UBC Theses and Dissertations

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UBC Theses and Dissertations

Remote oxidation of cyclic and acyclic esters Ma, Chun-Leung 1976

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REMOTE OXIDATION OF CYCL IC AND ACYCL IC ESTERS By CHUN-LEUNG MA B . S c . , C h i n e s e U n i v e r s i t y o f Hong Kong , 1 9 7 3 A THESIS SUBMITTED IN PARTIAL FULF I LLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SC IENCE i n t h e D e p a r t m e n t o f C h e m i s t r y We a c c e p t t h i s t h e s i s as c o n f o r m i n g t o t h e r e q u i r e d s t a n d a r d THE UNIVERS ITY OF BR IT I SH COLUMBIA J u n e , 1 9 7 6 (c) Chun-Leung Ma, 1 9 7 6 In p re sent ing t h i s t he s i s in p a r t i a l f u l f i l m e n t o f the requirements f o r an advanced degree at the U n i v e r s i t y of B r i t i s h Columbia, I agree that the L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r reference and study. I f u r t h e r agree tha t permiss ion fo r ex ten s i ve copying o f t h i s t he s i s f o r s c h o l a r l y purposes may be granted by the Head of my Department or by h i s r ep re sen ta t i ve s . It i s understood that copying or p u b l i c a t i o n o f t h i s t he s i s f o r f i n a n c i a l gain s h a l l not be a l lowed without my w r i t t e n permi s s ion . Department of CH EM I S TRY The U n i v e r s i t y of B r i t i s h Columbia 20 75 Wesbrook P l a c e Vancouver, Canada V6T 1W5 Date June 23 , 1 976 . i i -ABSTRACT The o x i d a t i o n o f o c t a d e c y l a c e t a t e ( 9 7 ; n = l 6 ) , d o d e c y l a c e t a t e ( 9 7 ; n=10), t e t r a d e c y l a c e t a t e ( 9 7 ; n = 1 2 ) , h e x a d e c y l a c e t a t e ( 9 7 ; n = 12j) and d o c o s y l a c e t a t e ( 9 7 ; n=20) by c h r o m i u m t r i o x i d e i n g l a c i a l a c e t i c a c i d / a c e t i c a n h y d r i d e t o a m i x t u r e o f m o n o - o x o - a c e t a t e s and t h e method u sed t o d e t e r m i n e t h e r e l a t i v e amount s o f i s o m e r i c o x o - a c e t a t e s p r e s e n t i n t h e p r o d u c t m i x t u r e , i s d e s c r i b e d . E v i d e n c e i s g i v e n f o r t h e v a l i d i t y o f t h e a n a l y t i c a l method t o e s t i m a t e t h e r e l a t i v e amount s o f i s o m e r i c o x o - a c e t a t e s . S u b s e g u e n t c o n v e r s i o n o f t h e m i x t u r e o f m o n o - o x o - h e x a d e c y 1 a c e t a t e s ( 9 8 ; x+y=13)> m o n o - o x o -d o d e c y l a c e t a t e s (98; x + y = l 9 ) , a n d m o n o - o x o - t e t r a d e c y V a c e t a t e s ( 9 8 ; x+y=1l) t o t h e c o r r e s p o n d i n g m i x t u r e o f m o n o - u n s a t u r a t e d a c e t a t e s i s d e s c r i b e d . The se compounds a r e c o n s i d e r e d t o be s e x phe romones f o r t h e b e r t h a a rmyworm, oak l e a f r o d l e r moth and some f r u i t moths r e s p e c t i v e l y . The o x i d a t i o n o f 1 6 - h e x a d e c a n o 1 i d e (117 ; ' n = 15) » 15 " . p e n t a d e c a n o 1 i d e ( 1 1 7 ; n = 14) and 1 2 - d o d e c a n o 1 i d e ( 1 1 7 ; n =11) by c h r o m i u m t r i o x i d e i n g l a c i a l a c e t i c a c i d / a c e t i c a n h y d r i d e to a m i x t u r e o f m o n o - o x o - 1 a c t o n e s and t h e method e m p l o y e d t o d e t e r m i n e t h e r e l a t i v e amount s o f i s o m e r i c m o n o - o x o - 1 a c t o n e s p r e s e n t i n t h e p r o d u c t m i x t u r e , i s r e p o r t e d . S u b s e g u e n t c o n v e r s i o n o f t h e m i x t u r e o f m o n o - o x o - 1 6 - h e x a d e c a n o l i d e s ( 1 1 8 ; x+y=14) t o t h e m i x t u r e o f m o n o - u n s a t u r a t e d h e x a d e c a n o 1 i d e s ( 1 2 3 ; a +b=13 ) has been a c h i e v e d . The l a t t e r m i x t u r e i s b e l i e v e d t o be p a r t o f t h e s e x phe romone o f t h e oak l e a f r o l l e r m o t h . The o x i d a t i o n o f cyc1 o p e n t a d e c y 1 a c e t a t e ( 1 3 5 ) and c y c 1 o t r i d e c y 1 a c e t a t e ( 145 ) by c h r o m i u m t r i o x i d e i n g l a c i a l a c e t i c a c i d / a c e t i c a n h y d r i d e t o a m i x t u r e o f m o n o - o x o - c y c 1 i c a c e t a t e s and t h e method u sed t o i d e n t i f y and d e t e r m i n e t h e r e l a t i v e amounts o f i s o m e r i c c y c l i c o x o - a c e t a t e s , i s d e s c r i b TABLE OF CONTENTS Page A b s t r a c t i i T a b l e o f c o n t e n t s i v L i s t o f schemes v L i s t o f f i g u r e s v i A c k n o w l e d g e m e n t s x i i Abb r ev i a t i on x i i i I n t r o d u c t i o n 1 (A) L a b o r a t o r y r emote o x i d a t i o n o f a c y c l i c and a l i c y c l i c s u b s t r a t e s 2 (B) B i o l o g i c a l r emote o x i d a t i o n o f a c y c l i c and a l i c y c l i c s u b s t r a t e s 20 D i s c u s s i o n 33 (A) Remote o x i d a t i o n o f a c y c l i c a c e t a t e s . . . . 33 (B) Remote o x i d a t i o n o f m a c r o c y c l i c 1 a c t o n e s 76 (C) Remote o x i d a t i o n o f m a c r o c y c l i c a c e t a t e s 93 E x p e r i m e n t a l 116 B i b 1 i og r aphy 151 - v -L I ST OF SCHEMES Scheme Page 1 7 2 8 3 12 h 13 5 14 6 15 7 97 8 98 9 99 10 102 11 103 12 104 13 105 - v i L I S T OF FIGURES F i g u r e Page 1. Pho t o - o x i d a t i on o f t h e C-| ^ e s t e r 3 2. P h o t o - o x i d a t i o n o f t h e C-jg e s t e r 3 3. O x i d a t i o n o f m e t h y l s t e a r a t e [ d a t a f r o m t h e low r e s o l u t i o n (l5eV) mass s p e c t r u m o f a c e t a l s ] . . . 3^ 4 . O x i d a t i o n o f m e t h y l d o c o s a n o a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f t h i oa ce t a 1s] 3^ 5. O x i d a t i o n o f o c t a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a ce t a 1 s] 43 6. O x i d a t i o n o f o c t a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s ] 44 7. O x i d a t i o n o f o c t a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] 45 8. O x i d a t i o n o f o c t a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s ] 46 9. O x i d a t i o n o f d o d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] . . . 4 7.. - v i i -10 . O x i d a t i o n o f d o d e c y l a c e t a t e |_data f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a 1s] . . . 48 11 . O x i d a t i o n o f d o d e c y l a c e t a t e ([data f r o m t h e low r e s o l u t i o n (l5eV) mass s p e c t r u m o f a c e t a l s ] . . . 49 12. O x i d a t i o n o f d o d e c y l a c e t a t e [[data f r o m t h e l ow r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s ] . . . 50 13- O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] . . • 51 14. O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ da t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s ] . . . 52 15- O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( 1 5eV) mass s p e c t r u m o f a c e t a l s j . . . 53 16. O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s] . . . 5^ 17- O x i d a t i o n o f d o c o s y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n (l5eV) mass s p e c t r u m o f a c e t a l s ] 55 18. O x i d a t i o n o f d o c o s y l a c e t a t e [ d a t a f rom t h e low r e s o l u t i o n ( 70eV) mass s p e c t r u m o f a c e t a l s ] 56 19- O x i d a t i o n o f d o c o s y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] 57 2 0 . O x i d a t i o n o f d o c o s y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s ] 58 2 1 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n ( l 5eV ) 'ma s s s p e c t r u m ] . . . 59 2 2 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ da ta f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m ] . . . 60 - v i i i -2 3 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n mass s p e c t r a ] 61 2k. Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (l5eV) mass s p e c t r u m ] . . . . 6 2 2 5 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t rum] . . . . 63 2 6 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [data f r o m t h e low r e s o l u t i o n mass s p e c t r a ] 6k 27. Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n ([data f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m ] . . . . 6 5 2 8 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t rum] . . . . 66 2 9 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [da ta f r o m t h e low r e s o l u t i o n mass s p e c t r a ] 67 30 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [data f r o m t h e low r e s o l u t i o n ( ! 5eV ) mass s p e c t rum] . . . . 68 3 1 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [da ta f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t rum] . . . . 69 3 2 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n (data f r o m t h e low r e s o l u t i o n mass s p e c t r a ] 70 33- Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [data f r o m t h e low r e s o l u t i o n (l5eV) mass s pec t r um] . . . . 71 34 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t r u m ] . . . . 7 2 35 - Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n j d a t a t ' f rom t h e low r e s o l u t i o n mass s p e c t r a ] 73 d a t a f r o m t h e low r e s o l u t i o n ( ! 5eV ) mass s p e c t r u r n J . . . . I k - i x -3 6 . O x i d a t i o n o f o c t a d e c y l a c e t a t e i n t e n t i m e s amount o f s o l v e n t and t h e same amount o f C r 0 ^ - A c 2 0 [ l  s p e c t r u m ] 7 437 - O x i d a t i o n o f o c t a d e c y l a c e t a t e i n t e n t i m e s amount o f s o l v e n t and t h e same amount o f C r 0 ^ - A c 2 0 [ d a t a f r o m t h e l ow r e s o l u t i o n ( 70eV ) mass s p e c t rum] . . . . 75 3 8 . O x i d a t i o n o f 1 6 - h e x a d e c a n o l i d e [ d a t a f r o m t h e low r e s o l u t i o n ( 15eV ) mass s p e c t r u m o f a c e t a l s ] . . . 8'1 39 - O x i d a t i o n o f 1 6 - h e x a d e c a n o 1 i d e [ d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s ] 82 4 0 . O x i d a t i o n o f 1 6 - h e x a d e c a n o 1 i d e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] 83 4 1 . O x i d a t i o n o f 1 6 - h ex a de c a no 1 i de [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0eV ) mass s p e c t r u m o f a c e t a l s ] 84 4 2 . O x i d a t i o n o f 1 5 - pe n t adec an o l i d e (d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] 85 4 3 . O x i d a t i o n o f 1 5 _ p e n t a d e c a n o l i d e [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0eV ) mass s p e c t r u m o f a c e t a l s ] 86 44 . O x i d a t i o n o f 1 5 _ p e n t a d e c a n o l i d e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] 87 4 5 - O x i d a t i o n o f 1 5 _ p e n t a d e c a n o l i d e [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0eV ) mass s p e c t r u m o f a c e t a l s ] 88 46 . O x i d a t i o n o f 1 2 - d o d e c a n o l i d e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ] 89 - x -k7. Oxidation of 12-dodecano 1ide [data from the low r e s o l u t i o n (70eV) mass spectrum of a c e t a l s ] 90 48. Oxidation of 12-dodecanolide [data from the low r e s o l u t i o n (l5eV) mass spectrum of ac e t a l s ] 91 49- Oxidation of 12-dodecano 1 ide [data from the low r e s o l u t i o n (70eV) mass spectrum of a c e t a l s ] 92 50. Mass spectrum of d i a c e t a l of 1 , 4-cyclopentadecy1 -d i one [low.reso1 ut ion (15eV)] 106 51. Mass spectrum of d i a c e t a l of 1 ,4-cyc1 opentadecy1-dione [low r e s o l u t i o n (70eV)] 107 52. Mass spectrum of d i a c e t a l of 1 , 5 -cyc1 opentadecy1 -dione [low r e s o l u t i o n (l5eV)] 108 53- Mass spectrum of d i a c e t a l of 1 , 5 -cyc1 opentadecy1 -dione low r e s o l u t i o n (70eV)] 109 54. Mass spectrum of d i a c e t a l of 1 , 8-cyc1 opentade cy 1 -dione [low r e s o l u t i o n (l5eV)] 110 55. Mass spectrum of d i a c e t a l of 1 , 8-cyc1 opentadecy1-dione [low r e s o l u t i o n (70eV)] 111 56. Mass spectrum of mixture of d i a c e t a l s of 1,4-cyclo-t r i d e c y 1 - d i o n e and 1 ,5-cyc1otridecy1 -dione [low re s o l u t i on ( 1 5 e V ) ] 112 57- Mass spectrum of mixture of d i a c e t a l s of 1 , 4-cyclo-t r i decy 1 - d i on e and 1 ,5 - cy c 1 o t r i de cy 1 - d i on e [low re s o l u t i on (70eV)] 113 - x i -5 8 . Mass s p e c t r u m o f m i x t u r e o f d i a c e t a l s o f 1 , 6 - c y c l o -t r i d e c y 1 - d i o n e and 1 , 7 ~ c y c 1 o t r i d e c y 1 - d i o n e [ l o w r e s o l u t i o n ( 1 5 e V ) ] 114 5 9 - Mass s p e c t r u m o f m i x t u r e o f d i a c e t a l s o f 1 , 6 - c y c l o -t r i d e c y 1 - d i o n e and 1 , 7 " c y c 1 o t r i d e c y 1 - d i o n e [ l o w r e s o l u t i o n ( 7 0 e V ) ] 115 - x i i -ACKNOWLEDGEMENTS I w o u l d l i k e t o e x p r e s s my s i n c e r e t h a n k s t o D r . Thomas Money f o r h i s s u p e r v i s i o n t h r o u g h o u t t h e c o u r s e o f t h i s w o r k . A s p e c i a l t h a n k s goes t o D r . N. Darby and D r . M . S . A l l e n f o r r e a d i n g t h i s t h e s i s and t h e i r h e l p f u l d i s c u s s i o n s . I w o u l d a l s o l i k e t o t h a n k my s i s t e r E m i l y f o r h e r h e l p i n t y p i n g t h i s t h e s i s . - x i i i -AB B R EVI AT I 0 N b r o a d s b r o a d s i n g l e t b r o a d m b r o a d m u l t i p l e t m i x e d t m i x e d t r i p l e t s s i n g l e t t t r i p l e t m m u l t i p l e t - 1 -I NTRODUCTION The a b i l i t y o f e n z y m i c s y s t e m s t o f u n c t i o n a l i se s u b s t r a t e s a t p o s i t i o n s r emote f r o m a c t i v a t i n g g r o u p s i s w e l l d o c u m e n t e d . R e a c t i o n s o f t h i s t y p e i n c l u d e t h e b i o l o g i c a l o x i d a t i o n o f s t e a r i c a c i d t o o l e i c a c i d and t h e m i c r o b i o l o g i c a l h y d r o x y 1 a t i o n o f CH ( C H ) , (lO H ^ CH (CH ) CH = CH(CH ) CO H 3 2 1 6 2 3 2 7 2 7 2 s t e a r i c a c i d o l e i c a c i d k s t e r o i d s i(i e . g . p r egn - 1 8 , 1 9n o r-A. - 3 , 2 0 - d i o n e ) i n t h e c o m m e r c i a l p r o d u c t i o n o f c o r t i c o s t e r o i d s s u c h as c o r t i s o n e . The t e r m " r e m o t e HO. c o r t i cos t e ro i ds ( e . g . c o r t i s o n e ) 4 pregn-18,19 n o r - A - 3 , 2 0 - d i o n e o x i d a t i o n " has been g i v e n t o d e s c r i b e o x i d a t i v e t r a n s f o r m a t i o n s o f t h i s t y p e and r e c e n t r e s e a r c h i n s e v e r a l l a b o r a t o r i e s ( p r i n c i p a l l y t h o s e o f P r o f e s s o r R. B r e s l o w i n C o l u m b i a U n i v e r s i t y , N.Y. ) has been c o n c e r n e d w i t h t h e d e v e l o p m e n t o f l a b o r a t o r y methods t o 1 a c h i e v e s i m i l a r r emote f u n c t i o n a 1 i s a t i o n o f n a t u r a l p r o d u c t s . F o r t h e p u r p o s e o f d i s c u s s i o n , r emote o x i d a t i o n w i l l be d i v i d e d i n t o two c a t e g o r i e s ; l a b o r a t o r y and b i o l o g i c a l r emote o x i d a t i o n . - 2 -(A) L a b o r a t o r y r emote o x i d a t i o n o f a c y c l i c and a l P c y c l i c s u b s t r a t e s In t h e p a s t . s e v e r a l l a b o r a t o r i e s have d e v e l o p e d t e c h n i q u e s t o a c h i e v e s e l e c t i v e f un c t i on a V i s a t i o n of •  un a c t i va t e d and o t h e r w i s e w . „ - _ ... 2 u n r e a c t i v e c h e m i c a l p o s i t i o n s . P r o c e s s l i k e t h e B a r t o n r e a c t i o n , 3 h t h e L o e f f 1 e r - F r e y t a g r e a c t i o n , t h e Yang p h o t o l y s i s , and t h e 5 H e u s l e r r e a c t i o n a l l i n v o l v e t h e p r o d u c t i o n o f a r e a c t i v e h e t e r o a t o m r a d i c a l i n a m o l e c u l e w h i c h t h e n , by i n t r a m o l e c u l a r a t t a c k on a h y d r o g e n atom l o c a t e d s i x a toms away , i n i t i a t e s f u n c t i o n a 1 i s a t i o n o f a c h e m i c a l l y u n a c t i v a t e d p o s i t i o n . More r e c e n t l y , a p r o c e s s d e f i n e d as " r emote o x i d a t i o n " 6 was d e v e l o p e d by B r e s l o w and h i s c o - w o r k e r s . A s e r i e s o f u n b r a n c h e d a l i p h a t i c e s t e r s o f b e n z o p h e n o n e c a r b o x y l i c a c i d was u s ed as s t a r t i n g m a t e r i a l . On i r r a d i a t i o n , t h e b e n z o p h e n o n e g r o u p i s e x c i t e d t o a t r i p l e t s t a t e w h i c h i s c a p a b l e o f a b s t r a c t i n g a h y d r o g e n e&fcgW f r o m a m e t h y l e n e g r o u p r emote f r o m t h e e s t e r f u n c t i o n a l i t y . A summary o f t h e r e g i o s p e c i f i c i t y o f t h i s p r o c e s s i s shown i n f i g u r e s 1 and 2 . The r e s u l t s i n d i c a t e d t h a t some p o s i t i o n s i n t h e a l i p h a t i c c h a i n we re p r e f e r e n t i a l l y f u n c t i o n a 1 i s e d and i t was s u g g e s t e d t h a t t h i s c o u l d be a s s o c i a t e d w i t h t h e p r e f e r r e d c o n f o r m a t i o n o f t h e s u b s t r a t e i n t he r e a c t i o n med ium. S u b s t r a t e s w i t h known p r e f e r r e d c o n f o r m a t i o n s w e r e l a t e r e x a m i n e d . F o r e x a m p l e , p h o t o l y s i s o f t h e e s t e r (1) d e r i v e d f r o m b e n z o p h e n o n e - k - p r o p i o n i c a c i d and 3 c h o 1 e s t a n o 1 p r o d u c e d 14 .7 A - cho 1 es t - 3 ct-eno 1 (2) and a m i x t u r e o f l a c t o n e s ( 3 ) - The - 3 -S i t e s o f o x i d a t i o n F i g u r e 1. P h o t o - o x i d a t i o n o f t h e C-j^ e s t e r . 0 F i g u r e 2 S i t e s o f o x i d a t i o n P h o t o - o x i d a t i o n o f t h e C 1 Q e s t e r . l a c t o n e s (3) we re d e h y d r a t e d , h y d r o l y s e d and o x i d a t i v e l y c l e a v e d oa (3) t o p r o d u c e 1 2 - k e t o c h o 1 es t a n - 3 oro 1 (k) and 7 - k e t o cho 1 es t an - 3 ct-o 1 ( 5 ) - A l t e r n a t i v e l y , t h e l a c t o n e m i x t u r e (3) can be d e g r a d e d by (4) -H2O RuO/j h y d r o l y s i s (3) > »- " y + l e a d t e t r a a c e t a t e o x i d a t i o n t o p r o d u c e A - c h o 1 e s t e n - 3a~o1 (6) - 5 -[derived from a lactone attached at C ( l 4 ) ] and a mixture of A 7 r and A -cholesten-3 a-ols (7) and (8) [derived from a lactone attached at C ( 7) ] l (7) (8) (7CU) S e l e c t i v e f u n c t i o n a 1 i s a t i o n at C- 14 and C-9 was l a t e r obtained by an i n t r a m o l e c u l a r halogenation process. I r r a d i a t i o n 0 / • of e s t e r (9) in ch<l>6 r ob en ze ne at -25^9 u l t i m a t e l y provided 14 A -cho1esteny1-3 a-acetate (10) ( 5 3 1 y i e l d ) while e s t e r (11) (53%) (9) 9 C 1 1 ! ( 1 0 ) 8 a f t e r p h o t o l y s i s gave A -cho1esteny1-3a-acetate in k3% y i e l d . 6 ^ The s e l e c t i v e a t t a c k a t 0 1 4 i n (9) and f>9 i n (11) i s c o n s i s t e n t w i t h p r e d i c t i o n s f r o m m o l e c u l a r mode l s a s s u m i n g h y d r o g e n a b s t r a c t i o n by t h e c h l o r i n e a tom i n t h e [ A r - I - C l ] - i n t e r m e d i a t e . ( 1 M - 7 -e x p l a n a t i o n o f t h e s e s e l e c t i v e ha 1 o g e n a t i o n s i s t h e r a d i c a l r e l a y m e c h a n i s m ( scheme 1) i n w h i c h (15) can be g e n e r a t e d by t r a n s f e r o f a c h l o r i n e atom t o (13) f r o m an e x t e r n a l r a d i c a l r e a g e n t . Scheme 1 A p p l i c a t i o n o f t h i s r emote h a l o g e n a t i o n by u t i l i s i n g an e x t e r n a l A r l C l • r a d i c a l was f o u n d u s e f u l i n s y n t h e s i s o f c o r t i s o n e 10 ( s cheme 2) . C o r t e x o l o n e - 8 -BMD d i h y d r o c o r t i s o n e a c e t a t e Scheme 2 F u r t h e r a p p l i c a t i o n o f t h i s r e m o t e f u n c t i o n a 1 i s a t i o n t o h a l o g e n a t e s e l e c t i v e l y a t C-17 i s t h e key s t e p i n an e f f i c i e n t c o n v e r s i o n o f 33 -cho1es tano1 t o a n d r o s t e r o n e a c e t a t e . The s t e r o i d s t r u c t u r e (16) shows t h a t C-9 i s d i r e c t l y a t t a c h e d t o r i n g A w h i l e C-17 i s a t t a c h e d t o r i n g A w i t h t h e s i x - m e m b e r e d r i n g C. I n s e r t i n g a p h e n y l e n e i n t o m - i o d o b e n z o i c a c i d t o g i v e (16) s h o u l d - 9 -p r o v i d e a r e a g e n t c a p a b l e o f a t t a c k i n g C-17 f r o m C - 3 - Thus p h o t o l y s i s o f (16) w i t h Ph IC12 i n c a r b o n t e t r a c h l o r i d e g a v e , a f t e r 16 p r o c e s s i n g , k\% o f A -3 or ch o 1 e s t e ny 1 a c e t a t e ( l 7 ) w h i c h by r e a c t i o n w i t h N - p h e n y 1 t r i a z o 1 i n e d i o n e i n m e t h y l e n e c h l o r i d e p r o v i d e d t h e ene a d d u c t ( 1 8 ) . The s t e r e o c h e m i s t r y o f t h e d o u b l e bond w o u l d r e s u l t f r o m a a t t a c k on t h e s t e r o i d and i n t r a m o l e c u l a r h y d r o g e n t r a n s f e r . (18 ) was t h e n s a p o n i f i e d and r e d u c e d w i t h l i t h i u m i n e t h y l a m i n e t o g i v e Z - A ' L 7 ^ - 2 C ' ^ - 3 a " c h o l e s t e n o l ( 1 9 ) . A c e t y l a t i o n o f (19 ) f o l l o w e d by o z o n o l y s i s p r o v i d e d (20 ) - 10 -M i l l e r and h i s c o - w o r k e r s r e p o r t e d t h a t a l k a n e s (21) and a d a m a n t a n e s (22) we re o x i d i z e d t o p r o d u c e a c e t a m i d e at a 1 2 p l a t i n u m anode i n a c e t o n i t r i 1 e . The o x i d a t i o n i n v o l v e s (CHg.) 2 C H - C H ( C H 3 ) 2 (21 ) p t anode CH.3CN, H 2 0 -> ( C H 3 ) 2 C H - N H C 0 C H 3 (22 ) p t anode Ch! CN, H O 3 2 NHCOCH d i r e c t e l e c t r o n t r a n s f e r f r o m hy d rocai i rbon t o t h e e l e c t r o d e . A f t e r i n i t i a l e l e c t r o n t r a n s f e r and s u b s e q u e n t f r a g m e n t a t i o n , (21) p r o v i d e d t h e i s o p r o p y l c a t i o n s w h i c h a r e t h e p r e c u r s o r s o f a c e t a m i d e s i n a c e t o n i t r i 1 e . The p r e s e n c e o f i n t e r m e d i a t e c a r b o n i u m i o n s was a l s o d e m o n s t r a t e d i n t h e o x i d a t i o n o f a d a m a n t a n e s . The p r e s e n c e o f a d a m a n t y l c a t i o n was i m p l i e d by t h e e x i s t e n c e o f a c e t o n i t r i 1 i u r n i o n (23) w h i c h was v e r i f i e d by q u e n c h i n g t h e - 2e (22) NDCOCH (2 5). NH=CH,C10. I 3 * 0CH„ - 11 -r e a c t i o n a f t e r e l e c t r o l y s i s w i t h d e u t e r i u m o x i d e and w i t h me t h ano1 . The se a n o d i c ox i d a t i onsv-we. re v v e r y ' - u s e f u 1 i n a c e t am i da t i on 13 1 4 o f k e t o n e s and e s t e r s a t r emote p o s i t i o n s . O x i d a t i o n o f 2 - h e x a n o n e (26 ) p r o d u c e d 5 - a c e t a m i d 6 - 2 - h e x anone (27) and 4 , 4 -d i m e t h y 1 - 2 - p e n t a n o n e (28) o x i d a t i o n p r o d u c e d 4 - a c e t a m i d o - 4 -m e t h y 1 - 2 - h e x an one ( 2 9 ) . The p r o p o s e d m e c h a n i s m f o r t h e s e p t a n od e C H , C 0 ( C H o ) , C H , 3 2 3 3 (26) CH3CN, H 2 0 p t anode NHCOCH, l|ih'CC: Chl C O C H C H C H C H . , 3 2 2 3 (27) CH 3 C 0 C H 2 C ( C H 3 ) 3 C H 3 C N , H 2 0 C H 0 C H , 1 2 5 CH.CONHCCH-COCH, 3 I 2 3 CH, (28) (29 ) o x i d a t i o n s i n v o l v e s ( i ) d i r e c t o x i d a t i o n o f t h e k e t o n e , ( i i ) an i n t r a m o l e c u l a r a t t a c k on t h e r emote h y d r o g e n - c a r b o n bond by o x y g e n and a s e c o n d e l e c t r o n t r a n s f e r , and ( i i i ) t r a p p i n g , o r r e a r r a n g e m e n t and t r a p p i n g r e a c t i o n s o f t h e r e s u l t i n g c a r b o n i u m i o n s . T h i s can be e n v i s a g e d f o r (28 ) as shown i n scheme 3- A d i r e c t o x i d a t i o n o f s u b s t r a t e a t t h e e l e c t r o d e i s i n d i c a t e d s i n c e b a c k g r o u n d c u r r e n t a t 2.3V i s o n l y ^2% o f t h a t (28 ) H 0 + + CH 0 OH l 2 ii -H CH ,CCH 0 CCH. 3 I 2 ; CH, + H - 1 2 -C H 9 C H , ; C H 9 C H , | 2 3 1 . C H 3 C N I + C C H 2 C 0 C H 3 > C H 3 C 0 N H C C H 2 C 0 C H 3 + C H 3 2 - H 2 ° C H 3 ( 2 9 ) Scheme 3 due t o added k e t o n e . S i m p l e e s t e r s can be c l e a n l y m o n o - a c e t a m i d a t e d and s t r a i gh t - ch a i n e s t e r s u n d e r g o e p r e f e r e n t i a 1 OJ - 1 ( c a r b o n n e x t t o t h e end o f t h e c h a i n ) s u b s t i t u t i o n , e . g . p t anode C H 3 ( C H 2 ) 2 C 0 2 C H 3 •>- C H 3 C H C H 2 C 0 2 C H 3 C H 3 C N , H 2 0 NHCOCHo As i n r emote a n o d i c a c e t a m i d a t i o n o f k e t o n e s , t h e r e a c t i o n o c c u r s v i a c a r b o n i u m i o n i n t e r m e d i a t e s . F o r s t r a i g h t c h a i n e s t e r s t h e c a r b o n i u m i o n i s f o r m e d a t t h e s e c o n d a r y p o s i t i o n most r emote f r o m t h e e 1 e c t r o n - w i t h d r a w i n g e s t e r f u n c t i o n , and as t h e c h a i n becomes l o n g e r , more w - 2 p r o d u c t i s o b s e r v e d . A n o d i c o x i d a t i o n o f c a r b o x y l i c a c i d s i n f l u o r o -s u l p h u r i c a c i d p r o v i d e s l a c t o n e s and u n s a t u r a t e d c y c l i c 15 k e t o n e s . F o r e x a m p l e , o x i d a t i o n o f o c t a n o i c a c i d ( 3 0 ) p r o d u c e s ' ( 3 1 ) , ( 3 2 ) and ( 3 3 ) . In s t r o n g l y a c i d i c m e d i u m , t h e p t anode C H 3 ( C H 2 ) 6 C 0 2 H ( 3 0 ) ( 3 1 ) ( 3 2 ) C331 - 13 -e 1 e c t r o a c t i v e s p e c i e s i s t h e p r o t o n a t e d c a r b o x y l i c a c i d RCO H + 2 2 b e c a u s e o f t h e e q u i l i b r i u m R C 0 2 H + H S 0 , F 3' ^ R C 0 2 H 2 + F S 0 3 The p r o d u c t s f r o m t h i s a n o d i c o x i d a t i o n c o u l d be r a t i o n a l i s e d by t h e r e a c t i o n scheme h. + - 2 e " + C O 2 H 2 + C 0 2 H 2 (3D (32) (33) Scheme h - \k -S t e r e o s p e c i f i c r emote h y d r o x y 1 a t i o n o f c y c l o h e x a n o l was a c h i e v e d w i t h f e r r o u s i o n - h y d r o g e n p e r o x i d e r e a g e n t . The m a j o r p r o d u c t i s c i s - 1 , 3 - c y c1 oh e xane d i o l ( 3 *0 t o g e t h e r w i t h s m a l l 16 amounts o f 1 , 2 - d i o l s ( 3 5 ) . T h i s p r o c e s s p r o c e e d s by d i r e c t o x i d a t i o n t h r o u g h a c y c l i c t r a n s i t i o n s t a t e by a bound i r o n s p e c i e s , f o r m a l l y e q u i v a l e n t t o a f e r r y l i r o n ( 3 6 ) , and l e a d i n g t o d i s c r e t e r a d i c a l and c a r b o n i u m i o n i n t e r m e d i a t e s ( s cheme S)• F e r r y l i o n (36) can a l s o be o b t a i n e d by p h o t o r e d u c t i o n o f f e r r i c + 2+ H 3+ -Fe + H 9 O 9 *-Fe + OH + • OH Scheme 5 c i s - 1 ,3~cyc1ohexane dio1 formation as was observed in the 17 ferr o u s ion-hydrogen peroxide r e a c t i o n . This s tereos pe c i f i c hydroxy1 ation upon photoreduction of iron ( i l l ) p r o f f e r s evidence that r e g i o s p e c i f i c i t y observed is due to a l c o h o l -oxidant comp1 ex a t i o n . Cyclohexane, 1-octyl t r i f 1 u o r o a c e t a t e , heptane and deeane are o x i d i z e d by Fe ( I I ) - Et o NO in C F - J C O O H and the 3 18 > r e a c t i o n s stop at the alcohol stage. In the o x i d a t i o n of 1-octyl t r i f 1 u o r o a c e t a t e , 12% s e l e c t i v i t y in the 7 p o s i t i o n is shown. This is due to p o l a r s e l e c t i v i t y which favour o x i d a t i o n at the penultimate carbon. Although the mechanism is not yet completely e s t a b l i s h e d , i t is b e l i e v e d that hydrogen a b s t r a c t i o n by R^N*- ! " , producing an a l k y l r a d i c a l , is i n v o l v e d . The a l k y l r a d i c a l is then converted i n t o the e s t e r product v i a an encumbered carbonium ion, produced by Fe(I I I) o x i d a t i o n (scheme 6)„ + R'3N0H+ + F e ( l l ) ^ F e ( l l l ) + R ' 3 N. + + R' 3 N' + RH R 1 3 NH + R-R- + Fe ( I I I ) - ^ F e ( l l ) + R + + + R T + CFfC0 2H *CF 3C0 2R + H Scheme 6 Carbony TCarbony1-o1efin metathesis is a p p l i e d to s y n t h e s i s of trans-non -6-en - 1-o1 (40) , a sex a t t r a c t a n t of the Mediterranean 19 - 16 -f r u i t f l y , by J o n e s and h i s c o - w o r k e r s . P h o t o l y s i s of.-'"... p r o p i o n a 1dehyde and c y c 1 o h e x a - 1 , 3 - d i e n e i n a c e t o n i t r i l e gave (37) (80% exp-) i n 77% y i e l d . H y d r o g e n a t i o n o f (37) t o (38) was q u a n t i t a t i v e . P y r o l y s i s o f (38) a t 270-340°C gave (39) w h i c h was t h e n r e d u c e d by L i A l H ^ t o g i v e (40). The t h e r m a l d e c o m p o s i t i o n o f b i c y c l i c o x e t a n s i s h i g h l y r e g i o s e 1 e c t i v e . I t f a v o u r s t h e f o r m a t i o n o f m e t a t h e s i s p r o d u c t s o v e r r e g e n e r a t e d c a r b o n y l -o l e f i n p a i r s . CP, Et Et (37) (38) (40) OH (39) R e g i o s p e c i f i c h y d r o p e r o x i d a t i o n o f a d o u b l e bond was o b s e r v e d i n t h e p h o t o s e n s i t i z e d o x y g e n a t i o n o f t r a n s , t r a n s - 1 -20 m e t h y 1 c y c 1 o d e c a - 1 , 6 - d i e n e (41) w i t h s i n g l e t o x y g e n . A m e t h a n o l s o l u t i o n o f (41) was i r r a d i a t e d i n t h e p r e s e n c e o f m e t h y l e n e b l u e at 10°C f o r 4.5 h r . w h i l e p u r e o x y g e n was b u b b l e d t h r o u g h t h e s o 1 u t i on . A°ts i n g 1 e p r o d u c t (42 ) was i s o l a t e d i n ; '55% y i e l d . 00H ^ - \ J / \ h v , m e t h y l e n e b l u e 0 2 , Me OH (55%) (41) (42) I r r a d i a t i o n o f 3 g - a c e t o x y c h o 1 e s t a n e (43) c o n t a i n i n g 10 mo 1 e q u i v . o f p e r a c e t i c a c i d r e s u l t e d i n h y d r o x y I a t i o n a t t h e 2 5 - and 5 a ~ p o s i t i o n s [ i . e . p r o d u c t (44) and ( 4 5 ) ] . T h i s method i s u s ed t o i n t r o d u c e a h y d r o x y l g r o u p a t 25 p o s i t i o n i n -21 c h o l e s t e r o l . 0 5 ) A n o t h e r o n e - s t e p r e g i o s p e c i f i c and s t e r e o s p e c i f i c h y d r o x y1 a t i o n a t p o s i t i o n 5 o f d e o x y c h o l i c a c i d has been 2 2 r e p o r t e d . A 4:1 m o l e c u l a r c o m p l e x i s f o r m e d by m i x i n g (46) w i t h s t o i c h i o m e t r i c amounts o f d i - 1 - b u t y 1 d i p e r o x y c a r b o n a t e (47 ) o <s H e a t i n g o f t h e c o m p l e x a t 90 C o r p h o t o l y s i s a t 25 C l e a d s t o f o r m a t i o n o f two m a j o r p r o d u c t s (48 ) (15%) and (49) (15%) and t r a c e s o f (50 ) . C501. C y c l o a l k a n e (51) w i t h c o m p l e t e l y u n a c t i v a t e d C-H bonds was f o u n d t o r e a c t w i t h p h e n y 1 ( b r o m o d i c h 1 o r o m e t h y 1 ) m e r c u r y t o g i v e d i ch 1 o rome t h y 1 c y c l o a l k a n e (52) i n r e a s o n a b l e y i e l d (48-23 83%) . The i n t r o d u c t i o n o f t h e d i h a l o m e t h y l s u b s t i t u e n t p r o v i d e s a r e a c t i v e s i t e f o r f u r t h e r t r a n s f o r m a t i o n . n = 6, 7, 11 n = 6 , W ; n = 7,83 %;n = 11 ,6h% (51) (52) a - k e t o c a r b o n i u m i o n (53) f o r m a t i o n i s b e l i e v e d t o be i n v o l v e d i n t h e deha 1 o g e n a t i o n o f a-bromo c a r b o n y l compounds 24 (54) w i t h A g S b F g . The i o n (53) i s s t a b i l i z e d by h y d r i d e s h i f t t o g i v e (55) w h i c h i s t h e n h y d r o l y s e d w i t h w a t e r t o p r o v i d e (56) and ( 5 7 ) . Thus t h e h y d r o x y l g r o u p i s r e g i o s p e c i f i c a 1 1 y i n t r o d u c e d t o t h e c i s - 4 p o s i t i o n . - 20 -(B) B i o l o g i c a l r emote o x i d a t i o n o f a c y c l i c and a l l c y c l i c s u b s t r a t e s Many r e a c t i o n s i n v o l v i n g r e g i o s p e c i f i c o x i d a t i o n at u n a c t i v a t e d C-H bonds a r e i n a c c e s s i b l e t o o r g a n i c c h e m i s t s b u t can o c c u r r e a d i l y i n m i c r o o r g a n i s m s . A l t h o u g h m i c r o b i a l o x i d a t i o n i s w i d e l y a p p l i e d i n b o t h i n d u s t r y and r e s e a r c h , l i t t l e i s known a b o u t t h e a c t u a l m e c h a n i s m o f t h e e n z y m a t i c p r o c e s s r e s p o n s i b l e f o r o x i d a t i o n o f u n a c t i v a t e d C-H b o n d s . The f o l l o w i n g d i s c u s s i o n w i l l be g r o u p e d i n two a r e a s (1) s t e r o i d s , and (2) i s o p r e n o i d s . ( 1) S t e r o i d s When a s o l u t i o n o f 5 a - a n d r o s t a n - 1 7 - o n e (58) i n e t h a n o l i s i n c u b a t e d w i t h C a l o n e c t r i a d e c o r a f o r 2 d a y s , t h e 1 8 , 6 a -25 d i h y d r o x y - 1 7 - k e t o n e (59) i s f o r m e d c l e a n l y . In a s i m i l a r e x p e r i m e n t , u s i n g d i m e t h y l s u l p h o x i d e as t h e med i um, (58 ) i s C a l o n e c t r i a d e c o r a Cko%\ (58) o x i d i z e d uli.w t t h -.'t -Gia,h'o'n:e:c,t--r-,'ira) nd;e exnria .thT;hie n'i 't \ a I p r o d u c t (59) i s f u rf-he r * o-xl^i ze^ r § ^ y the" f^-hysfcSxy-g roup" and t h e n h y d r o x y l a t e d - 21 -a t C- 19 t o g i v e 6 a , 1 9 - d i h y d r o x y - 5 a - a n d r o s t a n e - 1 , 1 7 " d i o n e (60 ) 26 i n 36% y i e l d . The a c e t a l s (61) d e r i v e d f r o m 5 ct-an d ros t an - 1 6 -I? C. deco ra C. deco ra ( 5 8 ) > ( 5 9 ) > Me 2 S0 H 1 OH C3 .6*l one i s h y d r o x y l a t e d more e f f i c i e n t l y t h a n i t s p a r e n t k e t o n e (62 ) ( 7 U ) C. deco ra HO-. O H ( 62 ) M i c r o b i o l o g i c a l h y d r o x y 1 a t i o n o f a l a r g e number o f mono- and d i - o x y g e n a t e d C i q s t e r o i d s has been i n v e s t i g a t e d - 22 -i n o r d e r t o a s c e r t a i n t h e e f f e c t o f v a r y i n g t h e . p o s i t i o n s o f t h e o x y g e n f u n c t i o n s on t h e h y d r o x y1 a t i o n p a t t e r n . A few e x a m p l e s a r e i l l u s t r a t e d . T h i s s t u d y s h o u l d e v e n t u a l l y l e a d t o p r e d i c t i o n s HO (52%) (33%) (53%) r e g a r d i n g t h e p o s i t i o n o f m i c r o b i o l o g i c a l h yd r oxy1 a t i o n o f s t e r o i d s w i t h c e r t a i n m i c r o o r g a n i s m s . The s t e r o i d s u b s t r a t e s f o r t h i s s t u d y c a r r y o x y g e n s u b s t i t u e n t s at two o f t h e 3,7,17 - 23 -p o s i t i o n s and a r e o x y g e n a t e d a t t h e p o s i t i o n s t h a t c a r r y i n g no o x y g e n a t o m . 3 8 - h y d r o x y - 5 a - a n d r o s t a n e - 7 - o n e 0 - 2k -5 a ~ a n d r o s t a n e - 7 , 1 7 - d i o n e (3k%\ + (52%) (IU) Mucor g r i s e o - v c y a n u s 33 (35%) t e s t o s t e r o n e Muco r p a r a s i t i c u s , Muco r g r i s e o - c y a n u s and H e l i c o s t y l u m p i r i f o rme a r e f o u n d t o o x y g e n a t e p r o g e s t e r o n e , d e o x y c o r t i c o s t e r o n e 33 (63) and 1 1 - d e o x y c o r t i s o l (6k). O c ^ / Muco r g r i s e o - c y a n u s , Mucor p a r a s i t i c u s o r H e l i c o s t y l u m p i r i f o r m e p r o ge s t e r o n e 0; CH 2 0H M. g r i s e o - c y a n u s , M. p a r a s i t i c u s o r H. p i r i f o rme 0 H 2 0 H (63) C6M - 25 CH-OH OH. H. p i r I f o r m e 0 ^ / C H 2 0 H *0H (6.U) 0 ^ / C H 2 0 H (15%) The a c r o m y r m e x f u n g u s o b t a i n e d f r o m t h e n e s t o f t h e a n t s p e c i e s A c r omy rmex o c t o s p i n o s u s i s an e f f i c i e n t 11a-h y d r o x y1 a t i n g o r g a n i s m i n s p i t e o f t h e c o m p l e x i t y o f t h e m i x t u r e as e x e m p l i f i e d by t h e i n c u b a t i o n o f a n d r o s t a n e-3 ,17' d i o n e (65) and p r e g n a n e - A -3,20 -d ione (66). (65) Ac romy rmex g f u n g u s ] A c r o m y r m e x — f u n g u s  C66) (1U) (19%) - 26 -D e g r a d a t i o n o f t h e s i d e c h a i n o f s t e r o i d s can be c a r r i e d o u t by u s i n g m i c r o b i a l o x i d a t i o n . E x a m p l e s a r e g i v e n f o r 35 36 p o n a s t e r o n e A (67) and c r u s t e c d y s o n e ( 6 8 ) . OH HO ! R . a r r h i z u s , R. n i g r i c a n s o r C u Avu'Pa'r-Pa'" "L l au FI a t a t a (68) Pos t s t e r one A h e t e r o c y c l i c s t e r o i d l i k e 3 6 _ a c e t o x y - 1 7 a - a z a - D - h o m o -a n d r o s t - 5 - e n - 1 7 - o n e (69) i s o x i d i z e d by Cunn inghame11 a e l e g a n s t o g i v e a c o m p l e x m i x t u r e , w h i l e i t s s t e r o i d a l k e t o n e (70) g i v e s 37 a m i x t u r e w i t h more d i o x y g e n a t e d p r o d u c t s . - 28 -( 2) I sop rerio i ds The c l a s s i c a l e x a m p l e of m i c r o b i o l o g i c a l o x i d a t i o n i s t h e h y d r o x y 1 a t i o n o f ( + ) campho r by P seudomonas p u t i d a . ( + ) camphor (71) i s o x i d i z e d t o g i v e a m i x t u r e c o n t a i n i n g 5 _ e n d o -and 5 - e x o h y d r o x y campho r (72 and 73) and 2 , 5 - d i ke t oc amph.an e 38 (74) . (71) (72) (73) (74) In o u r l a b o r a t o r y , we a r e i n v e s t i g a t i n g t h e o x i d ' a t i o n o f b o r n y l a c e t a t e by He 1 m i n t h o s p o r i u m s a t i v u m t o g i v e a 39 m i x t u r e o f t h r e e p r o d u c t s . b o r n y l a c e t a t e 4 : 1 : 1.5 On i n c u b a t i o n w i t h Cunn inghame11 a b 1 a c k e s 1 e e a n a , g e r m a c r o n e (75) g i v e s e p o x i d e s ( 7 6 ) , (77) and d i e p o x i d e s ( 7 8 ) . A s t e reochem i s t i - c a 1 s t u d y shows t h a t a l l t h e e p o x i d e s h a v e t h e same c o n f o r m a t i o n as t h a t o f (75) and t h u s t h e m i c r o o r g a n i s m a t t a c k s p r e f e r e n t i a l l y one - 29 -o f t h e 40 e n a n t i o m e r i c c o n f o r m a t i o n s . (78) G i b b e r e 1 1 i n s , a c l a s s o f n o n - d i t e r p e n e s w h i c h have t h e g i b b a n e s k e l e t o n (79), have an u n u s u a l i n f l u e n c e on t h e g r o w t h and d e v e l o p m e n t o f p l a n t s . I t i s b e l i e v e d t h a t g i b b e r e l l i n s a r e b i o s y n t h e s i z e d i n p l a n t s v i a e n t - 1 6 - k a u r e n e (80) o r c o r r e s p o n d i n g d e r i v a t i v e s . B e c a u s e o f i t s i m p o r t a n c e , e x t e n s i v e r e s e a r c h has been c a r r i e d o u t . I n c u b a t i o n o f d i e n o l (81) w i t h G i bbe re 1 l a f u j i ku ro i g i v e s t h r e e a c i d s w h i c h a r e i s o l a t e d as t h e m e t h y l 41 e s t e r s (82, 83 , 84) . (79) (80) - 30 -(84) 1 7 - n o r ka u r an - 1 6 -on e (85) and en t - 1 7 -no r k a u r an - 1 6 -on e (86) a r e h y d r o x y l a t e d a t C - 1 , C - 3 , C-7>.or C-9 p o s i t i o n s by t h e f u n g u s A s p e r g i l l u s n i g e r and R. n i g r i c a n s . A m e c h a n i s m i s p r o p o s e d f o r t h e s e r emote h y d r o x y 1 a t i o n s . The h y d r o x y l a s e f i r s t b i n d s t o t h e o x y g e n f u n c t i o n a t C-16 i n s u c h a way t h a t t h e s i t e o f o x y g e n a t i o n o f t h e s u b s t r a t e b e a r s a f i x e d g e o m e t r i c a l r e l a t i o n s h i p t o t h e c a r b o n y l . The enzyme t h e n s e e m i n g l y s i n g l e s 42 o u t t h e most f a v o r a b l e p r o t o n . - 31 -B i o t r a n s f o r m a t i o n can a l s o be c a r r i e d o u t by mammals. C e d r o 1 s ( 8 7 ) i s f u n c t i o n a 1 i s e d by r a b b i t s a t an u n a c t i v a t e d s i t e . The p r o d u c t s so f o r m e d a r e ( 8 8 ) , (89) and ( 9 0 ) . The most u s e f u l t r a n s f o r m a t i o n o f t h i s t y p e i s t h e o x i d a t i o n o f H (90) p a t c h o u l o l (91) t o g i v e p r o d u c t s w h i c h can be u sed t o o b t a i n kk n o i i r - p a t c h o u 1 e n o l ( 9 2 ) , t h e o d o u r c a r r i e r o f p a t c h o u l i o i l . - 32 -The o c c u r r e n c e o f n o r - p a t c h o u 1 e n o l i n p a t c h o u l i l e a v e s may be due t o t h e b i o - o x i d a t i o n o f p a t c h o u l o l i n t h e p l a n t , f o l l o w e d by an e l i m i n a t i o n r e a c t i o n . C92) - 33 -DISCUSSION (A) Remote o x i d a t i o n o f a c y c l i c a c e t a t e s Somet ime a g o , B r e s l o w and h i s c o - w o r k e r s e l a b o r a t e d a s y n t h e t i c p r o c e d u r e ( r e m o t e o x i d a t i o n ) , t o f u n c t i o n a 1 i s e some s t r a i g h t - c h a i n s u b s t r a t e s . The r e s u l t i n g p r o d u c t s c o u l d t h e n be c o n v e r t e d t o p r o d u c t s w i t h a new c a r b o n y l g r o u p s e l e c t i v e l y 45 i n t r o d u c e d i n t o t h e c h a i n . T h i s i n v i t r o r e a c t i o n i m i t a t e s t h e s e l e c t i v e f u n c t i o n a 1 i s a t i o n by an enzyme o f u n a c t i v a t e d m e t h y l e n e g r o u p s . L a t e r , f r o m t h i s l a b o r a t o r y , a n o v e l o x i d a t i o n o f u n a c t i v a t e d m e t h y l e n e s i n f a t t y a c i d m e t h y l e s t e r s by c h r o m i u m 46 t r i o x i d e i n a c e t i c a n h y d r i d e was r e p o r t e d . The f a t t y a c i d e s t e r s (93) we re o x i d i z e d by C r 0 3 - A c 2 0 t o g i v e a m i x t u r e o f k e t o - e s t e r s (94) w h i c h we re t h e n i d e n t i f i e d by e x a m i n i n g t h e mass s p e c t r a o f t h e c o r r e s p o n d i n g e t h y l e n e a c e t a l s (95) and e t h y l e n e t h i o a c e t a l s (96). The r e s u l t s ( c f . f i g u r e s 3 and 4) i n d i c a t e d t h a t t h e r e was C r 0 n / A c 2 0 C H 3 ( C H 2 ) n C 0 2 C H 3 > C H 3 ( C H 2 ) x C O ( C H 2 ) y C 0 2 C H 3 n = 16 , 20 (93) (94) C H 3 ( C H 2 ) x C + C ( C H 2 ) y C 0 2 C H 3 ^ -CH, (CH ) C ( C H J CO CH 3 2 x 2 y 2 3 (95) (96) x=o x=s - 3** -m o d e s t s e l e c t i v i t y f o r a t t a c k a t b i o l o g i c a l l y i n t e r e s t i n g U 6 8 10 12 tt 16 18 S i t e s o f o x i d a t i o n F i g u r e 3- O x i d a t i o n o f m e t h y l s t e a r a t e [ d a t a f r o m t h e low r e s o l u t i o n (!5eV) s p e c t r u m o f a c e t a l s (95; x+y=15) - x x - b a s e d on f r a g m e n t C H ^ C h ^ ) : - o — — o - b a s e d on f r a g m e n t £ ( CH 2 ) y CO 2 CH 3] . + S i t e s o f o x i d a t i o n F i g u r e k. O x i d a t i o n o f m e t h y l d o c o s a n o a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f t h i o a c e t a l s (96; x+y=19):~x x - b a s e d on f r a g m e n t C H , ( C H 2 ) „ C : - o o-b a s e d on f r a g m e n t C ( CH 0 ) C 0 o CH->! . c x c + s ^ + 2 y 2 3 J U - 35 -p o s i t i o n s . T h i s p r o v i d e d e v i d e n c e t h a t c e r t a i n m o l e c u l e s a r e s u s c e p t i b l e t o o x i d a t i o n a t c e n t r e s w h i c h a r e g e n e r a l l y c o n s i d e r e d t o b e u n r e a c t i v e . To e x t e n d t h e s e i n v e s t i g a t i o n s , we h a v e e x a m i n e d t h e hi o x i d a t i v e v u l n e r a b i l i t y o f a c y c l i c a c e t a t e s . T r e a t m e n t o f p u r e 1 - o c t a d e c y l a c e t a t e ( 9 7 ; n = l 6 ) i n g l a c i a l a c e t i c a c i d / a c e t i c a n h y d r i d e w i t h c h r o m i u m t r i o x i d e / a c e t i c a n h y d r i d e ( i . e . c h r o m y l a c e t a t e ) a t room t e m p e r a t u r e f o r h8 h o u r s p r o v i d e d a m i x t u r e o f m o n o - o x o - a c e t a t e s ( 9 8 ; x+y=15) and s t a r t i n g m a t e r i a l . C a r e f u l c o l u m n c h r o m a t o g r a p h y [ W o e l m s i l i c a g e l g r a d e I I I (1: 5 0 ) ; p e t . e t h e r / e t h e r ] s e p a r a t e d t h e o x o - a c e t a t e s f r o m s t a r t i n g m a t e r i a l . The y i e l d o f p r o d u c t b a s e d on consumed s t a r t i n g m a t e r i a l was ^ 3 0 % . The mass s p e c t r u m , e l e m e n t a l a n a l y s i s , i n f r a r e d and NMR d a t a w e r e s a t i s f a c t o r y f o r m o n o - o x o - a c e t a t e s . The i n f r a r e d -1 s p e c t r u m ( C C l ^ ) showed a b s o r p t i o n bands a t 1737 and 1715 cm and t h e NMR s p e c t r u m e x h i b i t e d r e s o n a n c e s a t x 6 . 00 ( t , 2H , -CH_ 2 0Ac) , 7 -70 ( t , 4H , -CH_ 2C0CH_ 2-) , 8 . 02 ( s , 3H , - 0 2 C C H _ 3 ) , 8 .70 ( b r o a d s , 26H , C H 3 ( C H _ 2 ) 1 3 ) and 9 - 1 0 ( t , 3 H , C H _ 3 ( C H 2 ) n ) . In a d d i t i o n , t h e mass s p e c t r u m showed t h e c o r r e c t m o l e c u l a r i o n peak at 3 2 6 . I t was a s i m p l e m a t t e r t o d e t e r m i n e t h e p o s i t i o n o f o x i d a t i o n s i n c e t h e r e s u l t i n g a c e t a t e s c o u l d be c o n v e r t e d i n t o t h e c o r r e s p o n d i n g e t h y l e n e a c e t a l a l c o h o l s ( 9 9 ) , w h i c h c o u l d be e x a m i n e d by mass s p e c t r o s c o p y , t o d e t e r m i n e w h e r e f u n c t i o n a 1 i s a t i o n had o c c u r r e d . At low i o n i z i n g v o l t a g e s , (99 ) f r a g m e n t e d m a i n l y a t t h e c a r b o n c a r r y i n g t h e a c e t a l t o g i v e - 36 -CH (CH ) CH OAc 3 2 n 2 (97) C rO /Ac^O/HOAc NaBH, CH (CH ) CO(CH ) CH OAc 3 2 x 2 y 2 (98) 1. ( C H 2 0 H ) 2 / H + 2 . KOH/MeOH OH C H 3 ( C H 2 ) x C H ( C H 2 ) C H 2 0 A c ( 101 ) 1. M s C 1 / C 5 H 5 N 2. c o l l i d i n e / A A CH ( C H J CH=CH(CH„ ) , CH OAc 3 2 a 2 b 2 C H 3 ( C H 2 ) x C ( C H 2 ) y C H 2 0 H (99) 0 ^ 0 + CH (CH ) C + C(CH ) CH OH 3 2 x 2 y 2 ( 102 ) ( 1 0 0 a ) ( 100b ) f r a g m e n t s ( I 0 0 a , b ) . H o w e v e r , d i s c r e p a n c i e s b e t w e e n t h e two s e t s o f r e s u l t s ( f r o m i o n s 100a and 100b) a t t h e t e r m i n a l s i t e s ( f i g u r e s 5 -6) i n d i c a t e d t h a t t h e f r a g m e n t a t i o n p r o c e s s was n o n -random when t h e a c e t a l g r o u p was l o c a t e d t o w a r d s t h e end o f t h e c h a i n . T h i s d i s c r e p a n c y c o u l d be a v o i d e d i f t h e p e r c e n t d i s t r i b u t i o n was c a l c u l a t e d on b a s i s o f t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 00a ) and ( 1 0 0 b ) , as shown i n f i g u r e s (7 - 8) . The r e s u l t s c l e a r l y i n d i c a t e t h a t o c t a d e c y l a c e t a t e - 37 -can be d i r e c t l y o x i d i z e d t o a m i x t u r e o f mono -oxo d e r i v a t i v e s , and t h a t t h e p r o c e s s i s p a r t i a l l y r e g i o s p e c i f i c . The a n a l y t i c a l t e c h n i g u e u s ed h e r e t o d e t e r m i n e t h e p o s i t i o n o f f u n c t i o n a 1 i s a t i o n i n a s t r a i g h t - c h a i n s u b s t r a t e i s v a l i d on t h e a s s u m p t i o n t h a t t h e r e l a t i v e i n t e n s i t i e s o f t h e peak s i n t h e mass s p e c t r a o f t h e e t h y l e n e a c e t a l s (99) a r e a t r u e r e p r e s e n t a t i o n o f t h e r e l a t i v e amount s o f i s o m e r i c o x o -a c e t a t e s p r e s e n t i n t h e p r o d u c t m i x t u r e . A c o n d i t i o n f o r t h i s a s s u m p t i o n i s t h a t t h e i n t e n s i t y o f t h e p a r e n t peak i s s m a l l c o m p a r e d t o t h a t o f t h e c t - c l e a v a g e p e a k s i n t h e mass s p e c t r a . L a t e r s t u d i e s showed t h a t d o d e c y l a c e t a t e (97; n=10), t e t r a d e c y l a c e t a t e (97; n=12) and d o c o s y l a c e t a t e (97; n=20) were o x i d i z e d t o a m i x t u r e o f m o n o - o x o - a c e t a t e s by t h e c h r o m y l a c e t a t e r e a g e n t . By t h e a n a l y s i s d e s c r i b e d a b o v e , t h e d i s t r i b u t i o n o f i s o m e r i c o x o - a c e t a t e s a r e as s u m m a r i z e d i n f i g u r e s 9 - 20. The se r e s u l t s i n d i c a t e t h a t t h e o x i d a t i o n o f s h o r t e r c h a i n a n a l o g u e s ( f i g u r e s 9 — 1 6) i s more r e g i o s p e c i f i c t h a n t h e l o n g e r c h a i n a n a l o g u e s ( f i g u r e s 5-8, 17 - 20). T h i s i s r e a s o n a b l e b e c a u s e i n a s t r o n g l y p o l a r med ium, t h e l o n g e r t h e n o n - p o l a r c h a i n t h e more i t p r e f e r s t o f o l d a r o u n d i t s e l f and more m e t h y l e n e h y d r o g e n s a c h i e v e c l o s e p r o x i m i t y t o t h e chromat.e o x y g e n s . T h i s e x p l a n a t i o n i s h y p o t h e t i c a l b e c a u s e t h e c o n f o r m a t i o n s o f n o n - p o l a r c h a i n i n p o l a r s o l v e n t a r e n o t w e l l s t u d i e d . The v a l i d i t y o f t h e mass s p e c t r o s c o p i c method u sed t o e s t i m a t e t h e r e l a t i v e amounts o f p o s i t i o n a l i s o m e r s was t e s t e d - 38 -by u s i n g m i x t u r e s o f e t h y l e n e a c e t a l s o f known c o m p o s i t i o n d e r i v e d f r o m s y n t h e t i c 3-, 1 0 - , 1 1 - and 1 5 _ o x o - 1 - o c t a d e c a n o 1 . The l o n g - c h a i n h y d r o x y a c i d ' , ( 1 0 3 ; n = 10) was c o n v e r t e d t o a c e t o x y a c i d ( 1 0 4 ; n=10) by r e a c t i o n w i t h a c e t i c a n h y d r i d e / p y r i d i n e . O x a l y l c h l o r i d e t h e n gave t h e c o r r e s p o n d i n g a c i d c h l o r i d e ( 1 0 5 ; n = 1 0 ) , w h i c h was t r e a t e d w i t h h e p t y l z i n c b r o m i d e (106 ; m=6) t o g i v e t h e k e t o - a c e t a t e ( 1 0 7 ; n=10, m=6); t h i s was i n t u r n c o n v e r t e d t o t h e e t h y l e n e a c e t a l a l c o h o l ( 1 0 8 ; n = (ij'0 , m=6) t h r o u g h t h e i n t e r m e d i a t e e t h y l e n e a c e t a l a c e t a t e . The same r e a c t i o n s e q u e n c e was used t o s y n t h e s i z e 1 5 - o x o - 1 - o c t ade cy 1 a c e t a t e ( 1 0 (7 ; n = 1 4 , m=2) w h i c h was t h e n c o n v e r t e d t o t h e e t h y l e n e a c e t a l a l c o h o l ( 1 0 8 ; n = l 4 , m=2). In o r d e r t o ge t t h e e t h y l e n e a c e t a l s o f 9- and 1 0 - o x o - 1 - o c t a d e c a n o 1 ( 1 1 2 a and b ) , b o r a n e - d i m e t h y 1 s u l f i d e i n t e t r a h y d r o f u r a n was added t o a s o l u t i o n o f m e t h y l o l e a t e ( 109 ) i n t e t r a h y d r o f u r a n ; a f t e r 3 h o u r s a t room t e m p e r a t u r e , s o d i u m h y d r o x i d e and h y d r o g e n p e r o x i d e we re added t o g i v e , a f t e r a f u r t h e r 1 h o u r r e f l u x , a m i x t u r e o f m e t h y l 3~ and 1 0 - h y d r o x y s t e a r a t e ( 1 1 0 a , b ) . J o n e s o x i d a t i o n n o f ( 1 1 0 a , b ) gave a m i x t u r e o f m e t h y l 9 - and 1 0 - k e t o -s t e a r a t e ( I 1 1 a , b ) w h i c h was t h e n c o n v e r t e d t o t h e e t h y l e n e a c e t a l ; e s t e r s . R e d a c t i o n o f e t h y l e n e a c e t a l e s t e r s w i t h L i A l H ^ p r o v i d e d a m i x t u r e o f e t h y l e n e a c e t a l s o f 9 _ and 1 0 - o x o - 1 -o c t a d e c a n o l ( I 1 2 a , b ) . The mass s p e c t r a o f t h e known m i x t u r e o f e t h y l e n e a c e t a l s d e r i v e d f r o m s y n t h e t i c 3~ , 1 0 - , 1 1 - and 15~ o x o - 1 - o c t a d e c a n o 1 showed c l e a n f r a g m e n t a t i o n and p r o v i d e d a - 39 -q u a n t i t a t i v e d i s t r i b u t i o n i n good a g r e e m e n t w i t h t h e known c o m p o s i t i o n s o f t h e m i x t u r e s ( f i g u r e s 2 1 - 3 5 ) . A c 2 0 / p y r H0(CH ) COOH 2 n (103) -> AcO(CH ) COOH 2 n (104 ) 1 . ( C H 2 0 H ) 2 / H + H 0 ( C H j CG>(CHj CH <r 2 n 2 m 3 ( 108 ) 2.KOH/MeOH (COC 1 ) ->AcO(CH ) C0C1 2 n ( 105 ) C H 3 ( C H 2 ) m Z n B r (106 ) Ac0(CH-.) C 0 ( C H „ ) CH 'r 2 n 2 m ~ 3 ( 107 ) 1 .B H 3 .Me 2 S C H 3 ( C H 2 ) 7 C H = C H ( C H 2 ) 7 C 0 2 C H 3 (109 ) 2 .NaOH, H 2 0 2 Ho 1 . ( C H 2 0 H ) 2 / H+ N X C H 3 ( C H 2 ) m C ( C H 2 ) n 0 H «e ( 1 1 2 a ; m=8, n=7) ( 1 1 2 b ; m=7, n=8) 2 . L i A l H/, OH ->CH (CH J CH(CH„) CO CH„ 3 2 m 2 n 2 3 ( 1 1 0 a ; m=8, n=7) ( 1 1 0 b ; m=7, n=8) J o n e s r e a g e n t C H 3 ( C H 2 ) m C O ( C H 2 ) n C : 0 2 C H 3 ( 1 1 1 a ; m=8, n=7) ( 1 1 1 b ; m=7, n = 8) We a t t e m p t e d t o i n c r e a s e t h e s e l e c t i v i t y o f t h e r e a c t i o n - 40 -by c a r r y i n g o u t t h e o x i d a t i o n o f ( 9 7 ; n = l 6 ) i n t e n t i m e s t h e amount o f s o l v e n t and t h e same amount o f C r 0 3 - A c 2 0 . The r e s u l t s shown i n f i g u r e s 36 and 37 i n d i c a t e t h a t t h i s a t t e m p t was u n s u c c e s s f u l : a b r o a d e r d i s t r i b u t i o n o f p r o d u c t s c o v e r i n g c a r b o n s 3 t o 17 was o b t a i n e d . F u r t h e r a t t e m p t s t o i n c r e a s e t h e s e l e c t i v i t y by u s i n g o t h e r o x i d i z i n g a g e n t s a l s o f a i l e d . F o r e x a m p l e , no t=e ac-jb i on o c c u r r e d b e t w e e n t h e s u b s t r a t e ( 9 7 ; n = l 6 ) and N a 2 C r 2 0 7 / H 2 S 0 Z t / H 2 0 . The m e c h a n i s m o f t h e s e o x i d a t i o n r e a c t i o n s r e m a i n s u n c e r t a i n . It m i g h t be p r o p o s e d , as a f i r s t s t e p , t h a t t h e p o l a r f u n c t i o n a l g r o u p s ( e s t e r s ) can i n t e r a c t w i t h c h r o m y l a c e t a t e t o f o r m a r e a c t i v e c o m p l e x (113 ) i n s u c h a way t h a t t h e s i t e o f o x y g e n a t i o n o f t h e s u b s t r a t e b e a r s a g e o m e t r i c a l r e l a t i o n s h i p 48 t o t h e m e t a l . The s e c o n d s t e p i n v o l v e s an i n t r a m o l e c u l a r h y d r o g e n a b s t r a c t i o n . T h i s c h e l a t i o n o f c h r o m y l a c e t a t e by s u b s t r a t e and h y d r o g e n a b s t r a c t i o n l e a d s t o d i s c r e t e r a d i c a l i n t e r m e d i a t e s (114 ) w h i c h a c c o r d i n g l y a r e e x p e c t e d t o be o x i d i z e d by c h r o m i u m (V) t o g i v e h y d r o x y a c e t a t e c o m p l e x (115 ) -F u r t h e r o x i d a t i o n o f (115 ) p r o v i d e s k e t o - a c e t a t e s ( 1 1 6 ) . 0 II AcO-C r -OAc il 0 AcO^ y |^0 A c O ( C H 2 ) n C H 3 - ^ ^ C r + 0 S 7 ^ J Q " + AcO,' C H 3 C 0 ( C H 2 ) £ C H ( C H 2 ) y C H 3 (113 ) - 41 -AcO ^0 \ ^ ii AcO AcO 0 \ * C r + 0 7 _ 3 > C H , C 0 ( C H _ ) C H ( C H C ) CH 3 2 x 2 y 3 OH C H „ C 0 ( C H „ ) C H ( C H - ) C H , 3 2 x 2 y 3 ( 114 ) (115 ) Lei - > C H 3 C 0 2 ( C H 2 ) x C 0 ( C H 2 ) y C H 3 ( 116 ) An i n t e r e s t i n g a p p l i c a t i o n o f t h i s w o r k i s t h a t i t p r o v i d e s a s i m p l e s y n t h e t i c r o u t e t o a m i x t u r e o f m o n o -u n s a t u r a t e d a c e t a t e s (102; a+b=12) . R e c e n t r e s e a r c h h a s s h o w n t h a t t h e p o t e n t s e x p h e r o m o n e p r o d u c e d by t h e f e m a l e b e r t h a 49 a r m y w o r m i s c i s - 1 1 - h e x a d e c e n - 1-y1 a c e t a t e . T h e b e r t h a a r m y w o r m i s an i n s e c t t h a t i n f l i c t s m a j o r d a m a g e t o r a p e s e e d c r o p s o f t h e C a n a d i a n p r a i r i e p r o v i n c e s . T h e d i s c o v e r y o f t h i s p h e r o m o n e , c i s -1 1 - h e x a d e c e n - 1 - y 1 a c e t a t e , p r o v i d e s a p o s s i b l e way t o c o n t r o l t h i s i n s e c t b i o l o g i c a l l y . W i t h t h e u s u a l o x i d a t i o n r e a g e n t , h e x a d e c y l a c e t a t e s ( 9 7 ; n = l 4 ) w a s e c o n v e r t e d t o a m i x t u r e o f m o n o - o x o - a c e t a t e s ( 9 8 ; x+y = 13) w h i c h w e r e t h e n r e d u c e d w i t h { s o d i u m b o r o h y d r i d e i n m e t h a n o l . T h e h y d r o x y h e x a d e c y 1 a c e t a t e s (101; x+y=13) w e r e t h e n r e a c t e d w i t h m e s y l c h l o r i d e . E l i m i n a t i o n o f t h e mesy1 a t e s ( h o t c o l l i d i n e ) p r o v i d e d a m i x t u r e o f m o n o -u n s a t u r a t e d C ^ a c e t a t e s (102; a+b=12) w h o s e s e x p h e r o m o n a l a c t i v i t y w a s t e s t e d by D r . M . D . C h i s h o l m ( P r a i r i e R e g i o n a l - kz -L a b o r a t o r y , S as ka t o o n ) ./ 'The' r e s u l t s showed t h a t t h e s y n t h e t i c 50 m i x t u r e i s p o s i t i v e l y a c t i v e t o t h e ma le b e r t h a a rmyworm. The o c c u r r e n c e o f u n s a t u r a t e d a c e t a t e s i n b e r t h a armyworm may be due t o t h e o x i d a t i o n o f h e x a d e c y l a c e t a t e s i n t h e i n s e c t , f o l l o w e d by an e l i m i n a t i o n r e a c t i o n , w h i c h i s t h e b i o l o g i c a l e q u i v a l e n t o f t h e s t e p ( 1 0 1 ) > ( 1 0 2 ) d e s c r i b e d ,etacr\l ci e r . R e c e n t r e p o r t s have r e v e a l e d t h a t t h e s ex phe romone o f t h e oak l e a f r o l l e r moths, c o n t a i n s a s e r i e s o f t e t r a d e c e n y l 51 a c e t a t e s h a v i n g d o u b l e bonds i n p o s i t i o n s 2 t o 12 / and t h e s e x phe romone o f some f r u i t moths ( c a b b a g e l o o p e r m o t h , o r i e n t a l f r u i t moth and g r a p e b e r r y moth) i s a m i x t u r e o f m o n o - u n s a t u r a t e d 52 a c e t a t e s . F o l l o w i n g t h e same r e a c t i o n scheme ( s e e P . 3 6 ) , t h e c o r r e s p o n d i n g m i x t u r e o f m o n o - o x o - t e t r a d e c y 1 a c e t a t e s ( 9 8 ; x + y = 1 l ) and m o n o - o x o - d o d e c y 1 a c e t a t e s ( 9 8 ; x+y=9) w e r e c o n v e r t e d t o m i x t u r e s o f m o n o - u n s a t u r a t e d a c e t a t e s ( 1 0 2 ; a+b=10) and mono-uns a t u r a t e d a c e t a t e s ( 1 0 2 ; a+b=8) whose s e x p h e r o m o n a l a c t i v i t y i s c u r r e n t l y b e i n g e v a l u a t e d r e s p e c t i v e l y by P r o f e s s o r L . B . H e n d r y ( P e n n s y l v a n i a S t a t e U n i v e r s i t y ) and P r o f e s s o r W . L . R o e l o f s ( C o r n e l l U n i v e r s i t y ) . S i t e s o f o x i d a t i o n F i g u r e 5 . O x i d a t i o n o f o c t a d e c y l a c e t a t e [ d a t a s p e c t r u m o f a c e t a l s ( 9 9 ; x + y = 1 5 ) : - o -b a s e d on f r a g m e n t ( 1 0 0 b ) ] . f r o m t h e 1ow - o - b a s e d on r e s o l u t i o n ( 15eV) mass f r a g m e n t (1 0 0 .a) : - A A " S i t e s o f o x i d a t i o n F i g u r e 6 . O x i d a t i o n o f o c t a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0 e V ) mass s p e c t r u m o f a c e t a l s ( 9 9 ; x + y=15 ) : - o 0 - b a s e d on f r a g m e n t ( 1 0 0 a ) : - A — A -b a s e d on f r a g m e n t ( 1 0 0 b ) ] . CT "> 10 CT C o 3 XL D n n D. 6 7 3 9 10 S i t e s o f o x i d a t i o n 11 12 13 14 15 16 17 F i g u r e 7- O x i d a t i o n o f o c t a d e c y l a c e t a t e [ d a t a f r o m t h e low. r e s o l u t i o n (15eV) mass s p e c t r u m o f a c e t a l s ($3; x+y= 1 5) • bas ed on ' ' t h e ••comb i ned r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 0 0 a and b ) j . 1 0 - J cr c o 3 XL 6 7 8 9 10 S i t e s o f o x i d a t i o n 1 1 12 I t 13 14 15 16 17 F i g u r e 8. O x i d a t i o n o f o c t a d e c y l a c e t a t e " d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass 15J b a s e d on t h e c o m b i n e d s p e c t r u m o f a c e t a l s (99; x+y= o f f r a g m e n t s ( 1 0 0 a and b ) j . r e l a t i v e i n t e n s i t y S i t e s o f o x i d a t i o n F i g u r e 9. O x i d a t i o n o f d o d e c y l a c e t a f e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ( 9 9 ; x+y = 9 ) : - o o - b a s e d on f r a g m e n t (10 0a) : -A — A -b a s e d on f r a g m e n t ( 1 0 0 b ) ] . F i g u r e 10. O x i d a t i o n o f d o d e c y l a c e t a t e [ d a t a f rom s p e c t r u m o f a c e t a l s ( 9 9 ; x+y=9 ) : - o o -b a s e d on f r a g m e n t (10 0 b ) J . the low r e s o l u t i o n (70eV) mass b a s e d on f r a g m e n t (100 a ) : - A — A -a-? o «• 20 c r o 3 1 0 XL n n 3 4 5 S i t e s o f ox i da t i on U L i _ 1 I l ' l F i g u r e 1 1 . O x i d a t i o n o f d o d e c y l a c e t a t e ( "data f r o m t h e s p e c t r u m o f a c e t a l s ( 9 9 ; x+y=9) o f f r a g m e n t s ( 1 0 0 a and b ) j . ow r e s o l u t i o n (l5eV) mass b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o " 2 0 — in 1 0 — \ n n n II 1 1 J i I . '7 J J Jo J 1 S i t e s o f o x i d a t i o n F i g u r e 1 2 . O x i d a t i o n o f d o d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0 e V ) mass s p e c t r u m o f a c e t a l s ( 9 9 ; x+y=9) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 0 0 a and b ) ] . F i g u r e 13. O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s (99; x+y = 1 l ) : - o o - b a s e d on f r a g m e n t (10 0a) : - A——A -b a s e d on f r a g m e n t (100b)]. S i t e s o f ox i d a t i on F i g u r e 1 4 . O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t r u m o f a c e t a l s ( 9 9 ; x + y = 1 l ) : - o o - b a s e d on f r a g m e n t ( I 0 0 a ) : - A A -b a s e d on f r a g m e n t ( l O O b ) J . 10 JL -O- SL 4 5 6 7 S i t e s o f o x i d a t i o n 10 1 1 1 2 13 F i g u r e 15 . O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ( 9 9 ; x+y=11) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 0 0 a and b ) j . in 20 — cr c o - E -1 0 X L XL J l 4 5 6 7 S i t e s o f o x i d a t i o n 10 1 1 1 2 13 F i g u r e - 16. O x i d a t i o n o f t e t r a d e c y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t r u m o f a c e t a l s (99; x+y=1l) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t ' s (100a and b ) ] . - 55 -i < in I e i <u o L A o o c .- CD +-> e ^ cn — fD O i -</> <D i - C O O - o — CO in <D fO e o o o fD I •M •• fD - — -- o o~\ ll <u >-fD x • i 1 <U • — s O CTi - O fD <Ti O — - O >- (/) (/) — O (D +J O  cu <D E fD CD i4- ro O M - L. O c O £ C — 3 O 4-1 1-fO 4-1 "O -ooo) — a) a) x a n O </) JD 4 -L A 3 % D i s t r i b u t i o n S i t e s o f ox i d a t i on F i g u r e 18. O x i d a t i o n o f d o c o s y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t r u m o f a c e t a l s (99; x + y = 1 9 ) : - o — o - b a s e d on f r a g m e n t (100a ) : -A~A-b a s e d on f r a g m e n t (l00b)"|. C3 1 0 CT' C O 3 n _X3 r p • i r i 3 4 5 7 8 9 10 11 S i t e s o f o x i d a t i o n 12 13 14 15 16 17 18 19 20 21 F i g u r e 19- O x i d a t i o n o f d o c o s y l a c e t a t e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s (99; x+y=19) b a s ed on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s (100a and b ) ] . CT in rr -\ O" c 10 o 3 Ul CO - O C 3 _ - C l C3_ 6 7 8 9 10 11 S i t e s o f o x i d a t i o n 12 13 14 15 16 17 1 3 19 20 21 F i g u r e 20 . O x i d a t i o n o f d o c o s y l a c e t a t e s p e c t r u m o f a c e t a l s (99; x+y o f f r a g m e n t s ( 1 00a and b ) J . [ d a t a f r om t h e low r e s o l u t i o n (70eV) mass =19) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y - 59 -CH 3(CH 2) Y ( C H 2 ) y C H 2 0 H % 9 :10:11 :15 = 2 6 . 4 : 2 6 . 4 : 2 1 . 7 : 2 5 - 4 e x p e c t e d % f o u n d % ~ ' z1 > 7—1 70 60 50 AO 30 20 10 l ow r e s o l u t i o n (l5eV) C(CH 2) y0H 10 11 15 % 70 60 50 40 30 20 10 CH3 ( C H 2 ) x Y 10 11 15 F i g u r e 21. Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (!5eV) mass s p e c t r u m ] - 60 -o C H 3 ( C H 2 ) x C ( C H 2 ) y C H 2 0 H % 9 : 1 0 : 1 1 : 1 5 = 2 6 . 4 : 2 6 . 4 : 2 1 . 7 : 2 5 - 4 e x p e c t e d % ~ 1 f o u n d % rr / / 7-7—i low r e s o l u t i o n ( 7 0eV ) 70 60 50 AO 30 20 10 C (CH„ ) OH 2 y 9 10 11 15 ib 60 50 40 30 20 10 C H 3 ( C H 2 ) x C 10 11 15 F i g u r e 2 2 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n j d a t a - f r o m t h e low r e s o l u t i o n ( 7 0 p V ) m a e c C o«^ i -^. ,„ l - 61 -^ o CH„ (CH J Y( CH J CH OH % 9 : 1 0 : 1 1 : 1 5 = 2 6 . 4 : 2 6 . 4 : 2 1 . 7 : 2 5 . 4 3 2 x 2 y . 2 % 70 60 50 40 • 30 20 10 expected % u.... -1 found % CZZZ~? < j—A ow r e s o l u t i o n (l5eV) 10 11 1 5 9" 70 1 60 50 -40 30 20 •-} 1 0 low r e s o l u t i o n (70eV) 10 11 T 15 Figure 2 3 - Q u a n t i t a t i v e study of mixture of known composition [data from the low r e s o l u t i o n mass s p e c t r a based on the combined r e l a t i v e i n t e n s i t y of Fragments (100a and b)J . 62 C H 3 ( C H 2 ) Y ( C H 2 ) CH 2 0H % 9 : 1 0 : 1 1 : 1 5 = 4 0 . 5 : 4 0 . 5 : 8 . 3 : 1 0 . 8 0 / 70 '0 60 50 40 30 20 10 e x p e c t e d % ' f o u n d % u=z=z=zn-zn l ow r e s o l u t i o n ( l 5 e V ) C ( C H 2 ) y 0 H 10 11 15 % 70 60 50 40 30 20 10 ( f x ) - ^ 0 + •CH ( C H 2 ) X C 10 11 15 F i g u r e 24 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (l5eV) mass s p e c t r u m ] - 63 -o CH (CH ) C ( C H o ) CH OH % 9 : 1 0 : 1 1 : 1 5 = 4 0 . 5 : 4 0 . 5 : 8 - 3 : 1 0 . 8 3 2 x 2 y 2 % 70 60 50 40 30 20 10 % 70 60 50 40 30 20 10 e x p e c t e d % C I f o u n d % Z2Z2-AJ-JZnzn low r e s o l u t i o n ( 7 0 e V ) C ( C H 2 ) y 0 H 9 10 11 C H 3 ( C H 2 ) x C 10 11 15 15 F i g u r e 2 5 - Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m j - 64 -o CH 3(CH 2) xC(CH2)yCH 20H % 9:10:11:15=40 . 5:40 . 5 : 8 . 3:10 . 8 expected % r i found % CZZZZZZ2IZZZZ1 70 60 50 ' 40 -30 20 1 0 % 70 60 50 40 30 20 10 1 low r e s o l u t i o n (15 e V) 9 10 11 low r e s o l u t i o n (70eV) 1 5 10 11 15 Figure 26. Q u a n t i t a t i v e study of mixture of known composition [data from the low r e s o l u t i o n mass s p e c t r a based on the combined r e l a t i v e i n t e n s i t y of fragments (100a and b)] .' 65 o C H 3 ( C H 2 ) x C ( C H 2 ) y C H 2 0 H % 9 : 1 0 : 1 1 : 1 5 = 8 . 9 : 8 . 9 : 1 1 . 0 : 7 1 . 2 e x p e c t e d % I ~ i f o u n d % I--' ••' < / j—U low r e s o l u t i o n ( l 5 e V ) 70 60 50 40 30 20 10 X 70 60 50 40 30 20 10 C ( C H - ) OH 2 y 10 11 0X.;0 + CH (CH ) C 3 2 x 10 11 15 15 F i g u r e 27 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (.15eV) mass s p e c t r u m ] - 66 -o CH (CH ) C(CH ) CH OH % 9 : 1 0 : 1 1 : 1 5 = 8 . 9 : 8 . 9 : 1 1 . 0 : 7 1 - 2 3 2 x 2 y 2 e x p e c t e d % j.. I f o u n d % rr-r-r/- / / \ %' 70 60 50 40 30 20 10 % 70 60 50 40 30 20 10 l ow r e s o l u t i o n (70eV) CCCH ) OH 2 y 9 10... i l : 0 ^ , C H 3 ( C H 2 ) x C 15 9 10 11 15 F i g u r e 2 8 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t r u m ] - 67 -r~\ C H 3 ( C H 2 ) x C ( C H 2 ) CH 20H % 9 : 1 0 : 1 1 : 1 5 = 8 . 9 : 8 . 9 : 1 1 . 0 : 7 1 . 2 70 60 ' 50 h0 30 -) 20 1 0 70 60 1 50 ho 30 20 10 + e x p e c t e d % L. f o u n d % izzzzizzz:. low r e s o l u t i o n ( 1 5eV ) 9 10 11 15 low r e s o l u t i o n ( 70eV ) 10 11 15 F i g u r e 29 - Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n mass s p e c t r a b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 0 0 a and b)] . - 63 -CH (CH ) C ( C H j CH OH % 9 : 1 0 : 1 1 : 1 5 = 1 0 . 3 : 1 0 . 3 : 6 3 . 0 : 1 6 . 4 3 2 x 2 y 2 % 70 60 50 40 30 20 10 % 70 60 50 40 30 20 10 e x p e c t e d % jr. f o u n d % 7-r-7—7—r 1ow r e s o l u t i o n ( l 5 e V ) C CH„) OH 2 y 10 11 15 / / / / / / / / / / oQ)+ C H 3 ( C H 2 ) x C 10 11 15 F i g u r e 3 0 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m ] - 69 -O C H 3 ( C H 2 ) x C ( C H 2 ) C H 2 0 H % 9:10:11 :15 = 10 . 3:10 . 3 : 6 3-0 : 1 6.4 % 70 6 0 5 0 40 30 2 0 10 % 70 6 0 5 0 40 30 20 10 e x p e c t e d % L_ f o u n d % r 7 7 T V /-J-1ow r e s o l u t i o n (70eV) C ( C H 0 ) OH 2 y 10 11 15 0 ^ 0 + C H > 3 ( C H 2 ) x C 10 11 15 F i g u r e 31. Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0 e V ) mass s p e c t r u m - 70 -CH (CH ) C(CH ) CH OH % 9 : 1 0 : 1 1 : 1 5 = 1 0 . 3 : 1 0 . 3 : 6 3 - 0 : 1 6 . 4 3 z x z y z % 70 60 50 40 30 20 1 0 70 60 50 40 30 2 0 1 0 9 '0 e x p e c t e d % f o u n d % low r e s o l u t i o n ( ! 5 e V ) 9 10 11 low r e s o l u t i o n ( 7 0eV ) 15 10 11 15 F i g u r e 3 2 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n ( d a t a f r o m t h e low r e s o l u t i o n mass s p e c t r a b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 0 0 a and b ) ] . - 71 -C H (C H ) C(CH ) CH OH % 9 : 1 0 = 5 0 : 5 0 .3 2 x 2 y 2 * • 70 '0 60 50 AO 30 20 10 o, 70 '0 60 50 40 30 20 10 e x p e c t e d % f o u n d % ./ / / / / ~ZL 1ow r e s o l u t i o n ( l 5 e V ) C(C H 0 ) OH 2 y 10 C H 3 ( C H 2 ) x C 0 + 9 10 F i g u r e 33- Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n ( ! 5 e V ) mass s p e c t r u m j - 7 2 CH (CH ) C(CH ) CH OH % 9 : 1 0 = 5 0 : 5 0 3 2 x 2 y 2 0 / 70 60 50 40 30 20 10 e x p e c t e d % f o u n d % low r e s o l u t i o n ( 70eV ) I C ( C H 2 ) y 0 H 10 o, 70 60 50 40 30 20 10 C H 3 ( C H 2 ) Y 9 10 F i g u r e 3 4 Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ da t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s -pec t rum - 73 -0 C H 3 ^ C I V x ^ C I V y C H 2 0 H ^ 9 : 1 0 expected % found % = 50 :50 9 /a 6 70 -60 -50 -40 -30 20 . 10 4 r r v / zzzi low r e s o l u t i o n ( l 5 e V ) T-L-l L - i ^ ^ 9 10 70 60 50 4 40 30 20 10 low r e s o l u t i o n ( 70eV ) 9 10 F i g u r e 3 5 . Q u a n t i t a t i v e s t u d y o f m i x t u r e o f known c o m p o s i t i o n [ d a t a f r o m t h e low r e s o l u t i o n mass s p e c t r a b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 0 0 a a n d b ) ] . 1 2 3 4 5 6 7 8 9 10 S i t e s o f o x i d a t i o n 11 12 13 14 1 5 1 6 17 F i g u r e 36. O x i d a t i o n o f o c t a d e c y l a c e t a t e i n t e n t i m e s amount o f s o l v e n t and t h e same amount o f C r 0 3 - A c 2 0 f d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s (99; x+y=15) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 0 0 a and b ) ] . 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 1 6 1 7 S i t e s o f o x i d a t i o n F i g u r e 3 7 . O x i d a t i o n o f o c t a d e c y l a c e t a t e i n t e n t i m e s amount o f s o l v e n t and t h e same amount o f C r O ^ - A c ^ O [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t r u m o f a c e t a l s ( 9 9 ; x+y=15) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s (100a and b ) ] . - 76 -(B) Remote o x i d a t i o n o f m a c r o c y c l i c l a c t o n e s A f t e r some p r e l i m i n a r y e x a m i n a t i o n o f f l e x i b l e l o n g c h a i n a c e t a t e s , we d e c i d e d t o e x p l o r e t h e o x i d a t i v e - v u l n e r a b i l i t y o f m a c r o c y c l i c l a c t o n e s , a c l a s s o f compounds w h i c h have l e s s f l e x i b i l i t y . The o x i d a t i o n o f m a c r o c y c l i c l a c t o n e s l e a d s t o a v a r i e t y o f w e l l - k n o w n and c l i n i c a l l y i m p o r t a n t m a c r o l i d e 53 a n t i b i o t i c s . T r e a t m e n t o f p u r e 1 6 - h e x a d e c a n o 1 i d e ( 1 1 7 ; n=15) i n g l a c i a l a c e t i c a c i d / a c e t i c a n h y d r i d e w i t h c h r o m i u m t r i o x i d e / a c e t i c a n h y d r i d e ( i . e . c h r o m y l a c e t a t e ) a t room, t e m p e r a t u r e f o r 5 day s p r o v i d e d a m i x t u r e o f mono - oxo - 1 6 -h e x a d e c ano 1 i des ( 1 1 8 ; x+y=14) and 5 k r s t a r t i n g m a t e r i a l . C a r e f u l c o l u m n c h r o m a t o g r a p h y |_Woelm s i l i c a g e l g r a d e I I I ( 1 : 5 0 ) ; p e t . e t h e r / e t h e r ] s e p a r a t e d t h e m o n o - o x o - 1 6 -h e x a d e c a n o 1 i d e s f r o m s t a r t i n g m a t e r i a l . The y i e l d o f t h e s e p r o d u c t s b a s e d on consumed s t a r t i n g m a t e r i a l was ^ 3 3 % . The e l e m e n t a l a n a l y s i s , i n f r a r e d and NMR d a t a i d e n t i f i e d t h e p r o d u c t s as mono-oxo - 1 6 - h e x a d e c ano 1 i des . The i n f r a r e d s p e c t r u m ( C C l ^ ) showed a b s o r p t i o n bands at 1738 and 1720 cm ^ and t h e NMR s p e c t r u m e x h i b i t e d r e s o n a n c e s a t T 5 . 9 7 ( t , 2H , - ,C 0 2 C H_2 -) , 7 -72 ( m i x e d t , 6H, - C H ^ C O C H ^ - , -CH_2C0 2 - ) , 8 . 4 2 , 8 . 7 0 (m, b r o a d s , 20H, - ( C H _ 2 ) 1 Q - ) . The p o s i t i o n o f t h e k e t o - ; g r o u p and r e l a t i v e amounts o f t h e i s o m e r i c m o n o - o x o - 1 6 - hex adec ano 1 i d e scicou.l dbbet dedu ced by e x a m i n i n g t h e mass s p e c t r a o f t h e e t h y l e n e a c e t a l s o f t h e co r r e s pond i n g hya^ lrc:6<h/o>1csi d s ( 1 20 ; x+y = 1 4 ) . In t h e mass s p e c t r a m e a s u r e d at 15eV and 70eV , t h e o n l y s i g n i f i c a n t peak s a r i s e f r o m - 77 -f r a g m e n t s (121 a , b) . T h e r e f o r e t h e method d e s c r i b e d e a r l i e r ( s e e P.36) c o u l d be a p p l i e d h e r e . The m i x t u r e o f o x o - 1 6 - h e x a -d e c a n o l i d e s (1 1 8; x + y = l 4 ) , on r e a c t i o n w i t h e t h y l e n e g l y c o l / HO-9 ^ n \ 0 ( 117 ) C r 0 3 / A c 2 0 / H 0 A c '(CH 2) y, ^ ° (CH 2) X-(122 ) 1 . Ms C l /C C H. -N 2 . c o 1 1 i d i n e/A ,CCH2), (123 ) NaBH 1 . ( C H 2 0 H ) 2 / H 2. KOH/MeOH 3. NH^CI H O ( C H 2 ) X C ( C H 2 ) C 0 2 H (119 ) 1 . M s C 1 / C 5 H 5 N } 2 . L i A 1 H . 6 0 H ( C H 2 ) x Y ( C H 2 ) CH 2 0H (120 ) V H ( C H 2 ) x C C ( C H 2 ) y C H 2 0 H ( 121a ) ( 121b ) - 78 -p - t o 1 u e n e s u 1 f o n i c a c i d f o l l o w e d by h y d r o l y s i s , y i e l d e d t h e a c e t a l s o f t h e o x o - 1 6 - h y d r p x y h e x a d e c a n o i c a c i d s ( 1 1 9 ; x + y = l 4 ) . T h e i r s t r u c t u r e s we re e s t a b l i s h e d by r e d u c t i o n t o a m i x t u r e o f a c e t a l s o f m o n o - o x o - h e x a d e c a n o 1 s ( 1 2 0 ; x+y= l 4 ) whose mass s p e c t r a showed b o t h t h e r e l a t i v e amount s o f t h e o x o - 1 6 - h e x a d e c a n o l i d e s and t h e p o s i t i o n o f t h e k e t o g r o u p ( f i g u r e s 3 8 - 4 1 ) . S i m i l a r o x i d a t i o n s we re c a r r i e d o u t on 1 5 ~ p e n t a d e c a n o 1 i d e ( 1 1 7 ; n = l 4 ) and 1 2 -d ode cano 1 i de * ( 1 1 7 ; n = 1 l ) . . a n d t h e p r o c e d u r e s d e s c r i b e d above we re u s ed t o d e t e r m i n e t h e r e l a t i v e amounts o f i s o m e r i c o x o - m a c ro 1 i d es . The r e s u l t s ( s u m m a r i z e d i n f i g u r e s 4 2 -49) i n d i c a t e t h a t t h e o x i d a t i o n o f d o d e c a n o l i d e ( f i g u r e s 4 6 - 4 9 ) i s more r e g i o s p e c i f i c t h a n t h a t o f t h e h i g h e r h o m o l o g u e s ( f i g u r e s 3 8 - 4 5 ) - A v e r y i n t e r e s t i n g f a c t i s t h a t we d i d no t o b s e r v e any * 1 2 - d o d e c a n o l i d e i s n o t c o m m e r c i a l l y a v a i l a b l e . I t was made f r o m c y c 1 o d o d e c a n o n e ( 124 ) by t h e a c t i o n o f t r i f 1 u o r o p e r a c e t i c 55 a c i d . C F 3 C 0 3 H 0 // - > < C H i n (124 ) ( 1 1 7 ; n = 1 1) - 79 -s i g n i f i c a n t o x y g e n a t i o n a t t h e f o u r c a r b o n s c l o s e s t t o t h e f u n c t i o n a l g r o u p . I f t h e m e c h a n i s m p r o p o s e d e a r l i e r ( s e e P.hO) a p p l i e d h e r e , t h o s e h y d r o g e n s t h a t a r e a t t a c h e d t o t h e f o u r n e a r e s t c a r b o n s c a n n o t r e a c h t h e r e a c t i v e o x y g e n on c h r o m i u m . A n o t h e r i n t e r e s t i n g a s p e c t i s t h a t t h e h i g h e s t y i e l d o f mono-oxo - m a c r o 1 i d e r e s u l t e d f r o m a t t a c k a t t h e c a r b o n atom most r e m o t e f r o m t h e l a c t o n e f u n c t i o n a l i t y , i . e . C-9 o f 1 6 - h e x a -d e c a n o l i d e ( 6 . 5 % ) , C-8 ( 6 . 1% ) o f 1 5 - p e n t a d e c a n o 1 i d e and C-7 ( 1 2 . 3 % ) o f 1 2 - d o d e c a n o l i ' de . A t t e m p t s t o o x i d i z e 8 - o c t a n o l i d e t o m o n o - o x o - 8 -o c t a n o l i d e we re no t v e r y s u c c e s s f u l . A f t e r o x i d a t i o n a t room t e m p e r a t u r e f o r 3 d a y s , u s u a l w o r k - u p p r o v i d e d a t r a c e o f deep brown o i l . Gas c h r o m a t o g r a p h y showed o n l y one peak w i t h a s h o u l d e r and no s t a r t i n g m a t e r i a l . The i n f i r a r e d and NMR d a t a showed t h i s brown o i l t o be composed o f m o n o - o x o - m a c r o 1 i d e s . The v e r y low y i e l d may a r i s e f r o m t h e d e g r a d a t i o n o f 8 - o c t a n o l i t o t a r i n s t e a d o f m o n o - o x y g e n a t i o n by t h e c h r o m y l a c e t a t e . E f f o r t s t o i n c r e a s e t h e s e l e c t i v i t y o f t h e o x i d a t i o n by u s i n g a n o t h e r o x i d a t i o n r e a g e n t ( N a 2 C ^ O ^ / h ^ S O ^ / H O A c ) f a i l e d No mono -oxo p r o d u c t s w w e r e f o r m e d . R e c e n t i n v e s t i g a t i o n ha^se shown t h a t amb r e t t o l 1 de : ( 1 2 3 ; a=5, b=8) and i t s i s o m e r s a r e p a r t o f t h e phe romone c o m p l e x o f t h e oak l e a f r o l l e r m o t h . T h i s i n s e c t d e s t r o y s m i l l i o n s o f d o l l a r s w o r t h o f f o r e s t i n t h e n o r t h e a s t e r n U n i t e d 56 S t a t e s . A m b r e t t o l i d e and s i m i l a r m a c r o c y c l e s have been - 80 -a s s o c i a t e d , w i t h s e x u a l a c t i v i t y i n musk o x e n , c i v e t c a t s , musk r a t s and b l a c k - t a i l e d d e e r . A m b r e t t o l i d e i s a l s o t h e p r i n c i p l e o d o r o u s c o n s t i t u e n t o f a m b r e t t e s e e d and i s an i m p o r t a n t b a s e f o r t h e p e r f u m e i n d u s t r y . A ^ v e r y i n t e r e s t i n g a s p e c t o f o u r r e s e a r c h i s t h a t we can now c o n v e r t 16 - h e x a d e c a n o 1 i d e t o a m i x t u r e o f m o n o - u n s a t u r a t e d h e x a d e c a n o 1 i d e s ( 1 2 3 ; a+b = 1 3 ) . R e d u c t i o n o f m o n o - o x o - 1 6 - h e x a d e c a n o 1 i d e s ( 1 1 8 ; x+y=14) w i t h s o d i u m b o r o h y d r i d e i n m e t h a n o l p r o v i d e d t h e h y d r o x y l a c t o n e s ( 1 2 2 ; x+y=14) w h i c h we^Vie t h e n r e a c t e d w i t h mesy l c h l o r i d e . Demesy 1 at i on , by h e a t i n g t h e mesy 1 a t e s '.irh co 1 1 i d i n e , g a v e a p l e a s a n t s m e l l i n g m i x t u r e o f m o n o - u n s a t u r a t e d h e x a d e c a n o l i d e s ( 1 2 3 ; a+b=13) whose s e x p h e r o m o n a l a c t i v i t y i s b e i n g e v a l u a t e d by P r o f e s s o r L . B . H e n d r y ( P e n n s y l v a n i a S t a t e U n i v e r s i t y ) . o w Cr c o 3 I co 4 5 6 7 8 S i t e s o f o x i d a t i o n F i g u r e 38. O x i d a t i o n o f 16 - hex a de c a n o 1 i "d e [ d a t a f r om t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s - (12 0 ; x+y = 1 k) :-o- o - b a s e d on f r a g m e n t ( l 2 1 a ) : - A — A -b a s e d on f r a g m e n t ( 1 2 1 b ) ] . <5^> CT in cr o 3 oo F i g u r e 39 4 5 6 7 8 S i t e s o f o x i d a t i o n O x i d a t i o n o f 16 -hex a d e c a n o 1 ide [ d a t a f r o m t h e low r e s o l u t i o n (70eV) mass s p e c t r u m o f a c e t a l s (.120: x+y = U ) : - o — o - b a s e d on f r a g m e n t (1 2 1 a) • - A—-A -b a s e d on f r a g m e n t ( l21b)|. 20 18 H 16 o 3 12 — 10 C O 8 — i 2 — 1 2 3 4 5 6 7 3 9 10 1 1 1 2 13 14 15 16 S i t e s o f o x i d a t i o n u r e 4 0 . O x i d a t i o n o f 1 6 - h e x adecano1 i d e [ d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s (120 x+y=14) ba sed on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s (121 a and b ) | . 20 1 8 16 in C o 3 1 2 10 6 H oo -C-10 11 12 13 14 15 16 F i g u r e 4 1 . 1 2 3 4 5 6 7 8 ; S i t e s o f ox i d a t i on O x i d a t i o n o f 16 -hex adecano1 i d e j d a t a f r o m t h e low r e s o l u t i o n ( 7 0eV ) mass s p e c t r u m o f a c e t a l s (. 1 20 •_ x+y = 1 4) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s ( 1 2 1 a and b ) | . S i t e s o f o x i d a t i o n F i g u r e 4 2 . O x i d a t i o n o f 1 5 - p e n t a d e c a n o 1 i d e ! d a t a f r o m t h e low r e s o l u t i o n ( l 5 e V ) mass s p e c t r u m o f a c e t a l s ( 1 2 0 ; x + y = 1 3 ) : - o — o - b a s e d on f r a g m e n t ( I 2 1 a ) : - A — A -b a s e d on f r a g m e n t ( l 2 1 b ) | . CO I 1 I ! 1 1 I I I I 1 j J I 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 S i t e s o f o x i d a t i . o n F i g u r e 4 3 . O x i d a t i o n o f 1 5 - p e n t a d e c a n o 1 i d e [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0 e V ) mass s p e c t r u m o f a c e t a l s ( 1 2 0 ; x+y = 1 3 ) : - o - — o - b a s e d on f r a g m e n t ( I 2 1 a ) : - A — A -b a s e d on f r a g m e n t ( 121b ) i . 18 16 cr c O 1 V 1 2 10 CO J l •i-T-T 13 14 15 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 S i t e s o f o x i d a t j o n F i g u r e 4 4 . O x i d a t i o n o f 1 5 - p e n t a d e c a n o l i d e j d a t a f r o m t h e low r e s o l u t i o n (l5eV) mass s p e c t r u m o f a c e t a l s ( 120 ;_ x+y = 13) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s (121 a and b) j . 1 8-o LO cr c rt O 16-14' 1 2" 10-co CO n J] n 10 11 12 13 14 15 1 2 3 4 5 6 7 8 : S i t e s o f o x i d a t j o n F i g u r e 4 5 . O x i d a t i o n o f 1 5 - p e n t a d e c a n o 1 i d e I d a t a f r o m t h e low r e s o l u t i o n ( 70eV ) mass s p e c t r u m o f a c e t a l s ( 1 2 0 ; x+y=13) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y o f f r a g m e n t s (121 a and b ) j . 30 — i i A O l/l cr C o 3 20 10 O '6 1 S i t e s of o x i d a t i o n Figure 47. O x i d a t i o n of 12-dodecano1 ide [data from the low r e s o l u t i o n ( 7 0 e V ) mass spectrum of a c e t a l s ( 1 2 0 ; x +y = 1 0) : - o-~- o - based on fragment ( I 2 1 a ) : - A - A 30 1/1 cr o 3 20 — i <J3 10 XL T 4 5 6 7 S i t e s o f ox i d a t i on 1 0 1'1 V2 F i g u r e 4 8 . O x i d a t i o n o f 1 2 - d o d e c a n o 1 i d e [ d a t a f r o m t h e low r e s o l u t i o n (!5eV) - • • — . — . . .^-JV/IUI.IV_>U ^ i j c v i mass s p e c t r u m o f a c e t a l s ( 1 2 0 A x+y=10) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t v 30—1 CT in cr o 3 20-1 o — XL J l 1 2 3 H 5 6 7 8 9 1 0 1 1 l" 2 S i t e s o f o x i d a t i o n F i g u r e 4 9 . O x i d a t i o n o f 1 2 - d o d e c ano 1 i de [ d a t a f r o m t h e low r e s o l u t i o n ( 7 0 e V ) mass s p e c t r u m o f a c e t a l s ( 1 20 ;., x+y= 1 0 ) b a s e d on t h e c o m b i n e d r e l a t i v e i n t e n s i t y - 93 -(C) Remote o x i d a t i o n o f m a c r o c y c l i c a c e t a t e s Few e x a m p l e s a r e known o f t h e m i c r o b i o l o g i c a l o x y g e n a t i o n o f s i m p l e m o n o c y c l i c s y s t e m s . I n c u b a t i o n o f c y c 1 o d o d e c a n o 1 ( 125 ) w i t h S p o r o t r i c h u m s u l f u r e s c e n s p r o v i d e d d i o x y g e n a t e d p r o d u c t s t h a t we re o x i d i z e d t o 1 , 5 - c y c 1 o d o d e c y 1 - d i o n e ( 1 2 6 ) , 1 , 6 - c y c l o -57 d o d e c y 1 - d i o n e (127 ) and 1 , 1 - c y c 1 o d o d e c y 1 - d i o n e ( 1 2 8 ) . ( 1 25) ( 1 26) ( 1 27) ( 1 28) O x y g e n a t i o n s o f eye 1 o t r i d e c a n o l t o 1 , 7 - c y c 1 o t r i d e c y 1 - d i o n e and o f c y c 1 o t e t r a d e c a n o 1 t o 1 , 6 - c y c 1 o t e t r a d e c y 1 - d i o n e w e r e a l s o o b s e r v e d w i t h t h e same o r g a n i s m . L a t e r J o n e s and h i s c o - w o r k e r s c a r r i e d o u t a s t u d y o f t h e i n c u b a t i o n o f two k e t o n e s , c y c l o p e n t a d e c a n o n e and c y c l o -58 d o d e c a n o n e , w i t h f i v e f u n g i . I n c u b a t i o n o f cyc1 o p e n t a d e c a n o n e (129 ) w i t h C a l o n e c t r i a d e c o r a f o r 3 day s p r o v i d e d t h e h i g h e s t y i e l d (26% b a s e d on consumed s t a r t i n g m a t e r i a l ) o f 8 - h y d r o x y - c y c 1 o -p e n t a d e c a n o n e (130) , w h i l e eye 1 o d o d e c a n o n e (13 1 ) gave 5 " h y d r o x y -c y c 1 o d o d e c a n o n e ( 1 3 2 ) , 6 - h y d r o x y - c y c 1 o d o d e c a n one (133) and J-h y d r o x y - c y c 1 o d o d e c a n o n e ( 1 3 4 ) . - 94 -( 1 3 1 ) (132) (133) (134) W i t h t h e s e e x a m p l e s i n m i n d , we d e c i d e d t o o x i d i z e a p p r o p r i a t e m a c r o c y c l i c a c e t a t e s w i t h c h r o m y l a c e t a t e ( C r O ^ - A c 2 O ) . T r e a t m e n t o f p u r e c y c 1 o p e n t a d e c y 1 a c e t a t e (135) i n g l a c i a l a c e t i c a c i d / a c e t i c a n h y d r i d e w i t h c h r o m i u m t r i o x i d e / a c e t i c a n h y d r i d e ( i . e . c h r o m y l a c e t a t e s ) a t room t e m p e r a t u r e f o r 5 d a y s p r o v i d e d a m i x t u r e o f m o n o - o x o - c y c 1 o p e n t a d e c y 1 a e e t a t e s ( 1 36) and s t a r t i n g m a t e r i a l . C a r e f u l c o l umn c h r o m a t o g r a p h y [_Woelm s i l i c a g e l g r a d e I I I (1 :5 0) ; p e t . e t h e r / e t h e r ] separated t h e a c e t o x y - c y c 1 o p e n t a -d e c a n o n e s f r o m s t a r t i n g m a t e r i a l . The y i e l d o f p r o d u c t b a s e d on consumed s t a r t i n g m a t e r i a l was 39 -2%. E l e m e n t a l a n a l y s i s , i n f r a r e d and NMR d a t a showed t h e p r o d u c t t o be composed o f a c e t o x y - c y c 1 o -p e n t a d e c a n o n e s . The i n f r a r e d s p e c t r u m ( C C l ^ ) showed a b s o r p t i o n -1 bands a t 1745 and 1720 cm and i t s NMR s p e c t r u m e x h i b i t e d r e s o n a n c e s a t T 5.27 (m, 1H, - C H O A c ) , 7.66 ( m i x e d t , 4H , - CH_2C OC H_ 2 - ) , OH A c 2 0 , py r ( C H 2 0 H ) 2 / H + ( 142 ) C r 0 3 / A c 2 0 / A c O H " (CH,) 2 ' x ( 135 ) ( C H ? ) y — I ;: ( 136 ) OAc 0 ^ (CH, ) ' 2 ' x J o n e s r e a g e n t .( KOH/Me OH 0. f ^ _ ( C H 2 ) x (CH 2 y ^ (CH, ) 0 ( ( 138 ) G .C . c o l l e c t i o n 20% DEGS, 200°C 2 ' y (13 7) 'OH ( C H 2 0 H ) 2 / H + ( C H 2 0 H ) 2 / H + ( 143 ) - 96 -8 . 0 6 , 8 .08 ( s , 3 H , - ( ^CCH, ) , 8 . 4 2 , 8.70 (m, b r o a d s , 22H , - ( C H 2 ) 1 r ) . The r e l a t i v e amounts o f t h e a c e t o x y - c y c 1 o p e n t a d e c a n ones ( 136 ) can be deduce.ld by c h r o m a t o g r a p h i c a n a l y s i s o f t h e m i x t u r e o f c y c l o p e n t a d e c y l - d i o n e s (138 ) , w h i l e t h e p o s i t i o n o f t h e k e t o : g r o u p can be d e t e r m i n e d by e x a m i n i n g t h e mass s p e c t r a o f t h e c o r r e s p o n d i n g d i a c e t a l s ( 1 4 2 , 1 4 3 , 1 4 4 ) . The a c e t o x y - c y c l o -p e n t a d e c a n o n e s ( 1 3 6 ) , on r e a c t i o n w i t h p o t a s s i u m h y d r o x i d e i n m e t h a n o l f o l l o w e d by J o n e s r e a g e n t , y i e l d a m i x t u r e o f c y c l o -p e n t a d e c y l - d i o n e s ( 138 ) w h i c h c o u l d be s e p a r a t e d by p r e p a r a t i v e o G .C . u s i n g a 20% DEGS co l umn at 200 C. T h i s p r o v i d e d 1 , 4 - c y c l o -p e n t a d e c y 1 - d i o n e ( 1 3 9 , 10 .3%), 1 , 5 - cyc1 o p e n t a d e c y 1 - d i o n e ( 1 4 0 , 17 .5%) and I , 8 - c y c l o p e n t a d e c y 1 - d i o n e ( 1 4 1 , 12.2%). The i n d i v i d u a l d i k e t o n e s w e r e t h e n c o n v e r t e d t o t h e i r d i k e t a l s . R e c e n t l y , F e t i z o n i n v e s t i g a t e d t h e f r a g m e n t a t i o n p a t t e r n o f c y c l a n o n e e t h y l e n e a c e t a l s i n t h e m a c r o c y c l i c r i n g . I t can be e x p l a i n e d e n t i r e l y on t h e b a s i s o f a r i n g c o n t r a c t i o n and -59 a s s o c i a t e d h y d r o g e n m i g r a t i o n s . U s i n g t h i s r a t i o n a l i z a t i o n , t h e 1 , 4 - d i k e t a l ( 142 ) w o u l d f r a g m e n t as shown i n scheme 7, and t h i s f r a g m e n t a t i o n i s c o n s i s t e n t w i t h t h e peak s f o u n d i n t h e mass s p e c t r u m ( f i g u r e s 5 0 - 5 1 ) . The 1 , 5 - d i k e t a l ( 143 ) and 1 , 8 -d i k e t a l ( 144 ) w e r e i d e n t i f i e d i n t h e same way ( s chemes 8-',.an'd 9 ; f i g u r e s 5 2 - 5 5 ) . The same r e a c t i o n s e q u e n c e was a p p l i e d t o c y c 1 o t r i d e c y 1 a c e t a t e ( 1 4 5 ) . I t was o x i d i z e d t o a m i x t u r e o f m o n o - o x o - c y c l o -- 100 -t r i d e c y l a c e t a t e s ( 1 4 6 ) . E m p l o y i n g t h e p r o c e d u r e d e s c r i b e d e a r l i e r , a m i x t u r e o f d i k e t o n e s (148 ) was o b t a i n e d . They w e r e OH OAc A c 2 0 , p y r C r 0 3 / A c 2 0 / A c O H I (CH, ) 2 ' x ( 145 ) z y >QAo (146 ) KOH/Me OH /0, (CH, ) V 2 x J o n e s r e a g e n t < ( C H 2 > * ( C H2 W (148 ) 0 ( C H 2 ^ ^ 0 H (147.) ( 149 ) 0 W (150 ) Xo ( C H 2 0 H ) 2 / H + (151 ) (152 ) - 101 -s e p a r a t e d by p r e p a r a t i v e G . C . u s i n g a 20 % D E G S / c o l u m n at 200°C i n t o two f r a c t i o n s . The f i r s t f r a c t i o n ( 149 ) was a m i x t u r e o f two i s o m e r s ( 1 1 . 9 % and 2 0 . 5 % o f t h e t o t a l m i x t u r e by g . c ) . The mass s p e c t r u m o f t h e d i a c e t a l s o f t h i s m i x t u r e i n d i c a t e d t h e i s o m e r s t o be 1 , 4 - c y c 1 o t r i d e c y 1 - d i o n e and 1 , 5 - cy c 1 o t r i de cy 1 -d i o n e ( f i g u r e s 56 and 57.V s chemes 10 and 1 1 ) . The s e c o n d f r a c t i o n ( 150 ) was a l s o a m i x t u r e o f two i s o m e r s ( 3 1 . 4 % and 3 6 . 2 % o f t h e t o t a l by g . c . ) and t h e mass s p e c t r u m o f t h e d i a c e t a l s showed t h e i s o m e r s t o be 1 , 6 - c y c 1 o t r i d e c y 1 - d i o n e and 1 , 7 - c y c 1 o t r i d e c y 1 -d i o n e ( f i g u r e s 58 and 5 9 ; s chemes 12 and 1 3 ) -S t u d i e s a r e c o n t i n u i n g on t h e o x i d a t i y e v u 1 n e r a b i 1 i t y o f c y c l o d o d e c y l a ce ta te s . . . - 102 -104 -m/e 143 Scheme 13 C 0.0 LTt D H -1 -(D 0) Ul Ul O Ul — • -c Ul rt T3 O ~ — • (D O O O rt -1 -c — » 3 -CD O -< -h CL O QJ O o -(D rt -QJ , — i _ M O ' O IV L O o • o m L O RELRTIVE INTENSITY 25.0 50.0 75.0 _ J L I 100.0 22 7 -283 -3£B - 90 1 -!0 c O.D o • RELRTIVE INTENSITY 25.0 50.0 75.0 _ J I L _ 100.0 _J o • •99 355 o • C3 -225 •227 (JV o 2S3 O " m •326 u r o o o - Z 0 1 -CO L U r — Z a . in L U CX _ J a Q_r \ j 18 ro a - i — i — i — i — I — i — " - ! — r 50.0 100.0 —I 1 1 i-^-i 1 1"!—r 150.0 200.0 g u r e 52. Mass s p e c t r u m o f d i a c e t a l o f 1 r e s o 1 u t i on (15 e V ) ] . ID I 1 250.0 300.0 350.0 M/E cy c 1 open t ad ecy 1-d i on e Mow m c -i CD OJD CD • -1 2 o 0) LO co o to c L0 rt XI o — CD o O O rt o 1 ,—. c •—1 3 o CD O < -h ( Q. i J o 0) o O CD rt CU IM O O O -h • o — > Ul n ~< o u i ~ * o o . XI o CD rt 01 Q_ CD LO O O ~< O 1 o CL I S O m CD LO Ul — ' CD O O CD RELRTIVE INTENSITY 25.D 50.0 75.0 _ J | I 100.0 •99 HZ 355 385 " 2 3 3 •233 •326 - 6 0 1 -RELRTIVE INTENSITY 0.0 25.0 50.0 75.0 100.0 1 I I I •99 -326 357 •17J - o n -\J1 D.D RELRTIVE INTENSITY 25.0 50.0 75.0 Ln IDD.D _ J -i L O o 01 LO CO O o 0> co ~o CD O r t C 3 o • o •99 CD o CD o o _L25_ 357 •171 o ~< o o -a CD r t CU CL CD n -< <i CL o CD CO-CD (VI u i • o •283 LO O • O m •326 LO UV C D I I I -CO L J J in L J J J Q C£r\j 9 _1 J. r^—i 1— r 8 (3 50.0 - 1 — 1 — 1 — r 1 1—r - 1 — 1 — 1 — r 100.0 150.0 200.0 250.0 300.0 M/E 350.0 400 g u r e 56. Mass s p e c t r u m o f m i x t u r e o f d i a c e t a l s o f 1 , 4 - c y c l o t r i d e c y l - d i o n e and 1 , 5 - e y e 1 o t r i d e c y 1 - d i o n e [ l ow r e s o l u t i o n (!5eV)]. cn L U in L U CE a o 9 id 8i i_o I 18 T 1 — i "" i | — r " i i f" | 1 1 — T — i i 50.0 100.0 150.0 ~i 1 1 r i — i — r 1 1 1 r 200.0 250.0 300.0 M/E 350.0 400.0 F i g u r e 57 • Mass s p e c t r u m o f m i x t u r e o f and 1 , 5 - c y c 1 o t r i d e c y 1 - d i o n e d i a c e t a l s o f 1 , k - c y c 1 o t r i d e c y 1 [ l o w r e s o l u t i o n (70eV)J. - c! i on e l O C -1 v n CO » >. CD l/l 1 in o -< in o "O — ' (D o n rt rt -1 — C CL 3 n> n O ~< - h i 3 Q. — • — X O rt c -\ (D O o - h s - i — • (D 0) W n O — 1 rt c OJ rt — • — • in O O ' — . — ' VTI v. CA < 1 O 1 1 -< • o —-» o rt - i D-CD O -< I CL. O ~3 a> 01 13 Q-D.D RELRTIVE INTENSITY 25.0 50.0 75.0 LD CD • o H o • o _r-99 LT)' o M o • IV) ui • o LO o • o m LO Ln • a 100.0 129 3<e 357 •233 •227 •255 O O - <7l I -CO LU I—IC3 . LU CE _ l a 9 i 8 fl to F3 50.0 i " " i i 1 — r — | — i — 100.0 150.0 200.0 250.0 I 1 300.0 350.0 400.0 M/E F i g u r e 59. Mass s p e c t r u m o f m i x t u r e o f d i a c e t a l s o f 1 , 6 - c y c 1 o t r i d e c y 1 - d i o n e and 1 , 7 - cy c 1 o t r i d ecy 1-d i on e [ l ow r e s o l u t i o n (70eV)]. - 1 1 6 -EXPERI MENTAL G e n e r a l I n f r a r e d s p e c t r a ( I R) we re o b t a i n e d on P e r k i n - E l m e r 137 and 710A s p e c t r o p h o t o m e t e r and c a l i b r a t e d by means o f t h e 1601 cm ^ band o f p o 1 y s t y r e n e . N u c 1 e a r m a g n e t i c r e s o n a n c e (NMR) we re r e c o r d e d on t h e f o l l o w i n g s p e c t r o m e t e r s : V a r i a n Mode l T -60 and X L - 1 0 0 . S i g n a l p o s i t i o n s w e r e r e p o r t e d on t h e T - s c a l e , w i t h CCl/j as s o l v e n t arid t e t r a m e t h y 1 s i 1 ane as an i n t e r n a l s t a n d a r d . Mass s p e c t r a we re r e c o r d e d on A t l a s CH-k and A . E . I . MS902 i n s t r u m e n t s . M i c r o a n a l y s e s we re p e r f o r m e d by Mr. P. B o r d a o f t h i s d e p a r t m e n t . M e l t i n g p o i n t s we re d e t e r m i n e d on a K o f l e r a p p a r a t u s and a r e u n c o r r e c t e d . Gas - l i q u i d c h r o m a t o g r a p h y ( g . l . c . ) was c a r r i e d o u t on V a r i a n A e r o g r a p h Model 9 0 - P , P e r k i n - E l m e r Model 900 and H e w l e t t - P a c k a r d Mode l 583OA, u s i n g t h e f o l l o w i n g c o l u m n s : 5 ' x £ " , 3% SE30 on 100/120 V a r o p o r t 3 0 ; 5 ' x £ " , 20% DEGS on 60/80 c h r o m o s o r b W; 6 l x l / 8 " " , 20% DEGS on 80/100 c h r o m o s o r b W AW-DMCS; 1 0 ' x 3 / 8 " , 20% DEGS on 60/80 c h r o m o s o r b W; 5 ' x i " , 10% FFAP on 60/80 c h r o m o s o r b W; 6 ' x l / 8 " , 5% 0V 210 on 80/100 c h r o m o s o r b W, w i t h h e l i u m as t h e c a r r i e r g a s . S o l v e n t s e m p l o y e d we re e i t h e r Reagen t g r a d e o r C e r t i f i e d g r a d e . The t e r m " p e t r o l e u m e t h e r " r e f e r s t o t h e low b o i l i n g f r a c t i o n o f C e r t i f i e d p e t r o l e u m d i s t i l l a t e ( b . p . 3 0 - 6 0 ° ) £ ) / . - 117 -Octadecyl acetate ( 9 7 ; n=l6) A c e t i c anhydride (16 ml.) was added to octadecanol (30t;g%) in p y r i d i n e ( 6 0 r m J . j and the mixture was r e f l u x e d o v e r n i g h t . A f t e r c o o l i n g , t h e s o l u t i o n was d i l u t e d with water and e x t r a c t e d with ether (3 X) . The combined e x t r a c t s were washed with d i l u t e i h y d r o c h l o r i c a c i d , s aturated sodium bicarbonate s o l u t i o n and dr i e d with anhydrous magnesium sul fiat-tee. Removal of so l v e n t provided a white s o l i d ( 2 8 . 5f£g-; ,83 %) . v m a x ( C C l / , ) 17^5, 1240 c m " T ; T ( C C l i t , 60 MHz) 5-96 ( t , 2H ,-CH_2-0A6) , 8.00 (s, 3H, -0 2CCH_ 3), 8.43, 8 .75 (broad s, 3 2 H , C H 3 - ( C H 2 ) l 6 ) , 9.10 ( t , 3H, C H 3 - ( C H 2 ) n ) . Oxidation of octadecyl acetate (97; n =16) Chromium t r i o x i d e (lxq..)\ in a c e t i c anhydride ( l4.mi j was added dropwise to a cold mixture of octadecyl acetate ( 9 7 ; n = 1 6) ( 5cg..'„ 0 . 0 1 6 moles) in g l a c i a l a c e t i c acid ( 20^1 > an d a c e t i c anhydride (9;rmlK;)) over a period of one and h a l f hours. A f t e r s t i r r i n g at room temperature f o r 5 days.water was c a u t i o u s l y added to the r e a c t i o n mixture. Excess a c e t i c anhydride was removed under reduced pressure and the r e s u l t i n g green s o l u t i o n was shaken with enough ether u n t i l o rganic layer present. The whole mixture was then f i l t e r e d through a th i n l a y e r of e e l i t e and e x t r a c t e d with ether (5x). The combined e x t r a c t s were washed s u c c e s s i v e l y with 2N sodium hydroxide (2x), s a t u r a t e d sodium bicarbonate - 118 -s o l u t i o n (4x) a n d w a t e r (2x). A f t e r d r y i n g w i t h a n h y d r o u s m a g n e s i u m s u l f a t e , , r e m o v a l o f s o l v e n t p r o v i d e d a y e l l o w s o l i d (3 • 2 ; g . ) wh i ch was s h o w n by g . l . c . ( 3 % S E 3 0 ) t o c o n s i s t o f o c t a d e c y l a c e t a t e (28%), a m i x t u r e o f k e t o - o c t a d e c y l a c e t a t e s ( 5 9 % ) ( u n r e s o l v e d on g . l . c . ) a n d a m i x t u r e o f p o 1 y - k e t o - o c t a d e c y 1 a c e t a t e s (13%). C a r e f u l c o l u m n c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r W o e l m s i l i c a g e l g r a d e I I I g a v e , by e l u t i o n w i t h p e t . e t h e r / e t h e r ( 9 8 : 2 ) , a m i x t u r e o f k e t o - o c t a d e c y l a c e t a t e s (98; x + y = 1 5 ) ( 1 . 33,33.,), 3 1 % b a s e d on c o n s u m e d s t a r t i n g m a t e r i a l ) . v m a x ( C C l z , ) , 1737, 1715, 1232 c m " 1 ; x ( C C 1 H , 60 MHz) 6 . 00 ( t , 2 H , - C H ^ O A t ) , 7.70 ( t , kH , - C H_£ C 0 C £2 - ) ~ 8 . 0 2 ( s-, 3H , - 0 2 CCH_ 3 - ) , 8.70 ( b r o a d s , 2 6 H , CH 3 ( C H_2) 1 3 ) , 9-10 ( t , 3 H , C_H_3 ( C H 2 ) n ) ; m/e 3 26 ( M + ) . A n a l . C a l c d . f o r C2QH^QO^: c» 73 - 6 1 ; H , 11.65- F o u n d : C, 73-67 ; H , 11.53-K e t o - o c t a d e c y l a c e t a t e a c e t a l s E t h y l o r t h o f o r m a t e (0 . 8rm'l..)), e t h y l e n e g l y c o l (0 . 2'm.l' '.) and p -1 o 1 u en e s u 1 f on i c a c i d (I9nm;g.'.)) w e r e a d d e d t o k e t o - o c t a d e c y l a c e t a t e s (4Q0nnrg..)). A f t e r 6 h o u r s a t 90°C, t h e s o l u t i o n was h e a t e d a t 150°C f o r 2 h o u r s w h i l e e x c e s s e t h y l o r t h o f o r m a t e d i s t i l l e d o f f . A f t e r c o o l i n g , 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 was a d d e d a n d t h e s o l u t i o n e x t r a c t e d w i t h e t h e r (3x). T h e c o m b i n e d e x t r a c t s w e r e w a s h e d w i t h s a t u r a t e d s o d i u m c h l o r i d e s o l u t i o n . A f t e r d r y i n g w i t h a n h y d r o u s m a g n e s i u m s u l f a t e , r e m o v a l o f s o l v e n t p r o v i d e d a y e l l o w o i l (378mmg))which w a s s h o w n by g . l . c . (3% S E 3 0 ) t o c o n s i s t o f s m a l l a m o u n t o f k e t o - o c t a d e c y l a c e t a t e s a n d a m i x t u r e o f k e t o -- 119 -o c t a d e c y l a c e t a t e a c e t a l s . D o u b l e c o l u m n c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r Woelm s i l i c a g e l ( g r a d e I I I ) g a v e , by e l u t i o n w i t h p e t . e t h e r / e t h e r , a m i x t u r e o f k e t o - o c t a d e c y 1 a c e t a t e a c e t a 1s (300 mg.) . v m a x ( C C 1 i t ) 1 748 , 1 232 , 1070 cm"';T ( C C 1 j, , 60 MHz) 6 .04 ( t , 2 H , - C H _ 2 0 A c ) , 6.20 ( s , 4H , -OCH^CH^O-) , 8.06 ( s , 3H , -OCOCIH3), 8 .72 ( b r o a d s , 30H , CH 3 ( CH_2) } 5) , 9-13 ( t , 3 H , C H 3 ( C H 2 ) n ) . K e t o - o c t a d e c a n o l a c e t a l s (99; x+y=15) Sod i um h y d r o x i d e (30 m g . ) , m e t h a n o l (5 m l . ) and k e t o - o c t a d e c y 1 a c e t a t e a c e t a l s (126 mg.) we re h e a t e d at 100°C f o r 5 h o u r s . M e t h a n o l was t h e n removed by d i s t i l l a t i o n . A f t e r c o o l i n g , t h e r e s i d u e was d i l u t e d w i t h w a t e r and e x t r a c t e d w i t h e t h e r ( 4 x ) . The c o m b i n e d e x t r a c t s we re wa shed w-Lfchu s.at.u:r a t e d sod i um c h l o r i d e s o l u t i o n (3*) » w a t e r ( 2 x ) , and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . R e m o v a l o f s o l v e n t p r o v i d e d a y e l l o w o i l (118 m g . ) . v m a x ( C C l 2 ( ) 3 4 0 0 , 1 070 c m " 1 ; T ( CC 1 ^ , 60 MHz) 6.20 ( s , 4H , -0CH_2CH_ 20-) , 6.50 ( t , 2 H , -Ch[ 2 0H) , J2r ( b r o a d s , 3 0 H , C H 3 ( C H 2 ) 1 5 ) , 9.10 ( t , 3H , C H 3 ( C H 2 ) n ) . A n a l . C a l c d . f o r C 2 o H 40 °3 : C» 73 .17; H, 1 2 . 2 0 . F o u n d : C , 72 . 61 ; H , 1 2 . 0 8 . O x i d a t i o n o f o c t a d e c y l a c e t a t e (97; n=l6) i n t e n t i m e s amount  o f s o l v e n t and t h e same amount o f C r 0 3 - A c 2 0 Chromium t r i o x i d e (7 g.) i n a c e t i c a n h y d r i d e (14 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f o c t a d e c y l a c e t a t e (97; - 120 -n = 16) (5 g - , 0 . 016 m o l e ) i n g l a c i a l a c e t i c a c i d (200 m l . ) and a c e t i c a n h y d r i d e (90 m l . ) . A f t e r s t i r r i n g at room t e m p e r a t u r e f o r 2 d a y s , u s u a l w o r k - u p as d e s c r i b e d e a r l i e r p r o v i d e d a y e l l o w o i l (4.48 g.) w h i c h was shown by g . l . c . ( 3% SE30) t o c o n s i s t o f o c t a d e c y l a c e t a t e ( 2 6 . 9 % ) , a m i x t u r e o f k e t o -o c t a d e c y l a c e t a t e s (44.3%) and a m i x t u r e o f p o l y k e t o - o c t a d e c y l a c e t a t e s ( 2 8 . 8 % ) . C h r o m a t o g r a p h y , as d e s c r i b e d e a r l i e r , p r o v i d e d a m i x t u r e o f k e t o - o c t a d e c y 1 a c e t a t e s ( 9 8 ; x+y=15) ( 1 - 1 9 g-> 25% b a s e d on consumed s t a r t i n g m a t e r i a l ) . V m a x ( C C 1 4 ) 1 7 5 0 ' 1 7 2 0 ' 1 2 3 5 c m " 1 ; T ( C C V 1 0 0 M H z ) 6.30 ( t , 2 H , -CH^OAc) , 7.72 ( t , 4H , - C H 2 C 0 C - ) , 8 . 0 5 ( s , 3H, -OCOCH.3) , 8.. 50 , 8 .75 ( b roadmm, s , 26H , C H3 ( C H2) 1 3 " ) » 9 • 1 1 ( t , 3H , C H 3 ( C H 2 ) n - ) . A n a l . C a l c d . f o r C ^ h ^ c j O j : C, 7 3 - 6 2 ; H, 1 1 . 6 6 . F o u n d : C, 7 3 - 5 8 ; H, 1 1 . 4 9 . A c e t a t e s o f d o d e c a n o l ( 9 7 ; n = 1 0 ) , t e t r a d e c a n o l ( 9 7 ; n = 1 2 ) ,  d o c o s a n o l ( 9 7 ; n = 20) , h e x a d e c a n o 11 (97 ; n = l4) D o d e c a n o l , t e t r a d e c a n o l , d o c o s a n o l and h e x a d e c a n o l we re c o n v e r t e d t o t h e a c e t a t e s as d e s c r i b e d f o r o c t a d e c y l a c e t a t e . T The I.R. and N.M.R. c h a r a c t e r i s t i c s o f t h e s e a c e t a t e s we re s i m i l a r t o t h o s e o f o c t a d e c y l a c e t a t e ( 9 7 ; n=l6). O x i d a t i o n o f d o d e c y l a c e t a t e ( 9 7 ; n=10) Chromium t r i o x i d e (7 g-) i n a c e t i c a n h y d r i d e (14 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f d o d e c y l a c e t a t e ( 9 7 ; n=10) ( 4 . 8 2 g . , 0 . 0 2 3 mo le ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and - 121 -a c e t i c a n h y d r i d e (9 m l . ) o v e r a p e r i o d o f one and h a l f h o u r s . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 2 d a y s , w a t e r was c a u t i o u s l y added t o t h e r e a c t i o n m i x t u r e . U s u a l w o r k - u p , as d e s c r i b e d e a r l i e r p r o v i d e d a y e l l o w o i l ( 2 . 8 l g.) w h i c h was shown by g . l . c . (3% SE30) t o c o n s i s t o f d o d e c y l a c e t a t e (55%) and a m i x t u r e o f k e t o - d o d e c y l a c e t a t e s (45%) ( u n r e s o l v e d on g . l . c . ) . C h r o m a t o g r a p h y , as d e s c r i b e d e a r l i e r , p r o v i d e d a m i x t u r e o f k e t o -d o d e c y l a c e t a t e s (98; x+y=9) ( 1 . 2 g . , 23% b a s e d on consumed s t a r t i n g m a t e r i a l ) . v m a x ( C C 1 i t ) 17^5 , 1 720, 1 235 c m " 1 ; ! (C C1 k , 60 MHz) 6 . 02 ( t , 2 H , -CH_ 2 0Ac) , 7 - 70 ( t , 4H, -CH^COCH^- ) , 8.03 ( s , 3H, -OCOCH^ ) , 8.70 ( b r o a d s , 14H, C H 3 ( C h [ 2 ) 7 ) , 9-11 ( t , 3 H , C H _ 3 ( C H 2 ) n ) . A n a l . C a l c d . f o r ^ ] ^ 2 6 ° 3 : C ' 6 9 - i , 2 5 H > 1 0-74. F o u n d : C, 69•22 ; H, 10.64. O x i d a t i o n o f t e t r a d e c y l a c e t a t e (97; n=12) Chromium t r i o x i d e (7 g.) i n a c e t i c a n h y d r i d e (14 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f t e t r a d e c y l a c e t a t e (97; n=12) (5-05 g . , 0 . 0 2 m o l e ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and a c e t i c a n h y d r i d e (9 m l . ) o v e r a p e r i o d o f one and h a l f h o u r s . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 4 d a y s , w a t e r was c a u t i o u s l y added t o t h e r e a c t i o n m i x t u r e . U s u a l w o r k - u p as d e s c r i b e d f o r o c t a d e c y l a c e t a t e ( c f . P .117 ) p r o v i d e d a p a l e y e l l o w o i l (3-19 g.) w h i c h was shown by g . l . c . (3% SE30) t o c o n s i s t o f t e t r a d e c y l a c e t a t e (49%), a m i x t u r e o f k e t o - t e t r a d e c y 1 a c e t a t e s (48%) ( u n r e s o l v e d on g . l . c . ) and a m i x t u r e o f p o 1 y k e t o - 1 e t r a d e c y 1 a c e t a t e s ( 3% ) . C h r o m a t o g r a p h y , as d e s c r i b e d f o r o c t a d e c y l a c e t a t e , p r o v i d e d a m i x t u r e o f k e t o - t e t r a d e c y 1 a c e t a t e s (98; x +y=1 l ) - 122 -( 1 . 04 , g . , 24% b a s e d on consumed s t a r t i n g m a t e r i a l ) v max ( C C 1 . ) 1 737 , 1 720 , 1 230 c m " 1 ; T ( C C l , , 60 'MHz) 6 . 00 ( t , 2 H , - C H _ 2 0 A c ) , 7 .72 ( t , 4H , - C H 2 C 0 CH 2 - ) , 8 . 0 7 ( s , 3H , - 0 C 0 C H 3 ) , 8 . 4 3 , 8 .72 ( b r o a d m, s , 18H, C H ^ C H ^ ) , 9 . 1 0 ( t , 3H , C H 3 ( C H 2 ) n ) . A n a l . C a l c d . f o r C ] 3 Q 0 ^ : C , 7 1 . 1 1 ; H, 1 1 . 1 1 . Found : C /F7J1U^0JS:;: (H,, 7ll 1.^22;.' / .. O x i d a t i o n o f d o c o s y l a c e t a t e ( 9 7 ; n=20) Chromium t r i o x i d e (7g9.-)) i n a c e t i i c a n h y d r i d e (14-rnl.. ) was added d r o p w i se t o a c o l d m i x t u r e o f d o c o s y l a c e t a t e ( 9 7 ; n = 20) ( 5 • 0 3 .g,. ,0 . 0 1 4 m o l e s ) i n g l a c i a l a c e t i c a c i d ( 2 0 ,nmil .•))'• and a c e t i c a n h y d r i d e (9rml1*..)) o v e r a p e r i o d o f one and h a l f h o u r s . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 2 days , . .water was c a u t i o u s l y added t o t h e r e a c t i o n m i x t u r e . U s u a l w o r k - u p , as d e s c r i b e d e a r l i e r p r o v i d e d a p a l e y e l l o w s o l i d (3 • 5 5 5g ••))! w h i c h was shown by g . l . c . (3% SE30) t o c o n s i s t o f d o c o s y l a c e t a t e ( 3 5 % ) , a m i x t u r e o f k e t o - d o c o s y l a c e t a t e s (44%) ( u n r e s o l v e d on g . l . c . ) and a m i x t u r e o f p o l y k e t o - d o c o s y 1 a c e t & t e s ( 2 1 % ) . C h r o m a t o g r a p h y , as d e s c r i b e d e a r l i e r , p r o v i d e d a m i x t u r e o f k e t o - d o c o s y l a c e t a t e s 9 8 ; x+y=19) ( l - IO ig . ; , , 24% b a s e d on consumed s t a r t i n g m a t e r i a l ) . v max ( C C l . ) 1 7 5 0 , 1720 , 1 2 3 5 c m " 1 ; T ( C C l . , 60 MHz) 6 . 0 2 ( t , 2H, -CH_ 2 0Ac) , 7-72 ( t , 4H , - CH^ C 0 CH^ -) , 8 .02 ( s , 3H , -0C0CH_ 3) , 8 *74 ( b r o a d s , 3 4 H , CHj (CH_2) , 7 ) , 9 . 10 ( t , 3H , CH_ 3 (CH 2 ) . ). A n a l . C a l c d . f o r C ^ H ^ ^ : C, 7 5 - 3 9 ; H, 1 2 . 0 4 . Found : C , 7 5 . 2 8 ; H, 1 1 . 9 3 -- 123 -O x i d a t i o n o f h e x a d e c y l a c e t a t e ( 9 7 ; n = l 4 ) Chromium t r i o x i d e (7 g • ) i n a c e t i c a n h y d r i d e (14 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f h e x a d e c y l a c e t a t e ( 9 7 ; n = l 4 ) (5 g - , 0 . 0 1 8 m o l e ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and a c e t i c a n h y d r i d e (9 m l . ) . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 3 d a y s , w a t e r was c a u t i o u s l y added t o t h e r e a c t i o n m i x t u r e . U s u a l w o r k - u p as d e s c r i b e d e a r l i e r , p r o v i d e d a y e l l o w o i l ( 3 - 3 2 g.) w h i c h was shown by g . l . c . ( 3% SE30) t o c o n s i s t o f h e x a d e c y l a c e t a t e ( 3 6 % ) , a m i x t u r e o f k e t o - h e x a d e c y 1 a c e t a t e s ( 4 9 - 7 % ) ( u n r e s o l v e d on g . l . c . ) and a m i x t u r e o f p o 1 y k e t o - h e x a d e c y 1 a c e t a t e s ( 1 4 . 3 % ) . C h r o m a t o g r a p h y as d e s c r i b e d e a r l i e r , p r o v i d e d a m i x t u r e o f k e t o - h e x a d e c y 1 a c e t a t e s ( 9 8 ; x+y=13) ( 1 . 1 8 g . , 26% b a s e d on consumed s t a r t i n g m a t e r i a l ) . v m a x ( C C l l t ) 1 7 4 5 , 1 7 2 0 , 1 235 c m " 1 ; ! ( C C1 ^ , 60 MHz) 6 . 0 2 ( t , 2 H , - C H ^ O A c ) , 7 .70 ( t , 4 H , -CH^COCH^- ) , 8 .03 ( s , 3H , - 0C0CH_ 3 ) , 8 .70 ( b r o a d s , 22H , C H 3 ( CH_2) ., 1 ) , 9.11 ( t , 3H , C H _ 3 ( C H 2 ) n ) . A n a l . C a l c d . f o r C 1 g H 3 ^ 0 3 : C, 7 2 . 4 8 ; H, 1 1 . 4 1 . F o u n d : C , 7 2 . 20 ; H , 1 1 .29 . i A c e t a l s o f k e t o - d o d e c y l a c e t a t e s , k e t o - t e t r a d e c y 1 a c e t a t e s , k e t o - d o c o s y l a c e t a t e s The o x i d a t i o n p r o d u c t s f r o m d o d e c y l a c e t a t e ( 9 8 ; x+y=9 ) . t e t r a d e c y l a c e t a t e ( 9 8 ; x + y = 1 l ) , d o c o s y l a c e t a t e ( 9 8 ; x+y=19) we re c o n v e r t e d t o t h e a c e t a l s as d e s c r i b e d f o r I j e t o - o c t adecy 1 a c e t a t e s . The I . R . a n d N.M.R. c h a r a c t e r i s t i c o f t h e s e a c e t a l s we re s i m i l a r t o t h o s e o f k e t o - o c t a d e c y l a c e t a t e a c e t a l s . A c e t a l s o f ke t o - d o d ec ano 1 s ( 9 9 ; x +y=9 ) , k e t o - t e t r adeca r i o 1 s ( 9 9 ;  x + y = 1 l ) , k e t o - d o c o s a n o 1 s ( 9 9 ; x+y=19) - 124 -A c e t a l s o f k e t o - d o d e c y 1 a c e t a t e s , k e t o - t e t r a d e c y 1 a c e t a t e s , k e t o - d o c o s y l a c e t a t e s w e r e c o n v e r t e d t o t h e a l c o h o l as d e s c r i b e d f o r k e t o - o c t a d e c y l a c e t a t e a c e t a l s . The I.R. and N.M.R. c h a r a c t e r i s t i c s o f t h e s e a c e t a l a l c o h o l s we re s i m i l a r t o t h o s e o f k e t o - o c t a d e c a n o 1 a c e t a l s . A n a l . C a l c d . f o r c2kHko°3: C ' 7 5 ' 0 0 ' H » 1 2 . 5 0 . F o u n d : C, 7 5 . 6 4 ; H, 1 2 . 8 3 . H y d r o x y t e t r a d e c y 1 a c e t a t e s ( 1 0 1 ; x+y=1 l ) Sod ium b o r o h y d r i d e (30 mg.) i n m e t h a n o l (1 m l . ) was added d r o p w i s e t o a s o l u t i o n o f k e t o - t e t r a d e c y 1 a c e t a t e s ( 9 8 ; x+y=1 l ) (300 mg.) i n m e t h a n o l (2 m l . ) . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r h a l f h o u r , e x c e s s s o d i u m b o r o h y d r i d e was d e s t r o y e d by t h e a d d i t i o n o f d i l u t e h y d r o c h l o r i c a c i d and t h e s o l u t i o n was e x t r a c t e d w i t h e t h e r ( 3 x ) . The c o m b i n e d e x t r a c t s we re wa shed w i t h 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 and s a t u r a t e d s o d i u m c h l o r i d e s o l u t i o n . A f t e r d r y i n g w i t h a n h y d r o u s magne s i um s u l f a t e , r e m o v a l o f s o l v e n t p r o v i d e d a c l e a r o i l (2 81 mg.) . v ( CC1 . ) 3 4 5 0 , 1 737, 1 235 c m " 1 ; T (CCiI.,, 60 MHz) 5-95 ( t , max k 4 2H , -CH_ 2 0Ac) , 6 . 4 0 ( b r o a d s , 1H, - C H 0 H ) , 8.07, ( s , 3H, -OCOCH^ ) , 8 . 2 5 , 8.63 ( s , b r o a d s , 2 3 H , C H 3 ( C H 2 ) 1 1 , - C H 0 H ) , 9-10 ( t , 3 H , C H 3 ( C H 2 ) n ) . M e s y 1 o x y t e t r a d e c y 1 a c e t a t e s M e s y l c h l o r i d e (0.1 m l . ) was added d r o p w i s e t o a s o l u t i o n o f h y d r o x y t e t r a d e c y 1 a c e t a t e s (256 mg.) i n d r y p y r i d i n e - 125 -(0.5 m l . ) a t 0 - 5 ° C u n d e r n i t r o g e n . A f t e r s t i r r i n g a t 0 -5°C f o r two h o u r s , t h e m i x t u r e was d i l u t e d w i t h 3N h y d r o c h l o r i c a c i d (2 m l . ) and e x t r a c t e d w i t h e t h e r (3x). The c o m b i n e d e x t r a c t s we re wa shed w i t h 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 and s a t u r a t e d s o d i u m c h l o r i d e s o l u t i o n . A f t e r d r y i n g w i t h a n h y d r o u s magnes i um s u l f &%§',, r e m o v a l o f s o l v e n t gave a c l e a r o I 1 (318 m g . ) ; v max ( c c l 2,) 1 737,1 365, 1 3*5, 1 235 , 1 1 80 , 9 10 c m " 1 ; T (CC1/j , 60MMH.Z )"5 . 3 7 ( b r o a d s , 1H, - C H O M s ) : 5 . 95 ( t , 2 H , - C H ^ O A c ) , 7.12 ( s , 3H, - 0 S 0 2 C h [ 3 ) , 8 .07 ( s , 3H , - OCOCH^) , ;8.6 3 ( b r o a d s , 2 2 H , CH ( C H 2 ) n ) , 9.10 ( t , 3H, CH ( C H 2 ) n ) . T e t r a d e c e n y l a c e t a t e s ( 1 0 2 ; a+b=10) A s o l u t i o n o f m e s y l o x y t e t r a d e c y l a c e t a t e s (321 m g . , vacuum d r i e d f o r two h o u r s ) i n d r y c o l l i d i n e (5 m l . ) was h e a t e d a t 140°C o v e r n i g h t . A f t e r c o o l i n g t o room t e m p e r a t u r e , t h e m i x t u r e was d i l u t e d w i t h w a t e r and e x t r a c t e d w i t h e t h e r (3x) . The c o m b i n e d e x t r a c t s we re wa shed w i t h 5% h y d r o c h l o r i c a c i d , 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 and w a t e r . A f t e r d r y i n g w i t h a n h y d r o u s magne s i um s u l f a t e . , r e m o v a l o f s o l v e n t gave a p a l e y e l l o w o i l (193 m g . ) . - 1 v m a x ( C C 1 V 1 7 3 7 ' 1 6 5 0 ' 1 2 3 5 c m ; * ( c c l 4 > 100 MHz) 4.68 (m, 2H , -CH=CH_-), 6.02 ( t , 2H , - C H ^ O A c ) , 8.07 (m, 7H , - CH^2 C= C C J ^ 2 - , -0C0CH_ 3) , 8 . 4 0 , 8.74 (m, b r o a d s , 1 6 H , C H 3 ( C H _ 2 ) g ) , 9.12 ( t , 3H, C H 3 ( C H 2 ) n ) . - 126 -H y d r o x y d o d e c y 1 a c e t a t e s ( 1 0 1 ; x+y=9) Sod ium b o r o h y d r i d e (48/mg.) i n m e t h a n o l ( 1-' ml .')• was added d r o p w i s e t o a s o l u t i o n o f k e t o - d o d e c y l a c e t a t e s ( 9 8 ; x+y=9) ( 3 1 3 .mg . ) i n m e t h a n o l ( 2 rm l : ! V. A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r h a l f h o u r , u s u a l w o r k - u p as d e s c r i b e d f o r k e t o - t e t r a d e c y 1 a c e t a t e s ( c f . P .124 ) p r o v i d e d a p a l e y e l l o w o i l (254 mg . )r. The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e h y d r o x y d o d e c y 1 a c e t a t e s we re s i m i l a r t o t h o s e o f hy d r o x y t e t ra.de cy 1 a c e t a t e s . M e s y 1 o x y d o d e c y 1 a c e t a t e s M e s y l c h l o r i d e ( 0 . 1 m m l } ) w a s added d r o p w i s e t o a s o l u t i o n o f hyd r oxy d o d e c y 1 a c e t a t e s ( 2 20 rrmg .}) i n d r y p y r i d i n e (0 . 5mrnl >.)*at 0 - 5 ° C u n d e r n i t r o g e n . A f t e r s t i r r i n g a t 0 - 5 ° C f o r two h o u r s , u s u a l wo rk up as d e s c r i b e d f o r h y d r o x y t e t r a d e c y 1 a c e t a t e s ( c f . P . 1 2 \ ) p r o v i d e d a p a l e y e l l o w o i l ( 235 :mg. ) . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e m e s y 1 o x y d o d e c y 1 a c e t a t e s we re s i m i l a r t o t h o s e o f m e s y 1 o x y t e t r a d e c y 1 a c e t a t e s . D o d e c e n y l a c e t a t e s ( 1 0 2 ; 2+b=8) A s o l u t i o n o f m e s y 1 o x y d o d e c y 1 a c e t a t e s ( 230 .mg. ) i n d r y c o l l i d i n e (5rcml-)) was h e a t e d a t 110 °C o v e r n i g h t . U s u a l w o r k - u p as d e s c r i b e d f o r m e s y 1 o x y t e t r a d e c y 1 a c e t a t e s p r o v i d e d a g o l d e n y e l l o w o i l ( 1 3 8 m m g ) ) w h i c h was c h r o m a t o g r a p h e d on a l u m i n u m o x i d e ( g r a d e I V ) ; p e t r o l e u m e t h e r ( 3 0 - 6 0 °C) e l u t e d t h e m i x t u r e o f d o d e c e n y l a c e t a t e s ( p a l e - y e l l o w o i l , 1 1 6.mmg ))./-. - 127 -The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e d o d e c e n y l a c e t a t e s we re s i m i l a r t o t h o s e o f t e t r a d e c e n y l a c e t a t e s . H y d r o x y h e x a d e c y 1 a c e t a t e s ( 1 0 1 ; x+y=13) Sod i um b o r o h y d r i d e (60r.mgi) i n m e t h a n o l (3 m i . ) was added d r o p w i s e t o a s o l u t i o n o f k e t o - h e x a d e c y 1 a c e t a t e s ( 9 8 ; x+y=13) (400rrmg.)) i n m e t h a n o l ( 7rrm L l).. A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 50 m i n u t e s , u s u a l w o r k - u p as d e s c r i b e d f o r k e t o -t e t r a d e c y l a c e t a t e s ( c f . P .124 ) p r o v i d e d a p a l e y e l l o w o i l ( 358 mg . ) . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e h y d r o x y h e x a -d e c y l a c e t a t e s we re s i m i l a r t o t h o s e o f h y d r o x y t e t r a d e c y 1 a c e t a t e s . M e s y 1 o x y h e x a d e c y 1 a c e t a t e s M e s y l c h l o r i d e (0 . 3r ml.}) was added d r o p w i s e t o a s o l u t i o n o f hyd r o x y h e x a d e c y 1 a c e t a t e s ( 358rmg..) i n d r y p y r i d i n e (0.7:m!.;,) at 0 -5 °.'C u n d e r n i t r o g e n . A f t e r s t i r r i n g a t 0 - 5 ° C f o r 2 h o u r s , u s u a l w o r k - u p as d e s c r i b e d f o r h y d r o x y t e t r a d e c y 1 a c e t a t e s ( c f . P. 124) p r o v i d e d a y e l l o w o i l ( 4 2 3 ' m g . ) . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e m e s y l o x y -h e x a d e c y l a c e t a t e s w e r e e s i mi 1a r t o t h o s e o f m e s y 1 o x y t e t r a d e c y 1 a c e t a t e s . - 128 -H e x a d e c e n y l a c e t a t e s (102; a+b=12) A s o l u t i o n o f m e s y 1 o x y h e x a d e c y1 a c e t a t e s (401 mg.) i n d r y c o l l i d i n e ( 5 m l . ) w a s h e a t e d at 140°C o v e r n i g h t . U s u a l w o r k - u p as d e s c r i b e d f o r m e s y 1 o x y t e t r a d e c y 1 a c e t a t e s p r o v i d e d a g o l d e n y e l l o w o i l ( 2 7 U m g ) ) w h i c h was c h r o m a t o g r a p h e d on a l u m i n u m o x i d e ( g r a d I V ) ; p e t r o l e u m e t h e r (30- 60°C) e l u t e d t h e m i x t u r e o f h e x a d e c e n y l a c e t a t e s ( p a l e - y e l l o w o i l , 201' mg.).. The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e h e x a d e c e n y l a c e t a t e s we re s i m i l a r t o t h o s e o f t e t r a d e c e n y I a c e t a t e s . A n a l . C a l c d . f o r C l g H 3 i 4 0 2 : C, 76.60; H, 12.07-F o u n d : C, 76 .55; H, 12.20. 11 - a c e t o x y u n d e c a n o i c a c i d ( 1 4 ; n=10) 1 1-hy d r o x y un d e c a n o i c a c i d ( 3gg )) i n p y r i d i n e ( 1 5 , m l . , ) a n d a c e t i c a n h y d r i d e (5mml.))was r e f l u x e d o v e r n i g h t and t h e n d i l u t e d w i t h w a t e r (50rtiml.)).'-. The aqueou s m i x t u r e was e x t r a c t e d w i t h e t h e r (3x) and t h e c o m b i n e d e t h e r e x t r a c t s we re wa shed w i t h 5% h y d r o c h l o r i c a c i d , 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 . A f t e r d r y i n g w i t h a n h y d r o u s magne s i um s u l f a t e , - , r e m o v a l o f s o l v e n t p r o v i d e d a w h i t e s o l i d ( 3 - 26gg .,, m . p . 3 1 - 3 2 ° C) . v m a x ( CC 1 4 ) 3300-2500, 1 735, 1 700, 1 240 cm" 1 ;t (C C 1 ^ , 60KMHz) 6 .00 ( t , 2 H , - C H ^ O A c ) , 7-70 ( t , 2 H , -CH^COOH) , 8 . 0 0 ( s , 3H, -0 2 CCH_ 3 ) , 8.75 (broad s , 16 H , " ( C H ^ g - ) . A n a l . C a l c d . f o r C ^ H ^ O ^ : 0 , 6 3 - 9 3 ; H, 9 - 8 4 . F o u n d : C, 6 4 . 3 0 ; H, 1 0 . 0 0 . - 129 -1 1 - a c e t o x y u n d e c y 1 c h l o r i d e ( 1 0 5 ; n=10) F r e s h l y d i s t i l l e d o x a l y l c h l o r i d e (2 m l . ) was added t o 11 - a c e t o x y u n d e c a n o i c a c i d (1.59 g . ) a t room t e m p e r a t u r e . The m i x t u r e was t h e n r e f l u x e d f o r a b o u t 2 h o u r s and t h e e x c e s s o x a l y l c h l o r i d e was removed u n d e r a t m o s p h e r i c p r e s s u r e . D i s t i l l a t i o n a t d i m i n i s h e d p r e s s u r e p r o v i d e d a c l e a r o i l ( 0 . 7 7 b . p . 1 2 6 - 1 2 7 ° C a t 0 . 04 m.m. H g ) . v (CC1 , ) 1 7 9 0 , 1 72 5 , 1240 cm 1 ; T (CC1 , , 60 MHz) 6 . 00 max 4 4 ( t , 2H , -CH^OAc) , 7 .13 ( t , 2H , - C H ^ C O C I ) , 8.00 ( s , 3 H , -0C0CH_) 8 . 67 ( b r o a d s , 16H , - ( C H ) -) . 2 o 1 1 - o x o - o c t a d e c y 1 a c e t a t e ( 1 0 7 ; n=10, m=6) A A m i x t u r e o f magnes i um t u r n i n g s ( 0 . 7 g-) and a s m a l l c r y s t a l o f i o d i n e i n d r y e t h e r (50 m l . ) was s t i r r e d u n t i l t h e brown c o l o r d i s a p p e a r e d . 1 - b r o m o h e p t a n e ( 1 . 6 m l . ) i n d r y e t h e r (50 m l . ) was added d r o p w i s e . A f t e r a d d i t i o n , t h e s t i r r e d r e a c t i o n m i x t u r e was r e f l u x e d f o r 2 h o u r s . A p o r t i o n o f t h i s G r i g n a r d r e a g e n t (10 m l . ) was d i l u t e d w i t h w a t e r (25 m l . ) and 0 . 05 N h y d r o c h l o r i c a c i d (50 m l . ) . The e x c e s s a c i d was t i t r a t e d wi:th s t a n d a r d 1 N s o d i u m h y d r o x i d e s o l u t i o n . The m o l a r i t y o f G r i g n a r d r e a g e n t was 0 . 1 5 -H e p t y l magne s i um b r o m i d e s o l u t i o n (15 m l . ) was added t o d r y z i n c c h l o r i d e (304 mg.) i n d r y e t h e r (10 m l . ) . A f t e r t h e i n i t i a l a d d i t i o n , t h e m i x t u r e was s t i r r e d and r e f l u x e d f o r 4 h o u r s . W i t h c o n t i n u e d s t i r r i n g , a s o l u t i o n o f 1 1 - a c e t o x y u n d e c y 1 c h l o r i d e (0 . 17 g.) i n d r y b e n z e n e (5 m l . ) was added d u r i n g t w e n t y m i n u t e s . The m i x t u r e was s t i r r e d and r e f l u x e d f o r a n o t h e - 1 3 0 -3 h o u r s and t h e n h y d r o l y z e d w i t h 5% h y d r o c h l o r i c a c i d (50 m l . ) . The aqueous l a y e r was s e p a r a t e d and e x t r a c t e d w i t h b e n z e n e (3*). The c o m b i n e d b e n z e n e s o l u t i o n was wa shed w i t h 5% h y d r o c h l o r i c a c i d ( 2 x ) , 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 (2x ) and w a t e r ( I x ) . A f t e r d r y i n g w i t h a n h y d r o u s s o d i u m s u l f a t e , r e m o v a l o f s o l v e n t p r o v i d e d a y e l l o w s o l i d (242 mg.) w h i c h was c h r o m a t o g r a p h e d on Woelm s i l i c a g e l ( g r a d e I I I ) ; 5% e t h e r i n p e t r o l e u m e t h e r ( 3 0 - 6 0 C) e l u t e d t h e p u r e 1 1 - o x o - o c t a d e c y 1 a c e t a t e (143 mg. , w h i t e s o l i d ) . v m a x ( C C 1 V 1 7 5 0 ' 1 7 2 5 ' 1 2 3 5 c m " 1 ; T ( C C 1 4 ' 6 0 M H z ) 6.00 ( t , 2H, -CH_ 2 0Ac) , 7.68 ( t , 4H, - CIH 2 CO CH_2 - ) , 8.00 ( s , 3H , - 0 2 C C H ^ ) , 8.67 ( b r o a d s , 26H , - ( CJH2) | 3 ~ ) > 9 -10 ( t , 3H , - C H ^ QH 2 ) n ) HI 326 (M + ) . e A c e t a l o f 1 1 - o x o - o c t a d e c y 1 a c e t a t e A m i x t u r e o f 11 - o x o - o c t a d e c y 1 a c e t a t e (96.7 mg . ) , e t h y l e n e g l y c o l (0.1 m l . ) and p - t o 1 u e n e s u 1 f o n i c a c i d m o n o h y d r a t e (5 mg.) i n b e n z e n e (10 m l . ) was r e f l u x e d f o r 43 h o u r s -W a t e r was removed by D e a n - S t a r k w a t e r s e p a r a t o r . The r e s u l t e d m i x t u r e was c o o l e d and washed w i t h 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 ( i x ) , w a t e r ( 2 x ) and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Removal o f s o l v e n t p r o v i d e d a y e l l o w o i l (87 mg.) w h i c h was c h r o m a t o g r a p h e d on a l u m i n a ( g r a d e I V) ; p e t r o l e u m e t h e r ( 3 0 - 6 0 ° C ) e l u t e d t h e p u r e a c e t a l o f 1 1 - o x o - o x t a d e c y 1 a c e t a t e (34 .1 mg. \ p a l e y e l l o w o i l ) . - 131 -v m a x ( C C V > 1 725 , 1 2 3 5 , 1070 c m " 1 ; T ( CC 1 4 , 60 MHz) 6 . 00 ( t , 2 H , -CH_ 2 0Ac) , 6 . 2 0 ( s , 4H , -0CH_ 2 CH_2.0-) , 8.06 ( s , 3H, -0C0CH ) , 8 .72 ( b r o a d s , 30H , CH (CH ) , _ ) , 9 - 13 ( t , 3H, C H , ( C H j A c e t a l o f 1 1 - o x o - o c t a d e c a n o 1 ( 1 0 8 ; n = 1 0 , m=6) A m i x t u r e o f a c e t a l o f 1 1 - o x o - o c t a d e c y 1 a c e t a t e (30 mg. and p o t a s s i u m h y d r o x i d e (9 mg.) i n m e t h a n o l / w a t e r (1 m l . : 0 . 5 ml was r e f l u x e d f o r 15 h o u r s . Then t h e m e t h a n o l was removed by d i s t i l l a t i o n . The r e s i d u e was d i l u t e d w i t h w a t e r and e x t r a c t e d w i t h e t h e r ( 3 * ) . The c o m b i n e d e t h e r e x t r a c t s we re wa shed w i t h s a t u r a t e d s o d i u m c h l o r i d e s o l u t i o n ( 2 x ) , w a t e r ( 2 x ) and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Removal o f s o l v e n t p r o v i d e d a p a l e - y e l l o w o i l ( 22 .1 mg . ) • v ( C C 1 . ) , 3 ^ 0 0 , 1070 c m " 1 ; T ( C C l , , 60 MHz) 6 . 20 max 4 4 ( s , 4H , -0CH_ CH_ 0- ) , 6 . 50 ( t , 2 H , -CH_ 2 0H) , 8 .72 ( b r o a d s , 30H , CH (CH ) - ) , 9 - 10 ( t , 3H, C H , ( C H . ) ) . 3 — I I 5 —3 2 n 1 5 ~ a c e t o x y p e n t a d e c a n o i c a c i d ( 1 0 4 ; n= l 4 ) 1 5 " h y d r o x y p e n t a d e c a n o i c a c i d was c o n v e r t e d t o t h e a c e t a t e s as d e s c r i b e d f o r 11 - a c e t o x y u n d e c a n o i c a c i d . The I.R. and N.MPR?.. c h a r a c t e r i s t i c o f t h i s 1 5 _ a c e t o x y -p e n t a d e c a n o i c a c i d we re s i m i l a r t o t h o s e o f 11 - a c e t o x y u n d e c a n o i c a c i d . - 132 -15 - a c e t o x y p e n t a d e c y 1 c h l o r i d e ( 1 0 5 ; n = 14) 1 5 - a c e t o x y p e n t a d e c a n o i c a c i d was c o n v e r t e d t o t h e a c y l c h l o r i d e as d e s c r i b e d f o r 1 1 - a c e t o x y u n d e c y 1 c h l o r i d e . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h i s 1 5 _ a c e t o x y -p e n t a d e c y l c h l o r i d e weiressihmi , l a r t o t h o s e o f 1 1 - a ce t oxy u n de cy 1 c h l o r i d e . 1 5 - o x o - o x t a d e c y 1 a c e t a t e ( 1 0 7 ; n=14, m=2) 1 5 - a c e t o x y p e n t a d e c y 1 c h l o r i d e was c o n v e r t e d t o 1 5 " o x o - o x t a d e c y 1 a c e t a t e w i t h n - p r o p y l magne s i um b r o m i d e as d e s c r i b e d f o r 1 1 - o x o - o c t a d e c y 1 a c e t a t e . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h i s 1 5 - o x o -o c t a d e c y l a c e t a t e we re s i m i l a r t o t h o s e o f 1 1 - o x o - o x t a d e c y 1 a c e t a t e . A c e t a l o f 1 5 - o x o - o c t a d e c y 1 a c e t a t e The a c e t a l o f 1 5 - o x o - o c t a d e c y 1 a c e t a t e was p r e p a r e d i n t h e same way as t h a t f o r a c e t a l o f 1 1 - o x o - o c t a d e c y 1 a c e t a t e . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h i s a c e t a l o f 1 o x o - o c t a d e c y 1 a c e t a t e s we re s i m i l a r t o t h o s e o f a c e t a l o f 1 1 -o x o - o x t a d e c y 1 a c e t a t e . A c e t a l o f 1 5 - o x o - o c t a d e c a n o 1 ( 1 0 8 ; n=]k, m=2) A c e t a l o f 1 5 - o x o - o c t a d e c y 1 a c e t a t e was c o n v e r t e d t o a c e t a l o f 1 5 - o x o - o x t a d e c a n o 1 as d e s c r i b e d f o r a c e t a l o f 1 1 -o x o - o c t a d e c a n o 1 . - 133 -The I . R . and N . M . R . c h a r a c t e r i s t i c o f t h i s a c e t a l o f 1 5 _ o x o - o c t a d e c a n o 1 we re s i m i l a r t o t h o s e o f a c e t a l o f 1 1 - o x o -o c t adecano1 . M e t h y l 9~ and 1 0 - h y d r o x y s t e a r a t e s ( 1 1 0 a S b) Bo r a n e - m e t h y 1 s u l f i d e ; ( 0 . 5 m l . ) was added d r o p w i s e t o a s o l u t i o n o f m e t h y l o l e a t e (1 .71 g.) i n d r y t e t r a h y d r o f u r a n ( 1 0 0 m l . ) a t 0 -5 C. F o l l o w i n g t h e a d d i t i o n o f t h e h y d r i d e , t h e c o o l i n g b a t h was removed and t h e s o l u t i o n was s t i r r e d at room t e m p e r a t u r e f o r 3 h o u r s . 3N agueous s o d i u m h y d r o x i d e (25 m l . ) o was t h e n a d d e d . A f t e r c o o l i n g t o 0 -5 C i n an i c e w a t e r b a t h , 30% h y d r o g e n p e r o x i d e s o l u t i o n (35 m l . ) was a d d e d . Then t h e c o o l i n g b a t h was removed and t h e r e a c t i o n m i x t u r e was h e a t e d a t r e f l u x f o r 1 h o u r . The r e a c t i o n m i x t u r e was t h e n p o u r e d i n t o w a t e r ( 2 0 0 m l . ) and e x t r a c t e d w i t h e t h e r ( 3 x ) . The c o m b i n e d e t h e r e x t r a c t s we re washed w i t h s a t u r a t e d s o d i u m c h l o r i d e s o l u t i o n ( 2 x ) ,atw<at\e«irtt(2xi)2:and- idtrriue'da w Lit h rainhycdrrbU|Snm-agitli\eis i.-aimi'.s u-J f a t e ., :, ftem&tvad. p f s o l v e n t p r o v i d e d a w h i t e s o l i d ( 1 . 5 6 g . ) . v m - v ( C CU) 3450 , 1 750 c m " 1 ; T ( C C l , , 60 MHz) 6 . 40 ( s , 3H, CH^OCO-) , 6 . 5 3 ( s , I H , -CH0fil9i)-, 7 -18 ( b r o a d s , IH , -OH), 7 -80 ( t , 2 H , - C l ± 2 C 0 2 M e ) , 8.70 ( b r o a d s , 28H , CH ^  ( C H_2) ] ^ - ) , 9 . 1 0 ( t , 3H , C H 3 ( C H 2 ) n - ) . - 134 -M e t h y l 9 - and 10 - k e t o - s t e r a t e ( i l l a and b) M e t h y l 9 _ and 1 0 - h y d r o x y s t e r a t e ( 0 . 8 g .) we're, d i s s o l v e d i n a c e t o n e (5 m l . ) . J o n e s r e a g e n t ( C r O 3 ~ H 2 S 0 ^ - H 2 0 ) (3 m l . ) was added d r o p w i s e u n t i l o x i d a t i o n was c o m p l e t e . The m i x t u r e was d i l u t e d w i t h w a t e r (25 m l . ) and e x t r a c t e d w i t h e t h e r ( 3 x ) . The c o m b i n e d e t h e r e x t r a c t s we re washed w i t h 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 ( 2 x ) , w a t e r ( 2x ) and d r i e d w i t h a n h y d r o u s magnes i um s u l f a t e . Removal o f s o l v e n t p r o v i d e d a y e l l o w s o l i d w h i c h was c r y s t a l l i z e d f r o m p e n t a n e t o g i v e a w h i t e s o l i d ( 0 . 6 5 g - ) . V max (CC]0 1750 , 1735 c m - 1 ; x ( C C 1 k , 60 MHz) 6.41 ( s , 3H , - C 0 2 C H ^ ) , 7 -74 (3 o v e r l a p p i n g t r i p l e t s , 6H, - C H _ 2 C 0 2 C H 3 , -CH_ 2C0CH_ 2-) , 8.48, 8 .74 ( b r o a d s , m, 24H , CH 3 ( CH_2i) y 2 - '.) , 9 . 12 ( t , 3H , C H 3 ( C H 2 ) n - ) . M e t h y l 9~ and 1 0 - k e t o - s t e a r a t e a c e t a l s A m i x t u r e o f m e t h y l 9 f and 1 0 - k e t o - s t e a r a t e i (300 mg . ) e t h y l e n e g l y c o l ( 0 . 3 m l . ) and p - t o 1 u e n e s u 1 f o n i c a c i d m o n o h y d r a t e i n b e n z e n e ( 2'5 m l . ) was r e f l u x e d , f o r 43 h o u r s w h i l e w a t e r was removed by D e a n - S t a r k w a t e r s e p a r a t o r . U s u a l w o r k - u p p r o v i d e d a p a l e - y e l l o w o i l ( 2 4 2 . 7 mg.) w h i c h was c h r o m a t o g r a p h e d on a l u m i n a ( g r a d e I I I ) ; and e l u t e d w i t h p e n t a n e t o p r o v i d e p u r e m e t h y l 9 _ and 10 - k e t o s t e a r a t e a c e t a l s (120 mg.) . V m a x ( C C 1 /,) > 1 750Q 1150 c m - 1 ; T ( C C 1 ^ , 60 MHz) 6. 18 ( s , 4H, - 0 C H 2 C H 2 0 - ) , 6 . 4 0 ( s , 3H , - C 0 2 C H _ 3 ) , 7 -77 ( t , 2H , - C H _ 2 C 0 2 C H 3 ) , 8 . 4 8 , 8.76 ( b r o a d s , m, 2 8 H , CH 3 ( C H 2 ) , ^ - ) , 9 - 12 ( t , 3H, C H 3 ( C H 2 ) n - ) . - 135 -A c e t a l s o f 9 ~ and 1 0 - o x o - o c t a d e c a n o 1 (112 a and b) L i t h i u m a l u m i n i u m h y d r i d e (54 mg.) i n d r y e t h e r (15 m l . ) was r e f l u x e d f o r ^ i h o u r s . M e t h y l 9 - and 1 0 - o x o - s t e a r a t e . a c e t a l (120 mg.) i n d r y e t h e r (10 m l . ) was added d r o p w i s e . A f t e r s t i r r i n g and r e f l u x i n g f o r 2\ h o u r s , e x c e s s l i t h i u m a l u m i n i u m h y d r i d e was d e s t r o y e d by a d d i n g w a t e r (2 m 1 . ) . 2 N s o d i u m h y d r o x i d e s o l u t i o n (6 m l . ) was t h e n added and t h e m i x t u r e was e x t r a c t e d w i t h e t h e r ( 2 x ) . The c o m b i n e d e t h e r e x t r a c t s we re wa shed w i t h w a t e r ( i x ) and d r i e d w i t h a n h y d r o u s magnes i um s u l f a t e . Removal o f s o l v e n t p r o v i d e d a p a l e - y e l l o w o i l (89 m g . ) . v ( C C 1 . ) 3^00, 1070 c m " 1 ; T ( C C 1 ( , 60 M H Z ) 6.20 max 4 4 ( s , 4 H , -0CH_ 2CH^(D-) , 6.50 ( t , 2 H , -CH_ 2 0H) , 8.72 ( b r o a d s , 30H , C H 3 ( C H 2 ) 1 5 - ) , 9-10 ( t , 3H, C £ 3 ( C H 2 ) n - ) . O x i d a t i o m o f 1 6 - h e x a d e c a n o l i d e (117; n =15) Chromium t r i o x i d e (7-6 g.) i n a c e t i c a n h y d r i d e (16 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f 1 6 - h e x a d e c a n o l i d e (5-8 g . , 0.023 mo le ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and a c e t i c a n h y d r i d e o (9 m l . ) . The m i x t u r e was s t i r r e d a t 0-5 C f o r 3 h o u r s and t h e n a t room t e m p e r a t u r e f o r 5 d a y s . W a t e r (200 m l . ) was added i n and t h e e x c e s s a c e t i c a n h y d r i d e was r e m o v e d . The m i x t u r e was e x t r a c t e d w i t h e t h e r (6x). The c o m b i n e d e x t r a c t s we re wa shed s u c c e s s i v e l y w i t h 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 (4x), w a t e r (2x) and - 136 -d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Removal o f s o l v e n t p r o v i d e d a y e l l o w o i l (3 -6 g.) w h i c h was shown by g . l . c . (3% SE30) t o c o n s i s t o f 1 6 - h e x a d e c a n o l i d e ( 3 4 % ) , a m i x t u r e o f o xo - 1 h e x a d e c a n o I i d e s (62%) ( u n r e s o l v e d on g . l . c . ) and a m i x t u r e o f p o 1 y k e t o - 1 6 - h e x a d e c a n o 1 i d e s (4%). Column c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r Woelm s i l i c a g e l ( g r a d e I I I ) g a v e , by e l u t i o n w i t h p e t . e t h e r ( 3 0 - 6 0 ° C ) / e t h e r , a m i x t u r e o f mono -oxo - 16 -h e x a d e c a n o l i d e s (118; x +y= l 4 ) ( 1 . 7 2 g . , 33% b a s e d on consumed s t a r t i n g m a t e r i a l ) . V max < C C V 1 7 3 8 ' 1 7 2 0 ' 1 2 5 0 ' 1 1 7 5 c m " 1 ; T ( CC 1 ^ , 100 MHz) 5-97 ( t , 2H, -COOCH^) , 7-72 ( m i x e d t , 6H, - CH_2C0 CH_2 - , -CH_ 2 C00-) , 8.42, 8.70 (m, b r o a d s , 2 0 H , - ( C H 2 ) 1 ( J - ) . A n a l . C a l c d . f o r C]^2S°3: C ' 71.64; H > 10.45-Found : C, 71-43; H, 10 . 23 -A c e t a l s o f o x o - 1 6 - h e x a d e c a n o 1 i d e s A m i x t u r e o f o x o - 1 6 - h e x a d e c a n o 1 i d e s (361 mg. , 1.35 m i l l i m o l e ) , e t h y l e n e g l y c o l (0.4 m l . ) and p - t o 1 u e n e s u 1 f o h i c a c i d m o n o h y d r a t e (15 mg•) i n b e n z e n e (30 m l . ) was r e f l u x e d f o r 4 days and w a t e r was removed by D e a n - S t a r k w a t e r s e p a r a t o r The r e s u l t e d m i x t u r e was c o o l e d and washed w i t h 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 ( 2 x ) , w a t e r ( i x ) and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Removal o f s o l v e n t p r o v i d e d a y e l l o w o i l (371 mg.) w h i c h was c h r o m a t o g r a p h e d on a l u m i n a ( g r a d e I V ) ; pe i i i t ane e l u t e d t h e p u r e a c e t a l s o f o xo - 16 -- 137 -h e x a d e c a n o 1 i d e s (275 m g . ) . V max < C C V 1 7 3 8 ' ] 2 k 0 ' 1 1 5 0 ' 1 0 7 5 c m _ 1 ; T ( C C 1 Z , ' 6 0 M H z ) 5.97 ( t , 2H , - C 0 0 C H 2 - ) , 6.23 ( s , 4H, -OCH^CH^O-) , 7. 80 ( t , 2H , -CH_ 2 C00-) , 8 . 4 0 , 8.67 (m, b r o a d s , 24H , " ( C H _ 2 ) 1 2 - ) . A c e t a l s o f o x o - 1 6 - h y d r o x y h e x a d e c a n o i c a c i d s ( 1 1 9 ; x+y= l 4 ) A m i x t u r e o f o x o - 1 6 - h e x a d e c a n o 1 i d e a c e t a l s (160 mg.) and p o t a s s i u m h y d r o x i d e (41 mg.) i n m e t h a n o l (4 m l . ) was r e f l u x e d o v e r n i g h t and t h e n a c i d i f i e d t o ph 6. The m i x t u r e was e x t r a c t e d w i t h e t h e r (5x). The c o m b i n e d e t h e r e x t r a c t s we re washed w i t h w a t e r ( l x ) . a nFd- rd:rU <efd '.wfi tthr. a'nch-y'd rou's ma g n e s i u m |:s£ullef a>tfel.I cR'emro.vIa l( b5f0 siocl=v)e.nt p r o v i d e d a y e l l o w o i l (130 mg . ) . V max ( C C V > 3 4 0 0 , 3 0 0 0 - 2 5 0 0 , 1 7 1 5 , 1075 c m " 1 ; x (CC 1 ^ , 60 M H z ) , 3-65 ( s , 2 H , -C00H_, -OH.), 6.07 ( s , 4H , - 0 CH_2CJH_2 0-) , 6.37 ( t , 2H , -CH_ 20H) , 7-65 ( t , 2 H , -CH_ 2 C00H) , 8.57 ( b r o a d s , 2 4 H , - ( C H 2 ) 1 2 - ) . A c e t a l s o f o x o - h e x a d e c a n o 1 s ( 1 2 0 ; x+y=l4) M e s y l c h l o r i d e ( 0 .05 m l . ) was added t o a s o l u t i o n o f a c e t a l s o f o x o - 1 6 - h y d r o x y h e x a d e c a n o i c a c i d s i n d r y p y r i d i n e (0.21 m l . ) a t 0 -5°C . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 2 h o u r s , t h e s o l u t i o n was d i l u t e d w i t h w a t e r (5 m l . ) and e x t r a c t e d w i t h m e t h y l e n e c h l o r i d e (3*). The c o m b i n e d m e t h y l e n e c h l o r i d e e x t r a c t s we re washed w i t h s a t u r a t e d ammonium c h l o r i d e s o l u t i o n , w a t e r and d r i e d w i t h a n h y d r o u s magnes i um s u l f a t e . Removal o f s o l v e n t p r o v i d e d a g o l d e n y e l l o w o i l (119 mg.) w h i c h was d i s s o l v e d i n d r y t e t r a h y d r o f u r a n (10 m l . ) and added - 138 -t o a m i x t u r e o f l i t h i u m a l u m i n i u m h y d r i d e (127 mg.) i n d r y e t h e r (25 m l . ) w h i c h was r e f l u x e d f o r h a l f h o u r b e f o r e a d d i t i o n . A f t e r s t i r r i n g and r e f l u x i n g f o r 2\ h o u r s , e x c e s s l i t h i u m a l u m i n i u m h y d r i d e was d e s t r o y e d by a d d i t i o n o f w a t e r . The r e a c t i o n m i x t u r e was t h e n t r e a t e d w i t h 2N s o d i u m h y d r o x i d e s o l u t i o n , w a t e r and f i l t e r e d . The f i l t r a t e was e x t r a c t e d w i t h e t h e r (3x). The c o m b i n e d e t h e r e x t r a c t s we re washed w i t h s a t u r a t e d ammonium c h l o r i d e s o l u t i o n , w a t e r and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Remova l o f s o l v e n t p r o v i d e d a y e l l o w brown o i l (72 mg.) w h i c h was p a s s e d down a c o l u m n ( a l u m i n a g r a d e IV) and g a v e , by e l u t i o n w i t h 10% e t h e r i n p e t . e t h e r (30-60°C), a y e l l o w o i l (55 m g . ) . vm C C C l . ) 3^00, 1075, 1050 c m " 1 ; T ( C C l . , 100 M H z ) , max 4 4 6 .22 ( s , 4 H , -OCH^CH^O-) , 6.52 ( t , 2H , -CH_ 2 0H) , 8.58, 8.76 (m, b r o a d s , 26H , CH 3 ( C H_2) ] ^  - ) , 8.14 ( t , 3H , CH^ ( C H 2 ) n ~ ) . O x i d a t i o n o f 15 - p e n t a d e c a n o1 i d e (117; n = l 4 ) Ch romium t r i o x i d e (7-6 g.) i n a c e t i c a n h y d r i d e (16 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f 1 5 - hexa de cano 1 i d e (6 g . ,, 0.025 mo l e ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and a c e t i c a n h y d r i d e (9 m l . ) . The m i x t u r e was s t i r r e d a t 0-5°C f o r 3 h o u r s and t h e n at room t e m p e r a t u r e f o r 5 d a y s . U s u a l w o r k - u p , as d e s c r i b e d f o r 1 6 - h e x a d e c a n o l i d e ( c f . P.135) p r o v i d e d a y e l l o w o i l (3 -84 g.) w h i c h was shown by g . l . c . (3:% SE30) t o c o n s i s t o f 1 5 _ p e n t a d e c a n o l i d e ( 4 9 % ) , a m i x t u r e o f o x o - 1 5 - p e n t a d e c a n o 1 i d e s (48%) ( u n r e s o l v e d - 139 -on g . l . c . ) and a m i x t u r e o f p o 1 y - k e t o - 1 5 _ p e n t a d e c a n o 1 i d e s (3%). Co lumn c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r Woe 1m s i l i c a g e l ( g r a d e I I I ) g a v e , by e l u t i o n w i t h p e t . e t h e r ( 3 0 - 6 0 ° C ) / e t h e r , , a m i x t u r e o f m o n o - o x o - 1 5 - p e n t a d e c a n o 1 i d e s ( 1 1 8 ; x+y=13) ( 1 . 8 0 2 g g . , 36% b a s e d on consumed s t a r t i n g m a t e r i a l ) . v m a x ( C C 1 4 ) 1 7 36 , 1 716 , 1 2 5 0 , 11 75 c m " 1 ; x (CC1^ , 100 M H z ) , 5 .96 ( t , 2H, -C00CH_ 2 - ) , 7 .72 ( m i x e d t , 6H , - CH_2 COC h[2 - , - C H _ 2 C 0 0 - ) , 8 . 40 , 8 .72 (m, b r o a d s , 1 8H , - ( C H . ) Q - ) . A n a l . C a l c d . f o r C ^ H ^ O ^ C, 7 0 . 8 7 ; H, 1 0 . 2 4 . F o u n d : C, 7 0 . 8 4 ; H, 1 0 . 4 0 . C y c l o d o d e c a n o n e (124 ) J o n e s R e a g e n t ( 125 m l . ) was added d r o p w i s e t o a s o l u t i o n o f c y c l o d o c l e c a h o l ( 25 g . , 0 . 1 4 mo l e ) i n a c e t o n e (400 m l . ) . The r e a c t i o n m i x t u r e was s t i r r e d f o r 15 m i n u t e s . E x c e s s J o n e s Reagen t was d e s t r o y e d by a d d i n g i s o p r o p y f , a l c o h o l . The m i x t u r e was d i l u t e d w i t h w a t e r (200 m l . ) and e x t r a c t e d w i t h e t h e r ( 4 x ) . The c o m b i n e d e t h e r e x t r a c t s we re wa shed w i t h 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 ( 3 x ) , w a t e r ( 2x ) and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Remova l o f s o l v e n t p r o v i d e d a y e l l o w s o l i d w h i c h was c r y s t a l l i z e d f r o m p e t r o l e u m e t h e r ( 3 0 - 6 0 ° C ) t o g i v e a wh i t e so 1i d (24 g.) . v ( C C 1 . ) 1715 cm;] ; ; T ( C C 1 . , 60 MHz). 7 . 6 7 ( m i x e d t , max 4 4 + 4 H , -CH^COCH. - ) , 8.33 (m, 4 H , - C H CH CO CH CH^-) , 8.73 ( s , 14H, - < C H 2 ) 7 - > , - u o -1 2 - d o d e c a n o 1 ! d e ( 1 1 7 ; n=1 l ) A s o l u t i o n o f eye 1 o d o d e c a n o n e ( 1 1 . 8 g . , 0 . 0 6 5 mo le ) i n m e t h y l e n e c h l o r i d e (80 m l . ) was added d r o p w i s e t o p e r o x y t r i -f l u r o a c e t i c a c i d (78 m l . ) a t 0°C o v e r a p e r i o d o f 1 h o u r . The r e a c t i o n m i x t u r e was s t i r r e d f o r 3 h o u r s . S a t u r a t e d P o t a s s i u m i o d i d e s o l u t i o n (80 m l . ) was added and t h e m i x t u r e was s t i r r e d w h i l e a d d i n g s a t u r a t e d s o d i u m b i s u l f i t e s o l u t i o n (75 m l . ) u n t i l t h e c o l o u r o f l i b e r a t e d i o d i n e was d i s c h a r g e d . The p a l e y e l l o w m i x t u r e was e x t r a c t e d w i t h m e t h y l e n e c h l o r i d e ( 4 x ) . The c o m b i n e d e x t r a c t s we re washed w i t h 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 ( 3 * ) , w a t e r ( i x ) and d r i e d w i t h a n h y d r o u s s o d i u m s u l f a t e Removal o f s o l v e n t p r o v i d e d a p a l e y e l l o w o:« .1 . ( 1.4. g.) . Vacuum d i s t i l l a t i o n o f t h e p a l e y e l l o w o i l p r o v i d e d a c o l o u r l e s s o i l (6.8 g . , b . p . 6 1 - 7 0° C/0 . 0 1-0 . 0 3 mm.) w h i c h was then , ch r oma tog r aph on a l u m i n a ( g r a d e I V ) ; 5% e t h e r i n p e t . e t h e r ( 3 0 - 6 0 ° C ) e l u t e d t h e p u r e 1 2 - d o d e c a n o 1 i d e (4 .9 g . ) . v ( C C l . ) 1 7 2 5 , 1 248 , 1137 c m " 1 ; x ( C C l . , 100MHz) max 4 4 5 .92 ( t , 2 H , - C00CJj_2 - ) , 7.74 ( t , 2H , -00CCH_ -) , 8 .36, 8.67 (m, b r oad s , 1 8H , - ( C H 2 ) -) . A n a l . C a l c d . f o r e , „ H „ 0 : C, 72 .72 ; H, 1 1 . 1 1 . ,12 22 2 ' ' Found : C , 72 .76; H , 1 1 .007 O x i d a t i o n o f 1 2 - d o d e c a n o 1 i d e ( 1 1 7 ; n=11) Chromium t r i o x i d e (7 g.) i n a c e t i c a n h y d r i d e (14 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f 1 2 - d o d e c a n o 1 i d e (4.8 g . , 0 . 024 mo l e ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and a c e t i c a n h y d r i d e (9 m l . ) . The m i x t u r e was s t i r r e d a t 0 - 5°C f o r 3 h o u r s - 141 -and t h e n at room t e m p e r a t u r e f o r 5 d a y s . U s u a l w o r k - u p , as d e s c r i b e d f o r 1 6 - h e x a d e c a n o l i d e ( c f . P.135) p r o v i d e d a b rown o i l (2.57 g.) w h i c h was shown by g . l . c . (3% SE30) t o c o n s i s t o f 12 - d o d e c a n o1 i d e (22%), a m i x t u r e o f o x o - 12 - d o d e c a n o1 i d e s (73.8%) ( u n r e s o l v e d on g . l . c . ) arid a m i x t u r e o f po 1 y k e t o -1 2 - d o d e c a n o l i des (4.2%). Co lumn c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r Woelm s i l i c a g e l ( g r a d e I I I ) g a v e , by e l u t i o n w i t h p e t . e t h e r ( 3 0 - 6 0 ° C ) / e t h e r , a m i x t u r e o f m o n o - b x o - 1 2 - d o d e c a n o 1 i d e s ( 1 18 ; x+y=10) (1.868 g . , 4 0 % b a s e d on consumed s t a r t i n g m a t e r i a l ) . w ( C C l . ) 1 736 , 1716, 1238, 1150 c m " 1 ; x ( C C l . , 100 MHz) max 4 4 5.93 ( t , 2H , -C00CH_ -) , 7.69 ( m i x e d t , 6H , " C H ^ C O C H ^ - , - C H ^ C O O - ) , 8.36, 8.69 (m, m, 1 2H , " ( C I H ^ - ) . A n a l . C a l c d . f o r C ^ H ^ O : C, 67-92; H, 9-43-Found : C, 67 -60 ; H , 9 - 41 . A c e t a l s o f o x o - 1 5 - P e n t a d e c a n o 1 i d e s , o x o -12 - d o d e c a n o1 i d e s The m o n o - o x i d a t i o n p r o d u c t s f r o m 15 - p e n t a d e c a n o 1 ide (118; x+y=13) and 12 - d o d e c a n o1 i d e (118; x+y=10) we re c o n v e r t e d t o t h e a c e t a l s as d e s c r i b e d f o r o x o - 1 6 - h e x a d e c a n o 1 i d e s . The I.R. and N.M.R. c h a r a c t e r i s t i c s o f t h e s e a c e t a l s we re s i m i l a r t o t h o s e o f o x o - l 6 - h e x a d e c a n o l i d e ? a c e t a 1 s . A c e t a l s o f e6x6 = 1 g ?hyd ro.xy pen teadecano i-cc' ac i d s (: 1 1 9 ; "x+y = 1 3X o x o - 1 2 r h y d r o x y d o d e e a n o i l c oac i d s £ (1 19 '} " x * y ^ 10) ( . ' The a c e t a l s o f oxo-T5 =peritadecario1 ides and oxo-12-d o d e c a n o1 i d e s we re c o n v e r t e d t o t h e a c e t a l s o f o x o - 1 5 - h y d r o x y -- 1 hi -p e n t a d e c a n o i c a c i d s ( 1 1 9 ; x+y=13) and o x o - 1 2 - h y d r o x y d o d e c a n o i c a c i d s ( 1 1 9 ; x+y=10) as d e s c r i b e d f o r a c e t a l s o f o x o - 1 6 - h e x a -d e c a n o l i d e s . The I.R. and N.M.R. c h a r a c t e r i s t i c s o f t h e s e a c e t a l s we re s i m i l a r t o t h o s e o f o x o - 1 6 - h y d r o x y h e x a d e c a n o i c a c i d a c e t a l s ( 1 1 9 ; x+y=1k) . A c e t a l s o f k e t o - p e n t a d e c a n o 1 s ( 1 2 0 ; x+y=13)> k e t o - d o d e c a n o l s  ( 1 2 0 ; x+y=1Q) The a c e t a l s o f o x o - 1 5 - h y d r o x y p e n t a d e c a n o i c a c i d s ( 1 1 9 ; x+y = 13) and o x o - 1 2 - h y d r o x y d o d e c a n o i c a c i d s ( 1 1 9 ; x+y = 10) we re c o n v e r t e d t o t h e a c e t a l s o f k e t o - p e n t a d e c a n o 1 s (120 ; x+y = 13) and k e t o - d o d e c a n o 1s ( 1 2 0 ; x+y=10) as d e s c r i b e d f o r a c e t a l s o f o x o - 1 6 - h y d r o x y h e x a d e c a n o i c a c i d s . The I.R. and N.M.R. c h a r a c t e r i s t i c s o f t h e s e a c e t a l s we re s i m i l a r t o t h o s e o f k e t o - h e x a d e c a n o l a c e t a l s ( 1 2 0 ; x + y = l 4 ) . H y d r o x y - 1 6 - h e x a d e c a n o 1 i d e s ( 1 2 2 ; x+y=14) Sod ium b o r o h y d r i d e (16 mg.) i n m e t h a n o l (3 m l . ) was added d r o p w i s e t o a s o l u t i o n o f o x o - 1 6 - h e x a d e c a n o 1 i d e s ( 118 ; x+y=1n) (394 mg.) i n m e t h a n o l (7 m l . ) . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 50 m i n u t e s , e x c e s s s o d i u m b o r o h y d r i d e was d e s t r o y e d by t h e a d d i t i o n o f d i l u t e h y d r o c h l o r i c a c i d . U s u a l w o r k - u p p r o v i d e d a p a l e - y e l l o w o i l (330 m g . ) . - 143 -v maxCCCI^) 3 6 0 0 , 1740 c m ' 1 ; f f C C l ^ , 60 MHz) 5-95 ( t , 2H , - C 0 0 C H 2 ~ ) , 6 . 45 (m, 1H, - C H 0 H ) , 7-75 ( t , 2H , - C H ^ C O O - ) , 8 . 3 8 , 8 . 65 (m, b r o a d s , 24H, - ( C H 2 ) 1 2 - ) . M e s y l o x y - 1 6 - h e x a d e c a n o l i d e s M e s y l c h l o r i d e ( 0 . 2 m l . ) was added d r o p w i s e t o a s o l u t i o n o f h y d r o x y - 16 -hex adecano1 i d e s ( 302 mg.) i n d r y p y r i d i n e ( 0 . 7 m l . ) a t 0 - 5 ° C u n d e r n i t r o g e n . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 2 h o u r s , u s u a l w o r k - u p p r o v i d e d a p a l e y e l l o w o i l (326 m g . ) . v m a Y ( c c l J 1 735 , 1 350 , 1 3 3 3 , 1 2 3 6 , 1 1 7 5 , 910 cm 1 ; T ( C C I ^ , 60 MHz) 5 -37 (m, 1H, - C H O M s ) , 5-93 ( t , 2H , - C O O C H ^ - ) , 7 .13 ( s , 3H , - 0 S 0 2 C h [ 3 ) , 7 .76 ( t , 2H, -CH^COO-) , 8 .36, 8.63 (m, b r o a d s , 24H , " ( C H _ 2 ) 1 2 - ) . 1 6 - h e x a d e c e n o l i d e s ( 1 2 3 ; a+b=13) A s o l u t i o n o f m e s y 1 o x y - 1 6 - h e x a d e c a n o 1 i d e s (315 mg.) i n d r y c o l l i d i n e (6 m l . ) was h e a t e d a t 140°C o v e r n i g h t . U s u a l w o r k -up ( c f . P .125 ) p r o v i d e d a p a l e y e l l o w o i l (191 mg.) w h i c h was c h r o m a t o g r a p h e d on a l u m i n a Cg rade I V ) ; p e t r o l e u m e t h e r ( 3 0 - 6 0 ° C ) e l u t e d t h e p u r e 1 6 - h e x a d e c e n o I i d e s (a c o l o u r l e s s o i l , 135 m g . ) . v m a x C C C l ^ ) 1 7 3 5 , 1236 c m " 1 ; x ( C C I ^ , 60 MHz) 4.67 (m, 2 H , -CH = C H - ) , 5 -93 ( t , 2 H , -C00CH_ - ) , 7.83 (m, 6 H , -CH O C C H - 00CCH_ 2 ^ ) , 8 . 3 6 , 8.63 (m, b r o a d s , 1 8 H , ~(CH_ 2) - ) ; m/e 252 (M + ) . A n a l . C a l c d . f o r C^H28°2: C, 7 6 . 1 9 ; H, 1 1 . 1 1 . F o u n d : C, 76 . 199 ; H , 11 .20 . - 144 -Cyc1 o p e n t a d e c y 1 a c e t a t e ( 135 ) A c e t i c a n h y d r i d e ( 1 3 m l . ) was added t o c y c l o p e n t a -d e c a n o l (10 g.) i n p y r i d i n e (30 m l . ) and t h e m i x t u r e was r e f l u x e d o v e r n i g h t . A f t e r c o o l i n g , t h e s o l u t i o n was d i l u t e d w i t h w a t e r and e x t r a c t e d w i t h e t h e r ( 3 x ) . The c o m b i n e d e x t r a c t s we re washed w i t h d i l u t e h y d r o c h l o r i c a c i d , 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 and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Remova l o f s o l v e n t p r o v i d e d a g o l d e n y e l l o w o i l w h i c h was t h e n vacuum d i s t i l l e d and gave a c l e a r o i l ( 1 0 . 9 g . , b . p . 1 0 9 - 1 1 6 ° C a t 0 . 0 1 - 0 . 0 2 mm. Hg ). v ( C C 1 . ) 1 7 3 0 , 1240 c m " 1 ; T ( C C 1 . , 60 MHz) 5 - 2 4 max 4 k (m, 1H, -CHOAc) , 8.10 ( s , 3H, - 0C0CH_ 3 ) , 8.70 ( b r o a d s , 26H, - < C « 2 > , 3 - > . O x i d a t i o n o f cyc1 o p e n t a d e c y 1 a c e t a t e (135 ) Chromium t r i o x i d e ( 7 g.) i n a c e t i c a c i d (14 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f c y c l o p e n t a d e c y 1 a c e t a t e ( 5 g . , 0 . 0 19 m o l e ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and a c e t i c a n h y d r i d e ( 9 m l . ) . The m i x t u r e was s t i r r e d a t room t e m p e r a t u r e f o r 5 d a y s . W a t e r ( 200 m l . ) was t h e n added i n and t h e e x c e s s a c e t i c a n h y d r i d e was r e m o v e d . The m i x t u r e was e x t r a c t e d w i t h e t h e r ( 6 x ) . The c o m b i n e d e x t r a c t s we re washed s u c c e s s i v e l y w i t h 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 ( 4 x ) , w a t e r ( 2x ) and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Remova l o f s o l v e n t p r o v i d e d a y e l l o w o i l ( 3 - 2 g.) w h i c h was shown by g . l . c . - 145 -(3% S E 3 0) t o c o n s i s t o f cyc1 o p e n t a d e c y 1 a c e t a t e (35%), a m i x t u r e o f o x o - c y c 1 o p e n t a d e c y 1 a c e t a t e s (54.5%) ( u n r e s o l v e d on g . l . c . ) and a m i x t u r e o f p o 1 y - o x o - c y c 1 o p e n t a d e c y 1 a c e t a t e s ( 10 .5%) . Co lumn c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r Woelm s i l i c a g e l ( g r a d e I I I ) g a v e , by e l u t i o n w i t h p e t . e t h e r / e t h e r , a m i x t u r e o f m o n o - o x o - c y c 1 o p e n t a d e c y 1 a c e t a t e s ( 1 3 6 ; x+y = 13) (1-73 g . , 39-2% b a s e d on con sumed s t a r t i n g m a t e r i a l ) . v m a x (CC 1 ^) 1 7 4 5 , 1 720 , 1 245 c m " 1 ; T ( C C l j , , 100 MHz) 5 .27 (m, 1H, -CHOAc) , 7 -66 ( m i x e d t , 4H , - CH_2 C 0CH_ 2~) , 8 . 0 6 . 8 .08 ( s , 3H, -0C0CH_ 3) , 8 . 4 2 , 8 .70 (m, b r o a d s , 2 2 H , - ( C H _ 2 ) n - ) . A n a l . C a l c d . f o r C ^ H ^ O ^ C, 7 2 . 3 4 ; H, 10.64. Found C, 72 .60 ; H , 1 0 . 6 3 -H y d r o x y - e y e 1 o p e n t a d e c a n ones ( 1 3 7 ; x+y = 13) A m i x t u r e o f a c e t o x y c y c 1 o p e n t a d e c a n o n e s (690 mg.) and p o t a s s i u m h y d r o x i d e (246 mg.) i n m e t h a n o l (20 m l . ) was r e f l u x e d o v e r n i g h t . M e t h a n o l was t h e n removed by d i s t i l l a t i o n . A f t e r c o o l i n g , t h e r e s i d u e was d i l u t e d w i t h w a t e r and e x t r a c t e d w i t h e t h e r ( 4 x ) . The c o m b i n e d e x t r a c t s w e r e wa shed w i t h 5% h y d r o c h l o r i c a c i d (3x), w a t e r ( 2 x ) and d r i e d w i t h a n h y d r o u s magnes i um s u l f a t e . Remova l o f s o l v e n t p r o v i d e d a y e l l o w s o l i d (559 mg .) . v m a x ( C C l 2 t ) 3600 , 1 725 c m " 1 ; ! ( CC 1 ^ , 100 MHz, D 2 0 adde 6.44 (m, 1H, - C H 0 H ) , 7.65 ( m i x e d t , 4H , - CH_2 CO CH^-) , 8.39, 8.70 (m , b r o a d s , 22H , - (CH_ 2) 1 1 - ) . - 146 -O x o - c y c 1 o p e n t a d e c a n o n e s (13 8; x+y=13) H y d r o x y - c y c 1 o p e n t a d e c a n o n e s (300 mg.) we re d i s s o l v e d i n a c e t o n e ( 5 m l . ) . J o n e s r e a g e n t ( C r O ^ - H 2 S O ^ - H 2 0 ) (3 m l . ) was added d r o p w i s e u n t i l o x i d a t i o n was c o m p l e t e . The m i x t u r e was d i l u t e d w i t h w a t e r (25 m l . ) and e x t r a c t e d w i t h e t h e r ( 3 x ) . The c o m b i n e d e t h e r e x t r a c t s we re wa shed w i t h 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 ( 2x ) , w a t e r ( 2 x ) and d r i e d w i t h a n h y d r o u s magne s i um s u l f a t e . Remova l o f s o l v e n t p r o v i d e d a p a l e - y e l l o w s o l i d ( 2 5 4 mg w h i c h was shown by g . l . c . ( 20% DEGS, 10% F F A P , 5% 0V210) t o c o n s i s t o f 4 - o x o - e y e 1 o p e n t a d e c a n o n e ( 1 0 . 2 8 % ) , 5 - o x o - c y c 1 o p e n t a -d e c a n o n e ( 1 7 - 4 7 % ) and 8 - o x o - c y c 1 o p e n t a d e c a n o n e ( 7 2 . 2 5 % ) . Gas c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r t h e p r e p a r a t i v e 20% DEGS c o l u a t 2 00°C gave p u r e 4 - o x o - c y c 1 o p e n t a d e c a n o n e ( w h i t e s o l i d ) ( 139 ) , 5 - o x o - c y c l o p e n t a d e c a n o n e ( w h i t e s o l i d ) ( 140 ) and 8 - o x o - c y c l o -p e n t a d e c a n o n e ( w h i t e s o l i d ) ( 141 ) c o n s e c u t i v e l y . v ( CC I ^ ) 1 7 2 0 c m " 1 ; T ( C C 1 ^ , 100 MHz) 7 - 6 9 (m, 8H, (-CH_ 2C0CH_ 2-) 2 ) , 8 . 41 (m, 8H , ( - C H^ C H 2 C 0 CH 2 CH_2 - ) 2 ) , 8 . 7 7 ( b r o a d s , 10H, - ( C H _ 2 ) 5 - ) ; m/e 238 (M*). B i s - e t h y l e n e a c e t a l s o f 1 , 4 - c y c 1 o p e n t a d e c y 1 - d i o n e ( 142 ) A m i x t u r e o f 1 , 4 - c y c 1 o p e n t a d e c y 1 - d i o n e (19 mg . ) , d r y e t h y l e n e g l y c o l (0.1 m l . ) and p - t o 1 u e n e s u 1 f o n i c a c i d mono-h y d r a t e (5 mg.) i n d r y b e n z e n e (20 m l . ) was r e f l u x e d f o r 10 day s and w a t e r was removed by D e a n - S t a r k w a t e r s e p a r a t o r . The r e s u l t e d m i x t u r e was wa shed w i t h 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 ( 2 x ) , w a t e r ( i x ) and d r i e d w i t h a n h y d r o u s magne s i um - 147 -s u l f a t e . Remova l o f s o l v e n t p r o v i d e d a w h i t e s o l i d (26 mg . ) w h i c h was c h r o m a t o g r a p h e d on Woelm s i l i c a g e l ( g r a d e I I I ) , 5% e t h e r / p e t . e t h e r e l u t e d t h e p u r e b i s - e t h y l e n e a c e t a l s o f 1,4-c y c 1 o p e n t a d e c y 1 - d i o n e (17-6 m g . ) . v max (C C1^) 1080 , 1 100 cm ;x ( C C l ^ , 60 MHz) 6 .23 ( s , 8H, ( - 0 C H _ 2 C H ^ 0 - ) 2 ) , 8.47 ( s , 8H , - (CH^) ^ -) , 8.63 ( b r o a d s , 1 8H, - ( C H _ 2 ) g - ) ; m/e 3 26 (M + ) . A n a l . C a l c d . f o r C H , 0 , : C, 6 9 . 9 4 ; H, 1 0 . 4 3 - F o u n d : 19 3 4 4 C, 69 -48 ; H , 10.73 • B i s - e t h y l e n e a c e t a l s o f 1 , 5 - c y c 1 o p e n t a d e c y 1 - d ? o n e (143 ) 1 , 5 - c y c 1 o p e n t a d e c y 1 - d i o n e was c o n v e r t e d t o t h e d i a c e t a as d e s c r i b e d f o r 1 , 4 - c y c l o p e n t a d e c y 1 - d i o n e . ( C C l ^ ) 10 8 0 , 1 100 c m " 1 ; t ( C C I ^ , 60 MHz) 6 . 20 2 C i m/e 326 ( M + ) . v max ( s , 8H , (-0CJi2CH_20-) 2 ) , 8.63 ( b r o a d s , 26H , " ( C H_2 ) ., 3 - ) ; B i-s - e t-hy 1-en e - a ee t-a l-s--o f -1-78- eye 1 o p e n t a d e c y l - d i o n e (144) 1 , 8 - c y c l o p e n t a d e c y l - d i o n e was c o n v e r t e d t o t h e d i a c e t a l as d e s c r i b e d f o r 1 , 4 - c y c1 o p e n t a d e c y 1 - d i o n e . v m g x (CC 1 4 ) 1090 c m " 1 ; ! (CCI^ , 60 MHz) 6.23 ( s , 8H , (-CH_ 2 CH_20-) 2 ) , 8.60 ( b r o a d s , 2 6H , " ( C H _ 2 ) 1 3 - ) ; m/e 326 (M + ). A n a l . C a l c d . f o r C ^ H ^ O ^ : C, 69 -94; H, 10 .43- F o u n d : C , 69 -76 ; H , 10 . 2 0 . - 148 -C y c l o t r i d e c a n o l S od i um b o r o h y d r i d e (3.1 g.) i n m e t h a n o l (25 m l . ) was added d r o p w i s e t o a s o l u t i o n o f c y c 1 o t r i d e c a n o n e ( 1 4 . 8 g.) i n m e t h a n o l (25 m l . ) . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 2 h o u r s , e x c e s s s o d i u m b o r o h y d r i d e was d e s t r o y e d by t h e a d d i t i o n o f d i l u t e h y d r o c h l o r i c a c i d and t h e s o l u t i o n e x t r a c t e d w i t h e t h e r ( 3 x ) . The c o m b i n e d e x t r a c t s w e r e washed w i t h 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 and s a t u r a t e d s o d i u m c h l o r i d e s o l u t i o n . A f t e r d r y i n g w i t h a n h y d r o u s magne s i um s u l f a t e , r e m o v a l o f s o l v e n t p r o v i d e d a w h i t e s o l i d ( 1 4 . 8 5 g • ) • v m g x ( C C 1 4 ) 3400 c m _ 1 ; x ( C C 1 ^ , 60 MHz) 6 .33 (m, 1H, - CHOH) , 8 . 23 ( s , 1H, -CH0H_), 8 .63 ( b r o a d s , 2 4 H , - ( C H _ 2 ) 1 2 - ) . C y c l o t r i d e c y 1 a c e t a t e ( 145 ) C y c l o t r i d e c a n o l was c o n v e r t e d t o t h e a c e t a t e as d e s c r i b e d f o r cyc1 o p e n t a d e c y 1 a c e t a t e . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h i s a c e t a t e we re s i m i l a r t o t h o s e o f eye 1 o p e n t a d e c y 1 a c e t a t e . O x i d a t i o n o f c y c 1 o t r ? d e c y 1 a c e t a t e ( 145 ) Ch romium t r i o x i d e (7 g.) i n a c e t i c a n h y d r i d e (14 m l . ) was added d r o p w i s e t o a c o l d m i x t u r e o f c y c 1 o t r i d e c y 1 a c e t a t e (5 0 . 0 2 1 mo l e ) i n g l a c i a l a c e t i c a c i d (20 m l . ) and a c e t i c a n h y d r i d e (9 m l . ) . A f t e r s t i r r i n g a t room t e m p e r a t u r e f o r 5 d a y s , u s u a l w o r k - u p as d e s c r i b e d f o r cyc1 o p e n t a d e c y 1 a c e t a t e ( c f . P .144 ) p r o v i d e d a y e l l o w o i l ( 3 . 2 7 g.) w h i c h was shown by g . l . c . ( 3% S E 3 0 , 20% DEGS) t o c o n s i s t o f c y c 1 o t r i d e c y 1 a c e t a t e ( 3 4 % ) , a - 149 -m i x t u r e o f o x o - c y c l o t r i d e c y l a c e t a t e s (66%) ( u n r e s o l v e d on g. I . e . ) and a v e r y p o l a r m i x t u r e . Column c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r Woelm s i l i c a g e l ( g r a d e I I I ) g a v e , by e l u t i o n w i t h p e t . e t h e r / e t h e r , a m i x t u r e o f m o n o - o x o - c y c 1 o t r i d e c y 1 a c e t a t e s ( 1 4 6 ; x+y=11) ( 1 . 7 9 g . , 3 9 - 7 % b a s e d on consumed s t a r t i n g m a t e r i a l ) . v ( CC1 . ) 1 7 4 5 , 1 7 2 0 , 1245 cm 1 ; T ( C C 1 . , 100 MHz) max H 4 5.28 (m, 1H, -CHOAc) , 7.64 ( m i x e d t , 4H , - CH^ C0CH_2 - ) , 8 . 0 6 , 8 . 0 8 , 8 .12 ( s , 3 H , - 0C0CH_ 3 ) , 8 . 42 , 8 .72 (m, b r o a d s , 18H, - ( C H 2 ) g - ) . A n a l . C a l c d . f o r C 1 5 H 2 6 0 3 : C, 70 .86; H, 1 0 . 2 4 . F o u n d : C, 7 0 . 7 2 ; H, 10.59-H y d r o x y - e y e 1 o t r i d e c a n o n e s ( 1 4 7 ; x+y=1 l ) A m i x t u r e o f a c e t o x y c y c 1 o t r i d e c a n o n e s (926 mg.) and p o t a s s i u m h y d r o x i d e (375 mg.) i n m e t h a n o l (20 m l . ) was r e f l u x e d o v e r n i g h t . U s u a l w o r k - u p as d e s c r i b e d f o r a c e t o x y -cyc1 o p e n t a d e c a n o n e s ( c f . P .145 ) p r o v i d e d a y e l l o w o i l (700 mg . w h i c h s o l i d i f i e d upon s t a n d i n g . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e h y d r o x y c y c 1 o t r i d e c a n o n e s we re s i m i l a r t o t h o s e o f h y d r o x y - c y c l o p e n t a -d e c a non es . O x o - c y c 1 o t r i d e c a n o n e s ( 1 4 8 ; x+y=1 l ) H y d r o x y - c y c 1 o t r i d e c a n o n e s (630 mg.) was d i s s o l v e d i a c e t o n e (20 m l . ) . J o n e s r e a g e n t ( C r 0 ^ - H 2 S 0 M - H 2 0 ) (6 m l . ) was added d r o p w i s e u n t i l o x i d a t i o n was c o m p l e t e . U s u a l w o r k - u p as - 150 -d e s c r i b e d f o r h y d r o x y - c y c l o p e n t a d e c a n o n e s ( c f . P .146 ) p r o v i d e d a o i l y y e l l o w s o l i d (530 mg.) w h i c h was shown by g . l . c . (20% DEGS, 0 V 1 7 , 5% 0V210) t o c o n s i s t o f f o u r i s o m e r s . Gas c h r o m a t o g r a p h y o f t h e m i x t u r e o v e r t h e p r e p a r a t i v e 20% DEGS c o l u m n at 2 00°C gave t h e f i r s t f r a c t i o n ( w h i t e s o l i d ) ( 149 ) w h i c h was a o r a i x t u c e o f two i s o m e r s (11 .9% and 20.5% o f t h e t o t a l m i x t u r e ) and t h e s e c o n d f r a c t i o n ( p a l e - y e l l o w o i l y s o l i d ) ( 150 ) w h i c h was a l s o a m i x t u r e o f two i s o m e r s ( 3 1 - 3 7 % and 36.17% o f t h e t o t a l m i x t u r e ) . The I.R. and N.M.R. c h a r a c t e r i s t i c o f t h e s e o x o - c y c l o -t r i d e c a n o n e s w e r e s i m i l a r t o t h o s e o f o x o - c y c 1 o p e n t a d e c a n o n e s . E t h y l e n e a c e t a l s o f 1,4- and 1 , 5 ~ c y c 1 o t r i d e c y 1 - d i o n e ( 151 ) The m i x t u r e o f 1 , 4 - and 1 , 5 - c y c 1 o t r i d e c y 1 - d i o n e was c o n v e r t e d t o t h e d i a c e t a l s as d e s c r i b e d f o r 1 , 4 - c y c l o -p e n t a d e c y 1 - d i o n e . v The ( C C l . ) 10 90 c m " 1 ; * ( C C l . , 60 MHz) 6.20 ( s , 8H, max 4 4 ( -0CH CH 0 - ) 2 ) , 8.43, 8 . 5 0 , 8.63 ( b r o a d s , 2 2 H , - ( C H ^ j - ) ; m/e 298 ( M + ) . E t h y l e n e a c e t a l s o f 1 ,6- and 1 , 7 - c y c 1 o t r i d e c y 1 - d i o n e (152 ) The m i x t u r e o f 1,6- and 1 , 7 - c y c 1 o t r i d e c y 1 - d i o n e was c o n v e r t e d t o t h e d i a c e t a l s as d e s c r i b e d f o r 1 , 4 - c y c l o p e n t a -d e c y 1 - d i o n e . v m = v ( C C K ) 1100 c m " 1 ; x ( C C K , 60 MHz) 6 .20 ( s , 8H (71 a X H 1 (-OCH^CHjj ?>=•). 2 ) > 8-53 ( b r o a d s , 2 2 H , - ( C H 2 ) n - ) ; m/e 298 (M + ). - 151 -B I BL I OGRAPHY 1. R. B r e s l o w , Chem. S o c . R e v . , 553 (1972). 2. M. A k h t a r , A d v a n . P h o t o c h e m . , 2, 263 (1964). 3. K. L O f f l e r and C. F r e y t a g , B e r . , 42, 3427 (1909). 4. N.C. Yang and D.D.H. Y a n g , J . Amer . Chem. S o c , 80, 2913 ( 1 958) . 5. K. H e u s l e r and J . K a l v o d a , Angew. C h e m . , I n t . Ed . E n g l . , 3, 525 ( 1964) . 6. R. B r e s l o w and M. W i n n i k , J . Amer . Chem. S o c . , . 9 1, 3083 ' . . (1969) • 7. R. B r e s l o w and S.W. B a l d w i n , J . Amer . Chem. S o c , 92, 732 (1970) ; R. B r e s l o w and P. K a l i c k y , i b i d . , 93, 3540 (1971). 8. R. B r e s l o w , R. C o r c o r a n , J . A . D a l e , S. L i u and P. K a l i c k y , J . Amer. Chem. S o c , 96, 1973 (1974). 9. R. B r e s l o w , R . J . C o r c o r a n and B . B . S n i d e r , J . Amer . Chem. S o c . , 96, 6791 (1974). 10. R. B r e s l o w , B . B . S n i d e r and R . J . C o r c o r a n , J . Amer . Chem. S o c . , 96, 6792 ( 1 974). 11. R. B r e s l o w , B .B . S n i d e r and R . J . C o r c o r a n , J . Amer . Chem. S o c . , 97, 6580 ( 1 975). 12. T . M . S i e g e l , L . L . M i l l e r and J . Y . B e e k e r , J . Chem. S o c , 6hem.' Comm., 341 ( 1 974); V . R . Koch and L . L . M i l l e r , J . Amer . Chem. S o c , 95, 28'6 B 1 (3*03-) • - 152 -13 - J . Y . B e c k e r , L .R . B y r d and L . L . M i l l e r , J . Amer . Chem. S o c , 9 6 , 4718 ( 1 9 7 4 ) ; J . Y . B e c k e r , L .R. B y r d , L . L . M i l l e r and Y . H . So , J . Amer . Chem. S o c , 9 7 , 853 ( 1 9 7 5 ) . 14. L . L . M i l l e r and V. Ramachand ran , J . O r g . C h e m . , 3 9 , 369 ( 1974 ) . 15 - D. P l e t c h e r and C . Z . S m i t h , J . Chem. S o c , P e r k i n I, 948 ( 1975) • 16 . J . T . G r o v e s and M. Van Der P u y , J . Amer . Chem. S o c . , 9 6 , 5274 ( 1 9 7 4 ) . 17- J . T . G r o v e s and W.W. S w a n s o n , T e t r a h e d r o n L e t t . , 1953 ( 1 9 7 5 ) . 18. N.C. Deno and D.G. P o h l , J . Amer . Chem. S o c , 9 6 , 6680 ( 1974) . 19 - G- J o n e s , I I , M.A. A c q u a d r o and M.A. C a r m o d y , J . Chem. S o c . , Chem. Comm., 206 ( 1 9 7 5 ) . 2 0 . S .K . Chung and A . I . S c o t t , J . O r g . C h e m . , 40 , 1 652 ( 1 9 7 5 ) . 2 1 . R. Rotman and Y . M a z u r , J . Chem. S o c , Chem. Comm., 15 ( 1 9 7 4 ) . 2 2 . N. F r i e d m a n , M. L a h a v , L. L e i s e r o w i t z , R. P o p o v i t z - B i r o , C . P . Tang and Z. Z a r e t z k i i , J . Chem. - S o c . , Chem. Comm., 864 ( 1 975) . 23. D. S e y f e r t h and Y . M . C h e n g , S y n t h e s i s , 1 1l4 ( 1 9 7 4 ) . 2 4 . J . P . B e g u e , M. C h a r p e n t i e r - M o r i z e and C. P a r d o , T e t r a h e d r o n L e t t . , 4737 ( 1 9 7 1 ) . 2 5 . A . M . B e l l , P .C . C h e r r y , I.M. C l a r k , W.A. Denny , S i r Ewar t R.H. J o n e s , G.D. M e a k i n s and P.D. W o o d g a t e , J . Chem. S o c . , P e r k i n I , 1081 ( 1 972) . - 153 -2 6 . V . E . M . C h a m b e r s , W.A. Denny , S i r E . R . H . J o n e s , G .D . M e a k i n s , J . O . M i n e r s , J . T . P i n h e y and A . L . W i l k i n s , J . Chem. S o c . , P e r k i n I, 1359 ( 1 9 7 5 ) . 27 - J . M . E v a n s , S i r E . R . H . J o n e s , G .D . M e a k i n s , J . O . M i n e r s , A . P e n d l e b u r y and A . L . W i l k i n s , J . Chem. S o c . , P e r k i n I, 1 356 ( 1 975) . 2 8 . A . M . B e l l , W.A. Denny , S i r E . R . H . J o n e s , G .D . M e a k i n s and W.E. M u l l e r , J . Chem. S o c , P e r k i n I, 2579 ( 1 9 7 2 ) . 2 9 . A . M . B e l l , P .C . C h e r r y , I.M. C l a r k , W.A. Denny , S i r E . R . H . J o n e s , G.D. M e a k i n s and P .D. W o o d g a t e , J . Chem. S o c . , P e r k i n I , 2081 ( 1972) . 30 . V . E . M . C h a m b e r s , S i r E . R . H . J o n e s , G.D. M e a k i n s , J . O . M i n e r s and A . L . W i l k i n s , J . Chem- S o c , P e r k i n I, 55 ( 1 9 7 5 ) . 3 1 . A . M . B e l l , A. D a v i d B o u l , S i r E . R . H . J o n e s , G .D . M e a k i n s , J . O . M i n e r s and A . L . W i l k i n s , J . Chem. S o c . , P e r k i n I, 1364 ( 1 9 7 5 ) • 3 2 . A . M . B e l l , S i r E . R . H . J o n e s , G .D . M e a k i n s , J . O . M i n e r s and A . L . W i l k i n s , J . Chem. S o c , P e r k i n I, 2040 ( 1 9 7 5 ) . 3 3 . S . H . E p p s t e i n , P .D. M e i s t e r , D. H. P e t e r s o n , H .C . M u r r a y , H.M. L e i g h O s b o r n , A. W e i n t r a m b , L .M . R e i n e k e and R.C. Meeks , J . Amer . Chem. S o c , 80 , 3382 ( 1 9 5 8 ) . 34 . S i r E . R . H . J o n e s , G.D. M e a k i n s , J . O . M i n e r s , J . H . P r a g n e l l and A . L . W i l k i n s , J . Chem. S o c , P e r k i n I, 1552 ( 1 9 7 5 ) . 3 5 . D.M. R e v i l t , J . Chem. S o c , Chem. Comm., 2k ( 1 9 7 5 ) . 3 6 . L. Canon i c a , B. D a n i e l i , G . P a l m i s a n o , G. R a i n o l d i and B. M. R a n z i , J . Chem. S o c . , Chem. Comm., 656 (19 7 4 ) -- 154 -37 - T . A . C r a b b , P . J . Dawson and R.O. W i l l i a m , T e t r a h e d r o n L e t t . , 3623 ( 1975) . 3 8 . W.H. B r a d s h a w , H .E . C o n r a d , E . J . C o r e y , I .C. G u n s a l u s and D. L e d n i c e r , J . Amer . Chem. S o c , 8 1 , 5507 ( 1 9 5 9 ) . 3 9 - T. Money , M.S . A l l e n and R. Z e r r , u n p u b l i s h e d r e s u l t . 40. H. H i k i n o , C. K o n n o , T . N a g a s h i m a , T. Kohama and T. T a k e m o t o , T e t r a h e d r o n L e t t . , 337 ( 1 9 7 1 ) . 41. I .F . C o o k , P.R. J e f f e r i e s and J . R . K n o x , T e t r a h e d r o n , 251 ( 1 9 7 5 ) . 42. A . B . A n d e r s o n , R. M c C r i n d l e and J . K . T u r n b u l l , C a n . J . Chem. , 1 1 81 ( 1 9 7 5 ) ; R. M c C r i n d l e , J . K . T u r n b u l l and A . B . A n d e r s o n , J . Chem. S o c , P e r k i n I, 1202 ( 1 9 7 5 ) . 4 3 . B. Luu and G. D u r i s s o n , T e t r a h e d r o n L e t t . , 1881 ( 1 9 7 5 ) . 4 4 . B. Luu and G. D u r i s s o n , T e t r a h e d r o n L e t t . , 2211 ( 1 9 7 5 ) . 4 5 . R. B r e s l o w and M. W i n n i k , J . Amer . Chem. S o c , 9 1 , 3083 ( 1 9 6 9 ) ; R. B r e s l o w and P . C . S c h o l l , J . Amer . Chem. S o c , 9 3 , 233 1 ( 1 971 ) • 46. C .R . E c k , D . J . H u n t e r and T. Money , J . Chem. S o c . , Chem. Comm., 865 ( 1 9 7 4 ) . 4 7 . G . K K E i g e n d o r f , C . L . Ma and T. Money, J . Chem. S o c . , Chem. Comm., 1976 s u b m i t t e d f o r p u b l i c a t i o n . 48. K .B. W i b e r g , " O x i d a t i o n o f O r g a n i c C h e m i s t r y " P a r t A, A c a d e m i c P r e s s , New Y o r k , 1 9 6 5 , P. 6 9 - 1 8 4 . 49 . M.D. C h i s h o l m , W.F . S t e c k , A . P . A r t h u r and E.W. U n d e r b i l l , Can . E n t . , 1 07 , 361 ( 1 9 7 5 ) . 5 0 . P r i v a t e c o m m u n i c a t i o n f r o m Dr . M.D. C h i s h o l m ( P r a i r i e R e g i o n a l L a b o r a t o r y , S a s k a t o o n ) . - 155 -51. W.L. R o e l o f s and H. A r n , N a t u r e , 219, 513 ( 1968 ) ; W.L . R o e l o f s and J . P . T e t t e , N a t u r e , 226, 1172 ( 1970 ) ; L . B . H e n d r y , R . J . G i l l , A. S a n t o r a and R.O. Mumma, E n t . e x p . S a p p l . , 17, 459 ( 1974 ) ; L . B . H e n d r y , M .E . A n d e r s o n , J . J u g o v i c h , R.O. Mumma, D. R o b a c k e r and Z. K o s a r y c h , S c i e n c e , 187, 355 (1975 ) . 52. W.L . R o e l o f s , A. Comean and R. S e l l e , N a t u r e , 2 2 4 , 723 ( 1969 ) ; W.L . R o e l o f s , J . P . T e t t e , E . F . T a s c h e n b e r g and A. Comean, J . I n s e c t . P h y s i o l . , 17, 2235 (1971 ) . 53- M. B e r r y , Q. R e v . , Chem. S o c , 343 ( 1963 ) ; H. A c h e n b a c h , W. R e g a l and W. K a r l , Chem. B e r . , 108, 2481 (1975 ) . 54. G .K . E i g e n d o r f , C . L . Ma and T. Money, J . Chem. S o c . , Chem. Comm., 1976 s u b m i t t e d f o r p u b l i c a t i o n . 55- W.D. Emmons and G . B . L u c a s , J . Amer . Chem. S o c , 77, 2287 ( 1955) • 56. F INNIGAN ADVERTISEMENT, N a t u r e , C o v e r 3 ( M a r c h 13, 1975). 57- G . S . Fonken , M .E . H e r r , H.C. M u r r a y and L .M. R e i n e k a , J . Amer. Chem. S o c , 89, 672 (1967 ) . 58. M . J . A s h t o n , A . S . B a i l e y and S i r E . R . H . J o n e s , J . Chem. S o c . , P e r k i n I , 1 665 ( 1974) . 59- H .E . A u d i e r , M. F e t i z o n and J . C . T a b e t , O r g a n i c Mass S p e c t r o m e t r y , 10, 639 (1975 ) . 

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