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The reaction of styrene oxide with phenol

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The reaction of styrene oxide with phenol

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Content THE REACTION OF STYRENE OXIDE WITH PHENOL A T h e s is P r e s e n te d t o t h e F a c u lty o f th e G ra d u ate School 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 e q u ire m e n ts f o r th e Degree M aster o f S c ie n c e hy Homer R„ W illiam s August 1950 UMI Number: EP41593 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. Dissertation Publishing UMI EP41593 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQ uest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United S tates Code ProQ uest LLC. 789 E ast Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 -1 3 4 6 c ' TI Us 7 ^ This thesis, written by Horaer___R.___Willia ..................................... under the guidance of hX.§... 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 a ste r of S c ie n c e Faculty Committee .Q±. I Chairman a h . .... TABLE OF CONTENTS CHAPTER PAGE I , INTRODUCTION . . . . . . . . . . . . . . . 1 I I . HISTORICAL . . . . . . . . . ................................. 3 I I I . DISCUSSION .......................................................... 10 A. The E f f e c t o f S o lv e n t on th e B a se - c a t a l y z e d R e a c tio n o f S ty re n e Oxide w ith Phenol ............................................... 10 B. The A c i d - c a ta ly z e d R e a c tio n of S ty re n e Oxide w ith Phenol ......................... 27 IV, EXPERIMENTAL........................................................ 37 A. G e n e ra l E x p e rim e n ta l P ro c e d u re f o r t h e B a s e - c a t a ly z e d R e a c tio n o f S ty re n e Oxide w ith Phenol ..................... 37 B. The A c i d - c a t a ly z e d R e a c tio n o f S ty re n e Oxide w ith Phenol .......................... 39 C. The A c id - c a t a ly z e d R e a c tio n o f 3 - P h e n y l- 2 -p h e n o x y e th a n o l ( I ) w ith Phenol . . . . . . . .................................... . 43 D. The A c i d - c a t a ly z e d R e a c tio n o f 2 - P h e n y l- l- p h e n o x y e th a n o l ( I I ) w ith Phenol . . . . . . . .......................................... 44 E. The A c id - c a ta ly z e d R e a c tio n o f P h e n y la c e ta ld e h y d e w ith Phenol . . . . 45 CHAPTER PAGE F. P r e p a r a t i o n o f c < -(4 -H y d ro x y p h e n y l) - p h e n y l a c e t i c Acid and th e L acto n e o f « K - ( 2 -H y d ro x y p h e n y l)-p h e n y la e e tic A c i d .................................................................................. . 46 G. P r e p a r a t i o n o f 2 -(2 -H y d ro x y p h e n y l)- 3 - p h e n y l e t h a n o l ............................................................. 48 H. P r e p a r a t i o n o f '2 - ( 4 — H ydrox yph enyl)- 2 -p h e n y l e t h a n o l ............................................. 48 I ., P r e p a r a t i o n of l , 2 ~ D i b r o m o - l - ( 3 ,5 - d ib ro m o -4 -h y d ro x y p h e n y l) - 2 - p h e n y l - e th a n e . . . . . o . . . . . . . . . . . 49 J , P r e p a r a t i o n o f 4 -M e th o x y s tilh e n e . . . . 50 V. SBMMARY........................................ ......... ..................................... 51 BIBLIOGRAPHY................................................................................. 53 LIST OF TABLES TABLE PAGE I . The E f f e c t of S o lv e n t on C o m p o sitio n o f M ix tu re o f I s o m e r s ........................................ * . . 11 I I . The E f f e c t o f S o lv e n t on C o m po sitio n o f M ixture o f Iso m ers . . . . . . ....................... 14 I I I o The E f f e c t o f S o lv e n t on R ate o f R e a c tio n .......................................... . . . . . . . . 16 IV. The E f f e c t o f T em p eratu re on C om position of M ix tu re o f Iso m ers ..................................... 18 V. The A c i d - c a t a ly z e d R e a c ti o n s of S ty re n e Oxide w ith Phenol a t 7 0 ° C. . . . . . . . 29 CHAPTER I INTRODUCTION O le f in o x id e s a r e known t o r e a c t w ith a l a r g e v a r i e t y of o rg a n ic and I n o r g a n ic compounds. In p a r t i c u l a r th e r e a c t i o n w ith h y d r o x y l ! c compounds o c c u r s i n th e f o l lo w in g se n se : R-QR^CHg + R'OH * RCB-CRaQH + RQH-CHgOR 0 W hether th e r e a c t i o n p ro d u c e s th e p rim a ry a l c o h o l , th e se c o n d a ry a lc o h o l* o r "both, depends upon th e n a t u r e of R, p o s s i b l y R', and th e ty p e o f c a t a l y s t , which may be e i t h e r a c i d i c o r b a s i c . A r e c e n t i n v e s t i g a t i o n o f th e a l k a l i - c a t a l y s e d r e a c t i o n of s ty r e n e o x id e w ith phenol d i s c l o s e d t h a t th e medium i n which th e r e a c t i o n was c a r r i e d out a l s o had an e f f e c t on th e r a t i o o f th e two iso m e rs fo und . Under o th e r w is e i d e n t i c a l c o n d i t i o n s i t was o b se rv ed t h a t an a q ueous medium fa v o re d th e f o r m a tio n of t h e o rim ary a l c o h o l , w h ile i n d io x an e th e se co n d a ry a lc o h o l was t h e p re dom inant iso m e r. In t h i s same s tu d y th e a c i d - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith ph en o l was found t o produc m a t e r i a l s t h a t were a l k a l i - s o l u b l e and which were s t a t e d , w ith o u t s u p p o r t i n g e v id e n c e , to r e s u l t from a t t a c k o f th e o x id e on th e n u c le u s of th e p h e n o l. S u bsequent s t u d i e s showed t h a t , w ith s ty r e n e o x id e and 2 - n a p h t h o l , n u c l e a r a l k y l a t i o n o f th e 2 - n a p h th o l by t h e o x id e a c t u a l l y d id o c c u r . The p r e s e n t i n v e s t i g a t i o n was u n d e rta k e n i n o r d e r t o o b t a i n b e t t e r and more co m o lete d a t a on th e e f f e c t o f t h e medium, and a l s o o f t h e t e m p e r a t u r e , on t h e c o u rs e o f t h e a l k a l i - c a t a l y s e d r e a c t i o n o f s t y r e n e o x id e w ith p h e n o l. A se c o n d a ry o b j e c t i v e was t h e e l u c i d a t i o n o f - t h e n a t u r e o f t h e p r o d u c ts r e s u l t i n g from th e a c i d - c a t a l y z e d i n t e r a c t i o n o f t h e s e same r e a c t a n t s u n d er v a r i o u s c o n d i t i o n s . CHAPTER I I HISTORICAL B ro n ste d and h i s c o -w o rk e rs (1 ) made an e x te n s iv e s tu d y of t h e k i n e t i c s o f t h e r e a c t i o n of e th y le n e o x id e w ith w a te r, a q u eo us s o l u t i o n s of s a l t s , and aqueous s o lu t i o n s of a c i d s . S im ila r s t u d i e s were co n d u cted w ith g ly c id and e p ic h l o r o h y d r i n . The d a ta o b ta in e d from t h e s e s t u d i e s were i n t e r p r e t e d by th e i n v e s t i g a t o r s t o show t h a t th e r e a c t i o n s o f e th y le n e o x id e can p ro c e e d th ro u g h fo u r p a th s , d e p en d in g on th e c o n d i t i o n s . R ate c o n s t a n t s were d e t e r mined and p r e s e n t e d i n s u p p o rt of th e f o u r prooosed ty p e s o f r e a c t i o n s . While d e t a i l e d m echanism s were n o t p ro o o se d , i t was s t a t e d t h a t e th y le n e o x id e I s n o t a b a s e nor p se u d o - b a s e s in c e e th y le n e o x id e r e a c t s i n such a way t h a t th e p r o t o n i s n o t e x c l u s i v e l y i n v o lv e d . I t was p ro o o se d t h a t t h e f o llo w in g e o u a tio n s r e p r e s e n t th e mechanism s of th e f o u r r e a c t i o n s : c h 9 I + h 2 o C H o O H — > • i 2 C H g O H + 0 H c h 2 ^ + h 2 0 + H * * 1 T 2^ o c h 2 - C H o Q H --------> 1 2 C H g O H d - H g O + h 2 o + H + k 2 - 4 - + h 30 CHoOH — 1 2 + 0H 4C 1 ■ CH3C I K3 +H^0 CHgOH — > ) +HpO -K31T CHp C l K4 CHp III: I C ,E f CHp 17: 1 > CH .f The i n v e s t i g a t o r s b e l i e v e d t h a t v 5 3 „ h e ld over 2 4 a s u f f i c i e n t ra n g e of c o n d i t i o n s t o w a rr a n t t h e c o n c lu s io n t h a t th e c a t a l y s e d and u n c a ta ly z e d r e a c t i o n s were n o t in t r i n s i c a l l y d i f f e r e n t in n a t u r e . S e v e ra l a l k a l i - c a t a l y z e d r e a c t i o n s of u n sy m m e tric a l o l e f i n o x id e s w ith p h e n o ls and v a r i o u s a l c o h o l s have been r e p o r t e d i n t h e l i t e r a t u r e , and i n most c a s e s th e form a t i o n o f th e se co n d a ry a l c o h o l was p red o m in an t or e x c l u s i v e . A few exam ples a r e c i t e d i n th e f o l lo w in g p a r a g r a p h s . Chitwood and F r e u r e (2) have found t h a t p ro p y le n e o x id e r e a c t e d w ith e th a n o l i n th e p r e s e n c e o f b e s e t o y i e l d 82$ o f th e se c o n d a ry a lc o h o l and o n ly a sm all amount o f t h e p rim a ry a l c o h o l . S e x to n and B r i t t o n (3) r e p o r t e d t h a t th e a lk a l-' - c a t a l y z e d r e a c t i o n of p ro p y le n e o x id e and p h e n o l gave a 90$ y i e l d o f t h e se c o n d a ry a l c o h o l . The b a s e - c a t a l y z e d r e a c t i o n of a s e r i e s of p h e n o ls w ith pro p y le n e o x id e was i n v e s t i g a t e d by Boyd and M arie ( 4 ) , b u t th e d i r e c t i o n o f r i n g o p e n in g was n o t s t u d i e d . Kadeseh (5) c la im e d t h a t th e a l k a l i - c a t a l y z e d r e a c t i o n o f 3 , 4 - e p o x y - l - b u t e n e w ith m eth an ol r e s u l t e d p r e d o m in a n tly i n th e f o r m a tio n of th e seco n d ary a l c o h o l . T h is i n v e s t i g a t o r a l s o r e p o r t e d no s i g n i f i c a n t e f f e c t of te m p e r a tu r e on t h e d i r e c t i o n o f r i n g o p e n in g . The f i n d in g s o f B a r t l e t t and Ross (6) were s u b s t a n t i a l l y i n agreem ent w ith th o s e of Kadeseh; however B a r t l e t t and Rose were a b le t o d e t e c t some p rim a ry a l c o h o l from t h e a l k a l i - c a t a l y z e d r e a c t i o n . Swern, B i i l e n , rand K night (7) s t u d i e d th e i n t e r a c t i o n o f 3 , 4 - e p o x y - l - b u t e n e w ith a l l y l a lc o h o l i n th e p re s e n c e o f b a s e and claim ed t h a t t h e secondary, a lc o h o l was o b ta in e d e x c l u s i v e l y . Tan Tam elen, Tan Z yl, and Zuidema (8) r e p o r t e d t h a t th e r e a c t i o n of 3 , 4 -d ih y d ro n ra o h .th a le n e -l, 2 -o x id e w ith m alo n ic e s t e r r e s u l t e d in n u c l e o o h i l i c d is p la c e m e n t a t th e «<-carbon o f th e o x id e . On th e o t h e r han d , R u s s e l l and T un derR erf (9) have d e s c r i b e d th e r e a c t i o n o f s ty r e n e o x id e w ith m alo n ic e s t e r u n d e r th e custo m ary c o n d i t i o n s f o r t h e m alo n ic e s t e r s y n t h e s i s and r e p o r t e d t h a t t h e p r o d u c t p ro d u c t of th e r e a c t i o n r e s u l t e d e x c l u s i v e l y from th e b r e a k i n g o f th e ft -c a rb o n -o x y g e n bond t o form th e seco n d a ry a l c o h o l . Gilman and F u l l h a r t (10) r e p o r t e d th e p r e p a r a t i o n o f a s e r i e s o f /< ? - p h e n y l - ys - h y d r o x y e th y l s u l f i d e s from th e r e a c t i o n o f th e sodium s a l t s o f v a r i o u s m e rc a p ta n s with, s t y r e n e o x id e . The work was o f p a r t i c u l a r i n t e r e s t s i n c e no s o lv e n t was employed n o r, p re su m a b ly , was m er- c a p t a n p r e s e n t d u r in g t h e r e a c t i o n . Each of t h e p r o d u c ts from t h i s s e r i e s of r e a c t i o n s was i d e n t i f i e d a s a se co n d a ry a l c o h o l . The b a s e - c a t a l y z e d r e a c t i o n o f s t y r e n e oxide w ith m ethanol h a s been r e p o r t e d by R°eve and C h r i s t o f i e l (11) t o y i e l d 68-79$ o f a m ix tu re o f two is o m e r s . The s e c o n d a ry a lc o h o l c o n s t i t u t e d 65-75$ o f th e t o t a l o f b o th is o m e rs . These r e p o r t s c f t h e p red o m in an t f o r m a tio n of se co n d a ry a l c o h o l s from th e r e a c t i o n s o f s t y r e n e o xid e a r e i n a p p a r e n t c o n t r a s t w ith th e f i n d i n g s o f o t h e r s , Swern, B i l l e n , and K night (7) found t h a t a l l y l a lc o h o l and s t y r e n e o x id e r e a c t e d i n th e p r e s e n c e of b a se t o y i e l d 81$ mixed a l c o h o l s , 90$ o f which was th e p rim a ry a l c o h o l . Guss ( 1 2 ) , i n a stu d y o f t h e b a s e - c a t a l y z e d r e a c t i o n of s t y r e n e o x id e and p h e n o l, found t h a t th e p rim a ry a lc o h o l c o n s t i t u t e d 39$ t o 68$ o f t h e t o t a l e t h e r - a l e o h o l s when t h e r e a c t i o n was con ducted i n d lo x a n e a3 s o l v e n t . The h i g h e r p e r c e n t a g e o f th e p rim a ry a lc o h o l r e s u l t e d when r e l a t i v e l y low c a t a l y s t c o n c e n t r a t i o n s were em ployed. Comparable r e a c t i o n s co n d u cted i n w a te r gave t h e p rim a ry a lc o h o l i n y i e l d s of 70$ to 78$ o f t h e t o t a l I s o m e rs . An u n c a ta ly z e d r e a c t i o n , in t h e a b sen ce of s o l v e n t , p ro duced a m ix tu re of a l c o h o l s c o n t a i n i n g 88$ p rim a ry a l c o h o l . Guse and J u l e s (13) i n v e s t i g a t e d t h e b a se -c ^ t'-'ly z e d r e a c t i o n o f s t y r e n e o xide w ith 3 - n a p h th o l i n w a te r and i n d lo x a n e . T h is r e a c t i o n I n w ater y i e l d e d 12-17% o f th e p rim a ry e t h e r - a l c o h o l , 2 - ( 2 - n 3 p h th o ry ) - 2 - p h e n y l e t h a n o l , and up t o 51% o f th e o h e n o i- a lc o h o i , 2 - ( 3 - h y d r o ^ y - l - n a p li t h y l ) - ? ~ph::nyl.ethanol. The r e a c t ion in d io x an e y i e l d e d 4Z % > o f an a p p ro x im a te ly e q u al m ix tu re of the two .iso m e ric e t h e r - a l c o h o l s and o n ly 1*3% o f th e p h e n o l - a l c o h o l . The p h e n o l- a lc o h o l was th e one a l s o o b ta in e d in w a te r . I t s iso m e r, 1 - ( h - h y d r o x y - l - n a o h t h y l )- 3 - o h e n y l e th a n o i ,. was n o t i s o l a t e d from th e r e a c t i o n i n e i t h e r s o l v e n t . CH-CE20K OH CHp-CHOH 0 0 " 3 _ ( 2 - h y d r o x y - l - r a o h t h y l )■ 2 - p h e n y le th a n o l l - ( 2 - h y d r o y y - l - n a p h t h y l )■ 3 -p h e n y le th a n o l The a c id - c a ta iy - r e d r e a c t i o n of o l e f i n o x id e s w ith pn en o l and v a r i o u s a l c o h o l s a p p e a rs t o produce th e p rim a ry ■ a lc o h o l in relE--tively g r e a t e r am ounts. Chiiwoon and F r e u re (2) found t h a t th e a c i d - c a t a l y z e d r e a c t i o n of rrooy.lene oxide w ith e th a n o l y i e l d e d a t o t a l - 8 - o f 55$ t o 65$ mixed e t h e r - a l c o h o l s i n which t h e is o m e r ic e t h e r - a l c o h o l s were p r e s e n t i n a p p ro x im a te ly e q u a l q u a n t i t i e s . S exto n and B r i t t o n (3) r e p o r t e d t h a t th e a c i d - c a t a l y z e d r e a c t i o n o f p ro p y le n e o x id e w ith phen o l y i e l d e d 6 .5 $ of a m ix tu re o f e q u a l am ounts o f p rim a ry and se co n d a ry a l c o h o l s .- Kadeseh (5) r e p o r t e d t h a t th e a c i d - c a t a l y z e d r e a c t i o n o f 3 , 4 - e p o x y - l - b u t e n e w ith m eth an ol gave th e p rim a ry a l c o h o l . B a r t l e t t and Ross' (6) l i k e w i s e r e p o r t e d t h a t th e r e a c t i o n gave p re d o m in a n tly th e p rim a ry a l c o h o l . The l a t t e r i n v e s t i g a t o r s a l s o d e t e c t e d some c ro to n a ld e h y d e i n th e r e a c t i o n m ix tu r e . Swern, B i l l e n , and K n ight (7) r e p o r t t h a t t h e a c i d - c a t a l y z e d r e a c t i o n o f 3 , 4 - e p o x y - l - b u te n e and a l l y l a lc o h o l l e d t o a 79$ y i e l d of mixed a l c o h o l s , c o n s i s t i n g m o stly o f th e p rim a ry a l c o h o l . A cco rd in g to Reeve and C h r i s t o f f e l ( 1 1 ) , th e a c i d - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith m ethano l gave a 43$ y i e l d o f mixed e t h e r - a l c o h o l s , of which 90$ was th e p rim a ry e t h e r - a l c o h o l . Swern, B i l l e n , and K n igh t (7) c la im e d t h a t s t y r e n e o x id e and a l l y l a lc o h o l r e a c t e d i n t h e p r e s e n c e of a c i d t o g iv e 83$ o f t h e se c o n d a ry a l c o h o l . Guss (12) r e p o r t e d t h a t th e a c i d - c a t a l y z e d r e a c t i o n o f s t y r e n e o xide w ith phen o l i n th e a b se n c e o f s o l v e n t s y i e l d e d u n i d e n t i f i e d a l k a l i - s o l u b l e p r o d u c t s r a t h e r th a n th e e t h e r - a l c o h o l s . When w a te r was u se d a s a s o l v e n t , a low y i e l d (14$) o f mixed iso m e rs was o b t a i n e d , and 67$ o f th e m ix tu r e was t h e p rim a ry e t h e r - a l c o h o l . Guss and J u l e s (13) found t h a t th e a c i d - c a t a l y z e d r e a c t i o n of s t y r e n e o x id e w ith 2 - n a p h th o l gave, a s a m ajor p r o d u c t , 1- p h e n y l - 1 , 2 - d i h y d r o n a p h t h o - ( 2 , 1 - b ) - f u r a n , p ro b a b ly r e s u l t i n g from t h e c y c l o - d e h y d r a t i o n of t h e p rim a ry p h e n o l - a l c o h o l form ed by n u c le a r a t t a c k o f s t y r e n e o xid e on t h e c<~carbon of 2 - n a p h t h o l . T here was a l s o o b ta in e d a s u b s t a n t i a l amount o f a x a n th e n e r e s u l t i n g from th e a c i d - c a t a l y z e d re a rra n g e m e n t o f s t y r e n e o x id e to p h e n y l- a c e ta ld e h y d e . CHAPTER I I I DISCUSSION A* The E f f e c t o f S o lv e n t on th e B a s e - c a t a ly z e d R e a c tio n o f S tv re n e Oxide w ith P h e n o l. The work of Guss (13) d e m o n s tra te d t h a t t h e b a s e - c a t a l y z e d r e a c t i o n of s t y r e n e o x id e w ith ph en o l g a v e, in most i n s t a n c e s , good y i e l d s o f 2 -p h e n y l- 2 -p h e n o x y e th a n o l ( I ) and l- p h e n y I - 2 - p h e n o x y e th a n o l ( I I ) . The r a t i o o f I to I I was found to d e c r e a s e when th e s o l v e n t f o r t h e r e a c t i o n was changed from w a te r t o d lo x a n e .. J In th e p r e s e n t i n v e s t i g a t i o n e x p e rim e n ts were con d u c te d i n which th e s o l v e n t was v a r i e d . The r e s u l t s a r e summarized i n T ab le I . The e t h e r s gave a r e l a t i v e l y g r e a t e r p r o p o r t i o n o f 1,1 th a n d id th e o t h e r s o l v e n t s . The h y d r o x y l ic s o l v e n t s fa v o re d th e f o r m a tio n o f I by w id e ly v a r y i n g d e g r e e s , w h ile th o s e s o l v e n t s h a v in g n e i t h e r e t h e r l i n k a g e s nor h y d ro x y l g ro u p s a p p e a re d t o f a v o r t h e form a t i o n of I t o a p p ro x im a te ly t h e same e x t e n t i n a l l c a s e s . o ^ ° o CHCHoOH + I I I TABLE I THE EFF SCT OF SOL72FT OF FIXTURE OF ' ON CO!F>OSIT I307ERSa ION S olvent Time. h r . Temp. °0. Y ield of m ix tu r e , I I I , AT " J o y« p-. of m ix tu re , °C . I j m ixt\ * 75 3.; c c . 3 g. of t e t r h y d ro fu ran (0.1 mole) of m ethanol 22 70 41^>C 5 1 .0 28 35 c c . of t e t r a h y d r o f u r a n 3 93 81 48.5 43 25 c c . of dioxane 3 100 77 53.5 47 25 c c . of a c e t a l 3 100 65 58.5 55 25 cc. of e th a n o l 3 94 84 59.5 57 25 c c . of a l l y l a lc o h o l 3 100 80 63 .0 64 35 cc. of e th y le n e g ly c o l 3 100 88 6 5 .0 68 25 cc. of methanol 3 70 85d 65.5 69 25 c c . o f 0 n itro b e n z e n e 3 100 56 66.5 71 25 c c . of t o lu e n e e 3 10 0 70 6 7 .0 72 25 c c . of th io p h e n e e 3 94 61 67.5 73 1 M H I TABLE I ( c o n t in u e d ) THE EFFECT OF SOLVENT ON CO‘roOSITIOH' OF MIXTURE OF ISOMERSa S olvent 7.5 c c . of w ater 14 .1 g. of phenol* Time h r. 1 3 Tgmp, C 0 100 100 Y ield of m ix tu re , I I I , T O ______ so 50 M.p. of mi x tu r e , m ix tu re , °0. 60.5 75 .0 I in m ix tu re , * 77 88 8 R e a c ta n ts : S tyrene oxide (0.05 m ole), added over a 3-m inute p e rio d . Phenol (0.15 m ole). Sodium (0.05 mole) w ith non-aqueous s o lv e n ts . Sodium hydroxide (0 .05 mole) w ith w ater as th e s o lv e n t. These were a l l one-phase r e a c t i o n s except as n o te d . ■ w R e a c ta n ts : S ty ren e oxide (0.0 5 m ole). Phenol (0.1 m ole). Sodium (0.1 m ole). c A n a ly sis: C alc, fo r C ^ H ^ O g : C, 78.48; H, 6 .5 9 . Found: C, 78.44; H, 6.58 d A n a ly sis: C alc, f o r C14H140? : C, 78.48; H, S . 59. Found: CG, 78.90; H, 6 .2 7 e Some sodium phenoxide rem ained u n d is s o lv e d . ^ T h is amount i s in a d d it i o n to th e q u a n ti t y p r e s e n t in a l l ru n s . - 1 3 - Most o f th e d a t a i n T ab le I was o b ta in e d from e x p e rim e n ts i n which th e p h e n o l- o x id e r a t i o was t h r e e - t o - o n e . I t was p o s s i b l e t h a t t h i s e x c e s s oh en o l m ight h a re a f f e c t e d t h e r e s u l t s so o b t a i n e d . A second s e r i e s o f e x p e rim e n ts was co n d u cted i n which t h e s o l v e n t e f f e c t o f t h e e x c e s s f r e e ph enol was red u ced by a d d in g h a l f o f t h e p h e n o l w ith th e s t y r e n e o x id e a t a v e ry slow r a t e to a s o l u t i o n o f sodium p h e n o x id e . The r e s u l t s a r e summarized i n T a b le I I . When compared w ith th e d a t a i n T ab le I , th e y show t h a t a r e d u c t i o n i n f r e e p h e n o l r e s u l t e d in th e f o rm a tio n of r e l a t i v e l y g r e a t e r am ounts o f I I i n ev ery c a s e . Even i n th e e x p e rim e n ts sum m arized i n T a b le I I some f r e e phen o l was n e c e s s a r i l y p r e s e n t . To e f f e c t i v e l y r e duce t h e p h e n o l t o a n e g l i g i b l e l e v e l , an e x p erim e n t was c o n d u c te d i n w hich o n ly o hen oxid e io n and a sm a ll amount o f m ethanol was r e a c t e d w ith s ty r e n e o x ide i n a l a r g e v o l ume o f t e t r a h y d r o f u r a n . T h is r e s u l t e d i n th e maximum r e l a t i v e p r o p o r t i o n o f I I i n th e is o m e r ic m ix tu r e . The r e s u l t s o f t h i s r e a c t i o n a r e summarized i n T able I ( f i r s t r u n ) . A s tu d y was made to d e te rm in e th e e f f e c t o f d io x a n e , e t h a n o l , m e th a n o l, and phen o l on th e r a t e of th e b a s e - . c a t a l y z e d r e a c t i o n of s ty r e n e o x id e and p h e n o l. I n t h i 8 i n v e s t i g a t i o n th e b a se c o n c e n t r a t i o n was o n e - h a l f t h a t TABLE I I THE EFFECT OF SOLVENT ON COMPOSITION OF MIXTURE OF ISOMERSa S olvent A d d itio n tim e h r . ’ T o ta l r e a c t i o n ' tim e h r . Temp. °c Y ield of m ix tu re , I I I , % M.p. m ixture, °C. I in rrilxtu: * 25 c c . of te t r a h y d r a f u r a n 2 .5 5 .5 74-90° 50b 47.5 34 20 c c . of dioxane 3 6 .0 44.0 100 59b 44.0 38 20 c c . of dioxane 1.75 3.7 5 100 30b 44.0 38 25 c c . o f e th a n o l 3 0 .0 2 1 .0 70 89 54.5 49 25 c c . of methanol 2 0 .0 2 1 .0 70 79 62.5 63 7.5 c c . of w ater 1 .0 2 .0 100 700 64.5 67 cl R e a c ta n ts : S tyrene oxide: (0.05 m ole). Phenol (0 .1 m ole). Sodium (0.05 mole) w ith non-aqueous s o lv e n ts . Sodium h yd ro x id e (0 .0 5 mole) with w ater a s th e s o lv e n t. O n e-h alf of th e phenol was added w ith th e sty re n e oxide over th e s t a te d p e rio d to th e s o lv e n t and rem ainin g phenol a s sodium phenoxide. When dioxane was th e s o l v e n t, an a d d i t i o n a l 10 c c. of dioxane was added w ith sty re n e o x id e-o h en o l m ix tu re. b Some s ty r e n e oxide was re c o v e re d . c The phenol and s ty re n e oxide was added t o a r e f l u x i n g s o l u t io n , th e r e f l u x tem p e r a t u r e of which in c r e a s e d as th e a d d i t i o n p roceded. - 1 5 - . employed i n th e f o r e g o i n g s tu d y o f s o l v e n t e f f e c t s . In t h e a l c o h o l i c s o l v e n t s , and in d io x a n e , th e p h e n o l- o x id e r a t i o was t h r e e - t o - o n e , so th e d a t a c o u ld n o t b e i n t e r p r e t e d a s r e p r e s e n t i n g s o l e l y th e e f f e c t o f t h e s i n g l e s o l v e n t . When phenol was employed a s t h e s o l v e n t , s u f f i c i e n t e x c e s s ph en ol was u se d t o g iv e a m ix tu re w ith a volume com parable t o t h e m ix tu re s i n t h e o t h e r s o l v e n t s . A g r a p h ic d e t e r m i n a t i o n o f th e h a l f - t i m e o f th e r e a c t i o n s was made and i s in c lu d e d w ith th e e x p e r im e n ta l d a t a which a r e summarized i n T ab le I I I . I t i h s i g n i f i c a n t t h a t th e i c o m p o s itio n o f t h e is o m e r ic m ix tu re rem a in e d r a t h e r con s t a n t a t d i f f e r e n t d e g r e e s of c o n v e r s io n . In a d d i t i o n t o i n c r e a s i n g th e r e a c t i o n r a t e o f th e b a s e - c a t a l y z e d r e a c t i o n , p h e n o l a s th e s o l v e n t d i r e c t e d th e r e a c t i o n to w a rd th e f o r m a tio n of r e l a t i v e l y l a r g e am ounts o f a l k a l i - s o l u b l e p r o d u c t s . T h is was a phenomenon which c o u ld n o t have o c c u r re d so e x t e n s i v e l y i n t h e e t h e r o r th e h y d r o x y l ic s o l v e n t s i n view o f th e h ig h y i e l d s of th e e t h e r - a l c o h o l s t h a t were o b t a i n e d . The r e l a t i v e l y low er y i e l d s o f e t h e r - a l c o h o l s o b ta in e d i n n i t r o b e n z e n e , t o l u e n e , and th io p h e n e m ight have b een due t o t h e f o r m a tio n o f a l k a l i - s o l u b l e p r o d u c t s ; however t h i s was n o t i n v e s t i g a t e d e x p e r i m e n t a l l y . The e f f e c t of te m p e r a tu r e on th e r e a c t i o n i n t h r e e d i f f e r e n t s o l v e n t s was i n v e s t i g a t e d , and th e r e s u l t s a r e - 1 6 - TABLE I I I THE EFFECT OF SOLVENT CN OF REACTION®' HATE S o lv e n t Time h r . Y ie ld of m ix tu r e , M.p. of I I I , m ix tu r e , 4 > °c . I i n m ix tu r e , % d io x a n e 7 .0 33 63.5 65 14.0 52 60.0 61 2 3 .0 64 6 0 .0 61 4 8 .0 79 6 0 .0 61 '90.0 88 6 0 .0 61 e th a n o l 0 .7 5 31 6 4 .5 67 1 .5 51 6 6 .0 70 3 .0 71 64 .5 67 1 4 .0 87 S3.5 65 m eth an o l 0 .7 5 39 6 6 .5 71 1 .5 57 6 7 .0 72 3 .0 86 6 7 .0 72 1 4 .0 84 6 6 .5 71 p h e n o l^ 0.1 8 5 26 7 7 .5 93 0.37 34 7 8 .0 94 0 .7 5 48 7 8 .0 94 1 .5 39 78.5 95 14.0 43 73.5 93° m in u tes 830 69 48 - 17- TABLS I I I (co n tin u e d ) THE EFFECT OF SOL7ENT ON RATE OF REACTION3, S o lv e n t p h en o l ( u n c a t a ly z e d ) Time h r . 0 .3 7 2 .5 Y ie ld o f m ix tu r e , I I I , 1 _ L 31 37 M.p. o f m ix tu re , °C. ‘ 7 5 .5 7 5 05 ' I i n m i x t u r e . % 89 89 m in u te s 8 .5 a R e a c ta n t s : S ty re n e o x id e ( 0 ,0 5 m o le ). Phenol (0 .1 5 m o le ). Sodium Q0.025 m o le ). The r e a c t i o n was cd n d u cted in 25 c c . o f s o l v e n t , o r i n 26 g. of a d d i t i o n a l p h e n o l when ph en ol was employed a s th e s o l v e n t . The s t y r e n e o x id e was added o v e r a 1 -m in u te p e r i o d t o th e m ix tu re a t 7 2 °. ^ The l o r y i e l d s i n t h i s a e r i e s r e s u l t e d from s i d e r e a c t i o n s l e a d i n g t o a l k a l i - s o l u b l e p r o d u c t s . c In a d d i t i o n t o th e is o m e r ic e t b e T - a l c o h o l s , o r o d u c t s of n u c l e a r a t t a c k were a l s o i s o l a t e d . The y i e l d s w ere: ? _ ( p - h y d r o x y p h e n y l ) - 2 - p h e n y l e th s n o l , 0 .4 g. (3.7%) and 2 - ( 4 - h y d r o x y p h s n y l ) - 3 - p h e n y l e t h a n o l , 0 .9 g. (8 .4 & ). “18- TABLE IV THE EFFECT OF TEMPERATURE ON COMPOSITION OF MIXTURE OF ISOMERS3- Y ie ld of m ix tu r e , ¥ . d . o f I i n S o lv e n t Time h r . Terao. °C. 1 1o1 1 ' m ix tu r e , °C. m i x t u r e , 4 35 c c . o f m eth an o l 4 0 .0 23 44b 7 1 .0 80 35 c c . of m eth an ol 3 .0 74 84 6 5 .0 68 7 .5 c c . o f w a te r 0 7 3 .0 0 13b 7 7 .0 92 7 .5 c c . o f w a te r 4 .5 70 81 7 3 .0 82 7 .5 c c . of w ater 1 .0 100 80 6 9 .5 77 1 4 .1 g. of o h e n o lc 6 0 .0 24 44 7 7 .0 92 1 4 .1 g. of p h e n o l0 3 .5 70 54 7 5 .5 89 1 4 .1 g. of o h e n o l0 3 .0 100 50 7 5 .0 88 1 4 .1 g. o f p h e n o l 0 .5 13 8 59 7 0 .5 79 1 4 .1 g. o f p h en o l 0 .3 5 190 74 6 4 .0 66 a R e a c ta n tB ; S ty re n e o x id e (0 .0 5 m o le ). Phenol (0 .1 5 m o le ). Sodium (0 .0 5 mole), w ith n o n -aq u e o u s s o l v e n t e . Sodium h y d r o x id e .( 0 .0 5 m o le ) with, w a ter a s th e s o l v e n t . Then phenol was used a s the s o l v e n t , th e amount s t a t e d i n th e t a b l e above was i n a d d i t i o n t o t h a t p r e s e n t i n a l l o f t h e rim s . The s ty r e n e o xide was added over a 3 -m in ute p e r i o d . Some u n r e a c te d s ty r e n e o x id e was r e c o v e r e d . 0 Some sodium p h en o x id e rem ain ed u n d i s s o l v e d . eummarized i n T a b le I ? . The s o l v e n t s , w a te r and m eth an o l, showed s i g n i f i c a n t d e c r e a s e i n th e p ro m o tio n o f t h e form a t i o n of X a s t h e te m p e r a tu r e was r a i s e d from a p p ro x im a te ly 25 ° t o 70°» In c o n t r a s t , phenol a s a s o l v e n t showed only a n e g l i g i b l e change i n e f f e c t over th e same t e m p e r a tu r e r a n g e . However, a pro n o u n ced t r e n d d e v e lo p e d when phen o l was u sed a s th e s o l v e n t a t te m p e r a tu r e s betw een 100° and 1 9 0 ° . B e s id e s d e c r e a s i n g th e f o rm a tio n of I i n o h e n o l, h i g h e r t e m p e r a t u r e s a l s o i n c r e a s e d th e o v e r a l l y i e l d of t h e e t h e r - a l c o h o l s . W in e te in and H e n d erso n ( 1 4 ) , i n a r e v ie w o f th e c h e m is tr y o f e p o x id e s , d is m is s e d a mechanism o f b a s e - c a t a l y z e d n u c l e o p h i l i c d is p la c e m e n t r e a c t i o n s of e p o x id e s . T h is r e a c t i o n was i n d i c a t e d a s f o llo w s : In s u p p o r t o f t h i s g e n e r a l mechanism th e a u t h o r s c i t e d s e v e r a l r e f e r e n c e s t o work which e s t a b l i s h e d t r a n s - a d d i t i o n i n b o th a c i d - and b a s e - c a t a l y 2 ed r e a c t i o n s o f s e v e r a l t e p o x id e s . In e x p l a i n i n g th e b a s e - c a t a l y z e d r e a c t i o n s o f s t y r e n e o x id e t h e s e a u t h o r s u se d , a s s u p p o r t i n g e v id e n c e , t h e i r own work w ith raetjhanol and s t y r e n e o x id e . A lso u se d t o s u b s t a n t i a t e t h e i r c o n c l u s i o n was t h e work o f VanderW erf - 3 0 - w ith s t y r e n e o x id e and m a lo n ic e s t e r . Both o f t h e s e i n v e s t i g a t i o n s l e d W in s te in and H end erso n t o th e c o n c l u - ! s i o n t h a t s t y r e n e o xid e c o u ld "best he re p re se n te d , a s r e a c t i n g a s i n d i c a t e d : T h is i s i n a c c o r d w ith t h e s ta te m e n t "by W in ste in and H enderson t h a t f o r o r d i n a r y n u c l e o p h i l l c d is p la c e m e n t on c a rb o n th e r a t e se q u en c e, p r i m a r y s e c o n d a r y y t e r t i a r y , i s g e n e r a l , and t h i s a c c o u n ts i n g e n e r a l f o r t h e d i r e c t i o n o f o p e n in g o b se rv e d i n th e r e a c t i o n o f th e n e u t r a l oxides,, T h is c o n c l u s i o n , w h ile i t i s c o n s i s t a n t w ith some r e a c t i o n s r e p o r t e d i n th e l i t e r a t u r e , does n o t s u g g e s t th e mechanism th ro u g h which d i v e r g e n t r e s u l t s have b een o b ta in e d i n th e t « p r e s e n t i n v e s t i g a t i o n . t h e a l & a l i - o a t a l y z e d r e a c t i o n s of s t y r e n e o x id e w ith n u c le o - p h i l i c r e a g e n t s . R u s s e l l and VanderW erf ( 9 ) , on th e b a s i s o f t h e i r work w ith s t y r e n e o x ide and m alonic' e s t e r , p ro p o se t h a t th e r e a c t i o n co u ld be e x p la in e d a s r e s u l t i n g from th e tX 8 e f f e c t o f th e p hen y l g ro u p . T hus, th e y r e p r e s e n t s t y r e n e o x id e a s i n d i c a t e d : O ther i n v e s t i g a t o r s have D roposed mechanisms f o r Sh ( cooh) - 2 1 - T k is view h a s b een c r i t i c i z e d r e c e n t l y by van Taraelen and h i s c o -w o rk e rs ( 8 ) . These i n v e s t i g a t o r s found t h a t m a lo n ic e s t e r a t t a c k e d th e o< - c a r b o n of 3 ,4 - d i h y d r o n a p h t h a - l e n e - 1 , 2 - o x i d e . They c o n clu d ed from t h i s t h a t th e a t t a c k o f m a lo n ic e s t e r on th e > 5 * - c a r b o n o f s t y r e n e o x id e c o u ld be e x p la in e d by l e s s e r s t e r l c h in d r a n c e a t t h a t p o i n t , r a t h e r th a n by e l e c t r o n i c i n t e r p r e t a t i o n p ro p o se d by Rus s e l l and VanderW erf, Swern and c o -w o rk e rs (? ) i n v e s t i g a t e d th e r e a c t i o n o f s ty r e n e oxide w ith a l l o x i d e io n and c o n c lu d e d t h a t s t y r e n e oxide c o u ld be p i c t u r e d a s f o llo w s : N e i t h e r th e view s o f Swern n o r th o s e of R u s s e l l and Van derW erf a r e i n harmony w i t h a a l l o f t h e f a c t s o bserved in t h e p r e s e n t i n v e s t i g a t i o n . The mechanisms t h u s f a r p ro p o se d were bimolecular (SffS) and were a p p l i e d to th e baee-Gatalyzed r e a c t i o n . For th e a c i d - c a t a l y z e d r e a c t i o n a u n lm o le c u la r (Sjjl) r i n g o p e n in g was o ro p o se d by s e v e r a l i n v e s t .i g a t o r e (5 , 15, 1 5 ). W hile th e d e t a i l s o f th e proposed S^l r e a c t i o n mechanism d i f f e r e d s l i g h t l y , th e u n lm o le c u la r r i n g o p ening o f an e p o x id e t o form a carbonium io n could be r e p r e s e n t e d as - 2 3 - i n d i c a t e d : R 'O H R~GH~pHp £ t R-CE-CH,, o' a H > R-CH-CH^OH +H+ Such a u n im o le c u la r r i n g o p e n in g o f s t y r e n e o xid e -would p r o b a b ly fa v o r th e fo r m a tio n o f th e se c o n d a ry earbonium io n which c o u ld be r e s o n a n c e - s t a b i l i z e d . T h is would t h e n le a d t o n u c l e o p h i l i c a t t a c k on th e o< - c a r b o n . In g e n e r a l , t h e b irn o le c u la r r e a c t i o n (SN2) s h o u ld le a d t o b irn o le c u la r k i n e t i c s (b e in g f i r s t o r d e r w ith r e s p e c t t o each r e a c t a n t ) , w h ile t h e u n im o le c u la r mechanism ( S ^ l ) sh o u ld , i n f i r s t a p p ro x im a tio n , l e a d t o f i r s t o r d e r k i n e t i c s ( 1 7 ) . I f t h i s i s u se d a s a c r i t e r i o n , i t a p p e a rs t h a t t h e b a s e - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith e x c e s s phenol i s S ^ l, s i n c e p heno x id e h a s l i t t l e o r no e f f e c t on th e r a t e o f r e a c t i o n . T h is e x p l a n a t i o n + H H - 2 3 - i n v o lv e s t h e f o r m a tio n of a carbonium io n th ro u g h u n i - m o le c u la r r i n g o p e n in g o f th e hy drogen-bo nded s t y r e n e o x id e o x id e - p h e n o l complex a s i n d i c a t e d : B ecau se o f th e g r e a t r e a c t i v i t y o f th e oarbonium io n , th e r a t e o f i t s fo r m a tio n w o u ld p r o b a b ly be t h e r a t e - d e te r m i n i n g s t e p , and h e n c e th e p h e n o x id e io n concen t r a t i o n would n o t e x e r t any s i g n i f i c a n t i n f l u e n c e on th e r a t e o f t h e r e a c t i o n . I t a p p e a rs p o s s i b l e t h a t such a u n lm o le c u la r r i n g o p e n in g o f s t y r e n e o x id e i n b a s i c s o l u t i o n may o c c u r a l s o , l e s s e x t e n s i v e l y , i n o th e r n y d r o x y lic s o l v e n t s , such a s w a te r and a l c o h o l , th e r e b y f a v o r i n g to a l e s s e r d e g re e t h e f o r m a tio n o f th e p rim a ry e t h e r - a l c o h o l . In a d d i t i o n t o th e u n lm o le c u la r r i n g o p e n in g of s t y r e n e o x id e , t h e c u r r e n t l y fa v o re d SN2 m e c h a n is m 'a ls o a p p e a r s t o o p e r a t e in th e b a s e - c a t a l y z e d r e a c t i o n of. s t y r e n e o x id e w ith p h e n o l. P r e v io u s i n v e s t i g a t i o n s have n o t i n d i c a t e d t h a t b a s e - c a t a l y z e d r e a c t i o n s o f e p o x id e s m ight be i n f lu e n c e d by th e s o l v e n t s i n which t h e r e a c t i o n s were C o n d u c te d , and h en ce th e p o s s i b l e r o l e o f s o l v e n t s h a s not - 2 4 - been c o n s id e r e d by o t h e r i n v e s t i g a t o r s . The d i f f e r e n t r a t e s of r e a c t i o n o f th e b a s e - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith p hen o l i n d i f f e r e n t s o l v e n t s s u g g e s ts t h a t th e f o r m a tio n o f a h y drogen bond betw een s t y r e n e o x id e end a h y d r o x y l ic s o l v e n t l e a d s t o a. lo w e r a c t i v a t i o n en erg y r e q u ire m e n t f o r th e t r a n s i t i o n s t a t e f o r th e r e a c t i o n . The Sn2 r e a c t i o n o f h y d ro g en -b o n d e d s t y r e n e o x id e w ith p h e n o x id e io n i n h y d r o x y l ic s o l v e n t s may be r e p r e s e n t e d a s f o llo w s : T h is r e p r e s e n t a t i o n shows d is p la c e m e n t a t th e - c a r b o n , how ever i t a p p e a rs t h a t a t t a c k o f th e p h e n o x id e io n on th e <X - c a r b o n would l i k e w i s e be a id e d by p o l a r i z a t i o n in d u ce d by h y d ro g e n -b o n d in g a s i n d i c a t e d . I t i s not o b v io u s w h e th er one o c i n t o f d is p la c e m e n t would be fa v o re d more t h a n t h e o t h e r by weak h y d ro g e n -b o n d in g o f s t y r e n e o x id e : how ever a s t h e s t r e n g t h o f th e h y drogen bond i s i n c r e a s e d , t h e p o l a r i z a t i o n o f th e c arb o n -o x y g e n bond would a l s o be e x p e c te d t o i n c r e a s e . T h is b e in g t h e c a s e , t h e v e ry h i g h ly - 2 5 - o o l a r i s e d s t y r e n e o x id e m o le cu le c o u ld hyve some o f th e c h a r a c t e r ! s t i e s o f a carbons urn io n , and h e n c e t h e a t t a c k a t t h e o( - c a r b o n would be e x p e c te d i n t h e c a s e o f t h e carbohiura i o n . The r e s u l t s o f th e p r e s e n t i n v e s t i g a t i o n do n o t i n d i c a t e what t h e p r o b a b i l i t y i s o f such a r e a c t i o n mechani sm. A th ird , p o s s i b l e b a s e - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith phen o l i s t h a t o c c u r r i n g i n a medium i n which t h e r e i s l i t t l e or no h y d ro g en b o n d in g to th e s t y r e n e o x id e . T h is c o n d i t i o n was a p p ro a c h e d in th e f i r s t e x p e rim e n t o f T a b le I . In t h i s r e a c t i o n d is p la c e m e n t o c c u r re d m o stly a t t h e •f - c a r b o n . The only a n a lo g o u s r e a c t i o n i n th e l i t e r a t u r e was t h a t r e p o r t e d by Gilman (10) i n which sodium m er- c a p t i d e s r e a c t e d w ith s t y r e n e o x id e i n t h e a b se n c e o f a s o l v e n t t o y i e l d p r o d u c ts r e s u l t i n g from d is p la c e m e n t a t t h e - c a r b o n e x c l u s i v e l y . The sm a ll amount o f in fo rm a t i o n on t h e r e a c t i o n s o f s t y r e n e o x id e i n n o n - h y d r o x y lic s o l v e n t s d o e s n o t o e rm it a c r i t i c a l e v a l u a t i o n o f p o s s i b l e m echanism s which would le a d to a t t a c k on th e yS - c a r b o n i n n o n - h y d r o x y lic s o l v e n t s . The e f f e c t o f t e m p e r a tu r e a p p e a rs t o be c o n s i s t e n t w ith a mechanism i n v o l v i n g hy drogen b o n d in g . I t i s known t h a t h y d ro g en b o n d in g d e c r e a s e s w ith i n c r e a s i n g te m p e ra t u r e ( 1 8 ) . T hus, i t m ight be e x p e c te d t h a t a t t a c k on th e «K -carbon would d e c r e a s e w ith i n c r e a s i n g t e m p e r a t u r e . - 2 6 - T h i e i s i n h a r m o n y w i t h t h e e x p e r i m e n t a l d a t a . The e x p e r im e n ta l work o f t h i s i n v e s t i g a t i o n h a s shown t h a t i n e x c e s s p h e n o l th e b a s e - c a t a l y z e d r e a c t i o n o f s ty r e n e o x id e w ith o h e n o l l e a d s t o t h e f o r m a tio n of th e p rim a ry a l c o h o l ( I ) i n am ounts tw e n ty tim e s t h a t of t h e se co n d a ry a lc o h o l ( I I ) . When o t h e r s o l v e n t s a r e em ployed, th e p re p o n d e ra n c e o f I o v e r I I i n th e p ro d u c t d e c r e a s e s i n th e o r d e r , w a t e r > m e t h a n o l > e t h a n o l > dio xane> t e t r a h y d r o f u r a n . In t h e l a s t s o l v e n t , t e t r a h y d r o f u r a n , i t was found t h a t th e r a t i o o f I t o I I was re d u c e d t o a v a l u e o f l e s s th a n o n e - h a l f . When th e r a t e o f r e a c t i o n was s t u d i e d i n s e v e r a l s o l v e n t s , i t was found t h a t th e r a t e d e c r e a s e d i n th e o r d e r , p h e n o l > m eth an ol > ethanol^>> c io x a n e . From t h e s e f a c t s i t a p p e a rs t h a t th e f o r m a tio n o f th e p rim a ry a lc o h o l ( I ) from th e b a s e - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith p h e n o l i s c o r r e l a t e d w ith t h e s o l v e n t ’ s e f f e c t on th e r a t e o f r e a c t i o n . T h is may he p a r t l y e x p la in e d by p o s t u l a t i n g a u n lm o le c u la r r i n g o p e n in g of s t y r e n e o x id e t o a s i g n i f i c a n t e x t e n t i n s o l v e n t s such a s p h e n o l, and t o a l e s s e r e x t e n t , i n w a te r and a l c o h o l s . An S^ 2 r e a c t i o n a l s o a p p e a r s t o be p r o b a b le i n h y d r o x y l ic s o l v e n t s . The e f f e c t o f a h y d r o x y l ic s o l v e n t would be to lo w e r th e e n erg y o f th e t r a n s i t i o n s t a t e th ro u g h h y d ro g e n b o n d in g t o th e e p o x id e r i n g . Both th e Sjjl and S 2 m echanism s, a s p ro p o se d in - 3 7 - t h i s d i s c u s s i o n , a r e m o d i f i c a t i o n s o f w id e ly a c c e p te d t h e o r i e s on e p o x id e r i n g o p e n in g . However t h e e x p e r i m e n ta l d a t a 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 i n d i c a t e s t h a t an SN1 d is p la c e m e n t on s t y r e n e o x id e by phen ol may be p o s s i b l e i n a b a s e - c a t a l y z e d r e a c t i o n . I t seems t h a t w h ile th e Sjj2 a t t a c k on s t y r e n e o x id e by p h e n o x id e io n i s by a mechanism s i m i l a r t o t h a t f a v o r e d by t h e m a j o r i t y o f i n v e s t i g a t o r s , th e s t r o n g i n f l u e n c e o f h ydrog en bond in g on th e d i r e c t i o n and r a t e of th e e p o x id e r i n g o p e n in g m ust be c o n s id e re d b e f o r e th e i n f l u e n c e of th e p h e n y l group on th e e p o x id e r i n g may be e v a l u a t e d . T h is f a c t o r was n o t c o n s id e r e d in p u b l is h e d d i s c u s s i o n s o f th e d i f f e r i n g d i r e c t i o n s o f r i n g o p e n in g o b se rv e d f o r s t y r e n e o x id e . B. The A c i d - c a t a ly z e d R e a c tio n o f S ty r e n e Oxide- w ith P h e n o l. The a c i d - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith p h e n o l h a s b e e n r e p o r t e d t o y i e l d u n i d e n t i f i e d a l k a l i - s o l u b l e p r o d u c t s ( 1 2 ). B ecause a l k a l i - s o l u b l e p r o d u c t s had been o b ta in e d i n some b a s e - c a t a l y s e d r e a c t i o n s a l s o , i t a p p e a re d p o s s i b l e t h a t a s i m i l a r mechanism was i n v o lv e d i n b o th c a s e s . I t was re a s o n e d t h a t i f th e a l k a l i - s o l u b l e and t h e a l k a l i - i n s o l u b l e p r o d u c t s were s i m i l a r i n b o th t h e a c i d - c a t a l y z e d and b a s e - c a t a l y z e d r e a c t i o n s , a - 3 8 - s i r a i l s r mechanism would b e p r o b a b le . The c o n d i t i o n s chosen f o r th e a c i d - c a t a l y z e d r e a c t i o n s were s i m i l a r t o th o s e u se d -when b a s e - c a t a l y p i s was em ployed. The r e a c t i o n was c a r r i e d o u t by a d d in g s t y r e n e o x id e t o a s o l u t i o n o f a l a r g e e x c e s s o f p h e n o l, c a t a l y t i c am ounts of p - t o l u e n e e u l f o n i c a c id rr.onohydrate,^* o and s o l v e n t a t 70 . At th e end o f th e r e a c t i o n tim e th e t a l k a l i - i n s o l u b l e p r o d u c ts were rem oved, and th e a l k a l i - s o l u b l e com ponents were th e n i s o l a t e d by a c i d i f i c a t i o n and e t h e r e x t r a c t i o n o f th e aqueous s o l u t i o n . Removal o f th e e x c e s s p h e n o l was e f f e c t e d by vacuum d i s t i l l a t i o n , and th e r e s i d u e was t h e n f r a c t i o n a l l y d i s t i l l e d under vacuum to g iv e -a rough s e p a r a t i o n of p r o d u c t s . The d i s t i l l a t i o n f r a c t i o n s were f r a c t i o n a l l y c r y s t a l l i z e d t o o b t a i n t h e v a r i o u s u r o d u c t s . The i s o l a t e d a l k a l i - s o l u b l e p r o d u c ts r e p r e s e n t e d s l i g h t l y l e s s th a n h a l f th e w eig ht o f t h e combined a l k a l i - s o l u b l e p r o d u c t s . The r e s u l t s f o r t h e a c i d - c a t a l y z e d r e a c t i o n s a r e summarized i n T able 7, B e s id e s t h e e t h e r - a l o o h o l s , I and IT, 2 - ( 2 - h y d r o x y - p h e n y l ) - 2 - p h e n y l e t h a n o l ( I I I ) , 2 - ( 4 - h v d r o x y p h e n y l) - 2 - p h e n y le th a n o l (1 7 ), 4 - s t i l b e n o l (V), a p r o d u c t b e l i e v e d t o be t h e d ip h e n y l e t h e r of p h e n y l g ly c o l ( V i) , and- 1 The d e s i g n a t i o n , HOTs, w i l l be used h e r e a f t e r to d e s i g n a t e p - t o l u e n e s u l f o n i c a c id m onohydrate* TABLE V THE ACID-CATALYZED REACTION OF STYRENE OXIDE V TITH PHENOL AT 70° C. T o ta l a l k a l i - Y ie ld , $ s o lu b le m a te r ia l S olv en t Time I II III II I O t h e r s ________ g._________ none 7 min. 15.1 1 .0 1 3 .9 12.5 3 .6 c 12.1 none 2 3 h r s. ------ n o t d e term in ed ----------------- d 14.24 50 CC.« ,d io x sn e e 1 5 min. not d eterm ined----------------- f 1 .6 7 100 co» to lu e n e 15 min. 4 8 .0 3 .0 not d e te rm in e d — g 7.65 a R e c c t: n t s : S tyrene oxide (0 .1 0 m ole). Phenol (0 .60 m ole). EOTs (0.0021 m ole). 0 Time includes- th e 7-m inute a d d i t i o n tim e fo r s ty r e n e oxide. 0 C r y s t a l l i n e m a t e r i a l , m e ltin g a t 1 2 7 .0 -1 2 7 .5 ° was o b tain ed i n 0 .0 8 g. y i e l d by c r y s t a l l i z a t i o n of th e a l k a l i - i n s o l u b l e f r a c t i o n d i s t i l l i n g a t 165-230^/1 mm. The a n a l y s i s corresp ond ed to th e din h en y l e t h e r of phenyl g ly c o l (V I). A n a ly sis: C alc, f o r C2 0 H1 8 02 : C, 82.80; H, 6 .2 1 . Found: C, 8 3 .2 7; H, 6 .2 3 . * The a l k a l i - i n s o l u b l e pro d u ct c o n s is te d of 0 .4 9 g. of v isc o u s o i l . 3 R e a c ta n ts : o n e - h a lf th e u su a l amounts. p The y i e l d of a l k a l i - i n s o l u b l e p ro d u ct was too sm all t o be d i s t i l l e d . A l a r g e vol ume o f sty re n e oxide was re c o v e re d , i n d i c a t i n g a slow r e a c t i o n . '5 The d ip h en y l e t h e r of phenyl g ly c o l (VI) was re c o v e re d from th e h ig h b o i l i n g a l k a l i - i n s o l u b l e f r a c t i o n i n '0.98 g. y i e l d . 1 , 1 -b i e (4 -h y d ro c y p h er.y l ) - ? - o h e n y le t h s n e (VTl) r e r e i s o l a t e d . The l a s t comoound (V II) was p r o b a b ly p r e s e n t i n th e r e a c t i o n m ix tu re of s t y r e n e o x id e and o h enol; however i t was i s o l a t e d o n ly from th e r e a c t i o n m ix tu re of p h e n o l and p h e n y l& o eta ld e h y d e end from t h e r e a c t i o n m ix tu r e o f I w ith p h e n o l. V II OH The i d e n t i f i c a t i o n o f I I I and IV was a c c o m p lish e d by a l t e r n a t e s y n t h e s e s , c * - ( 4 - H y d r o x y p h e n y l ) - p h e n y l a c e t i e a c i d and th e l a c t o n e o f o i - ( 2 -h y d ro x y p h e n y l)F -p h e n y la c e tie a c i d were p r e p a r e d by th e c o n d e n s a tio n o f phen o l and m a n d e lic a c i d in t h e p r e s e n c e o f 73$ s u l f u r i c a c i d . oh I I I 4 [ ~ \ c h - c h 2oh + Q c ^ Q , I I I IV V + - 3 1 - R e d u c t i o n o f t h e a c i d a n d t h e l a c t o n e w i t h l i t h i u m a l u m i n u m h y d r i d e g a v e t h e c o r r e s p o n d i n g p h e n o l - a l c o ^ o l s . OH f ^ 6 h c o 6 h + J ^ j ■Z3l»ag2*» H J _ ^ 0 LiAlH4 * h H C - C O O H L iA lH . •OH , h c - c h 9 ch OH HC-CHoOH I I I 1 7 M i x e d m e l t i n g p o i n t s s h o w e d t h e s y n t h e s i z e d c o m p o u n d s , I I I a n d 1 7 , t o b e i d e n t i c a l w i t h t h o s e f r o m t h e r e a c t i o n m i x t u r e . I d e n t i f i c a t i o n o f 7 w a s m a d e b y i t s m e l t i n g p o i n t , i t s a n a l y s i s , a n d b y th e p r e p a r a t i o n of t w o d e r i v a t i v e s . T h e m e l t in g p o i n t o f 7 was 1 8 6 . 5 - 1 8 7 . 5 ° , a s c o m p a r e ^ w i t h th e l i t e r a t u r e v a l u e s o f 1 8 4 . 5 ° ( 1 9 ) a n d 189° ( 8 0 ) . The te tr a b r o m o d e r i v a t i v e m elted a t 1 9 6 - 1 9 8 ° , a s compared w i t h t h e . ' l i t e r a t u r e v a lu e o f 3 01° (3 0 ). The m ethy l e t h e r m e lte d a t 1 3 5 .0 - 1 3 5 .5 ° , as compared t o t h e l i t e r a t u r e v a lu e o f 135° ( 1 9 ) . The f o r m a tio n o f 4 - s t i l b e n o l (¥) was p r o b a b le th ro u g h t h e d e h y d r a t i o n , b e f o r e or d u r i n g d i s t i l l a t i o n , o f one o r b o th o f two compounds. The f i r s t compound, 3 - ( 4 - h y d r o x y - p b e n y l ) - l - p h e n y l e t h a n o l , c o u ld h a v e b een form ed by n u c l e a r a t t a c k o f th e > < 9 - c a r b o n o f s t y r e n e o x id e on p h e n o l. The second concound, l - ( 4 - h y d r o x y p h e n y l ) - 3 - p h e n y l e t h a n o l , c o u ld have r e s u l t e d from th e a c i d - c a t a - - l y 2 ed c o n d e n s a tio n o f p h e n y la c e ta ld e h y d e w ith p h e n o l. T h is l a s t r e a c t i o n seemed th e more p r o b a b le b e c a u s e s t y r e n e o x id e has b e e n d e m o n s tr a te d t o r e a r r a n g e t o p h e n y l a c e t a l d e hyde u n d er c o n d i t i o n s s i m i l a r t o th o s e em ployed i n t h i s r e a c t i o n ( 1 3 ) . To f i n d i f th e a c i d - c a t a l y z e d r e a c t i o n o f p h e n y la c e ta l d e h y d e and Dhenol l e d t o V, an e x p e rim e n t was c o n d u c te d in which th e a c i d - c a t a l y z e d r e a c t i o n o f p h e n y l- a e e t r l d e h y d e and p hen o l was e f f e c t e d u n d e r c o n d i t i o n s s im i l a r t o t h o s e o f th e a o i d ~ c a t a l y z e d r e a c t i o n s o f s t y r e n e 2 - (4 -H y d ro x y p h e n y l) 1 - p h e n y l e th a n o l ■ l - ( 4 - H y d r o x y p h e n y l ) - 3 -ph e n y l e t h a n o l - 3 3 - o x id e and p h e n o l. By c r y s t a l l i z a t i o n o f th e p r o d u c t i t was p o s s i b l e t o s e p a r a t e i n 2 0 .4 $ y i e l d a compound m e l t in g a t 1 3 9 - 1 4 0 ° . The a n a l y s i s o f t h i s compound c o rre s p o n d e d t o a compound r e s u l t i n g from th e c o n d e n s a tio n o f two m oles o f p h e n o l p e r mole of p h e n y la c e ta l d e h y d e . Both t h e a n a l y s i s and m e l t in g p o i n t c o rre s p o n d e d t o 1 , 1 - b i s (4 - h y d r o x y p h e n y l) - 2 - p h e n y le th a n e ( V I I ), a s r e p o r t e d by Cam pbell ( 2 1 ) . A tte m p ts t o c r y s t a l l i z e o t h e r p r o d u c t s from t h e r e a c t i o n m ix tu r e were u n s u c c e s s f u l ; however vacuum d i s t i l l a t i o n o f t h e m other l i q u o r gave t h e e x p e c te d 4— s t i l b e u o l (V) in 6 .4 $ y i e l d . B ecause lo n g r e a c t i o n tim e s l e d t o th e d i s a p p e a r a n c e o f I and I I from th e r e a c t i o n m ix tu r e , i t seemed p o s s i b l e t h a t th e i s o l a t e d a l k a l i - s o l u b l e p r o d u c t s m ight have r e s u l t e d from r e a c t i o n s i n which I and I I were i n t e r m e d i a t e s . To t e s t t h i s h y p o t h e s i s , I was r e a c t e d w ith p h e n o l i n a 1 : 6 r a t i o i n t h e p r e s e n c e o f HOTs f o r one h o u r a t 7 0 ° . S e p a r a t i o n and d i s t i l l a t i o n of t h e a l k a l i - s o l u b l e p r o d u c t s in t h e u s u a l manner gave 1 8 .5 $ o f I I I , 1 4 .6 $ o f IV, and 3 .9 $ of V. In a d d i t i o n , 0 .7 4 $ o f V II was o b t a i n e d . The r e a c t i o n was th e n r e p e a t e d w ith th e tim e re d u c e d t o s e v e n m in u te s . In t h i s c a s e 78$ o f t h e s t a r t i n g m a t e r i a l , i I , was r e c o v e r e d , t h e r e b y p r e c l u d i n g t h e p o s s i b i l i t y t h a t I was th e n e c e s s a r y i n t e r m e d i a t e f o r I I I , IV, and V. Com parable c o n d i t i o n s were employed f o r th e r e a c t i o n o f I I w ith p h e n o l. A l k a l i - s o l u b l e p r o d u c t s were - 3 4 — o b t a i n e d , b u t a t t e m p t s t o i s o l a t e and i d e n t i f y them were u n s u c c e s s fu l,, The f o r m a tio n o f a l k a l i - s o l u b l e p r o d u c t s from th e r e a c t i o n o f I and I I w ith p h e n o l u n d e r c o n d i t i o n s o f a c i d - c a t a l y s i s c o u ld -b e e x p e c te d , s in c e a l k y l a t i o n o f phen ol e t h e r s o f p h en y l c a r b i n o l e h a s b een shown t o o c c u r u n d e r c o n d i t i o n s o f a c i d - c a t a l y s i s ( 2 1 ). The fo r m a tio n o f VII a p p a r e n t l y c o u ld h av e r e s u l t ed o n ly from th e a c i d - c a t a l y z e d e t h e r c le a v a g e and s u b s e q u e n t r e a rr a n g e m e n t o f I t o p h e n y la c e ta ld e h y d e , fo llo w e d by c o n d e n s a tio n w ith p h e n o l. T h is p r o d u c t was p r o b a b ly a l s o p r e s e n t i n t h e p r o d u c t o f t h e r e a c t i o n o f s t y r e n e o x id e and p h e n o l. I t c o u ld have been e a s i l y o v e rlo o k e d i n t h e m ix tu r e b e c a u s e i t was n o t r e a d i l y c r y s t a l l i z e d . The e f f e c t of s o l v e n t s on th e a c i d - c a t a l y z e d r e a c t i o n was i n v e s t i g a t e d t o a v e ry l i m i t e d e x t e n t . I n to lu e n e a c o n s i d e r a b l e i n c r e a s e i n th e y i e l d o f e t h e r - a l c o h o l s o c c u r r e d ; however th e r a t i o o f I to I I was unchanged from t h e r a t i o i n t h e r e a c t i o n w ith o u t s o l v e n t . The e f f e c t o f t h e d io x a n e a s a s o lv e n t was a p p a r e n t l y t h a t o f a s o lv e n t more b a s i c t h a n s t y r e n e o x id e . The h i g h e r b a s i c i t y o f d io x a n e p r e v e n t e d th e i n i t i a t i o n o f t h e a t t a c k o f t h e p r o t o n on t h e o x id e r i n g . I n t h i s way d io x a n e f u n c t i o n e d i n a s i m i l a r manner w ith b o th a c i d and p h e n o l. Thus, th e slow a c i d - c a t a l y z e d r e a c t i o n i n d io x an e was t o be e x p e c te d . There were some s i m i l a r i t i e s i n th e r e a c t i o n of s t y r e n e o x id e w ith e x c e s s p henol a s a s o l v e n t w hether t h e c a t a l y s t was an a c i d o r a b a s e . B oth r e a c t i o n s were c h a r a c t e r i z e d by th e f o r m a tio n o f p re d o m in a n tly th e p r i mary e t h e r - a l c o h o l ( i ) and by th e f o r m a tio n o f p r im a ry p h e n o l - a l c o h c l s , T h is would s u p p o rt a s i m i l a r mechanism i n b o th r e a c t i o n s . On th e o th e r h an d , t h e a c i d - c a t a l y z e d r e a c t i o n l e d t o th e f o r m a tio n of p r o d u c t s which a p p e a re d t o r e s u l t from th e a c i d - c a t a l y z e d re a r r a n g e m e n t o f s t y r e n e o x id e t o p h e n y la c e ta l d e h y d e . I f t h i s a c i d - c a t a l y z e d r e a rr a n g e m e n t p ro c e d e d th ro u g h t h e i n i t i a l f o r m a tio n o f th e c o n ju g a te a c i d or carbo niu m io n o f s t y r e n e o x id e , i t rnight have b een e x p e c te d t h a t a s i m i l a r re a rr a n g e m e n t would have o c c u r r e d i f t h e s t y r e n e o x id e formed a con j u g a t e a c i d o r a carbonium io n i n th e b a s e - c a t a l y z e d r e a c t i o n . No e v id e n c e was found f o r such a r e a rr a n g e m e n t of s t y r e n e o x id e t o p h e n y la c e ta ld e h y d e i n th e b a s e - c a t a l y z e d r e a c t i o n . The a c i d - c l e a v a g e o f I i n e x c e s s p h e n o l l e d t o y i e l d s o f v a r i o u s a l k a l i - s o l u b l e p r o d u c ts ?/hich were v e ry s i m i l a r t o t h e y i e l d s of th e a l k a l i - s o l u b l e p r o d u c ts from th e a c id - c a t a l y z e d r e a c t i o n of s t y r e n e o x id e and p h e n o l. T h is seem s t o s u g g e s t a common i n t e r m e d i a t e which m ight have b e e n a carb oniu m io n , or p o s s i b l y , th e c o n ju g a te a c i d of s t y r e n e o x id e . The o v e r a l l a c i d - c a t a l y z e d r e a c t i o n of s t y r e n e o x id e w ith p h en o l i s i n d i c a t e d i n th e f o l lo w in g e q u a t i o n s : -c§ - ch2 * h A U M k W f l A 0 C Z > 6 h -o h 3 oh -h I j - ' 1 i - j. H 0 H-CHgO I I OH 0OH i ‘0 ^ ' Q . W \sr=3r 0 H H OH O H - O H a O ^ ^ VI v\ / / OH if VcHoCHO H -r 0 OH OH3 CHOH - h8 o / \ H 0 OH K ^ O E __ { " " " Y CH~CH2 0H + // ^-O H -C H gO H I I I IV /7~ ~ \ CH=CH OH CHAPTER IV E X P E R I M E N T A L ( 2 2 ) A * G e n e r a l E x p e r i m e n t a l P r o d e d u r e f o r t h e B a s e - c a t a l y ? e d R e a c t i o n o f S t v r e n e O x i d e , T h e b a s e - c o t s l y z e d r e a c t i o n s w e r e c o n d u c t e d i n a V - s h a p e d , t h r e e - n e c k r e a c t i o n f l a s k , w h i c h w a s e q u i p o e d w i t h 2 s t i r r e r , d r o p p i n g f u n n e l , a n d r e f l u x c o n d e n s e r . T h e p h e n o l w a s d i s s o l v e d i n w a t e r a n d s o d i u m h y d r o x i d e w h e n w a t e r w a s t b s s o l v e n t . f c h e n n o n - a p u e o u s s o l v e n t s w e r e " e m p l o y e d , t h e s o d i u m w a s a d d e d ' t o t h e p h e n o l a n d s o l v e n t , e x c e p t w h e n i t w a s c o n s i d e r e d p o s s i b l e t h a t a n i r r e v e r s i b l e r e a c t i o n b e t w e e n t h e s o l v e n t a n d s o d i u m m i g h t r e s u l t . I n t h e s e c a s e s t h e s o d i u m w a s d i s s o l v e d i n t h e p h e n o l b e f o r e t h e s o l v e n t w a s a d d e d . T h e m i x t u r e w a s t h e n b r o u g h t t o t h e d e s i r e d t e m p e r a t u r e i n a s u i t a b l e b a t h , a n d 30 s t y r e n e o x i d e ( n ’J ^ 1 , 5 3 5 3 2 ) w a s a d d e d f r o m t h e d r o p o i n g f u n n e l o v e r t h e p e r i o d i n d i c a t e d i n t h e s u m m a r i e s . T h e p h e n o l a n d t h e s o l v e n t s , o t h e r t h a n d i o x a n e a n d - t e t r a h y d r o f u r a n , w e r e c . p . , a n h y d r o u s p r o d u c t s . T h e d i o x a n e a n d t e t r a h y d r o f u r a n w e r e c o m m e r c i a l g r a d e p r o d u c t s » M c h h a d b e e n r e f l u x e d a t l e a s t s i x h o u r s w i t h Bodium a n d t h e n d i s t i l l e d . S e p a r a t i o n o f t h e i s o m e r s w a s e s s e n t i a l l y t h e s a m e i n a l l r i m s . T h e r e a c t i o n m i x t u r e w a s p o u r e d i n t o 1 0 0 g . o f i c e and w a te r c o n t a i n i n g sodium h y d ro x id e s l i g h t l y i n e x c e s s o f t h a t r e q u i r e d t o r e a c t w ith t h e f r e e p h e n o l i n i t i a l l y p r e s e n t in th e r e a c t i o n m ix t u r e . A f t e r th o ro u g h s h a k in g , th e m ix tu re was e x t r a c t e d w ith t h r e e 35-'CC. p o r t i o n s o f e t h e r . The e t h e r s o l u t i o n was d r i e d o v e r 15 g . o f a n h y d ro u s p o ta s s iu m c a r b o n a t e , and th e e t h e r was removed by e v a p o r a t i o n o v e r a steam b a t h . The r e s i d u e was th en d i s t i l l e d i n a m o d ifie d C la is e n f l a s k p a ck ed w ith 2 W o f l / 8 M g l a s s h e l i c e s . I n most c a s e s s o l v e n t was r e moved a t low t e m p e r a t u r e s a lo n g w ith some s t y r e n e o x id e and , i n some c a s e s , m a t e r i a l which a p p e a re d t o be th e r e a c t i o n p r o d u c t o f s t y r e n e o x ide and t h e s o l v e n t . Col l e c t i o n o f th e p r o d u c t was begun a t 1 3 5 ° / l nun. and was c o n tin u e d t o 1 6 5 ° /1 mm. C ro ssed p o l a r o i d s were u se d t o d e te r m in e th e m e l t in g p o i n t o f th e p r o d u c t i n a Beckman ty p e f r e e z i n g p o i n t a p p a r a t u s , u s i n g an o r d i n a r y therm o m eter. The r e l a t i v e am ounts of I and I I were e s t im a t e d by means o f th e p h ase d ia g ra m r e p o r t e d by Guss ( 1 2 ) . S e p a r a t io n of th e a l k a l i - s o l u b l e p r o d u c t s from th e b a s e - c a t a l y z e d r e a c t i o n m ix tu r e was made i n o n ly one i n s t a n c e (sum m arized i n T ab le I I I ) . A f t e r t h e a l k a l i - i n s o l u b l e m a t e r i a l was removed by e t h e r e x t r a c t i o n , th e a l k a l i n e a q u eo u s s o l u t i o n was slo w ly a c i d i f i e d w ith c o n c e n t r a t e d h y d r o c h l o r i c a c i d . When no f u r t h e r s e p a r a t i o n o f o i l y m a t e r i a l o c c u r r e d , t h e m ix tu r e was e x t r a c t e d w ith “• V u** e t h e r . The e t h e r s o l u t i o n was shaken w ith 10 c c . of s a t u r a t e d sodium b i c a r b o n a t e s o l u t i o n f o llo w e d by two 10 c c . p o r t i o n s o f w a te r . The p h e n o l and e t h e r were d i s t i l l e d o f f u n d e r a s p i r a t o r p r e s s u r e . The r e s i d u e was v a c u u m - d i s t i l l e d i n a m o d ifie d C l a i s e n f l a s k packed w ith 2 W o f 1 / 8 ” g l a s s h e l i c e s . The f i r s t f r a c t i o n , c o l l e c t e d from 1 6 5 - 2 0 0 ° / l mm., weighed 2 .5 6 g. The second f r a c t i o n , c o l l e c t e d from 2 0 0 - 2 1 5 ° / l mm., weighed 1 .6 8 g. A t o lu e n e s o l u t i o n , s a t u r a t e d a t room te m p e r a t u r e , was p r e p a r e d from each o f th e f r a c t i o n s , and upon s t a n d in g each s o l u t i o n d e p o s i te d c r y s t a l l i n e m a t e r i a l . From th e lo w e r b o i l i n g f r a c t i o n 2 - ( 2 - h y d r o x y p h e n y l)- 2 - p h e n y l e t h a n o l ( I I I ) was o b t a i n e d i n 0 .4 0 g. (3.7$>) y i e l d a s c ru d e ma t e r i a l , ra.p. 7 1 -7 4 ° . The h i g h e r b o i l i n g f r a c t i o n y i e l d e d 0 .9 0 g. (8.4$») o f c ru d e 2 - ( 4 - h y d r o x y p h e n y l ) - 2 - p h e n y l - e t h a n o l (IV ), m .p. 8 8 -9 0 ° . I d e n t i f i c a t i o n o f I I I and IV was made by mixed m e l t in g p o i n t d e t e r m i n a t i o n s w ith au t h e n t i c sam p les o f I I I and IV, which were o b ta in e d by a l t e r n a t e s y n t h e s i s d e s c r i b e d e ls e w h e re i n t h i s c h a n t e r . JB. The A d d - c a t a l y z e d R e a c tio n o f S ty r e n e Oxide w ith P h e n o l. A s o l u t i o n o f 5 5 .2 g . ' ( 0 .6 .! m ole) o f p h e n o l and 0 .4 g. (0 .0 0 2 1 ) mole o f HOTs was h e a te d t o 70° i n a 500 o c . round b o tto m f l a s k . To t h i s was added, w ith s t i r r i n g , 1 2 . 0 g. ( 0 . 1 m ole) o f s t y r e n e o x id e a t a r a t e s u f f i c i e n t — 40— - t o m a in ta in th e t e m p e r a tu r e a t 6 9 -7 2 ° w ith o u t e x t e r n a l h e a t i n g . T h is a d d i t i o n r e q u i r e d seven m in u te s , a f t e r which th e r e a c t i o n m ix tu re was ooured im m e d ia te ly i n t o 300 c c . o f c o ld 144 sodium h y d ro x id e s o l u t i o n . The a l k a l i - i n s o l u b l e p r o d u c ts were removed by ex t r a c t i o n w ith f o u r 3 5 - c c . p o r t i o n s o f e t h e r . The e t h e r s o l u t i o n was d r i e d w ith 15 g. of a n h y d ro u s p o ta s s iu m c a r b o n a te , a f t e r which th e e t h e r was removed o ver a steam b a t h . The r e s i d u e was v a c u u m - d i s t i l l e d i n a m o d ifie d C l a i s e n f l a s k h a v in g 2 ". o f 1 / 8 ” g l a s s h e l i c e s a s p a c k in g , and t h e e t h e r - a l c o h o l s , I and I I , were c o l l e c t e d from 1 3 5 - 1 6 5 ° /! mm. i n 3 ,4 4 g. (1 6 .1 $ ) y i e l d , The m e l t i n g p o i n t o f t h e m ix tu r e was 7 8 °, c o rr e s p o n d in g t o a m ix tu re o f is o m e r s c o n t a i n i n g 94$ o f I . A secon d a l k a l i - i n s o l u b l e f r a c t i o n , a v is c o u s m a t e r i a l * w e ig h in g 0 .8 5 g . , was c o l l e c t e d a t 1 6 5 - 2 3 0 ° / l mm. C r y s t a l l i z a t i o n o f t h i s m a t e r i a l from is o p r o p y l, a l c o h o l y i e l d e d 0 .0 8 g» o f f i n e c r y s t a l l i n e p r o d u c t, m.p* 1 2 3 -1 3 4 ° . Seve r a l r e c r y s t a l l i z a t i o n s from i s o o r o o y l a lc o h o l r a i s e d th e m e l t i n g p o i n t t o 1 2 7 - 1 2 7 .5 ° . The a n a l y s i s o f t h e p ro d u c t c o rre s p o n d e d t o t h a t f o r th e d ip h e n y l e t h e r o f p h e n y l g l y c o l ; how ever f u r t h e r e v id e n c e f o r i t s s t r u c t u r e m s n o t o b t a i n e d . A n a l y s i s ; C a l c u l a t e d f o r c ,> 0 ^ 1 8 02 : C, 8 2 ,8 0 ; H, 6 .2 1 . Found; C, 8 3 .3 7 ; H, 6 .2 3 . The a l k a l i n e s o l u t i o n o f th e a l k a l i - s o l u b l e com ponents of t h e r e a c t i o n m ix tu r e was slo w ly a c i d i f i e d . w i t h c o n c e n t r a t e d h y d r o c h l o r i c a c i d u n t i l n o f u r t h e r c l o u d i n e s s w a s b r o u g h t a b o u t w h e n a c i d w a s a d d e d . T h e p h e n o l i c l a y e r r a s t h e n s e p a r a t e d a n d t h e a q u e o u s l a y e r w a s e x t r a c t e d w i t h t w o 2 5 - c c . p o r t i o n s o f e t h e r , w h i c h w e r e c o m b i n e d w i t h t h e p h e n o l i c l a y e r . T h e e t h e r a n d p h e n o l w e r e r e m o v e d f r o m t h e m i x t u r e u n d e r r e d u c e d p r e s s u r e . T h e r e s i d u e w a s t h e n v a c u u m - d i s t i l l e d i n a m o d i f i e d C l a i s e n f l a s h h a v i n g 2 " g l a s s h e l i c e s a s p a c k i n g . A 1 2 . 1 g . y i e l d o f a l k a l i - s o l u b l e p r o d u c t w a s o b t a i n e d f r o m t h e d i s t i l l a t i o n a t 1 2 0 - 2 3 0 ° / l m m . T h i s m s r e d i s t i l l e d o v e r t h e s a m e r a n g e , a n d f i v e c u t s t o t a l l i n g 1 1 . 4 7 g . w e r e o b t a i n e d . T h e i n d i v i d u a l f r a c t i o n s 7 / e r e d i s s o l v e d i n s u f f i c i e n t t o l u e n e t o f o r m a s a t u r a t e d s o l u t i o n a t r o o m t e m p e r a t u r e . T h e s o l u t i o n s w e r e t h e n c o o l e d t o 0 ° f o r 1 5 h o u r s . F r o m t h ’ - e , t h r e e h i g h e s t b o i l i n g f r a c t i o n s 2 . 6 8 g . ( 1 3 . 5 % ) o f I V s e p a r a t e d , a s c r u d e m a t e r i a l , m . p . 8 7 . 0 - 8 9 . 5 ° . A m i x e d m e l t i n g p o i n t s h o w e d t h e m a t e r i a l f r o m t h e r e a c t i o n m i x t u r e t o b e i d e n t i c * ; . ! w i t h I V , m . p . 9 3 - 9 4 ° , p r e p a r e d b y s y n t h e s i s d e s c r i b e d e l s e w h e r e i n t h i s c h a p t e r . F r o m t h e s e c o n d e n d t h i r d f r i c t i o n s 0 . 7 1 g . ( 3 . 1 % ) o f V s e p a r a t e d a s a c r u d e p r o d u c t , m . p . 1 8 0 . 0 - 1 8 2 . 5 ° . M o s t o f t h i s m a t e r i a l c r y s t a l l i z e d o u t a t r o o m t e m p e r a t u r e . U p o n s e v e r a l r e c r y s t a l l i a c t i o n s f r o m t o l u e n e t h e m e l t i n g p o i n t w a s r a i s e d t o 1 8 8 . 5 - 1 8 7 . 5 ° . T h e l i t e r a t u r e v a l u e s f o r t h e m e l t i n g p o i n t o f 4 - e t i l b e n o l ( V ) a r e 1 8 4 . 5 ° ( 1 9 ) a n d - 4 3 - 1 8 9 ° ( ? 0 ) . T h i s p r o d u c t t h e r e a c t i o n m i x t u r e w a s s h o w n b y m i ^ e d m e l t i n g p o i n t t o h e i d e n t i c a l w i t h t h e 4 - e t i l b e n o l ( Y ) , f r o m w h i c h t h e t e t r a b r o m o d e r i v a t i v e a n d t h e m e t h y l e t h e r d e r i v a t i v e w e r e p r e p a r e d * T h e p r e p a r a t i o n o f t h e s e c o m p o u n d s i s d e s c r i b e d e l s e w h e r e i n t h i s c h a p t e r . T h e t o l u e n e s o l u t i o n s o f t h e u n a r y s t a l l i z e d a l k a l i - s o l u b l e p r o d u c t s w e r e r e c o m b i n e d , a n d t h e t o l u e n e w a s r e m o v e d u n d e r a s p i r a t o r p r e s s u r e . T h e r e s i d u e w a s f r a c t i o n a l l y d i s t i l l e d a t 1 4 5 - 3 3 0 ° / ! m m . t o y i e l d t h r e e f r a c t i o n s w h i c h t o t a l e d 5 . 8 4 g . T h e s e f r a c t i o n s w e r e d i s s o l v e d i n w a r m t o l u e n e . U p o n c o o l i n g t o r o o m t e m p e r a t u r e , t h e h i g h e s t b o i l i n g f r a c t i o n d e p o s i t e d 0 . 1 8 g . ( 0 . 5 % ) o f c r u d e V , m . p . 1 7 9 - 1 8 3 ° . T h e t o l u e n e s o l x r f c i o n s m e r e t h e n c o o l e d t o 0 ° a n d s e e d e d w i t h a v e r y f e w s m a l l c r y s t r l s o f I I I . O v e r a p e r i o d o f o n e w e e k 3 . 9 9 g . ( 1 3 . 9 % ) o f i l l c r y s t a l ! ! z e d a s l a r g e c r y s t a l s , m . p . 7 0 - 7 3 ° . M i z e d ' m e l t i n g p o i n t s h o w e d t h i s p r o d u c t t o b e i d e n t i c ? ! w i t h I I I , m . p . 7 6 . 5 - 7 7 . 5 ° , p r e p a r e d b y a n a l t e r n a t e s y n t h e s i s d e s c r i b e d e l s e w h e r e i n t h i s c h a p t e r . T h e a c i d - c s t a l y z e d r e a c t i o n s o f s t y r e n e o x i d e w i t h p h e n o l i n v a r i o u s s o l v e n t s a n d t h e s e p a r a t i o n o f t h e p r o d u c t s w e r e c o n d u c t e d i n a ' m a n n e r w h i c h w a s s i m i l a r t o t h a t d e s c r i b e d f o r t h e a c i d - c a t a l y z e d r e a c t i o n w i t h o u t s o l v e n t , w i t h t h e e z c e p t i o n t t r - ' t e x t e r n a l h e a t i n g w a s r e p a i r e d t o m a i n t a i n t h e t e m p e r a t u r e d u r i n g t h e a d d i t i o n o f s t 3> rr e n e - 4 3 - o x i d e w h e n d i o x a n e w a s e m p l o y e d ? e t h e s o l v e n t . I n a l l c a s e s i n w h i c h t h e r u c t i o n t i m e e x c e e d e d t h e s t y r e n e o x i d e a d d i t i o n t i m e , a h a t h w a s u s e d t o m a i n t a i n t h e r e a c t i o n t e m p e r a t u r e a t 7 0 ° . G o T h e A c i d - c a t a l y z e d R e a c t i o n o f 2 - P h e n y l - 3 - p h e n o r y - e t h a n o l ( X ) w i t h P h e n o l . A s o l u t i o n o f 8 . 0 g . ( 0 . 0 3 7 4 m o l e ) o f I , m . p . 7 6 . 5 - 7 9 . 0 ° , i n 2 0 . 0 g . ( 0 . 3 1 3 m o l e ) o f o h e n o l w a s h e a t e d t o 7 0 ° i n a 1 2 5 c c . E r l e n m e y e r f l a s h . T o t h i s m i x t u r e w a s a d d e d 0 . 1 4 p . ( 0 . 0 0 0 7 3 5 m o l e ) o f H O T s w h i c h w a s d i s s o l v e d b y s t i r r i n g . T h e m i x t u r e w s . s m a i n t a i n e d a t ! 7 0 ° f o r o n e h o u r , a f t e r w h i c h i t w s s p o u r e d , i n t o 1 0 0 c c . o f c o l d 1 8 1 » s o d i u m h y d r o x i d e s o l u t i o n . T h e s e p a r a t i o n o f t h e a l k a l i - i n s o l u b l e a n d . a l k a l i - s o l u b l e f r a c t i o n s w a s a c c o m p l i s h e d b y t h e m e t h o d d e s c r i b e d i n t h e g e n e r a l p r o c e d u r e f o r t h e a c i d - c a t a l y z e d r e a c t i o n o f s t y r e n e o x i d e w i t h p h e n o l . ’E v a p o r a t i o n o f t h e e t h e r s o l u t i o n o f a l k a l i - i n s o l u b l e m a t e r i a l l e f t 1 . 2 3 g . o f m a t e r i a l w h i c h w a s n o t i d e n t i f i e d . ' D i s t i l l a t i o n o f t h e a l k a l i - s o l u b l e m a t e r i a l a t 1 5 5 - 2 5 0 ° / ! m m . g a v e f o u r f r a c t i o n s w e i g h i n g 7 , 6 5 g . F r a c t i o n a l c r y s t a l l i z a t i o n o f t h e s e f r a c t i o n s , a s d e s c r i b e d i n t h e g e n e r a l p r o c e d u r e , g a v e 1 . 4 8 g . ( 1 8 , 5 $ ) o f I I I , m . p . 7 1 - 7 4 ° ; 1 . 1 7 g . ( 1 4 . 0 & ) o f I V , m . p . o f 8 8 - 9 0 ° ; 0 . 3 1 g . ( 3 . 9 ) * ) o f V , m . p . - 4 4 - 1 7 9 -1 8 2 °; and 0 .0 8 g . (0 .7 4 $ ) o f V I I , m .p. 1 3 2 -1 3 4 °. The a c i d - c a t a l y z e d r e a c t i o n o f I w ith p hen o l was r e p e a t e d w ith o n e - h a l f t h e q u a n t i t i e s o r i g i n a l l y em ployed. The tim e o f t h e r e a c t i o n was re d u c e d t o seven m in u te s . S e p a r a t i o n o f t h e a l k a l i - i n s o l u b l e f r a c t i o n by t h e u s u a l p ro c e d u r e gave 78$ o f th e s t a r t i n g m a t e r i a l , I . The a l k a l i - s o l u b l e p r o d u c t s were n o t i n v e s t i g a t e d . Do The A c i d - c a t a l y z e d R e a c tio n o f 3 - F h e n v l- l- p h e n o x y - e th a n o l ( I I ) w ith P h e n o l. A s o l u t i o n o f 4 . 0 g . (0 .0 1 8 7 m ole) o f I I , m .p, 5 8 - 6 1 ° , and 8 ,0 (0 .0 8 5 m ole) o f p h e n o l was h e a t e d t o 70° i n a 50 c c . E rlenm ey er f l a s k . To t h e m ix tu r e was ad d ed 0 .0 5 0 g . (0,00 0 2 6 2 m ole) o f HOTs which was d i s s o lv e d by s t i r r i n g . The m ix tu re was m a in ta in e d a t 70° f o r tw e n ty -tw o h o u r s , a f t e r which th e a l k a l i - s o i u b l e and a l k a l i - i n s o l u b l e com ponents were s e p a r a t e d by th e method d e s c r i b e d i n t h e g e n e r a l p r o c e d u r e . The a l k a l i - i n s o l u b l e r e s i d u e c o n s i s t e d o f 3 .3 0 g . o f v i s c o u s m a t e r i a l which y i e l d e d 1 .3 9 g . o f m a t e r i a l upon d i s t i l l a t i o n a t 1 80 - 2 2 0 ° / l mm. A y i e l d o f 1 .7 5 g . o f a l k a l i - s o l u b l e m a t e r i a l was o b ta in e d by d i s t i l l a t i o n o f th e a l k a l i - s o l u b l e f r a o - t i o n a t 2 1 0 - 2 7 5 ° / l mm. No c r y s t a l l i n e p r o d u c t s c o u ld b e i s o l a t e d from e i t h e r t h e a l k a l i - s o l u b l e o r a l k a l i - i n s o l u b l e f r a c t i o n s . - 4 5 - I £ . T h e 4 c i d - c s t g l y z e d R e a c t i o n o f P h e r i y 1 ? c e t a l d e h y d e 7<1 t h P h e n o l . k s o l u t i o n o f 2 2 . 6 , g . ( 0 . 2 4 m o l e ) o f p h e n o l a n d 0 . 2 0 g . f 0 . 0 0 1 0 5 m o l e ) o f H O T e w a s h e a t e d t o 7 0 ° i n a 1 0 0 c c . r o u n d b o t t o m f l a s k . T o t h i s , 6 . 0 g . ( 0 . 0 5 m o l e ) p l i e n y l a c e t a l d e h y d e ( n n 1 . 5 3 6 6 ) v a s a d d e d o v e r a f i v e m i n u t e p e r i o d d u r i n g ; w r i e r t h e t e m p e r a t u r e w a s 6 9 - 7 2 ° . o T h e m i x t u r e w a s m a i n t a i n e d a t 7 0 f o r o n e h o u r . T h e r e a c t i o n m i x t u r e w a s t h e n d i s s o l v e d i n 5 0 c c . o f e t h e r a n d s h a k e n w i t h 1 0 c c . o f s a t u r a t e d s o d i u m b i c a r b o n a t e s o l u t i o n , f o l l o w e d b y t v . o 1 0 - c c . p o r t i o n s o f w a t e r . T h e p h e n o l a n d e t h e r w e r e r e m o v e d b y d i s t i l l a t i o n o f e v e r y t h i n g b o i l i n g b e l o w 1 0 0 ° / 2 m m . , a n d t h e r e s i d u e w a s d i s s o l v e d i n 5 0 c c . o f h o t t o l u e n e . U p o n c o o l i n g , t h e s o l u t - ' o n d e p o s i t e d 3 . 0 0 g . ( 2 0 . 4 $ ) o f c r u d e 2 , 2 - b i s ( 4 ~ h y d r o x v p h e n y l ) - l - p h e n y l e t h a n e ( V I I ) , m . p . 1 1 5 - 1 2 6 ° . S e v e r a l r e c r y s t a l l i n a t i o n s f r o m t o l u e n e r s i s e d t h e m e l t i n g p o i n t t o 1 3 9 - 1 4 0 ° . T h e m e l t i n g o o i n t r e p o r t e d f o r V I I i s 1 4 0 ° ( S I ) . A n s l ^ s i s : C a l c u l a t e d f o r C ^ q H ^ C s : C , 8 2 . 8 0 ; F , 6 . 2 1 . F o u n d : C , 8 7 . 8 5 ; H , 8 . 1 5 . T h e t o l u e n e s o l u t i o n w a s t h e n c o o l e d t o . 0 ° f o r o n e w e e k d u r i n g v k i c h s. s m a l l a d d i t i o n a l a m o u n t o f V I I s e o a - r a t e d . T h e c o l d s o l u t i o n w a s f i l t e r e d , a n d t h e t o l u e n e w a s r e m o v e d u n d e r a s p i r a t o r p r e s s u r e . T h e r e s i d u e w a s - 4 6 - d i e t i l l e d a t 1 mm. The d i s t i l l a t e , c o l l e c t e d up t o ' 3 5 0 ° / l • mm., w eighed 3 .8 g. and y i e l d e d 0 .6 g. ( 6 . 1 1 $ ) o o f 7 , m .p. of 1 8 6 .5 - 1 8 7 .5 , upon c r y s t a l l i z a t i o n from t o l u e n e . A n aly si s : C a lc u la t e d f o r C^4 % 2 0 : C, 8 5 .7 0 ; H, 6 . 1 3 . Found: C, 8 5 .7 0 ; H, 6 .2 1 . F . P r e p a r a t i o n o f o ( - ( 4 -H v d ro x y p h e n v l) - p h e n v l a c e t i c Acid and th e L ac to n e o f o<- ( 2 -H y d ro x y p h e n y l) - p h e n v l a c e t i c A c id . The method o f B i s t r z y c k i and F l a t a u (24) was used t o p r e p a r e o < - ( 4 - h y d r o x y p h e n y l) - p h e n y la c e tic a c i d and t h e l a c t o n e o f - ( 2 - h y d r o x y p h e n y l ) - p h e n y l a c e t i c a c i d . A m ix tu r e o f 50 g. (0 .3 3 m ole) m a n d e lic a c i d and 70 g. ( 0 .7 4 m ole) o f phen o l was d i s s o l v e d i n 200 c c . o f c o ld 73$ s u l f u r i c a c i d i n a 500 c c . E rle n m e y er f l a s k . The s o l u t i o n was h e a t e d slo w ly on a steam b a t h so t h a t a t e m p e r a tu r e o f SO0 was a t t a i n e d a f t e r tw e n ty m in u te s . The s o l u t i o n was th e n h e a t e d r a p i d l y by a flam e t o 1 2 5 °. T h is te m p e r a t u r e was m a in ta in e d f o r two m in u te s , a f t e r w hich th e s o l u t i o n was c o o le d by an i c e b a t h . The r e a c t i o n m ix tu re was po ured i n t o 500 c c . o f c o ld w a te r and e x t r a c t e d w ith 300 c c . o f e t h e r which was s u b s e q u e n tly washed w ith 100 c c . o f c o ld w a t e r . The e t h e r was t h e n e x t r a c t e d w ith 300 c c . o f 10$ sodium b i c a r b o n a t e s o l u t i o n t o remove t h e - 4 7 - o < - ( 4 - h y d r o x y p h e n y l ) - p h e n y l a c e t i c a c i d . A t t h i s p o i n t s o m e l a c t o n e o f t h e o ( - ( 2 - h y d r o x y p h e n y l ) - p h e n y l a c e t i c i a c i d p r e c i p i t a t e d . I t v a e r e m o v e d b y f i l t e r i n g b o t h t h e a q u e o u s a n d e t h e r l a y e r s . A f t e r f i l t r a t i o n , t h e a q u e o u s l a y e r v a s b o i l e d t o r e m o v e t h e d i s s o l v e d e t h e r , a n d a s m a l l a m o u n t o f l a c t o n e w h i c h p r e c i p i t a t e d w a s r e m o v e d b y f i l t r a t i o n . T h ^ a q u e o u s s o l u t i o n w a s a c i d i f i e d a n d t h e c < - ( 4 - h y d r o x y p h e n y l ) - p b e n y l a c e t i c a c i d s e p a r a t e d a s a n o i l w h i c h s o l i d i f i e d t o a w a x y s o l i d o n s t a n d i n g . T h e s o l i d i f i e d p r o d u c t , r e m o v e d b y f i l t r a t i o n , w e i g h e d 2 0 . 2 g . T h e p r o d u c t w a s h e a t e d w i t h 3 0 0 c c . o f t o l u e n e , b u t o n l y p a r t i a l s o l u t i o n o c c u r r e d . T h e h o t t o l u e n e s o l u t i o n w a s t r e a t e d w i t h c h a r c o a l a n d a l l o w e d t o c o o l . U p o n c o o l i n g , 3 . 8 g . o f c < - ( 4 - h y d r o x y p h e n y l ) - p h e n y l a . c e t i c a c i d s e p a r a t e d a s a w h i t e p o w d e r , m . p . 1 7 1 - 1 7 3 ° . T h e r e p o r t e d m e l t i n g p o i n t , o f c < - ( 4 - b y d r o x y p h e n y l ) - o h e n y l a c e t i c a c i d * i s 1 7 5 ° ( 2 4 ) . T h e e t h e r s o l u t i o n c f t h e l a c t o n e o f ( 4 - h y d r oxy p h e n y l ) - p h e n y l a c e t i c a c i d w a s e v a p o r a t e d , a n d t h e r e s i d u e w a s a d d e d t o t h e l a c t o n e c o l l e c t e d b y f i l t r a t i o n . T h e c r u d e y i e l d w a s 2 4 , 5 g . ( 3 5 , 5 $ ) o f t h e p r o d u c t , m . o . 1 1 1 - 1 1 2 ° . B e c r y s t a l l i z a t i o n f r o m t o l u e n e g a v e c r y s t a l s , m . p . 1 1 3 - 1 1 4 ° . T h e r e p o r t e d m e l t i n g p o i n t o f o q - ( 4 - h y d r o x y - u h e n y l ) - p h e n y l ? . c e t i c a c i d i s 1 1 3 - 1 1 4 ° ( 2 4 ) . - 48- G. P r e p a r a t i o n o f 2 - ( 3 - H v d r o x y p h e n y l) - 3 - p h e n v le th a n o l ( I I I ) . P r e p a r a t i o n o f 2 - ( 2 - h y d r o x y p h e n y l) - 3 - p h e n y le th a n o l was a c c o m p lish e d th ro u g h t h e r e d u c t i o n o f t h e l a c t o n e o f th e c o r r e s p o n d in g a c i d w ith l i t h i u m aluminum h y d r id e by th e g e n e r a l m ethod o f Uystrom and Brown ( 2 5 ) P A s o l u t i o n of 2 0 .1 g . (0 .0 9 9 m ole) o f th e l a c t o n e o f c K - ( h y d r o x y p h e n y l ) - 2 - p h e n y l a c e t i c a c i d , m .p. 1 1 1 - 1 1 2 ° , i n 150 c c . o f a b s o l u t e e t h e r was slo w ly added t o 4 .7 5 g. (0 .1 2 5 m ole) o f l i t h i u m h y d r id e d i s s o l v e d i n 150 c c . of a b s o l u t e e t h e r i n a 1 - l i t e r t h r e e - n e c k f l a s k eq u ip p e d w ith s t i r r e r and r e f l u x c o n d e n s e r . The 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 o v e r a steam b a th a n d t h e n h y d ro ly z e d by th e slow a d d i t i o n o f w a te r fo llo w e d by 1 0 $ o f s u l f u r i c a c i d t o c l a r i f y t h e m ix t u r e . . The e t h e r l a y e r was washed w ith 1 0 0 c c . o f 1 0 $ sodium b i c a r b o n a t e s o l u t i o n and d r i e d o v e r p o ta s s iu m c a r b o n a t e . E v a p o r a tio n o f t h e e t h e r l e f t 19*23 g. (91$) o f c ru d e 2 - ( 2 - h y d r o x y p h e n y l) - 2 - p h e n y l- e th a n o l ( I I I ) , m .p. 7 0 -7 2 ° . R e c r y e t a l l i z a t l o n from t o l u e n e gave f i n e g r a n u l a r c r y s t a l s , m .p . 7 8 .5 - 7 7 . 5 ° . A n a l y s i s ; C a l c u l a t e d f o r c;j.4 H1 4 0 2 : C, 7 8 .4 8 ; H, 6 .5 9 . fo u n d ; C, 7 8 .4 4 ; H, 6 .4 3 , H. P r e p a r a t i o n o f 2 - ( 4 -H y d ro x y p h e n y l) - 2 - p h e n y le th a n o l ( I V ) . The g e n e r a l method o f Nystrom and Brown (25) was employed t o r e d u c e c < - ( 4 - h y d r o x y p h e n y l ) - p h e n y l a c e t i e a c i d t o t h e c o r r e s p o n d i n g a l c o h o l . - 4 y - A s o l u t i o n o f 3 . 1 8 g . ( 0 . 0 0 9 6 m o l e ) o f o < - ( 4 - h y d r o x y - u h e n y l ) - o h e n y l r - c e t i c a c i d , m . o . 1 7 1 - 1 7 3 ° , i n 1 5 c c . o f a b s o l u t e e t h e r w a s a d d e d s l o w l y t o a s o l u t i o n o f 0 . 5 4 g . ( 0 . 0 1 4 0 m o l e ) o f l i t h i u m h y d r i d e i n 2 0 c c . o f a b s o l u t e e t h e r i n a s t i r r e r a n d r e f l u x c o n t i e n s e r - e ' u i i p p e d r e a c t i o n f l a s k . T h e m i x t u r e ~ a . s r e f l u x e d f o r t w e n t y m i n u t e s a i f d t h e n h y d r o l y z e d w i t h w a t e r , f o l l o w e d b y 3 0 $ > o f s u l f u r i c a c i d t o c l a r i f y t h e m i x t u r e . T h e e t h e r l a y e r w a s w a s h e d w i t h 2 5 c c . o f 1 0 # s o d i u m b i c a r b o n a t e s o l u t i o n a n d d r i e d o v e r p o t r i s s i u m c a r b o n a t e . E v a p o r a t i o n o f t h e e t h e r s o l u t i o n l e f t 0 . 9 g . ( 4 6 # ) o f c r u d e 2 - ( 4 - h y d r o x y p h e n y l ) - 2 - p h e n y l e t h a n o l ( I V ) , m . o . o 8 5 - 8 8 . R e c r y s t e l l i s a t i o n o f t h e p r o d u c t f r o m t o l u e n e g a v e f i n e n e e d l e s , m . p . 9 3 - 9 4 ° . A n a l y s i s : C e lg u la te d f o r C H O * C, 7 8 ,8 ; H, 14 14r 2 6 . 5 9 . F o u n d : C , 7 8 . 5 0 ; H , 6 . 5 7 . Preparation of 1 , 2-D ibro^o-l- ( 3 .5 -d lbrorro-4-hvdroxy- phenyl)-2-phenvlethene. T h e m e t h o d o f Z i n c k e a n d G - ^ i b e l ( 2 0 ) w a s u s e d t o p r e p a r e 1 , 2 - d i b r o m o - l - ( 3 , 5 - d i b r o r * o - 4 - h y d r o x y p h e n y l ) - 2 - p h e n y l e f h a n e . A s o l u t i o n o f 0 . 5 0 g . ( 0 . 0 0 3 9 m o l e ) o f 4 - s t i l b e n o l ( V ) , m . p . 1 8 4 - 1 8 6 ° , i n 2 0 c c . o f g l a c i a l a c e t i c a c i d w h s h e a t e d t o r e f l u x t e m p e r a t u r e i n a 5 0 c c . E r l e n m e y e r f l a s k . T o t h e r e f l u x i n g s o l u t i o n w a s s l o w l y a d d e d 0 . 5 c c . o f b r o m i n e . T h e s o l u t i o n w a s t h e n c o o l e d - 5 0 - t o room t e m p e r a t u r e , and 0 .4 3 g, (17%) o f 1 ,3 - d ib r o m o - l - ( 3 ,5 - d i b r o m o - 4 - h y d r o x y p h e n y l ) - 2 - p h e n y l e t h a n e was ob t a i n e d a s f i n e w h ite n e e d l e s . The p r o d u c t m e lte d a t 1 9 6 -1 9 8 ° upon r e c r y s t a l l i z a t i o n from t o l u e n e . The m e l t i n g p o i n t r e p o r t e d i n t h e l i t e r a t u r e was 2 0 1 ° ( 2 0 ) . J . P r e p a r a t i o n o f 4 - M e t h o x y s t il b e n e . The m e th y l e t h e r o f 4 - e t i l b e n o l (7 ) was p r e p a r e d by th e method d e s c r i b e d by F i e s e r ( 3 6 ) . C o n c e n tra te d sodium h y d ro x id e s o l u t i o n was added d ro p w is e t o a s u s p e n s io n o f 2 . 0 g. (0 .0 1 0 1 m ole) o f 4 - s t i l b e n o l (7) i n 1 0 0 co. o f h o t w a te r u n t i l a c l e a r s o l u t i o n was ob t a i n e d . M ethyl s u l f a t e was t h e n a d d ed , a few d ro p s a t a tim e u n t i l t h e s o l u t i o n was a c i d t o l i t m u s . Sodium h y d r o x id e was a g a i n added u n t i l th e s o l u t i o n became a l k a l i n e . M ethyl s u l f a t e and sodium h y d r o x id e were added a l t e r n a t e l y u n t i l no f u r t h e r s e p a r a t i o n o f t h e e t h e r o c c u r r e d . The p r o d u c t was f i l t e r e d o f f and washed w ith 1% o f sodium h y d ro x id e s o l u t i o n fo llo w e d by w a te r . The y i e l d o f t h e c ru d e p r o d u c t , m e l t in g a t 1 2 7 -1 2 9 °, was 3 .1 5 g. (1(X%). R e c r y s t a l l i z a t i o n from a lc o h o l gave l i g h t c o l o r l e s s p l a t e l e t s o f 4 - m e t h o x y s t i l b e n e , m .p. o f 1 3 5 .0 - 1 3 5 . 5 ° . The l i t e r a t u r e v a lu e f o r th e m e l t i n g p o i n t was 135° (1 9 ). CHAPTER V SUMMARY A s tu d y h a s b e e n made o f th e c o u rs e o f th e r e a c t i o n o f s t y r e n e o x id e w ith p h e n o l u n d e r v a r i o u s c o n d i t i o n s o f te m p e r a t u r e , s o l v e n t , and c a t a l y s t . From t h e " b a s e -c a ta ly z e d r e a c t i o n t h e e t h e r - a l c o h o l s , 2 - p h e n y l - 2 - p h e n o x y e th a n o l ( I ) and l - p h e n y l - 3 - p h e n o x y e th a n o l ( I I ) were o b ta in e d a s m ix tu r e s i n which I c o n s t i t u t e d from 2 8 -9 5 $ o f th e t o t a l . The y i e l d of I r e l a t i v e t o t h a t o f I I was found t o be i n c r e a s e d by th e u se o f h y d r o x y l ic s o l v e n t s and by low r e a c t i o n t e m p e r a t u r e . The r a t e o f t h e b a s e - c a t a l y z e d r e a c t i o n of s t y r e n e o x id e w ith oh en ol i n v a r i o u s s o l v e n t s was foun d to d e c r e a s e i n th e o r d e r , p h e n o l^ m e th a n o l> e th a n o l)/ d io x a n e . The r a t e o f r e a c t i o n o f s t y r e n e o x id e w ith o h e n o l i n th e a b se n c e o f s o l v e n t was found t o be in d e p e n d e n t o f b a s e c o n c e n t r a t i o n . These r e s u l t s a r e I n t e r p r e t e d i n th e l i g h t o f c u r r e n t l y fa v o re d m echanism s. P r o d u c ts o f n u c l e a r a t t a c k , 2 - ( 2 - h y d r o x y p h e n y l) - 2 - p h e n y le th a n o l ( I I I ) and 2 - ( 4 - h y d r o x y p h e n y l) - 2 - p h e n y le th a n o l ( IV ), were o b t a i n e d from b o th t h e a c i d - c a t a l y z e d and b a s e - c a t a l y z e d r e a c t i o n s i n e x c e s s o h e n o l. These were i d e n t i f i e d by c o m p a riso n w ith a u t h e n t i c s a m p le s . From t h e a c i d - c a t a l y z e d r e a c t i o n , 4 - s t i l b e n o l (V) was i s o l a t e d and i d e n t i f i e d by th e p r e p a r a t i o n o f d e r i v a t i v e s . A lso o b t a i n e d from t h e a c i d - c a t a l y z e d r e a c t i o n was t h e d ip h e n y l e t h e r o f o h e n y l g l y c o l (V I), th e s t r u c t u r e o f which was i n f e r r e d from th e a n a l y s i s . The p rim a ry e t h e r - a l c o h o l , I , was found t o r e a c t w ith ohenol i n th e p r e s e n c e o f a c i d t o y i e l d I I I , IV, V, and 3 , 3 - b i s ( 4 - h y d r o x y p h e n y l ) - l - p h e n y l e t h a n e ( V I I ). The i d e n t i f i c a t i o n o f V II was made by m e l t i n g p o i n t and a n a l y s i s . I t was shown t h a t th e f o r m a tio n o f - I I I , IV, and V by t h e a c i d - c a t a l y z e d r e a c t i o n o f s t y r e n e o x id e w ith ph en ol d i d n o t n e c e s s a r i l y r e s u l t th r o u g h th e i n t e r m e d i a t e f o r m a tio n o f I . I t was d e m o n s tr a te d t h a t V and V II were form ed from th e r e a c t i o n o f p h e n y la c e ta ld e h y d e and p h e n o l. BIBLIOGRAPHY (1) B ro n s te d , K i l p a t r i c k , and K i l p a t r i c k , J_. Am. Chem. S o c ., 51, 428 (1 9 2 9 ). ( 2 ) Chitwood and F r e u r e , J . Am. Chem. S oc. . 68. 680 (1 9 4 6 ). (3) S ex to n and B r i t t o n , J . Am. Chem. Soc. . 7 0 . 3606 (1 9 4 8 ). (4) Boyd and M a rie, J . Chem. Soc. . 1 0 5 . 3117 (1 9 1 4 ). (5 ) K adesch, J . Am. Chem. Soc. . 68. 41 (1 9 4 6 ). (6 ) B a r t l e t t and R o ss, J . Am. Chem. S o c . . 7 0 . 926 (1 9 4 8 ). (7) Swern, B i l l e n , and K n ig h t, J . Am. Chem. S oc. . 7 1 . 1152 (1 9 4 9 ). (8) Van Tam elen, Van Z yl, and Zuidema, J . Am. Chem. Soc. . 72, 488 (1 9 5 0 ). (9 ) R u s s e l l and V anderW erf, J . Am. Chem. S oc. . 6 9 . 11 (1 9 4 7 ). (1 0 ) Gilman and F u l h a r t , J . Am. Chem. S oc. . 7 1 . 1478 (1 9 4 9 ). (1 1 ) Reeve and C h r i s t o f f e l , J . Am. Chem. Soc. . 7 2 . 1480 (1 9 5 0 ). (1 2 ) G uss, J . Am. Chem. S o c. . 7 1 . 3460 (1 9 4 9 ). (1 3 ) Guss and J u l e s , J . Am. Chem. Soc. . (1 9 5 0 ), I n P r e s s . - 5 4 - (14) W in s te in and H e n d erso n , H e t e r o c y c l i c Compounds, E l d e r f i e l d , e d i t o r , New York: Jo h n W iley and Sons, I n c . , 1950, p . 1 . (1 5 ) Day, E l e c t r o n i c Mechan1 sms o f O rg a n ic R e a c t i o n s . F i r s t e d i t i o n ; New Y ork: A m erican Book Company, 1950, p. 105. (1 6 ) A le x a n d e r, P r i n c i p l e s o f I o n i c O rg an ic R e a c t i o n s , F i r s t e d i t i o n ; New York: Jo h n W iley and Sons, I n c . , 1950, p . 323. (1 7 ) Hughes, J . Chem. Soc. . 968 (1 9 4 6 ). (18) E r r e r a and Sack, T r a n s . F a r . S o c ., 34, 728 (1 9 3 8 ). (1 9 ) H e w itt, Lewcock, and Pope, J . Chem. S o c ., 1 0 1 . 605 (1 9 1 2 ). (2 0 ) 2 in ck e and G e i b e l , Ann. . 3 4 9 . I l l (1 9 0 6 ). (2 1 ) C am pbell, P r o c . Roy. Soc. B, 1 2 9 . 528 (1 9 4 0 ). (2 2 ) P r a t t , P r e s t o n , and D ra p e r, J . Am. Chem. Soc. . 7 3 . 1367 (1 9 5 0 ). (2 3 ) M e ltin g p o i n t s a r e u n c o r r e c t e d ; m i c r o a n a l y s i s f o r c a rb o n and h y d ro g en were p e rfo rm e d by Mr. J . P i r i e a t t h e 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 , Los A n g e les, C a l i f o r n i a and by E lek M icro A n a l y t i c a l L a b o r a t o r i e s , Los A n g e le s, C a l i f o r n i a . (3 4 ) B i s t r z y c k i and F l a t a u , B e r ., 28, 989 ( 1 8 9 5 ) , B e r . . 30, 130 (1 8 9 7 ). - 5 5 - "(25) Nyetrom and Brown, J . Am. Chem. Soc. . 6 9 . 2548 (1 9 4 7 ). (2 6 ) F i e s e r , E x p e rim e n ts in O rganic C h e m is tr y . Second e d i t i o n ; B oston: D. C. H eath and Company, 1941, p . 374. University of Southern California Literar?

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Creator Williams, Homer R (author)

Core Title The reaction of styrene oxide with phenol

Degree Master of Science

Degree Program Chemistry

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

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Language English

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Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-792062

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Rights Williams, Homer R.

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

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