
M s not te t» O&goilMonb&lly deten&lned
from the- tao- follow in g rules**
T routea*s ru le* . J* **'-21d7°
.■■■:'
~
..
..
. *g 21(273 + 180)
**-■B«2S It c&ls*
■-
2# ■ W ^tenterg1# n il# (*. Electroehem* 19X4* go* 444)*'
L ** 7*4 f X lo g f
' ■«- 7*4 (275 1-120)' Xlog 395
- _« 7*53 KMla«
lasas- latent teat
t* —
■^(3*25 *-7*5S)
■m
th a n
■
;
*jt|0O It OlllS#
i
c o rre c te d l a t e n t h e a t from b*p* 120° to room tamp* (2O°0) *
m 7*9 t 0*013 (1 2 0 .- 20)
1 64
t* l h *c o f fo rm fcIon fo r
Heat o f CG^bustion at" c o n sta n t -irotas©
732*29 K Ml*&uad;
Add c o rre c tio n f o r nHtP. tsee. nboire)
. ,. 1*1B„, . 11
f oo* *g* * *** i#XI
• *'Htat o f combustion a t c o n sta n t proa sure
9*2
C o rre ctio n f o r l a t e n t h e a t (so© above)
* #■ # *
<a:
Cw-v.ustion o f th e A b sen ts eoBpPi sifts <x^»dt!E«tb.ylailj'l eleo h o l
< 0 ^ 0 ) IUsing Talnea o f
Faiilihg* 1932
S C * 5 0,
■#fty
w**g
_j_
I. a
*2
_
8
-eSS^O
7C
3E
A
L
*-
id-p iie k * 1933 - ' Pauling* X®>
'5-iA
and
v alu es
471*9
472*1
341*9'
542*0'
813*8
*1
471*8
'
341*9
B est o f ato m isa tio n e f th e elem ents £n CrfL^0t«*
0 gi*gphita-rSO
;077*2
3 Eg ,— - ->10H.
8U *8
515
021*5
«£■*
617
■sa*s
69 '
55,1
Ofl
47*5
1197.6 ••*'{41
155
1
Xtiaa 'experimental t e a t of''formation o f specimen B fro m i t s
elem en ts• £i#t* +-(4)
($) ■.■—(2). **{!)_/
15X8*7 • - o r
' \ ;
?**
'■X ^n .B o r X2S§*a a
For specimen A (1*W o&rbinol ex ^ - d i m e t h y l a l l y l c h lo rid e )
'.the on ly d i f f e r e n c e 'i n th e above o elcul& tlon i s i n th e v alu e o f th e
t e s t o f co m b u stio n 'at cm atant'voliaiacir namely 748*37 K e&ls* in s te a d
o f 732*20 It e tls * , uasd above*
Honcc f o r specimen A*-the" experim ental ■h e a t .o f f e r m ti o n fro a
atoms is ? *
•■■.-■
r'
...
-
TV,
■ 1 5 0 2 , 5 o r 1570*3 o r 1252*6 K m lB *
.•
■ ■
.
t
■C alcu lated v alu es f o r t h e t e a t o f .format i o n ' o f (kT^dlme thyl& lly l
r * »ia m u r Tiwii KB iw rn *-! n i . r m * . ijm m a
I'H r m irir i i t r n ri ri-m i i .m
"fin-n r n - m i- T y-T“ r • ' n m w in n f i nr<if r trh -* O T ~ T ‘“ ‘^ ~ i i ' r i - ;>ff-Tni1,rr,', t " , ‘,i i i - ,,,r ■•■ ifi '
r— ~ — rr - ' t “ t r r * ‘- , " i i" i r '" ,r iT T lf T h 1
v#
:a lc o h o l
«w»g&
a t e s t r a i g h t ch ain s t r u c t u r a l .form ula is s * .-:■
■s*.
h : ii ' ii' ':h ■ ' a
... . I . I . ..
1|
i t * 0 * O f 0 » C"» C #-H
I
I I
m
■ h
■a
I
-;
"■
in which 'th e r e &r©. n in e 0 - Hf one 0 *» 0f ' one 0 * 0# on# 0 - II* and
thro© o — O bonds.#
■
v . . - .
9 X0 - E
XxC* O
1x0*0
'
- P auling,1032
■~ ,
900*3 :
148*9 '
88*8 '
tf i ng v alu es o f . .:
. ' .
• .Pauling &
■ Sidgwick, • P a u lin a ,;
2$hewasn, 1933
1933
•1239*.
■ '890*2 .
; 842*5
. .785*7 .
151*2
. 123*2 • ' 10O . •
83*9 .
' 70*0
70*0
con. fe/:-
15 6
1x0- S
100.8 . ,
3 X0 - 0
840,0
108
: 109.5
£58,4
;
110,2
£15*4
175.0
, 1408,8 : , , 1383,1.
ESSS«Sgf'
mX»!SS^aSSXSS
1496.7 .
; 1241.7
«gSSS^»3S3»
Hence difference Between th e experimental and calculated
h e a ts o f form ation fox* 0^.
a lc o h o l are?*
Vwimm v alu es o f
C
fgnXing#1932
For specimen A '
'* -
. *.
B
Sidg^Ick#l§33
1$*2
6*3
22*0
Pauling* 1939*
’
' 19*9 K oals*
32*4
■
27*1-■■
•Hence percentage d ifferen ces are?*
Far specimen A
* /
*
B
9*4
1*2
0*9 $
1*1
2*4
2.2%
fhe m u ll percentage difference Between •the a ^ e rte e n ta l and
calcu lated valu ea I s .I n s u f f ic ie n t to warrant the assum ption o f
■f**V
mesonarIsm in e ith e r ease*
;: Th&-' c y c lic form o f
f
;V ;
"'
' Vft?
\":'
Mi^i \#mt
*A
v,,
■V\
^ ^ d lm e th v l a ll f X alco h o l'
rw
^W
iSt*
0 / O --
......
" ’ : '
as postulated b y ' H ills* "Kenyon -and"Phillips'" {Chess* and. Xnd** 1933*..'
63*■ 660} G e n i i ’ c o n ta in te n 0 ’* H* tw o'O '* 0 and fo u r 0 * 0 Bonds*so
t h a t U1 0 c a lc u la te d beat, d T o n sa tlc n f o r i t would be: 4
W a lin g , 1932
1S10.1
SMgwi ok, 1633
1373,5
P a u lie s ,! ^
1247.4
: ■ I t i s readily- seea fey eoa$?arls«m w ith the e^erlm ent& lly
doter&lned heaia o f feraafcten* that Oh'the'feaeia o f the d ifferen ce
ef experimental and calculated value© alone* laeaomcrism w ith the
p ostu lated fo u r tim bered,ring la . an oven saore remote p o s s ib ilit y
than w ith the atrai^ ht ohain formala....... ■ -
;
Footnotes <» -she reference a t o . th e d i f f e r e n t a* tie o f m l u m used in
the.■calculation-arei**'
J,A*C#S», X932#'§4# S570#7
, Pauling aa&Sherimft* JV Chain* Pfeys##-X033f .
<Sldg^le&*‘*Covalent Mnk in Chssiiairyg 1953*
Pauling* M ature o f the chetalc&X Bond11* 1030*
606*
is a
Mut&r&i&tlen o f &* {•/-}- tfj'-M M ettoX allvl Aleohol*
and in th e
' preeenee o f -.Pro-*;and. Jin tiy Oxidants*
><*«>»»#.»»»■4*h.**mw«W !■ '" » '*»■" 'WnWllttJfifc v
. . X5g* JUf+ 5** <xfmt&MBti^®£Xfl a leo h o l w ith
lo
Or
-zt>
O ''
e®
O
<*/**•+ <M& I
«**■;#,■ + O.SOJ.° * * w ' '*-2*04
+0*51 |
«aa
- :
d iv id ed up in to th re o equal portions#"-' ■ fo cno 5g* o f-th e {-+5 earM n o l was added 0#01g*’bensosrl peroxide as a pre*eM #aat£
to
s second 5g* was' added 0*GXgi dlpgm ^X aalne as an
o
'
{hydroqulnane' co u ld n o t M used* as o t o s t sumpXe o f a i* o ^ -d im eth y l*
o l l f l •a lc o h o l bsea^# too d a rk in o o ^ o u r - f o r i t s r o ta to r y power to to
observed, a f t e r standing 4 weeks w ith hydroquln©no); .'/and t h e 't h i r d
Sg* was allowed to ratt&rct&io w ith o u t th e a d d itio n o f ®n' a d u lte ra n tt
a s a c o n tro l#
Each Sg* was s e p a ra te ly allow ed to sta n d a t r e ®
tem perature* and t h e i r changes in. epti©,al r o ta to r y power observed
o v e r ' a p e rio d o f 14 isontha*
5he •observed r o ta tio n s o f th e 3 eaiqples a re givan below *
m tta ro ta tlo n o f *!<*{•+}* c * ^ -M » th id a X lv l Alcohol <*•
tu
[o*. o f days
+ 0*50*
+ 2*04°
.+ 0*20
+ 0*30
+ I* f0
0*00
0*00
+ 1*28
XS> . + 0*22
. +0*05
+ 1*60
*»V
0,
04
15 .
80 : .
00 . .
110
'
C^5\2f?J
-
+ 0#3X" ,
19*5
—0*04 ...
+ 0*01
+1*28
050
04*5
-0*35
-0 * 2 4 '
+ 0*75
4 3 0 ‘‘ : '
16
.**0*05
+ 0*13
£13
■
^ +0*78
(1*1)#
159
Ifefcarotattcn o f d—(+ )•*'^.•^olinsthTia:
lly l. A lo ch el.eont&tninjs? Ben&ofX
V/ «*Brtim
fM
w
gyn**
Paroxlda* (I* XLa.---
• ' ■■;■: •:•
0.
; t .■;
Mo* o f 'days. '
O^-ss^s
m
m
'
; \0'" ;■
m
it
; ' SO
21
110
+ 0,33
+ 1.50
■' '+ 0 * 2 4
v"r;v + 0.60
: 24.8""
■ 256 . ' ’
!§
■450'
•' + 1*54°
+ 0*16
lf# S : ^.:":'-'+0#0 1 -■
■ .215
. +•0,43°
+ 2*14
.
:16
'
«•*
0,61
.+©#34^<
'
+0*04"
'
4*
+ 0,13
+ 1*25
**0.Xfl
' + 1 .0 5 "'
+0,07
+1*06
Miltmro t a t i on .o f &*£+)«•►
oU^^Mtaethyla
Cl
m
U
'.l
'A
!*-**l l y l Aldchol co n tain in g
X
Ho* o f days ;
■;t 0 :
;r
**■
'
2
*D?D
C
*' :
-'so
.-■ n o
■■' 215
4
: '•10''
■: i s :
19*5
■'
2S8 ■■
v 439-
.
, .16 ,
- ; ' '20' ;
m
: +
+o#xe+0*25.
■ -0*82 " ■
'
*0*17 '
m
.v •
■ '+1*88
+C#49;; V■"V
■ +0*37.-'
+0*64
—0*0S --•■■;■■.■■•■■+0*40
24
20 ''
^SU~b\
m
l <;+0#40*; 4
:
:■: ,
& V-3J-#
m
I S ...^ ..\ + 0 * » ° - ; '
■M
■"■:\
•*0*15
■-0*36
+ 1*65
. +1*9
+1*0
''*
•m
o
’■
" ' a s metlw#
alectgel has -&.'. steep temperature-*
j
I
r o ta tio n curve* i t in e s s e n tia l to e o r r e c t th e r o ta tio n s given above j
to th o se o f a -cosmcn tem perature b e f o r e .QCMp&rlsons earn bo made* •
ffais was don# bf Maas of the
* “■
whore
. ■
oc,
fortauls*
.
]
*, V ^ V £ p
,: "■;
and /oo] a r e the
■;■
'|
*&jf,
.
;
observed and s p e c if ic rotations
o f tho
--: .carblnoX a t th e -tem perature of- observation#
(X^'and (oy are the
observed and s p e c if ic rotations
of th e .
■' .... p& rhlnol a t 20*0. v
ci
and .g£,< a re th e
A
d e n s itie s o f th e e& rblnol a t th e
.• tem perature of., o b se rv a tio n o f the r o ta to r y
;, ..- .power and a t 20°0 re sp e c tiv e ly * ;
fM s fo rm la : Assumest h a t th e xm itorotated
o<^ -dime thyl&Xlyl
!.
a lc o h o l has th e same temper Atur*»rot&fclon curve' a s th e o r ig in a l
oarbinoX* p-
‘'
•
.j
■:;- Valuea 'o f d ,* d^ * £xjf" and £*/ are ■taken- from graphs
c o n s tru c te d from th e' fig u re s given bp B ills * K m jm and P h illip s
lif iita r o ta tie n o f 4*{+}<*<?yK^ |^ m # th v la l.ty X . A leohol «». Weftt .
w ith ■observed r o ta to r y powers c o rre c te d to
ZO
Z-0
•«. o f days
X st+b(
<-0.50° .
0; :
■H)«31°
+ 0.20
24
*-0*17
0.00
0*00
80
1X0
+ 0*14 :
+ 0.13
'
^
z0
(X»l)*e®
‘XiiSSS
+ 2,04°
+1.27
+1.23
+1,25
1
Bo. o f Days
213
430
"lo
ois<g^s
■0*04
-0 ,0 2
6
1
2.o
+0*01
^ yc. 3^3
+1*20:;
*»0#39 '
* 1 .0 1
+ 0*09
* 0.62 .
;
l&xtarQt&tlea of d»C+)^oo/ ^.Dimathylallyl Alcohol •containing'B m m yt
■•
-
1 .0
'fa ro x id e w ith Ohmmmd r e t a t o r r powers cercpoctftd id oc v
zo
<X5-813
10* -of Days
24
g(<g
■to
o(.5><6/
<x V-JS$
’+ 1*S6
+0*16
110
i
*£
+0.24
.+ 0*40
+ 1*78
+0.19
+ 0*41
+ X.S'S
+ 0.1S
+0*42
+0.01
+ 0 .1 5
£S* j?■*#
*»■W
258
(1*1)* .
*0,03
+1.25
/3 £**/ *4
+ 1.41
+ 0.83
^ o .o a
Kutarotatloa of d-i+J-o^-Msafc&ilallyl Alcohol erotainlns
*ra ea r r e eted to cx^ fX ^ l).
r.j*ine with observed'rot&ici
HO. eft Buys
vP
a5^3
S
0*30
0* 13
0*34
0 .4 0
<x*3Sg
0
■
33
80
no'
013
458
0*111
0.13
>0 * 0 8
*0.70
*0.17.
um
1 ,4
1*9 -
0.3S
■0,40
‘0,23
*0*56
1,2
16
A-{«*}••
2
-
diKiythxXuXlyX aid + *^
1 yielded. Isyiircnon plrthall# Mt*r» of
th e
f o l l o w i n 3 x u .l i t o r y p o w e i j -
:
:
- •'
.' .
?fT l ^ r ^ n hht Vsl ig
r ~tW ^ 3
0-{+}- « r -llr.'.tV ^ la llY l
" a lc o h o l resat
'
' 75-E«q
+ 23,0°
<£»(♦)*
*dtotliylaX X $X . ...
u ld o h 'il i b o n so jl
pzrostOn
,
... ;, , . .7 3 -0 ^ . . :.
p "i 6t 7&2
r
M
. .
' L
’y+-++/
M
L^ w f
' > 2 8 ,0 °
489»8°
..
,
Blmtm X * ^SpViryXmiiio
73-80°
■i t l a t i d i l y aaoa
•
. *8CUS° . ♦ 60*0i&
..
-
. *23*f0
..
.
'• *&i*8P
- **
a M i t t a i t o th e th ro o ' ;;v
, > 1 » of 'ilr,oh‘A hn?lrN,
'
r u t a ^ V itt o n r pr vo 3?
'-
ar# c r iro r lo d ' to" h fiyeipn. phtM Xio e s t e r s p asaasain ^ r o ta to r y
"rrmaro I l a a i l o s I t& ih ea.oh'other seit. s l§ a w ith thor»o c f th e ■"'"
o r ig in a l s t a r t i n g m t e r i a l , '■■' •- ■■
1
v*Vrtj* ■■*»■«*••<«* + # - w «*«<*
'- ■-■■
1 63
.
Avat ivss of &*$$»C**)**
'/ ■'■■. ■
*
)
'Alcohol* ■
■.’■
*
J^
alcohol* ’ signifies m o^dimsMb^t**
■m lly l sle o h o l which o r i g i n a l ly f m m n m d a p o s itiv e sig n r o ta tio n
.{ef- assumed cW 'c o n fig u ratio n )* ' M
whit^x tmn m taro .t& tsd
©U;
keeping to- o ’ e a rb ln o l w ith a n ep ttiva s ig n o f ro ta tio n #
■ ,
■
(1) (tendersion in to {+•}*> o(y*»* neiterlaXlTX Sensro&te* ■:■•"
/
■
j
i
!
•
j
-%* d^vt»}»o^»Biffl«thylsli5rl- alcohol/ «h©«* r o ta tio n had ■a lte r e d ■f roa |
<4L +^.7S° (1,2) . to, «T.^,, -S.23% : .*
^ . ■»8*5S°i <x"t,
j
'■.'■■ 1■©
I
( i f f 5 on keeping f o r IS m a th s d is so lv e d i n 3 g*. p y rid in e war© |
!
cooled in ic e d w ater .and..S#r> bensoyX chlor& ta. were .slowjy.'rtm in#
j
■ » ? f 03
*** '
A fter standing owe*m ight* the u> ••bentoate we a worked up i n the
■**
u su a l manner and. ( % r g*). had h . * X37*ISS°AS&*&#t ■■:;’
' W
O
£k
s£*?3
-f- 81*00°
i
'
( 1 ,0 .5 ) , . . .. :.
: This (*)»bens©l© a s t e r
7 * 9 7 .$■■_. - ■
;
|
j
' ;:-; ■1*5073 1
•**.
I
■■•■' ^ v 3 r f "'
.]
,. ,
®l$ Qf. th e .o p t.lo a i a c t i v i t y o f a (+-)~
basi&oi®. © sterw M ob would, b o ;o b tain ed .froas the- o r ig in a l
d l'm eth y lally l alco h o l o f .
\
■£ a specimen.©f (+}»e^fel&ol;«dth:
w ith
(<*] ^ , 3 +S0.6°s
+2S.S°}
O on^T^ten in to C-f5
:
.gawe a. (*)~b©nssoate
-[oifZsre
H ill a , -Seayon end .F lillllp a . Ig o . o l t J
.
;'
n#»Prowl
+57.S° -
■
; ; ■■' ; -.
>^1*
■.4*2g# - ^ 1 1 ^ VOtmethyXalXyX1alcohol;, whose rotatory powers had
z*>
©.*
2°
0;
z®
* q
©b&ngcd to o t ^ j «*0#4X
«»0#2.6 $
-^'1#9 (1,2)
164
a f t e r standing t m IS months* rap id ly absorbed hydrogen in the
p rism s© ol* a platinum bl&c& c a ta ly s t to f i e l d <r-)~methyl &~p&€pfl
erJrtsinol b , p * - m . & « m ' Witts, n i
1.407V «M
-H5.02®,
/ fto® i t fo llo w s th a t th e ( * } * » th y l ^ p w p f l c a fb in e l 00 ■
obtained possessed f * # o f the. o p tic a l a c t iv it y cf.tfce (r)~ saturcted
e&rlbincX which would be-obtained from the o r ig in a l
a llfl
f>
m le o h o X *
..
^
K i l l s f K enyon and P h i ll ip s
p re p a re d
<*•)«* c x ^ w d t e e t h jl& lX ^ X
■{
show ed
th a t ' f r e s h l y
a lc o h o l c o u ld b o re d u c e d t o
a (*-)«*
methyl ^ p r o p y l earfelnol# which wm Wi$ o p tic a lly active#
?c * *l> l e 'S eoar*tion of &*(*- J«*ftj^ D lis e th y la lly l Alcohol in to Two
Foma ■fev -D is tilla tio n #
■!?$$« d~ ( t-)«»
■
■
L
th ^ lallx X hydrogel* phttoXat#^w^s hydrolysed
w ith 5H# c a u s tic soda so lu tion, i m th e lib e r a te d ' c a rb in e ! steam
d i s t il l e d *
The cooled d i s t i l l a t e was s a tw a te d w ith potassium
carb o n ate and e x tra c te d w ith ether#
The •.liq u id * rem aining a f t e r •;
d rying o f th e e th e r e a l layer. and rem oval..of th e solvent# was-. ..,.'
slow ly d i s t i l l e d and two s e p a ra te f r a c tio n s were c o lle c te d * . (a) b*p#
u p .to . 121°
(b} b»p* 12X*4220.. ($$&•}* , . :Th© low b o ilin g f r a c tio n ' :;;
was stood over •ig n ite d potassium carbonate in e th e re a l s o lu ti on# and
f lim lly r e d i s t i l l e d to y ie ld a . f r a c ti o n b*p# !!0~ !2X °. • {/•* g+)»
• th e two fr a c tio n s m m s e p a ra te ly allowed to m a tu re ta t* a t
room tem perature and a s e r ie s o f ■observations, made o v er a .p e rio d
' o f 2§ years* . The r o ta tio n s a rc recorded 'below*
166
0bserved HotatonT Fowrs of '&*{-t~).**ou'«*:tjjmthiflsl111" Aieohoi
0
fc«2« 115-1E1 (1,0,5),
*of D
ays*
0
'1
84
120
-.
■
...
.'"“S
m
$
0
1
0
us .
ii ‘
<*r*^
..+0*07*
fCJO
'*»0*72
•0*59'
•0#83; ;
(X
s'9<f*.
-
, 0#00°- —
O
*os 0*00■
•
■ *0*73
•0.63
17" '
ai '
•0 * 7 3
/■0*7o"
*0*50'
'■
*0*70
♦0-*60
■•1*00
Observed R o tato ry Powers of d»(^ 5»^ »!'4seth jlallT l Alcohol b . t ,
o
12 1 - 12 ® ( 1 . 0 )
>*»*#»■
Hww-y**-
Ho# o f Dsyis
T
o ■
. .a t ; .
+ 0.S6
■v
84
. . 21 -
. •'•0.S2
‘ 120
17 :
440
as -
615
. 711.'.
. 0 .
761
980 •
£7
&"
.*-1,01
■ ^0#71
O
^<6 j&r>
o
+ um
■T
+ 1 .1 8
7*4*30
•0*47.. . '
-0 ,3 3
+1*30
'■^0*18
1,00
-*■2*10
- 1 ,2 3 .
■• I * ! !
-1 .0 1
*0*45
10-
•0*72
"■■•0*70
•0 .5 3
*1*03
22 "
• 1 ,3 5
•1*30
-1 .2 5
*• 0*20
-1 .4 S
'•1*49
•1*44
•0*45
. mm
•1*2*3
1•0*02
•0*53
<*#ri»sJr
24
■■ . -o*s«
' ■
•1 ,4 3 ■
'
.’.Owing to th# lange ® f f m t of fce&per&tur® on tlia r o ta to r y pmmv
of
B lm b o tp it is m m m -$ T $ p before co&$&?is©ns
oan ba made* 'to m v & m z the ©beerred rotatory powers to those of a
1 06
QQtmm.
' •’IM a mm &©xi© \?f m m m o f ■t t e 'fo m x ia givon
eft p* . j'(»0
fix© rotmfelons wei4© ©ori'aoWI, t o ' t « 20° s&nd 1 « 1
«ai&.&r©. givea belews
.
.
'.
Af C-OllOl
Cfeaeyyod,Kotaifrog,%,,gow&ffa,',pff &*(#}•
"Z-O
©
I?#©* .119-121' eoppeoted to
<X»3.5*
* *
Mo# o f
; ■:.
"
& S'* £f
0 0 7 a*
, **
0
. ': '; . l
■■■.
-e^>
^ ^ j3a- <r
+0*18* .
. +0 * 2 2
• 0 *1 2 * :
;:■■
+ 1*58 "
+1*82
■
■
84
: .■**2104
•1*78
-*1*58
. '
120
~ o .?a
**0 * 0 0
—1 *GO
■***O'#**1jLre
v$.
08§
.
’ * U 6 8 '"" "’
■’ -1*83
Ofeserwd l o t a t o w P©w#r# o f &*{+)*■<*/"- l*
.
fchA m t i l l Aleohol
-to
W
a
,
m
»
1
8
2
°
ja a m ssis& Jjo
*©
q^s'JT93
lo* o f Daya
<X >
(Jit
^
*
^ <?
0^ *e^ S' (f*
^s-*w
+ 0*39
+0 *6 0 °
+ 8*25"
+ 0*50
+ 0*03 •
+ 2*25
—0*41
•0*20
+ 0*72
0*00
0*00
+ 0*87
>■
—1*03
• 0*68
+0.23
615
—0 * 8 8
• 0# 1 ##
.+ 0*42
sm
—0*04
•0*75
# 0*11
mi
—1*58
•1*08
-0 * 2 9
W
•0*81
#0*66
-
0
■
1
84
;
■120
449
v w
.
-
*lF «i*4 M > < M F W I US* «»■«*#■<
0*01
167
, *&s two fj*#6fcio»a of d-.Cf-l-rlistfttlsflallyl alcohol wer®
£nv*fltig&t&& &f tei*
Mtb% a po3?;t iori wah
;: that. o f ; B*p* 119-121
lm l
/ <^2 ^ 4
iici to i t a M-hydPOgan p h th alie a s ta r
with a ,p ..
a » i f c L - s t S ^ ' 3' k J ^ t S 3* 0’
**
in chloroforo aoXuilos* ($# s 32 .3 1 f . 2L»2)| whilst th a t of b*p*.
121-122° .ted.
I S # p .*
(e *
and yfal&od a (+}*hytl¥&gen phttmll©.aster...
*>s-? f *
k ' & z z o % % jfi
adding t&*
OblorofOM sedation .
\ »
’ S o t h ." f a y d r o g w
p h th m lie
e s t e r s
w ars
prc -
r a d 'b y
i c l ..to a «ol^tion o f phttm llo unhjd^ida in' pyridine-
and standing. oror-nlght*
•
(X)
K ith An
••
a Suaoerioion o f 0*1oXub* dart -onate«
■
■■ . .
■:-
<’ V. "
0 ,'..
7g* {t-)*><X<f *diseChylftXXyX c h lo rid e w ith . <Xs'f+3 +0*^1 |
(&)
ti* 8 ) w?iS ehrd;«m w ith a suspension of 4*5g# s o lid calcium
ear* m a t# in lc* » eo ld water*
' There was trigoroua e ffe rv e sc e n c e , th e
ealeiitm ca rb o n ate r t r * 3 l i e a c tin g a s a s e l f in d ic a to r by gmcM!l\aiifd is s o lv in g , m%& a f t e r stan d in g f o r about an to u r th e whole ma■ e x tra c te d w ith e th e r , th e e th e r e a l la y e r washed, w ith w ater and d r t e l
w ith, potassium c a rb o n a te • to y ie ld M ^ o t f ^ d i ^ th y l & l ly l a lc o h o l
b t p# X i e - ia r andm
*- 0*19°
& r e p e titio n using, 10* %♦ (+}«*< x /^ im e th f XaXXyl c h lo rid e .
shaken w ith 5*3g« caXciu|i e&rton&ta and 5cc*e* w a te r, y ie ld e d 4g#
e *
' o
:, v*)«$teethyl&XlyX a lc o h o l b*p* 35 /X2m#&* and , .<*5**, *Xt4¥ * <*r^, ""
0
-*-%**?& ,#1^2)*
I t was r e d i s t i l l e d a t th e o rd in a ry p re s s u re fe*p*;'
<>■ X9
/9
o
o
/?
o
120 > ..a ^ • 1*4223 and oCy&s -+1*50 #
+-1#6S * ,
• {Jy>2}*
-Found 0 , 60*4$
; (e)
B* IX* 6 | • 0§S ^0 r e q u ir e s 0*69*7$ H,11*11$
A t h i r d 'oxpsxdmont w ith 14g* {t-}**<^*dimethyl&ilyl ••
c h lo rid e and an aqueous suspension o f fg* calcium carbonate y ield ed -xr
ft-|w(x ^ d t r n o t h y l a l l y l a le o to l b*p* 41~42o/20m*m* and
^ f-l*X4 $
+1,49°s
*♦?« +s.r® (ifs5«
Cd) ' A fu rth e r 4%* {-*-}«*otf'+tiimethylaXlyX chloride w ith <Xs-<+6r
7*83° (1,2} yielded {
/i"
**
t hyl al l yl -alcohol b*p* o3^/X2m*m*
tf
$■
/C
fi
/jr .
-o
1 6 0
{2}
A lcohol#:
$6
4*8g* (» )» ^ * d i m e t h f l a l i y l c h lo rid e ■ <X
;
0
I
<*X5#14.. -{1*2# was i
shaken w lth'20c#c* d ry m ethyl ■alco h o l and 0*Sf* calcium carb o m ts*
I
■Ifter 24 hours t fm m ajor p erU o n 'o f th e calcium carb o n ate had '
j
,.....■
j
d isiolv#4# . Tim whole was g e n tly warned and sto o d w ith excess s o lid j
e a l e i ® c h lo rid e to remove TirjresLCted ssetiiyl alco h o ls
a f t e r standing^;
th® s©mi«*solld maos was e x tra c te d w ith efcfter and th e e th e r e a l selu tto j
d r ie d w ith ealeltssa cfelorlda*..
Eesioml o f th e o th e r gave 2#Sg* (*}- j
' ° " 14*5
■'&
1
methyl** ^ ^ d i c i e t h y l a l l y l ' e th e r tup» 80*89# 5
' 1*4031 and
■
a ■'
•■'■"■■"'•<&
; /<f
© . - ■' ?■■.
0
•*0*53 s . * > „ « , -0 * 5 S >
<*5-**/ ' >0*33 j :
**0#!S
(8)
With n-M ferl Alee)
% • f-/-)~ ^* » d ir* © th y lally i c h lo rid e
*-1,47
0•
\
■j
(^*0*5) were j
heated with !So*e# jv tm ty l alcohol and'gg* e a le iim carbonate f o r
j
3 hour® on th e w ate r "bath* , On c o d i n g th e product was f i l t e r e d and j
washed with others ■the ethereal filtrate yielded M
«* 17
.
dim ethyl a l l y ! e th e r h*p* 150*161 f J»rj 1*4100}.-
(4)
with Silver geetata*
. 4g* (^ } # # o c ^ d im e th |la lly l.c h lo rid e
o ■■
«5*59|
. r?
oL ^z/sf
o
|
o
I
r0*24 '(2^0*$}
’■
4*4*61 $
0
f<f
: .■• -.
**XQ#§S (if0 * S ) were t r i t u r a t e d w ith 17g* s i l v e r
a c e ta te enrrohndsd by ice#
I .quite V igorous' r e a c tio n ensued and
a f t e r .the a d d itio n o f e th e r , 'the s i l v e r s a l t s were f i l t e r e d off# ••
After drying th e ethereal solution with salei n s chloride and
removal o f th e s o lv e n t, ( • * } * * t h y l a l l y l a c e ta te r e s u lte d w ith
I
|
j
!
j
1 70
'* . ... &
' ■■■' ■-.
^
$.6/
I ;
*0*1*4 . | - .
>>X*3I|
O'
*f-d
.(1^0*5)* ., fM s on. ro d ia tllla tio n b,p*-.37«»40'A^*n*dm d a " 1*4X13
✓r
t$*
f$
/&
« j.
and v
*-0ȣ3}
.-
—0*30 j .
* « x a - ° * 53° Ci»0,SG),
^ s^er ■*••35
'...;_
« * * » * * «MN*« « * « * * * M vM . MMM u r n - m * * * *
of
tv
'
'
**r>.i?^ ’tnyXaXlTX
1
Iht-h&l&te 11*1w ith •'
( J * r ii f tn v rtrrtnwir^i n i r ^ Ir> r In,M m i j r r h V T i r tf i* ;.-.i w r * ilM V * rt-m iN i « t i V ^ M lg n » iiiiir\» |in ^ T ^ |irrri(iy ri'> 'li> tiM > |iliiiiiB ~ O ir)'> M j.iii'> i< i''W tiw
Acid.# .. .
X*
• '-'
, n i . i-rt< W tiH iH .f r r . i'tf - r if H W ^
~i I lf
'
’
' ■■.
w ith ' ftsat jForgaie Acid t ' (a) 80©*.e# anhydrous fo rrd e nold ■
was added t o ■Ig* C-/*.)^dimet!^’M ly l,h y d ro g e n phfch&X&tes ■th e e s t e r •
rap.id 3.3r ..dissolved w ith 'th e to a e d ia to 'p r e c ip ita tio n of. phth& lie
o ■
;
. a c id , m*p# 2 0 S
.* fd e o ^ *>•)* " flie f i l t r a t e # -even &f tex* tre a tm e n t '•
. w ith d e c o lo u riz in g carbon# w&s too ©clour M :f o r
b e;observed*- .
..' — -
-
;
i t s r o ta t io n to :
■ '■
■ ; ;: '
X#' . ( b ) A r e p e t it i o n o f th e above* w ith completion, o f -the
o p e ra tio n s w ith in S m inutes, f ie ld e d a f i l t r a t e which was o p t i c a l ! j
in a c tiv e * u. u
.'■.:•
• 1* (e) : X3g* .(-/-)*> < ^ /v d ie is th fia llfl hydrogcb phthalafce was’ ’
t r i t u r a t e d , fo r 1$ m inutes, w ith 20g* ■anhydrous form ic a c id ^1*.#*
sm a lle r p ro p o rtio n o f form ic a c id th an in 1(a) o r Vo) J
’"• 4Ge*e« '
d r f e th e r were th e n added'and £ * % f phth&Xi© a c id f i l t e r e d ©ff j ■
th e e th e r e a l f i l t r a t e was .ex tra cted w ith ecdlms carbonate s o lu tio n
to rem ove' 8#0g*;. reco v ered {+■)* o c ^ ^ d lm th y X ^ llfl tad reg o n p h th a la te ;
w ith W f^ / 2 2 . 1 ° J
[ o l] ^
t 2 8 .0 °
{ e ,5,245*
1 ,2 ) In chloroform
s o lu tio n i#©* 93$ o f te© n o t i v i t f o f th e o r ig in a l hydrogen, p h th a lio
a s te r*
E v ap o ratio a o f ^ la driscl e th e r e a l s o lu tio n gave l#3e*e«
.
■■■ ■■
•
■■
-
■ •
■
.4*(+-)• ^«*aia»«aylaX l 5 l forsnat® B ith b,p» 122»123°,
1
71" j
1.4125
;
+ 0*23 { l y 0 * 5 ) # ' f f c u s th is e s te r i s produced w ith ..
and
0%7f* r&kenZlmt of o p tic a l a
e
j
t
: v*lth 1Yr>*do Aeid uaJnr chloroform as a diluent*
■I
• Cm) l #QX20jt« *'
W<* a f^& im V tijlp X Z y l hydrogen phthalate wm- d isso lv ed In 18e*e*
i
;e©Xd ehl-rcfor® and £©*©* anhydrous f o m ie acid were added*-' £j$© ■ ■
/? -.
; ■© .-...
'f
■■ o
/?
■-o "' i
.solution than had < * ^ 3. + 1*43 |
<* *?&*> ' **3U74 | '’
1*92 | J
./?
i
C ^ i); i t s r o ta tio n sXewly f o i l an d -after sta n lia g ;/.•;••••' j
~Zf
0
^
' ’ #J
a t room 'tetaper&tup* fo r f days i t had J oc r^ T ^0*94'f ■
+ X* 10 j
0
{2 #S)i
from th is p oint phfch&lio.. .,, •. j
.
’ ’ i
aald was slow ly d eposited and a fte r a fu rth er 6 :days, the xo.t&iXoa i
*
tL
0 ' Yr
'O ' ■‘ !
o f th© so lu tio n imd f a lle n to
<X s r ?y
0*50 . |
o^S9(ff + 0*60 I
j
■ - ■ ■ ■
( 1 , 2 )*-
• ■ ' ■ ■ ■
■
'
ih e jproduetsi o f reaction ware worked up, hut is o la tio n ©f ... j
tli# (^ * d im # th y la ll|rl fora&te fa ile d * . Hence
repeated on a la rg er scale* «►
. ■.
2
experiment w a s ''
'. • •
.
|
. '../.
, j
* {h)' Sg# { +Y*ty*&i&®khyl£XXjl- k urogan- . phfch&Xat© was , r.
\l
1
j
!
!
d isso lv ed l a 43«$c*o* chloroform tod f f 4o*e*. mnhydiKms formic acid
/cf
o
.wore adcisd to y ie ld a so lu tio n ■with ;"
f3..6CK. (i* 2 }* .. AS in
- ■
2
.
'
j
(a) c r y s ta ls o f . phth&Xle aoM. began to appear a f t e r , 7 days a t . ...; I
room temperature*
.- fbe so lu tio n reached*; a fte r a further 7 days,
i?
©
a ro ta to ry power o f •0^ * ,* &#0 O CJU2 ) a t which ¥alua i t remained
oonstant fo r I t we#k$* .'
■
L
■[
.; |
.^ ;
On working u p . thffcroduot, ..there wma oh tatin e C )~oy^&imethylaS
fOMate. b*p* ■- ‘ ■■. and :
together w ith
2
*0 g* o f
1
- d l f e t h y i a l l f l tedi^gea phtlm lste witti [<*]
recovery
(or 3#0OJI
hylrrgna
/fi reten $*iOH Of OptlO^l
p h tL m X a t©
la recovered -3<?ff ©
72
+1 1 , 8 °
tiWityjj- Whilst ti%S
p tte & lly -p u r © * '
v from csspertamta I-lei--and 2 (fc) shove* it fo llo w s that the:-.-,
conversion o f it)**<xj'+&isetfeyla.lXfX hydrogen phthalat® Into {i-}**^.«*
d ir ^ tlifla L ljl fona&te i s aeeoEpmled 't>y Inversion a lseo th e . (* )• ■
,/*%
4 I » t h y l& lly l 'alcohol {whleh g iv e s « ' (^)»hydreg®n p h th alie ©sto^) i t
' co n v ert# !:b y' tim w lm 4 snhy&Pl&e o f f t e s i e and s c a tla a cid s to. a
•C^J^forele e ste r [ u ill® § . Kenyon and P h illip s (io n »
SlthvO'Mci1cm'
'He&etions o f
wi^ifiy *itih
;
•iffr
m i l d ' H v d ^ o s r e n
I*?
w ith A ostle M id*
.j aigrtiiWtlitijiBcr*.f
;..!•
y«niq»win
l«Q024g* &*{-/•)» ^wdls&thylallyl hydrogen.phthaiate wem /
d isso lv e d in E0o*o* g l a c i a l aceti© a c id to y ie ld a s o lu tio n w ith
■/■I*32 |
(1^23*
^s^&o
^svtrf
1*©3 |
. &$ j*SdT ^3#4I)
|
As no change i n n o ta tio n was observed a f t e r stan d in g fo r-
. '5 .days a t mom tem perature* ttm s o lu tio n was k ep t f o r 6 w o k s a t
'. I
O
’'
j
37 * ' At th e end o f t h i s tins® th e r o ta to r y power o f th e 's o lu tio n hadts
O
'
/
o
:
^ s^ f 3 *0#15 f
|
reached th e c o n sta n t v alu e o f
+ 0*1® j
ts~
0 !
^ j r /0 * 3 S
fh® s o lu tio n was worked up i n the u ra a l maimer, j
to o b ta in a .w ry sm all m o u n t o f a liq u id w ith a sweet e s te r odour * j
presu sah ly . th e re q u ire d a c e ta te *
2#
■
A re p e a t experim ent u sin g 20 g* &»{*-}• o ^ d im e th y la X ly l
|
1 73
hydrogen phthoX ate;i n 75g> g l a c i a l .a c e tic a c id wm worked up a fte r .
■ ;'
'" 'o '
'
a t 37 •. f o r 3 stmt* e# by w hich-tim e t h e .s o lu tio n had"
d e p o s ite d '.ext tp p r e e ia M e •erruofc o f p h th a lfc acid*., ...There was
o b tain ed 7g# ..{»<**/' «»$i?**'P"'?ldl2y l hydrogen p h th a ia te ;w ith M s^<,3
+6*4 j ;..•'. [efJm ,
, t o ehlorefc.. i m lu tlo n ^ to g e th e r w ith 5e*e* J*
■(f-)-»ay^«»<2toeth^lall7X aeeta't# w ith b*p* ■41 /2%m*m« and
I?
C
'
,?
"
C
o<5^ * S ? |
pO*S
' : '
^
^
fb a s th e ( ^ h y d r o g e n p h th a la t* was
reco v ered 3 3 ^,a c tiv e * a n d ,th e .'{f*}«*aeefcfct* w m
., 3# -,
*-0*23'g _ j
7
{jl#0 #f>)#
ij
0 *8
$ o p ti c a ll y p u re * .
. A fu rth e r. o^psyXkr^at was o a ^ io d , out. by. d is s o lv in g 10g*
..hydrogen .phth&l&te, (
j;
s ^ 6r
I
. |
■.-*2X#75°j .
I
l a chloroform s o lu tio n ) i n 3%* -g la c ia l a c e t ic a c id .{ l* e ,. s&sse..
p ro p o rtio n s a s . in..experim ent
7*5 months*
2
).f&nd allowed to. stand, a t 37 -..for
..I
.
';
fh e r o ta to r y power o f lac s o lu tio n f e l l ’ s te a d ily frees
<Xd-w ♦7#43° C1 |S} during'X*5i&onths ' to" <*5-^, *1*84° ( 1$2 )# from
which tiM . th e In c re a s in g d e p o sitio n o f p h th a lle a c id made th e
. o b serv a tio n o f r o ta to r y power u n re lia b le * - ■ .afte r a- t o t a l o f 7*5 .. . .1
-0:
''
- -i
mant h e a t' 37 ,. th e p ro d u cts o f ., th e .re a c tio n wort. worked tip# . to y ie ld ;
jlr< x ^ ^ d im o th /la X ly l a c e ta te w ith,b#p* 40Vl7ri#is* and X3S*X5$°/..;
760m*n»f
1*4130 an d ..,^ w -■■£$*< (if.0*5)*
■ ' P h illip s * lo e , e l t . g iv e a ,*9 1 .4 1 7 9 ).'
: . .
.. {H ills* Kenyon and .
...
,4*7 f&e a f f e c t o f added a c e ta te io n s on th e above r e a c tio n was
1
In v e s tig a te d . in a p r a ils lim r y manner* ,.ty: d is s o lv in g 0*S43Og* &»{<*)•
f
* * a irrth y la lly l hedrogen p h th a ls to ( W ^*^30*2° in...chloroform. •
coin t lost) .in
20
e*e# g l a c i a l a c e tic acid c o n ta in in g 5 f by ■
.w eight o f.
d isso lv e d anhydrous sodium -a c e ta te * - ■fh e a e lu tio n was a llo w e d .t o
sta n d a t mam tempera to r# and i t s r o ta to r y power was observed o v er a
I
j
:i
, :, .
17 4
' '
p e rio d o f 1 7 '» n tte '* ''' The vmlxim s te a d ily f e l l ’ from
.£*0.
2Z0
-Zf
;■^
Siftf
■
■
'■
■
■
’
|
O ■
'
<X y*»8*10 |-
' ^
<X vJ5"<f
.-
o( ^
^4-ffc-S
a =■•
«"0#10 .
|
( |,* 2 )
to
^
z. i
O
«*X*71 f •
.0
*>0*00
|
■ ., ■
:
i# # t to a p r a c t i c a l l y in a c tiv e
s o lu tio n p re s'O B sb lf'o o n tB in lB g 'fllw ^ ^ d iiB eth y lslly l ' s o e tste *
’ T h is - is i n c o n tr a s t t o experim ents J and 0 above* wtiere th e "
s o lu tio n s reached c o n s ta n t.o p t le a l r o ta to r y powers c o n ta in in g
a c tiv e a c e ta te s *
*r\ ■
•
’
," •
f o r reaso n s s im ila r to th o se 'q u o te d above f o r t h e occurrence
o f a Walden in v a r s i on l a craver-sica o f
1 ; ^ 'hydrogen
'p tith a la te in to i t s j> te d . format#* i t "can be r e a d ily deduced. t h a t a
' s im ila r in v e rs io n o f ; e e n fig u ra tio n ta k e s . p la c e in th e . conversion
'
o f the. ^*.(+)»hydrogen.
th a lic , e s t e r 't o ^th e JL»{f-)^aatic .e ste r*
fta&etlens o f &*{r)«* o g ^ iH ^ th y la lly l llydrogart phthalate 'with ■Phenol*
■" v; A s o lu tio n o f 2%* 13 mole*) phenol and 03*4g* {1 mol*) § r M m
^ .d i m a t h y l a l l y l hydrogen’p h tte la t# i n '50e«c# d ry o th e r was allowed to
■’ sta n d a t rom 'teE jperatufe*- ; PhtSmlio a e ld was slow ly d e p o sit# # and .
a f t e r 14 days* .the whole m a ssa&e a lk a lin e and e x tr a c te d w ith other*
'' She e t h e r e a l s o lu tio n * a f t e r d r y in g * . gave $e*e« {~}*>phCnyi**<*</'«*
dim etl l y l a l l y l ', ethw* b .p . W °A 3a*a* » a ° 1*5090 and <X*&3 -C .3S 0 ;
r fr^ -Q * ? * 0 #
^ llP l4 ^
*<.*«- *0*55° ( £ , 0 . 5 ) .
s q u i r e s 0*81*6;
H* 8*6jf)* -
(Pcam d.C ,81,7f
The aqueous a lk a lin e
s o lu tio n * a f t e r 'a e ld if io a t lo n * y ie ld e d ' ISg* reco v ered
*
rx J
H, 8 ,6 j
176
aiffisthylallyl hy<1reg«n p h th « l» t» with,
^ ^ s *° Co.5.031;
1*2)' i s chloroform so lu tio n#' /
'
' I t was n o t p o s s ib le to determ ine ■■whether o r no the' eb b W
re a c tio n had o ccurred w ith In v e rsio n o f c o n fig u ra tio n sin ce attem p ts
to p re p are phenyl**/' '*•d im th y laX ly l e th e r d i r e c t l y
ca rb in e!' fa ile d *
;
the "'•
. .
# # * * # * » « * Hit *«• « * «W .«*<** W « *
'
<S>;.
HorwPccamisntien o f
*/mOHWJlWMTOr
(+
- ) jnothyX&llyX Hydrogen ■Fhthal&te i n
(J
^'tTTiTrir iir'Ti~rft^T|Tii,i»i>#i~piti-3HiTi|ri) inifrfm rThri-it-‘m T Yrif ~ rtiT«ii#frT.lriifrtririiritH i <i i#m nirf|>i> »ii mvimwmHMi > run nmpirmtinjn <31 Ml,j ■( r■1*^ ' *)#~Mtwr‘'i| iiy'»W
y c fhy 1 iilo o h o l a t 31 >
A s o lu tio n o f dj-tv-)** tf/^dim etfeyX allyl hydrogen phth&l&te
r 7
o
■' ’ '
•(
30*0' i n c b lc m fo r a so lu tio n ) in m ethyl alco h o l w as.kept
|
1
!
a t 31° f o r 3 te n th s * .., However*. th e r o ta to r y powers o f the so lu tio n * j
r7 ■
. .■/•.:©-’|
determ ined a t room .teqpeimteara*' remained unchanged at. (s*JTf 9£ 28*8 | . ]
& l w * +31«&0» M s '* t +S* ' 5°* ' £ 7 w
daring th e whole e;«pwiBent*
r « • » * > * S.3S0?
1 ,2 )
Bso< * eatlo n o f d»(*) -*o^y~ M e t h y l s XIj ! Hydrogen Fhth& late in
I**
Kltrome thane a t 51%
iW t^ nWjfiYWt(\*J*##.+ * » <"****&'• W5t«y»yy
f.v m ••-•«<■
l#O180g# d » ( r ^ ^ D i % t h y l a l l y l hydrogen phth&X&te was
d is s o lv e d in n itr o m th m e en d _th e s o lu tio n made -up' to £Qe*&* sad.
allow ed to stand a t mom temperature*
/?
c
powers were 'U naltered a t 'O fw + a *<ia t
A fte r 5 days I t s r o ta to r y
/ 7
° ■
e
**?*)£<>
^2 #72 | ' ^ s-tf.(rf * 3* Xtf*
<*+,**+ * ’ m ° t«*5‘ 0S5» ,1*2)^ so i t was then leapt a t 31° f o r 2
month*!
I
Ifef
t in # i t s "Jpot&iory
1 76
a t yocaa' tampe*ater@
hm4 reaehodi.a e o n a ta n t;v alu e ms i s seen fFom’- the ta b le telcri?* ■
.fha m innis .o f ■t&®.TOtmtory. pstei* p lo tte d a g a in s t bia#*. l i t ©a a
■smooth cRaxw# '
'
■ :
'
ObaeyTOd- R o t a t e s Pf^7^r*s of' d»C^W (X ^^BI»tli;7lall
Ph trsmlate in 11 t e a r i m {1 *2) #
ITo. .©£-.Days#
■1
ry
.
2 ■
.1 * 8 0 .'
...3..--.‘.-.
;
Otifi 3 Si
Otssis
©. •
*“3*31 ...
2*00
+ 2 .5 0 °
■
<£T»**■%
«***
+•3*03°
■1,83 ;
■■■. ■2 .3 0 '■■;
-■8' 1
■. ’' , 1*58 ;
■ '1 ,6 3
■'■8 ;■■
■■;':■ 1*55: '
'.... 1*63
■
' ao
.
-■- 12 .■
. -.
i,4 S .
■:-'l#53 ■;■■
■.
■ X*2X
■■** ■
‘ IS •-■ ■ :■ - X,XS' 14
'r*s
:..
, 1*12
■■■5.50.
**»
4*55
■■;■,3*85
1*85 : .; . ' . : 3*85
‘ ;
1*61 '
; :;S*S5'
1 #44 ■
■
■1* 41
.
' :1 .S 0 ■v
15 . .
• ’..0*03-;;.
16
... 0*86 , v.:- .■-; 1*00
. -19
0# 53
. ■■■0*81:- • ;
; ■1*10 .-
■; .0*83,
2 .8 0
, ■1*40 . , ...
- .1*23 '.
. -,1.14
3*00
■. :■0*80
. , 2*53 ,
'
-.2.40 ■
'■■/■■■:■;■ 0*95 :
,1 .0 0
* 25
•■■ © *7a,
■- ' .0*81.;
■ ,0*83
.m
23
-; 0 * 0 5 '
■■ ;•8*80 -.
■/. .\0 .8 3
, 1*5
SI
- ,6*5f
0*59 ■
0*72
36
*STf
wt
■:",
■,:
.0*50 -'■
.0 * 4 7 .
'
0 .5 4 '
■0.58 ■
«*
**«>
*>«>
«•
.&
0*52 '
0.58 •
■m
■ 42
0*55 ‘■
0.56
0*50 ’
' ;v\ ' •. 56"
" 0.50'’
■'0.54
' 0*37
m'
0*27 ■
0*08
' 0*33
X
61
8.23
' 8*38
■0*34
e ^ s t a l s ©t phthmXlo ao ld began to separate*
...
0,70
m
«*
0.70
i 7
ffa# ssblutloa on e la b o ra tio n y ield ed 0*05g* -solicit which was
sep a rated w ith d ry chloroform', In to 0*X439&* ..phthelic a c i d ' end
0*4428g# ■dri^)-* ^ *diwefchyXal1yl hydrogen pbth&lai® rAth:[oQsr<s>7J.
+ 2 .4 3 °;
. ( e , 8.056*
1 ,0 ,6 ) ,
Proa th e se fig u res..
;/ i t can ho c a lc u la te d th a t 20$ o f . th e ■■■{+■)~hydrogen p hhhalle e a te r
ha.® decomposed w ith 11b t r a t i e n o f phth& llc &eldt w hile the
rem ainder has fcecosa® m cetalsed to th# e x ta n t o f 90$*
■
'■
4*
«* * * » « » * ■ « * i . : * * *»«*>■ « M * e
ftaactlon® ' o f
'
r^oooafo w ith FomioACld*
©
1* 20*9g* ]U*C^3~ ^ ^ D ta e th y l& liy l b en t oat® (: ot.Tyl/
«»7#$d f
1 #0.*5) w as' d isso lv e d in m k $ ' S#4g* anhydrous form ic a c id end
heated f o r SO hours on th e steam 'bath*
fh s so ro w olttil® 'pro**
d u et h*p* < 9$ /SOrii*®# was washed w ith sodium earbdn&te ■so lu tio n *
d rie d and r e d i s t i l l e d to "y ield $e*c* '
■ ^ - ' IS '
fo ra u ia b.p* -122-183 $
1*4163 and
^
'- f
ly l
■/H.■-■
^0*22c Cl*0*S)# / ..
From th e le s s v o l a t i l e p ortion* th e re wa$ is o la te d I2 e ,e* 1® W ~ . |
.
ro
-0
• d i ^ t h y l a l l y l
hen Boat® b*p* I24*126/13m*as*# »*%&'together,
with Bg* b enzoic .acid*
with
had
1 *2 $
fha <+)*
was therefor® produced ’- |
reten tio n o f a c tiv ity * w hile th e rccovcredf** )<»feexu50ftt* -I
$ o f the
a c t iv it y -o f th e . o r ig in a l benso&te# .■
...
2# . A 'repent experiment-using l^ ^ J ^ ^ - d is ie t h y la lly l
b e n so a fo
/
v
..
'
'
° ^ s y H
o
» 4 * 4 S
*
forai® a ste r {Poundi.. c ?68*3| .
«■ s*» jv*/\
.
h ow ever*
y ie ld e d
the
d j« *r
CW
Tiq O^. requires C* 63*1$\, •■
!
;
i
j
1 78
m t m into the.
' "la' tte'.ifeov® eonveralem o f th e
j^'-+}~fes*mIo a f t e r no' is v o rs io fi o f eo n flg a p a tic n ' hag ensued!f o r 1 ^''j^(^)^ elo o 3 b o l I s eortvertad w ith ’fowle<*&ee’tie.- a is l^ d r i^
td th e
e s t e r , 'end with berd&yl-o&Leri&e- fee th e
•..
.'(•}4t3enscdo e s t e r «►b o th ''^ se tio a s'-fe in rie u e ly oeouw lng w ith o u t '
Inversion of cenfl’
gufatiba-'- ■
'
■"■■■■■ *: -
i^^t-tdonm o f 4 » t+ )« fcK- «Z%xrat&yl&llyX Befifo&te w lth ' Methy l Alcoholi
., .
_ .
,.
|
'
1* .A. .prelim inary
e a r r ie d o a t by d is s o lv in g
|
v
• ^ © "• . I
l#0S51g* &»{*•)•<*/'**d^% tkflallyX h m m jc tte {
■+ 9 * n . f
■■.. j
_
.-• < X > * tB *l§%
<X«3ifS + S^*30fi|O #S ) i n HOo*e* m ethyl e lto h o l .
j
'm d ohB rg in g th e .ebsnge in r o t a t o r y p « e r o f th e ‘- elu tio n , on . ^ ..
.
'-
.
..
■
■
.
.
,. j
j
--
standing* ; A fter 1 week.'at. room tm m n m tm m i t s . r o ta to r y p o w e r j
w^a u n a lte re d a t ,
+2»$ i° f .
*-5*50° j _ .
*-?*30d .
j
{1*2)#
i t mm th en k e p t a t -31 f o r 11 weeks d u rin g w hleh tim e . i
:
"
’■•" 4-■'■ ■
; "
" o* ■'■■■■" ■
•©
j
■th e v alu es ‘f e l l , s t e a d i l y to <*«>*? ' •+ 0*04 |..
* 0*34 | <xw * j
: • 0 -'-.U
.■- -.V; .."
+1*05 C3L*2)i-*
■-..-
- .
’■■
\,
,- ■• »
•' . |
v alu es whloh %mm. u n a lte re d a f t e r a f u r t h e r
—
week;!
-
s o lu tio n most probably now .eo atain ed .a (- ^ m e th y l ether*.
■■2 * ';:ii s o l u t io n -©f l§g* {+•)«*<x^~d4methyXiflXyI■b ea so ate
^
. . . O'
, . . ■' ■• • : , ■■
{ ^stfbi *+U«*3 I 1#0# 5J- l a 40g* dry m ethyl^lcohol was. kept a t
O'
'■
■
31 fo r 7 days, follow ed by. d ls& llatloa' on a stean bath* : ■In
I
|
. I
order to com pletely;remove th e M rs v o la tile , w t h y i ^ " d im eth yl*
*X lyl o th e r from bm & ole atttd and m ethyl bm ss a te
.:
'
a m l l a » m t s o f m ethyl alco h o l were added to •th e
su cc essiv e ' •j
.' '
1
h% h$ boiling|
re s id u e '
d i s t i l l e d '. o f f wader s l i g h t l y dim inished p ressu re*
|
a le e h o lie d i s t i l l a t e s fCO^*} w s ®M&%
to
■j
j
j
'
70^# p e w ie rti ualtiB ia
stood w e rn ig h t* ■
' The eeni«*
.t
j
.."
m llA -tm B B m .s
wiMx d ry e t& e riiM ' a f t e r ressw al o f th e j
■eolTOafc th e r e & i& tit'w a s 'f r a e tio n a ilf - d is tille d to y ie M fo u r
. 1
prc&&etatf * , fe) 4o*o*
JL* *thyi«l l y l eth er# b*p* ....
0
I s!
' ' /?
ft
‘ >*f'
0
■]
OS.S - ©0.5 I
1 .4 3 :0 fe d .( X ^ *•1*03 }. « ^
* 8 .0 f
.j
r
0
|
ti* © . 5)( E l l a ,E s a j o n end I M l l i p a ,
Ioe» etts. , ’giv® .to.p* ©0
I
a^8 1*4045? (b) 6g« m tf a jl beaseafc© b*p» 168.5 «.S00e sad n T
' X?
• ..
"'
^
1.5143, [?mlsin , J .C .S ., CO, 1174 gts'aa b*js» 209°j .C otton end
'
' *fPS’
imitoii* mm* Chim# fhys## It^lSje/ # gf.» 214 g:lvo *C^V. 1*SM4*J
j
'
fe ) %* tm reaef^-<|*(+)«* ^ '•* €k2»i3*eIn y la H y l ■b e n sc a ts b,p»231»12S / j
' '•'
' ' ' 0 '
!
iru s *
< X ^y . .^11*1 ©n& f d ) . 4*7g* bfensole. aeid* Therefore# j
tfea
e th e r tmd re ta in e d 4*3>l o p tio n ! . j
# ‘uM Io th e
J^)«(X/'^ciiisefeh3fImil,:fibeisso&t®.was
. J
reco v ered «&th 03,1 r e te n tio n o f .epfcieal ftctit& ty#
•
&hen. tho e o a re re io a o f b m n e a te to m ethyl e th e r wag
;
■0 f f # 0 t© d'by 'reflus&ag- th e m ethyl e d e o te ilo s o lu tio n fo r SO hours
;
. th e r e s u ltin g m ethyl eth er-sm s o p t ic a ll y i m e t i r e imd
j
'.
f e e
-
reeoirersd b&nsoefce wag p r s o t l e a l l f eo isp lately raeemised#
:
■■■■.'■': The shore- oenirerslcsi o f j|* f+)<» ^ «niimfchyl&XIyX- bensoete to
;
**&lmethylaliyl ■e th e r eoeura w iih in ire rg io ri o f
c o n fig u ra tio n on th e
:.f
a llo w in g evidences
'
.. .]
j
'■'alcohol- i s ee tm rtesl# by m esne-of benssoy! e h l- itd # fco
:
• d t e t h y l a l l y l''h e a s 0 a t e # end r i a - t h e petasel<Mierir&fcXire to
■';
^ d ia ttf e y ia llf i eth er*
Bofe th e s e w a e tio n a a m
1 80
t m l i i c t o Xmd, to lnm®Qkcis% j M -3 0 tb« {+-)*bea^eato eM («•}<*.
m©t&yl: et&©3»
tha; sasii' ^cW1* configasf'atioa.*
■
•a©
. . . .
, .
fe..
ll 8
■8 X I* ffi R IS* S H U
'ssmim
O
ii* i .
.
U
2
8 Sf
[ i
.
F2?®T?aration of.
m ^ m r n m m e m m ^ m m
'
:
,
■ '
. .. .
.:
':. . . . ”
:
•' *
s
:
was ppgpftMd from r^rnrnl alcohol nslfig th© js&S&iod
■of /Xzhn and CsnmXmm {Bon*#* l r3?# ff,0« 1807)*
frtA&gl alcohol
mftes?" oxidation to mmlormldolifd® is e©nw*ted to <x^teome**
,
n^iraieral&ehfd# diethflaoetaljt bf the notion of fused eftustlo
potash fch# lattes*.is c<m#fft#d'to oc^pontanal dittbflaoeisl* ’".
whleh on treatment with dllut© ouiphn^lo''a0M field# th#
h ©paired (X-^pentonaX#
'
"'"
:
I
j
.
[
[
:
-. HJ&0* ..
^
^ o riL.cir _ A _ v 0/^*0110■^— — s— ^■o ^ c r ^ a m —^ '• . :'; !
,
v
r.and-.ilght ;,::'v-. ■
,y.
................ -.... . :
/. .... ;,
EtOH ■
■ ., EOS ■
.-------------------- 'cost) —— ?0 n €*1 r 0 ucacoit)-—-* ''
■: 3 7 .....
. 2 _. / , . g. 5 .- . . 7 .
. ,. % .
I L S D j
‘
_ i_ iU 0 H'CH z C3*t2I0
;
8-5
‘
‘
:■■- • . -.■■ *
.
' I
I
.
:
.
.
i
.. I
j
$*• b*p* 133»X50®) wort
o
heated in a 3 litno distilling flash to-ICO- by. mean# of a wall ■ >
boiXXng watei* bath*.:. By mj&mm of ■
.,# dropping ■■'
j
ftosel a w#». solution.of .ftodltaa diohawsaieit# {
in I
concentn&ted eulphtu?!# mold C270g*f diluted -with water (650o*6*)»
was inm into th# hot fvs^X,aleotoi ..dnidng .the cewse of m horn*
(the opttete tira® forthis. operation)*...■ A rather■rigorous , -, '
reaction.enswl
liberated j^mler&ldehfdo was aolleoted
n ^felep sM el^d s# ■,
n<a»wwh»j>w»> wfe>^T3ai-•
x * xa *
«f
using a w#ll cooled ecndariAgr#
a lc o h o l/£*>
.
y
I fhm, a l l the: tJtoesaie a d d had been ru n i% th e
-
grooa reactio n , ]
'
i
■
"mixture- was m ra p id ly a s 'p o s s ib le attain d i s t i l l e d to a l l a y
-
.'
‘
•
'
' •.
th e f h r th e r ex id a t i on e f th e |t*y& lersldehyda; rem aining i n th e
■
j
i
j
I
*
V... £ to o upper -layer. o f th e combined d i s t i l l a t e s was' run o f f and '
lower- aijaeeus l a y e r ’ e x tra c te d w ith e th e rj
t h i s extract* was
eaucd to &h e :.o r i g i n a l ' upper. l a y e r and th e whole* w ithout a
■p re liis in a ry drying* ■f r a c t i o n a l ly d i s t i l l e d through an e ig h t Ineh
eeluasa#
■
o
S h e . f i r s t fraction.--w as•c o lle c te d up to ' 120 and a f t e r drying
. w ith 'calcium -e h lo rM e w a s.r e f r a e tio tm a ts d . t o , y ie ld •th e d e s ire d
o
j^ v e le ra ld e h y d e . b*p* 93»110:<3SjS y ie ld a f t e r ; allow ing f o r
reco v ered j^amyX alco h ol)# , F u rth e r f r a c tio n s o f the crude
. product" y ie ld e d Q »m $l alo o h o l m d a ls o jj^&syl v a le r a te «*-b#p# 190
Qt«#r ^
e d ieth y l* a© te l *
j
j
g ^ V a le ra ld e h ^ e :(126g*) d is so lv e d to chloroform (lC0c*e# ~ d rie d - j
w ith calcium c h lo rid e and d i s t i l l e d ) were p laced in a th ro e
j
'. neoiced f l a s k su p p lied w ith s t i r r e r and surrounded by fre e z in g •
m ixture#
£
- ■Eromine-C6Sc#o*) d isso lv e d to 'chloroform (6Bc#e#) was slow ly
; r m 'In to th e v ig o ro u sly s t i r r e d l i q u id illu m in a te d by a SOD w att
j
%mp9 tho te n p e ra tu re o f . th e r e a c tio n m ixture being k ep t below
^^during to© whole ad d itio n . f t | .hours^# ,.... . , t o e ,r e t i r e d
■«*XS
j
j
low fcori^or&twe was a tta in e d h f
«* s o lid e&rbon d io x id e
fix tu re * ''
. ;fh # straw ©©lowed XicpM a f t e r being s t i r r e d f o r a f u r th e r
• ■§■ hour#- was slow ly ponr&d .■in to
a b so lu te elecfio l (l*lQOe*e«).
■■w ith '.e o n ste n t’' .shaking j th e .tem perature d u rin g ' t h i s o p e ra tio n was
■■.■kept 'below *10 .* ■ ' ^
‘
'
. ;
' ;■■'A fter, sta n d in g 40 hours a t room tan.uuN rture*' th e produeb
•.' was- s t i r r e d ' In to ' *- eo o led -'eau stlo socia s o lu tio n '(170ve»e* o f 2M) «
: ,
^
•
■•■
..
..
■ ■
■©.■.":
,;■ so t h a t th e beisper&tur© d id n o t ' r i s b ' above *10 * . fix® rod
eoloured. ohloroform la y e r was run' o f f end th e
la y e r
: f o r t h ©r © xtreeted wittySimll m o u n ts o f e h lo ro fo m t i l l fch# f i n a l ' {
ehlcroform e x tr a c t w a s'a c io u rle sa * - fh e eoscbihed e h lo ro fo ra •
■J fxwr&Ots* 'a f te r " V y in g w ith p o ta a o ii^ e a rb o m te and r^;;o?al o f
■•■ th e a d v e n t u s i n g 's f r a e tio m a tin g © olum *. were w&mmm d i s t i l l e d
, ;".ov©r s o l i d :potassium ,o& rbom te* ■ & #' f i r s t 'ifraetibn# p re so m h ly
■d?»bra& *^v&Xer^defoyde» wm used •I n a ’f u r th e r a s . |
,
Xlit
(X ^brom n-valoraM shyds d io th f l'a e e ta l fead b*p« 95*104 /10m*rn#j
1^.
;
■n £ “V1*4550*. ,(0:1%*■■ ;61# y leM i* h ■■h/;
■
^*Pfm to n a l
- - o(•►Brom^ii^TOleraldelrrde d l* •
0•
.e&&^{&eetal (21% *) was h eated f o r .10 h o w s a t 150 w ith e a u a tle
" p o t a s h p e l l e t s ’(440g*) l a t l . l i t r e ro u n d .b o tto m ed .flask f i t t e d
w ith a re fItm ec ^ ^ *ser and s t i v e r #
. a f t e r ©©ollng.jths m elt was
d isso lv e d i n . th e le a s t , ataount. o f w ater.an d e x tra e te d s e v e r a l . tim es
w ith e t V r j
t h i s e th e r/-e x tr* e t wm washed w ith water* d rie d with. i
© alcim -cale rid ® ' s M fix© 'prodnot d i s t i l l e d *
eliattiy laee.tai had fc.p* 160-170°t
b>
fh e , cx - p e n tm a l ;
1.419® (XOSg.j
76^ y ie ld ).
.ot
d le th v la e e ta l (86g*) was shaken w ith
j
sulphay*!©1acid {820©*©* of 21*) •ami th e liberated: cx^ponterxaX stem
■ ■■’ ;■■..■'■- .:
'. -■
••■.■.-.
i
distilled off* ' the steam d i s t i l l a t e ' was cjuV*»act©d several times i
with; e th e r and s f t v r washing w ith w ater and d ry in g w ith calcium
chlexl de th e e t h e r \ms- slowly diitllie d off tta m g h a f r a e t l o m a t i ^
■eolxxm* : tho PrnrnInins li q u id wn d i s t i l l e d 't o y ie ld ■
. (X ^pentenaljj
; ■ '■'
■..■■■
■••■;
© j;
■*;€ pungent '^Oiling md-iachrysiatery liquid- <
•■
■
'.with b*pp 101*125
(CCg* '■■78jS y ie |d ; jta*te, and
lloe*. f **».«») g iv e fc#p*
123°. Delaby and © u illo ta lle g re # (Cteapb* Bend*# ;lC51#
glv# b*p#'
1 2 S°J
;
,
4
122*
M S?)
,.
, ;■. ■'' Oae /b std x o f ' o<*penteaai d ie th y la e e ta l was eonverted to
using, a saturated t&rt&rle acid so lu tio n
{c.3 used-by fiseh er* E rtel and
Bor** 1031* .64* S3 i&r
co n v ertin g /4-methyX, crotenaldehyde d ie th y la e e ta l to
©roton&Xdohyd©)* Im t t h i a ’m th o d r e s u lte d in only a 00$ y i e l d o f
(Xmpmtmrnl*
cn" and B esolutlon-'of (Xk *.Di e t h y l A lly l *1 er*ol
V■£
2
r
w
&
a
prejjap*! i n 67,i to ? i ; y ie ld s
.by o d iin g an e th e r e a l s o lu tio n o f <x**penbeml •t o e th y l m gnesitsa
•-■
■. ••■cloeomposlto
■-■• ■
:e!ilo^iix0 f and/the produo t . with Is# and a^inomltm chloride*
tha
Bxpmmm la y e r w asabeam til'»tille<V th e d i s t i l l a t e s a l te d o u t w ith
rot^seium carbonate* e x tra c te d . wi th ©ther and .the combined e t h e r .
crt* acb $ a f t e r d ry in g w ith potassium carb o n ate y ie ld e d th e
•
"
'
Q
required ot^*dle1&ylatlyX alcohol b*p* 58*64 /X5m*m*f 154*1860 /
jj
1 8 6
. 1
2
. «.»
d^.
.Yt,i*3»s,| » 1,4384;..
■C,Z C3.
•
•: (3 .»till
C,73.41
’ B# '1 2 ,4 £ ) ,•• ■
jz l
a ^
. 0.8384;
J31
0,02X0 end d ^
H, 1 2 .3 , ■ C^SL 0 rsq iiires C,73,7j
'.■■■• ■;.■■■■
;.
:
dl-oO '-r.it*' ,rl a l i y i hylpcr.'rn r-hthalato*
Slm oty «*ei©$»ylallyl
''/alcohol Vt X7g#) was added ,to « solatiem o f phtSxalio■anhydr&de ( 2 2 #%*)
/Im pyridine { 1 %*) tad
If
'turnin 'm the water t^S§4 After,
;. working up* the .d ^ ix ^ d ie tk y lo lly l hydrogen phfchelet* {30g*jj 77$
-0 h ■
yield). had &*p«. 64*6?°*
*TMs on r e e r y st^ llisa tio ii. from l ig h t
■'■■ot: '
'o ;
potreleiim (40*60 ) te d m#p* C&*C3 , (Foimdb 0 * 6 8 * if H*, 7 *0 f
&#*;• £C3t % tifcr&fcim.with IlaQB,
‘;
l.S * 863)* .
'..,■ ' '
son*ratIon o f dl*<Xy
■d s f -*1 *' tron3 3*^^ e rs bv- f r**©t f
...
^r.
.requires
0*
63*7|
'
■
rl IyX hydro#©*! ehtbAle&e in to
©■**7 0 *'#isim c io it* ■
fcydrogm p h tlm lstt ;was repeatedly
. ' erys^allieed. frcsa l ig h t potrol#nm; {40*40°') imd from It-w ore obtained
■: ;dl* ^ ^ d i e t h y l a l l y l hydrogen phthalate of. m#p»- 69*71Q and
«*
\
’ © .■ ■
•▼-x •• t . .ciieth ylil;lyi. hjvlrogon. phthsl&t© o f . m#p* 66*67 *
BUth products
ya
\.
wore o f I^lontioai'Hioloeular weiglxt -{itend* by. t it r a t io n . f S h laOS
.;■.. 863-5/ th eo ry .requires 060)*-Mt'the'possibility-of■. th e ir te ln g o is*
.-
;.:;W ans'Isomers was r a le l 'out as there was no d ep ression -of ‘m elting
©
p o in t -whm.a jadxed:m elting p oin t w as(tekea {$t«p* 66*63' ) | a lso " ;.
;: I cun crops, o f hydrogen pbthalate readily'.gave'ealt^fef Id e n tie e l
.. . ; ,
"melting p o ia j 158*100® w ith etryehnin© 'in acetone solution# ' ;
!l 8 7
■
*P*' / I r 1l y l h r
rhtbftlp.t.o*
S g '< ^ * M e tb y X s llfi hydrogen phthalat© (5% *)
d isso lv e d ' in ' h o t
• a c e to n e ' a * CCOc*e#) end strychnin© ■(68g*> w as'added i n portions^ ' '
making" c e r t a i n ' t h a t e&oh p ortion'' dlseeiw ed’ befor# adding th e na-^t#
A fter, th ro # re c ry s fc a llle a tIo n s ’ th e stry c h n in e s a l t o f ( )* •. *.
• dlethyl& llyX hydrogen phfcfcaifce (4% *) was ■o b tain ed w ith is*p# 173* \ ;
'•1?8°«!
t h i s on d so riT O sitlo a y le lo s d
>
* d ls th y la ily l. hy*drogon
<
"s - r
[<xj
hphfchal&te CI%*) w ith ,m*p# 0 7 1 j
0
/-X8*7
(0*1*6175)
\
■
' t?hi»;.on’ ro o ry s tk llis a tio n .f r o m . l i g h t petroleum {40*60 J ■g a v t {v-)*<V f
■0
**41 e th y ia lly l hydrogen p litte l& t# ;w ith M*p* 70*73 ‘| '
(0f :4*4905i*
, . . : ; . / . ; / ' ;v . . '
■(«»)«* v y m
t P
l &
V
h
tiktHryiate*
r
L
^
I s ¥ 6 f
■^
'1 9 * 3
o '
i
'.'V-v
., .'
!
. *% oc7^osltion o f t h e m other liq u o r s o f th e a hove, r o o r y s t a l l i s a t i m o f j
t 0tryohnln© s a l t f ie ld e d %* + §%<* #
h y l& lly l hydrogen p h th n la to
■r
■'
fS3g*) w ith
»10#1 (0*4*0050) ;th ia : c^ .reo ^ sb a llieg ii ^ ■ ,;
j
|
j
■trarloo;ffoa l i g h t ‘petroleum (40*60°)"g a v e ..( » ) ^ ( ^ * d i e th y l a l i y i . y . ;|
r
o
o
■■*
■hydrogen p h th a lftt* . w ith [xl
*19*1 . (6*4*0245)1'. m#p# 73*75 # ..
i
fh rM io r.re o ry s ta llls & tlo n rajtsod n e ith e r th e m olting p o in t m h th e . . !
/(o p tic a l
had .boon..ottainodj.
t h i s i s f u r th e r b o m s c u t,b y th e
; s ^ sronfc in r o ta to r y pe##t* o f
e s te rs # 7 , ,
y. y'-y,-..;.
p h tlm lle
-
7-
.■■■■■' , ■ <7. - •-■ :3
;
-y
■ -Equal amounts of. (+5 *■ mnA ■{* )* <^*diathylallyl hydrogen
phtbslmt© of; m#p# 73*75° wore m alted te g e th s r and alio w id to • o
I '-..the r e s u l t a n t hydrogen p h th a lio e s t e r had ,a*p# §7*i§
■:r e so lid ify - -..F
f
;
;
8.8
s s r e e ln g 'w ild i .t M t e f t h e d ig e s te r * ,.
. ,
fh© s p e t& fio 'r o ta to r y p m o m c f (*)* og^&ieibyl&lXyX hydrogen
phih&Xate l a aim . solvent© .a n d .a t .v a rio u s c o n c e n tra tio n s a re reco rd ed
l a Table ■ X S " .
■■
;
alcohol*
• •- C
m
) ^It!i Of# caustic 2v»ln cr.lntJc**
(_
^
aspecimen of «3Utf-V dV
/-
-7
. oQvdiati-iyiii l y i hydrogen phth&l&be (2*3g#> Ax./
^16*1° was h e a te d *1
U
L -'SV^
-hour on the' steam h a th with'. soditam hydroxldo s o lu tio n ($ 0 *0 * ©f 51*)
•‘ A fter 'steam d i s t i l l a t i o n * th e d i s t i l l a t e wan s a l t e d 'o u t w ith
; .'potassium c a r b o n a te / o x tr a c tc l w ith ©t&er* th e © th e re a l^ y e r d rie d ■ .
.■■■"■'■ : w ith' poi& oslus c a rb o n a te 'a n d th e .'r e s u lta n t {+)«*<^ »& tefcbylallyl
alq o h o l d i s t il l © ! .* '
■'
•©
i
t
)
■
■
' t h i s (-+) e a rb ln o l m ^ e e o n v e rte d to th e
■r.■)**£ -: o \ .
:■ •-. '
. hydrog®a p h th a lio e s t e r w ith /<x/ 'r +Xi*$ , ** l#e* p o ssessin g 90$
+$#80
■ •V
It.'h a d b*p* X53**XS.sPf ; <^s^ 3 + 4*90of
.. {1#$*$! horioeenoouaj*
, ■■'•’. ■of th e o p t i c a l a c t i v i t y - o f th e o r ig in a l t+J^bylrogen p h th a lio e a te r*
' (b) • *I lb. r ♦. filc^.hollo o ny i t l e
g o litla h * ,
o
«*19*1 j w a s .tre a te d with.
^^5
.e tiiy la liy l.h y d ro g e n phthalsi©-'(&#©g#);.
aqneous-alooholio ©eusfele potash eolation ($©*©«.. &
f. 51*) -as ahovo#
the;resultant- {«*)**a^dlethylally1.alcohol 'had ,c* ^ J**5*69°f
'© (I.i9#5| hom geaeoua)# KM® was eomr&rted by th e u s u a l
*•6*6$
^*4
0
procedure ..to {«»)<*^**aiebhylalX yX hydrogen phfchai&te w ith '
«»17*0
I*®*, w ith 09$ o f : th e o p tic a l a c t i v i t y o f th e o r ig in a l (~)~kydr©gm
plithall©- ostar*-. •'■'.■
■
'
■
>
j* "7
{+ )* <^~B le tfe^l&llyl hydrogen phth&l&t© .( 8 «Xgt)
0.
M
+-19*3 t
5"^<< ;
was h eated cm th e m t e r h a th ojfca? *J h o w w ith aqueous e& nstie soda
(15c*o* ©f Si*),
fh# i/-)^ale©la©l;wt:s a to m d i s t i l l e d off* s a lte d
. o u t w ith potassium o a rh o m te # - t m o t e d w ith ethoa? mad th e e th e re a l
. .e x tra c t d rie d ^ i t h potassium, oaphonato*. ; .Hh© r o s u lta n t {-©)«* <x/-~
'&>
. . .tW e th y lsily l e le o h o l (3»0g»J S5J? y is M ) 1 i i b ,p . 154-15S® end
■ fg.r
0
'g-so
,s r
, o
<*sx*s®*m t .■■':■'°
^
/ - . **«* +-19*® fjt*0 *Sf : hoiaog«fflMma)# - •
dhe o p tic a l ro ta to ry .powws o f -the {-©|*‘<x^ ♦ d io th a lly % aloohol are ~
recorded in Table J<yT,
•
A fte r sta n d in g i s a c lo sed p o l a r l » t o r tut©..w ith sealo&»on
end x le tc 3 f o r 9 m a t h s » th e
possessed t t a
^ d io th y la lly l a lm h n l
r ,i. /A n:y pawor©:
[<Xf9gd, ♦S.C9°»- ■^<5V^ ’; * ^ d 0-,
<X5 m
* fh r4 °,
.
.
*11*03° {1*0*51* : tfhoso '
m in e s a re 97, j o f Vxoco w h ich .th e o rig in a l .{4-) «*0^ '~dl©thyX&llyl
alo o h o l pasaessed a t B l°;
th u s showing t h a t no m ta r o ta ti o u
had occurred during th is period*
■■
.
1 90
$ 1 1 1 1
XK.
***********m
'Observed E e t a t o r j Edwers end D e n s itie s -of (->)** o<k » D l e t ! w l a l l f l
tr
' -'0 ;. , ;., .t. . ■■
« C
<
■■,is.6. 0,8397
v e7: ’:; a '
;'•
0
^
0
A
«*►
■t-4*40
!
& o . . .
‘n . 5
2
+5.63°
+8.81
. 5*21
3 , ©5
6.40.
«•»
; ; S3*3; o *eg 7 o '
1'■
1000^
+ 5*09
. 2*90
m
a ■ 0.8333 ""4*85
,
f H
■'
O
"
^tf-3SZ
, 7.83
11.93
''vtsecf
.+8.10* +12«2S° " 1 *80
1 ,8 7
11.25 " ■1,87
4*95 ; 5*54
8,01..
7.10
$•42
4,08
5*05
7 ,3 3
1.93
6.60
7,80
12,33
1,87
■5*38
■;■
^SoSL
5* tO
% vu
« # . M ra * w i * » « i « « > w w # « i « # * ( « « ) * * * *
8 v y i i f i e ,R 6t,*fc'w !r F o ^ r « e f
X r ^ D i e t l w l a l l v l S M ro ^ e n P h th a la te
in V irions r c t v ^ t s a t fn^n I1 ^ ^ n t ,re#
Solvent*
l t g0
c :
fog
L 'Ji
0 8 0 0 - 8 3 .8 °
3400 . 24,0
Jii
<V6-A/
4»8?"n
^ /t-?,r
(1*2}* ;
(yl???o
&L,
6 U
*30*0° •55*7* +•44,1
43.2
■Jfc**/*V' ' ‘33*8 , 30*5
27,8
20-4■/****' *&
19*5
58*0
.
ao ■a
22*9
54*? ■
2,£ 7
24*3
23*0
43.0
32-7
S3.2
.f 5 .0 1 7 0
CA
30,9
IS.!,5083
,
19.0 *
CEC13 f4»46€
: 15*1 ■ 17*0
12.2452 10.0* 16.0*
16*9
Z5-/*
18*3
«*
CS
r 14.1010 0.48 0*85
1.13
2.02
*»■
”*1.26
-0*05
-0#S3
>0*10 ' **
+■0*10 ■ +0.42
**
**>
SI—/+-0.9S
rl*16
/7 v
14.8
16.9
—
M*3SS
73*9 '
71*1
^>0 - £>
58*5'
' .54*0
ZS:b
attf?
a on
- S . 95
-2 .6 4
-L%w2L
"'OOtv“ *u"&
<7I ■
X = Oo^reoted v a l u e i , a c t u a lly A et^ m tned fox* (> )* e 8 te ?
«l .= ( l m 4
Cb)
d;itnrea of Dr* *!* OoVrj in tho
ppotwtiDii '■■of, t!i# tlagBsaif prssciBto^ te '%h±&. t^ asis
is crutofull? aol'c^o\dc^,co^*
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