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The preparation of p-Nitrostyrene Oxide and its alkali-catalyzed reaction with phenol

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The preparation of p-Nitrostyrene Oxide and its alkali-catalyzed reaction with phenol

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Content THE PREPARATION OF p-NITROSTYRENE OXIDE
A N D ITS ALKALI-CATALYZED REACTION WITH PHENOL
A T h esis
P resen ted to
The F a c u lty o f th e Departm ent o f C hem istry
U n iv e rsity o f S outhern C a lifo rn ia
In P a r t i a l F u lfillm e n t
o f th e R equirem ents fo r th e Degree
M aster o f S cience
by
Henry George M autner
Jan u ary 1950
UMI Number: EP41577
All rights reserved
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This thesis, written by
HENRY- G EO RG E -M AUJUEEt.............................
under the guidance of hi&-— Faculty Committee,
and approved by all its members, has been
presented to and accepted by the Council on
Graduate Study and Research in partial fulfill
ment of the requirements for the degree of
m s x E 8 ....o .F .s c m c E .
Faculty Committee
U N IV E R S IT Y O F S O U T H E R N C A L IF O R N IA
LO S A N G E L E S 7
Jan u ary 30, 1950
Doheny L ib ra ry
U .S.C.
In co n n ectio n w ith th e u se o f E l i t e ty p e in
p re p a rin g th e t h e s i s su b m itted by Mr. Henry George
M autner, t h i s th e s i s was su b m itted to and approved
by a five-m an com m ittee c o n s is tin g o f P ro fe s so rs
Benson, D oscher, K harasch, M ysels and m y self.
Approval o f th e c o n te n t, form , and ty p e s iz e used
was g iv en .
A s s is ta n t P ro fe s so r o f
C hem istry
COG/aak
F O R E W O R D
The a u th o r w ishes to ex p ress h is a p p re c ia tio n fo r th e co n tin u in g
i n t e r e s t and h e lp fu ln e s s o f Dr. Cyrus 0„ Guss, iN rh o has c o n trib u te d in no
sm all measure to w hatever o f v alu e may be c o n tain ed in t h i s t h e s i s .
CONTENTS
C hapter page
I . INTRODUCTION . . . . . . . . . . . . . 1
I I . HISTORICAL . . . . . . . . . . . . . . 2
I I I . DISCUSSION . . . . . . 4
A, The P re p a ra tio n o f p -N itro s ty re n e Oxide ., . . 4
B. The A lk a li-C a ta ly z e d R eactio n o f p -N itro sty re n e
Oxide w ith Phenol . . . . . . . . . 6
IV. EXPERIMENTAL . . . . . . . . . . . . . 12
A. The P re p a ra tio n o f p -N itro s ty re n e Oxide . . . 12
1. P re p a ra tio n o f p-N itro aceto p h en o n e . . . 12
2. P re p a ra tio n o f p -N itro p h en acy l Bromide . . 14
3. P re p a ra tio n o f Aluminum Iso p ro p o x id e . . . 15
4 . P re p a ra tio n o f p -N itro s ty re n e Bromohydrin ( I ) 15
5. P re p a ra tio n o f p -N itro s ty re n e Oxide ( I I ) . . 16
6. P re p a ra tio n o f p -N itro p h en y l G lycol ( I I I ) . . 17
7. P re p a ra tio n o f p -N itro cin n am ic Acid . . . 18
8 . P re p a ra tio n o f p - N i t r o s t y r e n e ................................... 18
B. The A lk a li-C a ta ly z e d R eaction o f p -N itro sty re n e
Oxide w ith Phenol . . . . . . . . . 19
1. Form ation o f 2-p -N itro p h en y l-2 -P h en o x y -
e th a n o l (IV^A) ............................................ 19
2. P re p a ra tio n o f p -N itro b en zo ate o f 2 -p -N itro -
phenyl-2-P henoxyethanol (IV -A )...................................21
3. R eduction o f 2 -p -N itro p h en y l-2 -P h en o x y eth an o l
to 2-p-A m inophenyl-2-Phenoxyethanol (VI) . .2 1
4. D eam ination o f 2-p-A m ino-2-Phenoxyethanol to
2-Phenyl-2~PhenoxyethanoX (V II) . . . . 22
5. O xidation o f 2 -p -N itro p h en y l’ 2-Phenoxyethanol
(IV-A) .................................. ' . . . 23
6. R eactio n o f 2 -p -N itro p h en y l-2 -P h en o x y eth an o l
(IV-A) w ith Lucas Reagent . . . . . . . 24
7. A ttem pt to P rep are p -N itro p h en acy l Phenoxide 24
8. R ea ctio n o f F ra c tio n C (V-A) w ith P h th a lic
A nhydride ................................... 25
9. P re p a ra tio n o f p-N itV dbenzoate o f F ra c tio n C
(V-A) 25
10. R eactio n o f F ra c tio n C(V-A) w ith Benzene-
diazoniura C h lo rid e ................................... 26
11. A ttem pt to P rep are A ry lo x y acetic Acid D eriv
a tiv e o f F ra c tio n C (V-A) . . . . . . 26
12. Attempt to P rep are th e 2 ,4 -D in itro p h e n y l
E th er o f F ra c tio n C (V-A) . . . . . . 26
V. S U M M A R Y ................................. 28
BIBLIOGRAPHY ........................................................................................ 29
CHAPTER I
INTRODUCTION
I t has been known fo r a long tim e th a t th e a lk a li- c a ta ly z e d r e a c tio n
o f unsym m etrical o le f in e o xides w ith hydroxy compounds r e s u l t s p rim a rily
in th e fo rm atio n o f iso m eric e th e r -a lc o h o ls .
R-CH-CHo ♦ R'OH ---- » R-CH-CHo-OH ♦ R-CH-CH2-0R'
z I I
0 O R * O H
These r e a c tio n s have been shown to be o f th e n u c le o p h ilic d isp lacem en t ty p e .
The n a tu re o f th e group s u b s titu te d on th e e th y le n e oxide r in g ap
p ea rs to have a s ig n if ic a n t in flu e n c e on th e d ir e c tio n o f th e opening o f
th e r in g . For example in th e above e q u a tio n , where R i s m ethyl, th e e x c lu s
iv e o r predom inant p ro d u ct i s th e secondary a lc o h o l.
S ty ren e o x id es a re p a r tic u la r ly s u ita b le f o r th e stu d y o f th e f a c to r s
a f f e c tin g th e d ir e c tio n o f rin g opening sin c e s u b s titu e n ts can be in tro d u c e d
in to th e arom atic r in g to e f f e c t a c o n d itio n o f e le c tro n w ithdraw al o r e le c
tro n r e le a s e . Because a re c e n t stu d y had shown th e i d e n t i t y o f th e e th e r -
a lc o h o ls formed by th e a lk a li- c a ta ly z e d r e a c tio n o f sty re n e oxide w ith
p h en o l, i t appeared in te r e s tin g to examine i f and how th e s u b s titu tio n o f
an e le c tr o p h ilic group on th e benzene rin g o f s ty re n e oxide would m odify
th e d ir e c tio n o f th e opening o f th e o x ira n e r in g . The n i t r o group was
s e le c te d fo r t h i s purpose fo r th e reaso n th a t i t i s th e most pow erful o f
e le c tr o p h ilic g ro u p s; hence i f e le c tr o p h ilic groups a re to e x e rt any e f f e c t
on rin g -o p e n in g , th a t o f th e n i t r o group should prove to be p a r tic u la r ly
easy to o b serv e.
CHAPTER I I
HISTORICAL
As e a r ly as 1894 Roithm er (l ) d isco v e red th a t th e o x id e s o f e th y le n e
and propylene re a c te d w ith phenol, i f th e components were h eated to 150°C.
f o r s e v e ra l h o u rs. In 1914 Boyd and M arie (2 ) showed th a t t h i s re a c tio n
was s tro n g ly c a ta ly z e d by a lk a li and th a t a m ix tu re o f iso m eric e th e r -
■ * s
a lc o h o ls was o b ta in e d . Sexton and B ritto n (3 ) in v e s tig a te d th e i d e n t i t y
o f th e p ro d u cts o b tain ed from th e a lk a li- c a ta ly z e d r e a c tio n o f p ropylene
ox id e w ith phenol and found t h a t th e secondary a lc o h o l was formed predom
in a n tly , although both th e prim ary and th e secondary a lc o h o l were is o la te d
in th e p resen ce o f an a c id c a ta ly s t. S im ila r r e s u l t s were o b tain e d by
Chitwood and F reure (4) and o th e rs (5 * 6 ), who showed t h a t th e re a c tio n o f
a lip h a tic a lc o h o ls w ith propylene o x id e , o r 3 ,4 -e p o x y -l-b u te n e , in th e p re s
ence o f an a lk a lin e c a t a l y s t, y ie ld e d p redom inantly th e secondary a lc o h o l.
These r e s u l t s are ex p lain ed on th e b a s is o f an e le c tro n r e le a s e by th e a lk y l
o r a lk e n y l group which th e re b y d i r e c t s th e n e g a tiv e a lk o x id e o r phenoxide
anion to th e more p o s itiv e carbon atom, which i s th e l e a s t s u b s titu te d
carbon atom in th e ox id e r in g . This i n t e r p r e t a t i o n has been found to be
g e n e ra lly v a lid f o r th e re a c tio n s o f many e th y le n e o x id es p o sse ssin g a
s a tu ra te d a lip h a tic group s u b s titu te d on th e oxide r in g w ith many d if f e r e n t
an io n s ( 7 ,8 ,9 ) .
Swern, B ille n , and K night (70) examined th e r e a c tio n s o f 3 ,4 -ep o x y -
1-b u te n e and s ty re n e oxide w ith sodium a llo x id e , and re p o rte d th a t in both
cases th e prim ary a lc o h o l was formed alm ost e x c lu s iv e ly . These a u th o rs
p o s tu la te d e le c tro n a t t r a c t io n by th e phenyl group to e x p la in th e p re fe rre d
form ation of th e prim ary a lc o h o l in th e case o f s ty re n e o x id e. A mechanism
in v o lv in g e le c tr o n - r e le a s e by th e v in y l group was used to e x p la in th e form
a tio n o f th e prim ary alc o h o l from 3 , 4-epoxy-1 -b u te n e . P rev io u s i n v e s t i
g a to rs (6 ) u sin g m ethanol and 3»4-epoxy-1 -b u te n e found th e secondary a lc o h o l
to be th e predom inant p ro d u ct.
Guss ( l l ) in v e s tig a te d th e a lk a li- c a ta ly z e d re a c tio n o f sty re n e oxide
- w ith phen o l, and showed th a t under c e r ta in c o n d itio n s th e prim ary alco h o l
was th e main product fonaed; although some secondary a lc o h o l was a lso ob
ta in e d , th e r a tio o f prim ary to secondary a lc o h o l was th re e to one. The
a c id -c a ta ly z e d re a c tio n was re p o rte d to form an a lk a li- s o lu b le m ix tu re .
Thus i t ap p ears th a t th e n a tu re s o f th e c a t a l y s t, o f th e h y d ro x y lic
compound, and-of th e oxide in v o lv ed in t h i s ty p e o f re a c tio n a l l have a
s ig n if ic a n t in flu e n c e on th e d ir e c tio n o f th e opening o f th e o x irsn e rin g .
CHAPTER I I I
DISCUSSION
The purpose o f th e p re se n t work was to in v e s tig a te th e co u rse o f
th e a lk a li- c a ta ly z e d re a c tio n o f phenol w ith s ty re n e oxide so s u b s titu te d
as to induce a v ery d ecid ed p o la r ity a t th e o x ira n e rin g . In view o f th e
very s tro n g ly e le c tr o p h ilic c h a ra c te r o f th e n i t r o group, i t was decided
th a t p - n itr o s ty r e n e o x id e, h ith e r to unknown, could be u t i l i z e d fo r t h i s
purpose. The known o - n itr o s ty r e n e oxide (12) was n o t u se d , to avoid any
co m p licatin g e f f e c ts o f s t e r i c h in d ran ce.
A. The P re p a ra tio n o f p -M itro sty re n e O xide. — p -N itro s ty re n e ox id e ( I I )
was p rep ared by th e fo llo w in g r e a c tio n sequence:
0;>N
0
it
CC1
0
Mg+EtOH
CH 2 (C00Et)
CCH(C00Et)2
0
I t
OpN
CCH 2Br
O H Br
I ' I
ch- ch2
H* 02N
— C02
-EtOH
NaOH
0
/ ^ .C C H 3
ch- ch2
-HBr 02 N
Br-
A1C1
I I
p -N itroacetophenone was p rep ared by th e method o f W alker and Hauser
0 3)> whereby p -n itro b e n z o y l c h lo rid e was caused to r e a c t w ith m agnesio-
m alonic e s te r . The r e s u ltin g crude d ie th y l acy lm alo n ate was hydrolyzed and
d e c arb o x y la te d , th u s y ie ld in g 59J& o f th e d e s ire d p ro d u ct.
- 5 -
p -N itro p h en acy l bromide was p rep ared by th e b rom ination o f p - n itr o -
acetophenone acco rd in g to th e procedure o f E n g ler and Z ie lk e ( l4 ) in a y ie ld
o f 62%. As t h i s method d id n o t appear to be co m p letely s a tis f a c to r y , a
s y n th e s is analogous to t h a t used by Cooper and D avidson (1 5 ) f o r /th e prep
a r a tio n o f phenacyl bromide from acetophenone was u sed . This ra is e d th e
re a c tio n y ie ld to 81$ and improved th e p u r ity o f th e p ro d u c t.
p -N itro s ty re n e brom ohydrin (1) was sy n th e siz e d by th e re d u ctio n o f
p -n itro p h e n a c y l brom ide. A m o d ific a tio n o f th e M eerw ein-Ponndorf re a c tio n
as re p o rte d by W instein (l6 ) was u t i l i z e d to o b ta in an 81% y ie ld o f I .
The dehydrobrom ination o f I to p - n itr o s ty r e n e ox id e ( I I ) was accom
p lis h e d w ith sodium hydroxide a t room te m p eratu re in a J&fo y ie ld .
On re flu x in g th e oxide I I w ith a v ery d i l u t e h y d ro c h lo ric acid s o lu
t i o n , a 55.4% y ie ld o f p -n itro p h e n y lg ly c o l ( I I I ) was o b ta in e d . I t i s i n t e r
e s tin g to n o te t h a t on r e flu x in g I I w ith w ater in th e absence o f a c id , no
g ly c o l at a l l was form ed, w h ile sty re n e o x id e, under th e s e circu m stan ces,
g i v e s .r is e to an e x c e lle n t y ie ld o f sty re n e g ly c o l ( 1 7 )»
02N-
0
^ / \
ch- ch2
I I
h20 (H*)
0a N-
O H O H
CH-CH2
h i
An a l t era a t e method o f sy n th e siz in g I I which wes c o n sid ered i s th e
fo llo w in g :
OoN
A
U
CH«CH-CQOH
cju .i'tio U n e-
OoN
CH»CH3
C 0 0 0 H
CH-CH.
I I
- 6 -
However, i t was found th a t th e d e c a rb o x y la tio n of p -n itro c in n a m ic
a c id by means o f copper powder and q u in o lin e acco rd in g to th e procedure o f
W ilay and Smith (1 6 ) y ie ld e d o n ly a 7 . 8$ y ie ld o f p - n itr o s ty r e n e , and th e
p r o je c t was abandoned.
B. The A lk a li-C a ta ly z e d R eaction o f p -N itro s ty re n e Oxide w ith P henol. —
From th e r e a c tio n o f p - n itr o s ty r e n e ox id e ( I I ) and phenol, in th e p resen ce
■of aqueous sodium hyd ro x id e, 2 -p -n itro p h e n y l-2 -phenoxyethanol (IV-A) ' was
is o la te d and i d e n t i f i e d . A nother compound, which m ight be 2 -p -n itro p h e n y l-
2-p-hydroxyphenyl e th a n o l (V-A), was a ls o is o l a t e d , b u t i t s s tr u c tu r e was
n o t d e f i n it e l y proved.
OoN
A 0H
/ V ch -ch2
sj + U
W aO H m
CH-CH2 0H
0
0 2
A
u
IV+A
CH+CHa O H
V-A
R efluxing p - n itr o s ty r e n e ox id e and phenol in an aqueous sodium
hydroxide s o lu tio n f o r v ary in g p e rio d s o f tim e gave r i s e to a 55 “74 $ y ie ld
o f IV-A in th e form o f f in e , l i g h t ta n n e e d le s m e ltin g a t 93-94°C ., w hile
V-A, which was is o la te d in th e fprm o f a yello w o i l , was o b tain e d in a
y ie ld o f 10-17$. The rem aining product was a lk a li- s o lu b le and was n o t
s e p a ra te d .
A n aly sis e s ta b lis h e d th a t IV-A had th e e m p iric a l form ula C, ^H, 3 O4.N,
which co rresp o n d s to e ith e r o f th e expected phenoxy a lc o h o ls IV-A o r IV-B:
0‘ N- O oH ~°H20H o, h^ > CH-OH.O
f)
IV-A IV-B
The f a c t th a t in most cases one o r two r e c r y s t a l l i z a t i o n s s u ffic e d
to is o la te . IV-A as a p u re, sh a rp ly m e ltin g compound, as w e ll a s th e f a c t
th a t IV-A y ie ld e d a pure p -n itro b e n z o a te , m e ltin g a t 12T-7 22°C. in a 91$
y ie ld , tended to show th a t th e a lc o h o l in q u e stio n was a pure compound and
n o t an iso m eric m ix tu re o f IV-A and IV-B.
A Lucas t e s t perform ed on IV-A was n e g a tiv e , which im p lie d , but did
n o t p rove, th a t th e compound was a prim ary a lc o h o l.
I t was th e r e fo r e decided to attem p t to cause IV-A to undergo th e
fo llo w in g tra n sfo rm a tio n s :
02m - ^ ~ % > ch- ch2oh
A
IV-A V
SnCXj
HC1
h2n< ^ A >ch- CHoOH
VI
H 3PQ2
H O N O
CH-CtyOH
A
VII \ s
V
- 8 -
The n i t r o compound IV-A was reduced by means o f stannous c h lo rid e
and h y d ro c h lo ric a c id to 2-p-am ino-2-phenoxyethanol (V I). Deam ination o f
t h i s crude amine by th e procedure of Kornblum and I f f la n d (1 8 ) gave r i s e
to a 39*4$ y ie ld o f 2-phenyl-2-phenoxyethanol (V II), A mixed m e ltin g p o in t
d e term in a tio n w ith an a u th e n tic sample (11 ) o f VII showed no d e p re ssio n ,
proving u n e q u iv o ca lly th a t IV-A was 2 - p- n i t r o p h eny 1 - 2 - ph enoxv e t hano 1.
An attem p t was a lso made to e lu c id a te th e s tr u c tu r e o f IV-A by means
o f an o x id a tio n r e a c tio n , as th e r e s u lt o f which th e prim ary alco h o l IV-A
should have y ie ld e d an a c id , and i t s secondary isom er IV-B a k eto n e. Al
though a wide v a r ie ty o f re a c tio n c o n d itio n s was u t i l i z e d , th e o n ly o x id a tio n
product th a t was o v er o b ta in e d was p -n itro b e n z o ic a c id , most o f th e s ta r t i n g
pro d u ct bein g reco v ered unchanged.
A nother method o f s tr u c tu r e proof th a t was in v e s tig a te d was th e f o l
low ing s y n th e s is :
CO-CH2Br ♦ NaO
IV-B
However, i t was found im p o ssib le a f t e r many a tte m p ts to i s o l a t e a
pure p ro d u ct from th e i n i t i a l W illiam son r e a c tio n , and th e p ro je c t was
abandoned.
I t now rem ained to e lu c id a te th e s tr u c tu r e o f th e aforem entioned
p roduct V-A. The o b se rv a tio n th a t t h i s m a te r ia l, a y ello w , n o n -c ry s ta l-
l i z a b l e o i l , was found to re a c t w ith p h th a lic an h y d rid e, showed th a t i t
was an a lc o h o l. I t gave a n e g a tiv e t e s t w ith Lucas re a g e n t, which tended
to show th a t i t was a prim ary a lc o h o l. That t h i s o i l was pure .with re s p e c t
to i t s c o n te n t o f h y d ro x y lic compound was in d ic a te d by th e sh arp m e ltin g
i
p o in t o f i t s p -n itro b e n z o a te , w hile th e f a c t t h a t t h i s p -n itro b e n z o a te had
a h ig h e r m e ltin g p o in t 0 41 -1 4 2 °C .) th an th e p -n itro b e n z o a te of.-IV-A (121-
122°C .) p rovided a b a s is fo r th e b e l i e f th a t th e o i l d id n o t c o n ta in IV-B,
sin c e in a l l known c a se s (4 ,6 ,1 0 ,1 1 ) th e m e ltin g p o in ts o f th e e s te r d e riv
a tiv e s o f th e prim ary e th e r-a lc o h o ls a re h ig h e r th an th o se o f t h e i r secondary
iso m ers. F urtherm ore th e compound IV-B would be expected to be a s o lid and
d i f f i c u l t l y se p a ra b le from i t s isom er IV-A, n e ith e r c o n d itio n b ein g s a t i s
fie d in th e p re se n t c a se . A carbon and hydrogen a n a ly s is , as w ell as a
m o lecu lar w eight d e te rm in a tio n , perform ed on th e p -n itro b e n z o a te o f t h i s
o i l showed, however, th a t t h i s compound was an isom er o f th e co rresp o n d in g
d e r iv a tiv e o f IV-A.
The p o s s i b i l i t y s t i l l rem ained th a t th e o i l m ight be th e p ro d u ct o f
d ir e c t n u c le a r a tta c k by th e phenoxide io n and th a t th e form ula o f t h i s
compound m ight be:
I t i s p o s s ib le th a t s t e r i c hin d ran ce m ight e lim in a te th e form ation o f V-B,
which would ex p lain why th e o i l behaves a s a pure a lc o h o l, as shown by th e
sharp m e ltin g p o in t o f i t s p -n itro b e n z o a te .
CH-CH20H
Of
V-A
O H
V-B
-1 0 -
I t now rem ained to show th a t th e o i l was p h e n o lic . The m a te ria l
was o n ly v e ry s li g h t l y s o lu b le in a l k a l i , and d id not show a p o s itiv e -
p h en o lic t e s t w ith f e r r i c chloride* re a g e n t. A ttem pts to p re p a re -the a r y l-
o x y a ce tic a c id d e r iv a tiv e , and th e 2 ,4 ~ d in itro p h e n y l e th e r o f V-A, were
u n s u c c e ss fu l, perhaps because o f th e m a te r ia l's low s o lu b i l i t y in a l k a l i .
On th e o th e r hand, re a c tio n w ith benzenediazoniuia c h lo rid e s o lu tio n gave
r i s e to th e form ation o f a dve, w h ile IV-A d id n o t.
From th e aforem entioned evidence i t may be seen th a t th b ; a l k a l i -
c a ta ly s e d r e a c tio n o f p - n itr o s ty r e n e o x id e w ith phenol y ie ld s a prim ary
phenoxy a lc o h o l IV-A, and an o th er prim ary a lc o h o l V-A, which may be phjenolic
in c h a ra c te rj i t i s b e liev e d th a t th e secondary a lc o h o l IV-B i s not formed
d u rin g t h i s r e a c tio n ,
Guss (ll) found th a t th e a lk a li- c a ta ly z e d re a c tio n o f s ty re n e oxide
w ith phenol y ie ld e d predom inantly th e prim ary e th e r -a lc o h o l, but he a lso
is o la te d i t s secondary iso m er. I t a p p e a rs, th e r e fo r e , th a t th e p resen ce o f
th e n i t r o group p rev en ted th e fo rm atio n o f th e secondary e th e r-a lc o h o l d u r
in g th e p re se n t r e a c tio n . I t i s w ell known (19) th a t th e p -n itro p h e n y l group
e x e rts a stro n g e le c tr o p h ilic e f f e c t . I t w ould, th e r e fo r e , be n o t a t a l l
s u rp r is in g i f th e aforem entioned group would fa v o r a n u c le o p h ilic a tta c k by
th e phenoxide io n on th e n o n -te rm in a l carbon atom, th e e le c tro n d e n s ity o f
which would have been low ered below th a t o f th e te rm in a l carbon atom.
N =
-
/ \
CH-CH-,
V III IX
- I I -
The q u e stio n now a r i s e s w hether th e n i t r o group e x e r ts i t s e f f e c t p rim a rily
by e l e c t r o s t a t i c in te r a c tio n as in (V III) o r as a r e s u l t o f resonance as
in (IX ). I f th e reso n an ce e f f e c t should be predom inant i t ap p ears prob
a b le th a t th e s u b s titu tio n o f two m ethyl groups in th e 3*5“ p o s itio n s o f
th e arom atic rin g o f p - n itr o s ty r e n e o x id e , which would b lo ck reso n an ce,
would change th e d ir e c tio n o f th e opening o f th e o x ira n e r in g .
CHAPTER IV
EXPERIMENTAL (20)
P re p a ra tio n o f p -N itro s ty re n e Oxide
?. P re p a ra tio n o f p -N itro aceto p h en o n e. — The method o f W alker and
Hauser (13) was u t i l i z e d .
In to a o n e - l i t e r round-bottom th re e -n e c k f la s k , equipped w ith a
m echanical s t i r r e r , a dropping fu n n e l, and a r e f lu x condenser, were
p laced magnesium tu rn in g s ( l 6 «l g ., 0 . 6 3 3 m ole), a b s o lu te e th y l a lc o h o l
(15 c c .) , and carbon te tr a c h lo r id e (1 .5 c c . ) . The use o f magnesium
powder in s te a d o f tu rn in g s was found to g iv e a low er y ie ld o f th e f in a l
p ro d u c t. The m ix tu re became q u ite warm, and a f t e r f iv e m inutes sodium-
d rie d e th e r ( 2 2 5 c c . ) was added thro u g h th e dropping funnel over a p erio d
o f f o r ty m in u tes. Then, w ith s t i r r i n g , a s o lu tio n o f e th y l m alonate
(701 g ., 0 , 6 3 3 m ole), a b so lu te e th y l a lc o h o l ( 6 0 c c ,) , and anhydrous
e th e r (75 c c .) was added dropw ise through th e fu n n e l. V igorous r e f lu x
in g ensued. A fte r th e r a te o f re flu x in g had d ec re ase d , th e m ixture was
h eated over a a t earn-bath f o r fo u r h o u rs, a t th e end o f which p erio d a l l
o f th e magnesium had gone in to s o lu tio n .
A s o lu tio n o f p -n itro b e n z o y l c h lo rid e (17 1.5 g . , 0.603 m ole, m .p.
7 1 o8 - 7 2 . 3 ° C .) in anhydrous e th e r ( 3 0 0 c c . ) was added through th e drop
ping fu n n e l to th e h o t s o lu tio n o f th e above m agnesiom alonic e s te r .
A fte r about tw o -th ird s o f t h i s m ix tu re had been added, th e o liv e -y e llo w
s o lu tio n became v ery v isc o u s, p e rm ittin g th e s t i r r e r to tu rn o n ly w ith
d i f f i c u l t y . A fte r th e a d d itio n had been com pleted, th e. m ix tu re was p e r
m itted to stan d o v e rn ig h t a t room te m p e ra tu re . The s o lu tio n was then
-1 3-
a c id if ie d to congo red w ith 6 N s u lf u r ic a c id . At t h i s p o in t th e re
was a sh arp t r a n s i t i o n in th e c o lo r o f th e s o lu tio n from, orange to
l i g h t g reen . The cooled m ix tu re se p a ra te d in to a c le a r , y ello w e th e r
la y e r , and a heavy, w h ite aqueous s lu r r y . The e th e r la y e r was sep
a ra te d , washed w ith w a te r, and tr a n s f e r r e d to a d i s t i l l i n g f la s k , from
which th e so lv e n t was th en d i s t i l l e d o f f . A p a le g o ld en -y ello w o i l ,
th e d ie th y l p -n itro p h e n y l m alonate, rem ained which was tr a n s f e r r e d to
a o n e - l i t e r round-bottom f la s k equipped w ith a r e f lu x co ndenser. To
t h i s o i l was slow ly added a s o lu tio n o f g la c ia l a c e tic a c id (180 c c .) ,
c o n c e n tra te d s u lf u r ic a c id (2 2 .5 c c . ) , and w ater ( l 20 c c .) . The r e s u l t
in g m ix tu re was h eated over a steam -b ath , whereupon th e re was a v igorous
e v o lu tio n o f carbon d io x id e , and a change in th e c o lo r o f th e o i l y la y e r
a t th e bottom o f th e f la s k from y ello w to g reen . The e v o lu tio n o f gas
was d e te c te d by means o f a tu b e le a d in g from th e to p o f th e condenser
in to a. v e s s e l f i l l e d w ith w a ter. H eating was co n tin u ed fo r tw elv e hours,
a t which p o in t no more gas was being given o f f .
The r e s u ltin g c l e a r , g o ld en -y ello w s o lu tio n was c h ille d in an i c e -
b a th . A 2 0 $ s o lu tio n o f sodium hydroxide was added slow ly u n t i l th e
s o lu tio n was b a s ic to litm u s , 700 cc . o f base being n e c e ssa ry . The
m ix tu re was e x tra c te d w ith one l i t e r o f e th e r , which vra3 then d rie d
o v er anhydrous sodium c a rb o n a te . The e th e r was removed a t room tem per
a tu re under vacuum which r e s u lte d in th e se p a ra tio n o f v ery la r g e , beau
t i f u l , yellow prism s from th e th ic k e n in g s o lu tio n . A crude y ie ld o f
68 .2 g. o f p -n itro ac eto p h e n o n e , ra.p. 75~78°C. was th u s o b ta in e d . One
r e c r y s t a l l i z a t i o n from eth a n o l y ie ld e d 59 g. ( 59$) o f pure p ro d u ct, m .p.
79~80°C., in th e form o f sm a ll, yellow prism s. The m e ltin g p o in t re p o rte d
-1 4 -
by W alker and Hauser (13) was 79-80°C. The volume o f th e a lc o h o lic
f i l t r a t e was reduced to 1 0 0 cc, over a steam -bath to g iv e 2 . 0 g, o f
a d d itio n a l m a te r ia l, in.p. 78-80°C ., r a is in g th e t o t a l y ie ld to 60.5%.
2. P re p ara tio n , o f p -N itro p h en acy l Bromide. — S ince th e a d d itio n o f
bromine to a s o lu tio n o f p -n itro a ce to p h en o n e in g la c i a l a c e tic acid
acco rd in g to th e pro ced u re o f E n g ler and Z ie lk e (14) r e s u lte d in a y ie ld
o f o n ly 6 2 . i t was decided to u t i l i z e a p ro ced u re analogous to th a t
used fo r th e p re p a ra tio n o f phenacyl brom ide from acetophenone by Cowper
and Davidson (1 5)»
In to a 500 cc. th re e -n e c k f la s k equipped w ith a r e f lu x condenser,
a dropping fu n n e l, and a m echanical s t i r r e r , was p laced a s o lu tio n o f
p -n itro aceto p h en o n e ( 4 9 . 0 g ., 0 . 2 9 7 m ole) in sodium -dried e th e r ( 2 0 0 c c . ).
The s o lu tio n was c h ille d in an ic e - b a th , and anhydrous aluminum c h lo rid e
(0 .5 g . ) was in tro d u c e d . T his m ixture was s t i r r e d fo r f o r ty m in u tes, so
as to cause a l l th e s o lid to go in to s o lu tio n . Bromine (4 4 .9 g. , 0.297
m ole) was th en slow ly added through th e dropping fu n n e l. I t was found
to d e c o lo riz e im m ediately. A p a le yellow s o lid began to p r e c ip ita te
a f t e r about tw o -th ird s o f* th e bromine had been added. Two openings o f
th e f la s k were now corked, and su c tio n a p p lie d at th e t h i r d u n t i l a l l o f
th e e th e r and hydrobrom ic a c id had been removed. A b r i t t l e , yellow s o lid
rem ained, which was scraped o u t o f th e f la s k and washed w ith a 5 0 : 5 0 mix
tu r e o f petroleum e th e r and w ater. The m a te ria l was th en d rie d in th e
50°C. oven. I t s m e ltin g ran g e was found to be 88-94°C ., w h ile th e crude
y ie ld was 6 5 . 3 g.
T his m a te ria l was d isso lv e d in hot e th a n o l (220 c c . ) and p erm itted
to c o o lj fin e ,y e llo w , g l i t t e r i n g c r y s ta ls se p a ra te d . These were f i l t e r e d
- 15-
o f f , washed w ith cold e th a n o l, and d rie d in a 50°C. oven. A y ie ld o f
58.7 g. (81$) was o b ta in e d , m .p. 98-99°C. E ngler and Z ielk e (14) r e
p o rted a m eltin g p o in t o f 98°C.
)
3. P re p a ra tio n o f Aluminum Iso p ro p o x ld e . — T his m a te ria l was p rep ared
by th e method d e sc rib e d in O rganic R eactio n s (2 1 ). The muddy, g ray ,
crude p ro d u ct was d i s t i l l e d a t 1 34-144°C ./7 raw. w ith an o il- b a th tem per
a tu re o f 1 9 2 - 2 0 0 ° C . to give a 90$ y ie ld o f syrupy, c o lo r le s s liq u id .
4. P re p a ra tio n o f p -M itro sty re n e Bromohydrin ( I ) . — T his s y n th e s is
was c a rrie d p u t by th e use o f th e m o d ific a tio n o f th e M eerwein-Ponndorf
re a c tio n re p o rte d by W instein 0 6 ).
A one-m olar s o lu tio n o f aluminum iso p ro p o x id e in iso p ro p y l a lc o h o l
( 5 0 0 c c .) was p laced in a tw o - lite r round-bottom fla s k equipped w ith a
r e f lu x condenser w ith a d ry in g tube and h e a t e d t o th e b o ilin g p o in t.
Through th e condenser was added slow ly a hot s o lu tio n o f p -n itro p h e n a c y l
bromide (3 0 .0 g ., 0.123 m ole) in d ry iso p ro p y l a lc o h o l (738 c c . ). The
dark re d s o lu tio n was h eld a t r e f lu x f o r n in e te e n m in u tes, and th en was
c h ille d by immersion in an ic e - b a th . The c o ld m ix tu re was poured over a
s lu r r y o f one l i t e r o f crushed ic e and 6 N h y d ro c h lo ric a c id (308 c c . )
and p e rm itte d to rem ain o v e rn ig h t in th e iceb o x . The cloudy l i g h t orange
m ix tu re was then e x tra c te d w ith seven 100-cc. p o rtio n s o f e th e r . Since
iso p ro p y l a lc o h o l was a ls o taken up by th e e th e r , two l i t e r s o f c le a r ,
orange s o lu tio n were o b ta in e d . The volume o f th e combined e x tr a c ts was
reduced to 3 0 0 cc. by means o f d i s t i l l a t i o n over a steam -b ath , whereupon
th e m ix tu re se p a ra te d in to a heavy orange la y e r and a l i g h t y ello w la y e r .
On b ein g p e rm itte d to c o o l, th e h e a v ie r la y e r s o li d i f i e d , y ie ld in g g l i s
te n in g orange-brow n c r y s ta ls . This p ro d u ct was d rie d in a vacuum d e s ic -
- 16-
c a t o r to g iv e 24.6 g. ( 8 1 .3 $ ), m .p. 8 l-83°C . o f p - n itr o s ty r e n e
brom ohydrin ( I ) .
A sm all p o rtio n o f t h i s m a te ria l was r e c r y s ta lliz e d tw ice from
a b enzene-heptane m ix tu re. F in e, f l a t , g l i t t e r i n g yellow p rism s, m.p.
8 6 - 8 6 . 5 °C ., were o b ta in e d . T his m a te ria l was found to be s o lu b le in
benzene, e th y l e th e r , and e th y l a lc o h o l, and in s o lu b le in heptane and
w ater.
A n a ly s is : C a lc u la ted f o r CgHg03NBr; C, 39.03$; H, 3.37%.
Found: C, 39.25$; H, 3.58$.
5 . P re p a ra tio n o f p -N itro s ty re n e Oxide ( I I ) . — In to a 500-cc, round-
bottom f la s k equipped w ith a m echanical s t i r r e r was p laced a suspension
%
o f fin ely -p o w d ered p - n itr o s ty r e n e brom ohydrin (2 4 . 6 g ., 0 , 1 0 0 m ole) in
1 N sodium hydroxide (350 c c . ) . The m ix tu re r a p id ly tu rn e d murky brown.
S tirrin g ,w a s m aintained f o r one hour a t room te m p e ra tu re. The rem oval
o f th e bromine from th e brom ohydrin could be follow ed c o n v e n ie n tly by
perform ing a Volhard t i t r a t i o n upon th e aqueous la y e r . F i l t r a t i o n sep
a ra te d a brown, s a h d -lik e m a te r ia l, which was washed w ith w ater and
d rie d in a vacuum d e s ic c a to r. The crude pro d u ct was found to be q u ite
im pure, i t s m e ltin g range b ein g 65-82°C. A y ie ld o f 1 6 . 8 g. (100$) was
th u s o b ta in e d .
The crude m a te ria l was r e c r y s ta lliz e d tw ice from 200 -cc. p o rtio n s
o f e th a n o l, c a re being tak en t h a t th e' tem p eratu re o f th e s o lu tio n d id
n o t r i s e above 60°C. C ooling o f th e s o lu tio n p r e c ip ita te d p - n itr o s ty r e n e
o x id e ( I I ) in th e form o f f in e , g L itte rin g , yellow p l a t e l e t s , •m.p. 8 5 .5 -
8 6 °C. A y ie ld o f 8 .3 g. (50$) o f pure m a te ria l was o b ta in e d .
~ T 7 -
R eduetion o f th e volume o f th e combined c r y s t a l l i z a t i o n f i l
t r a t e s to 1 0 0 cc, r e s u lte d in th e fo rm atio n o f 4 . 8 g. a d d itio n a l prod
u c t, m .p, 8 3 - 8 5 °C ., th u s r a is in g th e t o t a l y ie ld to 7 8 %.
A n a ly sis: C a lc u la te d f o r C8H 7O3N: C, 58.18%; H, 4.2 * $ .
1
Found: C, 58.24%; H, 4.53%.
This m a te ria l was found to be in s o lu b le in benzene, co ld m ethanol,
I
hot e th a n o l, and to a l e s s e r e x te n t in p ro p an o l. I t wa's, in s o lu b le in
hot w ater and in h ep tan e.
6 . P re p a ra tio n o f p -N itro p h en y l G lycol ( I I I ) . — In to a 125 cc. E rlen -
meyer f la s k equipped w ith a r e flu x condenser was p laced p - n itr o s ty r e n e
oxide (l.OO g . , 0.00607 m o le), d i s t i l l e d w ater (50 c c . ) , and s ix drops
o f c o n c e n tra te d h y d ro c h lo ric a c id . The m ix tu re was h e ated to b o ilin g ,
whereupon th e o i l slow ly began to d is s o lv e . R eflu x in g was m ain tain ed
fo r fo u r h o u rs, a t th e end o f which p erio d a l l th e o i l , w ith th e ex cep tio n
o f a sm all amount o f t a r r y re s id u e , had gone in to s o lu tio n . The hot
m ix tu re was f i l t e r e d . The c le a r ; yellow f i l t r a t e was p e rm itte d to cool
t b room te m p e ra tu re , and then ev aporated to d ry n ess under vacuum, a
p ro c ess which re q u ire d e ig h ty h o u rs. A th ic k , brown o i l was o b tain ed
which was tr a n s f e r r e d to th e iceb o x . Sm all, yellow ish-brow n c r y s ta ls
C
were soon found to form w ith in th e s e m i-so lid . On r e c r y s t a l l i z i n g t h i s
m a te ria l from benzene, v ery f in e , w h ite n e e d le s were o b tain ed in a y ie ld
o f 0.615 g . (55.4% ), m .p. 7 4 -7 4 .5°C.
A n a ly s is : C a lc u la te d forG *H 9 0*B: C, 52.43%; H, 4.95%.
Found: C, 52.40%; H, 5.01%.
-1 8 -
T his m a te r ia l was extrem ely s o lu b le in w ater and in h o t benzene.
I t was in s o lu b le i n h ep tan e.
The re a c tio n d e sc rib e d h ere was re p e a te d under id e n tic a l con
d i t i o n s , b u t in th e absence o f h y d ro c h lo ric a c id . E x tra c tio n o f th e
r e a c tio n m ix tu re w ith e th e r r e s u lte d in th e reco v ery o f 92$> o f th e
s ta r t i n g m a te r ia l, but showed no evidence o f g ly c o l fo rm atio n .
7. P re p a ra tio n o f p-N itrocinnam ic, A cid. — The method o f Drewsen (22)
was u t i l i z e d . Cinnamic a c id was n i t r a t e d and th e e th y l e s te r s o f th e
o rth o and p ara isom ers p rep ared , which were th en se p a rated by f r a c tio n a l
c r y s t a l l i z a t i o n from e th a n o l. The e th y l p -n itro c in n a m a te was hydrolyzed,
and an o v e r a ll y ie ld o f 27.6$ o f p -n itro c in n a m ic a c id , m .p. 288-289°C .,
was achiev ed . Drewsen re p o rte d a m e ltin g p o in t o f 288°C. (2 2 ); but he
d id n o t r e p o rt h is y i e l d . '
8 . P re p a ra tio n o f p -W itro sty re n e . — A method s im ila r to th a t employed
by W iley and Sm ith (2 3 ), fo r th e p re p a ra tio n o f m -n itro sty re n e from
m -n itro cin n am ic a c id , was used .
In to a 125 cc. Erlenraeyer f la s k equipped w ith a r e f lu x condenser
was p laced p -n itro c in n a in ic a c id (5 .0 0 g ., 0.0259 m o le), q u in o lin e (19 c c . ) ,
copper powder (0 .7 5 g . ) , and hydroquinone (0 .2 g . ). The tem p eratu re was
r a is e d by means o f an o il- b a th to 1 8 5 °C ., a t which p o in t th e e v o lu tio n
o f carbon d io x id e became p e rc e p tib le , as shown by a tu b e le a d in g from
th e to p o f th e condenser in to a c le a r s o lu tio n o f lim e -w a te r. A fte r one
and o n e -h a lf h o u rs, no more gas was b ein g evolved and h e a tin g was d i s
c o n tin u ed . A v isc o u s, brow nish-black s o lu tio n was o b ta in e d . A fte r th e
m ix tu re had been p e rm itte d to reach room te m p e ra tu re , 3 N h y d ro c h lo ric
-1 9 -
a c id ( 8 4 . 7 c c .) was added, which r e s u lte d in th e fo rm atio n o f th ic k ,
w h ite fumes. .S te a m - d is tilla tio n o f th e s o lu tio n y ie ld e d a m ilky liq u id
o f p le a s a n t o d o r, which was e x tra c te d w ith chloroform . The c le a r ,
yellow chloroform s o lu tio n was d rie d o v er anhydrous calcium s u lf a te .
The s o lv e n t was th e n removed by d i s t i l l a t i o n . A th ic k , yellow liq u id
( 1 . 0 c c .) was o b ta in e d , which was d isso lv e d in m ethanol ( 1 0 c c .) .
Immersion o f th e f la s k in a d ry ic e -c a rb o n te tr a c h lo r id e m ixture r e s u lte d
in th e se p a ra tio n o f 0 . 3 0 g . (7 . 8$ ) o f a y e llo w ish -w h ite amorphous s o lid ,
m .p. 20-22°C., S tra ssb u rg , Gregg, and W alling (24) re p o rte d th e m eltin g
p o in t o f t h i s compound as 2 1 . 4 °C.
B. A lk a li-C a ta ly z e d R eaction o f p -M itro sty re n e Oxide w ith P henol.
1 . Form ation o f 2 -p -N itro p h e n y l-2 -P henoxyethanol (IV -A ). - - In to a
25 cc. Erlenm eyer fla s k equipped w ith a r e f lu x condenser were p laced
p - n itr o s ty r e n e oxide ( 1 . 0 0 0 g . , 0 . 0 0 6 0 6 m o le )| phenol ( 1 . 7 1 0 g . , 0 . 0 1 8 2
m o le), sodium hydroxide ( 0 . 2 4 3 g . > 0 . 0 0 6 0 6 m ole), and w ater ( 1 . 5 c c .) .
T his m ix tu re was h eated on a steam -b ath fo r th re e hours w ith o c c a sio n a l
sh ak in g , th e c o lo r o f th e r e a c tio n m ix tu re ra p id ly tu rn in g b ro w n ish -b lack .
The one-phase r e a c tio n m ix tu re was th en p e rm itte d to co o l to room tem
p e r a tu re , and poured in to 1 0 0 cc. o f w ater c o n ta in in g 017 g . o f sodium
h y droxide. The m ix tu re se p a ra te d in to a heavy, dark brown o i l and a
m ilk y -y ello w aqueous la y e r . T his o i l was e x tra c te d w ith th re e 5 0 -cc.
p o rtio n s o f e th e r , and th e c le a r , y ello w e th e r la y e r' d rie d over anhydrous
potassium c a rb o n a te . Removal o f th e e th e r under vacuum l e f t 1.386 g.
(8 8 .3 $ ) o f an o ran g e-y ello w s o lid , m .p. 78-84°C. The rem aining 11.7$ o f
p ro d u ct presum ably c o n s is te d o f a lk a li- s o lu b le m a te r ia l.
-2 0 -
The s o lid was d iss o lv e d in 30 cc. hot e th y l a lc o h o l to which
1 5 cc. o f w ater was th en added. On co o lin g to room tem p eratu re a heavy
orange o i l se p a ra te d from which th e s o lv e n t was removed by d e c a n ta tio n .
T his product s o li d i f i e d on sta n d in g . A y ie ld o f 0.305 g. 09*4% ) 0;f
t h i s m a te r ia l, which w ill be re fe r r e d to- a s s f r a c tio n A, was th u s ob
ta in e d . One r e c r y s t a l l i z a t i o n from e th a n o l and w ater y ie ld e d l i g h t
pink n e e d le s. Y ield 0.7 63 g . , m .p. 89-90°C.
The l i q u i d , from which f r a c tio n A had been s e p a ra te d , was h eated
to b o ilin g , and enough w ater added to tu rn i t j u s t b a re ly cloudy. Addi
tio n o f one drop o f e th y l a lc o h o l th en d is p e lle d t h i s c lo u d in e ss . The
so lu tio n .w a s p e rm itte d to cool to room tem p eratu re which r e s u lte d in
th e fo rm atio n o f lo n g , p a le yellow n e e d le s. These were f i l t e r e d o f f ,
waxhed w ith w a te r, end d rie d in th e 50° oven. A y ie ld o f 0.846 g.
(5 4 .0 $ ), m .p. 92-93°C ., o f t h i s f r a c tio n B was o b ta in e d . One f u r th e r
r e c r y s t a l l i z a t i o n from e th a n o l and w ater lig h te n e d th e c o lo r o f th e se
n e e d le s to alm ost pure w h ite , and r a is e d t h e i r m e ltin g p o in t to 9 3 . 5”
94°C. T his m a te ria l v/as l a t e r shown to be 2 -p -n itro p h e n y l-2 -p h e n o x y -
e th an o l (IV -A ). A m ixed-m elting p o in t d e te rm in a tio n showed th a t th e
com position o f th e p u r if ie d f r a c tio n s A and B were i d e n t i c a l .
A n a ly sts: C a lc u la te d f o r Cj/,H1 3 0 ^ : C, 6 4 .8 8 $ j H, i5^0'5$.
Found: C, 65.01$, H,
A ddition o f ex cess w ater to th e f i l t r a t e from which f r a c tio n B
had been se p a ra te d produced a th ic k , w h ite c lo u d in e s s . A fte r sta n d in g
fo r s e v e ra l days in th e iceb o x , a heavy, c le a r , p a le y ello w o i l p re c ip
i t a t e d . S c ratc h in g and c o o lin g in a d ry ic e -a c e to n e m ix tu re d id n o t
-2 1 -
induee c r y s t a l l i z a t i o n . T his s o lu tio n was e x tra c te d w ith 100 c c . o f
e th e r. The c le a r , yellow e th e r la y e r was th en d rie d over anhydrous
potassium c a rb o n a te . Removal o f th e e th e r under vacuum l e f t a c le a r ,
y ello w o i l , which became syrupy on being cooled but could nev er be
brought to c r y s t a l l i z e . This m a te ria l w ill be r e fe r r e d to a 3 f r a c tio n C.
I t was o b ta in e d in a y ie ld o f 0.281 g. (1 7 .9 $ ). A ttem pts to r e c r y s t a l -
l i z e t h i s o i l from benzene and hept'ane, e th a n o l and w a te r, and dioxane
K
and w a te r, were u n s u c c e ssfu l.
2. P re p a ra tio n o f p -N itro b en zo ate o f 2 -p -N itro p h en y l-2 -P h en o x y eth an o l
( IV-A) . — The p ro ced u re o f Henstock (25) was used.
In to a 10 c c. Erlenm eyer f la s k equipped w ith a r e f lu x condenser
were p la ce d 2 - p -n itro p h e n y l-2 -phenoxyethanol ( 0 . 3 g . ), p -n itro b e n z o y l
c h lo rid e (0 .3 g . )> and anhydrous p y rid in e (3 c c . ) . The m ix tu re was
h eated on a steam -b ath fo r f if t e e n m in u tes. On co o lin g th e whole s o lu
tio n s o li d i f i e d , form ing a y e llo w ish -w h ite cake. On r e c r y s t a l l i z i n g
t h i s m a te ria l from e th y l a lc o h o l, 0 . 4 3 5 g. (92$) o f f in e y e llo w ish -w h ite
n e e d le s , m .p. 1'21-1 21,5°C . were o b ta in e d . A second r e c r y s t a l l i z a t i o n
a lte r e d n e ith e r th e appearance n o r th e m e ltin g p o in t o f th e m a te r ia l.
A n a ly sis: C alculated fo r C21H1607N 2 : C, 61.77$; H, 3.9 4 $ .
Found: C, 6l , 88$; H, 3.89$.
3. R eduction o f 2-p-W itrophenyl-2-P henoxyethanol to 2-p-A m inophenyl-2-
Phenoxyethanol (V I). — In to a 50 cc. Erlenm eyer f la s k equipped w ith
a r e f lu x co ndenser, was p laced 2 -p -n itro p h en y l-2 -p h en o x y e th a n o l (IV-A)
(0 , 4 0 0 g . , 0 . 0 0 1 5 4 m ole) in eth an o l ( l 0 c c . ) , and th e s o lu tio n h ea te d to
-2 2 -
b o ilin g , Through th e re flu x , condenser was th en added a h o t s o lu tio n
o f stannous c h lo rid e d ih y d ra te (1 . 3 5 g . , 0 , 0 0 5 8 9 m ole) in c o n c e n tra te d
h y d ro ch lo ric a c id (2 .2 c c , ) , T his r e s u lte d in an im m ediate re a c tio n
accompanied by th e e v o lu tio n o f h e a t. A g re e n ish -y e llo w c o lo r appeared
as th e re a c tio n m ix tu re was h eated o v er a steam -b ath under r e f lu x f o r
f '
f o r ty m inutes. A fte r c o o lin g to room te m p e ra tu re , th e s o lu tio n was
poured in to cold 2 0 % sodium hydroxide ( 5 0 c c .) , form ing a cloudy, yellow
m ix tu re from which a f t e r two hours a sm all q u a n tity o f brown o i l began
to s e p a ra te . T his s o lu tio n was e x tra c te d w ith two 30 c c .- p o r tio n s o f
e th e r . The l i g h t yellow e th e r la y e r was d rie d over anhydrous potassium
c a rb o n a te . Removal o f th e e th e r tinder vacuum l e f t 0„26l g. (73=8%) of
a heavy, c le a r brown o i l .
A ttem pts to c r y s t a l l i z e t h i s am in e (VI) from e th a n o l, d ioxane,
benzene, and heptane were u n s u c c e ss fu l.
T his m a te ria l was found to form both an a c e ty l d e r iv a tiv e and a.
benzene s u lfo n ic a c id d e r iv a tiv e , b u t in n e ith e r case could th e se com
pounds be p u r if ie d . .
4. D eam ination o f 2-p-A m ino-2-Phenoxyethanol to 2-P henyl-2-P henoxyethanol
(V II). — The deam ination re a c tio n was c a rrie d o u t by th e procedure
o f Kornblum and I f f la n d 08).
In to a s ix in ch t e s t tu b e was p laced crude 2-p-araino-2-phenoxy-
e th a n o l (0.261 g . ), and 50% hypophosphorous a c id (2 c c . ) . A c le a r , brown
s o lu tio n was o b tain ed which was d ilu te d w ith 2 c c. o f w a te r. A fte r f i l
t r a t i o n i t was cooled to 5°C ., and a p re v io u sly copied s o lu tio n o f
sodium h i t r i t e ( 0 . 0 8 3 g*» 0 . 0 ^ 1 2 0 m ole) in w ater (0 . 3 c c .) was added.
An in sta n ta n e o u s re a c tio n was found to ta k e p la c e , w ith gas bein g
-2 3 -
em itted v ig o ro u s ly . A fte r one hour th e r e a c tio n m ix tu re was removed
from th e ic e - b a th and p e rm itte d to rea ch room te m p eratu re. A sm all
amount o f brown t a r was found to s e p a ra te , fo llo w ed , a f t e r stan d in g fo r
fo u r h o u rs, by th e p r e c ip ita tio n of a p each -co lo re d flo c c u le n t s o lid .
T his m ix tu re was l e f t to stan d o v ern ig h t in th e iceb o x . The s o lid ,
which in th e meantime had tu rn e d l i g h t o ran g e, was f i l t e r e d o f f (th e
p re v io u sly m entioned t a r stu ck to th e w a lls o f th e t e s t tu b e ), washed
w ith w a te r, and d rie d in a vacuum d e s ic c a to r.
The d ry , l i g h t brown m a te ria l was r e c r y s t a l l i z e d from h ep tan e.
Clumps o f w h ite , n e e d le - lik e c r y s ta ls were o b ta in e d , which were f i l t e r e d
o f f and d rie d . A y ie ld o f 0,096 g. (39*4$) was o b ta in e d , m.p. 76-79°C.
A second r e c r y s t a l l i z a t i o n from heptane produced c lu s te r s o f b e a u tif u l,
w h ite , fe a th e ry ;n e e d le s , m .p. 80-81°C. A mixed m e ltin g p o in t d eterm in
a tio n w ith a u th e n tic 2 -p h e n y l-2 ~phenoxyethanol showed no d e p re ssio n ,
which proved th e s tr u c tu r e o f IV-A.
5. O xidation o f 2-p-N itrophenyl-2~ P henoxyethanol (IV -A ). — A m ix tu re
o f potassium perm anganate (0 .4 0 0 g ., 0 . 0 0 2 5 3 m o le), 2 -p -n itro p h e n y l- 2 -
phenoxyethanol (IV-A) (0 .5 0 0 g . , 0.00193 m o le), magnesium s u lf a te
( 0 . 3 1 0 g . , 0.00387 m o le), and w ater ( 1 0 c c .) was p laced in a 25 c c .'
Erlenm eyer f la s k . The m ix tu re was tr a n s f e r r e d to a 50° oven and l e f t
to stan d th e re f o r tw e n ty -fo u r h o u rs. On f i l t e r i n g , a c le a r , l i g h t
v io le t f i l t r a t e (th e pH o f which was found to be 7 .5 ) and a brown p re c ip
i t a t e c o n ta in in g w h ite n e ed le s were o b ta in e d . The c o lo r o f th e f i l t r a t e
was d isch a rg ed by th e a d d itio n o f a tr a c e o f sodium b i s u l f i t e . A c id if i
c a tio n o f th e s o lu tio n w ith 6 N s u lf u r ic a c id , and subsequent c o o lin g ,
-2 4 -
r e s u lte d in th e form ation o f p a le yellow p l a t e l e t s . These were f i l
te r e d o f f and d rie d to y ie ld 0.098 g j, m .p. 234-240°C. o f t h i s a c id .
The f a c t th a t a mixed m eltin g p o in t d e term in a tio n w ith a u th e n tic p - n itr o -
f
benzoic a c id showed no d e p re ssio n proved th e i d e n t i t y o f t h i s m a te r ia l.
The aforem entioned brown p r e c ip ita te was p laced in 100 cc. o f 1%
sodium hydroxide ,s o lu tio n and h eated to 50°C. f o r two h o u rs. On c o o lin g
th e c le a r , y ello w s o lu tio n , a w h ite s o lid was o b tain e d which was f i l t e r e d
o f f . T his p r e c ip ita te was d iss o lv e d in e th y l a lc o h o l (30 c c . ). On
adding w ater to th e h o t s o lu tio n and c o o lin g , f in e , w h ite n e e d le s ,
0.347 g ., m .p. 92~94°C. , were o b ta in e d , w hich, as shown by a mixed m elt
in g p o in t d e te rm in a tio n , were shown to be u n re a c te d s t a r t i n g m a te r ia l.
6 . R eactio n o f 2 -p -N itro p h en y l-2 -P h en o x y eth an o l (IV-A) w ith Lucas
R eagent. — To 2 -p -n itro p h e n y l-2 -p h en o x y e th a n o l (0.1 g . ) was added
f r e s h ly p rep ared h y d ro c h lo ric a c id -z in c c h lo rid e Reagent ( 2 6 ) ( l . 0 c c . ) .
The c o n ta in e r wag .stoppered and shaken v ig o ro u s ly . On sta n d in g a t room
tem p eratu re a pink to p la y e r began to be p e rc e p tib le a t th e end o f te n
h o u rs.
i
7. Attem pt to P rep are p -N itro p h en acy l P henoxide. — The procedure o f
Reid (27) f o r th e p re p a ra tio n o f p -n itro b e h z y l a ry l e th e rs was adapted
fo r th e p re se n t s y n th e s is . p -N itro p h en acy l bromide and phenol were
h eated in an a lc o h o lic sodium hydroxide s o lu tio n . Although w id ely v ary
in g r e a c tio n c o n d itio n s were u sed , th e o n ly pro d u ct th a t was ev er o b ta in e d
was an amorphous, yellow s o lid , which could n o t be p u r if ie d by any means,
b u t w hich, as shown by a mixed m e ltin g p o in t d e te rm in a tio n , was n o t
id e n tic a l w ith th e s ta r t i n g pro d u ct (p ro d u c t, m^p. 94-107°C. ) .
-2 5 -
8 . R eactio n o f F ra c tio n C (V-A) w ith P h th a lic A nhydride. — According
to Cox, N elson, and C re tc h e r (2 8 ), o n ly prim ary a lc o h o ls w ill be e a s ily
e s t e r i f i e d by a b o ilin g p h th a lic anhydride s o lu tio n . I t was decided
to ap p ly t h i s t e s t to th e aforem entioned F ra c tio n C.
To t h i s o i l (0.480 g . ) was added p h th a lic an hydride (3 .4 g . ) ,
dioxane (15 c c . ) , and anhydrous p y rid in e (2 .4 cc.). The c le a r , yellow
s o lu tio n was h eated on a steam -bath f o r o n e -h a lf ho u r, end th en p e rm itte d
to stand a t room tem p e ra tu re f o r f iv e h o u rs. Then e th e r (l 0 0 c c .) was
added, and th e s o lu tio n e x tra c te d w ith 1 0 $ h y d ro c h lo ric a c id ( 5 0 .cc.).
The aqueous la y e r was d isc a rd e d , and th e e th e r la y e r e x tra c te d w ith two
5 0 - c c . p o rtio n s o f 5$ sodium b ic a rb o n a te . Some foam ing was found to
o c cu r. To th e b ic a rb o n a te la y e r 10$ sodium hydroxide s o lu tio n (60 cc.)
was added v ery slow ly. T his s o lu tio n was h eated o v er a steam -b ath fo r
f if t e e n m in u tes. On c o o lin g a y ello w o i l p r e c ip ita te d , which tu rn e d
o u t to be i d e n tic a l w ith th e s t a r t i n g p ro d u ct. . E v ap o ratio n o f th e
e th e r la y e r to d ry n ess d id n o t y ie ld an y th in g ex cep t a non-w eighable
q u a n tity o f dark brown t a r .
9. P re p a ra tio n o f p -N itro b e n z o a te o f F ra c tio n C (V-A). — Treatm ent o f
f r a c tio n C w ith p -n itro b e n z o y l c h lo rid e and p y rid in e acco rd in g to th e
p re v io u sly u t i l i z e d procedure o f Henstock ( 2 5 ) r e s u lte d in th e form ation
o f sm all, y ello w p l a t e l e t s , m .p. 123~132°C. One r e c r y s t a l l i z a t i o n from
dioxane and w ater gave g l i t t e r i n g , f a i n t l y yellow p l a t e l e t s , m .p. 1 4 1 “
142°C. A second r e c r y s t a l l i z a t i o n changed n e ith e r th e appearance nor
th e m e ltin g p o in t o f th e p ro d u ct.
A n a ly s is : C a lc u la te d f o r Ca i H 1 6 0 7 N 2 : C, 6 l <,77$; H, 3 .94$; m ol.
w t. 4 0 8 . Found: C, 62.10$; H, 4 .0 3 $ ; mo}, w t. (c ry o sco p ic method in
( ’ ■
-2 6 -
camphor), 40? .8.
10® R eaction o f Fraction C (V-A) with Benzenediazonium C hloride, —
Into a six -in c h t e s t tube was placed a so lu tio n o f a n ilin e (1*0 c c . )
in concentrated hydrochloric acid (2 c c .) . This m ixture was c h ille d to
0°C. in an ic e bath and trea ted w ith an ic e -c o ld so lu tio n o f sodium
n i t r i t e (t.O g . ) in water (5 .0 c c .) .
Half o f t h is m ixture was poured in to a so lu tio n o f fr a c tio n C
(0 .5 c c .) in water (5 .0 c c . ) , con tain in g sodium hydroxide (0 .2 g . ) . The
so lu tio n im m ediately turned orange. A fter f iv e m inutes a reddish-black
s o lid p r e c ip ita te d , which was f ilt e r e d o f f and washed w ith cold w ater.
This m aterial was s lig h t ly so lu b le in hot w ater, in so lu b le in cold
w ater, Very so lu b le in ethanol and aceton e. Even very d ilu te so lu tio n s
ex h ib ited a b e a u tifu l, b rig h t s c a r le t c o lo r . Attempts to c r y s t a lliz e
the dye from ethanol were u n su cce ssfu l.
Treatment o f 2-p-nitrophenyl-2-phenoxyethanol (IV) with the other
h a lf o f the diazonium ch lo rid e so lu tio n did not r e s u lt in dye form ation.
1?. Attempt to Prepare A ryloxyacetic Acid D eriv a tiv e o f Fraction C(V-A). —
An attem pt to prepare th e a ry lo x y a cetic acid d e r iv a tiv e o f fr a c tio n C
according to the procedure o f Koelsch (29) resu lted in the com plete re
covery o f a l l the ch lo r o a ce tic acid used.
12. Attempt to Prepare th e 2.4-D in itrop h en yl Ether o f Fraction C (V-A). —
A n a lc o h o lic so lu tio n o f fr a c tio n C, sodium hydroxide, and 2 ,4 -d in itr o -
phenylchlorobenzene was heated according to the procedure o f Bost and
Nicholson (3 0 ). The ad d ition o f water to the rea ctio n m ixture r esu lted
-2 7 -
in th e p r e c ip ita tio n o f w h ite, g lit t e r in g n e e d le s, m„p. 91. 5-92°C .,
which were shown to be a n a ly tic a lly pure 2 ,4 -d in itr o p h e n e to l. O n re
p eatin g the above rea ctio n in the absence o f fr a c tio n C id e n tic a l
r e s u lts were obtain ed .
C H A PT E R V
S U M M A R Y
t . p -N itrostyren e bromohydrin (I ) was syn th esized and dehydrobrominated
to y ie ld p -n itro sty ren e oxid e ( I I ) . From t h is compound p-nitrophenyl
g ly c o l ( I I I ) was prepared.
2. The a lk a li-c a ta ly z e d rea ctio n o f p -n itro sty ren e oxid e with phenol
was in v e stig a te d and shown to y ie ld th e primary e th e r -a lc o h o l, 2-p -n itr o -
phenyl-2-phenoxyethanol (IV -A ), which was is o la te d and id e n t if ie d . A com
pound b eliev ed to be an isom eric primary a lc o h o l, 2-p -n itr o p h e n y l-2-p -
hydroxyphenyl ethanol (V-A) was a lso is o la t e d , but i t s stru ctu re was only
in fe r r e d . I t was shown th at the secondary eth er-a lco h o l (IV-B) isom eric
w ith (IV-A) was not formed during th is r e a c tio n .
3. An in te r p r e ta tio n o f th e e f f e c t o f th e n itr o group on the rin g
opening rea ctio n o f th e oxid e i s p resented.
-2 9 -
BIBLIOGRAPHY
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(2 ) Boyd and M arie, J . Chem. Soc. , 105. 2117 (1 9 1 4 ).
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(4 ) Chitwood and Freure. ib id . . 68. 680 (1946).
(5 ) Kadesch, ib id . . 68. 41 (1946).
(6) B a r tle tt and R oss, i b i d ., 2 0 , 926 (1948).
(7 ) Buchman and Richardson, ib id . . 6 7 . 395 (1945).
(8) Glickman and Cope, ib id . . 67. 1012 (1945).
(9) Easton, Gardner and S teven s, ib id . . 69. 2941 0 947).
(10) Swern, B ille n and Knight, ib id . . 71. 1152 (1949).
(11) Guss, i b i d ., 2L > 3460 (1 9 4 9 ).
(12) Arndt, B er ., 60, 451 (1 9 2 7 ).
(13) Walker and Hauser, » J . A m . Chem. Soc. , 68. 1387 (1 9 4 6 ).
(1 4 ) Ehgler and Z ie lk e , Ber. , 22. 204 (1889).
(15) Cowper and Davidson, Organic Syntheses, C o ll. V ol. I I ; B la tt,
E d itor, 2nd e d itio n , New York, John W iley and Sons, In c.
1940, page 480.
(16) W instein and Jacobs, J, Org. Chem. . 11 . 153 (1946).
(17) Guss, P riv a te Communication.
(18) Komblum and I ffla n d , _J. A m . Chem. Soc. , 71. 2140 (1949).
(19) B a r tle tt, "The E lectro n ic Theory o f Aromatic S u b stitu tio n s" , in
H. Gilman, Organic Chem istry. I , 2nd e d itio n , New York, John
W iley and Sons, I n c ., 1943, pages 205-213.
-3 0 -
(20) M elting p o in ts are corrected } m icroanalyses fo r carbon and hydrogen
were performed in the Microchemical L aboratories o f the C a lifo rn ia
I n s t it u t e o f Technology, Pasadena, C a lifo r n ia , by G.A. Swinehart,
and in the Elek Micro A n a ly tica l L ab oratories, 4763 West Adams
B lv d ., Los A ngeles, C a lifo r n ia , by S. Elek.
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University of Southern California Dissertations and Theses

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Creator Mautner, Henry George (author)

Core Title The preparation of p-Nitrostyrene Oxide and its alkali-catalyzed reaction with phenol

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, inorganic,OAI-PMH Harvest

Language English

Contributor Digitized by ProQuest (provenance)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-792386

Unique identifier UC11348151

Identifier EP41577.pdf (filename),usctheses-c17-792386 (legacy record id)

Legacy Identifier EP41577.pdf

Dmrecord 792386

Document Type Thesis

Rights Mautner, Henry George

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA