Date of Graduation

1972

Document Type

Dissertation/Thesis

Abstract

I n a l l o f th e a lc o h o l o x id a tio n s r e f e r r e d to p r e v io u s ly , th e a lc o h o l was c o n v e rte d to some o th e r s u b s ta n c e (_e._g., t o s y l a t e , h a lid e ) b e fo re r e a c t i o n w ith DMSO. Many a lc o h o ls , how ever, have b een a llo w e d to r e a c t w ith DMSO w ith o u t p r i o r c o n v e rs io n . 49 T r a y n e lis e t a l . found t h a t d e h y d ra tio n was th e u s u a l r e s u l t when s e c o n d a ry and t e r t i a r y b e n z y lic a lc o h o ls o r t e r t i a r y a l i p h a t i c a lc o h o ls w ere h e a te d a t 160-185° in DMSO f o r n in e to s ix te e n h o u rs (e q u a tio n s 53 and 5 4 )- The d e h y d ra tio n o f e le v e n OH c e 3 ch 3 (C g H ^C -O H (C2a5 ) 2C-0HCH3 78f. (54) a lc o h o ls was r e p o r te d , and e v id e n c e s u g g e s te d a carbonium io n m echanism . 50 A s u b se q u e n t m o d if ic a tio n o f r e a c t i o n c o n d itio n s ^ p e rm itte d th e d e h y d ra tio n o f a lc o h o ls p r e v io u s ly found to be r e s i s t a n t . A h ig h e r r e a c t i o n te m p e ra tu re (190°) was n e c e s s a r y , a s w e ll a s e x te n d e d r e a c t i o n tim e s (48 h o u r s ) . 1 -A lk y lc y c lo a lk a n o ls w ere a ls o r e p o r te d to d e h y d ra te , b u t p in a c o ls n o t o n ly d e h y d ra te d b u t r e ­ a rr a n g e d . T h is l a t t e r o b s e r v a tio n , a s w e ll a s th e fo rm a tio n o f e t h e r a s w e ll a s o l e f i n i n some e x p e rim e n ts , f u r t h e r r e in f o r c e d th e carbonium io n h y p o th e s is , a lth o u g h no d e t a i l s o f m echanism w ere ad v an c ed . A lso in 1 9 6 4 , T r a y n e lis and H e rg e n ro th e r" ^ r e p o r te d t h e i r r e s u l t s o f a s tu d y o f b e n z y l a lc o h o l o x id a tio n s . V a rio u s o rth o and p a r a s u b s t i t u t e d b e n z y l a lc o h o ls w ere found t o u n dergo conv e r s io n to th e c o rre s p o n d in g a ld e h y d e i f th e DMSO s o l u t i o n was r e f lu x e d and i f a s tre a m o f a i r was p a s s e d th ro u g h i t . V eiy l i t t l e o x id a tio n o f th e a ld e h y d e to th e c o rre s p o n d in g a c id o c c u rre d . S e v e ra l th in g s w ere i n t e r e s t i n g . A lth o u g h oxygen i s n e c e s s a ry f o r th e r e a c t i o n , i t d id n o t a p p e a r to be consum ed a s th e o x id a tio n p r o g r e s s e d . I f th e r e a c tio n s w ere c a r r ie d 1 o u t u n d e r a b la n k e t o f n it r o g e n , no o x id a tio n to o k p la c e . I t t - b u t y l p e ro x id e was i n t r o ­ duced u n d e r o x y g e n -fre e c o n d itio n s , th e n a ld e h y d e fo rm a tio n was n o te d . The re q u ire m e n t f o r oxygen, and th e s u c c e s s o f th e r a d i c a l i n i t i a t o r , seem ed to r e q u ir e a f r e e r a d i c a l m echanism f o r th e r e a c t i o n . On th e o th e r h an d , e l e c tr o n w ith d ra w in g s u b s t i t u e n t s in th e p a r a p o s i t i o n o f b e n z y l a lc o h o l seem ed to slow th e o x id a tio n r e a c t i o n , w hereas e l e c tr o n r e l e a s i n g ones g r e a t l y in c re a s e d i t . The l a t t e r r e s u l t s seemed t o r e q u ir e a carbonium io n i n t e r p r e t a t i o n . I t was to s e t t l e t h i s q u e s tio n t h a t a d e t a i l e d 's t u d y o f th e o x id a ­ t i o n m echanism was u n d e rta k e n . R e p ro d u c e d with perm ission of th e copyright ow ner. F u rth er reproduction prohibi

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