The synthesis of polyalkylnaphthalenes

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Content TEE SYNTHESIS OF POLYALKYLNAFHTHALENES A T h e s is P r e s e n te d t o th e F a c u lty o f th e D epartm ent o f C h e m istry The U n i v e r s i t y o f S o u th e rn C a l i f o r n i a In P a r t i a l F u l f i l l m e n t o f th e R eq u irem en ts f o r t h e D egree M a ste r o f S c ie n c e i n C h em istry hy H e r s h e l Leon H erzog December 1946 UMI Number: EP41558 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI EP41558 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 This thesis, written by Hexsiiel-Le-on.-Her-z.og-.......................... under the guidance of h.^.9.... Faculty Committee, and a p p r o v e d 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 q ste * ' o f S c i e Kice Secretary D ate. Faculty C om m ittee Chairman ■ ( / ^ — Acknowledgement The a u th o r i s in d e b te d t o D r. M .C .K L oetzel 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 encouragem ent d u rin g t h i s i n v e s t i g a t i o n . Table of Contents II* D is c u s s io n o f R e s u l ts A* S y n th e s is o f 1 ,2 ,4 - T r i e t h y l n a p h t h a l e n e 2 B* A c e t y l a t i o n o f 1 ,2 - D ie th y ln a p h th a le n e 4 C. D ie ls - A ld e r S y n th e s is o f D ia lk y l- N a p h th a le n e s 5 I I I . E x p e rim e n ta l A* 1 , 2 , 4 - T r ie th y ln a p h th a le n e from 1 , 2 - D ie th y ln a p h th a le n e • ,8 B. 1 , 2 , 4 - T r i e th y l n a p h th a le n e from Benzene 9 C. 1 , 2 - D im e th y ln a p h th a le n e from o < , 0 - D im e th y ls ty re n e 17 IV. Summary ..20 V. B ib lio g r a p h y 21 Introduction 1 ,2 ,4 - T r i e t h y l n a p h t h a l e n e h as b een s y n th e s iz e d by th e 5 m o d if i c a t io n o f a r e a c t i o n seq u en ce , w hich h as been u se d g e n e r a l l y f o r th e p r e p a r a t i o n o f d i - and t r i m e t h y l n a p h t h a l e n e s . The compound was s y n th e s iz e d t o p ro v e th e s t r u c t u r e o f 4 - a c e t o - 1 ,2 - d i e t h y l n a p h t h a l e n e , w hich was i s o l a t e d as th e p r i n c i p a l p ro d u c t when 1 ,2 - d i e t h y l n a p h t h a l e n e was a llo w e d t o r e a c t w ith 1 a c e t y l c h lo r id e i n th e p re s e n c e o f alu& inum c h lo h id e . C o n v e n tio n a l m ethods f o r s y n t h e s i s o f p o ly a lk y ln a p h th a le n e s a r e g e n e r a l l y tim e -c o n su m in g . A new and p o t e n t i a l l y s h o r t e r m ethod was d e v is e d and a p p lie d t o th e p r e p a r a t i o n o f 1 ,2 - d im e th y ln a p h th a le n e . Discussion of Results A c e t y l a t i o n o f 1 ,2 - d i e t h y ln a p h t h a l e n e by a F r i e d e l - C r a f t s r e a c t i o n h a s y i e l d e d a compound w hich K l o e t z e l and 1 C lose c o n s id e r t o be 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e . R e a c tio n a t th e f o u r p o s i t i o n seems th e m ost l i k e l y p o s s i b i l i t y s in c e i t 13 h a s been shown by Bachmann and Cronyn t h a t a c e t y l a t i o n o f 1 ,2 ,3 ,4 - t e t r a h y d r o p h e n a n t h r e n e y i e l d s p r i n c i p a l l y 9 - is o m e r, and by K ruber and Schade t h a t s u l f o n a t i o n o f 1 , 2 - d im e th y l- n a p h th a le n e y i e l d s l ,2 - d i m e t h y l n a p h t h a l e n e - 4 - s u l f o n i c a c i d . I f th e sup posed a c e to d i e t h y l n a p h t h a le n e were re d u c e d by th e Clemmensen m ethod t o 1 , 2 , 4 - t r i e t h y l n a p h t h a l e n e , and th e l a t t e r w ere s y n th e s iz e d by an u n e q u iv o c a l m ethod, co m p ariso n o f th e p h y s i c a l c h a r a c t e r i s t i c s o f th e compounds o b ta in e d by th e two m ethods s h o u ld e s t a b l i s h th e s t r u c t u r e o f th e k e to n e . The s y n t h e s i s o f 1 , 2 , 4 - t r i e t h y l n a p h t h a l e n e h a s been a c c o m p lish e d i n t h e f o llo w in g f a s h i o n : - 2 •*:C-CHgCHe - C O O C R j o c,% Csrctf-CHjCooH u f lc /a n l c a t. Or Cl Us CH-CH£CHl CooH JE R c t a m C JJL o s o c ± 'o M 0 o C fi j O - C - C - O C H } ■ » A/aOCHs ii o CiHs C 2H 5 C & H g l)_N «O H _ C aH sM aB f f ^ T \ - HC0°H ■ ^ r s ^ r ^ s r CiHs * ■ * ■ 0 2 m HO c* w* j s c *w* 2 2 C* Hi- Po/ ^ C*H* 2 L i The r e a c t i o n o f benzene w ith s u c c i n i c a n h y d rid e i n th e 3 t y p i c a l F r i e d e l - C r a f t s f a s h i o n , f i r s t r e p o r t e d by H aw orth , and 4 s u b s e q u e n tly by S o m e r v ille and A lle n , was u se d t o p r e p a r e 0 - b e n z o y lp ro p io n ic a c id (X ) i n y i e l d s o f 85%-90%. The m e th y l e s t e r o f X r e a c t e d w ith ethylm agnesiu m brom ide t o y i e l d 4 - p h e n y l- 3 - 3 ,5 h e x e n o ie acid(lC) , w hich was q u a n t i t a t i v e l y red u c ed w ith hyd ro g en o v e r Adams c a t a l y s t t o t h e s a t u r a t e d 4 -p h e n y lh e x a n o ic 5 0 acid (U F ) * . The c o n v e rs io n o f TZT t o 4 - e t h y l - l - t e t r a l o n e was a cc o m p lish e d i n y i e l d s o f 70-80% by c o n v e rs io n o f M t o th e c o rre s p o n d in g a c i d c h l o r i d e , fo llo w e d by F r i e d e l - C r a f t s i n t r a - 6 7 m o le c u la r c o n d e n s a tio n * . T h is m ethod was found t o be s u p e r i o r t o r i n g c lo s u r e o f UT w ith 80% s u l f u r i c a c id w hich gave y i e l d s o f 50-55% .^ The c o n d e n s a tio n o f 15T w ith m e th y l o x a la te gave th e 1 8 g ly o x alate (3 Z T ) * . Carbon m onoxide was s p l i t o ut o f XL by h e a t in g th e compound w ith powdered s o f t g l a s s , y i e l d i n g 2 - 8 c a r b o m e th o x y - 4 - e th y l- l- te tr a lo n e C E T ) . The o v e r a l l y i e l d from J5T t o 2 T was 50%, a c e r t a i n amount o f d e c o m p o sitio n t o t a r r y p ro d u c ts o c c u r r in g d u r in g th e s p l i t t i n g o u t o f th e carb o n mono x i d e . Compound 3D T i s a £ - k e t o e s t e r , and c o n s e q u e n tly gave th e u s u a l a c e t o a c e t i c e s t e r - t y p e c o n d e n s a tio n w ith e t h y l io d id e t o 1,8 form 2 - c a r b o m e th o x y - 2 ,4 - d ie th y l- l- te tr a lo n e ( 3 5 E ) i n 65% y i e l d . S a p o n i f i c a t i o n and su b se q u e n t d e c a r b o x y la tio n o f 321 gave 2 ,4 - d i e t h y l - l - t e t r a l o n e ( 3 2 E J w ith 73% c o n v e r s io n . T rea tm en t o f TZZU Z w ith e th y lm ag n esiu m brom ide r e s u l t e d i n th e fo rm a tio n o f 1 - h y d ro x y -1 , 2 , 4 - t r i e t h y l - 1 , 2 , 3 , 4 - t e tr a h y d r o n a p h th a le n e (3* ) w hich was c o n v e rte d t o l , 2 , 4 - t r i e t h y l - 3 , 4 - d i h y d r o n a p h t h a l e n e (JST) by t h e d e h y d r a tin g a c t i o n o f fo rm ic a c i d , th e o v e r a l l y i e l d from SET t o 3C b e in g 74%.5 Compound J2C was d e h y d ro g e n a te d o a t 290 w ith p a lla d iu m - o n - c h a r c o a l c a t a l y s t t o g iv e th e d e s i r e d 1 , 2 ,4 - tr ie th y ln a p h th a le n e ( X E ) i n 85% y i e l d ; th e y i e l d was b a se d on c o n v e rs io n o f 2X t o i t s t r i n i t r o b e n z e n e a d d i t i o n 5 com plex, w hich was form ed i n th e c o n v e n tio n a l way , and m elted a t 9 4 -9 5 ° . An a u t h e n t i c sam ple o f 1 ,2 - d i e t h y ln a p h t h a l e n e ^ was c o n v e rte d t o th e acebo d e r i v a t i v e by a F r i e d e l - C r a f t s r e a c t i o n w ith a c e t y l c h lo r id e i n n i t r o b e n z e n e . The l i q u i d p r o d u c t, a f t e r d i s t i l l a t i o n , am ounted t o 75% o f th e t h e o r e t i c a l y i e l d . C r y s t a l l i z a t i o n o f th e l i q u i d from hexane gave 55% o f a s o l i d o i . m e ltin g a t 6 1 .5 - 6 2 .5 , th e re m a in in g 20% o f th e o r i g i n a l y i e l d b e in g i s o l a t e d as a y e llo w o i l , a f t e r th e e v a p o r a tio n o f th e h e x a n e . The s o l i d p ro d u c t was re d u c e d by th e Clemmensen m ethod t o th e c o rre s p o n d in g h y d ro c a rb o n i n 72% y i e l d , th e r e s u l t i n g l i q u i d fo rm in g a t r i n i t r o b e n z e n e a d d i t i o n compound o w hich m e lte d a t 95-96 . A m ixed m e l t in g p o in t w ith th e d e r i v a t i v e p r e p a r e d from th e a u t h e n t i c 1 , 2 , 4 - t r i e t h y l n a p h t h a l e n e showed no d e p r e s s io n . I t i s o b v io u s , t h e r e f o r e , t h a t a c e t y l a t i o n o f 1 , 2 - d ie th y ln a p h th a le n e o c c u rs p r i n c i p a l l y i n th e f o u r p o s i t io n * 5 C h a r a c t e r i z a t i o n o f th e l i q u i d b y -p ro d u c t from a c e t y l a t i o n by th e fo rm a tio n o f a p i c r a t e gave a p ro d u c t m e ltin g a t 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e , th e l a t t e r m e ltin g a t 88' i c a l fo rm u la w hich i s i d e n t i c a l w ith t h a t o f th e l a t t e r , from w hich may be drawn th e c o n c lu s io n t h a t th e l i q u i d by p ro d u c t i s an iso m e r o f 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e . te tr a h y d r o p h e n a n th r e n e r e s u l t s i n th e f o rm a tio n o f a 9 - iso m er and a 7 - is o m e r , i n th e r a t i o o f 2 : 1 . I t seems l i k e l y , t h e r e f o r e , t h a t th e l i q u i d isom er i s 6 - a c e t o - l , 2 - d i e t h y l n a p h - t h a l e n e . I n th e c o u rs e o f t h e a fo re m e n tio n e d s t u d i e s a p o t e n t i a l l y c o n v e n ie n t s y n t h e s i s o f c e r t a i n d i a l k y l n a p h t h a l e n e s o c c u rre d t o th e i n v e s t i g a t o r . The p ro p o sed r e a c t i o n seq u en ce i s as f o l l o w s : - o 1 1 8 -1 1 8 .5 , w hich was n o t i d e n t i c a l w ith th e p i c r a t e o f 8 8 .5 ° A n a ly s is o f th e fo rm er p i c r a t e i n d i c a t e s an em pir 13 Bachmann and Cronyn have shown t h a t a c e t y l a t i o n o f 1 , 2 , 3 , 4 - CHS fH3 « XU Z H L 0 6 A cetophenone r e a c t e d w ith eth y lm ag n esiu m brom ide t o 13 g iv e m e th y le th y lp h e n y lc a rb in o l(2 3 2 J i n 84$ y i e l d . Dehyd- 5 ,1 2 r a t i o n o f th e c a r b i n o l was e f f e c t e d w ith fo rm ic a c i d , th e b e s t y i e l d o b ta in e d b e in g 63$. L o sse s i n v a r i a b l y o c c u r re d by p o ly m e r iz a tio n o f th e < A ,^ d im e th y ls ty r e n e ( X E ) , even i n th e p re s e n c e o f p i c r i c a c i d . I t a p p e a re d n o t u n l i k e l y t h a t th e D ie ls - A ld e r ty p e c o n d e n s a tio n betw een Yflf and m a le ic an h - 10 y d r id e m ig h t f a i l . R obinson and Hudson , a f t e r what a p p e a rs t o have been a c a r e f u l s tu d y , co n clu d ed t h a t D ie ls - A ld e r r e a c t i o n s in v o lv in g a d ie n e s y s te m h a l f o f w hich i s p a r t o f a benzene r i n g w i l l g iv e a sim p le ( 1 :1 ) a d d u c t o n ly when t h e r e i s an a l k y l s u b s t i t u e n t i n th e ^ - p o s i t i o n o f th e s id e c h a in , and a m -alk o x y g ro u p on t h e r i n g . T hese a u th o r s c i t e d i s o s a f r o l and is o e u g e n o l as i n s t a n c e s i n w hich th e a d d i t i o n s u c c e e d e d , and c i t e d no i n s t a n c e s w here s u c c e s s was o b ta in e d w ith a com pound w hich d id n o t c o n ta in an e l e c t r o n donor i n th e p - p o s i t i o n . How ever, t h e p re s e n c e o f an e l e c t r o n donor i n th e p - p o s i t i o n was n o t m e n tio n ed as a r e q u i r e d f e a t u r e f o r s u c c e s s f u l a d d i t i o n . In th e l i g h t o f th e c o n c lu s io n s R obinson and Hudson have made t h e r e a p p e a re d t o be no b a s i s f o r e x p e c ta ti o n o f good r e s u l t s i n th e p ro p o se d r e a c t i o n o f J < J ]f w ith m a le ic a n h y d r id e . However, t h e r e h a s b een o b ta in e d what seems t o be a 1 :1 a d d u c t i n y i e l d s as h ig h a s 61$. I t a p p e a r s , t h e r e f o r e , 7 t h a t t h e p r e s e n c e o f a m -alk o x y g ro u p i n t h e d ie n e i s n o t n e c e s s a r y f o r th e D ie ls - A ld e r a d d i t i o n , s in c e i n d im e th y ls ty r e n e t h e r e i s no g ro u p p r e s e n t w hich i s e q u iv a l e n t i n e l e c t r o n d o n a tin g e f f e c t t o t h e m -alk o x y g ro u p . F u rth e rm o re , a c o n d it i o n w hich R obinson and Hudson f a i l e d t o s p e c i f y , n a m e ly , t h e p re s e n c e o f a p - a lk o x y g ro u p o r i t s e q u i v a l e n t ( i n t h i s c a se t h e <k- a l k y l g ro u p ) w ould a p p e a r t o be im p o r ta n t. The a d d u c t o b ta in e d from th e r e a c t i o n o f ZHTwith m a le ic a n h y d rid e was c o n v e rte d t o th e c a lc iu m s a l t and p y ro ly z e d a t 4 5 0 -5 0 0 ° (e s tim a te d te m p e r a tu r e ) i n a s tre a m o f n itr o g e n * The l i q u i d p ro d u c t was d e c o l o r iz e d by c h ro m a to g ra p h ic a d s o r p t io n on a lu m in a , and c o n v e rte d t o t h e p i c r a t e i n th e u s u a l f a s h i o n . A dm ixture w ith th e p i c r a t e from an a u t h e n t i c 5 sam ple o f 1 ,2 - d im e th y ln a p h th a le n e cau se d no d e p r e s s io n i n m e ltin g p o in t* The y i e l d o f t h e c ru d e h y d ro c a rb o n from p y r o l y s i s r e p r e s e n te d 25$ o f th e t h e o r y ; how ev er, a p o r t i o n o f t h i s , p ro b a b ly l e s s t h a n 50$, was p u re 1 ,2 - d im e th y ln a p h th a le n e . I t i s a p p a r e n t, t h e r e f o r e , t h a t t h e s u c c e s s o f t h e p ro c e d u re i s s t i l l d ep en d e n t on t h e developm ent o f a good p y r o l y t i c mfethod. 8 E x p e rim e n ta l A. S y n t h e s i s o f 1 , 2 , 4 - t r i e t h y l n a p h t h a l e n e from 1 , 2 - d i e t h y l - n a p h th a le n e A c e t y l a t i o n o f 1 , 2 - d ie t h y ln a p h t h a l e n e The a c e t y l a t i o n was ru n p r e c i s e l y as d i r e c t e d by K l o e t z e l and C lose'1 ', t h e b e s t y i e l d o b ta in e d b e in g 75$. The p ro d u c t was r e c r y s t a l l i z e d from hexane g i v in g a 55$ y i e l d o f c r y s t a l l i n e 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e , th e re m a in in g 20$ o f th e i n i t i a l y i e l d b e in g h e ld i n th e h e x a n e . E v a p o ra tio n o f t h e s o lv e n t gave a y e llo w , o i l y l i q u i d w h ich f a i l e d t o c r y s t a l l i z e on f u r t h e r t r e a tm e n t w ith s o l v e n t s o r on c o o li n g . The y e llo w , o i l y l i q u i d ( 1 . 9 g . ) gave 0 .8 g . o f a o p i c r a t e w h ich m e lte d a t 1 1 8 -1 1 8 .5 , w h e rea s th e p i c r a t e o o f 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e m e lts a t 8 8 -8 8 .5 . A n a l. C alc*d f o r C22H210 ^ f3 i N, 9 .2 2 $ . Found: N, 9 .0 9 $ R e d u c tio n o f 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e t o 1 , 2 , 4 - t r i e t h y l n a p h t h a l e n e (XT) Am algamated z in c was p r e p a re d by s h a k in g f o r f i v e m in u te s a m ix tu re o f 29 g . o f m ossy z i n c , 2 .9 g . o f m e rc u ric c h l o r i d e , 40 c c . o f w a te r and 3 .5 c c . o f h y d ro c h l o r i c a c i d . The s o l u t i o n was d e c a n te d and th e f o llo w in g r e a g e n ts w ere added i n o r d e r ; - 35 c c . o f b e n z e n e , 68 c c . o f m e th a n o l, 45 c c . o f h y d r o c h l o r i c a c id and 1 1 .9 g . o f 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e . The f l a s k was f i t t e d w ith 9 a v e r t i c a l c o n d e n se r c o n n e c te d t o a g a s a b s o r p tio n t r a p , and t h e r e a c t i o n m ix tu re was b o i l e d v ig o r o u s ly f o r tw e n ty - f o u r hours* The m ix tu re was d i l u t e d w ith w a te r and t h e o r g a n ic l a y e r was s e p a r a t e d . A f te r w ash in g w ith w a te r and s b d iu m ,c a rb o n a te s o l u t i o n c o n c e n tr a ti o n o f t h e benzene s o l u t i o n 'a n d d i s t i l l a t i o n o f th e r e s i d u e y i e l d e d 8 g . ‘ (7 1 .5 $ ) o f c o l o r l e s s 1 ,2 , 4 - t r i e t h y l n a p h t h a l e n e (XT’ ) , b . p* 1 2 5 - 1 2 7 ° /l mm. B. S y n th e s is o f 1 , 2 , 4 - t r i e t h y l n a p h t h a l e n e from benzene 4 - P h e n y l- 3 -h e x e n o ic a c i d ( I T ) To an i c e - c o l d s o l u t i o n o f 1 9 .2 g . o f m e th y l - b e n z o y lp r o p io n a te ( 0 .1 m o le ), p r e p a r e d a c c o rd in g t o 5 K l o e tz e l , d i s s o l v e d i n 100 c c . o f an h y d ro u s e t h e r i n a 500 c c . , t h r e e - n e c k f l a s k , e q u ip p e d w ith H e rsh b e rg s t i r r e r and d ro p p in g f u n n e l , was added d ro p w is e , w ith s t i r r i n g , t h e G rig n a rd r e a g e n t (0 .1 3 8 m ole) p r e p a r e d from 3 .3 6 g . o f m agnesium , 1 5 .0 g . o f e t h y l brom ide and 65 c c . o f a n h y d ro u s e t h e r . Each d ro p o f G rig n a rd r e a g e n t r e a c t e d v i g o r o u s l y w ith t h e e s t e r c a u s in g im m ediate s e p a r a t i o n o f a w h ite p r e c i p i t a t e , and c a re was ta k e n t o k eep th e te m p e r a tu re o f t h e r e a c t i o n m ix tu re n e a r z e r o d e g re e s d u r in g th e a d d i t i o n . The m ix tu re was k e p t i c e - c o l d f o r t h i r t y m in u te s a f t e r t h e a d d i t i o n o f t h e G rig n a rd r e a g e n t was com plete and was th e n a llo w e d t o warm up t o room te m p e r a tu re o v e r a t h i r t y m in u te p e r i o d . Dry to lu e n e (100 c c . ) was th e n added and th e e t h e r was d i s t i l l e d . An a d d i t i o n a l 50 c c . o f t o lu e n e was added and t h e m ix tu re was h e a te d f o r t h r e e t o f i v e h o u rs on a b o i l i n g w a te r b a t h . The m ix tu re was th e n h y d ro ly z e d w ith 3N h y d ro c h l o r i c a c i d , th e t o lu e n e was w ashed w ith w a te r , and t h e p ro d u c t was e x t r a c t e d w ith d i l u t e , aqueous sodium c a r b o n a te . The c a rb o n a te s o l u t i o n was a c i d i f i e d w ith 6N h y d r o c h lo r ic a c id w h ile c o o l e d .i n i c e , th e p ro d u c t was e x t r a c t e d w ith e t h e r , w ashed w ith w a te r , and d r i e d o v e r sodium s u l f a t e . The y i e l d o f 4 -p h e n y l-3 - h e x e n o ic a c i d was 6 0 -7 0 $ ; b . p . 1 6 3 -1 6 7 ° /5 mm. 4 -P h e n y lh e x a n o ic a c id (2 T ) When a s o l u t i o n o f 9 6 .5 g . o f 4 - p h e n y l-3 - h e x e n - o ic a c id i n 250 c c . o f g l a c i a l a c e t i c a c id c o n ta in i n g 500 mg. o f Adams c a t a l y s t was shaken w ith hydrogen a t 1 0 -4 0 l b s . p r e s s u r e th e r e q u i s i t e volume o f h y d ro g en f o r one d o u b le bond was a b so rb e d i n two h o u r s . A f te r rem o v al o f th e a c e t i c a c id u n d e r re d u c e d p r e s s u r e 8 9 .5 g . o f 4 -p h e n y lh e x a n o ic a c i d (92$) d i s t i l l e d a s a c o l o r l e s s l i q u i d a t 1 6 0 -1 6 3 ° /5 mm. 4 - E t h y l - l - t e t r a lo n e (IST) I n a 500 c c . , ro u n d -b o tto m f l a s k f i t t e d w ith r e f l u x c o n d e n s e r, c a r r y i n g a t th e to p a tu b e l e a d in g t o a g as a b s o r p t io n t r a p , w ere p la c e d 3 1 .5 g . o f 4 - p h e n y l h e x a n o ic a c id and 1 6 .5 g . o f t h i o n y l c h lo rid e (E a s tm a n Kodak w h ite l a b e l ) . The m ix tu re was c a r e f u l l y h e a re d on a s te a m - b a th f o r t e n o r f i f t e e n m in u te s , a f t e r th e c o m p le tio n o f th e i n i t i a l , v ig o ro u s r e a c t i o n . The f l a s k was th e n c o n n e c te d t o th e w a te r pump, e v a c u a te d , h e a te d f o r t e n m in u te s on th e s te a m - b a th , and f i n a l l y f o r two o r t h r e e m in u te s o v e r a sm a ll fla m e , i n o r d e r t o remove th e e x c e s s t h i o n y l c h l o r i d e . The f l a s k was th e n c o o le d , 175 c c . o f carb o n d i s u l f i d e was ad d ed , and th e s o l u t i o n was c o o le d i n an i c e - b a t h . Then £5 g . o f an h y d ro u s alum inum c h lo r i d e was a d d e d l a l l a t o n c e, and t h e m ix tu re was s lo w ly warmed t o t h e b o i l i n g p o in t on a s te a m - b a th . A f te r t e n m in u te s o f h e a t i n g th e r e a c t i o n m ix tu r e was c o o le d t o z e ro d e g re e s and t h e alum inum c h lo r id e com plex was d e c omposed by c a r e f u l a d d i t i o n , w ith s h a k in g , o f 100 g . o f i c e . T w e n ty -fiv e c c . o f c o n c e n tr a te d h y d r o c h lo r ic a c id was th e n ad d ed , and t h e carb o n d i s u l f i d e was removed by d i s t i l l a t i o n . S e p a r a tio n o f t h e w a te r and k e to n e l a y e r s was fo llo w e d by t h e w ash in g o f th e w a te r l a y e r w ith e th e r The e t h e r was combined w ith th e k e to n e l a y e r and w ashed w ith p o r t i o n s o f w a t e r , 10$ sodium c a rb o n a te s o l u t i o n , and w a te r a g a in . A f t e r d r y in g th e e t h e r e a l s o l u t i o n o v e r sodium s u l f a t e t h e e t h e r was removed by d i s t i l l a t i o n and ■ o , t h e r e s i d u a l k e to n e was d i s t i l l e d i n v acu o , 131-135 / 4 mm Y ie ld s v a r i e d betw een 70$ and 80$. 4 - E t h y l - l - t e t r a l o n e se m ie arb a zo n e m e lte d a t 1 8 2 - 6 1 8 3 °. Levy , who p r e p a r e d th e k e to n e by a d i f f e r e n t m eth o d , r e p o r t e d 1 8 3 °. 13 C o n d e n sa tio n o f ~J\T~with m eth y l o x a la te S o dium (7.85 g . ) was d is s o lv e d i n 1 0 6 .5 c c . o f a n h y d ro u s m eth an o l in a one l i t e r , th r e e - n e c k f l a s k . The e x c e ss a lc o h o l was d i s t i l l e d o f f u n d e r re d u c e d p r e s s u r e , and th e re m a in in g s o l i d cak e was b ro k en u p . To t h e sodium m e th y la te was added 4 0 .5 g . o f m eth y l o x a l a t e and 170 c c . o f d r y , t h i o p h e n e - f r e e b e n z e n e , a f t e r w hich t h e f l a s k was e q u ip p e d w ith a d ro p p in g f u n n e l , H e rsh b e rg s t i r r e r w ith a r u b b e r s e a l , and a r e f l u x c o n d e n s e r. The sy ste m was f l u s h e d w ith d ry n i t r o g e n f o r f o r t y - f i v e m in u te s , d u r in g t h e f i r s t t e n o f w hich th e m ix tu re was r e f l u x e d t o a c h ie v e homogen e i t y . F o llo w in g t h e f l u s h i n g th e f l a s k was c o o le d i n an i c e - b a t h , th e s t i r r e r was s t a r t e d , and a s o l u t i o n o f 2 9 .8 g . o f 4 - e t h y l - l - t e t r a l o n e i n 100 c c . o f d r y , t h i o p h e n e - f r e e b en zen e was added i n a d ro p w ise f a s h i o n . N itro g e n flo w was c o n tin u e d th ro u g h o u t t h e r e a c t i o n p e r i o d . S t i r r i n g was sto p p e d t h i r t y m in u te s a f t e r a l l th e k e to n e had been ad d ed , and th e i c e - b a t h was rem oved one h o u r a f t e r th e k e to n e a d d i t i o n was c o m p le te . The ' m ix tu re was a l l o w e d 't o 's t a n d an a d d i t i o n a l f o u r and o n e - h a l f h o u r s , a f t e r w hich i t was h y d ro ly z e d w ith 600 g . o f i c e . S u f f i c i e n t 5$ p o ta s s iu m h y d ro x id e s o l u t i o n was added t o d i s s o l v e a l l th e p r e c i p i t a t e form ed, t h e 13 b e n zen e l a y e r was s e p a r a t e d and w ashed with, s e v e r a l p o r t i o n s o f 5$ p o ta s s iu m h y d r o x id e , th e w ashin gs b e in g added t o t h e o r i g i n a l d a r k , aqueous l a y e r . The a queous s o l u t i o n was t r e a t e d w ith 5 g . o f c h a r c o a l , f i l t e r e d w ith s u c t i o n , c o o le d i n i c e a n d . a c i d i f i e d w ith 15$ h y d r o c h lo r ic a c i d , w hereupon th e p ro d u c t s e p a r a t e d as a y e llo w o i l . E th e r e x t r a c t s o f th e w a te r l a y e r w ere com bined w ith th e o i l and d r ie d o v e r sodium s u l f a t e , y i e l d i n g , a f t e r rem o v al o f th e e t h e r , 92$ o f c ru d e g l y o x a l a t e (-M ). 2 - C a r b o m e th o x y - 4 - e th y l- l- t e t r a l o n e (SEC) F i f t e e n grams o f fin e ly -p o w d e re d s o f t g la s s ( B r a u n ) was added t o 5 0 .5 g . o f cru d e g l y o x a l a t e (-21) a t 1 5 0 ° , o and t h e te m p e ra tu re was r a i s e d t o 180 u n t i l t h e e v o l u t i o n o f carb o n m onoxide was c o m p le te ( tw e n ty - f iv e m in u t e s ) . A f t e r c o o lin g t h e p ro d u c t was d i s s o l v e d i n a c e to n e and d e c a n te d from t h e g l a s s . The s o l u t i o n was t r e a t e d w ith N o r i t e , f i l t e r e d and vacuum d i s t i l l e d f o llo w in g th e rem o v al o f t h e a c e to n e ; y i e l d 18 g .( 6 7 $ ) o f j2E , b . p . 164-170°/4: mm. 2 ,4 - D ie th y l- 2 - c a r b o m e th o x y - l- te tr a lo n e ( 2 H ) To a s o l u t i o n o f 7 .8 g . o f sodium i n 160 c c . o f an h y d ro u s m eth an o l c o n ta in e d i n a one l i t e r f l a s k f i t t e d w ith a d ro p p in g f u n n e l and a r e f l u x c o n d e n se r was added 14 a s o l u t i o n o f 40 g . o f 2 - c a r b o m e th o x y - 4 - e th y l- l- t e t r a l o n e i n a m ix tu r e o f 80 c c . o f a n h y d ro u s benzene and 80 e c . o f an h y d ro u s m e th a n o l. The r e a c t i o n m ix tu r e was r e f l u x e d f o r f i f t e e n m in u te s , a f t e r w hich i t was c o o le d t o room t e m p e r a tu r e , 77 g . o f e t h y l i o d id e was added and t h e m ix tu re was r e f l u x e d f o r t h r e e h o u r s . ‘A f t e r c o o lin g , t h e s o l u t i o n was n e u t r a l i z e d w ith a c e t i c a c id and t h e s o l v e n t s w ere rem oved u n d e r re d u c e d p r e s s u r e The r e s i d u e was ta k e n up w ith w a te r and b e n z e n e , and t h e aqueous l a y e r was e x t r a c t e d tw ic e w ith b e n z e n e . The combined b enzen e e x t r a c t s w ere w ashed w ith sodium b ic a r b o n a te and t h e benzene s o l u t i o n was d i s t i l l e d , o , t h e f r a c t i o n b o i l i n g a t 140-157 / I mm. b e in g c o l l e c t e d . T h is f r a c t i o n was th e n c a r e f u l l y r e d i s t i l l e d and th e o f r a c t i o n b o i l i n g 152-155 / I mm. was c o l l e c t e d ; y i e l d 2 0 .5 g . o f 3Z 2T . T h i r t e e n and o n e - h a l f gram s o f f o r e r u n was assum ed t o be u n r e a c te d 3ZT , and t h e y i e l d b ased on r e a c t e d s t a r t i n g m a t e r i a l was 6 4 .5 $ . A n a l. C alc *d f o r Cl 6 H2C)03 : C, 7 3 .8 2 $ ; H, 7 .7 4 $ Found: C, 7 3 .9 i $ ; H, 7 .9 3 $ 2 , 4 - D i e t h y l - l - t e t r a l o n e (sZ H T ) Twenty and o n e - h a l f gram s o f liZ Z T was h y d ro ly z e d by r e f l u x i n g w ith 140 c c . o f 20$ sodium h y d ro x id e s o l u t i o n and 36 c c . o f e th a n o l f o r t h r e e h o u r s . The r e s u l t i n g m ix tu re was a c i d i f i e d w ith 1 :1 s u l f u r i c a c i d , c a u s in g 15 a v ig o ro u s e v o lu t i o n o f c a rb o n d i o x i d e . Com plete d e c a r b o x y la tio n was e f f e c t e d by w arm ing th e a c i d i f ie d s o l u t i o n on th e s te a m - b a th . The k e to n e was e x t r a c te d w ith b en zen e and t h e e x t r a c t s w ere-w ashed w ith d i l u t e sodium b i c a r b o n a t e . D i s t i l l a t i o n o f t h e p r o d u c t y i e l d e d 11 g . o f E T b o i l i n g a t 1 1 8 -1 2 1 ° /1 mm. 5 The se m ic a rb a z o n e p re p a re d a c c o r d in g t o K l o e tz e l m e lte d a t 1 8 1 -1 8 3 °. A n a l. C a l c 'd . f o r C15H210K3 : 1 6 .2 0 $ ; Found : N, 15.9*f$ 1 , 2 , 4 - T r i e t h y l - l - t e t r a l o K E T ) To t h e c o ld G rig n a rd r e a g e n t p r e p a r e d from 1 0 .9 g . o f e t h y l b ro m id e , 2 .4 3 g . o f m agnesium and 80 c c . o f e t h e r was added d ro p w is e , w ith s w i r l i n g , 10 g . o f iZ H T dissolved i n 40 c c . o f e t h e r . The r e a c t i o n m ix tu re was a llo w e d t o warm up t o room t e m p e r a tu r e , and was th e n r e f l u x e d f o r two and o n e - h a l f h o u r s . H y d ro ly s is o f t h e r e a c t i o n m ix tu re w ith ic e and ammonium c h lo r i d e was fo llo w e d by t h e e x t r a c t i o n o f t h e w a te r l a y e r w ith two p o r t i o n s o f e t h e r . The com bined e t h e r e a l s o l u t i o n s w ere d r i e d o v e r sodium s u l f a t e , and t h e e t h e r was removed by d i s t i l l a t i o n * Ten gram s o f v is c o u s o i l rem ain ed PQ Q , and was u se d d i r e c t l y i n th e f o llo w in g r e a c t i o n . 16 1 . 2 . 4 - T r i e t h y l - 3 , 4 - d ih y d r o n a p h th a le n e ( X .) The a fo re m e n tio n e d cru d e t e t r a l o l was added t o 40 c c . o f an h y d ro u s fo rm ic a c i d , and th e m ix tu re was a llo w e d t o s ta n d two h o u rs a t room te m p e r a t u r e . Two h u n d red c c . o f w a te r was th e n ad d ed , and t h e p ro d u c t was e x t r a c t e d w ith s e v e r a l p o r t i o n s o f e t h e r , th e e x t r a c t s b e in g combined and w ashed w ith w a t e r , aqueous sodium c a r b o n a te , and w a te r a g a in . A f t e r d r y in g o v e r sodium s u l f a t e c a r e f u l d i s t i l l a t i o n y i e l d e d 7 .4 g . o f p r o d u c t, b . p . 1 1 8 -1 2 1 ° /3 mm. The d i s t i l l a t e was d i s t i l l e d from sodium t o y i e l d 6 g . o f c o l o r l e s s , o . b . p . 106-109 / I mm. A n a l. C alc *d. f o r C ^ H ^ : C, 8 9 .1 8 $ ; H, 1 0 .8 2 $ Found : C, 8 9 .4 6 $ ; H, 1 0 .5 2 $ 1 . 2 . 4 - T r i e t h y l n a p h t h a l e n e ( S I ) D e h y d ro g en a tio n o f was a c c o m p lish e d by h e a t in g a 2 g . sam ple w ith 0 .2 g . o f p a lla d iu m - o n - c h a r c o a l a t 280° u n t i l t h e e v o lu tio n o f h y d ro g en s to p p e d . The g as e v o lv e d was m easured by d is p la c e m e n t o f w a t e r , and was found t o occupy a volume 20$ i n e x c e s s o f th e t h e o r e t i c a l am ount. The p ro d u c t was ta k e n up i n 35 c c . o f a n h y d ro u s m e th a n o l and t h e c a t a l y s t was f i l t e r e d from t h e s o l u t i o n . To t h e s o l u t i o n was added 2 .0 g . o f t r i n i t r o b e n z e n e . The m ix tu re was h e a te d u n t i l t h e t r i n i t r o b e n z e n e 17 had c o m p le te ly d i s s o l v e d , and was a llo w e d t o c o o l s lo w ly t o room te m p e r a tu r e . A d d itio n com p le x ! 3 .4 g . ) , m e ltin g a t 9 1 -9 3 ° , was r e c r y s t - o a l l i z e d once g iv in g a p ro d u c t m e ltin g a t 94-95 . The m ixed m e ltin g p o in t w ith a sam ple p re p a re d o v i a m ethod A was 94-95 . C. S y n th e s is o f 1 ,2 - d im e th y ln a p h th a le n e from s/.,§ -d im e th y l- s t y r e n e M e th y le th y lp h e n y lc a r b in o l( S D To th e i c e - c o l d G rig n a rd r e a g e n t p re p a re d from 15 g . o f m agnesium , 66 g . o f e t h y l brom ide and 350 c c . o f e t h e r , was add ed 55 g . o f a e e t o - phenone w ith v ig o ro u s m e c h a n ic a l s t i r r i n g . The s t i r r i n g was c o n tin u e d f o r o n e - h a l f h o u r a f t e r t h e a d d i t i o n was c o m p le te , and th e m ix tu re was th e n decom posed w ith i c e and ammonium c h l o r i d e . E th e r e x t r a c t i o n , d r y in g o v e r sodium s u l f a t e and d i s t i l l a t i o n y ie ld e d 58 g . o f K U , b . p . 1 0 2 °/1 4 mm. J L - d im e th y ls ty r e n e {Ml) Ten gram s o f Z3I was d i s s o l v e d i n 40 c c . o f an h y d ro u s fo rm ic a c i d t o w hich a t r a c e o f p i c r i c a c i d had b een added a s a p o ly m e r iz a tio n i n h i b i t o r . The m ix tu re was a llo w e d t o s ta n d two h o u r s , and th e n 200 c c . o f w a te r was a d d e d , th e p ro d u c t was e x t r a c t e d w ith e t h e r , d r i e d o v e r sodium s u l f a t e , 18 and d i s t i l l e d i n t h e p re s e n c e o f a t r a c e o f p i c r i c a c i d . The y i e l d o f M f was 6 3 b. p . 8 1 - 8 3 ° / l? ram. P r e p a r a t i o n o f JSDTand c o n v e rs io n t o i t s sodium s a l t T w e n ty -e ig h t grams o f < ^ ,$ -d im e th y ls ty re n e was h e a te d i n an o i l - b a t h a t 1 00-1 30° o v e r a two h o u r p e r io d w ith 160 g . o f d i s t i l l e d m a le ic a n h y d r id e . The r e s u l t i n g s o l i d was le a c h e d s e v e r a l tim e s w ith h o t w a te r , and th e re m a in in g v is c o u s s e m i - s o l i d was b o i le d w ith a s o l u t i o n o f 20 g . o f sodium h y d ro x id e i n 600-700 c c . o f w a te r . A f t e r a s much o f th e s o l i d d i s s o l v e d a s p o s s i b l e t h e s o l u t i o n was f i l t e r e d w h ile h o t , and a llo w e d t o c o o l s lo w ly . I f no p r e c i p i t a t e form ed th e s o l u t i o n was c o n c e n tr a te d and a g a in a llo w e d t o c o o l. U n d isso lv e d s o l i d from sodium h y d ro x id e tr e a tm e n t was b o i le d anew w ith aqueous sodium h y d ro x id e u n t i l com plete s o l u t i o n was a t t a i n e d . T o ta l y i e l d o f c r y s t a l l i n e sodium s a l t was 35 g .( 6 1 $ ) . 1 , 2 -D im e th y ln a p h th a le n e {JS0 The sodium s a l t o f JCiiwas d is s o lv e d i n a m in imum o f w a te r and 7 .2 5 g . o f c a lc iu m o x id e was ad d ed . E v a p o ra tio n o f t h e s l u r r y t o d r y n e s s gave a s o l i d ;' w hich was p u l v e r i z e d and m ixed w ith tw ic e i t s w e ig h t o f c a lc iu m o x id e . P o r tio n w is e d r y d i s t i l l a t i o n from an 8 - in c h t e s t tu b e by h e a t in g w ith a d i r e c t flam e y i e l d e d sm a ll q u a n t i t i e s o f brown l i q u i d d i s t i l l a t e . A b en zen e s o l u t i o n o f t h e p ro d u c t from s e v e r a l ru n s was d e c o lo r iz e d by p a ssa g e th ro u g h an 8 - in c h column packed w ith a c t i v a t e d alum ina* C o n c e n tr a tio n o f th e d e c o lo r iz e d s o l u t i o n gave a y e llo w l i q u i d w ith a c h a r a c t e r i s t i c n a p h th a le n ic o d o r, A 0 .5 g . sam ple o f t h e h y d ro c a rb o n was d is s o lv e d i n 5 c c . o f an h y d ro u s m e th a n o l, 0 .7 3 5 g . o f p i c r i c a c i d was a d d e d , t h e s o l u t i o n was b o i le d and a llo w e d t o c o o l slo w ly t o room te m p e r a t u r e . C r y s t a l l i z a t i o n was in d u c e d by c o o lin g , and t h e p i c r a t e f i l t e r e d , m. p . 1 1 3 -1 2 0 °. R e p ea te d c r y s t a l l i z a t i o n from m e th a n o l e v e n t u a l l y r a i s e d th e m e l t in g p o in t t o 1 2 7 -1 2 8 ° . M ixed w ith th e p i c r a te ( m . p . 1 2 9 -1 3 0 °) from an a u t h e n t i c sam ple o f 1 ,2 - d im e th y ln a p h th a le n e 1- 1 -, th e m a t e r i a l showed no a p p r e c i a b l e d e p r e s s io n o f m e ltin g p o i n t . so Summary A c e t y l a t i o n o f 1 , 2 - d i e t h y l n a p h t h a l e n e has been shown t o y i e l d 4 - a c e t o - l , 2 - d i e t h y l n a p h t h a l e n e . R e d u c tio n o f t h e a c e to d e r i v a t i v e y i e l d e d 1 , 2 , 4 - t r i e t h y l n a p h t h a l e n e , w hich was a l s o s y n th e s iz e d from 4 - e t h y l - l - t e t r a l o n e by 5 an u n e q u iv o c a l m ethod . 1 , 2 -D im e th y ln a p h th a le n e h a s been p re p a re d by a new m ethod, in v o lv in g a d d i t i o n o f m a le ic a n h y d rid e to < A ,0 - d i m e t h y l s t y r e n e . 21 B ib lio g r a p h y 1 . K l o e tz e l and C lo s e , J . Org. Chem. 1 1 , 395(1946) 2 . K ru b er and S c h a d e , B e r. 6 8 , 11(1935) 3 . H aw orth, J . Chem. S o c . 1125(1932) 4 . S o m e rv ille and A lle n , "O rg a n ic S y n th e s e s " , C o l l. V o l. 2, 8 1 , John W iley and S o n s, N .Y ., 1943 5* K l o e t z e l , J . Am. Chem. S o c . 6 2, 825(1940) 6 . L evy, Compt. r e n d . 197, 772(1933) 7 . M a r tin and F i e s e r , " O rg a n ic S y n th e s e s " V o l. 1 5 , 77, Jo h n W iley and S o n s, N .Y ., 1935 8 . Bachmann, C o le , and W ild s, J . Am. Chem. S o c . 6 2 , 825(1940) 9 . F i e s e r , "E x p e rim e n ts i n O rg an ic C h e m is try " , 2 e d . , 4 2 2 , John W iley and S o n s, N .Y ., 1941 1 0 . R obinson and H udson, J . Chem.. S o c . 715(1941) 1 1 . Bachmann and K l o e t z e l , J . Am. Chem. S oc. 6 0 , 2204(1938) 1 2 . K la g e s , B e r. 3 5 , 3507(1902) 1 3 . Bachmann and C ronyn, J . O rg. Chem. 8 , 4 5 6(19 43) 1 4 . Z e lin s k y and T u ro w a -P o lla k , B e r. 5 8 , 1295(1925)

Asset Metadata

Creator Herzog, H. L. (author)

Core Title The synthesis of polyalkylnaphthalenes

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-c17-790474

Unique identifier UC11345875

Identifier EP41558.pdf (filename),usctheses-c17-790474 (legacy record id)

Legacy Identifier EP41558.pdf

Dmrecord 790474

Document Type Thesis

Rights Herzog, H. L.

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...

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