The synthesis of 1,2,3,4-tetramethylnaphthalene and its reaction with maleic anhydride

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Content THE SYNTHES I S.. OP 1 , 2 , 3 , 4 - TETRAMETHYLN APHTHALENE
AND ITS REACTION WITH MALEIC ANHYDRIDE
A Thesis
p r e s e n t e d t o
tiie F a c u l t y o f t h e .D e p artm en t o f
C h e m is try
t h e U n i v e r s i t y of S o u th e rn C a l i f o r n i a
I n P a r t i a l F u l f i l l m e n t
o f th e R e q u ire m e n ts f o r t h e D egree
M a s te r o f S c ie n c e inuCUiemis^tr^
by i
R hodes P*vJ )a y to n .
J u n e 1948
U M I Number: EP41563
All rights reserved
IN FO R M A TIO N TO ALL USERS
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and there are missing pages, these will be noted. Also, if material had to be removed,
a note will indicate the deletion.
Dissertation Publishing
UMI EP41563
Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author.
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ProQuest LLC.
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C -. 'Y * D>7 4“ f
This thesis, written by
under the guidance of h^Ca... 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
MASTER OF SCIENCE
Date.
J u n e 19^8
Faculty Committee
y * * i
Chairman
A cknow ledgem ent
The a u t h o r i s i n d e b t e d t o D r. M. C. K l o e t z e l f o r
h i s i n v a l u a b l e a s s i s t a n c e and e n c o u ra g e m e n t d u r i n g t h i s
i n v e s t i g a t i o n .
T a b le o f C o n te n ts
Page
I , I n t r o d u c t i o n 1
I I . D i s c u s s io n o f r e s u l t s 10
I I I . ; E x p e r im e n ta l
A. S y n t h e s i s o f 1 , 2 , 3 , 4 - t e t r a m e t h y l h a p h t h a l e n e 17
B. R e a c ti o n o f 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e
w ith m a le ic a n h y d r id e 21
C . The r e a c t i v i t i e s o f d u re n e and h e x a m e th y lb e n -
ze n e to w a rd m a le ie a n h y d r id e 24
IV . Summary 26
B i b l i o g r a p h y 27
I n t r o d u c t i o n
The d ie n e s y n t h e s i s , o r D i e l s - A l d e r r e a c t i o n , was
n o t r e c o g n iz e d a s a g e n e r a l r e a c t i o n u n t i l a b o u t 1925 a lth o u g h
i s o l a t e d ex am p le s w ere r e p o r t e d some tim e b e f o r e t h i s . The
p u b l i c a t i o n i n 1928 o f th e w ork o f D i e l s a n d A l d e r ^ b r o u g h t
a t t e n t i o n t o t h e g e n e r a l i t y o f th e r e a c t i o n b e tw e e n co n
j u g a t e d d i e n e s and u n s a t u r a t e d compounds now known a s d i e n o -
p h i l e s . The r e a c t i o n i s a 1 , 4 - a d d i t i o n o f th e o l e f i n i c c a r
b o n s o f t h e d i e n o p h i l e t o th e c o n ju g a te d d ie n e sy s te m fo rm in g
a s i x membered r i n g ; f o r e x a m p le ,
f 0 + r R .
X ^ 1 1 i i i
Cxc / C
w here R u s u a l l y c o n t a i n s a c a r b o n y l g ro u p i n t h e a lp h a p o s i
t i o n t o th e d o u b le b o n d , a s i n a c r o l e i n , c r o t o n a ld e h y d e ,
m a le ic a n h y d rid e and p - b e n z o q u in o n e , However t h e s u b s t i t u e n t
c a r b o n y l g ro u p may be r e p l a c e d by o t h e r a c t i v a t i n g g ro u p s
s u c h a s n i t r i l e , n i t r o , s u l f o n e , s u l f i d e , h a lo g e n o r a n o th e r
o l e f i n i c l i n k a g e ^ . C e r t a i n c o n d i t i o n s f o r t h e d ie n e r e a c t i o n
h ave b e e n n o t e d : (1 ) w h ile t h e d ie n e r e a c t i o n may o c c u r a t
room te m p e r a tu r e w ith th e more r e a c t i v e s p e c i e s , i n g e n e r a l
a n a p p r e c i a b l e r a t e i s o b t a i n e d o n ly upon h e a t i n g ; (2 ) a lt h o u g h
♦
c a t a l y s i s i s u n n e c e s s a r y , i n some i n s t a n c e s a s p e c i f i c c a t a l y s i s
h a s b e e n o b s e r v e d .^ 3
2
The c h i e f c h a r a c t e r i s t i c o f th e d ie n e sy s te m i s
t h a t i t m u st be c o n ju g a te d s i n c e no r e a c t i o n i s o b s e rv e d
w ith a l l e n e s w ith o u t p r e v i o u s r e a r r a n g e m e n t to a c o n ju g a te d
sy ste m * The g e n e r a l i t y o f t h e r e a c t i o n i s su c h t h a t i t
h a s b e e n p ro p o s e d a s a t e s t f o r d ie n e sy ste m s* The i s o
l a t i o n o f a n a d d u c t may be u s e d a s a p o s i t i v e t e s t f o r t h e
p r e s e n c e o f a c o n ju g a te d d i e n o i d sy ste m * H ow ever, th e a b s e n c e
0$. a n a d d u c t c a n n o t be u s e d a s c o n c l u s i v e e v id e n c e f o r th e
a b s e n c e o f a c o n ju g a te d d i e n e s y s te m , s i n c e some d ie n e
sy s te m s do n o t g iv e t h e D i e l s - A l d e r r e a c tio n ® * 8 *
A c o n ju g a te d d ie n e s y s te m h a s b e e n shown to be p r e
s e n t i n a n th r a c e n e by th e f o r m a t io n o f th e a d d u c t 9 ,1 0 -
d i h y d r o a n th r a c e n e - e n d o - a - < 3 - s u c c in ic a n h y d rid e fro m th e
r e a c t i o n o f m a le ic a n h y d r id e w ith a n th r a c e n e *
cco +
The p r e s e n c e o f th e c o n ju g a te d d ie n e s y s te m i n a n th r a c e n e
i s a l s o i n d i c a t e d b y o t h e r r e a c t i o n s t y p i c a l o f d ie n e s y s te m s
s u c h a s ( 1 ) th e C - 1 0 - a l l c y l a ti o n o f 9 - a n t h r a n o l o b s e r v e d to
o c c u r a lo n g w i t h O - a l k y l a t i o n when an a l l c y l a t i o n h a l i d e i s
em p lo y ed 2 5 , an d (2 ) th e r e a d y r e a c t i o n w ith sod ium 3 8 *
On th e o t h e r h a n d , when n a p h th a le n e and m a le ic a n h y d rid e
a r e h e a t e d t o g e t h e r no a d d u c t i s fortaed * T h is i n d i c a t e s t h a t
t h e c o n ju g a te d s y s te m i n n a p h th a le n e i s to o a r o m a tic i n
3
c h a r a c t e r t o show a c t i v e d i e n o i d c h a r a c t e r by t h i s r e a c t i o n .
D e s p ite t h i s f a c t t h e r e a r e a num ber o f r e a c t i o n s w h ich i n d i
c a t e t h a t u n d e r t h e p r o p e r c o n d i t i o n s o f s u b s t i t u t i o n on t h e
n a p h th a le n e n u c le u s th e d i e n o i d s y s te m m ig h t be a c t i v a t e d a n d
a r e a c t i o n made to o c c u r w ith m a le ic a n h y d r i d e . F o r e x a m p le ,
i t i s p o s s i b l e t o a d d h y d ro g e n to t h e 1 - an d 4 - p o s i t i o n s o f
n a p h th a le n e u s i n g sodium an d a l c o h o l ^ i n a m anner a n a la g o u s
t o th e 1 , 4 - a d d i t i o n o f h y d ro g e n t o c o n ju g a te d a l i p h a t i c d ie n e
s y s te m s . O th e r r e a c t i o n s c i t e d a s e v id e n c e f o r a M i l l s -
i 7
N ixon e f f e c t i n n a p h th a le n e 4 - a l s o i n d i c a t e t h e p o s s i b i l i t y
o f s u f f i c i e n t l y a c t i v a t i n g th e a l p h a p o s i t i o n s on th e naph
t h a l e n e n u c le u s to o b t a i n a r e a c t i o n w ith m a le ic a n h y d r i d e .
The ty p e o f s u b s t i t u e n t r e q u i r e d f o r a c t i v a t i o n i s
s u g g e s t e d by th e r e a c t i o n o f m a le ic a n h y d r id e w ith a -
v i n y l n a p h t h a l e n e o r $ - v i n y l n a p h t h a l e n e to y i e l d a t y p i c a l
D i e l s - A l d e r a d d u c t 1 7 . i n t h i s h y d ro c a rb o n th e d ie n e sy s te m
i s p a r t i a l l y i n th e a r o m a tic n u c le u s an d p a r t i a l l y i n th e
s i d e c h a i n . The r e q u i r e m e n t f o r a c t i v a t i o n o f th e n a p h th a
l e n e n u c le u s a p p e a r s t o be th e i n t r o d u c t i o n o f s u b s t i t u e n t s
w h ic h , th r o u g h c r o s s c o n j u g a t i o n w ith t h e n u c l e u s , w ould
r e d u c e t h e a r o m a tic c h a r a c t e r o f th e s u b s t i t u t e d r i n g an d
a c t i v a t e th e a lp h a p o s i t i o n s on th e s u b s t i t u t e d r i n g . A
s i c o n d r e q u i r e m e n t o f th e s u b s t i t u e n t , w h ic h a u t o m a t i c a l l y
e l i m i n a t e s an o l e f i n i c s u b s t i t u e n t , w ould be t h a t i t w ould
n o t a c t a s p a r t o f t h e d ie n e system * I t h a s h e e n fo u n d ^ t h a t
9 - m e th y la n th r a c e n e a n d 9 , 1 0 - d im e th y la n th r a c e n e r e a c t m ore
r a p i d l y th a n a n th r a c e n e w i t h m a le ic a n h y d r i d e . The e f f e c t o f
t h e m e th y l g ro u p s upon th e r a t e o f r e a c t i o n o f a n th r a c e n e an d
th e p o s s i b i l i t y o f h y p e r c o n j u g a t i o n i n v o lv in g , th e m e th y l
3 1 1
g r o u p * s u g g e s t e d th e p o s s i b i l i t y o f u s i n g m e t h y l - s u b s t i
t u t e d n a p h th a le n e s a s d i e n e s . C o m p ariso n o f th e s t r u c t u r e
o f a n th r a c e n e w i t h t h a t o f n a p h th a le n e show s t h a t a n th r a c e n e
i s 2 ,3 - b e n z n a p h t h a l e n e , t h a t i s , a n a p h th a le n e n u c le u s s u b
s t i t u t e d i n th e 2 - an d 3 - p o s i t i o n s by a g ro u p c a p a b le o f
c o n j u g a t i o n w i t h th e n u c le u s * Prom t h i s c o m p a riso n i t was
c o n c lu d e d t h a t 2 ,3 - d i r a e th y l n a p h t h a le n e m ig h t show d i e n o i d
c h a r a c t e r and r e a c t w ith m a le ic a n h y d rid e a t an a p p r e c i a b l e
r a t e , f u r t h e r a n a lo g y to th e m e t h y l - s u b s t i t u t e d a n t h r a c e n e s
i n d i c a t e d t h a t i f 2 , 3 - d im e th y ln a p h th a le n e u n d e rw e n t th e
d ie n e s y n t h e s i s w ith m a le ic a n h y d r i d e , th e n 1 , 2 , 3 - t r i m e t h y l -
n a p h th a le n e a n d 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e s h o u ld r e a c t
w ith m a le ic a n h y d r id e a t a n e v e n f a s t e r r a t e . Work s t i l l
i n p r o g r e s s had shown t h a t when 2 , 3 - d im e th y ln a p h th a le n e
an d m a le ic a n h y d r id e w ere h e a te d t o g e t h e r i n b e n z e n e s o l u
t i o n a r e a c t i o n o c c u r e d , p re s u m a b ly th e f o r m a t io n o f a n
a d d u c t . N e g a tiv e r e s u l t s had b e en o b t a i n e d u n d e r s i m i l a r
c o n d i t i o n s w ith th e 1 , 2 - , 1 , 3 - , and 1 ,4 - d i r a e th y l n a p h t h a le n e s
and w ith 1 , 3 , 4 - t r i m e t h y l n a p h t h a l e n e . 1 ,2 ,3 - T r i m e t h y l n a p h t h a l e n e
5
a n d 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e had n o t h e r e t o f o r e b e e n
t e e t e d •
The p u r p o s e o f t h e p r e s e n t i n v e s t i g a t i o n was th e
s y n t h e s i s o f one o f th e s e com pounds, 1 , 2 , 3 , 4 - t e t r a m e t b y l -
n a p h t h a l e n e , and th e s t u d y o f th e e x t e n t o f th e r e a c t i o n , i f
18
a n y , b e tw e e n t h i s compound and m a le ic a n h y d r i d e . H ew ett
had p r e v i o u s l y r e p o r t e d th e s y n t h e s i s o f 1 , 2 , 3 , 4 - t e t r a
m e th y ln a p h th a le n e fro m 2 , 3 - d im e th y ln a p h th a le n e by e h l o r o -
m e t h y l a t i o n t o l - c h l o r o m e t h y l - 2 ,3 - d i r a e t h y l n a p h t h a l e n e , c a t a
l y t i c h y d r o g e n a tio n t o 1 , 2 , 3 - t r i m e t h y l n a p h t h a l e n e , c h l o r o -
m e t h y l a t i o n t o l - c h l o r o m e t h y l - 2 , 3 , 4 - t r i m e t h y l n a p h t h a l e n e an d
c a t a l y t i c h y d r o g e n a tio n to 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e
w ith a n o v e r a l l y i e l d o f a b o u t 4 8 $ . , W h ile t h e p r e s e n t i n
v e s t i g a t i o n was i n p r o g r e s s , th e s y n t h e s i s o f 1 , 2 , 3 , 4 -
t e t r a m e t h y l n a p h t h a l e n e was r e p o r t e d by S i s i d o a n d U o z a k i3^
i n a b o u t 2?$ y i e l d fro m 3 ,4 - d i c h l o r o - 3 ,4 - d i m e t h y l h e x a n e an d
b e n ze n e by a P r i e d e l - C r a f t s r e a c t i o n . T h ese a u t h o r s c la im e d
t h a t d u r i n g t h e c o u rs e o f t h e r e a c t i o n i s o m e r i z a t i o n o c c u r r e d
w ith s u b s e q u e n t r i n g a l k y l a t i o n .
I t was th o u g h t t h a t 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e
c o u ld be p r e p a r e d m ore r e a d i l y a n d i n h i g h e r y i e l d from
p r e h n i t e n e th a n by th e above m e th o d s. The p ro p o s e d r o u t e
f o r th e s y n t h e s i s was a s f o l l o w s : th e s u c c i n o y l a t i o n o f
p r e h n i t e n e to y i e l d th e new k e to - a c id ( 3 - ( 2 , 3 , 4 , 5 - t e t r a -
6
m e t h y l b e n z o y l ) - p r o p i o n i c a c i d ( I ) ; t h e Clemmensen r e d u c t i o n
o f I t o y i e l d a new a c i d , 2 f - ( 2 , 3 , 4 , 5 - t e t r a m e t h y l p h e n y l ) -
b u t y r i c a c i d ( I I ) ; t h e c y c l i z a t i o n o f I I th r o u g h th e a c i d
c h l o r i d e , o r u s i n g 30% s u l f u r i c a c i d t o y i e l d th e p r e v i o u s l y
u n p r e p a r e d k e t o n e , 5 , 6 , 7 , 8 - t e t r a m e t h y l - l - t e t r a l o n e ( I H ) ;
t h e Clem m ensen r e d u c t i o n o f I I I t o y i e l d t h e h e r e t o f o r e
u n r e p o r t e d 5 , 6 , 7 , 8 - t e t r a m e t h y l t e t r a l i n ( I V ) ; a n d t h e dehy*^
d r o g e n a t i o n o f IV w i t h s u l f u r o r a p a ll a d i u m c a t a l y s t to
y i e l d th e d e s i r e d 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e (V ).
s i b l e r e a c t i o n . The i r r e v e r s i b i l i t y i n many more i n s t a n c e s
i s due t o s e c o n d a r y r e a c t i o n s , su c h a s t h e s h i f t i n g o f a
d o u b le bond o r t h e s p l i t t i n g o u t o f an endo b r i d g e , w h ic h
change th e c h a r a c t e r o f t h e a d d u c t a n d r e n d e r t h e r e a c t i o n
e o U S f t h> c
vfi
Pd-C ;
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HCI
IE
The D i e l s - A l d e r r e a c t i o n i s i n many c a s e s a r e v e r -
7
i r r e v e r s i b l e . The f i r s t q u a n t i t a t i v e s t u d y o f th e r e v e r s i
b i l i t y o f t h e a d d u c t f o r m a t io n was t h e s t u d y , made b y Bachmann
and K l o e t z e l 1 , o f th e e q u i l i b r i u m o f th e r e a c t i o n s b e tw ee n
m a le ic a n h y d rid e a n d a n th r a c e n e and s e v e r a l s u b s t i t u t e d
a n th r a c e n e d e r i v a t i v e s . T hey fo u n d t h a t t h e r e a c t i o n b e tw e e n
th e h y d ro c a r b o n and m a le ic a n h y d rid e was r e v e r s i b l e an d t h a t
t h e e x t e n t o f f o r m a t io n o f t h e a d d u c t a t e q u i l i b r i u m was
i n c r e a s e d b y low t e m p e r a t u r e s and e x c e s s m a le ic a n h y d r i d e .
I t was a l s o fo u n d t h a t t h e p r e s e n c e o f s u b s t i t u e n t s on th e
a n th r a c e n e n u c le u s had an a p p r e c i a b l e e f f e c t b o th upon th e
r a t e o f r e a c t i o n a n d u p o n th e e x t e n t o f th e r e a c t i o n a t
e q u i l i b r i u m . M e th y l g ro u p s i n th e meso p o s i t i o n s had l i t t l e
e f f e c t upon th e p o s i t i o n o f th e e q u i l i b r i u m , t h e r e s u l t s
b e in g , i d e n t i c a l w i t h i n t h e l i m i t s o f e x p e r i m e n t a l e r r o r .
H ow ever, t h e - r a t e Of t h e r e a c t i o n , com pared to t h a t w ith
a n t h r a c e n e , was d e c i d e d l y i n c r e a s e d when 9 - m e th y la n th r a c e n e
was u s e d a n d e v e n more m a rk e d ly i n c r e a s e d when 9 , 1 0 - d i m e th y l -
a n th r a c e n e was e m p lo y e d .
By a n a lo g y w i t h t h e a n th r a c e n e s e r i e s , a n d s i n c e i t
h a s b e e n shown t h a t 2 , 3 - d im e th y ln a p h th a le n e r e a c t s w ith
m a le ic a n h y d r i d e , i t was ho p ed t h a t t h e s u b s t i t u t i o n i n
1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e w ould i n c r e a s e t h e r a t e o f
r e a c t i o n o f th e n a p h th a le n e n u c le u s w i t h m a le ic a n h y d r id e t o
fo rm 1 , 2 , 3 , 4 - t e t r a m e t h y l - 1 , 4 - d i h y d r o n a p h t h a l e n e - 1 , 4 -e n d o -
8
- s u c c i n i c a n h y d rid e (V I)
a
I f an i s o l a b l e r e a c t i o n p r o d u c t was o b t a i n e d w i t h e q u im o la r
q u a n t i t i e s o f t h e r e a c t a n t s , i t was p ro p o s e d to s t u d y th e
e q u i l i b r i u m o f th e r e a c t i o n . I f n e c e s s a r y , a l a r g e e x c e s s
o f a n h y d rid e was t o be em ployed to o b t a i n a maximum y i e l d
o f a d d u c t .
n a p h th a le n e h a s d e m o n s tr a te d a d i e n o i d s y s te m p a r t l y i n th e
n u c l e u s , and th e p r e v i o u s l y m e n tio n e d a d d i t i o n o f h y d ro g e n
t o t h e 1 - , 4 - p o s i t i o n s o f n a p h th a le n e h a s i n d i c a t e d t h e p o s
s i b i l i t y o f t h e p r e s e n c e o f a d i e n o i d s y s te m c o m p le te ly
w i t h i n th e n a p h th a le n e n u c l e u s . H ow ever, i f m a le ic a n h y d r id e
r e a c t s w i t h 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e to y i e l d an
i s o l a b l e p r o d u c t , th e n i n two i n s t a n c e s , 2 , 3 - d im e th y ln a p h
t h a l e n e an d 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e , i t w i l l h av e b e e n
show n b y a t e s t s p e c i f i c f o r c i s - d i e n o i d s y s te m s t h a t u n d e r
c e r t a i n c o n d i t i o n s o f s u b s t i t u t i o n th e n a p h th a le n e n u c le u s
d o e s l o s e a p a r t o f i t s s t r o n g l y a r o m a tic c h a r a c t e r and
u n d e rg o e s a n o th e r r e a c t i o n t y p i c a l o f a l i p h a t i c c o n ju g a te d
d i e n e s y s te m s . Such a c o n d i t i o n m ig h t be e x p l a i n e d on th e
b a s i s o f h y p e r c o n j u g a t i o n i n v o l v i n g th e s u b s t i t u e n t m e th y l
g r o u p s a n d m ig h t o f f e r a d d i t i o n a l e v id e n c e f o r th e e x i s t e n c e
The r e a c t i o n o f m a le ic a n h y d r id e w ith 1 - o r 2 - v i n y l
o f s u c h h y p e r c o n j u g a t i o n ,. T h is ty p e o f h y p e r c o n j u g a t i o n
on
h a s b e e n o b s e r v e d i n o t h e r i n s t a n c e s s u c h a s th e n i t r a t i o n ^
an d s u l f © n a t i o n 22 o f p-cyraene w h ic h , c o n t r a r y to th e r e l a
t i v e i n d u c t i v e e f f e c t s , g av e m o n o s u b s t i t u t i o n p r o d u c t s i n
th e 2 - p d s i t i o n ; th e r a t e o f b r o m in a tio n o f t o l u e n e i s a b o u t
f o u r tim e s a s f a s t a s t h e b r o m in a tio n o f t - b u t y l b e n z e n e 7 *1^);
and th e r e l a t i v e o r d e r o f th e r a t e s o f h y d r o l y s i s and a l c o -
h o l y s i s o f p - a l k y l b e n z h y d r y l c h l o r i d e s was m e th y l > e t h y l >
i s o p r o p y l > t e r t i a f y . b u t y l 1 9 , w h ic h i s t h e o r d e r t o be e x
p e c t e d when h y p e r c o n j u g a t i o n p l a y s a n i m p o r t a n t r o l e .
I n a d d i t i o n t o th e t h e o r e t i c a l i m p l i c a t i o n s o f th e
r e a c t i o n i n q u e s t i o n , t h e r e i s i t s s y n t h e t i c v a lu e a n d , a l s o ,
th e f a c t t h a t . t h e so d iu m s a l t s o f t h e s e a d d u c ts a r e som ew hat
w a te r s o l u b l e . I f t h e s u b s t i t u t i o n o f m e th y l g ro u p s on
c a r c i n o g e n i c h y d r o c a rb o n s w i l l c a u s e them t o r e a c t w ith
m a le ic a n h y d r i d e , a q u e o u s s o l u t i o n s o f t h e so d iu m s a l t s o f
th e a d d u c t a c i d s c o u ld be u t i l i z e d f o r t e s t i n g t h e p h y s i o
l o g i c a l a c t i v i t y o f th e h y d r o c a r b o n s .
10
D i s c u s s i o n o f R e s u l t s
The s y n t h e s i s of* 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e (V)
by th e s e q u e n c e p r o p o s e d i n th e i n t r o d u c t i o n was s u c c e s s f u l .
B ach o f t h e p r o d u c t s , I , I I , I I I , IV* an d V, was o b t a i n e d
i n good y i e l d * The r e d u c t i o n o f t h e c y c l i c k e to n e ( I I I )
y i e l d e d 84$ o f th e t e t r a m e t h y l t e t r a l i n and th e re m a in in g
y i e l d s w ere i n e x c e s s o f 9 4 $ .
S u c c i n o y l a t i o n o f p r e h n i t e n e , p r e p a r e d fro m p e n t a -
3P
m e th y lb e n z e n e a c c o r d i n g t o t h e m ethod o f S m ith an d Lux ,
was r u n u s i n g s - t e t r a c h l o r o e t h a n e a s a s o l v e n t . I t was
fo u n d t h a t t h i s s o l v e n t c o u ld be r e p l a c e d b y p u r i f i e d
n i t r o b e n z e n e w ith no m a t e r i a l d i f f e r e n c e i n y i e l d . The
a d v a n ta g e o f th e t e t r a c h l o r o e t h a n e l a y i n th e g r e a t e r e a s e
o f s te a m d i s t i l l i n g t h i s s o l v e n t , b u t th e n i t r o b e n z e n e
y i e l d e d a s l i g h t l y p u r e r p r o d u c t .
R e d u c tio n o f t h e k e t o a c i d ( I ) by t h e M a r tin m o d i-
2 4
f i c a t i o n o f t h e Clem m ensen r e d u c t i o n p r o c e e d e d s m o o th ly .
An a t t e m p t to p u r i f y th e p r o d u c t by r e c r y s t a l l i z a t i o n fro m
e t h e r an d p e tr o le u m e t h e r w ith o u t a p r e v i o u s d i s t i l l a t i o n
o f th e p r o d u c t was u n s u c c e s s f u l .
C y c l i z a t i o n o f th e s u b s t i t u t e d b u t y r i c a c i d ( I I )
was e f f e c t e d w ith 80$ s u l f u r i c a c i d , an d a l s o by th e m ethod
em ployed b y Bachraann an d G hem erda^ i n w h ich p h o sp h o ru s p e n t a -
c h l o r i d e a n d s t a n n i c c h l o r i d e w ere u s e d f o r a s i m i l a r
11
c y c l i z a t i o n . The c y c l i z a t i o n th r o u g h t h e a c i d c h l o r i d e was
n o t a p p r e c i a b l y . a f f e c t e d b y t h e s u b s t i t u t i o n o f t h i o n y l
c h l o r i d e f o r p h o s p h o ru s p e n t a c h l o r i d e , o r b y th e u s e o f
a n h y d ro u s alum inum c h l o r i d e i n p l a c e o f fu m in g s t a n n i c c h l o r
i d e a s t h e c y c l i z i n g c a t a l y s t . U s in g t h i s m ethod t h e y i e l d s
w ere 7 0 -8 0 # w h ile w i t h 80# s u l f u r i c a c i d th e y i e l d s w ere a s
h i g h a s 95#*
The m ethod o f d e h y d r o g e n a tio n u s in g , s u l f u r w a s com
p a r a t i v e l y u n s a t i s f a c t o r y , s i n c e t h e p r o d u c t was o b t a i n e d
a s y e llo w c r y s t a l l i n e m a t e r i a l i n r e l a t i v e l y p o o r y i e l d ( 8 8 # ) ,
a s com pared t o t h e n e a r l y q u a n t i t a t i v e y i e l d s o f c o l o r l e s s
2 3
p r o d u c t r e s u l t i n g fro m t h e u s e o f a p a ll a d i u m c a t a l y s t . The
m e l t i n g p o i n t o f t h e 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e (V ),
1 0 6 .5 -1 0 7 ® , was i n a g re e m e n t w ith t h a t r e p o r t e d by H ew ett^®
( 1 0 6 .5 - 1 0 7 * 5 ° ) , an d t h a t r e p o r t e d b y S i s i d o an d N o z a k i3 ^ -
( 1 0 6 ° ) • S i s i d o an d N o zak i r e p o r t e d t h a t t e t r a m e t h y l n a p h t h a
l e n e c r y s t a l l i z e s fro m 95# e t h a n o l a s c o l o r l e s s p l a t e s , w h ile
i n t h i s w ork t h e compound was fo u n d t o c r y s t a l l i z e fro m 95#
e t h a n o l a s c o l o r l e s s p r i s m s . The o b s e r v e d m e ltin g , p o i n t o f
th e 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e p i c r a t e , 1 8 2 .5 - 1 8 3 ° , was
l i k e w i s e i n a g re e m e n t w i t h t h e 1 8 2 -1 8 3 ° m e l t in g p o i n t r e p o r t e d
b y H e w e tt, b u t was s l i g h t l y h i g h e r th a n th e 1 8 1 ° m e l t i n g
p o i n t r e p o r t e d by S i s i d o a n d N o z a k i.
When 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e and m a le ic
12
a n h y d r id e w ere h e a t e d i n sgrlene s o l u t i o n , a r e a c t i o n o c c u rr e d *
An i n i t i a l y e llo w c o l o r was o b s e rv e d a s i n th e e a s e o f many
d ie n e a d d i t i o n s 8 7 »8 9 * When t h e h y d r o c a r b o n was h e a te d w i t h a
l a r g e e x c e s s o f m a le ie a n h y d r id e i n b e n z e n e , a y i e l d o f 90%
o f ah a d d u c t was o b ta in e d * The a d d u c t was p resu m ed t o be
1 , 2 , 3 , 4 - t e tram e t h y l - 1 , 4 - d i h y d r o n a p h t h a l e n e - l , 4 ^ e n d o - <*,j3 -
s u c c i n i c a n h y d rid e (V I)* An e le m e n ta r y a n a l y s i s o f th e a d
d u c t , a n d a l s o o f th e d im e th y l e s t e r o f t h e a d d u c t , i s i n
a g re e m e n t w ith t h i s p o s t u l a t e d s t r u c t u r e * P e n d in g a p r o o f o f
t h e s t r u c t u r e o f th e a d d u c t , i t c a n n o t be s a i d d e f i n i t e l y
t h a t VI r e p r e s e n t s t h e s t r u c t u r e o f t h e a d d u c t*
In t h e c a s e o f th e r e a c t i o n o f m a le ic a n h y d r id e w ith
2 ,3 - d i m e t h y l n a p h t h a l e n e i t c o u ld be p o s t u l a t e d t h a t th e
m a le ic a n h y d r id e s u b s t i t u t e d on c a rb o n num ber one o f th e
n a p h th a le n e n u c le u s w ith th e s h i f t o f t h e h y d ro g e n to th e
b e t a c a rb o n o f t h e m a le ic a n h y d rid e to fo rm 2 , 3 - d i m e th y l -
1 - n a p h t h y l s u c c i n i c a n h y d r i d e , a s i n th e c a s e o f th e fo rm a
t i o n o f 2 - m e t h y l - 5 - p y r r y l s u e c i n i e a c i d fro m 2 - m e t h y lp y r r o l
an d m a le ic a n h y d r i d e 1 3 ; f u r a n and a c r o l e i n r e a c t s i m i l a r l y
i n th e p r e s e n c e o f a t r a c e o f s u l f u r d i o x id e to y i e l d a
m ix tu r e o f 2 - f u r a n p r o p io n a ld e h y d e a n d 2 , 5 - f u r a n - d i - p r o p i o n -
a ld e h y d e 2 8 ; a n d m a le ic a n h y d rid e and s t y r e n e y i e l d a p o ly m e r8 8 *
H ow ever, i n t h e c a s e o f th e t e t r a m e t h y l n a p h t h a l e n e (V ), t h e r e
i s no h y d ro g e n on c a rb o n num ber o n e ; c o n s e q u e n t ly , t h i s ty p e
o f s u b s t i t u t i o n i n th e r i n g c a r r y i n g t h e m e th y l g ro u p s can
n o t o c c u r i n th e r e a c t i o n o f t h i s h y d r o c a r b o n w ith m a le ic
a n h y d rid e * A s u b s t i t u t i o n on c a rb o n num ber f i v e seem s im
p r o b a b l e s i n c e i t w ould r e q u i r e a s e c o n d a r y a c t i v a t i o n o f
t h e u n s u b s t i t u t e d a r o m a ti c n u c le u s by th e m e th y l s u b s t i t u e n t s
on t h e o t h e r n u c le u s * I n s t e a d i t w ould seem more p r o b a b l e
t h a t a o n e - f o u r a d d i t i o n t o th e s u b s t i t u t e d n u c le u s by th e
m a le ic a n h y d r id e s h o u ld o c c u r i n th e m anner commonly o b s e r v e d
i n t h e d ie n e s y n t h e s i s * Such a n a d d i t i o n c o u ld be f a v o r e d
b y t h e r e s o n a n c e c o n t r i b u t i o n s o f s u c h n o -b o n d re s o n a n c e
fo rm s a s th e f o l l o w i n g :
©
A B C D
The a f o r e d e s c r i b e d ty p e o f re s o n a n c e w ould te n d to
i n c r e a s e th e r e a c t i v i t y o f th e a r o m a tic n u c le u s a t th e one
a n d f o u r p o s i t i o n s to w a rd s d i e n o p h i l e s com pared to t h a t
fo u n d i n t h e u n s u b s t i t u t e d n a p h th a le n e n u c le u s * S in c e th e
d i e n e s y n t h e s i s i s p o s t u l a t e d t o be a f o u r - c e n t e r r e a c t i o n
r e q u i r i n g a h ig h e l e c t r o n d e n s i t y on th e one and f o u r c a r
b o n s o f th e d i e n e , i t i s e x p e c te d t h a t 1 , 3 , 3 , 4 - t e t r a m e t h y l
n a p h th a le n e s h o u ld u n d e rg o t h e d ie n e s y n t h e s i s m ore r e a d i l y
t h a n th e u n s u b s t i t u t e d n a p h t h a l e n e . From t h e f a c t t h a t a
r e a c t i o n i s o b s e r v e d i n th e c a s e o f 3 , 3 - d im e th y ln a p h th a le n e
14
a n d ra a le ie a n h y d r id e h u t n o t w ith 1 , 4 - d im e th y l n a p h th a l e n e i t
i s e v i d e n t t h a t th e r e s o n a n c e s t r u c t u r e s o f ty p e A c o n t r i b u t e
m ore t o th e r e s o n a n c e h y b r i d th a n do t h e r e s o n a n c e s t r u c t u r e s
o f ty p e B . A lth o u g h c o rre s p o n d in g , s t r u c t u r e s can be p o s t u
l a t e d f o r n a p h t h a l e n e ,
s u c h s t r u c t u r e s s h o u ld c o n t r i b u t e so l i t t l e to th e re s o n a n c e
h y b r i d t h a t t h e y a r e n e g l i g i b l e ., c o n s e q u e n t ly no D i e l s - A l d e r
r e a c t i o n i s o b s e r v e d w ith n a p h th a le n e *
I n a d d i t i o n to th e r e s o n a n c e e f f e c t t h e r e i s th e i n
d u c t i v e e f f e c t o f t h e m e th y l g ro u p s t o be c o n s i d e r e d . S in c e
th e m e th y l g ro u p i s l e s s e l e c t r o n e g a t i v e t h a n h y d ro g e n , th e
s u b s t i t u t i o n o f f o u r m e th y l g ro u p s on th e on e r i n g w i l l i n
c r e a s e t h e e l e c t r o n d e n s i t y a ro u n d th e c a r b o n atom s o f t h i s
r i n g , th u s i n c r e a s i n g . t h e r e a c t i v i t y o f t h i s r i n g com pared
t o t h a t o f n a p h t h a l e n e . T h e r e f o r e , b o th th e r e s o n a n c e e f f e c t
an d th e i n d u c t i v e e f f e c t te n d to i n c r e a s e t h e e l e c t r o n d en
s i t y a ro u n d c a rb o n s num ber one a n d f o u r o f 1 , 2 , 3 , 4 - t e t r a
me th y l n a p h t h a l e n e , t h e r e b y i n c r e a s i n g th e r e a c t i v i t y o f t h i s
compound to w a rd d i e n o p h i l e s . C o n s e q u e n tly , 1 , 2 , 3 , 4 - t e t r a
m e th y ln a p h th a le n e s h o u ld be more r e a c t i v e th a n n a p h th a le n e
to w a rd m a le ic a n h y d r i d e .
15
The r e a c t i o n o f 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e and
m a le ic a n h y d r id e was shown t o be r e v e r s i b l e , f o rm in g a b o u t
/
6 .4 $ o f th e a d d u c t a t e q u i l i b r i u m i n r e f l u x i n g x y le n e s o l u
t i o n , When m a le ic a n h y d r id e an d 1 ,2 ,3 ,4 - t e t r a m e t h y l n a p h t h a - *
l e n e w ere h e a t e d i n r e f l u x i n g x y le n e s o l u t i o n , 9 3 ,5 # o f th e
i n i t i a l t e t r a m e t h y l n a p h t h a l e n e was r e c o v e r e d i n 46 h o u rs
and on two o t h e r r u n s 9 3 ,7 ^ was r e c o v e r e d i n 72 h o u r s . When
t h e a d d u c t (V I) was h e a te d i n r e f l u x i n g . x y le n e s o l u t i o n ,
h y d r o c a r b o n c o r r e s p o n d i n g t o 9 3 ,5 ^ o f th e i n i t i a l a d d u c t was
r e c o v e r e d i n 72 h o u r s , w i t h no i n c r e a s e when t h e r e a c t i o n
m ix tu r e was h e a t e d f o r 95 h o u r s . S in c e th e a p p r o a c h o f th e
e q u i l i b r i u m by th e h e a t i n g t o g e t h e r o f th e a n h y d rid e and
h y d ro c a rb o n was r u n on l a r g e r sa m p le s and was p r o b a b l y a
l i t t l e more a c c u r a t e , a v a lu e o f 9 3 ,6 ^ was ta k e n a s th e
a v e r a g e r e c o v e r y o f th e s t a r t i n g h y d r o c a r b o n . T h is p e r c e n t
a g e o f a d d u c t a t e q u i l i b r i u m i s much lo w e r th a n t h e v a lu e s
o b s e r v e d by Bachmann an d K l o e t z e l i n th e a n th r a c e n e s e r i e s ,
i n w h ic h th e v a lu e s v a r i e d fro m 16# o f a d d u c t i n th e c a s e
o f 9 ,1 0 - d i p h e n y l a n t h r a c e n e t o 99^ f o r a n t h r a c e n e .
S in c e t h e r e p la c e m e n t on th e n a p h th a le n e n u c le u s
o f a 2 ,3 - b e n z o g ro u p by two m e th y l g ro u p s l e a d s t o a d ie n e
s y s te m i n th e s u b s t i t u t e d r i n g w hich i s much l e s s r e a c t i v e
to w a rd m a le ic a n h y d r i d e , i t c o u ld be p r e d i c t e d t h a t th e
r e p la c e m e n t o f th e s e c o n d benzo g ro u p by m e th y l g ro u p s a s
16
R
R
O k
c %
I?
R
w here' R s H o r CH3 ,
s h o u ld l e a d t o a d ie n e s y s te m w h ic h i s s t i l l l e s s r e a c t i v e *
The r e a c t i o n s o f t h e s e h y d r o c a rb o n s w ith m a le ic a n h y d rid e
s h o u ld o c c u r t o a much s m a l l e r e x t e n t th a n t h e r e a c t i o n o f
th e n a p h t h a l e n i c a n a lo g u e s u n d e r s i m i l a r c o n d i t i o n s . T h is
p r e d i c t i o n was c o n firm e d w i t h d u re n e and h e x a ra e th y lb e n z e n e ;
no a d d u c t was i s o l a t e d fro m t h e r e a c t i o n m ix tu r e i n e i t h e r
i n s t a n c e .
E x p e r im e n ta l
A. S y n t h e s i s o f 1 , 2 , 3 ,4 - t e t r a m e t h y l n a p h t h a l e n e (V)
S u c c i n o y l a t i o n o f P r e h n i t e n e
F o r t y gram s o f p r e h n i t e n e was s u c c i n o y l a t e d by th e
5
p r o c e d u r e em ployed by B a r n e t t a n d S a n d e rs f o r th e s u c
c i n o y l a t i o n o f t o lu e n e a n d o - , m - , and p - x y le n e s * The
p r o d u c t was o b t a i n e d a s a w h ite lum py m a t e r i a l ; y i e l d ,
6 3 .7 g . ( 9 7 £ ) , m .p . 1 1 4 -1 2 0 ° . The / 2 > - ( 2 , 3 , 4 , 5 - t e t r a -
m e th y lb e n z o y T ) - p r o p io n ic a c i d r e c r y s t a l l i z e d fro m a n
e t h e r - p e t r o l e u m e t h e r s o l u t i o n i n lo n g t h i c k c o l o r l e s s
n e e d l e s , m .p . 1 2 4 -1 2 5 ° .
A n a l. C a l c 'd f o r C, 7 1 .7%; H, 7 .7
F ound: C, 7 2 .0 ^ ; H, 8 . 0 £ .
R e d u c tio n o f & - ( 2 , 3 , 4 , 5 - t e t r a m e t h y l b e n z o y l ) - p r o p i o n i o
a c i d ( I )
A m algam ated z in c was p r e p a r e d by s h a k in g f o r f i v e
m in u te s a m ix tu r e o f 355 g . o f g r a n u l a r z i n c , 3 5 5 c c . o f
w a t e r , 12 c c . o f c o n c . h y d r o c h l o r i c a c i d and 3 5 .5 g . o f
m e r c u r ic c h l o r i d e . The s o l u t i o n was d e c a n te d a n d th e
f o l l o w i n g r e a g e n t s w ere a d d e d i n o r d e r : 550 c c . o f c o n c .
h y d r o c h l o r i c a c i d , 12 c c . o f e t h a n o l , 24 c c . o f t o lu e n e
an d 5 8 .0 g . o f th e k e to a c i d ( I ) . An a d d i t i o n a l 800 cc*
The m e l t i n g p o i n t s a r e u n c o r r e c t e d . A ll a n a l y s e s by
D r. G. O p penheim er o f th e C a l i f o r n i a I n s t i t u t e o f
T e c h n o lo g y .
18
o f h y d r o c h l o r i c a c i d was add ed d u r i n g t h e r e f l u x p e r i o d
o f f o r t y h o u r s . The r e a c t i o n m ix tu r e was e x t r a c t e d w ith
b e n z e n e an d w ashed w i t h sodium c a r b o n a te s o l u t i o n and
w a t e r . C o n c e n t r a t i o n o f th e b e n z e n e s o l u t i o n f o llo w e d
by d i s t i l l a t i o n fro m a C l a i s e n f l a s k o f t h e r e s i d u e u n d e r
r e d u c e d p r e s s u r e y i e l d e d 5 1 .6 g . (9 5 $ ) o f y * ( 2 , 3 , 4 , 5 *
t e t r a r a e t h y l p h e n y l ) - b u t y r i c a c i d ( I I ) s u f f i c i e n t l y p u re
f o r c y c l i z a t i o n . The a c i d r e c r y s t a l l i z e d fro m e t h e r -
p e tr o le u m e t h e r i n c o l o r l e s s l e a f l e t s , m .p . 1 0 6 .5 - 1 0 7 .5 ° •
A n a l. C a l c ’d f o r C14H2 0 02 : C, 7 6 .3 2 # ; H, 9 .1 5 # .
F ound: C, 7 6 .5 1 # ; H, 8 .9 1 # .
C y c l i z a t i o n o f S- ( 2 , 3 , 4 , 5 - T e t r a m e t h y l p h e n y l ) - b u t y r y l -
C h lo r id e
The a c i d c h l o r i d e , p r e p a r e d fro m 6*2 g . o f V .(2 ,3 ,4 ,5 * *
t e t r a m e t h y l p h e n y l ) - b u t y r i c a c i d ( I I ) w i t h p h o s p h o ru s
p e n t a c h l o r i d e , was c y c l i z e d w ith s t a n n i c c h l o r i d e a c c o rd *
i n g t o th e m ethod em ployed by Bachmann a n d p b e m e rd a 2 f o r
th e c y c l i z a t i o n o f ^ - ( S - p h e n a n t h r y D - n - v a l e r i e a c i d , t o
y i e l d 4 .4 g . (7 6 # ) o f c ru d e k e t o n e . 5 , 6 , 7 ,8 -T e tra m e th y l-*
1 - t e t r a l o n e c r y s t a l l i z e s fro m 95# e th a n o l i n c o l o r l e s s
p r i s m s , m .p . 1 0 5 * 1 0 6 °.
A n a l. C a l c ’d f o r C14H180 ; C, 8 3 .1 2 # ; H, 8 .9 7 # .
F o u n d : C, 8 3 .3 3 # ; H, 9 .2 2 # .
19
C y c l i z a t i o n o f ^ ( 8 , 3 , 4 t 5 - T e t r a m e t h y l g h e n y l .) - b u ty r l c A cid ( I I )
T h i r t y - t h r e e grains o f I I was c y c l i z e d , a c c o r d i n g to t h e
g e n e r a l m ethod em ployed by B a r n e t t and S a n d e rs 5 f o r th e
c y c l i z a t i o n o f o t h e r a r y l - n - b u t y r i c a c i d s , u s i n g 185 cc*
o f 80$ s u l f u r i c a c i d a n d h e a t i n g f o r two h o u r s on th e
ste a m b a t h . The d a r k r e d s o l u t i o n was p o u re d i n t o 600 c c ,
o f w a te r and e x t r a c t e d w ith b e n ze n e* F o llo w in g c o n c e n t r a
t i o n o f t h e b e n z e n e s o l u t i o n th e p r o d u c t was d i s t i l l e d a t
1 5 6 -1 6 3 ° a t a p r e s s u r e o f 1 -8 mm* The d i s t i l l a t e (28*8 g*)
was d i s s o l v e d i n b e n z e n e and w ashed w i t h p o ta s s iu m h y d r o
x id e s o l u t i o n an d w a te r to rem ove a n y u n c y e l i z e d a c i d
w h ic h m ig h t h a v e d i s t i l l e d . C o n c e n t r a t i o n o f t h e b e n zen e
s o l u t i o n y i e l d e d 28*5 g . (9 4 $ ) o f 5 , 6 , 7 , 8 - t e t r a m e t h y l - l -
t e t r a l o n e , m .p . 1 0 4 - 1 0 6 ° ,
Clem m ensen R e d u c tio n o f 5 , 6 , 7 , 8 - T e t r a m e t h y l - l - t e t r a -
l o n e ( I I I )
To 104 g . o f z i n c , am alg am ated a s p r e v i o u s l y d e
s c r i b e d , w ere a d d e d i n o r d e r : 160 cc* o f c o n c . h y d ro
c h l o r i c a c i d , 6 c c . o f e t h a n o l , 18 c c . o f t o l u e n e and
20*2 g . o f th e k e to n e ( I I I ) , An a d d i t i o n a l 125 cc* o f
c o n c . h y d r o c h l o r i c a c i d was a d d ed d u r i n g th e r e f l u x
p e r i o d o f f o r t y - e i g h t h o u r s . The r e a c t i o n m ix tu re was
e x t r a c t e d w ith b e n z e n e . A f t e r w a s h in g w ith w a te r and
c o n c e n t r a t i n g t h e b e n ze n e s o l u t i o n , d i s t i l l a t i o n o f th e
20
r e s i d u e y i e l d e d 15*9 g* (8 4 # ) o f 5 , 6 , 7 , 8 - t e t r a r a e t h y l -
t e t r a l i n ( I V ) ; b . p . 1 1 9 -1 2 2 ° a t 1 -1 * 5 ram*; m .p . 7 2 - 7 8 ° .
T h is m a t e r i a l c r y s t a l l i z e s fro m low b o i l i n g p e tr o le u m
e t h e r i n c o l o r l e s s l e a f l e t s , m .p . 7 9 - 7 9 . 5 ° .
A n a l. C a l c 'd f o r Cl 4 H2o : C, H, 1 0 .7 1 # *
P o u n d : C, 8 9 .3 5 # ; H, 1 0 .5 2 # .
D e h y d ro g e n a tio n o f 5 , 6 , 7 , 8 - T e t r a m e t h y l t e t r a l l n (IV )
A m ix tu r e o f 7 .5 2 g . o f IV and 0 .7 5 g . o f a 30#
p a ll a d i u m on c h a r c o a l c a t a l y s t was p l a c e d i n a h e a v y
t e s t t u b e . F o llo w in g e x p u ls io n o f t h e a i r i n t h e tu b e
by c a r b o n d i o x id e l i b e r a t e d fro m a p e l l e t o f d r y i c e ,
th e tu b e was h e a t e d i n a m e ta l b a th f o r a p e r i o d o f 3
h o u rs,c o m m e n c in g a t a t e m p e r a tu r e o f 2 00° a n d s lo w ly
r a i s i n g t h e t e m p e r a tu r e t o 3 1 5 ° a t su c h a r a t e a s to
m a i n t a i n a s te a d y flo w o f h y d ro g e n . The h y d ro g e n c o l
l e c t e d was m e a su re d c r u d e l y and c o rr e s p o n d e d t o 102#
o f th e t h e o r e t i c a l . A f t e r c o o l i n g th e r e a c t i o n m ix tu r e
was e x t r a c t e d w ith b e n z e n e , and th e b e n z e n e s o l u t i o n
was f i l t e r e d . F o llo w in g e v a p o r a t i o n o f t h e b e n z e n e t h e
r e s i d u e was r e c r y s t a l l i z e d fro m 95# e t h a n o l ; y i e l d 6 .3 2
g . (8 6 # ) o f c o l o r l e s s p r i s m s , m .p . 1 0 6 .5 - 1 0 7 ° . C oncen
t r a t i o n o f th e f i l t r a t e y i e l d e d a n a d d i t i o n a l 0 .7 8 g .
(1 1 # ) o f c o l o r l e s s 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e , m .p .
1 0 4 - 1 0 5 .5 ° . The p i c r a t e o f th e 1 , 2 , 3 , 4 - t e t r a m e t h y l -
n a p h th a le n e m e lte d a t 1 8 8 * 5 -1 8 3 ° , a s com pared to th e
v a lu e s o f 1 8 8 -1 8 3 ° r e p o r t e d b y H e w e tt* 8 , an d 1 8 1 ° r e
p o r t e d b y S i s i d o and N o z a k i3 1 *
R e a c tio n o f 1 , 2 , 3 , 4 - T e t r a m e t h y l n a p h t h a l e n e w i t h M a le ic
A n h y d rid e
P r e p a r a t i o n o f 1 , 8 , 3 , 4 - t e t r a m e t h y l - 1 , 4 - d i h y d r o n a p h t h a -
l e n e - 1 ,4 - e n d o - A m ix tu r e o f 1*000 g* o f 1 , 8 , 3 , 4 - t e t r a m e t h y l n a p h t h a -
l e n e , 15*95 g . o f f r e s h l y d i s t i l l e d m a le ic a n h y d r id e and
20 cc* o f a n h y d ro u s b e n z e n e was r e f l u x e d f o r s e v e n ty - tw o
h o u rs and th e n t r e a t e d b y th e m ethod o f Baehmann and
K l o e t z e l * w h ic h was a s f o l l o w s : a f t e r e v a p o r a t i o n o f th e
s o l v e n t by a c u r r e n t o f a i r , th e r e s i d u e was h e a te d f o r
a few m in u te s on th e s te a m b a t h w ith a b o u t 50 cc* o f 40#
p o ta s s iu m h y d r o x id e s o l u t i o n ; th e m ix tu r e was c o o le d and
th e p o ta s s iu m s a l t o f th e a c i d was rem oved by f i l t r a t i o n
a n d d i s s o l v e d i n h o t w a t e r ; th e u n r e a c t e d h y d ro c a rb o n was
e x t r a c t e d w ith b e n z e n e ; th e b e n ze n e s o l u t i o n was t r a n s
f e r r e d to a p r e v i o u s l y t a r e d f l a s k , t h e b e n z e n e e v a p o r a te d
a n d th e r e s i d u a l h y d ro c a rb o n w e ig h e d ; fro m t h e a q u e o u s
s o l u t i o n th e d i c a r b o x y l i c a c i d was p r e c i p i t a t e d by a d d i
t i o n o f h y d r o c h l o r i c a c id * T here was o b t a i n e d 1*48 g .
(9 0 # ) o f th e d i c a r b o x y l i c . a c i d o f th e a d d u c t a s a w h ite
pow der m e l t i n g a t 1 4 4 -1 4 7 ° w ith d e c o m p o s itio n * When t h i s
22
a c i d was d i s s o l v e d i n e t h y l a c e t a t e c o n t a i n i n g some a c e t i c
a n h y d r i d e , th e a d d u c t c r y s t a l l i z e d i n c o l o r l e s s h e x a g o n a l
p r i s m s . The a d d u c t may be p u r i f i e d by r e c r y s t a l l i z a t i o n
fro m a n h y d ro u s e t h y l a c e t a t e .
When t h e a d d u c t was h e a t e d i n a m e ltin g p o i n t t u b e ,
a y e ll o w m e l t r e s u l t e d . The m e ltin g , p o i n t was in d e p e n
d e n t o f w h e th e r o r n o t t h e m e l t i n g p o i n t tu b e was s e a l e d ,
b u t v a r i e d w ith t h e te m p e r a tu r e a t w h ich th e sa m p le was
i n tr o d u c e d i n t o th e m e l t in g p o i n t b a t h and t h e r a t e a t
w h ic h th e b a t h was h e a t e d . F o r t h i s r e a s o n th e m e l t in g
p o i n t o f th e a d d u c t was t a k e n . a s f o l l o w s : t h e b a t h was
h e a t e d t o a te m p e r a tu r e n e a r th e m e l t i n g p o i n t , a c a p i l
l a r y c o n t a i n i n g a d d u c t was im m ersed i n th e b a t h , an d th e
tim e r e q u i r e d f o r th e sam p le to m e l t was t a k e n ; th e m e lt
i n g p o i n t was ta k e n a s th e . t e m p e r a t u r e a t w h ich a n i n
c r e a s e i n th e b a t h te m p e r a tu r e d i d n o t d e c r e a s e th e tim e
r e q u i r e d t o o b t a i n a m e l t . T h is te m p e r a tu r e was a p p ro x
i m a t e l y 195° *
When p l a c e d on a h o t - s t a g e m e l t in g p o i n t a p p a r a t u s
a t 160° and c o v e re d w ith a c o v e r s l i p , t h e a d d u c t a p p e a re d
to s u b lim e to t h e c o v e r s l i p , a n d th e r e s i d u e gave t h e
a p p e a r a n c e o f a h o llo w s h e l l . W here th e s u b lim a te made
c o n t a c t w i t h th e c r y s t a l , a m e lt was o b t a i n e d , th e w hole
g i v i n g a y e llo w m e lt a t a b o u t 1 8 2 ° . When th e a d d u c t
I)
d 23
was p l a c e d on th e h o t s t a g e a t 180 w i t h o u t a c o v e r s l i p ,
th e c r y s t a l p a s s e d t h r o u g h a y e llo w s t a g e to a n opaque
w h ite s t a g e , t h e n s lo w ly s u b lim e d . An i n s t a n t a n e o u s m e lt
was o b t a i n e d when a c r y s t a l o f th e a d d u c t was p la c e d on
t h e h o t s t a g e a t 215°*
A nal* C a l c 'd f o r Gi s H-lq0 3 ; C» 7 6 .5 7 # ; H, 6.43#-* -
F o u n d : C, 7 6 .7 2 ; H, 6 .4 4 # *
E q u i l i b r i u m o f 1 , 2 , 3 , 4 - T e t r a m e t h y l n a p h t h a l e n e and M a le ic
A n h y d rid e i n X ylene
An e q u im o l e c u la r m ix tu re o f 1 , 2 , 3 , 4 - t e t r a m e t f a y l -
n a p h th a le n e (1 * 0 0 0 g * ) and f r e s h l y d i s t i l l e d m a le ic
a n h y d rid e (0*533 g*) i n 20 c c . o f x y le n e w%s h e a te d a t
r e f l u x te m p e r a tu r e f o r v a r i o u s p e r i o d s o f tim e a n d th e
s o l u t i o n was w orked up by th e m ethod o f Bachmann an d
K l o e t z e l a s d e s c r i b e d a b o v e . The r e s u l t s o f th e e x p e r
im e n t a r e p r e s e n t e d i n t a b l e I .
T a b le i
Run No.
X II X I I I XIV XV
B e f lu x t im e , h o u r s 46 46 72 72
H y d ro c a rb o n r e c o v e r e d , mg* 936 934 940 935
T hese r e s u l t s show t h a t a t e q u i l i b r i u m t h e r e i s p r e s e n t
a p p r o x im a te ly 9 3 .6 # o f t e t r a m e t h y l n a p h t h a l e n e c o r r e s
p o n d in g to 6 .4 # a d d u c t f o r m a t io n u n d e r t h e a b o v e co n
d i t i o n s . I n o r d e r to a p p ro a c h t h e e q u i l i b r i u m fro m th e
o t h e r d i r e c t i o n , 0 .3 0 7 g . o f a d d u c t an d 4 c c . o f x y le n e
w ere h e a t e d a t r e f l u x t e m p e r a tu r e f o r v a r i o u s l e n g t h s o f
t im e . The r e s u l t s o f t h i s e x p e r im e n t a r e p r e s e n t e d b elo w
i n t a b l e I I .
T a b le I I
Run n o . I I I IV V
R e f lu x t i m e , h o u rs 48 71 72 95
H y d ro c a rb o n r e c o v e r e d , mg.. 143 184 187 187
H y d ro c a rb o n r e c o v e r e d ,
%
7 1 .5 92 9 3 .5 9 3 .5
D im e th y l E s t e r o f 1 , 2 , 3 . 4 - T e t r a m e t h y l - l ,4 - d i h y d r o n a p h
t h a l e n e - 1 , 4 -e n d o -0 ',ff-> su c c in ic a c i d
To a f r e s h l y p r e p a r e d sam p le o f th e d i c a r b o x y l i c a c i d
o f t h e a d d u c t i n a c e to n e s o l u t i o n was a d d e d a n e x c e s s o f
a n e t h e r e a l s o l u t i o n o f d ia z o m e th a n e • F o llo w in g eyapora«»
t i o n o f t h e s o l v e n t s th e r e s i d u e was r e c r y s t a l l i z e d fro m
a n h y d ro u s e t h y l a c e t a t e . The e s t e r c r y s t a l l i z e d i n c o l o r
l e s s h e x a g o n a l p r i s m s , m .p . 1 5 7 - 1 5 7 .5 ° .
A n a l. C a lc * d f o r C20H240 4 : C, 7 3 .1 5 # ; H, 7 .3 7 # .
F o u n d : G, 7 3 .4 8 # ; H, 7 .4 7 # *
The R e a c t i v i t i e s o f D urene an d H e x am e th y lb en z e n e to w a rd
M a le ic A n h y d rid e
The R e a c t i v i t y o f D urene to w a rd M a le ic A n h y d rid e
A m ix tu r e o f 1 .0 0 0 g . o f d u r e n e , 2 1 .9 g . o f m a le ic
a n h y d r id e and 20 c c . o f a n h y d ro u s b e n z e n e was r e f l u x e d
f o r s e v e n ty - tw o h o u r s . The r e s u l t i n g y e ll o w s o l u t i o n was
t r e a t e d by t h e m ethod u s e d p r e v i o u s l y * S in c e d u re n e i s
so r e a d i l y s u b lim e d , th e r e c o v e r y o f d u re n e was n o t an
a d e q u a te c r i t e r i o n o f th e e x t e n t to w hich t h e r e a c t i o n
o c c u r r e d . H ow ever, no a d d u c t a c i d was r e c o v e r e d by t h i s
m ethod*
The R e a c t i v i t y o f H ex am e th y lb en z e n e to w a rd M a le ic A n h y d rid e
A m ix tu r e o f 1 .0 0 0 g . o f h e x a m e th y lb e n z e n e , m *p.
1 6 3 - 1 6 4 .5 ° , 1 8 .2 g_. o f m a le ic a n h y d rid e and 20 c c . o f
a n h y d ro u s b e n zen e was r e f l u x e d f o r s e v e n ty - tw o h o u r s .
The y e llo w s o l u t i o n was w orked up a s b e f o r e y i e l d i n g
0 .9 8 5 g . o f h e x a m e th y lb e n z e n e a n d no a d d u c t a c i d . The
a c i d i f i e d a q u eo u s s o l u t i o n o b t a i n e d by t h i s m ethod was
e x t r a c t e d t h r e e tim e s w ith e t h e r . The e t h e r s o l u t i o n
was e v a p o r a t e d and th e w h ite c r y s t a l s o b t a i n e d w ere r e -
c r y s t a l l i z e d tw ic e fro m w a t e r . The w h ite c r y s t a l s ob
t a i n e d m e lte d a t 1 2 8 -1 3 0 ° , c o r r e s p o n d i n g to m a le ic a c i d .
Summary
26
1 . 2 . 3 . 4 - t e t r a m e t h y l n a p h t h a l e n e h a s b een s y n t h e s i z e d
b y a r e a c t i o n se q u e n c e i n v o l v i n g s u c c i n o y l a t i o n o f p r e h -
n i t e n e f o llo w e d by r e d u c t i o n o f th e k e to a c i d , c y e l i z a t i o n
o f th e r e d u c e d a c i d , r e d u c t i o n o f th e c y c l i c k e to n e and
d e h y d r o g e n a tio n o f th e s u b s t i t u t e d t e t r a l i n .
1 . 2 . 3 . 4 - T e tr a m e th y ln a p h th a le n e h a s b e en fo u n d to
r e a c t r e v e r s i b l y w i t h m a le ic a n h y d r id e i n b o i l i n g x y l e n e .
A t e q u i l i b r i u m , th e a d d u c t , p re s u m a b ly 1 , 2 , 3 , 4 - t e t r a m e t h y 1 -
1 ,4 - d i h y d r o n a p h t h a l e n e - l ,4 - e n & o - c f ,$ - s u c c i n i c a n h y d r i d e , was
fo u n d to d i s s o c i a t e a b o u t 9 3 .5 # i n a s o l u t i o n c o r r e s p o n d in g
to a c o n c e n t r a t i o n o f 5# h y d ro c a rb o n a t c o m p le te d i s s o c i a
t i o n . T h is v a lu e was i n a g re e m e n t w i t h t h a t ( 6 .4 # a d d u c t
fo rm e d ) fo u n d fro m th e r e a c t i o n o f e q u im o le c u la r q u a n t i t i e s
o f m a le ic a n h y d r id e an d 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e i n
b o i l i n g x y le n e s o l u t i o n c o n t a i n i n g i n i t i a l l y 5# o f h y d ro
c a r b o n ,
A good y i e l d (9 0 # ) o f t h e a d d u c t h a s b e en o b t a i n e d
fro m t h e r e a c t i o n o f 1 , 2 , 3 , 4 - t e t r a m e t h y l n a p h t h a l e n e w i t h
a l a r g e e x c e s s o f m a le ic a n h y d r id e i n b e n z e n e s o l u t i o n .
I t h a s b e e n fo u n d t h a t u n d e r s i m i l a r c o n d i t i o n s
d u re n e and h e x a m e th y lb e n z e n e do n o t r e a c t w i t h m a le ic
a n h y d r id e t o g iv e a n a p p r e c i a b l e am ount o f a d d u c t .
BIBLIOGRAPHY
27
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University of Southern California Ll&fStt

Asset Metadata

Creator Dayton, Rhodes Pike (author)

Core Title The synthesis of 1,2,3,4-tetramethylnaphthalene and its reaction with maleic anhydride

Contributor Digitized by ProQuest (provenance)

Degree Master of Science

Degree Program Chemistry

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

Tag chemistry, organic,OAI-PMH Harvest

Language English

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-790810

Unique identifier UC11348251

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Legacy Identifier EP41563.pdf

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Rights Dayton, Rhodes Pike

Type texts

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