close

Вход

Забыли?

вход по аккаунту

?

The condensation of polyhydric phenols with urea and related compounds

код для вставкиСкачать
T h e C m d - m m tioo of polyftydrie ?fee»ol« with
B r m ana aelatta CoiagaoEm&i
Stated t&ad to lit# fa ea lt^ o f fch# dr&du&te school
te P a r tia l F«XfilXsa©Bfc of th« iteqfiirofnQ&ta
for U m D«$pre«# Doctor of Fhiloaapt^r,
i®, the Dapartmtat o f Chatsi ©try
Isdlaoa, Oniyaraitgr
a.6
J-ahfi *?♦ n io e a o r
Jo & e 1 9 4 0
Yvn^1
INDIANA UNIVERSITY
LIBRARIES
BLOOMINGTON
ProQuest Number: 10295164
All rights reserved
INFORMATION TO ALL USERS
The quality of this reproduction is d e p e n d e n t upon th e quality o f th e c o p y subm itted.
In th e unlikely e v e n t th a t th e author did not send a c o m p le te m anuscript
a n d th ere a re missing p a g e s, th e s e will b e n o ted . Also, if m aterial h a d to b e rem oved,
a n o te will indicate th e deletion.
Pro uest
ProQuest 10295164
Published by ProQuest LLC (2016). Copyright o f th e Dissertation is held by th e Author.
All rights reserved.
This work is p ro te c te d ag ain st unauthorized copying under Title 17, United States C o d e
Microform Edition © ProQuest LLC.
ProQuest LLC.
789 East Eisenhower Parkway
P.O. Box 1346
Ann Arbor, Ml 48106 - 1346
The author viehea to oppress hie ai&eere apprectaties to
Br* W illie lU i m g m B a«a Dr, Hebert &• l#ana
for their aagseetlo&e aisd eoeottFagemnt gives
aiirlBg the carryi-pg oat of thia r&eeareh.
XBtm£oct!oa»
1
Tefcrodactior
Tlit p rteiy object- of the Investigation d#ob rib e d
4 a 'U s i t t h e s i s m e
th e
Id e n tific a tio n
of
th e
crystalline product formed E$r the interaction of re*
aorcinol and area in the presence of anhydrous z i m
chloride*
m
a # m&srial ms conclusively established
Imvirig the atruatore of ^ -resorcylar^id% which
had net previooely fcoca reported as toeing foraed in
this reaction*
A study of the effect of a iiMber of axpertarBhal mrlablas on the yield of >s-re aorcylajai de
was then mde*
The following variables were c m m M ~
ered;
1.
^section tin©
2*
Tessera ttire
3* Proportion of aiJENS chloride
4*
Arjpmtof ■•urea
6*
Amountof r m m i m l and prolonged
stirring
6*
Method o f a d d itio n of sin e ch lo rid e
?*
Condensing agents other than »lne
chloride
S»
Method of 1© elation o f product
This liaise of the in v e s tig a tio n was followed
hgr a study of the mechanism of the re a c tio n and i t s
a
Xifcy tm oilier phmmX® and
relate# tftvwtfxral^r to area*
eo^oimas
P a rt
th is Ifeawi* deals with a study of tha re­
action o f reaereiwol with urea In the preseooe o f
fused sine chloride.
f'ka following equations show
the product of the reaction and the miwser in which
th is product is thought to be f snaed*
H O
k i - c —isi
7
Li
c
z*< c?u— >
7
|_|
H-^=C=o + n h 3
/3 o -/3 z ° e
I s o c y & n i c Acid
U rea.
C-N^ti
/3 0~I32°C
OH
OH
fiesorcinol
0 - fle s o > - c y te m J c f e
ftssorei&ol aiMi area were first allwed to
i
react together bj &* BtpnbaiM and d* lor I# who
heated two part# by weight of area with one part Sagr
weight of resorcinel in a retort
hath*
in an oil
at 9O0 C the mixture because liquid and' at
130 - 140
C |p# was evolved*
fhe temperature of
the o il hath was finally Increased to 2.60° whereupon,
the residue in the retort solidified and the evolution
of gas ceased*
the formula
il*e purified residue was found, to have
however, when this product
was heated at ilo® six molecules of water of crystal1 1 j f t U e a w ere
lo s t re s u ltin g
f o r w h i c h H ir B h a u m a n d L u r i e
in
th e
f o rj^ u ^ a
s u g g e s t th e
fo llo w in g
p o ssib le arrangem ent.
Q Hy OH)x
Cj
!
Cys.Ti uric ac/d- <//-o*y-yb/jen/Ze^e-ether
C3 A/3 ( O - Q H
h
-O H )x
■4 jg&re detailed siraetore was Bat g if©14
they con-
eluded that when urea aod weaoretaoi are heated the
m m is eoaverted 'Is oyasuric acta
bM
&2» M a j tho
ey&Biirte acid reacts with the rwsoreiitoX with the
sp littin g out of water to fora m pMngMm other m i
th# water se t free rsae&s with tiaelmsigea m m to
fora wssmntm eertewate.
Jjb a further stady of th is reaetioe.Bira-
batta and £&rie2 heated a @£xfcure of res&rclwsi* ey&i*»
wriw acid sail' sine chloride in am a il hath a t SS®0 C
«a3 obtained the following- reaetioa*
p
+ - ( H N C O ) j — Z n M h —» 3
t= o
- t- 3 N H 3
Cyanic acid was first suggested as tbe intermediate,
H -N -C = 0
(HNCOh
»
4
t
H -O -CZhl
+■
r
V
OH
Sines the ey&ntiric aol# m ®4 contained water o f
eryatailis&ttoii aa& the zinc chloride m s m t coin-
f N
/ ) i
5
pisfcely anhydrous ttw a e d u is n was also indicated as
fallows*
( h n c o ) 3 -f J H O H ------------> JC O ^ +• 3
/
oh
+
C O ji
nh3
>
C --0
—
tfO H
-t-
OH
ISfw w eiaporismiii marled ©at in th is thesis
In which ab so lu tely drar m m m im l and c^aimr ie acid
mm heated to g eth er at.
in the presesos o f fused
asla© ch lo rid e aatt no re a c tio n took: place-, the l a t t e r
'Is soismiihat favored*.
w* Svmlm $ Isgjr tfc© action o f s^&ni© ad d am
i^ soreim i In stbsr solafcioB, obtained resorcift-
A 'V
A
\ J
oH
h
0 - * * * = - A - 0- ^
p
—o —c
b
N
^
\ J
oH
ftsc reaction o f resoreiaol with area as
carried ©at In th is th©si$ closely r©»mM## the Hbtthei**
loosed! re a c tio n , which
aldefcytfe a^ntheaisu
im m extansioB o f Urn fcfcisrawm
4
the t e t t e iw n aM elifie epithesls ,
wbioi*, «qr be feg m M as a modified friedeX-Craft© re­
action, consists in the fcrsataMmt of phenols or phenol
ethers with a mixture o f hydrocyanic acid aaa hydrogen
chloride is the presence of aXomixxm chloride or slim-
6
mpwemm th is roa o tio n *
//-C-A/ +
HCl
»
C l-C -N -H
H
oH
oH
OH
OH
HOH
ftft&toram fm#tolated tH» £&%orinft&lat«
imlno Iterqpt OMori$% fomad a# s&owsi
tfetn
m
istslcts
witli ti# pim m t or pfeoml efcfcnr to ?i*3A
ttso a£$£fe&3o» ft*# a&iiMta# w m ttson
to
the «&MbpO»#
Bta&ol* Ay£$9g Mi iigrMB^ r@#*rd tfco iniarsBdiata in %M M lw n m ro&etloxi as e&l&ro
®etfe5rl0n® fSmMHtffttw H-N-CH~N=CHClffa®p determined
that in tte prooeae® of oltgstS&iai chloride hydrocyanic
acid ro & etti as
M m Jtarqyl
H-N-CH-N=C.
fhoy mpmmM : the tt&ttmn&ini reaction as occurring
according to the following tqwiioB*,
11 ,
V
(V
+ZHOH
2 = w -«
OH
0
ii
+• tfC-OH + NH3
OH
H
Q " + HOH
au
-h A/%
variation &t %h& tfa ttm m m
reaction i# Sot to a* Mmm mM I* itatgosw y6 tb t a ll« w 4
a ja ix fO T t o f g l u e c y a n id e a n a h y d r o g e n e h l o r i a ®
to act apoa tbe phenol* t&m m o ilin g %lm t^oublesos®
and dangeretis preparatica o f agftptfrotia t^dreear&aic
acid*
ffels imtthca mm# found to b* satisfactory for
bringing about react ions that soiafttls&ft m'al& not ac*
car *h®a tic c chloride was uasd as the coodonsing agent*
fte $«»r& isow r ^rcdoaimtca in the G&fctarmmm reaction if th is petition ia froct athsruias t&e
crtto Item r is formed,
The yield s ara usually bettor
with phonal ethera than with the free phenols.
WIUs
s
pfeeaol otters tt© jr&tM of artto eom*
parm
is *«iy oaUnfactorr.
ffeis reaction also takes
asa tti-fey$rie pttxxals* m»% re&aily w itt
P&m*
t t # a * t t soapcwMSa*
CMy one aMtfeyde grasp caa fee la -
tteftraNl fey ttia reaction*
Another iattreatiug r#aefclo» carried m% fey
$&tt#riB&f8i ana one w itt a degree o f sim ilarity i© tte
p rese n t
ttv e s tlg a tio a m s
t ts f e - o f e t a t t a d
fey p a M t t g
cfeloroffei«^iae (ci-CO-NHj]y&p®F® (which m m obtained
Isgr boating ay&iwie ml# ia a anmrsit of feyiragea ttla»
ride) Mreetly intt a fey#^«rfeoa caattlaiag attatiUm
tt&oriat
ma aeli- m im wm tomod* Tit# aats©
r#&#fci#& is a fe ttte i w itt pltanol otters feat w itt fro#
pfeomtt eaypfeamie awtt eatera are tttaimd*
- f HCl
OH
f [h-N=c - o + H a ]
OH
>
-f- /-/Cl
0
Oattemann awl amaaalpa# sta in e d amides igr treating
Um
nqy tgpSrocarboBS anfi phenol ettera with a si* -
to*® ®f c^m Sc a#|i' aad l^drogTO cilleries in tot
Baiting itolat
sa ltin g Point
of Correspondlag
e
T
o l S i C
C
N
I M
^
j f &
t s
of Corresponding
i i e
a m
wPc
A
c
S C
J
A
j j l s
r
4 kO S#
l «
e M
f
l T
ih m m
©
P
$ *
H 8
0
°
e
I 8
6
* t e
8
0
0
° C
1 ?
3
^ C
a o
®
h
s i m
e n
p
a
r t t o
e
n
i d
e
1
9
8
° C
1
6
3
° C
3
0
2
® C
2
3
4
* f e
e
l e
e
t e
l e
< 2
- ^
i p
b
t h
<2
- S
t e
p
b
o
l - M
a
t l i y
l
S
t h
e
r
0
r o
l
iS - ®
»
l - S
t h
y
l
3
t t x
s r
|1
a
i i
B
M
J . p
l i t l i O
l - S
t i l »
y
l
M
1
E
t h
e
r
i
8
a
4
C
6
° C
*
c
WO.. .. O. AO. ..w■<*
*
e
2n a re a c tio n i t a t i s in a seaso a conm eilng
Itm fc n e tw e tfs t o
C a tto ® i$ 8 $ r e a c t i o n
and
to e
B o o ts e s -
1000® reactio n * Sarror® f w p a r t i >8-rcsoi-cyteM s% €#
allo w in g
t o
p rese n c e
rm&miml to r e a c t w ito oj&m^gen bromide in
o f z i n c e & io ri& t*
3r-O N + H Cl
/
^
v o h
I
OH
- Zn ( a k
+
B r-C = N -C l^
> 5r-C = A /-C l
/ \ i «
a h
>1
J
*- OH
N "a
+
H £ r
fit*? in&araedi&te contained no taranfat therefore the
mechanism Is aa indicated.
The BoBtoea-Soeaeh reaction introduced Sgr
Boosdi1 0 Is an
of t o dattireaim reaction
to r o ln a lly l ani ary l a ltr tls s rsplac* Igtocy&iiis
acM* flia raaetisn oow iot3 in t o interaction of
pianola or pln.®l o to rs with aliphatia or w » i i e
B itrllss in $ry e to r sslstim in t o prog-one# of feytirssw d&orldo m®§- s t o d k to to or atolntm etxlorids*
la tlu i* Iv&wiilsri&ta i n formd wMafe an feya^alysl#
y io M
t o
a o rra s p g n & liig te to n o n *
H i t s .r e a c tio n w o rk s
psHletslarly m il for palyfeydrie ph%ml& in m idi t o
feyirossyl
«® «st& to o&cfc otor*
flio following t^oatiow rsprsmnt a typical
of this roastion»
N~H'HCl
s
\
oh
,
a £ < c"s
U + C//J-C3N " f c S g ^ lj
Yh
oh
N-H'HCl
o
^ /J
Y o /i
H 0 H-------------------------------+ MHtfCl
\ s
ttm m cb-m lm of the Kocbsa-HOsKfe reaction
ha© been the soitfect o f considerable Investigation,
II
BMamar
fctet m om eycllc pMrnl® mm% aanaXtgr
w ith a X J $ ta t4 o a if tr U e f t,
a p » U c
n%t r u e *
«r t^ ir ^ s n ie
aeU i& tli« pfaseooo o f fegr&rogea Gloria® io tho aiMiiG*
of stag otaorMii «r alsmtei® oMorM® to for© imM® M tor
l^rirooMori^s*
H-H'HCl
+ f l - C=N
------
tlh ® « ft t o o l t f t s r i& tp te & tte ,
I»
s tir#
e h lo rif#
o tito tl* *
tf c # ’ p r o w m *
o ro a a tic
f
‘0—
C“M
e r h fd m z m m *
o f c& o n iiM & t c h l o r i d e < r
c & t& 3 g r* tO | o o
p ro d a c ts a re
i-4 n
fo r^ d »
o t h e r t*aw8 n a t l a p
* a fc »
13
I t Has abrlouely of in terest to determine
. ^ »a—. yyi aM<A> aster hydrochlorides were infcepRwdiatesi
la the
of aldiaiaea and kehlmines, or whether
tits two reactions era entirely independent. Houbea pre­
pares pare samples of iiaiao ester hydrochlorides both
firoa aliphatic anfl vnm W t n itrite s . He attempted to
rearrange those teido enter hydrochlorides to ketisiaes
both by heating and by treatment with zinc chloride m
JmLw
At *jt- rtfi*-«SI~
€»*# ® $ it
af*tSM
OW
M
-Jt'M
Ka.J1■ITSS
iJu-.aUli &
ijtSiM
ilM
irtiiM
ililiO
fc'tM
ti
*3^&$ii?s3Jit3Si o iii® b i ® i 5 m w v i ^ i
tf * Ic&e
p m tk m
Isi&ig&NNl
# f
m w p p fr l& im g & o & e m
b u t tib lfc tlM l
t& * f a l l o w i n g
e q a a tio B ® *
(V/y-//a
o
R - O - C - ft —
> Fl-C-NHX + FI'CI
N-H-HCl
R -O -C -R ' — —— > R - 0 H ~t H C 2
A liphatic
R=Aromatic
In fcM mmnA m m Urn f&fc® o f the s^eoml aarawtie cm \nmn% i» «M>t krnom
Tfcla aftr&ogty m gm at* that Imido
are m% interi&edi&tea in the Smthe®--
eat®**
Bee®©fc r m ilm *
v & ti© & t t e t
In eo n fiiw tlo ii of th is I® th« obeer-
t h e t o t l m l i i e t* g ^ e e h l< & » £ & e i ® t t e
a m ly
$i*©% M ftte ft it*®® a eete-n itr il M i resw relw l art
mZM m®
to
w ith
o r w ith o u t a
m ® & ® m t n g a g e s s t*
flit laattrS t imido arjri atgrl eater ctald not b® prepared
i®«®rw
13
Th is compound
couU rtot b e m e d e
C-Cf/i
. ru
-hCHj
r - M CW>f h o r w i t h o u t
in awy way.
0 -C-CH3
N-H-WCl
\ rr*n
concfenslny^gen^ t \ Iv**
OH
OH
&&$ a e e t e & i t r i l r e a c t t o
t h e k e ttm lis ®
g iv e #
a ~ m p b t& s l o n th e
o th e r h« 3
a e o t a i i i t r i l &&0 h y i i » $ e » c h l o r S J e
e s te r & ni th e
& m &
* fc lle
p o s u iM ®
ts rio g : a t e i
eith er to the otto" oa$«r
a n i e U o r a e e t^ a l t r i l
th e
im id o
I t m s & ot
k e tim i& e
to
g iro
t h e m m r tr n g m m m t o f
conditions*
glm
the
a-if&phthol
M%$asdm is* the
U se m v ^ l
p g to e o o e # o £ h p § » g «
e th e r o f
<2-i*ip&t&aX fa ils to r ® m % i n either sense*
(4-H-HCl
OH
+ CHyCzN
HCl
/ V
" \ _ 0 -c -C tfj
V
V y
\ /
OH
+ CH,-C=N
HCl
_ o -C-cH3
1 N-H-HCl
+ CKHjrON
N-ti-HCl
c -c H i-a
14
M m lm m .
ems&adMi that
th e
eotor
ta ftto
im ~
» U m wft -rnmlmt ooaeomaMoft ax*
M ta g a ftia tlo 9 « i« U m »
m~
an d t h a t th e
«3Mq*lo cynfttooi* lovol*t* cmlxislwly direct m&oar
Is
c tte n
0 m m lm
r e a c t 8M m
nham m
th e
re a c tio n
oracM&tfoly t h a n t h e
is
th e
H i# p h e n o l i c
m m m p t i M i® g A r e #
Bmttms-flctsch
re & c tlim
o th e rlfl*
c i t t e of thi phenolic t^Oracrl group aagp
as in*
MMting effect, o* dm ohom with a-m$htlml mtl^rl
e th e r*
I s g o a o m l,
h o w e v e r,
p h e so l e th e rs m
a t
with flttrUn to gi#c the oxpootod feottaliw salt*,
A llo w in g
tahto g$vo*
th e j U M
is
a w rnm r
flic
of mo***
ftaHbhep omnplM of tbo tootn^Ii&oacih reaction mm
cite# is m article igr Beohoo ani Flakier*
Xp
,_________________ jm ol JUL.______________ __ ___________ _
v a m tim to
..........................................
'zn(Cl)2
£ te o o l + f r i c l i t e ^ a c c t « i t r i l
m
Z»(gL)a
S o M m lm ^ c ^ s d o z io a tie a
a
—
**
«****»
$$>
Phenetela +Mos0#hl0r-^ice toai ir il
—~
3*fiSI
w fa ® rn $ ® % a + m m W m *
*
~
p |j t # s 8 t o l o + ^ l « ^ l a r »
*
—
ph#n#iola+
*
4**
*
C K C m o c lH H ^ lo t if t O E ^
C2Mol@@) —
TOP
80~53$> C r u d e
100*
*
—
Bm
*
* * ,-
S 0 -? c ^
« «
xo^s
IS
1 1 1 4 ,* f to
m ( c i )2
m ( c i)2
9CV
70*
a # # o r < s i m l + t o i t o B t 't r t i L
70$
tig m m to m A + i M m n i t r f t l
88*
Besore iJKtfUdi$setfeyle Itier +■
10QS6
¥ri<&lar^<&teaiir 11 (2 saoXcMi}
W®F%r e m a i l
B i p & e i ^ X e t & s r + f jp ie & X j s p ~ a e « i o m i t r 1 1
%e
fc& e r +
% artlja is
f r i & l o p m a M % m i ‘$ t i l
iXiIoroglaeiBal + JMw-tooitrli
8
Phloroglucinol + mrnmltrlX
68*
4Igft& lafj&ttel + aeefcoaifcril
4 .5 $
i^rd fcri X
0
*
38*
#
**
+
#
*
+
#
*
+ frt€ ttX e r^
*
"
-fBexiMSltril
IB S
*
**
+Bessel oyanicS©
4
n
* 0 U^X®fcfaer + iM&&ooi t r il
«
*
*
aw
15*
88*
**(2 M o l e s )
#
«
1S-SQ*
#
n
0
*
C
r u
d
e
& » s*
+
88*
MoBocBlor-aeetoai tr il
«
SO*
^
f r i e h l o r - a e e f c « l &r11
feta fefititfeoX + Aefttoxiitril
—
.
9
5
$
Ha n u c l e a r C m u S e n e a tio o
10
The usefulm ee o f the
reaction
la m t coofimd to saoh staple case® as those llatefi
shove,
te tt
feleeala# o f a cs®sia»rable 0egre« o f cosploxlty
M m
ig ittte * ta a 4
ia
tb i»
J te m m sh
» « jt»
raelisria front guatool
a g rs to a to a
mB- tft& m g lm iM l N-HHCl
HC2 ~ X n (Cl)±
Dry £ t h e r
OH
ho
-0 ^ 0
0CH3
Wlwtow mB I w i 14 f r t p » # a p ls lo rttia m t&Xlmm <*
H-H-HCl
(CHZ)-C-
(CHi)r C- ,
OH
/* < r* -zw f« )x b
D rySther
‘
H<*
VOH
c-c«3
o - c- ch3
M
3w w '«na S M to r* 4taaS t o t ^ w i U t Mt*r iMW
m §
sm & U m i
tfhleb
y ie ld
«
la ta # la c to n e t r m
ce«ss©ria e» lc1 lit obtaia&d os i^&rolyain*
C=t4-H-HCl
HOH
+ fto-?-chrGN-ti& aj&HOh
sawfw MS #tor£&M o&tati&s t o following rental t® with
oyiuttgfta aaS ronoreiml*
N-tf
N-n
C -C -0 H
C ^N
c=N
HCt-z»(ci)±
D r y E th iiY '
.
17
A 0taa va&ctton waa irtwwrvea HCt-H-N N-H-HCl
OH
C3A/
oH
/ S
/\-O H
+ C=N
with
V
-on i
-
oh
H C l-Zrt(C l)L^
oH
°ry m e r
OH
oh
OH
arcyl glyoxylle acid asA^aria® is <*&*
tala&a.
9^3 N-H-HCl
n o*'1 ftfj
r
c - c =n
# C Z Zn(CZ)zy
Dry E th e r
HO
T’^
/y c -J r-o H
HOHy j
no
CHa
oo
/ v
-WW ^
'X/'Oh
cC °
\
C-0
Ho\/^o'
OStMtr reactions wltfc di-nltpils are wsparttsa by
**»
m ® a lta rs #
B#
r s B o r a if s o l bbB p t s t a s *
g lm tm l $a vmm% udtfo gXata^aaitrile m& a a i^ u itrii#
sMalMsg %lm mmt%B
Igr tto* tdilm ing &qm*
l* t$ M -
N-H-HCi
C-(cHtVCfH
0
O
C-m-C-OH
C=N
f a
cm
H C l-zn (C l)j.^
Dry E t h e r
N-H-HCl
C-(cH2) -O N
cm
O'
+
fa s
C=N
HO-i
H C l-Zn(C \)i
Dry E ther
Cr(CHx)r C-0H
OH
HOH
IS
^hMrngkm^iml taui
sltf* m etio # vfe*
f i t mm mm%%® w w
with
tm jpt#ura t© tfftprie
B & t& t8 » S tiM & M
tttre la tX
i i i ^
In t i t
Y t w a w M t o i ^ # # « * § tta & t aw n
*& $
m m %
w d l
w ills . a s t a
tn t p*s» 'im%m% mltk trttt#
teg »B0esri«§rlIt di- «n&
&&*.
Wmwptmmm^
t i t - %&*««
a l l r s a e t w iti
%M% Z t M t i S
Wa®Kfctbiti& t # m % 3 « m
him&'&mm $mmmm Hi# ®rHi# c^ «w iH ril :$r$» rtM t& q g »
n -h -hci
o
II
fi
, ^
C5N * r y E t h e r
"{
j
i „ H 'i
:
....
?rN
H o/ >OH / \
i
c
-
3
-
\
jZ o n
>
N
/
O H
W-HHC?
_ 2
^
«
n
/V
™
/
V
H o - f \ oh < i
C 5N ^ y £ * A e > ^> [1
0# M e t a-o r P a r a r
j
V*
°H A1eta*or P a r a -
__ _ /
Q+(\^ £M&>i TTta
-
o
X
C s N
j!
j
|
o
_ £ ’
lla /V>©//
* . (’ /
wo/'
\-m
gh
J
v
OH
ls
ic-o«
1C
CHj-C-N
^C-C/i;
C=N
H of
_n a-z»(ah s
Dry E ther
Sith pMoro&laetoil agj*3
CyUib£>OS*123obi
1 the
follow isog aid# re aeU k?lw- vi'i{%
£$ *0oWd.
M-HHC2
II
C
H o /\-O H
C=N
oH
1*
N-H-HCl
f|-^
W o/
-OH
oH
H O / >OH
oH
fto&ad t&at <^%M~c&lor M osoai t r 11
did » l condense with maorcinol and phlorogiucinel*
the ® t a and pom efeXorM aeooiirils condensed
with yields t t m
39 * €7f* ftaMa m iM r 30%m m
willi
torn I r i l showing th a t when t to
cy&iio group
0?m p m m
obtained
f a r tta&ogfr
from the in te rfe rin g
c & s s & e m & t i m § ® m take place*.
ffcmaeU&a^& found Ite t a*ia~ end pana-aiir©
bemonifcril© r e a c t Witts re so rc io o l and pi&oroglacinol*
however* ac re a c tio n
a itrila .
mm e is ta te d with or tho~ni trobettzo-*
f « a s i t i t a ^ a lso fousti t h a t U m three ieoaerlc
n£iro~phei3&cetsmiirils re a c t with p&Loroglucino 1 while the
aet&- and para- iao m ra re a c t with reeoreinol to give M ite r
y ield * o f condeaoatioti product than the y ield s of co rres­
ponding pre&e&ta obtained £ m m h m m m i i t l 1# fb io is explained
fcfe» t m o t is o f
M n d ro & c o ,
h o w w ti* ,
o rth o *
$ 0 0 # m t o e a fjto o e w i t h r o o o r o i a o l
a t . m il*
T w i a M 'f e ^
OH CH3
+»
V.
OM
e o rrJo d
H
H^-C-CiW^-f
" fc? ^
Drv
i\ ,
Dry E
E tt hh ee rr
-..s
fH/
H
,
f \ ---- O
I f» -JMML>
j
1I
i1
C% Cl
CH3
& X lm is g
\ ---- O
/
>
o u t t& * t o
r —- C - H x
C
I f1
{'_/■-«
.C-C-H
'oh/ YA
CH3
» .H.MC,
Vo« YJJ « in
HCWMJ oti CH,
^ -C -f-C -H
f \ 0 H H cHj
ft OH CH,
,-C -f - ^ - H
+ C H ' h
/
,
OH
jgna
B opoO bo m ad
o o ri* l« d
fowling jPo&otfoa £&o&i«& tto# fiiirlxt
hoasyl
1.
VWH CHj
y
OH
mitt t h o f o x opt met m
a
mlostt»B-llo##0b ro&otioa but
inofcaad ft 'eaadoaaoo as a ^g-festTOic amid xsltrlX with
o sp ei© a n d g & & o p o g io o im X *
m m rG im l,
~ Cx- Cff
-C ®
- O E«.
t.
/
I
'YOH ,-' \ c * N
4-
k ./
OH
\V/J
^oH
;'
H C l-Zn(C l)x
Acetic. Acid
««*''•
V
“!
!
,v
v OL
j' '■, hot
t
f°
I HOHy
j
I / " ... *
H\
x\ _/ *. V
f
« t-o -c
O
*T
ciN
/
\vAv i / \ ..,•
c-0 £ t
g
Ihrocht* WMwr «*m3 ssiaxmaa^ ot&to tismt the
m etttloa o f iwmoyl oymia® with reoorciaof scours m
fkXI W i^orofa- two aoloo o f ro o ^ o la o l mi*e »s»d -
21
H C \- Z y t CClh.
Dry E t h e r
oad n o t a s ialio& tod fcy itsrtli and 3 t e i ? t w h o ro~
ported the i ® m m % l m ©f 2 « 4
hemiX*
iiciff-y o
c—c
/ X-OH
C —CAf
H C l-Z n (C l)± .
D ry E th e r
AM
The ready addition ©f artmti© nuclei to
the terbsjn ni^gm ttcofcturatioii im hy&mgm cyanide
mml xiitriloa lsuitr£&at©d & msfb#r of investigations
Into the ro o etlv ttioo o f otbor co^poimds wife oudi
8®mm% &hms?mblm® imm boon imd©
of tlit ©oisdesiiia&lsm of plttnyX Iflooyaaat© with arw itic
oois$$tt&da»
25
lMctorfc' ’ allowed phei^liooeyanafc© to reaet with- hydrowrboiio, phm&l® and phenol other© im
the preooiioo of ataitoasi ©fcXoride*
ffiih the nydro-
©arbon® and phenol- tthere* 3f*ph#nyX acid amide© were
©btali»i while with the fro© phenol© S-phofyl ©arbasiie
ootoro wero foamed* this reaction ms carried
with the following
beacon©, toluene,
©» Hi- and p-^Xen% s w it y ie w , paetidocwoX, diphenyl,
p-crc-o&XhsibUK£l®t&«P* U ^rm X ^% h^X ii^^9 CL ~rmp-hU\ol
slfiol mteySBtftar, ph&ml o-credi>i,
i»%h3fX&*fc«r#
P*«n«olt ttapattX* SHMpbttoi aM ^-mpfcfcfeol*
m m n z lm l,
tfc* f@aoM« fco ta ste d tii#
e&toofccx#
smpe27
glyeol* pp^pOX®!,
^-issi^tfcoX, « # » ! B M t p i m w f l & r m ,p % m % *
fating ttefc t o waetioo w
TstlM#BB
aided i r j % tm p m m n m
of
»ialXXe eedlM*
N=C=0
0
+
0 •o
oH
29
Billotor
reported tlia coadt&0&tl&& of Ms-
s«m oolfaegrl leoqy&mt© wltls beu&erKi i n th© pro©©no*
o f aXosriLowa e&Xoria© to gioo
suifoxay 1 fcetisamia©
and
condensed swthyl-,
&&& phei^l^tMocy&mt@a with re*
phloroglue 1ml in Urn prooonoe of hydrog m chloride
aim chloride m d ©btaimd imiilo*
othyl-,
•aroinol
fhsao jftabotamoo on
with oodiim biiwbom te were converted
into iaido thiol ester#* fin tntid© thiol eater
t^drcchleriaca# mflwmd in aquooaa solution* were
hydrolysed to thiol esters*
M-H-wa
c-S-R
E
+
ft- 5 -C zN
J f' £ k : £ » M i >
OH
Jm tdo-ihiob
OH
Jm iV o -f h io l-e s tc > -
e s i e r mffCl
n - h -h c i
N-H
c- o r
c - o r '
'
H Cl
T h io l-ester
iTnino-ee'ter-ffCz
°tf
,
.
HC'l(H.±)>
Itni no- e s t e r
Borecho and Nie&ninf^- repeated the woric of
Kmfsmnn and A&mm with. phenyl thiocyaoata and- reported
the hydraXjaia of tin isnicfe-fchiol-esisr hydrochloride
o f reaoreinel to the amide but they did not, however,
characterise this product*
n
- h -h c i
II
C-S-/
S-CBN
o
OH
HCl-ZnCah^
0
Q
g&m
It is asvis&a that $h&
&*$-**«»thtise X&ategt in thlct^fcm un a c ts in th* mm*
mmnm& m that in a llty l c$mMm ^tmn tr*&tad with
mrtain pgganola In t&* ppmmmm of &yar©^»n ®&L$rt(39
and slae «&lari<3«.
Karrw and ifcl##3®
pol^hytSri©
pb^mlB with smt&fg six® ( ItftUtitt^ysxiateo) In Wm
pmmnm o f
zhlmM® aaS zinc. titHzriM* t©
s?itia Hii0«scia*a®ia® £$riv&tiifc8a
/\rO H
fill# ru ction m« eur*it& ©sat with Ui# f *1losing:
iltaoreiml +
1*3tklacyaatte
&6#orcln&2. + ftMttQrl
*
± te * s a r # l» e .l
*
+ £ » B & 3? M ^ y X
?hjL©r0gi.uelBoi +
#
Phi^oglii^iB^X + Skj^rspyi H
a^l&s&tiigX + Fh#^rx
*
25
Several meleotilea which era develop cartem
aitreapa uamturaUoa ia the coarse of reactiea have
fceea observed to eendeaee with reserciaol* sea and
3*1
MUteberjt*** report the reaction of rsssrelisoX with
urethane for which the follow log ,» c t o i # i is suggested.
6-Hydr oxy fmirto-flu or one
■\ similar reaction occurs with S-pfanqrl suad 3H&lgfesflgrl
crethaae*
Sisali and Hefota^ report the eoadeas&tiea of
hsimssSUSe sad l~phenyl &ea*a»lde with reserciael la
the presence of a mixture of phosphorous e^chloride
sad siao chloride to yield 2 • 4*
heasogheaoiie*
Bo eoadeasatloa occurs with phosphorous ©xychloriae alone*
+
OH
Po(ah+z»(cik a
OH
to ti»
f
% pw%
m
totrtdoeti#** to toft
Part
fhm #tmr**tloi» tv m which %m
% i m k ® m i u M m r V m 4 gm** m ® m f i *
i*» to# ooora#
of asm pr#limi«w^ ftxptrlmitto M&limg with Urn
possibility ©£ obtaining rotata® tom toft reaction o f
iwirciroX wito isroa*
EfteoreiiioX and wmm m m Im tod Xu a teal*
o f itoHMS sto# ahlort^i a t i®§ ~
tab# to Ito
13Q^C fa# 2 hour#*
$h» ni-m an# rMoreixsol m m to
to# ratio ®# om » t o o# w
#©reto©l*
to to© m l m
of ra-
a® i m i o f faaaa a t oe diloria# m s u&©a*
$feft wtotor#, whilft s t i l l ijUgftto* naa poured tot© .a.-t o r
a
cotorrd #it#p#fs^lo© wa« otrkaiB^t
f h ls mmtmmim mo haatoi to toiXto^ as?
•acidified with t^rttracft&ftrle a e li.
thm result ts&B a
practically ©toar light yellow m%®tic s nMc& ms al«
"lmm§ to ©tan# s u r flight*
Xta » x t day am afjraftaxvt
crap of light fallow crystals warn found to to# bottom
q£ toft boate##*
fh tf m m fbtnsi to m lt a t $3#Q*
aftor toeato riartim with i » i t o to ! savtral mhm qm^
m t^*m XU m % iwm tram alcohol and water, long whit#
mo&X&a n n attain ed which united a t
Stoe# to# react i®» tod tom carried art uatog
to© m to i *f r t n m lM l to on# m l# a f area* an# atoe#
fhaa# z i n c tolar to# to #a #fftotort mtoivwitotlrswlag
aga^t, Xt aaa thought that to® fatm tis® of to# product
3?
be represented by Uae following equations
'
OH
_ Z 2 L la )2
1*
1 '! e=o
*
! -HH0H
Z K|__ \ /
^
The malsGul&r eeigfct of to* indicated compound is
208* A solee&il&rweight
k m w u e m p m M as tag
v&lse of
aetemimtisn m
th e
t h e Bast camphor m t h o f t g m e a
This molecular ©eight value (later
foo&d to be In error) sewed to tea ismte teat tee resot ion te l t&lceii place ^tenea. one «cla of urea ana
©bXj obs m M
of reeereinel* leading possibly to tbs
formation of netA^igieayllraewtffgfe, as indicated;
on H-N-H
{ V-N-H
+
r=o — Z ziiC ik ^ j ] V -o
H-N-H
\z .
- f 2H0H
Bsta-plioi^leiii-orea tee a s&lscolar weight of 134*
which agrees w ith tee ex p ariaeiitally determined value
o f 128-133 which, as stated before, aas laser fossd
to be incorrect duo to an experimental error*
^sta-
phes^lftasurea la reported in te e literatyanr*0 as.
exiafciiaig only a s a pslyi&Br which brow^i a t SOO C but
which does **©
$. iasit »w® at 36O0C.
Since tee reaction
.suggested above for t o formation -*f noto-pinylonsle different from any recorded $i> the lite nature,
I t e s s te&ught t t e t tbs
wokMewu compound might be the
m&cmrl® fb m o f
in ard o r to
•tibotatttlat* tola • Ijoldolil altrogpsi dotomtofttioa
m i sado to aotomiiso t o percentage of &itro$B» la
t o t t l m m tb# mlm obtained m s 0.1OfS nitrogta.
1^0 calculator vstlo# far t o poroottta&e of Bitro£”m
In i&toto^lOMOHkrca is IS. 43$.
t o Sjeldshl snatocl
I t m s thought that
not havo detected a l l of t o
nitrogen la too eoj^ounh, &® a iDyufte aitrogon detersslmtioii m s wads9 which gave a m t o of 9 .1® nitrogen,
f h i i value ohotod m i l with too KjcM&hX mluo o f
t.i0 $ nitrogen and t o to te d tto t to# ujtoowa eon’*
pound m# quite different fl^oa either of too too
atructures so ftor suggested.
a second Heieoui&r
weight determination was made l^r t o hast ca^^sr
method and cheeked several tisaoa, giving a vuioe
152. P* 'ilio previously stated value Uf jLJe*"*Xc*3
d efin itely proved to lm\m Ueoo in error.
A ti&s&astion for to® detoisimiiois of t o
percentage of hydrogen aai e&rton in t o cwf»usd gave
t o following results $ 4.6^ hEfdrogoa and 5V73& carbon.
Smaarisin^ t o expeftont&X data i
Melting Point
-------- - - - - ----------
M olecular weight
- -
22S-220°C
---------------
Percentage o f oerbon ~ - • —
- ~
---- 54.73%
«
11 Qydro$en
*
*• aitoM gau---------------------
3.AS5
152.9
28
&®&iTtml tovmd*
ts&tf etwpeaafl was colealAta* as
follows
Carbarn
E lw g ii
<&
3Tge$
64*73$ 4 22#00
4*§60 4 0#6$S 6*9,-? 4 t« s Q m M n
4*02%4 1#003
4*083 4 0#&6§ 8»0r? & % m m Hy<Irageii
0# 2®%4 X 4 #« 0,65$ 4 0# 80S 1
^
31*42%4 IS# 00- 1*064 4 $#665 -8
Hui ais^irSml forw la thereto*#
t $ m m m m m & of this t r n m i l a *
&%m Mtragea
- Z Atom Q a s& ^ * n
o3) sc*
O ^ t i ^ s C3» feast a »2eeislar
satigtit of 153*0? wti.icb
very wen with ‘the essperi*
mXm oi i$8#B#
The following ego®*Uoa baaed on the above
a o a l y t l a a l d a ta #
« fe ic & & m m m
be. w r i t t e n ,
sh o w * e l e a r l y
that the reaction imu takeo plum fcy & las© of a®g©ala
Bat by the lea® o f « t » as earlier sa&gested*
-<N£»C7H7AI03 M-W.-I53.07
+
l./SZih.
CzQJLvJ&)\
H-k-ti
- t e ^ CyHffyOj M.W--I5Z.07 H M 7.Nx
Although both ax" yw ladies ted eospoiiods teva mlecul&r
i»J$kto t o y etow to the
the e#^r!»at&lSsr
^te-missed value#
aifcrogsm v&lee of 0*28%
defin itely ftiiatiiiatM ttm ompowA tom&& fey the eXlmim-
30
ttoa o f a m lm ul® at m tor Im tm m t o rtaotaato*
t m fattawiag ®qm%lm can Ummf®m mw
to
USP'SS^SS
7 r/-?->
H 9 M
<*/£<* +
H
t% m m m m m
- Z s £ n * - + C s f t s 0 JL- C - N H j L +
n
t o
a
t
t
N H 3
O
o
f
m
t i o
a
a
$mup(rC~NHi) b m
X
roptottd oittar m nuclear Iaerogun or a lwdrtgpo fro®
o® of t o iycroayl groupt in resort 1ml*
Ttort art
im t pmml’bX® ots^ounds Um.% mmM to £omm$, ty t o
taiiis&to equation
f
Q
\-OH
CL-ffesorcylamide
C-NHi
> 8 -/? e s o r c y l a m i d e
-oh W-Ijl-H
0
+ c=o
H-W-H
Z n (Cl)x
T-flesorcyla-mide
OH
q
0-c-NHx
in-Hydroxy-phenyl-carbamatc
Of to' powiMo nuclear outotltotod products*
^ *Msarssrlm£da^ omasd to to tot irot Xitolj beoaust
to r t to t functional group
o
occupies a position
orfeto to tot Issydrta^fl group and para to tot ototr*
f b it I t Q fto s rlljf to® point o f attack for nuclear sab-
n
Into m m m t m l *
t tew® i s ® m m i & m m s I ®
ttm Wwrntomm to *8* fropwatio® of £
m i s m tsrsm m M sM
wit® Urn pmp«uratlo& * f -
9 * 4» 21 * 4*
l^a Boobm
aaatf Hoowoh vmueMm m fo llo w t
N'H'tfC}
/
V o H //Cl-ZwCCZ?*^
P>»y S'th&T
V
O ’ Ac.
O
N-H-HCf
cOH
•OH
v
oH
0 Ac
Wmm tks, mmtl&m pim sm t gtwMiitlfc am S03U
M m
®Xm
ImIami
ani &~mmm&ymM® (% % te02~ €0*88^)*
wa* prodoood fcgr iiio
ft* fcwaar
o £ s & a t & l ehXorid#
mu® hy&roo&lario ml®}
(Irw
with m m m im l, as® tbs .J&tfctr
tho hyaroXyoio of
Tim aeic! aoXutiMi
crasbsuQgad
Ifem the hplrelyiiSJ* o f tho 2-4p d l a ettey *
fcgr&roxy ten® .pt5et»»imto
di~
was oxtraeted
* W a & * eewral t i m s n&d y» c m h l m d extracts
were
ai*«d with the otter from which the islisa i^roe& lcrlde
hod 9 { « n M
«fe*a the ether m s d ia tilled e f f pa
tiyrep remiaed IT * «»hiish white mm$M wimped cryotals
m%a&oa
m the addition of mter*
this m'li® ms
frwa m ur wImumnwni it
aalMS a t gglrMtf* C* I t s a^uaoua e o M ls e a « § a rod
I m i eelor with fterJUf etilorids*
Awmlm was evolved
(*>* alosiXy ftw a toiling oaastio soda aelot Ira sf
tfet mlM$ tb)+ mm rapidly if the solid ms first
with id® m tlto le acid aid Urn® boiled with
oaitatio mSs* {«)« Iwisedi&teXy when the solid was
heated a l« a *
fins oaqpaort was a ia ssifisd as
y5~reaorcytosidt- art fbart to- hawo the following peraoAtsgs <SBwp«iti«m* Oirtoe
art M tro$«
SS*!®* itf&rog&a
&
»O
S&
»
after the hydrolysis of the « i$ e
a e»U qmaatlty a# >
6-Fosorcylic aoia m-s isolated
tm m
the rtJtiitirt*
this 4mM sbtmlm® hp
lit regard# to >5
art Balden*
la- coi^&rrt In tto ft!~
teeHg taMa with list u ® & m m e a m p G .m % l art the ttosrstie&l m t m m
£m
>5-*wao«yXmida*
33
x p 'T
rfrt'Uhniiwnlffc
% %<Srogen
»
lipleeular ’&»ight
j o lt in g f o i s t
iF F 5 F
66.140
G.SW5I
64.370%
6.02$
0.416%
4.6060
4*i®
0, 015%
9.150$
a»xv
o#03»
9*030 -0.13$
30.81$
-
rn ^ im •o * o »
31.360% 33U48S
163.07
If if
221-882 C
—
JUKfc*
228-22B°C
Mmp viola t>~
i'snPic Chlsrid®
Bed «rown color
Heated above
QGmr of aima&ola
OSor Bmm&iJk
Aibaiioo
flydSalysl®
B lm m o lm tim
of mmmmM
Wo ovoltttion of
asgoo&ia wit &
iJelUng feist
Acid IM rolysis
f&xUmd iy
boillog with
•odium
hydroxide. )
of
rod oolflr«
a itter acptoua
op olctibOdLlc
evolattoa
S?m X1
mmwrn
o
f
>
s ~
r e
-
wm®$lie aoia $«otete® &on tlio
lp1ro%s£iBg
OOltltiOB.
la p ii evolution
of aw^oiifeiw Mo
^«raooroQrlte
m M Isolated
f t m tho
aiBg eolation*
U & a m
to * *
in t o m X ttm
m s a d lfftm s c e
o f
degrees
^ t o u ototn and t o t of £~r©~
M ^Xasll® a® r«|>artsti by 3fcoesnltb and Haldane* it
m& thought 'to t t o unknown co^orad a l t o s t i l l be
m y m» s* t o torn jraaorcyXic aeis! mtM® or saato
i t mis tougfci t o t this
could be easily proved by liydro.ly&lx>g t o £mk&3S& and
obtaining ona of t o following known compounds*
OH
H.N-G
^-2-nh
XoH
HOH
OH
HOH
OH
OH
OH
OH
HoH
oH
o
4-NHj
m .p.- i w
^
c
oH
o
oh
HO-O
-C-NH j
HOH
XCOz
-h W 3
m . p.* u o j 0
c
OH
attempts to hydrolyse the unknown eoapmnS by al&alios hydrolysis using both aqueous and al­
coholic solotion® of various coocotttx’&tlona failed to
evclm m y asaaMjis* Tfei© r e s i s t a n
ce
to h y d r o ly s is
nBy
he accountte€ for by the ch&r&eteris tic roslafc&aco to
o f wMm
immm&i&wP7* m a t*
to lm m l m tM * p lU m it m m m U in Mm £arn o f aaito,
m tftcm '%
■ too vigprmm tw&utto& §C tusaoaM npna addi­
tion of aS&aOi.
mm%i£i®&U wapom3it oto«r Itoi
reoorelnol* noaid tm Mo la tod t? m these noXatiom*
ft*##t bp$r*cfi&&t&
M m % U m - eompoml m m
imwmm%
* proved d efin itely
m b
ta&ieh m m M I m m hyii*c4 iMd very m@ily i n to® &1MU&*
ooM&i&iaa witli toft m m l m b l m m i w i t K
1% wm §m tM ®I toat U® qmmbHmbim feraalm%lm mnM ^ m m d efin itely wisetotp m? not to® mmpmmQ
ms
Br
oh
H,N~c~f \ - o H
_L 33 \orjx
(Br \
-r
HAsLy1 B |,
\j Br + 3 HBr
OH
fiie a ~ m m m $ % m i i $ s would h ® .m torw t m t m i m atom
siihe&ltotoi Into l i A IM Um &• and y«irae®p«yMssides
m m M
M
fc&v* only two r n v m t m atea® anto il totod
into torn m
B h tm m . by toe following s q m t i m m *
C-NHx
+
2 (B r), ^ jgc/a? HAc. ,^
Br
^ZnB r
36
Br
A
Gl&ci&l-HAc.
+ 2 HBr
[ 0
I
+ 2 (B A
OH
OH
S h ia W m tim tlm «
eorriod out In gXaei&i
&o
&eldl antotioii r a to r twa 1b &qo»s>aa &olutio& heeaas*
$£ t o fact t o t t o tossin&tioa of plitimla is m $ m m
i$oX$ti» ®£%m reoaXto ui %b» m&i&mm&b of m<s&
gp&v$B m **
«• cocn* $»4 *11%* t$r % tm lm § nisem
ortoe w para t# t o
• 3* jfouptl.
4 m t o C t i X & r m i g h t 0 e t o 3m i » t i o s i m
t o
ooHpou&a, lagf toft Bast csssato** mUm€$ $am
toft 'm lm 36&» the $&leslAto# ©oXoe*aXar m i f ^ t for the
dMarosain&ted <Mg?0t»)ft i# 1X0*9* fiiiS' sSefioitol^ ell©*
i &g mpr®mn%lm the atruefwe
I m t o .a
of t o osteons* &Mtouna since t o mX.a€i4.Iar weight
of t o
fcri I w i g e r t o f c i v *
of
cl
- re o o rc s rlo s s t
i#
396*0
■Of t o t o reminiBf p»g§iMXlii@s* ^S-r^a
o ro y X m id tt m cI
far t o &m* irtofcle*
t o
tm r n r
m om &
ty
Xt mo therefore dtoi&tft to
prepw® aoiao >5*»re»rc2rlwiite9,
an itictope&dent
to#i% for mqparjtoozt wltti t o unko&m 0&e$»&&i£* TM
following oqpfetAoiMi tosisatft too proo^NSiir® that was to
he f&aa»#a*
+
hkHC03 + COx.
OH
M Q k -s. i
]
_j_
hoH
c-cl
rOAc.
Ac.
oAc.
O
fc'-C2
#¥.
0
Ac.
O A c.
mt& wm pmrmmt ana e#ewi*fc#cl
it s
whleft ha «t a
®f X3$*>X3#€* At $$*!« t$ » i t
tfog tiffltoottn
>8
point.
d&el&©$ to
&& Uii© woulA £&?&
aAawiiag tiiii
-
i^i*. c£3&4|A"ul?t. to
■fi-e—»*<tVi»mU»t «nft iMmtax'-® i i weulfl net be raeo**
toiy to to n y out vmcUcxi J& a s aba an la the above
MPiM t f
MStytotoS tiatoow eonponnfi
eouia toon to
witte to# AtHtoetrl- £~i*##OFajX&~
mixip ,£was& to ftwrtta® to*
torn to t untuMrau eoK^omMi
mm aa»tyteto4 to «xMUy to© m m mmmi* m ttm
$ Hpwarc^lto &ai$ to** to#n ac^tsrtotoa {«^ atto
a ccaapauto w # ®&totoed tibiofe tatltod at X3$«»JJ#€f
tfhith to e x a c ts tli® « w a© to# sselttog paint ©f di~
aot tg?X~£ '***or*&:Li<> «M* a mtoto aftXttog paint
d©tormina tion witte « s» ©£ thl* en%>aani a**§ son©
d i - a ^ t y X * - a e t o ateottol m
tow ing ®tf
fit# eossptyto mm
to® meXttog point*
ea»*
eXntoft to to
fe w l
a##oi*6ing to to# # c p a ti« *
o
X
c 7h 7 n o ,
+ C
)o
CH-rC
Znfo^ > f
OAc.
A'-a cetyl-'fi-resorcyh'c-a.cid M.R-/36-{37°c.
Unknown
m & etlm mixtar® tmS Urn strong ehametortotio
m m «t o«*tMtd«»
fto tttftMMU o#n^sH»»a tea# ttoraftre totn
tow w a to to >6
farm®#
a
mm r©~
statin© - to# cois(l©iia&tia& of uraa with raaorclx&l to
tht pmmKw of ? » « s?|pc chloric©.
m
Itelat&w o f Ro&efcloii Tim
is m
Mtt* 3t i*ogo fitt oafi arsph 1* Fag© 5?)
$bt*a 1* llU & e mXoo In roxsoiog %tm mm% im
f0r $$**# t$»s ffcw tsiw® 00 tlm yioM of ^•i*eo©r^'X«mo
is w i ofgteofeoa appreciably
looapr h«atia& $o*ioda*
l^f&feio** of Ta^trat^r#
(St# faM# 4 . Bag# $8 w l Orapi % Pag# .59}
Tkm op ^tern Uaqpopa.taro tor urn csnMnmblm
of «**#& mS
im iio ^ m n m o f tmm4 z im
Timm %u l#s&
la
iii#
of
&4 Ifolo ioss^o«tsa»ot loss Xmsdtag of tte
atld teolSb « § ii# f i#M of >£«#ooortijy2ftiB^ it $Mj
immm®M $$r Mi$mr
V&riofcloo o f £mm&% of &ta Cil&tlit
(Sat' Table % Pag# 60 an# {gro-pfe 3, Pag® €3,}
amounts o f fi*a*kl &1b# diXsri^o gi#e
aii*SfrU$-
yloMs of ,8 -roaorcylocido*
T&o
Kidoi ao&vo&io&i affiouai of foood s-i&c ohlorl&i Is 2&*$®
(0%
l&H* In 0*220
XOf Uu# ooii»2ca«Mail00 of 7*^
(0*l2S ft&l*} of orsa ;;11L X5 jraao V W m mlm)
Of l‘#tOf 0i>£iOX«
r
w£XJu-ia #f f wSO'* 0 iaO OfliOiFJ^wlt
*it& b irrin g &»3 wi.te% tic t^clatlcm of Hi#
^ ~r#$ai*oyX**&te9 vhlXo * ff« c ii* c ©illy -■ vi-ry mckmi#
40
la
of Hr«
t&m tM m % Pa$» «a » $ Oraph 4* Pago 63)
ttsa t o t m-miu^ arc ootatotf
M*& waatatf to
&ia&
t o ^ywaUiias*
o«p|isolTOSi*
#X*toaai jgrma iw^to, mJs) of w » ’e i » l
•**&a a lto # 4 to $m ct wito
am *
m i
dte alXgjkt
C0*126 ®@1»> ogf
*jssj*aa af xHiamimi. mm
to pro«*
viato t o t o altoiafc ats&Xtotioiii of raaoreiisaX etottrv®&
at t o roacttoa to^to^toa*
Effect o f Bxetaa m m m im l aa& Frotetgt^
It w
w
ea m lto d t o t a a ito r exeeaa jMtaaretol
i» 3 « |p # # ito lE g &ad any affact as t o yiCli of
®%mm mf reaospclmX {owlet t o
mmm& mmm%)B bmmmrf mmmM the m&e&Im wte&mm i t
v5
4a
rm&la Xb%sM toteiigtoat t o tom tim
Mtm% «£ Mitog: z t o Cblarlda la s&aall
teow la
I t t o aatoa8«& to t* iia ito r a ^p®at asceeaa
of also Florida $ra<mt& a t tto atort of $to .ruMtioB*
oar t o «u$giti$a of zkm ch lo rto to t o ra&ciicm mixtor* la aaall portiosio tad &ay affact os t o fia&l
ji&M of £»r©aars^;toto*
M t o i o f Otor Comiirasiiig a&mto
&!$9^0tta aXuaisategi chlorto* calciom ckXsri^t
asft anppia a&Ufeto a l l gave cantina paaulto whon &p»
plied
m p&£Etibl£
Ci-j? th is reaction*
liailatl-cm e£ vS*Iie€0i^rlaMot
4 ft *
v fv
-.
,*
A«*W-j/ **Qu
t o
c*e«
,.,
3. 7 .
*.
»
WC&S
of rfik r
add& d
to
to
^ai**
vv&»u-^j
^ v.**.-iatarao^ XiQi a -A*** o#o* a u .u 3*t
’t o addition i>t %Ui& water <tmm& a coating of
ali^e l ^ r o x t o « J e t o r wafer fenoXohie
to
f«rj&
to® mrf&a# of t o solid in t o bottom of
to r fia#;* this o m tisg $reay# hindered f y r t o r Meansposltim s£ t o &$Xii aikMrwkfe* 00 it $as
S&m*. tto fe ito«
rawiie it ^
a feiek
to
ihis produced
M ta r eesap lstto o f th is operation
m$ mtod t&m to ftofc wife an
to to
additto& l 60 a*a* of wafer t o o a aoo e*c* Makar*
F i f t o s o*g* of OB. t^o ro felo rie acid m a a&dod to fee
itofers to OisaeXfe t o a t o igrdroxfea Z®?mS
fee
l^drnl/aiUi et a isc ckloridw* ffe rnmpem&m m s t o n
coded and fiitoradL
t o precipitate mo m to d wife
l a i «*c* of a i # r co&feiitog $ drepa of Oil l^reH felcrie
acid*
to
#eigtod*
&mMm l e f t on t o funnel wan dried and
t o n d r / ro o ito i m o to n . oua^ended in safer*
XO e*o* Mfeg ooo4 for eaoli &w& of re a lto *
$be ooo-
pension %» Mated to feilfeg and filtered hot* toi
residue m t o paper m e returned to t o Makar mM
again felled wife t o m
aroimt af wafer and filtered
feW Xfe residae ms watodt wife felling water* using
$ c*e# tw e&eh gram of the ®r%inal dry residue*
42
TM® %mmhot fiXtrofcee mm
and ollswed to cool
tor complete a^utalXis&itoii of the fi «re«er<QrlMdd*t
■which m$ p?$*iflM Uqt deeelorimfciei* with usrit® aa&
reeiy eo allim%&os tmm water.
KtlWI* fifthcd
X%«*mr ee&sl<tored % fm % the- high solubility
of «lae chloride &sd m m t e S j m l i n ether, is which
s r « , ey&mirle acid and ^-r^aorojlamlda are not soluble,
Eai^fct offer a
£ *reaercylmtde*
method for isolation of the
Kcmewer, isee stile tto s showed that ether
m m sot a^ite&fc&e to the separation of the
&mm%lm product©
mmt of the sine chloride
m t m m M l j had been converted to ether lia&oXuhXe mtwr*
tol© daring the coups© of the .reaction asd t^rafore
would sot dlwftelwe is the absolute -ether used.
Sulfide - Method
I t m s thought that a v®mmim% method ©t^fefc
originate fre© the treatment of the reaction mlx.ta.rs
with boiling water, filtering and saturating the f il­
trate «1 U* tjytfrogen sulfide, filtering off the sine sul­
fide and obtaining the £-rc-aar<^lam3.de £r:n; the cooled
concentrated filtrate,
it ;ms, however, concluded that
the adopted mathad w x $ proferablu to the hydrolysishydrogen aulfIdiKiaet&od because the former is quicker,
©iispXis/p, *'.md
y.e aillatent as the latter*
1%W i t&&igg|ibfc pi^tsabl^ tft&t Sia# caiKleii»|,isiitod $$yGi» p&ms* fc*sr»«*gb ttift
at* mqpouBd *uob
X
iisiumsai-
iacMspMla Mid #r cyaaaaside*
m
t k f t g a
af
e
r a
l »
d
e
r i v
e
d
s i m
p
l y
tr m w*m m
iiOKD ia the f&llculisg sc|mitis»#
^
M
A
H
N~C—ty
N-?-K l
7 fm't
Z i i M k — > H -N = C = 0
Z s J &
k ^ h L N - G N
-h N H 5
+
H O H
A
Skm' i&#*>qpmlG acid or cyaaamtde co.id tlss cosdena©
with rMerciaol a® Csdiawss
+ H -N =C =0
— £vJ£2L...> |
[
oh
OH
+
hjh - c sn
//o')
— z ” (<&** _ >
mn-:'
,— C-NHj,
/ VOH
$t*a
m d m n im
ia U m alspXer;
h& m m r,
l i ^ s s i e a c id j^tyiaorisocl witli auo& m>m to c&muriG
&eld# ■ti&mmli$® aaai otter pro&ucia ttat its axistcmeff
a t Z3O0O 0vm m 4 iapamioiifc int^m od la ta .jaigfst 4a
qu&atitta&d*
I e an attaint to- clarify this point an &W
tatapt to araplaoa y*m
mo ande*
t&lonroa in tta condensation
fine two possible reaction* in thia e&ae
are*
S
HlN-'c-NH j.
OH
.
Zn(ci)z. > j - j ^ - c i N + Hx5
.
-
„
a
N-H
^—C'^NH^
r Vow
,,*
Z'
OH
OH
O
- f MOM
OH
s
n
UN-C-NHj.
Z » Cc?)x
> H -N -C -S
*Z.
C—NH&
OH
-h
H~N-C:S — ~ ” (Cih >
+ 03
45
I f tot condensation toMit pMm through eyamisMe
ana m m m l M m *
to m m
product should tm obtained
irm tM m rm m& usrsa* i t on t o ©tor Mod Hit first
stop to t o loss of m m m . 1% t o m m of
glm rim to m
should
si nm mil attests to faritsg
t o o t a mn&snsation to toon thiourea ana rm^*miml
failed to yield « y product to it method far proving a
possible mechanism of the reaction was at»cto»i*
Mace eyaswie acid is a t r i w m r of cyanic
acid, it was thought that this sohstaacss might eon*
3*?»s@ with rssaroiiiol to faro ^ -!Pw#ort^i«fi3ld9# to®
stibs to n tta &iiig t o mehanism hflf » s s s of toosymnic acid
a s t o t& toim iltot**
AH attem pts to faring about t h is
cooSone&ttoo failed|
to. <gyanurto acid was completely
insoluble to to# laeltod res ©retool*
I f eyasaniicl® is t o
dt'«mti8ty p »
totorwMiiate
in t o
cy&swldt! might to expected to cantons*
r«3 ijy with resore tool* accordingly a stools
of
cy&mmicle was prepared amf allowed to react with re sonetool to t o presence of fused atoe ehlorid**
is auMe
ms obtained, ofeioh strongly suggest® t o t ©y&misito is
not th* Isterwdiaie.
in which
reseretool m s aUswed to react with pct&osiom cjyw&te
to t o presence of fused sine chtoridte, ‘t o product ob­
tained tr m this condensation was identified as >#-rescrcyl&mia* to a. yield of 26.56$, TM® reaction supports
to es^srtosnt was t o n carried out
tot igetonisn tavolvtog toscyasic sold as 'toe intermedia to
as>a I® illustrated a» taking pl&o* as follows;
/\-O H
Zntert
+ K OH
me »elw iam of the reaction im^Xwmg the
eaadeBoatiam of m m m m o l mu ui*m iii the pmmmrn o f
£&mh sine ehlopide In therefore &mwm8 %
q 'm lagjf a w
of the iAWroecliat* form tios of km^QfmtQ aei4 as
&hQmi -
o
Zn (a )z ^
/3o-/j^°e
OH
1£® possibility of
of sm
iiitemaaialin tsm U o a
m a a©» rec&gaisea.
#ia©t ififeep&ti&toa ottito very readily -^ith ftydr&xyl cm»
$»m ti* to £mm im ttbam * i t mm muhgfct th at urn
urethftoo might, bts foimg a# &
o interssediate and then
naa^ti* Vm tetitlmnom h i sin e etuorlae rearrange to the
4?
amide a® shewnf
o
O-C-NHi
OH
4 - H -N -C = 0
OH
OH
O
a
j
Y
OH
2. 77 (C 2)x
Rearrangem ent
OH
I t mm apparent it m% i t a condensation eoiaii
fee brought afeent with a ei^lky&»eiher a t rtsercisaoX
aad «w * tfesn the above
sftdtanlsat
could fee ruled out*
M eia-di-mthoay b o o m * was prepared ana an attem pt m s
mas be
i t with area as illustrated in tM
equation*
oit
+
O CHj
o c h
nh3
3
All efforts to bring about this condensation fa iled
The evidence therefore points soi&erwh&t in favor of the
wmfamim involving Urn
of a aretham as an
taterxi3Sdiatef especially sines 'the Hfeuben asi Hoeseh
eoadewsatio% which i s very sim ila r to the one involved
A.
.
3S
in the research! dees take place with a»di»B»thoay feenssene *
■ocMj
CHiOf ^ A*”
OCHj
<9£//3
%%m® dooidod nevertbolea® &a investigate
fiirtt*®**
of th is M c h a » l^
th u p s s a iM X i V
th#
in v o lv in g
of a vmtHmm m an ln%erm6la%e*
Ths
gmp$mbi.m of Urn mew phm&l jtretiaam of reooreim l
« r lth a
v l& w t e
tb ® s t u d y o f i t s
te b & v io r i n
th e
*&C0 of fused aix»o ehXsritte ma yH&d©ri*ik.®n*
p ?e*»
If ih$
m$m ph®*qf\ Hr*fcfe&B®i of jraaopciittl could be mde to
rcarras&e to tor- $»p£s®*^X avsctxtoted Mis® in tbs
of sis* chX&rto Uim %hln tm&tomim %%mM
tomm mmm definite support* fto tnXlmlog ®q,mbiom
prew w eor
illa a fc r a te *& & w
to
fe t a t t e s t e d *
N zC -0
O
(
°i* M
l.
VO-C-N
H ?• y
^
° - C' N-
/ \.
- C - N - /? \
'
~Zn ( C ? )x.
Rearrange™ en±
.
(
-<*
j J
\J
OH
S t ne$ a l l a tte m p ts to
p r o j ^ c t r * fcb® j b q o o p h o ^ y ! u r e ili& B ©
of vwereteel teMod, tbi* fittfeoa of Jjwroatigttiins; tbe
by mmm of tbs formtion of as tatejwdi&te
uretoACOy phmpmS totil®*
ttii®
to #
Mo fa rth e r is f c a ti g a tl 3ii of
y o t boon m dcu
49
WjsMn&inm
a®
t o Oswsdesaati&a
mm
t o
i s r i a a g
a
b
o
u
t
a
e
o
i *
donation sX mmtk- in to pr©s©see of xto chloride with
t o tQllmimg pftnolo* pto«0,t mtsch&l, I
and pbXarogluciaol* ft product ifttttifiatfui as a hjrcEroay
towmmlfim m tM ft aoporafced from
of ton© reaction
mix tares*.
ftm a atui^r of t o application of t o conftna&tiaa to uitroj®e»ot20 compounda a t o r to n area* t o
falftvlmg ra&uXta were obtained s
CoadeaafttiMMi Atttaiptod
Iff©Xd*
1* ftaorotatol + llrea * -
* -
-
40.8 $
2* ftaoroinoX +■ fttla^rXarna
- *
*
28*4 %
3* E@»pei»X rafeaaaium Cfcf&mt®
4* Etser©i » l +■iiitramroa * 5* U®mmiml 4- Ire tone
«* -
-
2§*efis
-
22*3 %
8* fta a re lftl •+*pftt^lnraa
- f t ¥ laid
* -
?♦
S.
Eoaorclnol-f-steipltaonyamto
ftaorclnol+C^amiric Acid «*
9*
aoaoreinol-H
~
X0« ftaareiimi+ Am%m.iM **■
0*5 %
^ «*
#
XI# BcaorclnoX-h th im tm
All jic ia # refer to
$
atftr mid** ccuXfl ft obtained*
l&mid© &a no
i t was hoped t o t to
condenoation co«iM bo applied to t f t preparation of
so
H-aXkjXmd IMwyX mmMU%uU4 retforcjrlanidea but thla is
net U r n m m *
Xu the ewtatawatiou of mtl^X-urea. with
x w e re ia o l, th® notltfL group la w ld r a tf y lo o t m methyl
Bmim tm fch® foiw U a® of laooyausic ae ia from the mt&ph*
urea m indicated^ *
ZnCcD z.
l30~/31*d
U~N-C:C.> 4- CHj-NHj
The isocynnle &ei® then imctod with the resorciaol to
giw the msmuhotltutod amide*
P h m t y l w r m reacted' with
rooorclnoX in the proaonce -of zinc chloride but
duct identifiable m
to pro*
>^»roaoi*cjijraiao eeeia ho
separated from the reaction, mixture*
The following equation is offered aa account*
ihg
fe a r
the
fo rm
tic® of $ •reaaregrl&nlde fTon the con-
dena&tlon of urethane with reaorQlnel in the presence of
ftiaed z i m chloride*
o
CjlHs -O -C -N H ^
Z.n (Cl)a.
/50-/3Z°(Z > H - N - C - 0 + CzHyOH
The iaocyanic acid then reacted with the rcTOrcinel to
give yS’-rcsoreylaalds to a yield of O.m.
$1
m m % im
of
with m m m k m l
In the m r n m n m of M no Chloride
f t * apparatas weed eonsiated oi a iso 0 , 0 *
Seachlat fl&ok equipped with a
stirrer
aai a wadnltitt eU erldt drying toil®* the naafc won iw
» f # a In a st&furi* M ii hath* too tas$«mtara of
which me m tetotosd tmtamm
for 4 hears.
the ffc&efc costa imd the fo ld in g s % & $ $ * a m
(0*1^5 swte) a# urea, 15 grama (0.136 nele) of rt~
oorelsol, ewftf M g m
f t a # i wine chloride*
(0.184 wole) of finely powdered
When the f la s k m s placed in the
snlfarle aei& t»tot which was sligh tly ahewe t$ 2 ®%
Wm m m aal resorc tool welted- together giving m eitor
light green hMogeweew liquid, mile %m zlm chloride
settled to the attorn of the flM lu
f i t stirrer was
started M i m %M z$m chloride bt|fm». to dissolve there
m e an ewelutiea of babbles of earboii dioxide thro«®$K
oat the m l% whioi1 reached a ua&tam daring the fir s t
1$ ttisate* of the reaction m3t then slndoemi ceaslder«
ably*
there m s a alight m blisatlon of resoreinol Into
the cooler s p ? part of tine flask.
th is resoreiikol « i
brought back §mm into the reaction wisiure W raising
the aelcl hath su fficien tly to cower the upper part of
the flash for a few seeoads*
The ml% Im ww m pkm
ani ware wtscows m the sine chloride eoafciiwiei to dls~
aelwet fin ally heaaAiaa too at i f f for actor stirring
a t tot end of 1i| hoars,
fheroaftor i t was stirred for
52
m m m im tm
l$r hand at W *
IB n lm to * *
fbe
n m ® k m m eetiM at tit «na *f tit 4 hour heating peri*.
I t 8W e*nt*ia»* a W m ® em m aolld wita a few parti*
*3** of
* l» ofelorfde*
Oat faeoftred e .c . o f « W P « 3 added to t i t
m v tM ta o f the flu te*
ffca M A ttlm of tfci* m t e r
m.um§
a mating of mine hp&miffe ai»S other water toacXiibX® p*#&mei* to- fo w tw i* the marftoee of the aollsi in t i t bottom
o f t i t flank,
f it # m a tin g g re a tly deHoreaeed further it*
eampeattlon o f the ooll4 imwierm&tb to tlrnt i t m o ateoo*
aary to car« 0 it loom* Iron tine to time.
Tht» reeaXted
in the fMiootiOB of a tMele yellewieh cream colored #ua-
pmmlMk a f t e r completion of tfite- operwbioa ti»« ampem*
eie& mo
from t i t tl&sk with an &&<HUeml $o c.e,
o f m t o r Into- a ISO c . o* beaker*
a m a lig h tly female to Xitma*
f i t r e m ltln g wixtar*
F ifteen e . t . o f S I
l |f d M b i # i o mold w® added to t i t
the mlae et& eride.
to dlaaolve
ffeie emmaed t i e auapensiea to fcecossae
aligbtS y learn th ic k and a l i t t l e mr&er in color* There
t a t no ev o lu tio n o f any game* apoi* ac id if ic a tio a .
acepenetcii m o them molt*! and f il te r e d ,
ffee
ffee p re c ip ita te
me mOhadl with 1 2 $ c.c. o f water eox»tmiM»® § drop* o f
6 a hydrochloric a c id .
men the reatdee l e f t on the
tm m l was aptea a t llo®C i t wtigiwS 10,1 gr®»e. th i s
roaldne eo n sitttO c h ie fly o f erode ,8 •wooreyl&mide with
a m l l e r anemata o f mine organic eaapounde and cy&naric
meld*
th e weight o f thim reeidee* iaao lcb le in eoM
d i l a t e hydrochloric acid*, to rapreoented o» the following
63
gp&pito bgr Xftue A*
ft® f ilt r a t e nhlofe contained z i m
eblaFiit* w a e l® # sta rtin g m to r ia lo , m& oolssblt tgr-pv*4iiatm mm diawrdM*
i i w gras® of tli In
rmt&m mm
f iM ti In m Ml) e*«* b*$teOF$ ® e. e# o f water m o -added s
Wo mix taro warn te&tog to boiling art filtered bot.
Wo
F o o iiw on Hit pftg&r w s m ta ra o d to IM Im®km$ ballo#
wttti go e*o* o f m tor rad fUtoFOg* Wo prooipitato
m o molxod wlHi a i e*c* # f boiling mtsr*
ffeo
grty Fwoiduo* |jr iw r iir organic sine emporaSo and qyamitrie acid mm aritd ami migM l*
Wo migfrt of tbio
grey, immlmhX® in boiling water* mmMm obtained from
Wo § gram mmphi mm % t$ gimm*
Since t&o to ta l weight
o f Wo arJ&lnol » iii3 @ , Ism iabi# im cold dilute hyc!re~
chloric acid, mo 10*1 g m ; Won if® total m tgbt o f
grey Fooi&f0 t imooltxblo in bailing mier* to bo obtail®# irm tMo ooaM too X*S
(Q*?g * 6
fb io m ig h t Im
** X i 10*1).
by Xim c. x t
r^pFooasito Wo t o t a l y ie ld o f fo a o tio a proOocto wh let*
art
iw clnM c Im b o ilin g
m to r*
A® ooafrineg f lltm too from iho abow operatioiMt mro eooloi to
Wo. ^*xmox^lm igo*
the ersrotallimtioxi of
I t crysWlXlasoa cat im lig h t tan
nooOleo tewing a s i t i n g p o in t o f t 2i% *
mro mote# witli go e*e* of cold mtor*
Wo oxyatalo
flit m igbt
o f tfeo dry crystal® o f >5~rea areylaeiat obtained from
t&o 0 gram omplo mo 3*25 g is ii,
3lm» Wo total
weight of Wo original imoolmbXe rooklm mm 10,1 gm m f
Urn totaX weight o f cryobal® to b# obteimd im m bhte
mmM 'tm 6*0 g m m {%B§ t $ tt I * 13* X).
IMe
might in eacpraoaoa arapMc&lly by lino 1* it ropra*
a*»ta the to ta l y i# 3J o f £ -rescr^r'totM# prcdscea by
tfeo reaction* 34*0# y ield in th is piirbfoiiMr mp«riisaxit»
tim ojyob&lo o f >9-r^m reytaaiae « c n it#*
» l » l in hot alootxol and tho lig h t yalloo colored solo*
% i m ot&alno# » a doooloriatd with aioiite*
fliters#
Wo dear
m e oaamofcmted until crystals bagao
to aopar&te m i M
oo.iwotiaa»
fro® obioh
m tar taa ncltM to oaaploto tte
Wa fin a l atyolaXlimtio** mo fro® mb#?*
10%
ntiito xm&Koo waro obtel&»4»
imm
united m
Wio
m $ wm um4 for
qoalitotioo rad qpaaabita&lve analytical Oatomimtiom*
jfiH P O M ftytay* i» soltfbX# Im te a follow lugs
3S
ly ir « i# t* $0$ ottiyX a&eofeol* M l mter* ooatrao
am# abtiyl ooototo*
I t i » mOfrratoly
in gX&ei&X
ambit acli % loo* w la 6 I lyOroe&lopie acid*
I t im
InmM'&l®. in otbort temras* cartel* Oioalf M® and
oblm>fom»
A * follow ing «te»im X tsetafio r mm mvted*
it
blmctoad a pteaooiam perwipsmtw^eiilforfo acid ediitioo*
a w w note* oolatioxi of i t fo rm a a white pr©~
eipitato with tarmint w t e r . i t prodsima a #««p ¥ioteb
rod color mim fo»i-t atanrido oaloUcaw It roaweod
fa&Xlage m l m t i m m i ammiaoal nlXw* nitrate solation#
tfitli eoli oafiH- itaypaotdosrlto' oolsitioa a red omn&p
m
eater m m
i&fc aM'tat lygttdb&crita nateltea
pm4mm® m wklU pro#!pftat»«
it. mm belted with
lo t rnmim tytii*wSAi a U & t ytltew eolorti gelation reUmm ms ©o owlatteii of aam&l% hmmmr9.
mlmrn it wm tumS wiife ©oil« 2^#?«iels a strong Mar
0-f Msoaia m s motod* Xt $&*© a pefiltiv* Um% fm* nXmalted but
trogott t$r the aMit® f usi-on mt&od*
A study o f t o e f f e c t SB t o yioM o f
v9~r«oroyX«id§ tjroag&t utout tsf dmBgiag t o mi4ios$
«ApiriWB%aX £*efcera mm mmM anil t o r®sa lts mm tedt*
m%mC in tlit
Wttteft ani gra$u®* t o oxgtort*
im&aX lactors w i l l m m to faltering*
following
Im Mtm% of mm%t®m %im* Table M IQempfo) IX
B* Effoet of mry-teg t o tes^emt«r«i* faMt #1 {Qra.pfe)#i
3» E ffect of mrying
Urn mmm% o f stee ehloriit*
Itefal* #S (Cfeapfe}
4* Effort of twying to mooat of
mm* f&bte #$
((Sbmpb) #&
It
Efftoot of ti&eooo
site! prolOBgM sfcirrlsg*
6,
S fftoi of adding t o *ine ahterld* In tw ill
7m sffbct of o to r ooBttBBiBg agenta*
Ca*) A3*iss» cbXoriese*
(h*> Ompmt aulf&te*
Co* i
@.
O&Xciw c&terida.
Wtomt o f o t o r asstodo o f aftp&ratlag t o ro a atlo a
products*
(a*)
I t o r xaatfood*
(b*) %&rely#to
&££«$&
fW
Hrt>fnrt*i¥niil"i|1m
irrniinmiM
miw*
the Hoacti-aci
/'v
\jg *f, n;„vr-Tr-n^
*Tn-<imni|inf.
—- Urt5!
m*
ei
Jmk*A* y&mi'X* feat*a that
■a coaling hot mfctr
«*% i >e^#.$r^lagtiaa)
h fram Total
M%k%q hot
Cgj^§i2*)j
nC
wU
^iFiKiirntiSnJ
••A*
tfi
2
S.J«
f\
%pm<->v’
1^2
4
10.10
'.•■•* .s Ui
s03
a
11.S5
'J# *. cJ
2'Sr^0%r
12*90
0*93
f* <3*5
\ > * 1.«&»'
t
ff«i4 I
** 4A
&>m
s^so
O •odJ
«.y*
>•.«•«
‘tar*
('l S.if'v
•'■■*
a), as
34,0%
6,93
ae*2f
7.ae
3?, TO
-*«HiftKr■*«**♦**.H
S-rtTW
IV
.'>»•*.
7im <*& Iwlieat^cl
im g vm tm * im»%aaPc
tttW s W M
mixture s
?*5 #%*:•:«
&rm (0*125 ^ le )
15*0 ggrK&vi
ike*&re4&a& £Q*X30&&le)
25,0 .sp-r^r of
si$e ehlapldt
£o*xa4 mZ®)
Jv .i-
It? &XX cdf
ttxper&s&ais ^sisr stlxriaig
mu f ti5.gr-tfeit £$r Xj 3a$ur#*
a&a*a;t of sadisaaliwfl
*t»c cfclari^ vm prmtim'lZiy the erne is* a ll oas&o*
ffcs rs&ril&m product in o ^ « r te t n t 14 m s vr*ry h a ri a t
the m® %t ste SO hour 5j©*tt5.n.£
por&turt ȣ thfc acid hath,
d ark er
in
e c lc r
avon a t th& Jmk
Till© product ma also sligh tly
%&m £ b * o t& c r® ,
fr o s t t h i s -d a ta I t e i
m s l i t t l e m l « i.u
4 houi%
tl^ yield is Ket
i^nytr h^aiiag*
tts n g lc tfe d
t& a t
for mare tha&
appmcVihl^ hy
e c t o f R e a c t i o n Time
i
t
j-----
:=======±tbA- t z z :
xmt o f
35
t tftia t c r y s i e .Ii'z e
t h e h o t w a te r - ex
Made in U. S. A.
TSFbSSF
Form
No. 5780E— 10 Squares per I n c h
Ms t e r is,1 in s oi u b] e
d i l u t e h y d ro ch lo r:.
ed z i
ss
Kffect ftl Vhryihg Mm ttempemttir*
^i4fjXiyk &M&&,\
Mat*! .to o l* Artt*4 t o o l *
Sxp.
Ha. fMp* e c M J it a t t * h s t m t e r
>ONM
kyjweweM
iH»aA
H
i»«iW
*,wrtuyu*
^W
liW
W
miHii^
T ® f« F
m
310%
4 .? g.
#2
X30%
10*1 g»
w
X§0%
14»0 g*
*W
JW
*<w»W
lW
fc
|
U$S
.1st*4 that crystal’d
m eoolisg hot water
ml«_l4 .^#8or<Bftomi^>..)
h ^M T ^M T T W li!
);
I*<«M
«I
0*4
3.X
i 16.2®
o*?s
JUS
6.5
34.®
1*30
3*?
6,7
[ 3 5.®
|*u»<i««e;»»Mid4Kl»iF,l)"-
T im - 4 hours
Ueactton mixture a
7.6 grams of urea (0. 12$ sole)
Xsapermtore » indicated XS.0 @ n s of res;>rcinal (0.136 mole)
25.0 grams of fused sine chloride
{0.XB4 mole. )
wm/nt*1***'>BW»i»aa*aa^w
w
X® experiment IX# v m a t 110% , Um mixture
wM
ho s tir r e d taarooghstjt the 4 ham* heating period*
Them m s mere tatdleealeed zim chloride le ft in this
reaction mtxtm* than I® §2 mt& #3* flit isixiiw I® J2
h ec iw too s t i f f to he s tir r e d fey the motor a t the end
of 14 hotir% while M
became t m
at Iff at U r n end of
1 hour*
Xt wo® «eeeitiaid frssa this data that a &e®~
pcraturs of 130% represents the epttoaa conditions*
there ms less
of the reaorctol at this
tea^eratsre* leas faming of the acid hath and the yield
m»
slightly Increased by higher temperatures*
Effect of Varying the Temperature
59
-£*
I/O uj
JOd s oavnbs
01308IS
:2fc:_=
= ii= iii
_______
IjCmplTi
-jrrys^bili t gfell ‘--pn—
koojbi hfe
°M w j o j
mhe -hot w a t e r e x t r a c t . ” “ (-P-Re s o r cylanfLare")
■v *S *n
“I
am
am
m
E ffect %f Iferying t o Aroint of Elne Chloride
a lto *
A 0
GT’T i i i l
hot mtir
SC a ISa'I erjitaSTS
m cooling' hot water
“£ *E^^ g r c y )
WSi^fWftT
ii 3 .£*
ai l,1 3<->W
0*3
g*
a4*m
m * i n
40.tt
Heaetian m&xt&mi
0 .!*? gpa®* ef area
jboI*)
toipttratim l$8*13srC 1S.0 graft* of r«#0rei®@I <0«X36 mole)
2#iac Chloride a® indicated.
f Uni
* 4 tour*
In
mxgmrtmmt #X t o mixture eculd is© s tir r e d
thre«s$haut t o 4 tear faeatis^ period* A ll of t o also
chloride MseeXwi in to e axpftrliwiitt asi ©n coding a
c le a r snbcr colored eel id
mm obtained, In ca^eriacxkt #3
Hiarc » s cooeideiwtfcle focualag ana t o aixt&re beeaas ic e
c l i f f f e r t o s o la r I® e i i r i t a t t o end ■«£ 2§ tBimtea*
t o r e was a t o eotoderable tolooeiwotf slno flo r id #
l e f t Im ttoi» a l x t o t *
Hr** t o e a t o i t wm c o n e lto d t o t increased
asotm ts o f sin e eh icrU e gaira © lightly iaoreaaea yield® o f
y0 •reaoreylaaide#
I « w r , large e&aaoxifco of foeed sine
chloride
i nterfared witli s ti r r in g &»a with t o la o la tio n
of t o
Hreeeveor3Mide9 while effecting only m very moderate
i n c a s e in I t s y ie ld .
Effect of Varying the Amount of Zinc Chloride
n r»p n
mA
1
j£3
u
1
11
[
1
14
/•j
] 4**
f/
12
/
/•
]n
/
/
✓
o
/
/
()
A
e
VIa, t, r 1a 1 1 n RO 1u h 1e
\
c V 1 a Ui 1 u Lb H \ C 1 ) •
1n
f
(/T
//
4
/
"VJ■N H
f
/
/
7
/
/
1/
I
(S
Form
J
L
q
n
B
j
TfigjgpEF
No. S780E— 10 Squares per I n c h
*
/
11
h
/
/
/
e=>B —
// ( r
f
f
n
A t, V-i tu
Am n
r*V y Rt, a 11 7,p d n n p. o n i 1 n o
Ltl e h b U Wcl Le i* t X. LI 1a c L •
r\ )
u I j- «iLclinXu.ts
\( P R
!
I!
/
/
i
L.»
U .S . A.
j
M ad « in
ilA
4 > 7,
-<h
i
—C +
f*
A
rt Oil ii b Tt LLo
11u LA1b u
1 n Rn 1 U i P 1 n 1o t, Vi R,t, Rr
v
1
')
")
1 )
jR
rt
Lt1* ii D u 1
pLH 11-
R
k )
,)
*J
h
pLu y
J. z 1 u c (J111 UI*1 d e
4h
S )
T ii Du L' b
r =}ir B a n R,t 1r R 1
1
"T
* a, 3ha_t 1 9-pj-—jT i jf-k-HR3 ft. •
'
r?R,' n R n f i r R,R
i 5 p 4 tJ<bt.n b u i r b J t*(J i n 0 1
a
A sa e U
7 LI J ^ 1JL Uj. .X1
slS A
-1Lj Xu.
X Qa 1 <
1
11
52
iSKSeeS of Varylog too *uksub& of Urea
kM
^M
i»|nM
M
■$£
J,,?3ffi» rtia:
ta t water
jsqn *
«w^ V
jjw £ £ •Siaowwlsnl to*)
?3 gram fa te l
II O
>
*'4 1
0 1
y H k W v h ^ N iii*
a.?«
0,0383
7,ao
0. 1Mm
MmM'
% m r$
m m
§»w m
f I®
tm maHiffy* tat mysf
~ 4 ta ire
ste&oe fy&o*
2% m
0.70 3U§
m *m
1 .40 L s
89*83
2.00 3*7
lta*eMo^ ii*tate« i
f « ^ - « t i w - 10B ~ia#C
1&.0
of r%mmtmHQ* 136 msl®}
$ 8 ,0 g i* B o f fu s t a z i m n hlorid *
W m m fiitte it# *
C■#.134 ml©.}
In «p#rtiTOtii #1 and #4 th® mLiter®# e&ald
Im stirred teroagtaat th& 4 tow taatlBg period.
partai nt M
tet ®fetor© b m m &
In m«>
tee ©tiff for »otor stir-
ring at te© #nd ®£ 1$ tfcssr® white In ®*p©rtainfc $3 i t
tea s t i f f after 2 hour®.
Tbm mmXminm arrival at fro® a ato$y af this
tote is that It is test to mm e^atestecutter qm^-tltim of
resarwlnal mM mm in mxvying mt this condensation#
63
Form
No. S780E— 10 Squares per I n c h
E f f e c t o f V a r y in g th e Amount o f Urea
Made in U. S. A.
!RrarzfaRiim!7tir3£iiK!
ol
Sri
ms
M oles o
es
rjc
m
Bft m t o f w*m«*
%% ms
andPmlmgBiI stirring
teott^tfc
U m t ii
tee
rm
etion mi&tare
sosOB h& stirred tv* & !#»©«** period a t %im tel© might
Increase te# yield of desired product* In order to doterai&o tel% 30 f*u@ (0*072 mol#} of roooreluo^ ?*§
gram* (0*126 molo) of area, and 28 gpmm <0*XS4 nolo.)
of fused s im cfelorl.de were reacted to&etear.
The
aa^ont of reserolnol seed to tel© experiment mm twice
tee uso&l aaegrat* Siriee reooroinel saslts at 110°C, tee
« X t r a il« r a Xlqaid teroo^feout tee 4 fcoar heating period
because of tee #30DO#8 resorclnol*
Ibis made stirring
possible for oi$r desired length of iitse whereas i t had
only been possible for X| tisurs when II gram (O*130
male) of reeerelnoX mo coed, oteor conditions being tee
woe* flie following results were obtained* 10*1 gmw
of material insoluble in hoi water, aoa 6*5 grass© of
material esysi&Xlssd on codling tee bet sister extract
( vB~resoje<^laeide )*
ITom tel© f e t a i t » a concluded th at n eith er
eseees recorcinoi ms* prdengsd stirring had any effect
on tee yield of desired product*
m
B f£ a # &
of
a d d i n g U s#
C h lo rid e
in
M&X AjammrtB
S i m In a ll IM preiriama exptriw nii Umm
m m 41 K^armai awliittag* o f carbon aiaxia# during tto
f l r a t 30 minutes of IM reaction* and a emMidarabi*
amount o t tto astmo chloride ma diseoXvsd during tbis
paritot it- m s thou##*! tto i the high earcratmtiatt ©f
sine chloride pmmmt a t bto s t a r t might be detrim ental
ta tM /la id of desired prtomefc# fh is was investigated
am itoXtwsf
?♦& g w
30 grams (C,2?2 ©to#) of ia# s o r e l» l amS
mala) mi urea war© i»He6 together In
a
flask equipped with a k p *
e a ^ » # « lr i atirrer and & thermometer* th ir ty § * »
ef raaarei&ol mmm used in this experiment m that it
cetod be stirred throqg&rot the beating period ©f
4 tours at X.t8«132C. fill# excess i^awaiBsl* as ahem
im the preceding expariiiMmt* torn no effect m the yield
bat mwm& tto reaction mixture to remim liquid Ur»%^
mat the r«* title imde stirring passible far tbs 4 boar
Matin#! period, » l » m % if only IB g m m i%%M tttoe)
mi resorclnto tod toem. wed ©tirriisg mould ton?® h&mm®
imswmlkX® m m time before this ancl farther a&aiiiom
©f sin© chloride could mot then have to®** brought into
Intimate momtact mlth the react! tan mixture*
^ha sine chloride m u added to the reaction
mixture in 3*5 gram portions through the third Beck of
tM reamtlam flask#
additions mere m-Se at 20 minute
ia te r e a la during the f i r s t 3 hmm, a t Urn #ih1 o f
whim tim
25
&mm (Q»3B4 mode) to fused z im chloride
toul tm m added# tM realties was- %hmi esstoswd for
1 hour wltheut aijy further additions*
fM z im chloride
addities* tod Xii&Xt effect os the temperature inside
the flask which remised pm etieally the $m& m that
to the aarreiai&ing acid totb* T m first three addt*
Uese of aim© Chloride camplet&ly dissolved with tom*
ing, tot thereafter there remised as increasing
aaorot to wMla**!**# z im ©blwrlde after e&ct* a&ditics*
toefc addition mmm4 m m ftoaliig which hm ^m r b&mm
Im m with Um latter addltittM*
Its® reaction mixture « i treated la the
regular mcsar giving Um following results* 10*1 grew
of aatorlal iaaolskXs is cold dilute hydrochloric aeid#
in hoi water, and 6*5
1*5 grams to material
gram at laateri&X ©ryaialiaed as cooling the hm% water
)»
extract <^
$& m
this
d a ta
it
m u
eoaeloded that neither
a great exesae to alas aaXatod# present at the start to
the reactics sap the addition to zim ehieride to the
reactias yttxtare la m m ll parties* tod may effect on
the final yield of ctoelp&hXe predttct#
m
ifft o t o f QUtw Coaataisiag
hbsmi.ii'm, Chloric
f$ «feti$y t&o o ffset of algniBWs obloridB mm
a eo&deii&itig
7#© gramit to# 126 mole) of area, i§
grama (0.136 molt) of rttoreliiol* and 26 grem (0.X3S
» 3 f) of finely povdtrea fused aXinsio.ts& ckXepiao tore
m ist# to g eth er im Um r w e lio B flosfe*
r m m i i m i look plaet m m
1nnerssd in % hm m M
& very vigorous
after the ro&ctioft £ l & # k m i
bathf mfriofc ma maintaiTO^ &% a
ttts^ftrators of iSSU1320C« t t m m m i eoDaiderabit fon -
img m mmh fetat m i tr o lv e a mftieh cmm$ sublim ation
of fe&t& re#orei»X « i al«lBaa cfolortae*
T&& product
rtmsfMsig in. tut flasfe » s charred- ana upon troataesst
in Hit regular losnnor gov* bo identifiable product*
i%# above txpsriamBt was repeated except ttmt
t&*
ehltridt urns &dd$d in. s m ll portions of
1 gram
reaction
Up®® mch addition a vigorous
w t U i m m i l % » aimilar to those oitainsd
In the above tseptrinoat*
10 IdeiitifiafcX® preduet m m
ototaiaea*
l^om tim mlmm data it mo eoneluded ttmt
aliMiBum shier la* reaeiea too vigorously to fee applied
ao a oonaoBSing agen t in t h is mmttm*
m
Copper Sulfate m
CoiArBsieg Apmt,
Xu this « p # ria » t 1$ gma# (0. X36 mole) ©f
reaersisol and ?*S g w i {0*12$ ii©1#> of urea mm mcltad
together la th* reaction flask giving a clear- melt,
The
flask ms l»er«eC la the acid bath which ms maintained
at a tesqpemtare of X2B*X38°C# To this clear melt 13#.5
grMS CO#mal e) of firmly pcwdorod abb^droa© copper
mSf&tt ima added#
fill® caused the melt to beeons* dark
brost* In color and acw^tei pasty*
There me also con­
siderable foraijsg open tbs addition of the copper sulfate*
The mlb m m
lost It# pasty a^mrwm and the foaming
slackened# After 30 minutes of reaction tise ted elapsed*
12#§ gram (0#Cf?3 stole) more- copper sulfa to me added
makiaig a total of 35 grams {0*X6S mol#}* This resulted
in a repetition z t U r n shove observed phenomena# The
mixture became too s tiff for motor stirring after 2
hours# At the end of 4 hwis the reaction mixtore was
cooled* A dark hroea opaque almost solid mss ms ob­
tained#
Upon treatment in the regular manner there
resulted 1& grams of dark hr#®® powder -wMah was Insoluble
in m M
dilute t^drocbXeric acid#
M e pokier ms com­
pletely ittsQlubie in belling mtor and failed to
identifiable product on further traatiaont*
the above d&tu it ms evident that copper
sulfate was wot & suitable e^odexusing agon# for the
production of ;3<^soreyla»lde.
Oft&OifMlOilferidt aa Condensing Agent
Fifteen grams (0*136 mole) of r-esorcinol and
¥.5 grame CO.% M stele} of urea m m
melted together in
tfae reaction Cl&afc reeaiting in a clear melt* ¥fe@ tea*
pirate® m i tec acid bate ® m ? r ® m C i & g U m flask ma
mi3»t&ixi&& at 122-*132®€.
f e teis clear melt 12. S p*a«
te.112 tislo) m i finely powdered iM&^dreu® c o ld * d*l©ride me ad#®#* f i i « w
a foaming but fe§ melt be-
e s a m dark feint in color.
T i m calcium chloride ms not
veuy soluble in the melt.
&fter 30 minutes of tfee re­
action time fend elapsed 13. fe grams <0.112 mole} more
calcium chloride m i aadsd.
till® resulted in forming a
paaty h i m m u m eoutaimisig email shite pieces of m l m i m
chloride dispersed tferoqgjbotft it*
The motor w m able to
stir tb# mixture for tee fu ll 4 asyr feeatlusg period.
Ob cooling ifee reaction mixture, a blue solid m e ©fe­
ta ined which bad a co&eider&bic amount of smdiaeolved
calcium chloride particle* dispersed throughout it*
Ob
treatment in tfee regular manner b© rater ia l iBSoJmfele in
cold dilute hydrochloric acid was ©fetalined, thee m
de­
sired product ms formed is the reaction.
Stona tee above date. It was concluded teat eel*
clus* chloride ms not a condonoing agent far % h im reaction.
I f f a ct o f Other Mntteaa
0f
separating tee stMetiaa product#
fttlsor netted
Fifteen ^Pft» (3wX3C> » la 3 ©f rocorviml,
?*& $ m m <0.125' m>2M) mi urea, and BB gr&m (Q.X84
m l ® ) of ftw i' z i m
teloriae m m
reacted tegetter for
€ hour® s i XgEW133-^C» $h® ceded reaction prodact %i
eave^ed with a leyep of absolute ether and let stand
fo r m m m X dcya, a t tea end of which li*so i t m s re -
l> » Um flaak and pulwrteed under a layer of
absolute ctecr*
the pulverised malarial m® exiracted
to loo fei th 2o0 ©.©. parttea# of bailing abaclat© ether.
S h irty nine 0<imw. o f a s te r t e l rem&lsied insoluble in tee
ether, therefore lean than S. 5 gram® of product was
dis&alwtl ty tee e teer, since tec total weight of
s;4w;i.rtiiig mriier1x1^
4?*is gpaisis C
*ly.0 —
33.0
.
0.0)
f a r t of th is 8*0 gpmm m® lo s t as $&© evolved during
the reaction*
itoea tee sm^terial iaaduble in ateaXot#
ether nas- expsued to tlx©air it took up water mute an
z im
chloride woulcb
$rs»*. ten above re®alt® it x m .a concluded that
ether cmre&hte& mm m% applicable to ike *eparaties
o f the r e a c tio n product®, bce&u** moat o f tee s in e t e le -
rid® ♦vldwn-tty had bee® converted to tbter insoluble m
a­
ter tele during the coarse of %im react Iso and therefore
would not dtecelve i n tee ate slut© ether used.
?X
S<ydn®2ysi»
©f
Hydrogen Sulfide - Method
mp&mbijig %m Heaotion products
i n tiki© method 15 graiio .{0*136 mol©) of
res&rcimoI,. 7*6 g w
<0*126 mole) ©f area
ami 26 gpmm
<0*184 m3©} ©f fused mine chloride w rs reacted
g eth er for 4 hours a t 12S~13£0C*
tm
m s suspended in 800 e#e* ©f m t e r .
reaction
to­
product
This suspension
» a h eated i s a b a ilin g m t e r hath Tor J hour and then
filtered*
?h# residue ©a the paper mi interned b©the
bt&Jss? w ith B0O c*e. o f mater and again heated on tho
b o ilin g w ater hath f a r & hour*
It
ms thou f ilte r e d
a n i m ahsd w ith 6© ©*e*. o f h o n in g water*
The residue
l e f t on the f i l t e r paper weighed S.0 gram© when i t m o
dried*
This resid u e m o composed c h ie fly o f .sine oxide,
s in e organic compounds and ©yamirlc acid*
the f Ultratoo t r - m above % m m combined in ©no
heater and then heated on a water hath* fhio tm % solution
m u saturated with hySrog&n sulfide gas*
Ton percent
sodim hydroxide mo added fro© time to time to teep the
solution slightly basic*
W m n completely saturated with
hydrogen sulfide it m i filtered and the rosidue s i m l m
sulfide ms washed with W ©•©• of boiling water*
The
filtrate ms made slightly acid and after a abort heating
period it m m filtered to free it from the m m l l aisoiait
©f sulfur that had separated* The so la tia mu* then
eemeen&rated on the water hath to approximately 200 c*c*
On coaling, %M m sire d product, ^ •re s a rc y lo m ia e .
© rystaliisii out in a yield of 6*8 grams.
a s lig h t iskereaee t»
j ImM
This is but
®mr the regular proeeaur®
wbleh gam 6*6 grams of the desired product fro© the
smi© starting mndltlons*
from tlie above data It ms concluded teat tee
regular pmm4wp® wm preferable to tec byarogen sulfide
»teM Just desoribed »im» it is wcsb simpler and prw*
ti m ll y
efficient*
73
A*aa^rtiga3L
mmS Cartm
£©r t&e 8&%frmlmiim ®t &im
a
gteroNttkftagg
U m
mi i^lr'agsm m s ooy*ima im l&$ eaopayafi g&m
S M J m ta ®
m m l% 3 $
mi hm>%$ kmkt. mp'fmmxUJM im$ mm^M * 7*88365 gssaag
&S29&JHM
tk
gm m
mtgk% o f m lQ im Gloria® %®%m a-fitr
* 51*09336 g*
'imtmm oembimUaa* S3U
l»Wf#
"
%mi feygragfMi Im m tu r =- li*138&
0*07333 1 0»1!33S& = 0^0088^11
0»00831 4 8w17735
of torgre&gti Imample
—
liigtit- o f p&tasftioa kytoxid# Mils &£t&r crniMmiltm* €8* 3531 g*
ocj^sassi^
&£ QB&mm 6 lag' *<
&
©I of owrb©©. Im carboa Oieecia® — 37*3735
5*3431 X 0*37373 =0*03321
of e&ftam is U&e suable
0*03631 4 0*177S = 63* 8&StfU*ta3
£&i**wU»3s* faotor obt&iiHK! £rsa aco&st&ilife so&2»ifttl*& I* 03&5
m * m X 1*0305 = 54*783 Oarftaa
of nitrogea la the
mu a*fc*mi»a<3i aeeerSiag to the method of Buaaa, giving
tM feXlearing re««£it& *
E :»ight « f floapXe
-----~ ~
0 .3 6 8 ? 5 g ,
Velum e f jiitregaa eelleateO over 30$ pefcaeeisasi hyartwciae
l&t* 3 1 .
0
«•■***. **
**• ** -*,» •* «•» 4* w< *a ,» rn «**»*» Mb
t$S, 0 0 C . C .
te^peMftktkur# (31^ 4- JI73P) —** ,»*»«•<•»•».»«» 304® JOje.
Iteper sroasaire ȣ
igrdrexide a t 31% -
Corrected baraneter read leg ~
~
f3*9
is. i§.
* ««««, <»
74Q.0 tun*
Pr@js.aiw em r tad fcgr the aifcregea (740,0 - S3,9} *
716, X is,®*
Oamwfcing the m m m te ataadard eendltione
38*00 ts,e* X
X iKi*<& =• '27,08 e ,c , of eitrogea a t
at&sx^ari osM i
^
1 e ,c . c f aitrogra.at etaadare eoiadi tissue weighs 0,00X26 grass*
2?, 03 e ,e ,
X
0,00X26 gr&sa = 0# 03336 sparo of citrogea is
«b* AGMjcOa,
O*03385 4 0.34875 = 0.18% MM^rnm^
i&$i€-rteB^sX
Vhlttt
$ C&rhaa -
* -
* -
%%dreg»st
- -
- -
% l li t r o g e i i
< * - « * •
% &qn&m {tyr titttmtom)
*flseoroti<saX value
^-aeaarejrlasiie
m **m
4, 02$
54. 37$
9, 1S$»
s .im
32, 4SS%
75
&&a«ifc3&r f&igtst StetaroimUoa
m'ternlM* ml$£$k% m® d rtem tea aoeordiiig
(living ¥fe« foXtawtqs r s m lte t
to tfe* &ast easspfcar
map!* « « • « » « *
i#t» of
of
6*073S M i
0.®£XXTprsasas
fT*.**»*
Woight of tuba* sample and. cmph&t of
at%f aw slo * .«*... - -
,._ 3 9 .7
m
/.
<*
*
S*StS7§ g M
.Q7'SgO j^am
2 X £300
A x 1*
If = M-slootal&r weight-
Sfcigbt Of
of
H
a©
a«presaicm
of !>it s it in g .point
A=
w =
'? =
i?6.fiaC
Hsltix^g; point o f par# omphop
ag aata* fif s h o t • .
fho deproaalow o f Vm
•
IIsJLjs
ag*Oi'^
“ ■f*3Jj O
'»*
p o in t, -
V-
' V ^"W r-.-S.r
-yrtrtntrtrr^
lloiigiCOi&iP i£Qf Mlt
ft*® t&»o»-tiC6tfL m i « oajjeuteted i w >£Hresor<&2Mid® - XS3#G7
76
Add %droty»te o f t o OnqptiMi
Wm am! pm half gmmm Pi t o mrn^mmm mm
refined with 6Q e»e* of. $W welfarie acid far oat half
Mm* A a0a@M0ra.hle anmomt of mrbon dteedUie ms tBl^d
during Us# rtflsmtegf, and ie t o t o by toting with lte@
water at t o top o f t o reflax eiacliiwin
The .r@ae.tim
mixture woo torfc rati at tins oxm
S of t o Mating period*
I t m i diluted with 2d e»a o f water end eooltd*
m m
m w&~
of aodtiww hyireaeiit was e&Sed te 10 @*0 * of fchie
solution ttoreopm* a strong edar of emmie me deteeted*
Tto rerouted*? of t o oolutto m@ extracted with eto rf
giving a olear «tra#t.
t o half of tote e to r eotetioxi
ms empor&ted to df*r»« mui the m y slight rowMoo ob­
tained m i diooolwod i m waters
chloride solution m m
a few grope of ferric
added to t o meter so lo tto of
t o reeidot wtorrypoii a eater stellar to t o t produced
to n ferric chloride is added to m m m i m X was noted*
lodie&tteig t o pretence af reeorelaoX as a protoci of t o
hydrolysis.
An a tte st » § mete to isolate /? -reaorcylic
acid from t o e t o r h alf of t o ether extract*
The ether
wae extracted with a saturated saint ion o f potosissa bicarbomte to rename aiagr
tow tom present.
acid that might
The poto&eimt bieorfeo&Ate extract
mo- tom acidified with concentrated hydrochloric acid
and them extracted with ether.
The ether
to t failed to yield any reeercyiie acid.
too
ewporated
77
utt af dilute teerdrcchlorlo acid (ap.gr.l.OS)
&a Uja hydralyaiBg •s<»*rt Saw
raaulta.
78
of %m : Confound
t» ia
®m © m of
tfc*
w i placed ia a 125 e*o*
SrXeiMsrer flask# aai m -eve* ©f && aquftosM ©elution eontim in g 10 gran* of potaattlun hydroxide m s added. Tb» re­
sulting seiiiiisrn » i refliawa m m a direct I t e t o
arear&X koarty bat failed to- emXv# augr asmoala* Her®
eOBCOBt^tod asptcttii aoXssttos of pataaalsvi hydroxide
gaw t*»
« i t negabfw mmX% misder%lm m m conditions*
€m g^m
iim A
containing 10
of
tli#
w m placed i n a 12$ c*e.
f i f t y a*e* o f a B$S a lc o h o l so lu tio n
of jm t& m tm iaplrmldt
r e s u ltin g a a la t lm m s refXuxad »
mm
added* The
& b o ilin g water batb
for ©tircmX ti»r% but failed ta t w i w ai^r asgaaaia*
Bj
tbe m m of' » r # eoncem tm tM a le o b e lic m X u % i® m o f potaaa i w % i r « i a t tta* earn aagativ# r e a a lt s were © t i l l ob­
tained*
fliisiofi wiib potaaaiua l^draxlde ta?#ver re-
salted in m strong w l i t l a of w » la *
70
BromimMoii of to C
mm p » o f the co*^au»a m s dissolved la
m a,e*. of g la cia l «uMtto acid ia & X25 e ,e , BfOcimycF
f t o * toevced la a to ilia g m ter hath,
She delivery
«a& o f a burette and a calcic® c h lo r ic drying bubo
passed throng the r u to r stopper in %m m nk of t o
fia&k,
A solution of & gmiss of brootto dtou>Xve&
in §§ c*e* o f fto o ia l s e ttle acid iai. nuftel by » a » of
t o burst** w
a period o f me t o r ,
t o nisiur* ro~
m inni la t o bsE iag wahor hath during th is addition
aad m s ^fgoroiisXjf totes® fro® iisao to tin s,
It m s
to n mmm® fmm t o boiling a l t ? hath and allowed to
siaad « w sight*
Hi# g la cia l acobio a e li and hydro-
bromic acid w#r# removed I# vacua® d istilla tio n ,
the
d is tillin g flask *® boated by a m tsr bath mint&imd
at 4S «* £$*€» tim resulting crystalllm product m a
mmm$ fmm t o flask by dlaaolvlasg It In alcohol and
t o alcohol so la tim was to n decolorised by boiling
with scribe,
Upon t o addition of mMr to th is solu­
tion t o product separated m ligh t cream colored crystals
with a m ltin g point of 241-42^0*
%en fusion with saebuXXlc sedia® t o product
$aw® a strong bromine and nitrogen test,
is ccaapletely soluble in e t o r .
t o notorial
80
Sfttftxvtafctlm
mt %h$ Stoloculitr fttlgbt
mt Hi# abominated Cods^dtnd
tli# m lm € km w#i#st of t&a hmmim.rn& cmmnm&
mm aetoralm id mmrMng to ttw s&at es®plmr met&od, giving
mm fallowing raaolts
St mi tttfeB <* -
-
&072& g r n
._<*
«»
«*
**
«w
T^p»W
»VW
«ir
so lv it of Mwt9 m ^ U am# oraplior * - misriit mi la'ii i i i m m tm «* «* *> * - - , * * - < * « * * *
^
5«3@33 gpmm
&*07&6 jarem#
0*slSSrgram
^ <& y
mrnrn M - loXaeulti* Ǥl#it
m = fMglst of mapl*
W= ^ i # it of ^apiior
A = ts» doproaoioi* o f Hit molting point
Halting point of par# e^lsoi*
- i?s.s°c
Sim d#{immim of Hi# molting point, -
**
It =
=■
ia*0#C
mi&m%
of ttoo Imnlfiatdd
oompoumi
tbo t&eorotle&l m ltii ealoalatea for a Gi-hromimtscl
r e m j^ lo ftid o i» 310* S*
ax
Acnstaxation of %M. CosipouiMi
t h i s r e a c tio n was carried cut aecordixig to
w® ^ *d<k* oi M* Jksrgmm
r. DaBgachato^
fchsj? d i ae^tpXaied ^ ~i*2sorq p lle acid*
to wfciefr
f iv e graass o f
the e s r e fu llp dried coiapoum! mx$ di^aolvod in ?5 ^r®m
of acofeic s!%?clrida 4b a sm all round bctotoj&sd fla s k
equipped with c. reflur; coadteasr G&rxying a caleia& &i?lorld*
S tjln g tuba*
Gae half grate of fated aine chloride m s
acldtd to toe con ten ts of toe flaak which was tiiSB te* to 4
in a toilin g water bato for f hours*
The atoe chloride
cosmic tely dissolved and toe oimractorietia odor of
SiCeiamiac wm e a s ilp S o tscta b le in to® re a rt im i&toiort*
Xiie r e a c tio n satot-are was poured into 100 c*c* o f erustsed
ie ® a n d w a t o r *
Tim o i l w h i c h s e p a r a t e d ,
sta n d in g , and isus f i l t e r e d off*
pur* i f l e d £§f d t o a e l v t o g t o
e a r h orn to
s a la t le a & m
s o lid ifie d
o»
T h is crude product was
to u s a tu r a te d
r s p r e c i p i fee t i n g
p o ta s s la © b i -
bp a c id if ic a t io n
o f too f i l t e r e d s o lu tio n w lto e a n e e a tra to d h y d ro c h lo ric
a s id *
Tkm p r & t i o o t m s d r i e d a i3 d fo u s a d t o h a v e a u n i t i n g
p o in t o f 138~13B0CX I t gave no to o t f o r ntfcrogoa by Um
sod i os fu sio n d*ethocU
sa
psq^par&fcftaa and AeetySatlai* of
acid
j5-3t0or0fMc acid4® mo prepared ty the fel~
laeing jaetaod*
l a a a>0 e.c,
tlm k f i t t e d wits* a r e f las
condenser, a solution of 20 g p & m of rcaorainol ana 34
arenas* of aadiu» blmrhomte in
200
e,e* of water ma
iieaiea almtty on a oUaa b&th far 4 hours*
tlm flask
mo then placed over a direct flame and rcfluxad v i^ rtslg f far 30 istai'toi*
a rapid atreaa of carbon dioxide
me paased through the solution during* tMs letter Imt*
period*
Hill# a tm hot U r n m U itios* me acidified ty
adding WO e*t* of oaneeisfcmted tydroctiXorie acid through
a mpwatarp ftnineJ* the dellveiy
of efeidb me below
the atsrfac* o f Ha# liquid la- the fl&ak,
fla sk m s
cooled to rcata teip«rmttir# and U w m cfellled la m
im
bath* The ) B ~ r € m r ® f lie acid cryatalllsed out in prism
having a alight pink colei** T h l ® extide predttct ms die*
aolved la hat water* deeeleriissed with aorite and filtered*
fit# crystals obtained an cooling the filtrate m r ® dried
and seltea *«, 8iS-217°C.
Fiot gram of ^reooreylie acid were acetylated In tmetty the eme manner m
m®
need to eeetyl&te
the eoppeaed y B Hwaerqylmide ( page-?/-!
* 3be resulting
product* 61 acetyl j#»rec&rtyiic acid bad a melting point
af 336->2a8** A mted m ltiag point with a portion of the
product obtained' from acetylatiBg: the amide m m ®6 m
lowering of the »Xtin® point*
83
A£te*spted .^ I lc a U w of the Boacbies.
V ariation o f the Phenolic C onstituent
I - ! .i®
n o t
& :? d
The a p p a r a t u s m s th e same a s tJm i used In
th e r a 3 0 r© in o X -u re n e x p e rim e n t*
fla s k
c o n ta in e d
m% B) o f u re a *
fh® ISO e*<u 3 m rh X et
t h e f o l l o w Is^* j a f c a t a m :
1 3 g r o n a <0*138 m l e )
? * g g r a s s {0* 1 2 6
o f p h e n o l, a n a
3 6 p * s ^ <0*13-1 m l e ) o f f i n e l y powdered fu se d s i n e c h lo ­
r id e *
f h m m ix t a r e gave a c l e a r brawn sir I t when i t was
placed in the -acid bath mintalBed at X38-X3a°0* Baritsg
the first- 6 ralasts s there was considerable Coming which
m m n slaekenrd and be*earn wry slight by the end of the
4 boor be&tisg period*
t& e b e a t %mg p e r i o d *
T tm mixture ms stirred throughout
a t t h e e n d o f w h ic h i t s ®
th e re r e -
mined bat ore omll particle of iindissoX^ed sine chloride^
upon Coe l i n g th e a l l u r e a c l e a r cterk g re e n brown s o l i d
was obtained*
O m hundred ana f i f t y c. e* o f water m s added*
w hereupon a, t h i c k g re y s u s p e n s io n was f o r s e d which m s
acid to Xitai#*
F ifte en c*e. o f 6 B hydro ch loric acid
was added which caused U » suspension to become darker in
color and decrease sorowhat in uiaount*
I t viao then f i l ­
tered and washed with. 125 c.c* o f water containing 5 drops
o f 6 U hydrochloric acid*
Upon drying the residue* 3*6
grasps o f b lu ish $?ey c r y s ta ls were obtained*
tr a te
w as e m p o r a te d a c o n s id e r a b le
phenol and area m s obtained*
$fce» the £11-
a n o u n t o f u n r -e a c te d
o f fc&e b l u i s h g r e y c r y s t a l s *
©b a w a t e r h a t h
re s id e s f t i i t e l
filte re d .
T h is m ix ta re m s th a n m r i ^ d
Cm h a l f a r;m &f d o r h hrow ii
©fc th e f i X t o r p a p e ry
ta iB @ -d a C C M 5 J 3 1 A r a b le a s o t m t o f « l r o *
.i-.tj^ed t o t h e f i l t r a t e
h a th an d f ilt e r e d *
t h i s r e s i d u e ©ob acm e n o r it e m s
'w hich w *e ih e a warinetf ©n th e w a t e r
hhe& t h e a c e t o n e m s e w p a r a t M
this fitteat© there ransklftqd 1..S
fr o m
o f white powder
fe&vl&g a im ltiB g p o in t of 140*143%*
This
9 ttli« g r la » i£ *
143%}*
p oint covers tbs r&Biye for hath
( i X * P * I 4 0 % ) aisc! p h e n y l c a r b a a a f c o 0 s » ? » 1 4 1 ~
-31tsce tbo s a h s ta n o a gave o f f ©arboBcUorlde whets
b o iled with water, a lco h o l or acetom i t wag cooeloded
that i t coyld not ha s a i l cylamide which la r e sis ta n t to
h y d ro ly s is *
as
Cstechol auoA tlrea
fht appamtus mu Um mm as itel used In
Um
& ® p ® v lm n U
? t m ISO e.e* SoxliXtb
t i ss& eo$ital»d the following mixtar©s 7*6 graw (0* 125
m U ) o f m a , 1 5 g n a w CO* 136 mol#} o f c a te c h o l aad
25 p w
chloride*
(0*104 molo) of finely poodorod ftsssd sine
This mixture gave a dark melt nti©» It w m
p£*eo6
the &oid bath maintained at 123*132%* aw*
Ihg the fir s t $ minutes there m s considerable foaming
©hid* m m slackened and pmctieaXSy ceased after
pairing the dark hrcim melt much stiffsr*
10
miaabea
The emit also
contained a csnaidsrafcle amount of tmdisaalved alee ehXorids.
At the cod of 20 minutes the melt was too s t if f for
m tor-stirring*
there mo same sublimation of the -catechol
into the upper part of the apparmtas* After 4 hoars beat­
ing the flask mo cooled giving a dark t o ® opaque solid
containing unaiasolved particle# of sine chXoride*
Oao hundred and fifty c*c* of mter was added
isMeti brought about the formtion of a grey suspension
covered with a alight ^pey froth,
this saapsnsioa ms
a©utral to 11turns* Fifteen e*e» of & M hydrochloric acid
ms added idmreapm the m ^ m l m
carbon dioxide m s evolved*
became darker grey and
fhe suspension m s filte r s#
and ol*iX« it ms s t i l l in His funnel it foamed consider­
ably and became a miy black pasty mss that ms not far­
ther investing ted*
m
tlraa
ftit mwmrntm m m
to * ©oqg m
t h a t %im& t o
me iwowtooa^ttwa eaqpftriaest* !ft* 150 <*•©• mmMrn%
ftasis
to# MUnelfle Mixturei 7#5 gram tO.X2S
j»X*) ®£ tir#% 16 grama CO*136 nolft) of
e&a
a® gran* CO*184 ttele) of finally pewderea feeea &too
elilertoe* Hitn fee naafe w # placed 1b fee mM hath#
mtot&toed at iaS-X^C* a gray m l t » s ©bt&toea wbife
IM S t e a M
q u i i t lltgttto*
ffet X ig tit t m
liq y ii m s
fille d wife m a il bubble# a»d foams* Moderately* %
■fee end *f fee f i r s t im if bom fee feamtag baa p ra c tic a lly
•tapped exoept for- a little- fringe of babbie* at fee edge
of fee m lU TSi® s s e l t F «al»5 l i q u i d m3 mm e t i r r e d %
fee motor throughout fee 4 lio-ar beating perled*
Upon coal-
1^0 fe© tacit a clear Xlgtit green brom sella was obtained
mhioh land sev e ral « a l l p a r tic le s ui tm&lmolw3 zim
a b ler toe diepereed feroutfiaat it*
added
which brought about the feimttoe of a grey etiflpeaoioit
Q m hundred m & £ i £ % f e*e* of mter mo
which shewed a slig h t acid reaction. tomrd litmus*
Fif­
teen c«e* of 6 1 J^rochXerto aeM was scklti which caused
fee suspension to beams® trow ana decrease aoMsbat to
affiamifc* The ea®penal an mm Umu filtered off* washed wife
125 c*a* of water eentatotog § drop® of 6 I hydrochloric
a d d * and dried,
The dry •browsla b g r e y restore weighed
U ssa a s r a o ll p o r t io n
o f to la
r e s id e e m e
37
te&itm wite m ter oarbast dioxide was evolved*
fo I ^ w s of tfcie residue, SO 0 *0 . of ass toot
ms added and Hit mixture teoroaghfy agitated ta p shaking.
tfg m
m u r in g
ttoera m m i m M
X.S grams of Insoluble dax*k
fcreun residue mhteii contained a eoi&idembla amount of
atae eoeiipeisttda* Three ar^ on© half
of fcrowjoiah
gre^ material was efctaiawia to evaporation of Hie fiXtrate*
fkit oaterial ms dissolved in a little acetone* sosae
©orite ms added and Hie eolation ms m & m & m &water
bate and tee® filtered*
A white precipitate ms obtained
on adding water to the clear filtrate*
t h is precipitate
me filtered off ana dried* it ©sited at
w m
It
eesioladed teat teis substance « s net tee deaired
a»6» dt
bemamide because of the ease wite which
earhe** dioxide ma twlftcl when it was boiled wite water
and bee&oa© it failed to show annealer when ferric
efolarldt
w ag
added to an aXeo&elie
probablsf p-phei^X#w**di-»«rtemte.
so l
of
it.
It is.
m
Phlaroglooiaoi and W m
Ttoto appar&fctas mo fete m m as ttet wood la
rnx^rimntm
tte
tXmk
the X® e*e« Soghlet
Um foXX-owlx^ mixture s 8#?8
(0*0635 mole) of or®% ?*t gpm (0*063? msls> of aahydro&o
ana 12 5 gram# C0*0S2 mole) of
*
finely powdered faoed sloo chloride*
veiy soon after
tte fX&efc tea teea pat in the m i ® teth the cantents
te § o » to foam w i y w i ^ r o s o l y &»d t e o r o i ©rang© l a c o lo r*
U s e fonun p r a c t i c a l l y
m im te a
fete m s #
mm
fille d
tt*
flita k *
A t Us® t e a
o f IS
t o o © t i f f f o r m o to r s t i r r i n g a n d t e a
tetco&ift d&r& red In color*
After teat lag at 1B&Xa&^O
l&r 4 Umm the mm® in tte flask mm traraieh ®mng®
and w i | .porous*
Sovoatjf five c*c* of m ter mo added to Um
flask which hreighth about Um tw rm tlm of a hrowaieh
orange -i$m$mmim which m e eligh ily acid to 11 trams.
Seven and ®i» t e lf c*c* of 6 II hydrochloric acid m s
added mm the etu^meiofi was then f i l tered and washed
with 6$ o*o* of water containing 3 drop# of 6 H hydro-*
chloric acid#
fte
residue
mm
tning
©b
the
filte r
per m s dried and welifted §*S ippojao* Tnis res 1b
lik e
«eterial mm faced to te eolubAe only i» pyridine*
tdsnUf table product ma o&SaiwS.
‘pa­
II®
80
thojsy S m m m
and Urea
I^p&mtiot* of lieta-Bi-M#tb&Hy leim#B©
fifty t l m
$$m m
(0*6 w le) of resoroinol ana
$& grew (1*0 sole) of potassium hydroxide m u dissolved
in 38$ £•<&* of mier#
Oae half of this solution m s
to 0»10% 1b a one 11tor flask and stirred wall
while 80 o*«» (0*8 solo) of di iimtliyl sulfate mis
talcing one half lieur for this addition*
fti# flask was
tested Is a tillin g water bath for am iaalf hoar and
ttea the reminder of the sodlra reaerctocOate solution
ms added* taking ton nlnofcos for this addition*
The
solution. ms reflated over a direct flans for 18 Shouts
and then allowed to eosl*
T h u upper layer ms separated from the lower
aqtmous layer which was extracted wits2 b & n m m *
T h u up­
per layer and the teasene oxtract! os wore united and
with 10%sediu© Sqydrmlde solution* than with
water* after which the h u m s u m solution m® dried over
m lc im
chloride*
.after the tems.se had h u m distilled
off the fraction belling at SXWBid^C
w * ® i * m U i & x p harness*
collected m
T h i u m terial was seed In the
fe ll wing experiment*
tte apparatus was the sanse as that ossd in
the remrei»el-tirea experiment*
im 150 e.e* lexklet
flask eosfteiaed tte following mixture * ?*S g p w m (0 *1 2 $
ml#) of urea* 20 e*o* (0*153 mole of ja-di-setho^ teaseat and 8S grass (0*284 sole) of finely powdered fused
m
z im
olilQFid&* A i i m r
at. 32S-1320 fw IS h o \ x t n
tlst 30 e*e* mf omH nathra? beaaw was pmeUeally a ll
tolio&fciiag t o t m rtaetioB tm& to e s plaet.
91
itett&ttm of tet Ml%m£pmn& Constituent
tb tou m and
ftm
%tm
mo tea mm mb teat used i n
z m im X e ^ # rte a » i*
Tim ISO c*e* S s a & te t
ilMBk c o n t a i n e d Urn t®lb3®l'&$
m lM ) o f
I S g rm m Co*lSS m l® ) o f m s m x s i m l
m d WS ,$ m m
cfeloridt*
9 . S $gemm (0 * 1 3 $
(0*134 mote) a t t u r n i p poodsrad t a m d sine
a ©tear gi* m n liquid r n X t was abt&lxiftd w h o m
%$m fX&sk «
im r n r m ®
i n tea sulfuric acid tete main­
tained at 2 M * * X SsPg* Sfew aslt fmatrii slightly ai Uie
« % » aaS b & m m im*m$? d y e in g te a 4 Ismir M a t i n g p e rio d #
Up0i3 cooling a dark
iarossa m l 14 m& 6btaln*d
wbldk coateiood approidUa&tely B graiaa of tinaiannl¥©d
sine chloride*
$ & ® m ma a® odor au.i;ssting tee evolu­
tion ©* sulfur cortalniiig eati^nmSs*
\ » hundred &ad fifty -sue* of mter
ms
a&ted tfMreupon a yellowish solution wan obtained which
contained a slight g@te.ii&ous precipitate*
reacted acid t* Xitessa*
solution
Fifteen c*c* af S II hydrochloric
acid mm a&M. which brought about tea® forma tioa s ! a
•lightly auFty dark ycddiflfri&rom solution which gave off
ai> odor of toytosgsa
after atendlag a few <!sy&
this octetio» m© filtered m i d te# residue regaining on
tes filte r pag?er ms msktd w i itfltfeS
' -vE
*&
!*xj
Ct O
'i-
tailing 3 drops of • 1 lydrochioric acid*
of
On eiimpcsratla©
fix I r a t e a considerable amount of tjaKcmcfcod re­
store teol was obtained*
TM d*y residue frs© above otiouoted
92
'%m am %pm ®!sie!s w s eomg&aedl
of cliear 11^%**
gm m &y*t&2&* tJpan ^ualyala fchem e**ratal& m m
%&
aulfu#* n
i t e ^ r iw * ana sine*
M iltsirsi px*Mm% wm obtaix&g t? m fc&is rmetioo*
03
JMiqrl Wm
Heeereinel
ftupum Uoft o f 1 - Hit&orl* ** Mmt&l W m 41
IIfty nine graijs (1.0 mXe} ef aoabiald# ma
dtemlved £& 80 gram (O.f etcAe) ef bmmlm in & em lite r
fleet*
ila© fi&sfe w j thorn iK&trmti in am lee~mber belli
M3 a
ee&tm J^p&mide moieties was &aa*3 im gmH
porticos is tbe eoM red mls%lm umfeil i t ternae y@iiow#
a® ©elation m e them mm&& gently on a bet mber belli
ana th® M3 i ties of the 10®
mm @mMwm$
im i » U portion* u n til the eolation wesM me- loader' betsm
r#s am e&aaaiai&t $be a3mr isia iim me
e» a
teik M t « |ie i tte B»»b&iiyX# Jg*««eeiyi erm eryeiat*
Use# m%
IM* material me reeegretalMeei tmm m ter
mm b&4 a »Xtlmg poitai o f 180%.
» * » « . « « ,w
tm SNaetIsyX, l^ eeeiyl urea prepared afeev* m s
dimelved im tbe leaet poa*t&2* aansaifc of eemmstrated aitrie aeld» fbie eelmtieo me belled for a fee isimbes and
-ffimm-mmlM v&mmw&m mm wea mitral© evyatailimd out.
fitoe eeletim mu le t etaae w e a ls # im'mi
bath
to eeo&iet* t&» eryemllleiaig of tt»e arm nitrate amd then
i t m e filtered bhreisgfe ©©beats** fli# filtr a te m e ag£ttr&l~
lm&- mlUi *ry barlm cerb®»tef «mpMmted os a hei mber
toetbv «»S 3rie3 ever eemoemtratsa eulfm ie eeid in a mourn
3e«ai^t«r* Xbla <3ry m terial ms «xbraet*a with abeelute
m
m & a g a in to i to
a lc o iio l,
gar*
I n s m c w m to m to m *
Tha wMt# '$py$b&Xllm* m t^ r! m i tom pmpm®&
t0 X%®€ m% 9®»10g^C* a& i$ imperial m
use#
Mm toh*
in
Im tog sxp&pta&afc,
T m - approtw m m
m e m m to to to iu o ll
mgnplMvsb*
to o m m
* £ to m
to
fch&fc ® m @ t o tbs
e*©» tafclefc £XssIk
O a m fe a lm S t a t £ & X lm ix i&
{ 0 * & 8 5 m a te )
&£ mrtftpl » » , 15 $swm {Q*2M «»X»}
s^sarata&l @ui
$$ |p?a®s&. fOblM sao&s) af t l m t y p m i 3 e r ® &
stas ^asrld#»
3fem Ui# flasJi, ms tawrosg la tte ^stlte*i® ael$ m t M » te*
ta & o s f t a t ls g K U @ ^ £ to n
pM m m m m
Q bm > rw & w m
Mm m m
to ttmfc m isb m w i i to Mm -m m ^m rnm lm l a^r& asm i#
ia rio g
'Wmm mg£ £&m&3
to s t t t o m
I B m i m t o n & £ t o n 4 soar h m % t o g p® **l® & M m t n g * »
m % w m ic k % im
1% w m
a c lm p
W$n®
Im m m m l ,U m m &&fcsl£»*& w fric ft
m c m t o f m & t& m X m ® m im
g i mmm
a m r f s lljb t
© J 4 la r i4 a #
®m tosti&to 'm& titis$r e*&* of mfcor m s &cidod
to &h$ £lm k
to im 4
a gr^iaii whlto nmp&mlm mm to*
wMeli
m m to &
a i ig & W t f m i &
IB «»s» &£ $ 3 lipir4Oli.l.0rle
to m m
W c m m lto
IS
&i«i» fllfttiwd &jd$
mmi
m*&
ta m rd
lltw & m
m n to&®4 Urn ^mimm-im
a w a a s s tf
|is m i # f
!fho
fl»
S.Q g m m *
10
a* e* 5#lsisg
in ®mm%+
sit& 1^6 cue* of wsiler
sonia iniag $ ttra-gB of $ B 2*^oot*:i&rie acid*
r ^ s ito -
:-$bm .
*&o dri©4
f h to oi^r resid u a saa #uasj«u3^
far oaeli grass of re a id ^ ,
MatM lo boiling
tm U
on U» p®@®p m s i*tS-iiriit€ to tlss b©afe&r aM
m
ag&fa t e lM4 witti tte m m ®mm% of watop and fii&orod
ImU
fte rm tS m mm w ln a v im to ilin g m tor, using
£ s»o» for ©act grim of tte original dry res Idas*
stem
tiriod a t XlflPC i t w tgted 1*1 &ipsm» fte tm hot filtr a te s
vst* uatod and alXsssd te cooi for Maplst*
tin*** fte yiol# of orystal* usaa $*#1 @ ns«
th is notorial
m # ro«$yst&lXis«tii fro© i t l t f a$t& molted at ssiM M ^
w M ofc f o
Hi©
m
i
as
tls o m o l t i n g p o i n t f u r j f i ^ t e s o s ^ l a a t d s *
Wmm a mlsad molting: point wm taken Witt saw of thim
m isri& l ani s o » ,£ -imsoro^lamXa®, tters mm m Immrtng
o f tbs melting point*
3te m o r ta l mm. titerofbr* oo&elisMl
to £*©^-rtaoreylwld©#
28*
of tfet tteomtt&sl*
1!3as yteld from tliia roae&los* w
96
llte ir e a aaa Hesareirel
of Urea Witete
Fifty grama of area waa dissolved in XOO e*c*
of water, th is solution w a aaxromlM with aa ice-salt
hath m & 65 e*c, of co&esiifcrated Bitrio acid ms added
slowly w ith a tirrls tg so th a t the taaporaturo did r e t r is e
o
above 10 C* Xh© p-reelpitated urea nitrate ms filtered
off with sootlew aaa washed twice with ©old 1-1 nitric
'Mi
wWW
k4W
OW
It ms then dried in a vacmwt dess lowtor and used
in the &U.ewi$g preparation*
Preparation of fiferourea^
Fifty ip^aas of carefully dried urea B ite te­
rns added in snail portions with stirring to 76 e.c* of
concentrated sulfuric acid, so that the temperature sever
rose above 0- C, After the last portion, ms added the
m M nillqr aisiare was allowed to stai^ for ore mimtte
aM
ms then poared into $50 c, c* of ice m s water,
fhe
fire white precipitate which, formed las filtered off by
jre&re of suction and dmtred as dry as possible,
Without
washing the resides i t wan ismdiately dissolved, while
s t i l l m % f In boiling alcohol,
the alcohol solution ms
filtered while hot end then chilled i n ice-mier whereupon
yiw nitre urea erysh&Xlired out in pearly leaves which
whma dried salted at 155-156-"C* this material ms used
i n the following experiment,
the apparatus used consisted of a three-reeked
m
§00
c.e. m m & bottom flask.
a 3do° thermometer passed
**• «C the aid® a**k» while ill® other iM# m c k
is a la$ c*e, t^teimyer
m m
m short piece o f rubber tubing having
of
20
fla s k
fy t m a m of
an inside diaxoeber
xn»m»« D m middle neck m m equipped with a m r c w y
Mai«d stirrer and. a calcium chloride dicing tub© which
ms open to tii® &teospk®i*s*
thirty graras (0.272 role) of resoreinol and
2§ g p m m CO.1S4 malt) of finely powdered fused! «im
m© added I® the rotud bottom flask.
tenth
126
chloride
Thirteen and one
(0.126 m It) of nitre urea me placed in the
e.e. Srleimyer flask.
D m sulfuric acid hath mix*-
taiaad at ISO 1% « a then brought around the round hot-*
tern fl&sk whereopen the resorcixiol melted.
The stirrer
was started and the first wry small portion (never more
than 0.26 gram at a tine) of nitre tarn ms added.
This
naueed the temperature within the flask to rise aomewb&t.
The addition of the nltro urea was coisplets at the end of
one and oat half hours. The additions of th© nitre urea
were muM in such a manner that the temperature inside
the flask, never rose above 12$%*
M
©father addition
ms i&nde until the testers tore within the flask had £ ax­
iom feelow 121%. After each addition there was eonsiderable
foaming. At the end of the 4 how heating period Hi© malt
dark hrcm and oont&ined a vary slight amount of un~
dissolved z i n c chi wide.
solid on ceelin©.
The melt did not become completely
O n treatment o f this product in the usual
m
w m m r 4»8B grama of material
w&tor extract*
from to® hot
this mtori&X tatltad at 22S~229aC wMdi
is toe ©aw as that for y#
4 sim d molt­
ing point of -sow of tola motorial wlto mmm yB^mmroyb'
Mia#
m d ^ g m m lm of tho molting point# t&© m t#rial mo ttaroforo oomelaM to to ^-rosor^rlmia©# fh@
yiolA from tnift reaction mo 22#
of too too»ro#io&l#
m
PJmyl
and ifceorcirol
ipreparaiioa of Phssyl
A solution of €$ gram* (0*$ ncl®? of aniline
hydrochloride aM 33U? gra» (Cw$2$ m M ) of urea in
SfiO e#o* of water wan boiled ie a mo c*c* fl&sfe. equipped
will* a refli&e condenser* After one hoar of heating crys~
tala began to asperate. At the m& of &» and am half
he are the mlxtsm ms cooled and the crystals which had
separated were filtered with aaetlon and then washed with
o*c* of bailing water* This hot filtra te m then
ehillca wharewpea phsnyl area crystallised oat* me f i l ­
tered o ff and mehed with a li t t le cels iit t r , The fir s t
filtrate me a#tia boiled far one and one half hours asf
100
the above
repeated, The above operations were
repeated at i l l a third tine* The mother liquor was
finally evaporated to one half its original volume aafi
an' additional crop of ptienyX urea waa obtained.
The phenyl urea ms purified by dissolving it
in the least passible amount of boiling water, mrlta
ms added and the- aoletiom ms boiled for a t m
and them filtered,
minutes
then tbs filtrate first began, to cool
a flocguleat precipitate of oarhoiilli<le ms deposited
which ms filtered off while the solution ms s t ill hot*
The filtrate on further cooling yielded long white
asedlea of phenyl or#a Ml&ing at 14?#C* This material
ms seed is the fallowing experiMet,
100
the
fcM
m s Um m m m that used la
$h* ISO e»e* soscblet
*M following m&xtmmt 17*0 gpmm (G*X25
m l»} of phenol i3X«% 10
<0*134 »X®> of rtaereiool
an® 2S p w Co*iB4 ®0lt ) of fim'Jzr
s im
chloride*
ffein aixtore «m te&lta at X2S~X32% for 4
hoere* 4 clew green IXfsld n elt mo obtained ehich
foaw40 coxseider&hly during the fir s t f i f teas mimtaa and
continue# to I m sligh tly thre«tf***t tbo heating period*
wmm %M ml% mm cooled a clear amter so il# mm ob­
tained which ooototnoO a mrgr slig h t « n m l of tmdissoXssg
%%m chloride* the mX% was stirred thresghoal the beat­
ing. period*
tip* hmtireg as# fifty «•«• of m tsr ms sa#ed
to too flaeOc titeexwipaB a thieh croon colored ouaponoloa
^sts obtained whldb resete# slightly teste towards Xitene*
ite r l& e* o* o f « lorOrooblorio <uei& m# a#ae# the one-
pension tecsse tan colored aw# decreased seaoteat ta
aanoa»t» ffcie ewponeioa m filter## and «® W with 125
0*o* of water oo»tai»iing &drop# of 6 1 hydrochloric mM*
The residue lo ft o» tbo filte r paper hOmkq dried weighed
X6*S gran*
Mm
of ttite residue mo toiled, with
100 e*c* of water am? filtered* ftere remise# on the
filte r paper a arms insoluble residue o f 1* & grams while
the filtr a te yielded an o il which pmm€ to he aniline*
$te» 5 gnasae of the 16*5
sasspls me dis­
solved W ttereagSMy etekteg with 125 e*e* of alcohol and
IjflflL
tutors#* tor# rraalms
a vsry ®Xi#t roatos.
to # a le to l m l m k i m m m , ponrsi into «u«r Bhsrsuposi
1*6 p i i
0 'f
t o f il t o t * again tm& m strssg odor at
tors# 0 ft.
aMIim.
toolttbXo mterlai ssp&r&t&d aud w a rn t ii-
$& fmdoei t o t oomid Imvt beosi t o a##lr#$
IS-tosiyl, 2-4 €1 l^ar©^ hmmmM®
m&UM)
mi&
obt&tii®# tost s i t o r t o a^^tasia or ale©~
bolle ftlirat##*
$ft* tvo 1.6 p w sattpiaa a t jmtarlaX Imoltibl#
Ib mtsr wart-' esnfeiii*# ana dtoolired t» aletol* bollsi
rnim m rtt# ami flltsr sd . t o alcoholic flltr a t# y l i M
long will to assAls* ttiicli ml%®& a t 23?-2BS^C. tors#
srsrmt&ls wrt oocaoistsly i m m h M m $ » boilt&jg mtsr*
I j f i W . B ito g tii analysis
24 .2 6 0*0* - 14.00 C.C.
A
t o following rosn lt.
1 0 .©S G*€.,
10.fS e .e . - 0.20 e.#« tfta»k
10. ?S ©.s.
10.fi c.c* ®f O.02404 ¥ sulftirle acid » » rsqolrsd to boot r a l t o tb s aiwosttm ssolwo# torn a 0 . 087 $ gram o&npls*
log ftetor
v. *»•
t8 M
- 10
Co*log g i «
fhia product » s eoMldsrsd to be oarbBnlliSs
toch m l to at 23S - 239*0 and eaat&las 13.23$ Bitogon.
lag
and Jfeeoreiiial
Im fera tto of Cyona&ide ®
thirty eight 0m m (0#.a m M ) of fin ely
fOP$#r#d tbiotsNKL m s 3§ix#d iaa a §00 e.e . tolc& mXI#df
wide Mtttood grgonenyer fSaito n i l 300 c.e* of other*
the. mercuric « t i# necessary for deeulAirtsiaig the tote*
i i w efee groperod by adding Hi# neoeeeery aaw st of eedlun
i^roki&e eolation to a te t water eolytlon o t 2m ^rnm of
aereuric eiil&rfde,
The well waelioi Mreorle oxide paste
mtet not b# allowed to dry aM should I» need soon after
i t Is prepared* in order that tit' iw tir le oxide ani thio­
urea mm b® m i l nlxei a# 000# as poeeibie several glass,
■erb&e* were plaoti in to# fXMtu tea c*e* of 00tor m®
M i and thou to# fir s t m m ll portion of saeretarlo oxide
past®.
In order to pawent the otoor from filin g * &m
to Hi# heat of to# reaction* to# fleaJc m i planed to an
iea-wattr hath, fbe eontente of too ftoofic were tosr easily
agitated and' ®m%®& before %mh mm addition of m m trlo
oxide* After a eeneider&ble aaotmt of to# iserearie oxide
past# had boon added tot refection » s tosto-d tor eo&pletien
bjr pip# tttog out a drop of too w&mm mlu% im tmm be­
neath to# other layer* th is drop of exgneoftie solution was
deposit## on a plooo o f filte r paper Jti&i previously mois­
tened with an amnenSaeal eelntien of silver nitrate, A
black spot w ill b® obtained If there is s t i l l anrt&ctod
thiourea progent,
fbe addition 0 f m m m ic oxide £0 con­
tinued u ntil to# spot toot etwee only to# bright y e llm
103
color of sliver eyaossiide, The mercuric sulfide Is f i l ­
tered s ff lagr suction and meshed several tines with ©iber,
flit ether layer in Hit filtra te is separated from the
sn ail sqtMfeo* layer* lbs latter then being extracted several
tinea with ether# The ether eolatlc» m s dried over &»~
hydros* eodiun sulfate and before eexmntrabing i t to *
w a ll voluue by meat® d istilla tio n one drop of acetic
acid m s added to decrease the polynKriaa.tloo of
te dieyaadiamide wMeli la insoluble in etl»er and separates
oat in em u saessit dnria;: tbe eoooexitrcttiosa Tbs concen­
trated ether solution m s filtered free of dldyssdtsnide
and then pieced in a m@n« dess tester, the yield of white
crystallise cyanamlde mo IS - 1? gram and it melted at
4#-4§®Ci This notarial mm used in the following ex.perfaenb#
TM apparatus mo the ssutse as that used in
Urn
experlnost,
The ISO e»e, soadilet
fla sk contained Has follow ing s ix tu re t
6*3 gras® (0,123
nolo) o f cyans® ide* IS grans (0,136 xaole) of resore ixiol
and 3S p i@ <0, 1B4 mole) of fin ely pondered fused oine
ch lo rid e,
h ears,
th is m ixture » i heated a t 128-132% fo r four
Boring the f i r s t IS ninotee a very vigeraoe re ­
a c tio n took place ftceeapaaied with coaeider&hle foanlag*
A very stiff dark tar-like product was obtained which com­
p le te ly dissolved when suspended in e a te r and s lig h tly
a c id ifie d ,
A second experiment m s made using the earn
s ta rtin g n a te ria le heated a t 103-110° fo r 4 hours,
The
n^mt negative results were obtained - m material Identifi­
able as J3-resorcylaiaide -mm obtained.
104
Ctyamrl® m u
and
tli® apparato® ma tk® f i n m Usafc u®»6 in tin®
«n a raperlmiii*
fM X® c*e« sox&l&t flask
contain®# ttt* following Mxtiirot 5*4 gram (0*042 ml*}
« f &i#Cydtroii& oy&iwie aeldf IS p m
(0*136 ml®) of r®-
mrniitoX a rt 26 g w
(0*104 m l® ) of fiatX r p®wd*r®d
fasfcd aim ofcl&rld®*
Unis srixiar® m $ m&tad a t 12B«X320
for 4 b*or*» tin® cyamrlc m M mold mb dim olw 1® t&«
rmmoiiMkl a©a tJm m lt tmmm dark porpl® in color* tin®
m m color is d*wl&g»*d when n m a iia i and aim ablorida
a rt baatod tagfttiifr viH m tt 4h® addition o f c^raiitsrie a d d .
Zhi® mggmt* that liiU ® or
terl takra p r i In aijgr m m tlm *
rm efclm intolar® to.
w m
o f tls® opsnri® acrid
Upon ire& m tat o f tfe®
aaunl zanimr Urn csriyanric acrid
marly q m m b i b ^ b i m ^ m m m m & § lowing U m b m
action iwd®tog II bad taken place*
re­
Tm apparatus m* the mom m that used la
the
^grn&imm* fto X®0 «*o* doschlet
ftesk #oatoia@*3 the following: i k i « 9 s 10*14 gr«® (0*X25
mels) of p d te ^ l* eys^tt* X0 tfprn* {®*\M ml®} &t. ra&ni 2# grans (0*134 Stele)
finely >powdered
ftoe# &lae chloride* 1M# sslEtijra m s n a M a t 1^2X$i% for 4 haarsw %ii hue flask a s first %mm$*m4
%m the hot acid toth a Xi^it Wmu pwty n&aa tuns eto
tala## nhioli foamed considerably sad to ea» quit® dark
a t the w rp edge* After ttftmma niaataa the brom pasty
ms* tooam too stiff fer motor stirring ai& tto foaiaing
to# sXaotomi eoissltemhly* at the end of tori^ mlmtes
tto siiataFd tod towns a# tori that i t could not to stirred
fggp hsui* At the as# of tot heating purled too reaction
mixture mm
hard* tut&m la tele** &ad eozitoiimd a w
mrsaete* aloe chloride*
Qto huadre# m$& f if t y c* c« o f rntor m s adds#
to tto cools# content* of the flask whertiipoii a 'thick ormm
colored ampomioa mm obtain®# which react©# slightly
basic tomr# litmus*
X*toa 16 e*c* of 6 $ hy&r tohloric
acid mo adds# to the suspension there m s a slig h t effer­
vescence am# the soopcttsieo decrease# somotot la amount*
The suspension « s filtered anS rn tsd with la s c.e* of
m to r containing $ drop® of 6 I hydrochloric acid leaving
a residue of 3*8 g r « s on the filte r when dried*
b a sis o f th is
So tot
0paia sample the fellaering re su lts wore
im
on treatment im Urn tt&ml
% 3*33
t®&u i»oXii&it in 'bo111%' water and S*X $pmm of m tertel
m s csryatallied fro® tte not m te? ox&raotion*
T&l#
wterlaX mo rooryoteXXiMfi firoa m ter &©S ifeuafi is tew
a
point i f S2SW88iS$C willed in teo
for j £ l a a £ £ t *
ssens
as tte t
*tea %aiso$ » lt t e g point m s
teten n ite »m» of teste m ter t e l anJ «om ,5 *roacr=QTX*
arntio te tro m # m ^gwoftoXoa o f tea m ltiv g point* tm
m te r te l » $
eo&elote# te S» /?-r©aow|te0&l&*f
soft Hit jte l# t a i tel# i*motion was 33* 6® af the
tk®»r6tt<K»i,
*07
IfeByl Isocyanate and aesorelneX
Tte apparatus ms the same as that aaed In
tte w p m ~ m m P Q i m l experlae&t,
The I S O e*c* teshlet
flask eei*fc&i©ea fch® folXowiosg m ixtum t
14*9 g w
(0*125
stole) of pteogrl isocyanate, X5 gr«@ (0,136 mole) of rosorcim l ami 25 grams (0*334 mole) o f finely pondered- fused
sine chloride,
liaess this mixture wm teaiad at 138*132^0
for 4 tears, moderate fearning oooaro<3, the s&lt became
reddish brown and a ll of the sine ebiortd* S iesolved*
$te reddish team solid obtained on coding was found is
bo losoXoblo in water*
It « i dissolved Ia a&etone and
poured late ISO c»c» of m t m r containing M c * e, of 6 H
!$rdroehXorlc acid*
This solution stood ovoroigfht and a s
then h m %
#6 to telling ana filtered*.
4 osssidombla Mount
of gm^y red residue r«®aM on the filter paper*
th is
resides ms dissolved in telling alcohol^ aecoleriaed with
mrits and filtered*
Tbs coolod filtrate yielded a large
©s*op of white ciysi&ls which melted at
bo the dl-tjtes^l^arethane of reooreinol*
fisb lo product m s obtained*
and proved to
lb otter Menti-
xos
W m um m
assd Kesorelsnl
f b m separates ms U m
m m
m
that used 1b
fh@ ISO c*e* aoxfclnt
tee
flask contained U m ft Hourlag mixtore# XX*X
» Ie ) of ore team , I S
(0*136
(0*136 nolo) of m m t ' d m l
ami as gpnas CO*134 » le ) of finely powdered sirie chloric?®*
T h i m mixture m » be&ted i m
4 hoar® at
tho ot»c eltXoride diseslved but m
1^X32%*
&1X of
t e a m i n g secured.
On
eooXlnyg, the melt 610 not M c m m completely solid and vat
oXmup red in color#
Ono hundred and fifty e*c* of mfcor w
sddod
which resulted 1b te@ fosmtlen of a ro&ttdh farosaa Xlqold
with a B l i g lit gelatinous precipitate*
acted acid isw d litmus*
ft*is solution re-
^ k m n 15 e*c# of 6 II hydrochloric
acid ms added tea solution became dark re6»fcrasii and con­
tained eniy a slight « i « l of insoluble imterl&X* This
solution ted a pleasant odor teat resembled teat Character­
istic of resoreinoX ethers*
The insoluble » teria l «&s filtered off, washed
and dried*
The filtrate ms emporated on a mter Sate and
a tacge amount of ttnreacted reeorcinol ms crystall 1sod out
from it*
the insoluble residue ro&ghed one tenth of a grai&j
ft »»« dissolved 1st a mall amount of Soiling water decolor­
ised wite norite and filtered*
<** cooling the filtrate,
o
fie# obits needles were obtained which m lted at 227-220 C*
Wmn m m
of tela material w
melted with m m ,ff-r©8orcyl-
amid® there was no depression of the melting point*
the
ms
Tim
cosiclnclad Is tm J$>-msore^laiaide*
% this rsaeti:® mm toss tteaa 0.5% $f th$
aai Jtieoorcinoi
appara&uo m i a U m m m
U r n resorcinol~ure& u z ^ r i m m U
m
that used in
T im i m
e*e« saxhlet
flank aonfcalned U m following fixture i 7 A $ p & m (0*125
aolo) of acntaQido, X$ g w
(0*13© m l m ) of m m m l n u l
and 25 grasao (QwX&4:mXt) of fis#% powdered fmatd zinc
e&Xorido* Shis fttgturo ms h m t m i at 2JSS*X3S°C for 4
fcotsrs* At first a clear thito »Xt « i obtained which
almi^ed to ,gpt®% iboi* aabcr and f iiaX% dark rod# All
of U m z i m
chlorlife bad dissolwd by fch® end of the first
hoar without producing a^f noticeable feasting#
£k> cool*
lag the melt became m r * / viscous bat did not solidify*
Qae h m i i m i and t i t t y e.e. o t water m u added
ffhereapaa a nurigr brownish saltation m u obtained which
m u cted acid to lit®#*
said mo added
Fifteen e*e* of I I hydrochloric
caused U m solution to clear ao®t~
fM i and become dark brown* T im . solution ms U m m f i l ­
tered leaving a llgfet brown residue of am t®.nUk of a
grans* <bt swaporation of U m filtrate a considerable amount
of transacted resopeinel ms obtained*
' i i i the on® tenth
gram of residue wan boiled with &cm 11 amount of » is r it
practioaXi^ a ll remained uadioaelwed, however, the solution
filtered ami ferric chloride added to the filtrate, no
color dewloped*
CkiMlissiens
I ll
avnievy and Conclusions
1* HfflMm» S 0r@i»X and urea are allowed to re­
act in the ppeseaee o f su&ydroui* sine chloride, a crystallin e product may tie isolated from the reaction mixture*
This product km tinea d o w fey analysis and structural in­
vestigation &® tie ^*rewor«ylamide«
0* I t was found that ,£ Hweornylamtde is formed
in the largest yield when on* molt of urea and out stole of
MeoreineX am allw ed to react fit the presence of 3 'm \m
of fused aloe chloride for four hoars* Under these condi­
tions the yield Is *$0.8% of the theoretical.
3*. I t was found that neither Um aao of an ex­
cess! of iwsere tael and prolonged stirrin g ©or the addition
of stee s&leride in wnall amounts bed any effect on the
yield o f
ids. Wm yl@M was m% appreciably
increased fey raisin® the teE^erature fro© 130% to 130%
nor h j increasing the reaction tits® above four horn®.
The
ttae of an excess of area had a detrimental effect on the
yield of ^-reaeroyXaiaide*
4.
Ho
•resef^lam lde m e obtained when anhy­
drous aluminum chloride* mieio® chloride or ctiprie sulphate
were used a® condensing agents in place of sine chloride.
5# I t ma not found possible to replace resoreinol
fey phenolf o&teetiol, feydroqulnoxw, phloroglucinol sr reeeretael dine'thylether*
6* The egperiisBist&l evidence indicates that the
reaction proeeeds via cyanic acid as an in terca la te,
it
Ha
m s m % poeeifcl© to aeeiongtr&te conclusively ttetoer
qranto ac&S eemsSamea directly with reeercinol is the
^•position or whether toart ia interned iate form i Ion
of &earhamie acid eeier followed hgr ire&rraaga«ah to
-reiiarejtaside*
Ih* failure of the dtoe toy1 ether of
reeareinol to endorse
o n with urea
tends
to
support tit# latter hgr^etiieeia*
?#
for area
S ie f o l l w l e g Gm&Qm&B were su b stitu ted
toe reaction with reooreinoli mttoyit«m#
phexifloresiy nltrmxrea, petaasluai eyaaate, urethane* phenyl
tgocg^aftate, Cymric acid, cyana«i&ef aeeteialde anfl thto~
urea*
Of these, only isrtoyXisr#% aitroswa., potaeeiiaa
cgraaato ana orethan* condensed*
la each case
amide was the reaction product* It is apparent that *anfler
toe conditions employed in this investigation, H-alisyX
mad B-aryl beimssiaes emmet he prepared.
BibXi0grmpi^
313
8il&i$gF»p&gr
2* Mvafesusi «fl hm U - - • - 3tr»SH M 9
(2880)
%
U
B
l t M
u
w
i
*
8
0
f c
a
r t *
-
-
•
•
B
a* fteutftt - - - - - - - 4*
e
r *
| i
X
7 S 4
8ir*aa«70
B
B
1 )
(38GNH)
mtmmrnrn - 8»r*& **48t X766 C1E»| $ 2?S <2B»)§
ffitt 310 (1309)
$* H a lil, id lin g as# M ju m - #* Chen* See* (2$$3) 2793
H*
7*
am! fiest&psnvy - «F* Aa»* CiMmw 3SS*
O s tte r m n
-
-
-
* -
- A n m lM 2 3
m& smmo^m ~ -
S *
% Karrer -
-
(.1 3 8 8 )
Btr*jg| 1183
(1360)
~ ~ - S@lf, Chlfib AOto. S 39 <1919)
IS* fiCNMMH -
- .
n*
.
Hftuban -
ISIS <1914)
-
•
- -
(2913)
-
<2886}
atp*a p a8y3
28* Staifem aiBft Fiseber
-
23* llmseh -
-
* -
-
Bar* fife 468
(132?)
14*
Fise&sr an i I W i ~
~ -
*
Bar* €gj 611
C lil? )
is*
B&ssr aii# ssMMs^ -
•
• *%r@ti*t%aw 2® 83 (1982) s
20* Kerrer m i Mrim, -
-
-Belv*C&lia*«t&* § 203 (1081)
- -
•
~ B tr*J| 2X22
4 * « A k Oi»«* |g 3 39 (1939)
c*a* tfnasM
<193x5
2?* tta&sfoite ~ - Ssl»aept*»Tetislci* 3&ip*fMtir* 1st* Series
Hi i §2
<203®) c*a* ,it 7m b
IB.
Xamti&lta -
-
it.
Orits
* 3ei*3^pts*<
Misim
-
m m
SeUBftpt^XttMso Xap*9iilv* 1 st aeries
88
mt
J § 221
iwm
<2929)
c X a? aoa?
a sm )
1st* Series
C* A * j & m
20*
Ifrnsstiitft
* - 0 e i * Be s t s *2 »s p*Ua i v*
22*
tfem feits - * scl*Eepta* tebsfefi X$ip*tJi*iif*
C X 930)
le t Series
IS 229 (1929} C*A
* Si S3 (1930)
1 s t*
series
SIS <2320) 0*-« 242440 USSO)
22.
Xea&sfcita -
-
3ei.Ke:jpts.Tot»faj Xrup.liniv, 1 s t S e rie s
2 | 205 (1335) C.A. 29 7316 (1936)
23.
Bsrsche and Mimuann - Ber.SgB 2043 (1929) | C.A.2£ 98 (1930)
24.
Soroche, '■■alter and A’ieusinn - a sr.688 1360 (1329),
0. . . a 4681 0&29)
26,
mavOk aaS Stephen - J.C te a . Sos. 2g7 1633 <1938)1
26,
Leuokort
CtXTlli 2946
-
J.p raict- Ghem. J J (2 )
Sna** -
-
28.
(W ise -
-
20.
a iiie te r
- - - - -
30
,
-
-
-
(1925)
-
Bex*, J»
-
2429
301 (1390)
(1385)
- ahs, eb ia. phya. 8 M 378 (1908);
O.A. 3“424 (1909)
Her, f£ ® 4
(1904)
Mm&mm 4 M am - J.Aia, Shea, See. J£ 1744 (1923)
mr.63M 1743(1929)
31,
terseis© and Mieiaann-
32,
Earr®r and M ias -
33,
3sa and M t e r j i
36,
Shah and isehfcs -
35.
" ie h le r and
36.
Shoesraith and Haldane - «T. Q msss. Sea. Jgg
37.
Cites - Qr&Ctea, ter Mt,sta!ntt, art-1 (Ssaetiaas).
CbnpUV, Page® 400-401.
38.
Sana -
.
39.
B srgE sann
& Dasagachat -
.
-
-
^ .In d ia n Cbtia,3ee. 7 S?R (1930):
C.A. g f^ 7 ? 9 (1930)
<T. Indian Q iaa.3fte.13 388 (1936)
C.A. ^ 3 1 9 2 (1936)
-
-
-
-
Bar. 14 2177
Hoteam - - - - - - -
(1381)
113
(1924)
-
a>r. § 2 923
(ISIS)
-
B e r .S a
379
(1919)
40 . Organic Syntheses, Vo1-10, Bags @4
41.
95 (1930)
Beiv.Chias.Aeta 12 554 (192®)j
C.aT J g m 3 (1929)
-
.
C .A . 2£
(1930)
B er.JJ, 2725 (1381)
HateaM* - - - - - - Bex*. 14, 2734 (1881)
43. Bavis and Blanchard - J./ua, Ciwm. Bos. (|j. 1794 (1929)
42.
44 . ftrpais sgrsthsass - Vol. §, page 85 (1323)
45.
f la ts r s ts in and Kung - A. physiol. Cbeis. J>9 143
(1903)
Документ
Категория
Без категории
Просмотров
0
Размер файла
10 079 Кб
Теги
sdewsdweddes
1/--страниц
Пожаловаться на содержимое документа