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FURTHER STUDIES ON THE USE OF HYDROGEN FLUORIDE AS A CONDENSING AGENT

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The P en n sylvan ia S t a t 8 College
The Graduate School
Department o f Cb.eaui.stry
F u rth e r S tu d ie s on tb e Use o f Hydrogen F lu o rid e
As a Condensing Agent
A T h esis
by
H erbert
P assino
Submitted in p a r t i a l f u lf illm e n t
o f th e req.uirem.ents
f o r th e degree o f
Doctor o f Philosophy
A ugust» 1940
TABLE OF CONTENTS
Subject
Page
T i t l e Page
-
Acknowledgment
-
Introduction.
1
H is to r ic a l
4
D iscussion
6
Experimental
19
A* P re p a ra tio n s :
19
Methyl Iodide
19
E th y l Iodide
19
E th y l A cetate
20
Methyl A cetate
20
Phenyl A cetate
20
T e r t i a r y Butyl
C hloride
21
T rim ethyl ethylene
21
Bromo acetone
22
Cycloherene
22
A rsenic Acid
25
Preparation, o f Acetamino D e riv a tiv e s
25
B® R eactio n s w ith Hydrogen F lu o rid e
24
Methyl Alcohol
and Benzene
24
Methyl Alcohol
and Phenol
24
Methyl Alcohol
and Toluene
25
Methyl A cetate
and Toluene
25
(TABLE OB CONTENTS)
Subject
Methyl Io d id e
and Benzene
26
Ethyl Alcohol
and Benzene
26
Ethyl Chlorocarbonate and Benzene
27
D iethyl E ther and Benzene
28
Ethyl Io d id e and Benzene
28
Ethylene and Benzene
29
Ethyl Alcohol
and Phenol
29
Ethyl A-cetat e
and Toluene
30
Phenyl A cetate and Benzene
30
Chiorobenzene and Benzene
31
Diphenyl E ther
31
Table I
32
T rim ethylethylene and T e r tia r y Butyl C hloride
33
T e r t ia r y Butyl Chloride and Cyelohesene
33
Naphthalene and Propylene
34
Phenol and T e r t ia r y Butyl C hloride
35
Acetone and T e r tia r y Butyl Chloride
36
Bromoacetone and Benzene
36
3-Efchylpentane and Tez-tlary Butyl C hloride
37
nAButyl Chloroearhonat e and Benzene
37
P y rid in e and D iethyl Ether
37
P y rid in e and Acetic Anhydride
38
Nitrobenzene and D iethyl E ther
38
Benzene and S u lfu ric .Acid
38
{ TABLE OF CONTENTS)
Sub.i ect
Benzene and Fluorosulfonic Acid
Benzene and S u lfu ric Acid
Cyclopentane and Fluorosulfonic Acid
Cyclopentane and S u lfu ric Acid
N itr ic Acid and Benzene
N itr ic Acid and Benzene
N itric Acid and N itro Benzene
N itr ic Acid and Fyx-idine
Arsenic Acid and Benzene
Arsenic Acid and Toluene
Arsenic Acid and Benzene
Phenylarsonic Aeid
Permanganate Oxidations
Potassium Dichromate Oxidations
Lead Dioxide and Benzene
Summary
Bi bliography
ACSKNOWLEDGaOHT
The a u th o r wishes to
ex p ress h i s g r a titu d e and s in c e r e
thanks t o P r o f e s s o r Joseph H„ Simons s th e d i r e c t o r o f t h i s
stu dy ,
f o r h i s p a tie n c e and guidance throughout i t s
and a ls o th an k s Dr® Sydney A rcher f o r h is
work®
co u rsej
cooperation i n t h i s
1
MJETHER STUDIES ON THE USE OE HYDROGMT FLUORIDE
AS A CONDENSING AGENT
In tro d uction
The use o f Hydrogen flu o rid e as a c a ta ly s t f o r th e a lk y la tio n of
the benzene rin g has been shown by Simons and Archer (1)
o rato ry .
of t h i s la b ­
In subsequent work using th e same c a ta ly st,, o th er sim ila r
re a c tio n s were accomplished, and c e r ta in lim ita tio n s of th e reagent
were found*
The o b je ct o f th e presen t work was to
fu r th e r study the
scope and lim ita tio n s o f th e use of hydrogen flu o rid e as a c a ta ly s t f o r
organic chemical reactions®
It
i s the hop© of th e author t h a t ,
from th e s e and previous r e s u l t s
and also from work to be done in th e fu tu re ,
some li g h t may be shed and
some information gained concerning p o s sib le mechanisms through which
th e se re a c tio n s might occur.
It
should be s ta te d eemphatically th a t no
sound conclusions concerning th e mechanism can be drawn from th e amount
o f data accumulated th u s f a r in th e se condensations u sing anhydrous hy­
drogen flu o rid e ,
and th a t th e author Intends not to p o s tu la te any mech­
anisms, but r a th e r hopes th a t th e r e s u l t s may in time be of some us© in
b uilding the f i n a l tr u e pictur© of what occurs In th e se reactions®
As hydrogen flu o rid e I s a comparatively new reagent fo r organic
chemistry, I t I s necessary to compare i t w ith b e t t e r known reagents®
Comparison w ill be drawn, between th e actio n o f hydrogen flu o rid e and
th e actio n of aluminum ch lo rid e , boron f lu o rid e ,
and s u lf u r ic acid®
These four d if f e r e n t reag en ts cataly ze the same types o f reactio n s and
th e same products are formed in many eases.
Each o f the reagen ts, how-
2
ev er, lias i t s own p e c u l i a r i t i e s and d esp ite tlie f a c t t h a t th ey also
have many s i m i l a r i t i e s such as in th e products formed, th© d e ta ile d
mechanism, of th e actio n may be d if f e r e n t f o r each o f them.
S u lfu ric a c id cataly zes such w ell known re a c tio n s as th e polym­
e r iz a tio n o f o le f in s and th e a lk y la tio n of arom atic and a l ip h a ti c
n u c le i! w ith o le f in s (37)
(38)®
It
is
ex ten siv ely used as a dehydra­
t i n g agent in most commercial and la b o ra to ry n i t r a t i o n s and also may
be used in e ffe c tin g a c y la tio n and r in g clo su res (51) „
hauer (39)
Meyer and Bern-
have found a lso t h a t i t promotes th e a lk y la tio n o f arom atics
w ith alco h o ls.
Aluminum ch lo rid e was shown in 1877 to
be an e x c e lle n t condensing
agent f o r a lk y la tio n s and a c y la tio n s by F rie d e l and C ra fts (4 1 ),
through th e use o f a lk y l and acyl h a lid e s .
(42)
O lefin s are r e a d ily polym­
erized* but a lk y la tio n w ith o le f in s must have hydrogen c h lo rid e p resen t
to be e f f e c tiv e .
(40)
N itr a tio n s have been catalyzed by aluminum ch lo rid e
and a l ip h a ti c acid s a c y la te in th e presence o f aluminum chloride.,
Alkyl a t i on s have been su c c e ssfu l u sing both e th e rs (47),
e s te r s (5 3 ),
(5 4 ),
(55)
Of a more recen t date,
(48)
and
in th e presence of anhydrous aluminum c h lo rid e .
alco h o ls have been found t o
s u c c e s s fu lly alky­
l a t e aromatics in th e presence o f aluminum ch lo rid e (27),
IM
In r e a c tio n s awhich carboxylic a c id s,
e s te r s ,
e th e r s ,
(45) s (46}„
and alco h o ls are
u sed, a considerable excess o f aluminum ch lo rid e i s needed and th e
co n d itio n s of th e re a c tio n s a re sometimes r a th e r drastic®
Boron flu o rid e w i l l promote a lk y l at ions w ith e th e rs (49),
(50), and e s te r s
(52),
a s w ell as w ith o le fin s (5 6 ),
alcoh o ls
but attem pted a lk y la -
ti o n s w ith alk y l h a lid e s in th e presence of boron flu o r id e have been un­
3
su c c e s s fu l.
Acylation I s r e a d ily promoted by boron f lu o r id e using
a l ip h a ti c anhydrid es.
It
should be p o in ted out th a t boron flu o rid e
re c e n tly has been shown to be e f f e c tiv e promoting c e r ta in n i t r a t i o n s
(5 8).
It
is
o f th e o r e tic a l i n t e r e s t t h a t boron flu o rid e d ir e c ts
p r in c i p a ll y to th e para p o s itio n in d ia lk y la tio n in c o n tra s t to aluminum chloride,, which y ie ld s meta d e r iv a tiv e s in most in s ta n c e s .
Anhydrous hydrogen flu o r id e has been shown by Simons and Archer
to be a very e f f e c tiv e condensing agent f o r a lk y la tio n s u sin g a lc o h o ls,
e s te r s
(8 ) ,
o le f in s ( 2 ) ,
(10 ),
e th e rs (12),
has been accomplished w ith both a c id s (7)
presence o f anhydrous hydrogen f lu o r id e ,
in t h i s medium ( 5 ) .
f lu o r id e i s
It
e f f e c tiv e ,
and h a lid e s ( 3 ) .
A cylation
and acyl (7) h a lid e s in th e
and o le f in s can be polymerized
has a lso been shown th a t anhydrous hydrogen
as w ell as promoting unique r e a c tio n s ,
in rin g
clo su res (1 8 ).
A more complete comparison p a r t i c u l a r l y of th e use o f boron f lu o r ­
id e i s
given by Archer (17) and w ill not be repeated hers®
p resen t work, howevers
In t h i s
some d iffe re n c e s between th e use o f hydrogen
f lu o r id e and aluminum ch lo rid e w ill be p resen ted .
C ertain lim ita tio n s have been found In a lk y la tio n re a c tio n s usin g
hydrogen flu o r id e ;
fo r example, m ethylations were not accomplished.
P henylations a lso f a il e d , whereas e th y la tio n s were accomplished w ith
ease®
A lk y latio n s f a i l e d w ith pyridine®
Sulfonation proceeded r e a d ily
in hydrogen flu o rid e media as did n i t r a t i o n .
c e s s fu l w ith th e exception o f one experiment®
O xidations were unsuc­
4
H is to r ic a l
Anhydrous hydrogen flu o r id e has been used very in fre q u e n tly in
organic chem istry as a condensing and polym erizing agent®
Freden-
hagen (13) re p o rte d i t was o f value in th e polym erization of many
o l e f i n s , and also used i t
n u c le i! (14)
in promoting th e n i t r a t i o n of aromatic
as did G leich (32)®
Yery l i t t l e
had been accomplished in organic chemistry through
th e use o f anhydrous hydrogen flu o rid e u n t i l Simons and Archer poin ted
out i t s value as a condensing agent {1 =1
1
)®
i n t h e i r s e r ie s o f pap ers,
th e y showed t h a t a lk y la tio n s could be accomplished by i t s use w ith
such a v a r ie ty o f reag en ts as o le f in s ,
alk y l halidesj,
and esters®
a l ip h a ti c alcohols,
and e th e rs ,
In most in s ta n c e s th e re a c tio n s gave very
good y ie ld s and were remarkably fre e from sid e products and t a r forma­
ti o n which one so o fte n encounters when u sin g most condensing agents®
They found t h a t acyl a t io n s also were cataly zed by anhydrous hydrogen
fluorici.es and th e y were successful in a c y la tin g aromatic n u c le i!
usin g a l ip h a ti c a c id s ,
It
acyl h a lid e s ,
and a lso
e s te r s in some cases®
has been shown th a t anhydrous hydrogen f lu o r id e promotes such re°
arrangements as th e F r ie s and Beckmann (1?)®
A study has also been
made ( 1 6 ) on th© r e l a t i v e r e a c t i v i t y o f v ario u s a lk y la tin g reagents
u sin g hydrogen f lu o r id e as th e catalyst®
I t was found t h a t a lk y l
flu o rid e s and o le f in s reacted to give th e b e s t s and n e a rly id e n tic a l,
y ie ld s , w hile th e a lco h o l,
c h lo rid e ,
bromide«
, and iodide reacted to
give r e l a t i v e y ie ld s in th e o rder mentioned®
It
should be noted th a t
in th e cases of th e io did e and th e bromide, no alk y late d products were
5
is o la te d in these p a r ti c u la r experiments*.
P rofesso r F e ise r and eoworkers at Harvard U n iv e rsity have used
anhydrous hydrogen flu o rid e in a number of in v e stig a tio n s involving
rin g c3_osures and have found i t
e ffe c tiv e in most cases (18-23)«,
Pro­
fe s s o r Newjian of Ohio S tate U niversity has also found hydrogen flu o rid e
u sefu l in promoting rin g formations in h is stu d ies of compounds possessing carcinogenic a c t i v i t y (57)®
The la b o ra to rie s o f E« I® duPont
d© Nemours and Company also have conducted comprehensive stu d ies on the
use of hydrogen flu o rid e as a condensing agent (24),
{25)0
6
D iscussion
A lthough, a t th e tim e th e p re s e n t
study was s t a r t e d ,
th e r e had
been much work done on th e use o f anhydrous hydrogen f lu o r i d e in th e
a lk y la tio n o f arom atic n u c l e i ! , no thorough study o f i t s
in m ethyl a t io n ,
e th y l a t io n ,
o r p h e n y la tio n had been made®
i t was b e lie v e d o f im portance to make t h i s
f in d w hether o r not i t
p o t e n t i a l value
would be u s e f u l in
Accordingly^
in v e s t ig a ti o n ,
not only to
such r e a c t io n s ,
but a lso t o
gain in fo rm atio n concerning p o s s ib le mechanisms®
In t h i s
study (12) „ an a lc o h o l,
in v e s t ig a ti o n of each r e a c t io n ,
e s te r,
and h a lid e were used in th e
and o th e r re a g e n ts such as o le f in s
and e th e r s were used in some in s ta n c e s .
u sin g m ethyl a lc o h o l, methyl a c e t a t e ,
Methyl a t ion was attem pted
and methyl iodide®
These r e ­
agent s were used in attem pted a lk y la tio n s o f benzene, to lu e n e ,
phenol a t tem p eratu res as high as 200°C and under p r e s s u re .
in every case to g iv e m ethylated p ro d u c ts .
h eated in a copper bomb a t
m ethylated p ro d u c ts.
around 180°G,
200
°G f o r t h i r t e e n hours did not y ie ld any
f a i l e d to y ie ld any x y le n e s.
of o b ta in in g c r e s o ls ,
They f a i l e d
Methyl alco h o l and benzene
Toluene, under s l i g h t l y l e s s d r a s t i c
methyl a lc o h o l did condense,
and
c o n d itio n s ,
Phenol when t r e a t e d w ith
but n o t i n th e expected manner.
I n s te a d
a n is o le was i s o l a t e d in y ie ld s o f around
2 0 %,
Sows, Hennion, and Hieuwland (26) had p re v io u s ly prepared a n is o le in a
vary s im ila r fa sh io n , namely, through th e use o f boron f lu o r i d e u sin g
phenol and methyl a lc o h o l.
They were a lso
p hen eto le i n an analagous r e a c t io n .
su c c e ssfu l in producing
T h e ir experiments were run in
clo sed tu b e s a t tem perature n e a r ly th e
same as o u rs.
An attem pt was
7
made to prepare phenetole using phenol# ethyl alcohol* and anhydrous
hydrogen fluoride*
hut ethylated products were obtained instead.,
In
some of th e se bomb re a c tio n s, where methyl alcohol was used, consider-*
able p ressure was encountered upon opening th e bomb®
been due to the formation of methyl flu o rid e .
This may have
In cases where reactio n
occurred such as w ith phenol, no p ressure was found when the bomb was
opened®
Attempted m ethylations of benzene and toluene using methyl a c e ta te
gave no methylated products and some pressure was noted when th e bombs
were opened®
Likewise methyl iodide did not condense with e ith e r
toluene or benzene a t temperatures as high as 120°C.
Iodine was formed
in th e 3 e re a c tio n s and th e re was considerable p ressu re at tim es.
The
r e s u lt s of these attempted methylations show one important difference
between th e use of hydrogen flu o rid e and such reagents as aluminum
chloride and boron flu o rid e .
Methylation may be re a d ily c arrie d out
using methyl chloride and aluminum chloride,
(12),
and recent in v e stig a tio n s
(13) have shown th a t aluminum chloride I s effe c tiv e in promoting
methylation using methyl alcohol®
Sowa (26) has shown th a t methylation
may be c a rrie d out through the use of methyl alcohol with boron flu o r­
ide as the condensing agent.
hydrogen f lu o rid e ,
In these in v e stig a tio n s using anhydrous
however, i t has not been found possible to produce
any a lk y la tio n of aromatic n u c le i! , such as benzene, toluene, or phenol
through th e use of methyl compoimds.
I t may o r may not be of import­
ance th a t th e higher members of the s e rie s are able to go through the
o le fin stage while methyl compounds cannot e x is t as o le fin !c i n t e r ­
mediates®
E th y la tio n , in c o n tra st to metiiylat i on, was c a rrie d out suc­
c e s s f u lly with, n e a rly every reagent used.
Ethyl alcohol condensed
w ith benzene a t 200°C to give over 80% of e th y la te d p rod u cts.
Di­
eth y l e th e r and e th y l chlorocarbonate gave eth y l benzene in y ie ld s o f
55% and 53% re s p e c tiv e ly .
The e th e r re a c tio n was performed a t 20Q°C,
w hile th e eth y l chlorocarbonate condensed r e a d ily w ith s t i r r i n g a t
0°Co
Ethyl iodide a t 100°C gave a 10% y ie ld o f eth y l benzene, while
eth y l a c e ta te re a c te d w ith to lu en e a t 100°C to give a 17% y ie ld o f pm ethylethylbenzene.
Ethylene was t r i e d a t 0°C, and although e th y l-
benzene could d e f in i te l y be noted by i t s
f i c i e n t q u a n titie s to i s o l a t e .
higher tem peratu res,
r e a d ily a t
p re s s u re s .
but i t
odor,
i t was not th e re in su f­
This re a c tio n was not attempted at
i s very probable t h a t i t
would proceed
s l i g h t l y elev ated tem peratures and under r e l a t i v e l y
It
small
should be s ta te d th a t one could undoubtedly in crease
th e y ie ld s in any of th e s e re a c tio n s by a more thorough study o f con­
d itio n s in each one.
Our I n te r e s t was mainly to
see i f th e re a c tio n
could or could not be c a rrie d o u t.
Chlorobenzenes phenol,
and phenyl a c e ta te , when tr e a te d with
e ith e r benzene or to lu en e at tem peratures as high as 200°C f a il e d to
give any phenylated p ro d u cts.
Phenyl a c e ta te re a c te d w ith benzene in
th e presence o f anhydrous hydrogen f lu o r id e a t 200°C to y ie ld small
amounts of phenol and acetophenone.
in an attempted p hen y latio n ,
Phenol was heated alone a t 200°
o r a p o s sib le
The only product, however, l e f t
sy n th esis of diphenyl e th e r.
a f t e r recovery of much o f th e phenol
was a very heavy tar- which did not d i s t i l l under 275°C a t
738 num., and
9
which, would not c r y s t a l l i z e .
Diphenyl e th e r was heated a t
210°C w ith
hydrogen f lu o r id e and a small amount o f phenol was i s o l a t e d ,
some benzene.
The arom atic e th e r s th u s seem to
as was
be much more s ta b l e
to th e a c tio n of anhydrous hydrogen f lu o r id e th a n a re th e a l i p h a t i c
e th e rs.
It
might a lso be p o in te d out t h a t
a r a t h e r pronounced d if f e r e n c e
e x i s t s between hydrogen f lu o r id e and aluminum, c h lo rid e in t h e i r re a c —
ti o n s w ith arom atic compounds a lo n e .
dense one r in g on to
Hydrogen f lu o r i d e does not
con-
an o th e r, w h ile th e r e a re a number o f c a se s (34)
where arom atics such as benzene and naphthalene are lin k e d to g e th e r in
th e p resen ce o f aluminum c h lo rid e w ith th e evo lu tio n o f hydrogen.
In
connection w ith a lk y la tio n s and attem pted a lk y la tio n s u sin g
anhydrous hydrogen f l u o r i d e g a few m iscellaneou s condensations w i l l
be d e sc rib e d .
Two o f th e s e r e a c tio n s Involve condensations between
an a l i p h a t i c h a lid e and an o l e f i n
(5 ).
These experiments were f o r th e
purpose of determ ining whether o r not a condensation would ta k e p la c e ,
and an in te n s iv e
study o f th e r e s u l t a n t p ro d u cts was n o t made.
In
one case t e r t i a r y b u ty l c h lo rid e and trim e th y le th y le n e r e a c te d a t 0oC,
and d i s t i l l a t i o n
o f th e p ro d u cts gave a co n stant b o ilin g f r a c t i o n o f
r e f r a c t i v e index 1.4279 - 1.4315.
19 num.
The b o ilin g p o in t was 63—
65° a t
This f r a c t i o n was d e f i n i t e l y o l e f i n i c
and i t s
p r o p e r tie s
cor­
respond to th e nonenes which one might espect to o b ta in from such a eon=»
d e n sa tio n .
Many o th e r p ro d u cts appeared to
be formed in t h i s
r e a c tio n as
th e r e was a long continuous tem p eratu re range in th e d i s t i l l a t i o n .
10
T e r tia r y b u ty l ch lo rid e also re a c te d w ith cyclohexene and d i s t i l ­
l a t i o n of* th e r e a c tio n products gave a f r a c tio n b o ilin g a t 14S°C a t
739 m®
The r e f r a c t i v e index was 1®4578®
and gave a very weak ch lo rid e test®
It
is
It
decolorized bromine
q u ite probable t h a t
t e r t i a r y b u ty l cyclohexene o r a s u b s titu te d
e ith e r
cyclohexylethylene had been
formed sin ce t h e f r a c tio n appears o l e f i n i c and does not correspond to
e i t h e r d i or t r i i so butylene®
was obtained in t h i s
A t r i i s o b u ty le n e f r a c tio n o f around
8$
experiment®
T his r e a c tio n between sn o le f in and an a lk y l h a lid e which i s pro­
moted through th e use o f amhydroxis hydrogen f lu o r id e has not been p re ­
v io u sly re p o rte d as being c ataly sed by any o th e r condensing agent®
As p re v io u s ly re p o rte d (2)
arom atics a re r e a d ily a lk y la te d by
o le f i n s i n th e presence of hydrogen fluoride®
in to a carbon te t r a c h l o r i d e
Propylene was passed
s o lu tio n of naphthalene a t 0°C and b e ta -
isopropylnaphthalene was obtained i n
40% yields®
D iisopropyl and t r i -
isopropylnaphthalenes were also is o la te d in y ie ld s o f
tively®
8%
and 5% resp ec­
P olym erization of th e propylene did not occur to an a p p re c ia b le
ext ent ©
Phenol was r e a d ily a lk y la te d by t e r t i a r y butyl ch lo rid e a t 0°CS and
d i s t i l l a t i o n o f th e re a c tio n products gave an 85% y ie ld o f p ara t e r t i a r y
b u ty l phenol which m elted a t 97-98°C«
A r e a c tio n between acetone and t e r t i a r y
butyl ch lo rid e a t 0°C gave
o f f hydrogen c h lo r id e s but no d e f i n i t e p roducts were isolated®
tilla tio n
Dis­
of th e pro du cts gave f r a c tio n s b o ilin g over a wi.de tempera­
t u r e range®
11
In a reactio n , between bromoaeatone and benzene, no benzyl metliyl
ketone could be found.
Hydrogen bromide was e x p e lle d during th e r e ­
a c tio n a t a teanperature o f 0°C, but th e o i l la y e r was very heavy and
t a r r y and decomposed w ith th e e v o lu tio n o f hydrogen bromide through­
out any attem p ts t o
d i s t i l l it*
An attem pt was made t o
b u ty l c h lo rid e to
a lk y la te
3 -e th y l pentane u sin g t e r t i a r y
g iv e such a product as shown below, namely;
3«ethyl-
3 - i sobut y lp e n t ane a
CH3
ch 3
t
C t
ch 3
-
cn3
-t-
-
CHg
-
CHg
-
CHg
ch3
->■
CH3
Cl
CH3
I
ch 2
I
CH -
—
CHg
CH3
CHg
i
— C —
i
- c I
ch 3
CHg —
CH3
+
HC1
CHS
The r e a c tio n was c a r r ie d out a t 0° G and a good hydrogen c h lo rid e t e s t
was o b tain ed w ith s i l v e r n i t r a t e
D is tilla tio n
during th e course o f th e reactio n *
of th e o i l l a y e r r e s u lt e d in much decomposition and r e ­
covery o f most o f th e 3-ethylpontane®
In t h i s
r e a c t io n ,
o f th e r e a c tio n s in v o lv in g only a lk y l r e a c t a n t s ,
a v ery lax-ge number
o f p roducts appear to be foxmed which a re d i f f i c u l t
appears,
i n most e a se s,
th a t
as in most
a lk y la tio n ta k e s p la c e ,
to
s e p a ra te .
but t h a t
It
some
12
amount o f polym erization, though, sm all,
does occur, which causes th e
form ation of m ixtures very d i f f i c u l t t o
s e p a ra te .
s ta b le c h lo rid e s appear to
R e la tiv e ly un­
be fomned as th e re i s much decomposition
and ev olu tio n o f hydrogen c h lo rid e during d i s t i l l a t i o n
la y e r .
I t has been shown (29) t h a t t e r t i a r y
o f th e o i l
c h lo rid e s re a c t w ith
anhydrous hydrogen flu o r id e at 0° C to y ie ld a complex m ixture o f
c h lo rid e s and o l e f i n s .
In t h i s work t e r t i a r y b u ty l c h lo rid e ,
w ith a number of o th e r a l ip h a ti c
y ie ld s from t e r t i a r y
along
c h lo rid e s, was obtained in 10-17$
amyl ch lo rid e and anhydrous HF.
Normal b u ty l chlorocarbonate and benzene in th e presence o f
hydrogen flu o rid e gave, a t 0° C, a 41$ y ie ld o f secondary b utyl ben­
zene.
0
CHg
C0g
HC1
This rearrangement i s in agreement w ith previous r e s u l t s in t h i s lab
o ra to ry (1 7 ).
f lu o r id e ,
In n e a rly a l l a lk y la tio n s w ith anhydrous hydrogen
except when a l i c y c l i c s
normal r e a c ta n ts y ie ld
such as cyclopropane are used (4 ),
secondary or t e r t i a r y products and secondary
r e a c ta n ts y ie ld t e r t i a r y
d e r iv a tiv e s .
13
During th e course of our work on a lk y la tio n s ,
various attempts
were made to a lk y la te and acy late suck u n reactiv e n u c le i! as n i t r o ­
benzene and p y rid in e ,
but even with tem peratures as high as 220° C
and under p re ssu re , they met w ith no success,,
In attranpting to in v e s tig a te d if f e r e n t phases of organic chem­
i s t r y in which anhydrous hydrogen flu o rid e might be of value, re a c ­
tio n s such as su lfo n atio n and n i t r a t i o n were considered.
Since they
both are re a c tio n s in which th e p rin c ip le step c o n sists o f the elim­
in a tio n of water between two molecules, th e powerful dehydrating
agent, hydrogen flu o r id e ,
densations.
could probably be used to promote such con­
This lin e of reasoning i s
su b sta n tia te d by th e f a c ts
th a t flu o ro su lfo n ic a c id , FSO^H, i s an ex cellen t
sulfo natin g agent (19),
and th a t Fredenhagan and Gleieh had su ccessfu lly used a mixture of
potassium n i t r a t e and hydrogen flu o rid e to n i t r a t e benzene and phenol
(14),
(32).
Benzene, when heated w ith s u lf u r ic acid and excess hydrogen
flu o rid e a t
steam bath temperatures in a closed copper v e sse l, gave a
75fo y ie ld of benzene su lfo n ic acid.
The remainder of th e s u lf u r ic
acid was d is s ip a te d In th e formation of diphenyl sulfone.
In a reac­
tio n between benzene and flu o ro su lfo n ic acid at 60°C, a 53$ y ie ld of
th e mono su lfo n ic acid was obtained.
I t i s probable th a t the excess
hydrogen f lu o rid e , -with i t s powerful dehydrating tendencies, re s u lte d
in a g re a te r degree of sulfonation.
This c o n tra st between flu o ro su lfo n ic acid and a mixture o f su l­
f u r ic acid and hydrogen flu o rid e was more marked In the sy nthesis of
sulfones than i t
was In the ease of th e su lfo n ic acid s.
F luorosul-
14
fo n ic acid reacted with benzene a t 160° to give a 14$ y ie ld o f d i­
phenyl sulfone, -while th e mixture of benzene,
s u lf u r ic a cid ,
end
hydrogen flu o rid e gave a 40$ y ie ld of diphenyl sulfone a t th e same
tem perature, 160°C.
An attempt was made t o
su lfo nate cyclopentane w ith both reag en ts.
The m ixtures were heated a t 140°C in sealed copper v e s s e ls ,
but f a ile d
to y ie ld any cyclopentane su lfo n ic a c id s .
Benzene was s u c c e s s fu lly n i t r a t e d a t s a l t - i c e tem peratures u sin g
a n i t r i c a c id , hydrogen f lu o r id e m ixture.
on t h i s f i r s t
The y ie ld o f nitrobenzene
experiment was 42$ d e sp ite the f a c t t h a t much of th e
n i t r i c acid was used up in
th e copper v e s s e l.
a re a c tio n between th e n i t r i c
acid end
The r e a c tio n was very v io le n t u n le ss th e n i t r i c
acid was added very slow ly.
The d i f f i c u l t y , which was encountered
before much of a study o f t h i s n i t r a t i o n
could be made, was th a t a
v e sse l could not be found which would not r e a c t w ith e ith e r th e n i t r i c
acid or th e hydrogen f lu o r id e .
Beakers and copper p o ts were coated
w ith a p l a s t e r p a r i s m ixture impregnated w ith calcium f lu o rid e ,
t h i s proved to be too porous.
d ish ,
Crepe rubber was used to
and an attempt made to harden t h i s
but
coat a copper
coating by polj'm erising i t
f u r th e r w ith hydrogen f lu o r id e .
The rubber was polymerized, but
became too b r i t t l e
P a r a f f in wax was found to be too
and cracked.
soluble in th e aromatic compounds we were attem pting to n i t r a t e .
We
f i n a l l y obtained a very high molecular wax from petroleum e x tra c tio n s ,
which could be melted and was r e l a t i v e l y in so lu b le in benzene and
nitrobenzene, th e two arom atics in which w e were i n t e r e s te d .
15
A fter coating a copper dish, w ith t h i s wax, another experiment
was performed a t s a l t - i c e tem peratures on benzene,,
of nitrobenzene was obtained®
th e re a c tio n prod u cts.
A y ie ld of 83%
There was no dinitrobenzene found in
Due to th e ease w ith which t h i s re a c tio n
progressed a t t h i s low tem perature,
i t was f e l t th a t
i t might be pos­
s ib le to n i t r a t e nitrobenzene a t tem peratures as low as 0°C o r 10°C«
Attempts at t h i s ,
however., were u n su ccessfu l.
Since no v essel was a v a ila b le in which a n i t r a t i o n
tr ie d
could be
a t a higher tem perature and under p re ssu re , no more n i t r a t i o n s
were t r i e d w ith th e exception o f an attempt to n i t r a t e p y rid in e a t
0°C which was u n su ccessfu l.
I n c e r ta in n i t r a t i o n s hydrogen flu o rid e might be a s u p e rio r de­
h y d rating agent to s u lf u r ic a c id .
llflhen th e l a t t e r agent i s used some
su lfo nated by-products a re u s u a lly formed®
have not been found,
in a lk y la tio n s ,
a c y la tio n s,
these,w ould not be expected in n i t r a t i o n
ta b lis h th i s ,
As flu o rin a te d by-products
end su lfo n a tio n s
experiments®
In o rd er to es­
however, t e s t s were made on benzene t h a t had been
t r e a te d w ith a mixture o f n i t r i c
acid and hydrogen f lu o r i d e .
f lu o r in e containing organic compound was found.
Ju st
No
as c e r ta in a l­
kyl a t in n s u sin g hydrogen flu o r id e as th e c a ta ly s t give products which
are absent o r found only in
small y ie ld s usin g o th er c a t a ly s ts , new
n i t r a t i o n products may conceivably be found.
It
is
also p o s s ib le th a t
re a c tio n s would proceed a t lower tem peratures and t h a t th e vaporiza­
ti o n o f th e hydrogen flu o rid e would remove heat in case th e re a c tio n
became very rapid®
B e tte r y ie ld s might r e s u l t .
A fter fin d in g th a t su lfo n atio n and n i t r a t i o n were catalyzed by
anhydrous hydrogen flu o rid e ,
i t was f e l t
th a t t h i s condensing agent
might be e f f e c tiv e in promoting arsonation®
The most general method f o r prep aring aromatic compounds o f
arsonic acid a t th e present time i s th e in te r a c tio n of a diazotized
amine and sodium arsenite®
ArNgCl
NagBAsGg ----------------------ArAsOgNa + NaCl + Ng
+-
Since t h i s i s not an easy re a c tio n to perform, a one step sy n th esis
o f a ry l arso nie acids would be of value.,
matic n u c le i!
It
should be noted th a t aro ­
such as phenol and a n ilin e , which have strong a c tiv a tin g
groups p re s e n t,
can be arsonated d i r e c t l y using syrupy arsen ic acid*
In th e se cases th e y ie ld s are very low,
since th e reactio n re q u ire s
a r a th e r high tem perature, and oxidation products of th e phenol or
a n ilin e compounds are formed*
I n the f i r s t
attempted a rsan atio n ,
carrie d out in a closed cop­
per v essel a t 180°C, using arsen ic a c id , HgAsO^EgO, as the arso n atin g
agent and benzene as th e aromatic nucleus, phenol was found as a
product*
tion*
This was e n tir e ly unexpected and required fu rth e r in v e s tig a ­
No phenylarsonic acid was is o la te d in t h i s reaction*
same copper v e s s e l,
Using th e
an attempt was made to prepare creso ls in t h i s
manner; namely, mild oxidation o f to luen e using arsen ic acid*
Upon
examination o f th e re a c tio n products from t h i s experiment, no creso l
was is o la te d ,
although a d e f in ite c re s o lic odor was present*
e f f o r t to study fu rth e r the oxidation o f benzene,
In an
since our to lu en e
17
r e a c tio n did n o t y ie ld c r e s o ls in ap p reciab le q u a n t i t i e s s another
experiment was performed under co n dition s id e n tic a l w ith th e one in
which phenol was obtained*
U n fo rtu n ately no phenol was obtained
e i th e r in t h i s o r in any o f a numerous s e t o f r e a c tio n s which were
subsequently performed®
could be noted*
Xn one o r two in s ta n c e s a phenolic odor
but no phenol compounds were isolated®
In a number
o f th e se re a c tio n s th e co n d itio n s were made as c lo s e ly p a r a l l e l to
th o se of th e o r ig in a l r e a c tio n as was experim entally possible*
and in
o th e rs v ario u s f a c to r s were changed such as time* temperature*
and
presence of catalysts®
ti o n
It
appears probable t h a t
in th e o r ig in a l re a c ­
some c a ta ly s t was p re s e n t in th e copper bomb which promoted t h i s
o x id a tio n and was s t i l l th e r e in small q u a n t iti e s when th e oxidation
o f to lu en e was attempted*
No benzoic acid could be found in t h i s a t ­
tempted o x id a tio n o f to lu e n e to a cresol®
Xn th e s e o th e r re a c tio n s
th e only product is o l a t e d w ith th e exception o f th e o r ig in a l
products* was a heavy o i l
layer®
s ta rtin g
e x tra c te d from a h ig h ly a c i d if ie d w ater
Upon examination t h i s appeared to
be o f ino rg an ic nature®
In f u r th e r attem pts to promote th e o x id a tio n o f benzene to phenol*
a number of a d d itio n a l o x id izin g agents were tried®
ganate and potassium diehrornate were t r i e d
benzene and toluene*
Potassium perman­
a t 0°C and 100°C w ith both
but no o xid atio n occurred®
Lead dioxide was
used a t 0°C and 100°C w ith benzene but no phenol was isolated®
It
appears t h a t anhydrous hydrogen f lu o r id e i s not a good ox id izin g
medium f o r th e o r d in a r i ly strong reagents* KMnC> 4 and EgCrgC^ as no
benzoic acid o r phenol was isolated®
18
In
ly s t,
some r e a c tio n s in which aluminum c h lo rid e was used as a cata °
phenols and p h en o lic odors have been noted (34) „ (6 1 ),
no p r e d ic tio n s
although
could be made as t o when o r when not th e y would be
found except th a t th e y were never found in th e absence o f oxygen*,
it
Thus,
ap p ears probable t h a t t h i s o x id a tio n may be an a i r o x id a tio n .
I n a l l th e re a c tio n s v/hich were run usin g o x id iz in g ag en ts such
as a r s e n ic
a c id , potassium perm aagsnates potassium diehrom ate,
and
le a d d io x id e , th e hydrocarbons such as benzene and to lu e n e were fused
w ith sodium and t e s t e d f o r f l u o r i n e .
No f lu o r in e was found.
19
Exp e r i ment a l
W f a w i Bin IL ip— JOBMi I e*n BU I atsm^mm*
Methyl Io d id e
A m ixture o f 1 .P moles (200 grams)
of w ater,
to
and 15 grams CaC03
65°C with, s tir r i n g ,,
added slowly®
of potassium io d id e ,
were added to
a lite r
100 c„e«.
f la s k and heated
157 grams o f dimethyl s u lf a t e were then
The methyl io d id e was d i s t i l l e d
d rie d over calcium c h lo rid e ,
a f t e r which i t
out of th e m ixture and
was r e d i s t i l l e d
over po­
tassium io d id e and th e f r a c ti o n "boiling at 40-43°C was collected®
The
y ie ld was 91%s
Io d id e
1 'i f t y
poured i n t o
rous®
cubic cen tim e ters o f ab so lu te a lc o h o l,
39--5 grams, were
a 250 OoC. f la s k which contained 5 grams of red phospho­
50 grams of powdered io d in e were th e n added very slowly w ith
shaking and coolings
T his m ixture was heated and reflu x ed f o r th r e e
hours, d i s t i l l e d ,
and th e d i s t i l l a t e washed w ith w ater,
s u lfite
and f i n a l l y w ith sodium hydroxide®
s o lu tio n ,
d ried over calcium c h lo rid e ,
6 8 -? 2
° collected®
d is tille d ,
sodium b i ­
The o i l was
and th e f r a c tio n b o ilin g a t
The y ie ld was 47 grams o f e th y l iodide®
20
Ethyl A cetate
F ifty c .c .
o f e th y l a lc o h o l, 39 *5 grams,
f u r ic acid were poured in t o
140°Go
and f i f t y
e *e„ of s u l­
a fla s k and th e m ix tu re was heated t o
Then a m ixture o f g la c ia l a c e t i c a c id and alco h o l (400 c» c®
o f each) was adm itted slow ly as th e e th y l a c e ta te d i s t i l l e d over®
The d i s t i l l a t e was shaken w ith sodium carbonate s o lu tio n and fre e d
from alco h ol by shaking w ith a so lu tio n of one hundred grams o f c a l­
cium c h lo rid e in one hundred grams o f water®
d ried over calcium c h lo rid e and the f r a c ti o n
collected®
The upper la y e r was
b o ilin g a t 76-78°C was
The y ie ld was 74$*
Meth y l A cetate
One mole (102 grams) was slowly added t o
one mole (32 grams)
of
methyl alcoh o l in a 500 c*c® fla s k f i t t e d w ith a r e f lu x condenser and a
gas trap®
A fte r th e a c e ty l ch lo rid e had been run i n ,
reflu x ed v ig o ro u sly f o r a p erio d o f fo u r hours®
th e m ixture was
The m ixture was then
d i s t i l l e d and th e f r a c t i o n b o ilin g from 55°-59°C a t
739 m* m® was used®
The y ie ld was 71$ o f th e th eo retical®
Phenyl A cetate
A m ixture o f n in e ty - f o u r grams o f phenol,
sodium a c e t a te ,
fifty
grams o f anhydrous
and one hundred s ix te e n grams o f a c e tic anhydride were
heated to r e f lu x te m p eratu res in an o i l bath and re flu x e d f o r two hours*
21
(Phenyl A cetate)
The m ixture was d i s t i l l e d ,
and r e d i s t i l l e d
th e d i s t i l l a t e
d rie d over calcium ch lo rid e
and th e f r a c t i o n b o ilin g a t 191° - 196°C was collected®
S eventy-three grams o f phenyl a c e ta te were obtained®
T e r tia r y Butyl Chloride
T h is p re p a ra tio n was c a r r ie d out much th e same as in "Organic
Synthesis** V III s page 80®
A fte r shaking a m ixture o f te n moles o f
t e r t i a r y b u ty l alco h o l and t h i r t y moles of h y dro ch lo ric a c id f o r
tw en ty -fiv e m in u tes, th e o i l l a y e r was sep arated and d ried overnight
over potassium carbonate.
When d i s t i l l e d ,
th e f r a c tio n b o ilin g a t
51-52°C was collected®
Trim ethy le t hylene
TFT—
II "
1l|IJ*
Two hundred seventy e® c.
added to
540 c_ e,
of t e r t i a r y
o f concentrated s u lf u r ic a c id were
o f w ater and when t h i s m ixture had cooled,
540 c. e«
amyl alcoh o l were dropped in slowly w ith constant agitation®
The m ixture was immediately p la ced on th e steam b ath and th e trim e th y lethylene was d i s t i l l e d as r a p id ly as th e alco ho l was dehydrated®
The
product was d rie d over magnesium s u l f a t e and d i s t i l l e d through a f r a c ­
tio n a tin g column®
512 grams were obtained®
22
Broiaoa ce t on e
A 5 l i t e r round-bottom fla s k was f i t t e d w ith s t i r r e r ,
fa n a e ls thermometer, and a re flu x condenser.
sep arato ry
The stem of th e
separa­
to ry funnel extended to th e bottom o f th e flaslc®
Eight hundred c.
e. o f w aters 250 c» c. o f acetone, and 185 c® c®
of g la c ia l a c e tic acid were added®
The fla s k was heated in a water
bath to 75° a f t e r which 5® 6 moles of bromine were slowly added®
When
the so lu tio n was decolorized, i t was d ilu te d w ith 400 c® c® o f cold,
water 9 cooled to 10°C, made n e u tra l to congo red with sodium carbonate
and the o i l
separated®
The o i l d i s t i l l e d a t 39-41°C a t a p ressu re o f
17 m illim e te rs o f mercury®
Cvclohexene
Four hundred grams of cyelohexanol and twelve cubic centim eters
of s u lf u r ic a c id were mixed in a one l i t e r f la s k ,
f i t t e d w ith a re f lu x
condenser, and heated a t 130-140° f o r t h i r t y minutes®
was d i s t i l l e d
The m ixture
and th e d i s t i l l a t i o n was continued u n t i l the odor of
su lfu r dioxide could be noted®
The d i s t i l l a t e was satu rated w ith s a l t
and th e cyclohexene was separated from th e water layer®
hexene was d rie d over calcium ch lo rid e ,
b o ilin g a t 79-82° was collected®
grams was obtained®
fra c tio n a te d ,
The cyclo—
and th e f r a c tio n
An 80$ y ie ld of two hundred f i f t y
One hundred f i f t y
grams o f n i t r i c
acid ( s p e c i f i c g r a v ity - 1*.42)
were dropped slow ly onto two hundred grams o f w hite a r s e n ic ,
tr i o x i d e .
a rse n ic
A very copious evo lutio n o f NgOgfuines r e s u lte d and th e r e ­
a c tio n went very r a p id l y .
A fte r NgOghad ceased to
evolve, th e dry
porous mass was h eated i n an e l e c t r i c oven a t 108° f o r tw enty-four
hours.
I t m elted ,
gave o f f w ater,
and re c r y s t a l l i z e d as
H ^A sO 4 &HgO s
P re p a ra tio n o f Acetamino D e riv a tiv e s (35)
One gram o f th e hydrocarbon was added t o
one m ixture of s u l f u r i c
and n i t r i c
a c id s .
h athc
of a one to
Heat was evolved and when
the m ixture was cooled,Awas poured onto i c e .
with e th e r a washed tw ice w ith w ater,
f iv e c . c .
The s o lu tio n was e x tra c te d
and th e n evaporated on th e steam
To t h i s o i l was added f iv e grams of g ran u la ted t i n ,
of h yd rochloric a c id and s u f f i c i e n t
the o i l .
e th y l alcoh o l to
Reduction took p la c e in about te n m inu tes.
f iv e c.
cQ
d is s o lv e most o f
The so lu tio n was
then poured in to tw enty—
f iv e c.
c. o f w ater,
e x tra c t th e t i n
A fte r washing th e e th e r s o lu tio n tv/lee
with w ater,
amine complex.
and e th e r was added to
th e e th e r s o lu tio n was d rie d ov er anhydrous KgC03.
The
e th e r was evaporated and th e o i l was tr e a t e d w ith a c e tic anhydride.
The a lk y l s u b s titu te d a e e t a n il id e c r y s t a l l i z e d and was r e c r y s t a l l i z e d
from a lc o h o l-w a te r s o lu tio n s .
24
'R e a c t i o n s
Methyl Alcohol and Benzene
S ix ty -f iv e grains of anhydrous hydrogen flu o rid e were d i s t i l l e d
into a m ixture of tw enty-four grams of methyl alcohol and 195 grams
of benzene which had prev io usly been placed in a copper p ressu re
vessel and cooled to 0oC.
The copper v essel was then sealed and
heated f o r t h i r te e n hours at a tem perature around 20Q°Ce
The copper
v e s s e l 9 which we s h a ll r e f e r to as a bomb, was then cooled i n ic e and
opened*
Considerable p ressu re was found upon opening.
The re a c tio n
mixture was poured onto ic e and n e u tra liz e d with sodium carbonate.
The o i l la y e r was separated and d ried f o r tw enty-four hours over cal­
cium c h lo rid e .
D i s t i l l a t i o n o f th e o i l la y e r gave only benzene and
no methylated benzenes were found.
Methvl Alcohol and Phenol
nn
<ni
c t—gsnatfn njn ior."'
mm
■
Sixty-one grams of hydrogen flu o rid e were added as above to a
mixture o f eighty grams o f phenol and 15.8 grams of methyl alcohol.
The r e s u lt in g so lu tio n was heated in an e l e c tr ic furnace f o r sixteen
hours a t a tem perature o f 200°C.
The bomb was cooled and opened, and
no p ressu re was noted.
The m ixture was poured onto ic e and n e u tra liz e d
with sodium carbonate.
The o i l la y e r was separated,
a c id ifie d and ex tracted w ith e th e r ,
the w ater la y er
and a f t e r d i s t i l l i n g o f f th e e th e r,
th is o i l was added to th e o r ig in a l o i l la y e r .
A fter drying f o r twenty-
zo
(Methyl Alcohol and Phenol)
fo u r hours oyer anhydrous magnesium s u l f a t e , d i s t i l l a t i o n
gave 9 .4
grams o f a f r a c t i o n 'boiling a t 54-55°C a t 18 m illim e te r s ,
and which
had an index o f 1.5169.
A p o rtio n o f t h i s was brominated and a w hite
c r y s t a l l i n e s o lid was obtained which m elted a t 86«5 a f t e r two r e c r y s t a l l i z a t i o n s from a b so lu te alcohol*
p h e ric p r e s s u r e ,
has an index of 1.5173 and gives a tribrom o d e r iv a tiv e
which m e lts a t 87°C.
y ie ld o f a n is o le ,
A nisole b o il s a t 154°C a t atmos­
Our constant f r a c ti o n th u s re p re s e n ts an 18$
C5 H5 OGH3 .
Methyl Alcohol and Toluene
To a m ix tu re o f 125 grams o f to lu e n e and 15.8 grams o f methyl
a lc o h o l,
79 grams o f hydrogen f lu o r id e were added as described in
th e above r e a c tio n s .
The v e s s e l was sealed and then heated f o r
seventeen hours a t 180°Co
d rie d ,
and d i s t i l l e d .
The bomb was then opened, n e u tra liz e d ,
No xylenes o r m ethylated products were i s o ­
la te d .
Methyl A cetate and Toluene
S l i g h tly more th a n s ix moles (128 grams) o f anhydrous hydrogen
f lu o r id e were added t o
a m ixture o f one mole o f methyl a c e ta te and
200 c,
Th© bomb was sealed and heated in th e steam
c» of toluene*
bath f o r f o r ty - e ig h t
hours*
The r e a c tio n products were examined as
2S
(Methyl A cetate and Toluene)
u sual but no xylenes were obtained upon f r a c ti o n a ti o n o f th e o il*
ketones which might be expected,
No
such as acetophenone, were is o la te d
in t h i s experiment®
Methyl Io d id e and Benzene
One hundred f i f t y
tille d
grams o f anhydrous hydrogen f lu o r id e was d is ­
in to a copper bomb which contained f i f t y
iodide and two hundred c® e® o f benzene®
then heated in th e
The bomb was sealed and
steam bath f o r tw en ty -fo u r hours®
opened, a co n sid erab le p re s s u re was found®
solution®
c® c. o f methyl
When cooled and
Io d in e was noted in th e
A fte r n e u t r a liz i n g w ith NagGGs and d rying over CaClg, th e
o i l was fractionated®
recovered,
The benzene and some of th e methyl iod ide was
but no to lu e n e o r polym ethylated p ro d u cts were found®
Ethyl Alcohol and Benzene
A fte r adding s i x t y - f i v e grams o f anhydrous hydrogen f lu o r id e to
a m ixture o f one hundred c.
a lco h o l,
c® o f benzene and a h a l f mole of e th y l
i n a copper bomb, th e v e s s e l was sealed and heated in an
e l e c t r i c fu rn ace a t 200°C f o r six te e n hours®
a f t e r cooling and opening th e bomb®
No p re s s u re was noted
The s o lu tio n was poured onto
ic e , n e u tr a liz e d w ith 11agCOg„ and d rie d over CaCXg f o r two days®
tilla tio n
gave two main c u ts ,
one b o ilin g a t 131-133°C a t
Dis­
732 m® m
®
27
(E thyl Alcohol aad Benzene)
and having an index o f 1,4952-1*4958 and t i e
178°C a t
firs t
o th e r "boiling a t 176-
732 m. m. and p o sse ssin g an index 1 .,4961-1 *4968o
cut
corresponds t o
The
e th y l benzene;, b o ilin g p o in t was 136° and
The 2 S 4 diacetam inoethylbenzene
th e r e f r a c t i v e index was 1®4S59®
was prepared and a f t e r two r e c r y s t a l l i z a t i o n s m elted a t 222°C as
compared to th e l i t e r a t u r e v alu e o f 223°c (35)®
monoethylbenzene was obtained®
cent y ie ld appeared to
A 33$ y i e l d of
Diethylbenzene in forty-height p e r­
be th e o th e r c h ie f product®
The h ig h e r cut
b o iled over a range from 176-179°C and had an index of X®4968®
O xidation y ie ld e d a s o l i d which did n o t melt and which sublimed
around 320°C®
T his in d ic a te d te r e p h th a lic acid and th e r e f o r e o r­
i g i n a l l y p ara diethylbenzene®
A monoac et ami no d e r iv a tiv e was p re ­
pared and m elted a t 112°CS \vhich checks th e l i t e r a t u r e v alu e of
112°G®
The o v e r a ll y ie ld o f e th y la tio n in t h i s r e a c tio n was 81$®
E thyl Chlorocarbonate and Benzene
A m ixture o f 300 c® c, o f benzene and one mole (108 grams)
e th y l chlorocarbonate was p laced in a one l i t e r
f i t t e d w ith an i n l e t
and o u t l e t tube*
of
copper r e a c tio n fla s k
and a copper s tirre r®
A fte r
cooling to 0°C? 150 grams o f anhydrous hydrogen f lu o r id e were d i s ­
tille d
in to th e mixtux*e®
T his s o lu tio n was then s t i r r e d
a t 0°C f o r
tw en ty -eig h t h o u rs, and hydrogen c h lo rid e was evolved throughout most
of t h i s
s t i r r i n g period®
processed as usual®
The s o lu tio n was then poured onto ic e and
D is tilla tio n
gave a 53$ y ie ld o f ethylbonzene of
(Ethyl Chloro carbon a t e and Benzenei
index o f 1.4950—
1.4957.
A d ia c e t amino d e r iv a tiv e was made and m elted
a t 222o5—
223°C®
D iethyl E th er and Benzene
A m ixture o f 125 e.
e th e r,
e.
o f benzene,
one t h i r d o f a mole o f d ie th y l
and e ig h ty grams of hydrogen f lu o r id e was placed in a heavy
copper bomb and heated a t 190-210° f o r tw en ty -fo u r hours.
cooled,
opened,
and no p re s s u re was found.
The bomb was
The o i l la y e r was sep arated
and d rie d a f t e r th e u s u a l n e u tr a liz a tio n w ith EagCOg.
D is tilla tio n
gave a 55$ y ie ld o f ethylbenzene o f index 1.4949-1.4957.
A diacetamino
d e riv a tiv e was p rep ared and m elted a t 221-222°C.
Ethyl Io d id e and Benzene
A fte r p la c in g f o r t y c.
benzene,
c.
o f e th y l io d id e ,
two hundred e„ c.
of
and two hundred grams o f hydrogen f lu o r id e in a copper boinb9
th e v e s s e l was sealed and heated f o r tw en ty-fou r hours a t 100°G.
When
opened th e r e was a s lig h t p re s s u re noted; th e gases coming o f f gave
a d e f i n i t e io d id e t e s t when t e s t e d w ith s i l v e r n i t r a t e .
was poured onto i c e ,
dried over CaClp»
n e u tr a liz e d ,
The m ixture
and th e o i l la y e r separated and
D i s t i l l a t i o n gave a 10$ y ie ld of ethylbenzene o f
index o f l e4949-1.4955.
d e riv a tiv e m e ltin g a t
A p o r tio n was used to make a diacetamino
221-222°C0
29
Ethylene and Benzene
A one l i t o r
o u t l e t tu b e ,
copper r e a c t i o n v e s s e l was f i t t e d
and a m ercury se a le d copper s t i r r e r .
w ith an i n l e t
200
e.
and
c. o f benzene
and 155 grams o f hydrogen f l u o r i d e were added.
The r e a c tio n vessel,
was flu s h e d out w ith e th y le n e thro u g h th e i n l e t
tu b e ,
tu b e was th e n connected t o
a mercury manometer.
m itte d v ery slow ly w ith s t i r r i n g
a t 0°C„
E th y len e was ad­
A c o n sta n t p re s s u re o f about
te n m illim e te r s o f mercury was m a in tain ed .
very much e th y le n e .
and th e o u t l e t
The s o lu ti o n did n o t
The a d d itio n o f eth y len e co n tin u ed f o r seven hours
and th e m ix tu re was s t i r r e d
f o r t e n hours more.
While n e u t r a liz i n g
and s e p a ra tin g eth y lb en zen e could c l e a r l y be d e te c te d by i t s
no e th y l a t ed benzene was i s o l a t e d upon f r a c t i o n a t i o n .
it
was o n ly p r e s e n t
absorb
It
o d o r, but
appears t h a t
in t r a c e s .
E thyl A lcohol and Phenol
In an attem p t to p re p a re p h e n e to le CQH5 " 0 CgH5 s 75 c.
one h a l f mole o f
e th y l a lc o h o l,
c. o f pheno l,
and 109 grams o f hydrogen f lu o r id e were
p laced in a heavy bomb and h eated a t 185-210° f o r tw en ty -fo u r h o u rs.
No p r e s s u re was n o te d upon opening th e bomb.
onto ic e ,
n e u t r a l i z e d w ith NagCQ^, th e o i l
w ater la y e r e x tr a c te d w ith d ie th y l e th e r .
to th e o r i g i n a l o i l l a y e r .
D is tilla tio n
The m ix tu re was poured
la y e r
s e p a ra te d ,
and th e
The e th e r e x tr a c t was added
gave no p h e n e to le ,
and a
m ixture o f e t h y l a t ed p h en o ls b o ilin g between 200 and 215°C was found.
so
Ethyl A cetate and Toluene
A f te r p la c in g 125 e.
c.
o f e th y l a c e ta te and 200 c,
c.
in a copper bomb, 110 grams o f hydrogen f lu o r id e were added.
was se a le d and heated in a steam b ath f o r s ix te e n h o urs.
o f benzene
The bomb
The products
were t r e a t e d as u s u a l upon opening th e bomb, and th e o i l la y e r was then
f r a c tio n a te d .
A con stan t f r a c t i o n
b o ilin g a t 157=159°C a t 736 m. m.
was obtained*
The r e f r a c t i v e index was 1.4940=1*4944*
A p o r tio n was
oxidized and gave te r e p h th a li c a c id .
P ara m ethylethyl benzene b o ils
a t 162°C and has an index o f 1.4943.
The y ie ld was 18% o f th e th e ­
o re tic a l.
Phenyl A cetate and Benzene
One t h i r d of a mole (45 grams)
o f phenyl a c e ta te and 200 c.
c.
of benzene were placed in a copper bomb, cooled to 0°C, and 93 grams
of hydrogen f lu o r id e added.
s ix te e n hours,
The bomb was heated in a steam bath f o r
cooled,, opened,
n e u tra liz e d w ith NaHCOg.
The o i l la y e r was separated and d rie d over
anhydrous magnesium s u l f a t e .
t r a c t e d xvith e th e r ,
a fte r d i s t i l l i n g
and co n ten ts poured onto ic e and
The w ater la y e r was a c i d if ie d
and ex­
and th e e x tr a c tio n s were added to th e o i l la y e r ,
o f f th e e th e r .
D i s t i l l a t i o n gave a 5% y ie ld of
phenol id e n t i f i e d by a tribrom o d e r iv a tiv e which m elted a t 94°G.
small amount o f acetophenone was is o la te d
m eltin g a t 196=197°G.
A t a r lik e
atio n had been completed.
A
and gave a semicarbazone
substance remained a f t e r th e f r a c tio n ­
31
r .h lo r o b a n z e n s a n d .B e n z e n e
One h a l f a mole (56 grams) of chlorobenzene and 200 c, c» of
benzene were placed in a heavy copper bomb; and a f t e r cooling to 0°CS
104 grams o f hydrogen flu o rid e were added„
The bomb was sealed and
heated a t 180~210°C f o r twenty™four hours.
Upon opening no p ressu re
was found and subsequent f r a c tio n a tio n o f th e o i l la y e r gave n early a
q u a n tita tiv e y ie ld o f th e o rig in a l ehlorobenzeme.
Diphenyl E ther
In t h i s experiment ^ mole (42.5 grams) o f diphenyl ether and
grams of hydrogen flu o rid e were heated in a heavy copper bomb a t
f o r eighteen hours.
86
2 0 0 °C
D i s t i l l a t i o n o f th e o i l la y e r a a f t e r processing
th e so lu tio n in th e usual mannera gave an
8 tfo
y ie ld of phenol, id e n tif ie d
by a tribromo d e riv a tiv e which melted at 94.5° - 95„5°C and a small
amount o f benzene which gave a d in itr o compound m elting a t
L ite r a tu r e values o f 2 S 4,
6
88
- 89°C»
tribromophenol and meta dinitrobenzene
are 95°C and 89°C resp ectively *
Table I follow s and summarizes b r i e f l y the p o s itiv e r e s u l t s ,
y ie ld s , p ro d u cts,
s t hyl at io n ,
e tc .
fo r t h i s s e r ie s of re a c tio n s on m ethylation,
and phenyl at ion .
32
TABLE I
Reagent
e th y l alc o h o l
(a)
P roduct
Y ie ld -^ 1
n2 0
|
t
e t hylbenzsne
p -d ie th y lb e n ­
zene
33
1*49 52-8
I
222—
222* 5 {f )
48
1.4960-7
I
112 (b)
H* r® der®
ethyl. c h lo ro carbonate (e)
S
I
ethylbenzene
53
1.4950-7
222.5-223 ( f )
e th y l e th e r (a)
1
ethylbenzene
55
1.4952-7
221-222
(b)
e th y l io d id e (d)
i
ethylbenzene
10
1.4953
221-222
(f)
p-met h y l e th y l­
benzene
17
1*4940-4
18
1.-5169
e th y l a c e ta te
U )(e )
......
i
methyl alco h o l
and phenol {a)
phenyl a c e t a te
diphenyl e th e r
(a )(h )
mi - i
iii m
i
n
i
a n is o le
(a)
* 1,11 "
■
300 (k)
'
|
phenol
1
acetophenone I
5
—
phenol
8
-
85.5-86 (g)
94„95 ( i )
196.5-197.0( j
1
1
9 4 .5 -9 5.5 ( i)
I
(a) Temperature o f r e a c tio n was 200° C<
( g) T ri bromoanisole,
(b) Monoacetamino d e riv a tiv e ,,
(h)
By its e lf ®
( c) Temperature o f reactio n , was 0° C»
(i)
Tribromophenol.
( d) Temperature o f r e a c tio n was 100° C.
( j ) Semicarbazone of
a c et ophenone .
( e) Tlie arom atic used was to lu e n e ,
(f)
Diaeetami.no derivative*.
(k) Te r e p h tlia lic acid ,
sublim es above 300°Ct
33
Tr irnet h y l e t hyl ene and T e r t i a r y B utyl Chloride
A one l i t e r
copper f la s k was charged a t 0°G w ith f o r t y - f i v e grams
o f anhydrous hydrogen f lu o r id e and one mole o f t e r t i a r y b u ty l c h lo rid e ,
p re v io u s ly cooled to 0°Co
o u tle t tu b e s and a b rass
The copper f la s k was f i t t e d w ith i n l e t
s tirre r*
and
One mole o f trim e th y le th y le n e was
then added over a p erio d o f approxim ately two hours w ith ra p id s t i r ­
ring*
The m ixture was th e n s t i r r e d
out th e a d d itio n o f th e o l e f i n ,
hydrogen chloride*
f o r an a d d itio n a l hour*
Through­
th e fumes being evolved were c h ie f ly
The m ixture was then poured in to w ater, n e u tra ­
l i z e d w ith NagCOg, and th e o i l la y e r separated and d rie d f o r s ix te e n
hours over magnesium su lfa te *
D is tilla tio n
pci
N
s
gave a f r a c ti o n b o ilin g a t 63-65° a t 19 m« m«
4279-1*4315*
weak c h lo rid e t e s t s *
The f r a c ti o n d eco lo rized bromine and gave very
P o s s ib ly a nonene o r m ixture o f nonenes con­
tam inated w ith some a lk y l c h lo rid e s was present*
f r a c ti o n was obtained and th e d i s t i l l a t i o n
No o th e r constant
range was very wide*
Butyl C hloride and Cyclohexene
A f te r charging a one l i t e r
grams o f hydrogen f lu o r i d e ,
added*
Keeping t h i s
138 grams of t e r t i a r y b u ty l c h lo rid e were
o
s o lu tio n a t 0 C, 78 grains of cyclohexene were
added w ith mechanical s t i r r i n g
hours*
copper f la s k w ith one hundred twenty
ovex* a p erio d o f fo u r and one h a l f
An EC1 t e s t was o b ta in ed , u sin g a s i l v e r n i t r a t e
out th e a d d itio n o f cyclohexene*
bead, through­
The r e a c tio n products were processed
54
(T e r tia r y B utyl C hloride and Cyclohexene)
as in th e p rev io u s r e a c t io n ,
a t 142
a t 739 m, m.
N
and d i s t i l l a t i o n
“ 1.4573-1.4579.
and gave a weak c h lo rid e t e s t e
gave a f r a c tio n h o ilin g
It
decolorized bromine,
A t r i i s o b u ty le n e f r a c tio n of
8$
was
obtained®
Naphthalene and
A one l i t e r
copper f l a s k was f i t t e d
a f t e r which 128 grams of naphthalene,
carbon t e t r a c h l o r i d e , were added®
hydrogen f lu o r i d e were d i s t i l l e d
w ith a mercury seal
d isso lv e d in 500 e.
A fte r cooling to 0°C,
in to t h i s
88
of
grams of
The r e s u l t i n g
m ixture was p la ced In an i c e
s a lt
to a propylene ta n k ,
system was flu sh ed out w ith propylene®
and t h e
bath®
solution®
e.
s tirre r
The i n l e t tube was connected
An open tu be mercury manometer was connected to th e o u tl e t tu b e .
Pylene was th e n adm itted f o r one hour and was r e a d ily absorbed.
m ixture was s t i r r e d
fo r two days,
in th e u su al manner1 and d i s t i l l e d .
a t 15 m. m.
The
and during th e l a s t twenty hours i t
was allowed t o warm to room temperature®
1.
F ro -
The s o lu tio n was th en t r e a te d
D i s t i l l a t i o n gave:
59.2 grams o f beta isopropylnaphthalene b o ilin g at 133-134°C
n 2 0 “ 1.5755-1.5771.
was 262-268° (20)
and n 2 0
= 1.5772.
L i t e r a t u r e v alu es,
A p i c r a t e was made and m elted at
86-87° as compared to 89° i n th e l i t e r a t u r e
38$ o f b eta iso p ro p y ln ap h th alen e.
b o ilin g p o in t
(2 0 ).
This rep resen te d
35
(Nanht halene and Propylene)
2. &%> y ie ld of b eta beta* diisopropylnapbtbalene b o ilin g a t 136139 C a t 15 nu m.
n^® —1.5671-1.5700.
point was 278-280°C ,
—1.5701 (2 0).
melted a t 84-85°C compared to
3.
8 6 °C
L i te r a t u r e v a lu e s 3 b o ilin g
A p i c ra te was prepared and
lis te d
in. l i t e r a t u r e
(20).
5% y ie ld o f triiso p ro p y ln a p h th a le n e b o ilin g at 157° - 164°C
at 15 m. m.
n
PO
= 1.5609-1.5612.
148-152°G (2 m. m.)
81-82°C»
=
L ite r a tu r e v a lu e s , b o ilin g p o in t was
1.5605. A p ic r a te was made and melted a t
L i te r a t u r e value " 84°C.
T herefore o v e r a ll p ro p y latio n of
51$ v/as obtain ed.
Phenol and Tertiary Butyl Chloride
One mole (94 grams) o f phenol was d isso lv ed in 200 e.
te tr a c h lo r id e and poured in to a one l i t e r
66
e. o f carbon
copper v e sse l cooled to 0°C.
grams of hydrogen f lu o r id e were then d i s t i l l e d
in to th e f la s k .
92
grams o f t e r t i a r y b u ty l c h lo rid e were added w ith s t i r r i n g and th e solu­
tio n was then s t i r r e d f o r s ix hours more in an ic e bath and f i f t e e n
hours lon g er a t room tem perature.
throughout th e s t i r r i n g p e rio d .
A good ch lo rid e ion t e s t was obtained
The m ixture was poured onto ic e and
n e u tra liz e d w ith sodium b ic arb o n ate.
The so lu tio n was ex tra c te d w ith
eth er and t h i s o i l la y e r was d i s t i l l e d .
D i s t i l l a t i o n gave 128 grams
of m a te ria l b o ilin g a t 234-238°C a t 732 m. m.
and melted a t 97-98°C.
added.
It
s o lid i f ie d on cooling
A pox’ti o n was dissolved in CCI4 and bromine
A fter evaporating some of th e CC14 and co o lin g 9 the
heavy o i l
s o l i d i f i e d , was f i l t e r e d ,
and r e c r y s t a l l i z e d twice from
36
(Phenol and T e r t i a r y Butyl Chloride)
eth y l alcoh o l
(955&)«
I t m elted a t 48—
49°C®
T his re p re s e n ts an 85%
y ie ld o f p a ra t e r t i a r y b u ty l phenol which m elts at 98°C and gives a
bromo d e r iv a tiv e m eltin g a t 50°C®
Acetone and T e r t i a r y Butyl Chloride
To a m ixture o f 350 c» c® o f acetone and 213 grams of hydrogen
flu o rid e*
two moles o f t e r t i a r y b u ty l ch lo rid e were slowly added over
a p e rio d of tw elve hours®
vals®
A weak ch lo rid e t e s t was o btained a t i n t e r -
Upon examining th e p ro d u cts a f t e r tw elve hours s t i r r i n g ,
constant b o ilin g f r a c tio n was obtained®
no
A very complex s o lu tio n ap­
peared to have been formed®
Bromoacetone and Benzene
A m ixture of f i f t y - f i v e grams of bromo a c e t on e , 110 c® e» of
benzene,
and sev en ty -fiv e grams o f hydrogen f lu o r id e ,
f i f t e e n hours in a bomb in a steam b a th ,
benzyl ketone as was hoped®
but th e m ix tu re,
when heated fo r
f a i l e d to y ie ld
any methyl
A good bromide ion t e s t was ob tain ed ,
as in th e above case, was very complex and nothing
d e f i n i t e was isolated®
37
5~Efch.yl Pentane and T e rtia ry Butyl Chi nnrja
The re a c tio n of 3-eth y l pentane and t e r t i a r y butyl chloride
w ith hydrogen flu o rid e at 0°C did not y ie ld an is o la ta b le heneicosane
fraction..
Much o f th e 3 -eth y l pentane was recovered, and the bulk of
th e re a c tio n products appeared to be a m ixture of alk y l ch lo rid es.
n-Butyl Chloro carbonat e and Benzene
A fter mixing 200 e. c„ (176 grams) of benzene and 140 grams of
hydrogen flu o r id e a t
0
° C in a copper f l a s k s
68
grams of n -b u ty l
chlorocarbonate were added over a h a l f hour p erio d .
The so lu tio n was
s tir r e d fo r two days and HC1 was evolved during much of th e s t i r r i n g
period.
The s o lu tio n was tr e a te d as usual and d i s t i l l a t i o n gave a
41% y ie ld o f secondary butyl benzene which was id e n tif ie d by a mono
acetamino d e riv a tiv e which melted a t 125°C as compared to the l i s t e d
12S°0,
found
13
1®4889-1„4898®
L ite r a tu r e value
s 1.4901,.
P v ridine and D iethyl Ether
One hundred c„ c. of pyridine (98 grams), 112 grams of enhydrous
hydrogen flu o r id e ,
and 50 c.
c<. (36 grams)
in a heavy copper v essel and th e v e s s e l,
a t 185-190°C fo r tw enty-eight hours.
o f d ie th y l ether were placed
a f t e r being sealed, was heated
A fter coolixig, th e bomb was
opened and a considerable p ressu re was noted.
onto ic e and n e u tra liz e d w ith NagCOg®
The mixture was poured
The water la y e r was extracted
58
(P y rid in e and D iethy l Ether)
w ith e th e r and d i s t i l l e d
along w ith th e o r ig in a l oil*.
Oyer 90$ o f
th e p y rid in e waa recovered hut no a lk y la te d products were obtained®
P y rid in e and A cetic Anhydride
Twenty-five grams o f a c e tic anhydrides 74 grams o f anhydrous
hydrogen f lu o r i d e ,
copper v e s s e l a t
and 74 grams o f p y rid in e were heated in a closed
200°G f o r tw en ty -eig h t hours®
No p re s s u re was noted
upon opening th e bomb, and a n a ly s is o f th e r e a c tio n products yielded
no a c y la te d pyridines®
N itrobenzene and D ieth y l E ther
N inety-one grams o f anhydrous hydrogen f lu o r id e were s.dded to a
m ixture o f 100 c® c.
o f d ie th y l ether®
(121 grams) of nitrobenzene and 37 c.
c® grams
The bomb was sealed and heated a t 200°C f o r 19 hours®
The bomb a f t e r cooling was opened and a con siderable p re s s u re was
noted®
D i s t i l l a t i o n r e s u lt e d in recovery o f th e n itro b en zen e, but no
a lk y la te d n itrobenzene was found®
Benzene and S u lf u r ic Acid
A m ixture o f 75 grams o f hydrogen f lu o r id e ,
a c id ,
and
100
24®5 grams of s u lf u r ic
c® c„ o f benzene was placed in a bomb and heated a t
steam bath tem peratures f o r six te e n hours®
The bomb was cooled and
39
(Benzene and S u lfu ric Acid)
opened*
The contents were poured in to a la rg e copper beaker, and th e
hydrogen f lu o r id e was driven o f f by heating*
The remainder was
poured in to w ater and th e o i l la y e r separated*
le s s th an one gram of diphenyl sulfone*
s l i g h t l y a lk a lin e with CaO and f i l t e r e d .
to dryness t o
tio n
65°„
d ig e ste d f o r one hour*
washed*
The water la y e r was made
The f i l t r a t e was evaporated
give calcium benzene sulfonate*
in w ater and heated to
The o i l la y e r gave
A sample was dissolved
.Ammonium o x alate was added, and the solu­
The calcium o x alate was f i l t e r e d
and
The p r e c i p i t a t e was d isso lv ed and t i t r a t e d w ith standard po­
tassium permanganate.
was 11.3$.
in t h i s
Calcium, c a lc u la te d was 11.3$.
Calcium found
A 75$ y ie ld o f calcium benzene su lfo n ate was accomplished
sulfonation*
Benzene and F luo ro su lfo nie Acid
This experiment was performed in th e chemistry annex which burned
and destroyed th e o r ig in a l d a ta fo r t h i s flu o ro su lfo n ic acid experi­
ment.
fire ,
However, from memory and from r e p o r ts w ritte n soon a f t e r th e
it
can be said t h a t a 53$ y ie ld of benzene su lfo n ic acid was
obtained from th e re a c tio n of benzene and flu o ro su lfo n ic acid at a
tem perature of from 60-7Q°C»
Benzene and Fluoro s u lf oni c Acid
Twenty-five grams o f fluc-rosulfonic acid and e ig h ty -e ig h t grams
of benzene were heated in a copper bomb a t
160
o
G f o r six te e n hours*
4-0
{Benzene and F lu o ro su lfo n ic Acid)
The bomb was cooled,
opened, and t r e a t e d as u s u a l.
A 14$ y ie ld o f
diphenyl s u lfo n e , m eltin g a t 127-128°C a f t e r two r e c r y s t a l l i z a t i o n s
from e th y l a lc o h o l,
1 28 .5 -12 9 .5°G.
6
c.
c.
added.
was o b tained.
The lite i* a tu r e m eltin g p o in t i s
1.5 grams o f th e s u l f one were placed in a beaker w ith
o f co n cen trated HgSO^ and
6
c.
c.
o f concentrated HNO^ were
The tem perature was never allowed to
s ip a tio n o f th e h eat of r e a c tio n ,
f o r f i f t e e n m inutes,
exceed 60° and a f t e r d i s ­
th e m ixture was heated at 50-60°C
poured onto i c e ,
and f i l t e r e d .
The d in itro p h e n y l-
sulfone ( b is met a-n itro p h e n y l s u lf one) was then r e c r y s t a l l i z e d once
from e th y l alco h o l and once from g l a c i a l a c e tic a c id .
The m elting
p o in t was 195.5-195.5 as compared to th e l i t e r a t u r e value of 197-198 (5 6 ).
Benzene and S u lf u r ic Acid
A m ixture o f 9„9 grams of HgSO^, 118 grams o f anhydrous hydrogen
f lu o r i d e ,
and
110
grams o f benzene were heated in a copper bomb a t
140“150°C f o r eig h teen hours.
Upon a n a ly s is of th e p ro d u cts,
of diphenyl su lfo n e m elting a t 127-128°C were is o la te d .
8.9 grams
A d in itr o
de­
riv a tiv e
(36) was prepared and m elted a t 196~197°C a f t e r one r e c r y s t a l ­
liz a tio n
from e th y l alco ho l and two from g la c ia l a c e tic a c id .
y ie ld o f diphenyl su lfo n e was 40% of th e t h e o r e t i c a l .
The
41
Gvclopentane and Fluoro su lfo n ic Acid
F if ty grams o f flu o ro su lfo n ic acid and t h i r t y —
fiv e grams of
cyclopentane were placed in a h e a v y copper bomb and heated at 140°C fo r
eighteen hours®
The products were analyzeds hut no cyclopentane s u l-
fonic acid was iso lated ^
and most of th e eyclopentane was recovered®
(This re a c tio n was also attempted a t 0°C w ith negative results® )
l
Cvolop ent ane and S u lfu ric Acid
Seventy-four grams o f hydrogen f lu o r id e # 17®5 grams of cyclopentane,
and 49 grams of s u lf u r ic acid were heated in a closed copper
v essel at 140°C f o r fou rteen hours®
Analysis o f th e products f a ile d
to y ie ld any sulfomated eyclopentane®
N itr i c Acid and Benzene
A mixture of 105 grams of anhydrous hydrogen flu o rid e and 125 c® c®
of benzene were placed in a copper fla s h f i t t e d w ith a copper s t i r i 'e r
and cooled to s a l t —
ic e temperatures®
acid was then added very slowly®
and much NOg was evolved®
liz e d with NagCOg®
of th e n i t r i c acid®
One fo u rth of a mole of n i t r i c
The re a c tio n was extremely v io len t
The mixture was poured onto ic e and n eu tra­
Two holes were made in th e copper v essel by th e actio n
Upon d i s t i l l a t i o n of the o i l la y e r,
of nitrobenzene was obtained®
e. 42% y ield
A p o rtio n was n itr a te d with n i t r i c
s u lf u r ic acids to y ie ld meta dinitrohenzene m elting at 88—
89°C as
compared to
the l i t e r a t u r e value of 89--90°C®
and
42
N i t r i c Acid and Benzene
A copper v essel was coated -with, a high m elting wax obtained from
th e petroleum la b o ra to ry ,
end f o r ty - f o u r grams of benzene and f o r ty -
seven grams o f hydrogen flu o r id e were added*
The re a c tio n v e s s e l was
cooled in a s a l t - i c e mixture a f t e r which one eighth o f a mole of
n itric
acid was added w ith s t i r r i n g over a p erio d of f i f t e e n m inutes.
The r e a c tio n proceeded smoothly and a n a ly sis o f the products gave an
83% y ie ld of nitrobenzene.
A portion, was n i t r a te d to y ie ld meta d i­
nitrobenzene m elting a t 89“-90°C<,
The benzene obtained in th e f r a c tio n ­
a tio n was te s t e d f o r flu o r in e a f t e r fu sin g w ith sodium, but th e t e s t
was n e g a tiv e .
N it r i c Acid and Nitrobenzene
F if te e n c.
c. o f n i t r i c
acid ( s p e c if ic g ra v ity » 1.42) were
dropped slowly w ith s t i r r i n g in to a mixture o f twelve grams of n i t r o ­
benzene and around tw en ty -fiv e grams o f hydrogen flu o rid e p rev io u sly
placed in a wax coated copper d ish and cooled to
products f a i l e d to y ie ld any d in itro b en zen es»
attempted u sin g th e above co n d itio n s,
0
°C.
A nalysis o f the
Another experiment was
and adding copper f i l i n g s in
small amounts in th e b e l i e f th a t t h i s might cataly ze the r e a c tio n ,
no dinitrobenzene was iso lated .,
but
43
N itr ic Acid and P y rid in e
F ifte e n c« c® o f n i t r i c acid ( s p e c if ic g ra v ity = 1®42) were
mixed w ith tw en ty -fiv e grams of hydrogen flu o rid e and 9 ®
8 grams of
pyridine®
The so lu tio n was s t i r r e d a t
0
°C f o r eig h t hours®
Frac­
tio n a tio n a f t e r processing th e so lu tio n re s u lte d in the recovery of
th e pyridine®
Arsenic Acid and Benzene
A m ixture of 110 grams of benzene, 105 grams of anhydrous
hydrogen flu o r id e ,
end 67®5 grams o f a rsen ic acid (H^AsO^-^Hg®) were
placed in a heavy bomb and heated a t 180°C f o r seventeen hours®
The
bomb was cooled, opened, and poured in to a la rg e
The
copper beaker®
beaker was heated in a water bath u n t i l th e hydrogen flu o rid e was
driven off®
rated®
The o i l was poured in to water and th e la y e rs were sepa­
The acid w ater la y e r was e x tra cted w ith two 50 c« c® p o rtio n s
o f ether®
The e th e r was d i s t i l l e d
and a heavy phenolic smelling o i l
remained®
This yielded 8®2 grams o f phenol upon fractionation®
A
p o rtio n was brominated and gave tribromopheno3. m elting a t 94° a f t e r
two r eery s t a l l ! sat ions from alcohol®
The o i l la y e r was d i s t i l l e d and
re s u lte d in th e recovery of th e benzene.
o f phenol®
This rep resen ts a 13% y ie ld
44
A rsenic Acid and Toluene
Eiglity-1hree grains o f hydrogen f lu o r id e ,
33,6 grams o f a rs e n ic
a c id and 8 7 grams o f to lu en e were heated in a heavy copper bomb at
o
160 C f o r a p erio d o f e ig h teen hours*
uhe p rod u cts were tr e a te d as
i n th e run between a rs e n ic a c id and benzene*
A very d e f i n i t e
odor was noted ,
and no para-m ethylphenyl-
but no c r e s o ls were is o l a t e d ,
c re s o lic
arso n ic a c id was is o la te d *
A rsenic Acid and Benzene
In attem p ting to
o x id ise benzene to phenol, many a d d itio n a l ex p eri­
ments were c a r r ie d out to
obtained*
check th e o r ig i n a l run in which phenol was
The r e a c tio n was run a t l e a s t
eig h t tim es d u p lic a tin g con­
d itio n s o f th e o r ig i n a l run as c lo s e ly as was experim entally possible*
R eactions were performed f o r s h o rte r and lo ng er p e rio d s and varying
amounts o f r e a c ta n ts were used*
I n two experiments in which th e o r ig in a l
co n d itio n s were d u p lic a te d a d e f i n i t e p h enolic odor was p re s e n t,
no phenol was is o la te d .,
s u lfa te ,
Y arious c a t a ly s ts were added such as:
cuprous c h lo rid e , HgS0 ^_s s i l v e r
s o ld e r,
but
zinc
end cupric s u lf a te in
attem pts to d u p lic a te anything which might p o s s ib ly have been p resen t
to
c a ta ly z e t h i s oxidation*
A ll were unsuccessful*
45
Phenylar.sonic Acid and Hydrogen F luo rid e
One hundred and te n grams o f benzene s twenty grams o f phenylarso n ic acid*
and n in e ty - f iv e grams o f hydrogen f lu o r id e were heated
in a copper bomb a t 180° f o r eighteen hours*
The r e a c tio n products
were t r e a t e d as in th e a rs e n ic a c id experiment s 8 but no phenol was
found*
The follow ing o x id a tio n s were attempted usin g potassium perman­
ganate as th e o x id izin g agent*
No oxidized products were is o la te d in
any o f th e experiments and no o x id a tio n appeared to occur as much of
th e KMn0
4
co lo r was reg en erated a f t e r th e hydrogen f lu o r id e s o lu tio n
was poured in to water®
Hydrogen flu o r id e reacted very v i o l e n tl y with
KWihO^ and g re a t care had to be tak en in adding th e hydrogen flu o r id e
to th e permanganate*
The hydrocarbons such as benzene and tolu ene were
fused w ith sodium a f t e r f r a c tio n a tio n and te s te d f o r f l u o r i n e s but th e
t e s t s were a l l negative*
The r e a c tio n products were analyzed as in th e
a r s e n ic acid experiments*
a. S ix teen grams o f hydrogen fluoride*
4*5 grams of KMnO^*
and 17 e6 grams o f benzene were s t i r r e d a t 0°C f o r s ix hours®
P roducts were tr e a t e d in th e usual manner*
b* F if te e n grams o f ICMn04s 67 grams of hydrogen fluoride*
and
88
grains of benzene were heated in a heavy bomb at
b ath tem peratures f o r ten hours*
steam
c. Thirty-tw o grams o f hydrogen f lu o r i d e s 2*6 grems of
to lu e n e ,
and 3.6 grams o f KM11O4 were s t i r r e d in an open, copper
v e s s e l f o r two hours*
Potassium Pichromate O xidations
No o x id a tio n products were is o la te d in th e following s e r ie s o f
re a c tio n s and no flu o rin e containing organic compounds were found*
The
ad d itio n o f dichromate to hydrogen flu o r id e gave a very vigorous r e ­
a c tio n .
a.
Six grams o f KgCrgOy, 14 grams o f hydrogen f lu o r id e ,
and
17.6 grams o f benzene were stirx*ed a t 0°C f o r six hours.
F ifte e n grams o f K2 Crg0r?s 56 grams of hydrogen f lu o r id e ,
and
88
grems o f benzene were heated in a copper bomb a t 100°C
f o r eig h t hours.
c. F if te e n grams o f K2 Crg0 7s> 75 grems o f hydrogen f lu o r id e ,
and 87 grams of toluene were heated a t 100°C in a copper bomb f o r
s ix hours.
Lead Dioxide and Benzene
Ten grams of lead dioxide,
hydrogen f lu o r id e were s t i r r e d
19.3 grams o f benzene, and 34 grams of
a t 0°C in a copper dish fo r s ix hours.
Analysis o f th e products gave no phenol, and r e s u lte d in th e recovery
47
{Lead Dioxide and Benzene)
o f th e benzene*
Twenty grams o f le a d dio x id e,
88
grams o f benzene,
and 94 grams o f
hydrogen f lu o r id e were heated in a copper bomb a t 100°C f o r f i r e hours*
No phenol was is o la te d *
48
SOMMAKY
1 . M ethylation of arom atic n u c le i! lias been attempted u sin g
methyl a lc o h o l, methyl io d id e ,
and methyl a c e ta te v;lth anhydrous
hydrogen flu o rid e a s th e condensing medium.
T his was u n successfu l
in a l l th e r e a c tio n s which were in v estig ated *
A nisole was synthesized
in. 18$ y ie ld from methyl alcoh o l and phenol a t 2Q0°C i n th e presence
of anhydrous hydrogen fl.u o rid e.
2
. E th y latio n o f benzene was s u c c e s s fu lly c a rrie d out w ith a
number o f su bstan ces, namely;
eh lo ro carbo n ate, 53$ y ie ld ;
10$ y ie ld ;
to
e th y l alco h o l,
d ie th y l e th e r ,
and eth y len e, t r a c e s .
give a 17$ y ie ld
81$ y i e l d 5 e th y l
55$ y ie ld ;
e th y l io d id e ,
Toluene re acted w ith eth y l a c e ta te
of p a ra m ethylethylbenzene.
An attem pt t o p rep are
p h en eto le from e th y l alco h ol and phenol was u n su c c e ssfu l,
3. P hen y latio n was attem pted,
but was u n su ccessfu l.
Phenol and
acetophenone were o btained fx*om phenyl a c e ta te and benzene.
e th e r was s p l i t w ith anhydrous hydrogen flu o rid e at
200
° to
Diphenyl
give a
small amount of phenol.
4o Various alkyl& tions were attem pted, w ith th e follow ing
re s u lts ;
a.
T e r tia r y b u ty l c h lo rid e and trim eth y l ethylene con-
densed to y ie ld
small amounts of an o le fin bearing the
propex’t i es o f a nonene.
49
b„ T e r tia r y butyl ch lo rid e end eyclohexene condensed to
y ie ld an o le f i n ic f r a c tio n which was not identified®
T r iis o ­
butylene was found in t h i s run®
c. Naphthalene and propylene gave a 51% y ie ld o f b eta
iso pro py l naphthalene^ a t 0°C in th e presence of hydrogen
fluoride®
d« Phenol was alk y late d a t 0°C w ith t e r t i a r y butyl alcohol
and gave an 85% y ie ld o f para t e r t i a r y b u ty l phenol®
e® R eactions between acetone and t e r t i a r y b u tyl c h lo rid e p
and bronoacetone and t e r t i a r y b u ty l ch lo rid e did not y ie ld any
d e f in i te p ro d u cts,
as was th e case in th e re a c tio n between
5 -e th y l pentane and t e r t i a r y b u ty l chloride®
f . Normal butyl chlorocarbonate and benzene condensed
to
give a 41% y ie ld of secondary b utyl benzene a t 0°C®
5® S u lfo n atio n was s u c c e s s fu lly c a rrie d out using e ith e r flu o ro su lfo n ic a c id o r a mixture o f s u lf u r ic acid and hydrogen fluoride®
fone form ation was promoted by both®
The s u lf u r ic aeid-hydrogen f lu o r ­
ide mixture was shown to be th e b e t t e r s u lfo n a tin g medium®
c essfu l attempt was made to
5® Benzene and n i t r i c
S ul-
An unsuc­
su lfo n a te cyclopentane®
acid a t 0°C in th e presence of hydrogen
flu o rid e gave an 83% y ie ld o f mononitrobenzene*
An unsuccessful
<
»
attempt was made to n i t r a t e nitrobenzene and pyrid<§pe by t h i s method
at
0
°C®
50
7. A rso n atio n was attem pt ed u s in g a r s e n ie
in th e p resen ce o f anhydrous hydrogen flu o rid e ..
ta in e d i n
15% y i e l d
in t h e f i r s t
a c id
(H^AsO^-g-ELgO)
Phenol was ob­
attem pted a rs o n a tio n o f benzene.
The r e a c t io n could n o t be d u p lic a te d alth o u g h p h en o lic odors could
be n o ted in t h r e e of t h e
a tte m p ts t o
d u p lic a te t h i s
re a c tio n *
number o f c a t a l y s t s were in v e s tig a te d in an attem p t to
phenol from benzene*
8
A
sy n th e siz e
A rso n atio n was u n su ccessfu l*
. P o tassiu m p en nanganates potassium dichrom ate„ and le a d di-=
oxide i n th e p resen ce o f hydrogen f l u o r i d e
o r to l u e n e , and no f l u o r i n e
in th e s e
experiments*
f a i l e d to
o x id iz e benzene
c o n ta in in g o rg a n ic compounds were found
51
B ib lio g r a p h y
1* Simons and Archer - J„ Am. Chem. Soc„ 60, 986 (1958).
2.
Simons and Archer - i b i d .
60, 2952 (1958).
3.
Simons and Archer - i b i d .
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