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Investigation of the action of selected oxidizing agents on D-Mannitol-1,2,3,5,6,-pentanitrate Sutherland, Shirley Anne Marguerite 1956

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INVESTIGATION OF THE ACTION OF SELECTED OXIDIZING AGENTS ON D-MANNITOL-1,2,3,5,6-PENTANITRATE BY  SHIRLEY ANNE SUTHERLAND B.A., U n i v e r s i t y o f B r i t i s h Columbia,  1953  A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science i n t h e Department of Chemistry 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 the r e q u i r e d s t a n d a r d  THE UNIVERSITY OF BRITISH COLUMBIA A u g u s t , 1956  A. C K N O W L E D G E  MENT  I would l i k e t o e x p r e s s my t h a n k s and a p p r e c i a t i o n t o D o c t o r L.D. Hayward f o r h e l p and encouragement d u r i n g t h e c o u r s e o f t h i s work. Thanks a r e a l s o due t o t h e P o w e l l R i v e r Company L i m i t e d f o r a s c h o l a r s h i p w h i c h was extended f o r a second y e a r .  ABSTRACT  The o x i d a t i o n o f D - M a n n i t o l - l , 2 , 3 . 5 > , 6 - p e n t a n i t r a t e  by  a s e l e c t i o n o f n o n - s p e c i f i c o x i d a n t s was i n v e s t i g a t e d under a c i d i c , b a s i c and n e u t r a l c o n d i t i o n s . R e s u l t s of p r e l i m i n a r y experiments l e d t o f u r t h e r study of t h e a c t i o n o f chromium t r i o x i d e i n a c e t o n e s o l u t i o n on the p e n t a n i t r a t e .  Short term o x i d a t i o n w i t h t h i s mixture  y i e l d e d a s y r u p y p r o d u c t w h i c h on h y d r o g e n a t i o n gave a f u r t h e r , o p t i c a l l y I n a c t i v e syrup which d i d not g i v e a p o s i t i v e t e s t w i t h Pacsu's k e t o s e r e a g e n t o r w i t h F e h l i n g ' s s o l u t i o n . When t h e r e a c t i o n was a l l o w e d  t o go t o c o m p l e t i o n ,  a white  c r y s t a l l i n e compound, w h i c h d i d n o t r e d u c e F e h l i n g s s o l u t i o n was i s o l a t e d f r o m t h e o x i d a t i o n m i x t u r e .  This  compound,  w h i c h was n o t i d e n t i f i e d , y i e l d e d D-mannitol on h y d r o g e n a t i o n but d i f f e r e d i n p h y s i c a l p r o p e r t i e s and i n f r a - r e d s p e c t r a from D - M a n n i t o l - 1 , 2 , 3 , 5 , 6 , - p e n t a n i t r a t e , r a t e and isomannide d i n i t r a t e .  D-Mannitol  hexanit-  TABLE OF CONTENTS  INTRODUCTION  1  HISTORICAL  3  EXPERIMENTAL  20  DISCUSSION  37  BIBLIOGRAPHY  kk  LIST OF TABLES  I. II.  Results of Oxidations  34a  N i t r o g e n C o n t e n t s o f Some Polyol Nitrates  39a  -1-  INTRODUCTlON  A number o f t h e p o s s i b l e a l d o - and 2-ketohexoses been found w i d e l y d i s t r i b u t e d i n n a t u r e .  have  They and t h e i r non-  n a t u r a l l y o c c u r r i n g i s o m e r s have a l l been s y n t h e s i z e d and extensively studied. ketohexose  isomers.  Such has n o t been t h e case w i t h t h e 3 A l t h o u g h t h e i r e x i s t e n c e h a s been p o s -  t u l a t e d , and has been t h e s u b j e c t o f c o n t r o v e r s y , as y e t no 3 - k e t o s e has been i s o l a t e d f r o m n a t u r a l s o u r c e s . P o r many y e a r s , two s u b s t a n c e s , ' g l u t o s e were b e l i e v e d t o be 3 - k e t o s e s .  1  and • g a l t o s e ' ,  Despite the fact that t h e i r  i d e n t i t y was l a t e r d i s p r o v e d , t h e g r e a t amount o f s p e c u l a t i o n w h i c h was a r o u s e d c o n c e r n i n g t h e f o r m a t i o n and b i o l o g i c a l a c t i v i t y of 3-ketoses l e d t o study o f p o s s i b l e une q u i v o c a l s y n t h e t i c r o u t e s t o a u t h e n t i c samples o f t h e s e sugars.  The p r e s e n t work d e s c r i b e s an attempt t o p r e p a r e D-  a r a b i n o - 3 - h e x u l o s e w h i c h has t h e s t r u c t u r e t o w h i c h L o b r y de Bruyn and A l b e r d a v a n E k e n s t e i n a s s i g n e d t h e name  c<-glutose.  O x i d a t i o n o f a s u i t a b l y s u b s t i t u t e d h e x i t o l would l e a d to a 3-hexulose.  N o r m a l l y , o x i d a t i o n o f an u n s u b s t i t u t e d  sugar a l c o h o l o c c u r s a t t h e ends o f t h e carbon c h a i n t o y i e l d aldohexoses  o r hydroxy a c i d s ( 1 , 2 ) , a l t h o u g h i t i s p o s s i b l e  by some methods, t o o b t a i n 2-ketohexoses  (3,l\.)»  No o x i d a n t s  2 s p e c i f i c f o r the h y d r o x y l a t carbon t h r e e of t h e u n s u b s t i t u t e d p o l y o l have so f a r been d i s c o v e r e d .  I f , however, a l l  o t h e r h y d r o x y l groups c o u l d be b l o c k e d , by s u i t a b l e s u b s t i t u e n t s , o x i d a t i o n might be i n d u c e d a t p o s i t i o n t h r e e on  the  c a r b o n c h a i n w i t h the f o r m a t i o n of a k e t o n i c group a t t h i s site.  Removal of t h e b l o c k i n g s u b s t i t u e n t s s h o u l d y i e l d  a  compound i s o m e r i c w i t h the known h e x o s e s . S i n c e i t p o s s e s s e d a f r e e h y d r o x y l group a t t h e d e s i r e d p o s i t i o n , D-mannitol-1,2,1}.,5>,6-pentanitrate appeared t o p r o v i d e a s u i t a b l e s t a r t i n g m a t e r i a l f o r the o x i d a t i o n .  The  n i t r a t e e s t e r groups were known t o be r e l a t i v e l y s t a b l e t o n e u t r a l and a c i d c o n d i t i o n s (£.) and t o o x i d a t i o n , y e t  could  be e a s i l y and q u a n t i t a t i v e l y removed when d e s i r e d by c a t a l y t i c hydrogenation ( 6 ) .  I t was  therefore postulated that  sel-  e c t i v e o x i d a t i o n of the f r e e h y d r o x y l group w i t h a s u i t a b l e o x i d i z i n g agent, f o l l o w e d by removal o f the n i t r a t e e s t e r g r o u p s , would complete t h e s y n t h e s i s of D - a r a b i n o - 3 - h e x u l o s e ,  HISTORICAL INTRODUCTION  GLUTOSE I n t h e i r study o f t h e i n t e r c o n v e r s i o n o f D-glucose ( I ) , f r u c t o s e ( I V ) said D-mannose ( I I I ) I n aqueous s o l u t i o n s under t h e i n f l u e n c e o f i n o r g a n i c bases ( p o t a s s i u m , sodium, c a l c i u m and l e a d h y d r o x i d e s , sodium a c e t a t e and sodium c a r b o n a t e ) , Lobry de B r u y n and A l b e r d a v a n E k e n s t e i n ( 7 ) found t h a t a nonf e r m e n t a b l e , a p p a r e n t l y homogeneous s y r u p c o u l d be o b t a i n e d i n y i e l d s v a r y i n g f r o m one t o twenty p e r c e n t .  This syrup, which  c o u l d be n e i t h e r c r y s t a l l i z e d n o r r e s o l v e d , was t e n t a t i v e l y i d e n t i f i e d as a h e x u l o s e  »glutose» ( V I , V I I I ) , i n w h i c h t h e  c a r b o n y l group was i n p o s i t i o n t h r e e on t h e carbon c h a i n . They p o s t u l a t e d t h a t a 3-hexulose c o u l d be formed by a cont i n u a t i o n down t h e carbon c h a i n o f t h e e p l m e r i c s h i f t s w h i c h r e s u l t e d i n t h e c o n v e r s i o n o f a l d o s e s t o 2-ketoses e n e d i o l forms ( I I , V , V I I ) .  through  Though e i t h e r I , I I I , o r I V c o u l d  be u s e d as s t a r t i n g m a t e r i a l s f o r t h e p r e p a r a t i o n o f " g l u t o s e * , Lobry de B r u y n and v a n E k e n s t e i n f o u n d t h a t t h e b e s t y i e l d s c o u l d be o b t a i n e d by h e a t i n g an aqueous s o l u t i o n o f I V w i t h lead hydroxide  (8).  The c o n v e r s i o n t o * g l u t o s e * , however,  appeared t o be i r r e v e r s i b l e .  F u r t h e r treatment of the pro-  duct w i t h a l k a l i f a i l e d t o y i e l d any t r a c e o f I , I I I o r I V .  H-C I H-C-OH » HO C H Ii H C OH I H C OH . I  H-C-OH  II C-OH I HO-C-H I H-C-OH I H-C-OH  I  CH 0H 2  CH 0H 2  II  CH 0H  2  C=0 I HO-C-H  I  H-C-OH I H-C-OH I  CH 0H 2  —  I HO-C-H  I HO-C-H  I H-C-OH . I H-C-OH I  CH 0H 2  III  CH 0H  2  H-0*°  I C-OH II HO-C  CH 0H 2  I H - C - OH I  C=0  I H-C-OH I  H-C-OH I  H-C-OH  H-C-OH  1  I  I  CH 0H 2  IV  CH 0H 2  VI  CHpOH  1  .  HO-C  II HO-C I H-C-OH I H-C-OH - I  CH 0H 2  VII  CH«OH I. . HO-C-H I -  C=0 I H-C-OH I H-C-OH I  CH 0H 2  VIII  ' G a l t o s e ' , a n o t h e r n o n - f e r m e n t a b l e s y r u p , a l s o thought t o be a 3"hexulose, was p r e p a r e d i n a s i m i l a r manner f r o m D - g a l a c t ose (9)»  Prom t h e r e s i d u e w h i c h remained as a b y - p r o d u c t o f  t h e commercial p r o d u c t i o n of a l c o h o l f r o m cane m o l a s s e s by f e r m e n t a t i o n , up t o s i x p e r c e n t o f a s y r u p a p p a r e n t l y i d e n t i c a l t o * g l u t o s e ' c o u l d be i s o l a t e d  (10).  Nef (11) q u e s t i o n e d t h e i d e n t i t y o f t h i s ' g l u t o s e ' , sugg e s t i n g t h a t i t was, i n f a c t , a p a r t i a l o x i d a t i o n p r o d u c t o f D-glucose (1), D-glucosone  ( I X ) . I X c o u l d n o t be r e c o n v e r t -  ed t o h e x o s e s , b u t would y i e l d o r g a n i c a c i d s a l t s on f u r t h e r 0—i  I  O H I  H - C - C = C - C - C - C H p O H  I  I  I  0 0 0 H  H  H  I  H  I  2  .  H  r  IX t r e a t m e n t w i t h base i n t h e p r e s e n c e o f a t m o s p h e r i c oxygen. Nef t h e n p r e p a r e d a n o t h e r s y r u p w h i c h he termed  'authentic  g l u t o s e * , by t r e a t m e n t o f I w i t h aqueous c a l c i u m h y d r o x i d e i n the c o l d w i t h t h e e x c l u s i o n o f a i r . L a t e r , Spoehre and W i l b u r (12), i n 19^1)., c l a i m e d t h a t I and IV were i n t e r c o n v e r t i b l e a t 38° i n t h e p r e s e n c e o f d i sodium a c i d phosphate. ported.  F o r m a t i o n o f some ' g l u t o s e ' was r e -  None of t h e p r o d u c t s were i s o l a t e d ,  conclusions  b e i n g based on r e d u c i n g power, o p t i c a l r o t a t i o n ,  alkalinity  and s u s c e p t i b i l i t y t o f e r m e n t a t i o n . B e n e d i c t , D a k i n and West (13), r e p o r t e d a t h i r t y - e i g h t  -6-  p e r c e n t y i e l d o f ' g l u t o s e ' p r e p a r e d by s h a k i n g  a solution of  i n v e r t sugar w i t h c a l c i u m h y d r o x i d e f o r s e v e r a l h o u r s .  Wlfch  regard t o p h y s i o l o g i c a l a c t i o n s , they noted that t h e i r g l u t o s e , i n c o n t r a s t t o t h e o t h e r h e x o s e s , was n e i t h e r absorbed n o r u t i l i z e d by t h e human body. Spoehr and S t r a i n (li{.) b e l i e v e d t h a t t h e ' g l u t o s e s ' p r e p a r e d by d i f f e r e n t methods were n o t i d e n t i c a l , however, they a t t r i b u t e d the v a r i a t i o n s i n r e a c t i v i t y t o the presence of i m p u r i t i e s w h i c h v a r i e d w i t h t h e method of p r e p a r a t i o n . They found t h a t t h e r e p o r t e d ' g l u t o s e p h e n y l o s a z o n e " c o u l d be s e p a r a t e d  i n t o s e v e r a l components by s o l v e n t e x t r a c t i o n  and t h a t t h e r e was no e v i d e n c e f o r t h e p r e s e n c e o f a 3-hexulose. Spoehr and S t r a i n t h e n o b t a i n e d c o u l d n o t be a 3-hexulose.  'Glutose'  evidence t h a t  formed a c y a n o h y d r i n (X)  w h i c h by h y d r o l y s i s and r e d u c t i o n c o u l d be c o n v e r t e d methylcaproic  s i n c e a t r u e 3-keto-hexose  HO-C-CsN  H-C-O-H H-C-O-H  H-C-C  1.  HOH  2. Ppeailg  H-C-H  >  H-C-H H-C-H  CH 0H 2  X  t o 2-  a c i d ( X I ) j t h i s a c i d must have been d e r i v e d  from a 2 hexulose,  H-C-O-H  'glutose'  XI  0 0 H  would y i e l d 2 - e t h y l v a l e r i c  acid  (XII). CH-,  CHoOH i c  H0-8-H  H-C-H  I  I  C=0 I  H-C-COOH 1.  H-C-OH i H-  2  *  HON, HOH p  red,l2  I  H-C-H i  .  H-C-H  C-OH  l CH 0H  i  CH,  2  VI  XII  S'attler and Zerban ( 1 5 » 1 6 ) i n 194-5* i s o l a t e d t h e u n f e r mentable r e d u c i n g s u b s t a n c e s i n cane m o l a s s e s and p r o v e d them i d e n t i c a l t o t h e h e t e r o l e v u l o s a n ( X I I I ) , p r o b a b l y 1 , 2 a n h y d r o - D - f r u c t o p y r a n o s e , and the d i h e t e r o l e v u l o s a n  (XIV)  r e p o r t e d by P i c t e t and Chavan ( 1 7 ) .  shown t o  be a d i f r u c t o s e  The l a t t e r was  a n h y d r i d e b y Schulbache and Behre  (18).  S a t t l e r and Zerban a l s o demonstrated t h a t t h e »glutosazone* r e p o r t e d b y p r e v i o u s workers was i d e n t i c a l t o D-glucosazone (XV). H C-K=K-H0 H^ 6  C -N=NHC^Hr^ HOPC-H I H-C-OH I  H-C-OH H-C. H  XIII  HO-C-H I  H-C-OH I  H-C-OH  I  CH^OH  XV  -8-O—i  H H H 0 92 I I I  H H H 0 0 f l I \j-c- C-C-C-Hp  Ho-c-c-c-c-c: I 11 2 Hp 0. . 0 .H ^Q.q' H H. CH  I  I  I  0... H H H .  tL  XIV  Evans and coworkers (19), n e v e r t h e l e s s , showed t h a t 2,3" e n e d i o l s were a c t u a l l y formed I n t h e c o u r s e o f a r e a c t i o n by i s o l a t i n g f o r m i c a c i d ( X V I I ) , l a c t i c a c i d ( X X I ) and t h e l a c t one o f D - g a l a c t o - ©< - m e t a s a c c h a r i n i c aline solution of galactose.  a c i d (XIX) from an a l k -  They p o s t u l a t e d t h a t f o r m i c  and l a c t i c a c i d s were formed t h r o u g h a i r - o x i d a t i v e c l e a v a g e of t h e double bonds o f t h e 1,2- and 3 , i i - e n e d i o l s ively  respect-  (XVI}'XX),, w h i l e t h e l a c t o n e was formed, by a s e r i e s  of s t e p s , f r o m t h e 2 , 3 - e n e d i o l , ( X V I I I ) . 0 H-C-OH II  C-OH I  II  HO-C-OH H0-C=0 I  HO-C -H  HO-C-H  OH-C -H  HO-C-H  I  I  H-C-OH I  CHpOH XVI  I  I  H-C-OH I  CH 0H 2  XVII  -9-  CHoOH  HO-C  I C-OH  I H-C-OH  It  I  C-OH  I  V-  HO-C-H  H-C-H  - I  HO-C-H  I  I  H-C-OH  H-C-OH  I  I  CH 0H  CH2OH  2  XVIII  XIX  CH 0H 2  H-C-OH I C-OH I) C-OH I H-C-OH  to]  CH, I * H-C-OH I HO-C=0 HO-C=0 I H-C-OH I CBL  CH 0H 2  XXI  XX  The e x i s t e n c e o f a 2 , 3 - e n e d i o l g a i n e d f u r t h e r s u p p o r t f r o m t h e f i n d i n g s o f Wolfrom and coworkers  ( 2 0 ) , who i n 19^-6  o b t a i n e d e v i d e n c e t h a t V must have been p r e s e n t i n a g l u c o s e s o l u t i o n a t pH 10 t o 1 3 » Prom t h e p r o d u c t s o f e l e c t r o l y t i c r e d u c t i o n o f D-glucose sorbital  I n b a s i c s o l u t i o n t h e y i s o l a t e d D-  (XXII) t h e expected product, i n t h i r t y percent  y i e l d , b u t a l s o found 2 - d e s o x y - D - s o r b l t o l ( X X V ) , ( 0 . 3 4 / 0 ; D-mannitol  (XXIV),(2.27$);  and 1 - d e s o x y - D - m a n n i t o l , ( X X I I I ) ,  ( 0 . 9 5 $ ) ; formed f r o m t h e 1 , 2 - e n e d i o l s h i f t  (il,IV).  -10D - a l l i t o l ( X X V I I I ) , ( 0 . 5 $ y i e l d ) , and a n unknown 2-desoxy hexose thought t o be 2 - d e s o x y - D - a l l l t o l ( X X V I I ) ,  {0.1$ y i e l d ) ,  w h i c h were a l s o i s o l a t e d , c o u l d have formed o n l y as a r e s u l t o f a 2 , 3 - e n e d i o l s h i f t (V,XXVI).  D-talitol  (XXIX),  which  c o u l d a l s o have been formed, was n o t o b t a i n e d .  H-C-OH II C-OH  CHpOH I  I  0=0  I  HO-C-H  CHoOH  .  H-C-OH  I  ^  HO-C-H  I  r  ,  n  HO-C-H  H-C-OH  H-C-OH  H-C-OH  H-C-OH  H-C-OH  H-C-OH  I I  I  I  CH 0H  CH 0H  II  IV  2  CH,  I  3  HO-C-H  I  I  H-C-OH  H-C-OH  \  |  d  H-C-H  l  HO-C-H  I  I  I  H-C-OH  H-C-OH  XXIII  XXII  CHoOH  o  I  HO-C-H  2  XlHl  CH 0H HO-C-H  I CH 0H  I  CH2OH  2  HO-C-H  I  I  H-C-OH  I  I CH 0H 2  XXIV  H-C-OH  I CH 0H 2  XXV  -11  CHpOH I  2  C-OH II  CHpOH  CHpOH  I  I  C=0  H-C-H  I  I  HO-C I H-C-OH  H-C-OH H-C-OH  H-C-OH  H-C-OH  H- C-OH  H-C-OH  I  CH 0H 2  I  .  [H]  I  H-C-OH I  -  I  CH 0H  I  I  2  CHgOH XXVII CH-OH I  2  H-C-OH I  CH20H I  HO-C-H I  H-C-OH  H-C-OH  H-C-OH  H-C-OH  I I  H-C-OH CHpOH XXVIIl  I I  H-C-OH I  CH 0H 2  XXIX  Only one 3 - p e n t u l o s e has been d e s c r i b e d i n t h e l i t e r a ture.  A3hwell and Hickman ( 2 1 ) i n 1954- i s o l a t e d f r o m  sploen  e x t r a c t s a m i c r o m o l a r q u a n t i t y o f a compound w h i c h t h e y t a t i v e l y i d e n t i f i e d as erythro-3-ketopentose  (XXXI).  ten-  They  p o s t u l a t e d t h a t ^ t h e compound was formed from r i b o s e (XXX) t h r o u g h an e n e d i o l  intermediate.  •12CH 0H  H-C  2  H-C-OH  HO-C-H H-C-OH  C=0  H-C-OH  H-C-OH  XXXI  XXX  Other compounds r e l a t e d t o t h e sugars w h i c h c o n t a i n t h e 3-keto group a r e k o j i c a c i d (XXXII and X X X I I I ) (22), t h e a s corbic acids  (23,2lf)  and 2,3-diketo-D-gluconic a c i d  (25).  K o j i c a c i d i s produced by t h e a c t i o n o f c e r t a i n m o l d 3 on hex' oses and v a r i o u s  saccharides.  I t s s t r u c t u r e i s t h a t o f an  u n s a t u r a t e d 3-hexulose a n h y d r i d e . postulated  B e e l i k and Purves (26)  t h a t t h e a c i d assumes an open c h a i n  structure  ( X X X I I I ) i n b a s i c s o l u t i o n s as a 3 - k e t o - e n e d i o l w h i c h r e c y c l i z e d almost q u a n t i t a t i v e l y on a c i d i f i c a t i o n .  II H-G 0 H XXXII L-ascorbic  II 9-CH 0H 0 H 2  XXXIII a c i d (XXXIV) ( V i t a m i n C ) , an e n e d i o l , was  found t o e x i s t I n a n e q u i l i b r i u m m i x t u r e w i t h a 3-ketoa c i d (XXXV), w h i c h was i s o l a t e d o n l y as a hydrazone  deriva-  -13-  tive. ing  The e q u i l i b r i u m m i x t u r e i t s e l f was u n s t a b l e , s u f f e r -  r a p i d o x i d a t i o n t o o x a l i c a c i d and L - t h r e o n i c a c i d s (XXXVI), 0=C I H-C-OH I  0=C H0)-C  II  HO-C  I 0  C=0 I  I  'J H-C-  H-C  I  I T-n—I  HO-C-H  HO-C-H CH OH 2  I  CH OH 2  XXXV  XXXIV  HO-C=0 I  HO-C=0 H0-C=0 I  H-C -OH I  HO-C-H I  CH 0H 2  XXXVI  2 , 3 - D i k e t o - D - g l u c o n i c a c i d was r e p o r t e d as a p r o d u c t o f low temperature  o x i d a t i o n o f D-glucose w i t h hydrogen p e r -  o x i d e i n t h e presence o f f e r r o u s s u l p h a t e ( 2 £ ) •  The compound  decomposed r e a d i l y on h e a t i n g y i e l d i n g c a r b o n d i o x i d e ,  oxalic  a c i d and t r i h y d r o x y b u t y r i c a c i d . A 3 - k e t o - D - g l u c o n i c a c i d has a l s o been p o s t u l a t e d t o o c c u r a t one s t a g e o f t h e Warburg-Dickens-Harecker  biologic-  a l c y c l e ( 2 7 ) • W i l s o n and C a l v i n (28) have p o s t u l a t e d t h e e x i s t e n c e o f a 3 - p e n t u l o s e as an i n t e r m e d i a t e i n t h e b i o l o g i c a l f i x a t i o n o f carbon d i o x i d e . R e c e n t l y , J.K.N. Jones ( 2 9 ) has r e p o r t e d t h e p r e p a r a t i o n of  2-0-methyl-L-xylo-3-hexulose  (XXXV).  By rearrangement  (XL) f r o m L - a s c o r b i c a c i d  of the 2-3-di-0-methyl ether (XXXVII),  of L - a s c o r b i c a c i d , he p r e p a r e d t h e m e t h y l g l y c o s i d e o f a 3 -  -34h e x u l o n i e a c i d , I s o l a t e d as t h e amide.  The r e d u c t i o n o f t h e  l a c t o n e o f t h i s a c i d ( X X X V I I I ) w i t h l i t h i u m aluminum h y d r i d e y i e l d e d a g l y c o s i d e o f t h e 3-hexulose  (XXXIX).  Upon a c i d  h y d r o l y s i s t h e f r e e sugar (XL) was o b t a i n e d , a i d was c h a r a c t e r i z e d as t h e c r y s t a l l i n e 2 , 5 - d l c h l o r o p h e n y l h y d r a z o n e . O x i d a t i o n o f t h e sugar w i t h p e r i o d i c a c i d y i e l d e d one mole of f o r m i c a c i d and an e s t e r ( X L I ) .  S i n c e g l y c o l a m i d e and  2,3-di-0--Methyl-D-glyceronic a c i d amide (XLTI) were o b t a i n e d t h r o u g h t r e a t m e n t o f t h e e s t e r w i t h m e t h y l I o d i d e and s i l v e r o x i d e , f o l l o w e d by a l c o h o l i c ammonia, t h e s t r u c t u r e o f t h e sugar was c o n f i r m e d as XL, p r o b a b l y i n t h e a l p h a f o r m . Jones a l s o r e p o r t e d t h a t 3 - h e x u l o s e s as y e t u n c h a r a c t e r i z e d , may be o b t a i n e d f r o m D - a r a b o - a s c o r b i e a c i d and D-gluco-ascorbic  acid.  o=c—  0=C~i  H-C—' I HO-C -H CH 0H 2  XXXVII  2  I  CH30-0 I  CH3O-C I  CH 0H  CH,0-C-H  CHoO-C-H  *  RATC ,  3  I  1  -O— CH3O-C I  H-C-0-4J I 0 HO-C-H I H-C H  1  XXXVIII  1  vCH3O-C . L'IAIH.  I  H-C -OH I HO-C -H H-C . H XXXIX  -15CH 0H  CH OH I. V CH3O-C-H  CHpOH  2  9  I  CHqO-C-H I  J  HO-C  NHo-C=0  o=c-  I  H-C-OH 0 I HO-C-H  1. C H r - f 3  HCOOH  HIO^  n o 3i  N  H  H-C-0  H-C-OCHo I * CHgOCH^  I  H-C H  H-C-  H XL  2 " f  XLII  XLI  D-MANNITOL PENTANITRATE  The n i t r a t i o n o f D-mannltol  to the hexanitrate  (XLIII)  was f i r s t a c c o m p l i s h e d i n 181^7 hy Domante and Menard ( 3 0 ) . No P r o d u c t s o f l o w e r degree o f n i t r a t i o n were  °2  N OpKOHpC —  .  H C—  H C—  N  N  6  6  XLIII  9  C H  isolated.  °2 N  9  C H  CHoONOp  -16-  I t was n o t u n t i l I86I4. when T i c h a n o w i c h ( 3 1 ) , i n v e s t i g a t i n g t h e a c t i o n o f anhydrous ammonia on an e t h e r e a l s o l u t i o n o f the h e x a n i t r a t e , i s o l a t e d a D-mannitol p e n t a n i t r a t e as a w h i t e c r y s t a l l i n e compound, s o l u b l e i n a l c o h o l and e t h e r and i n s o l u b l e i n water. M a r s h a l l and Wigner ( 3 2 ) , i n 1 9 0 2 , p r e p a r e d t h e same D-mannitol p e n t a n i t r a t e i n good y i e l d by t h e a c t i o n o f c o l d dry p y r i d i n e on t h e c o r r e s p o n d i n g also obtained D-raannitol.  hexanitrate.  Wigner ( 3 3 )  t h e same p e n t a n i t r a t e by c a r e f u l n i t r a t i o n o f A l t h o u g h t h e main p r o d u c t o f h i s r e a c t i o n was  D-mannitol h e x a n i t r a t e , a s m a l l q u a n t i t y o f t h e l o w e r n i t r a t e was i s o l a t e d by c o n c e n t r a t i o n o f t h e mother l i q u o r s . The  s t r u c t u r e o f W i g n e r s p e n t a n i t r a t e was n o t d e t e r 1  mined u n t i l 1 9 5 2 when Hayward ( 3 4 ) p r o v e d t h a t t h e u n e s t e r i f i e d h y d r o x y l was l o c a t e d on t h e t h i r d ( o r e q u i v a l e n t carbon of the h e x i t o l chain.  fourth)  M e t h y l a t i o n and subsequent de-  n i t r a t i o n o f D-mannitol p e n t a n i t r a t e y i e l d e d a monomethyl D-mannitol and p e r i o d a t e o x i d a t i o n o f t h i s compound, r e s u l t i n g i n t h e f o r m a t i o n o f two moles o f formaldehyde and one o f formic a c i d (XLVI), i n d i c a t e d the p o s i t i o n of the methyl s u b s t i t u e n t (XLV), and hence o f t h e o r i g i n a l f r e e group.  hydroxyl  T i c h a n o w i c h * s compound was t h e r e f o r e c o r r e c t l y t e r m -  ed D - m a n n i t o l - l , 2 , 3 » 5 » 6 - p e n t a n i t r a t e  (XLIV).  -17-  CH 0N0 o  I  2  >  CH20  2  0 N0-C-H HO-C-H  CHoO-C-H  H-C-ONO_  H-C-OH  H-C-ONO-  H-C—OH  1 I  H-C  HO-C-H  o  CHoO-C-H  *  CHoOHO  XLIV  XLV  XLVI  R e c e n t l y , E l r i c k , Marana and P r e c k e l (35) p r e p a r e d  (XLIV)  I n s e v e n t y p e r c e n t y i e l d by t r e a t m e n t o f t h e c o r r e s p o n d i n g h e x a n i t r a t e i n acetone s o l u t i o n w i t h s o l i d ammonium c a r b o n ate.  DENITRATTON OP NITRIC ACID ESTERS  Complete removal o f n i t r a t e groups f r o m  D-mannitol  h e x a n i t r a t e has been a c c o m p l i s h e d by a l k a l i n e h y d r o l y s i s . T i c h a n o w i c h (31) found t h a t t r e a t m e n t o f t h e n i t r a t e d compound w i t h a l c o h o l i c p o t a s s i u m h y d r o x i d e r e g e n e r a t e d t h e p a r e n t a l c o h o l , b u t a l s o y i e l d e d a n a n h y d r i d e , D-mannitan (1,4-anhydro-D-mannitol).  He a l s o o b s e r v e d t h a t t h e a c t i o n  of sodium amalgam on t h e h e x a n i t r a t e caused mannitan  form-  a t i o n , whereas magnesium and z i n c o x i d e s gave ' n i t r o m a n n i t a n , ,  -18a p p a r e n t l y a mannitan t e t r a n i t r a t e .  D-mannitol  could also  be r e g e n e r a t e d by t r e a t m e n t o f t h e n i t r a t e w i t h t h e weak base ammonium s u l p h i d e . M i l l s (36),  r e g e n e r a t e d D-mannitol  i n undetermined  y i e l d by warming t h e n i t r a t e d d e r i v a t i v e w i t h h y d r i o d i c a c i d . Vignon and Bray (5>), i n 1 9 0 2 , s t u d i e d t h e a c t i o n o f » metaphenylenediamine',  a n i l i n e , water and f i v e p e r c e n t  p h u r i c a c i d on D-mannitol, D - d u l c i t o l and D - e r y t h r i t o l rates.  sulnit-  They found t h a t b o t h n i t r a t e and n i t r i t e i o n s were  produced, w h i l e t h e a l c o h o l s were c o m p l e t e l y decomposed by the b a s i c reagents.  B o i l i n g water had no e f f e c t though de-  e s t e r i f i c a t i o n o c c u r r e d upon h e a t i n g t h e n i t r a t e s w i t h w a t e r i n a sealed tube.  Removal o f t h e e s t e r groups c o u l d be a c -  c o m p l i s h e d by r e f l u x i n g t h e n i t r a t e d p o l y o l s w i t h d i l u t e s u l p h u r i c a c i d , b u t some d e c o m p o s i t i o n o f t h e a l c o h o l r e sulted. Oldham (37) d e n i t r a t e d c a r b o h y d r a t e n i t r a t e e s t e r s w i t h i r o n powder i n g l a c i a l a c e t i c a c i d .  The p a r e n t  carbohydrates  were r e c o v e r e d f r o m t h e r e a c t i o n m i x t u r e s i n a p p r o x i m a t e l y t h i r t y percent y i e l d . A s a t i s f a c t o r y method f o r removal o f n i t r a t e  ester  groups, h i g h pressure hydrogenation of the n i t r a t e s w i t h a p a l l a d i u m c a t a l y s t , was developed by Kuhn (6) who o b t a i n e d almost q u a n t i t a t i v e y i e l d s o f t h e p a r e n t a l c o h o l s .  This  method was m o d i f i e d by Hayward (3l\.) who o b t a i n e d l o w h y d r o gen p r e s s u r e s i n a Paicrhydrogenator.  Kuhn (38) a l s o  proposed  -19-  t h e use of m e t h a n o l i c h y d r a z i n e w i t h a p a l l a d i z e d c h a r c o a l c a t a l y s t as a d e n i t r a t i n g agent f o r a l k y l n i t r a t e s , s i n c e t h e reagent would not reduce c a r b o n y l groups o r double bonds. However, i t was found ( 3 9 )  t h a t t h e use of h y d r a z i n e was  s u c c e s s f u l f o r c a r b o h y d r a t e n i t r a t e s because, due t o i t s b a s i c c h a r a c t e r , the r e a g e n t caused d e c o m p o s i t i o n o f the s e n s i t i v e sugars.  not  -20  EXPERIMENTAL  Special Precautions Due t o t h e e x p l o s i v e n a t u r e o f t h e h e x i t o l n i t r a t e s , no more t h a n 3 e v e n grams were h a n d l e d o r s t o r e d i n t h e d r y s t a t e .  A. MATERIALS D-Mannitol H e x a n i t r a t e D - M a n n i t o l was n i t r a t e d by t h e method o f S o k o l o f f (I|.0), i n 82$ y i e l d . ethanol.  The p r o d u c t was r e c r y s t a l l i z e d f r o m aqueous  M.p. 112-113°C. ( u n c o r r . )  tKJ**4-2.9° (C 1.027,  E t h a n o l , 1=1). D-Mannitol 1,2,3,5,6-pentanitrate 1.  Method o f M a r s h a l l aad Wigner (32,3l>.,ij.l).  D-manni-  t o l - p e n t a n i t r a t e was p r e p a r e d by t h e method of M a r s h a l l and Wigner i n 68.5$ y i e l d . 2.  Method o f E I r i c k , Marans and P r e c k e l (35)•  D-manni-  t o l h e x a n i t r a t e (7«50 gm.) was d i s s o l v e d i n acetone (35 ml.) a t 22°C. i n a 100 m l . f l a s k f i t t e d w i t h a condenser and a thermometer.  Ammonium c a r b o n a t e (2.17 gm.) was washed i n t o  the c o l o u r l e s s acetone s o l u t i o n w i t h water (5 ml.) and a c e t o n e (8 m l . ) .  W i t h i n f i f t e e n m i n u t e s a f t e r t h e a d d i t i o n of t h e  c a r b o n a t e , t h e c o l o u r o f t h e s o l u t i o n darkened t o a b r i g h t orange.  The t e m p e r a t u r e o f t h e r e a c t i n g m i x t u r e r o s e t o  -21-  3 ^ C . , t h e n f e l l t o 25°C. over a p e r i o d o f two h o u r s .  Rapid  0  e v o l u t i o n o f gases f r o m t h e warm s o l u t i o n was o b s e r v e d . I n i t i a l l y , t h e gas t u r n e d m o i s t l i t m u s paper b l u e and poss e s s e d t h e c h a r a c t e r i s t i c .odour o f ammonia.  A f t e r one hour,  t h e gas e v o l v e d t u r n e d b l u e l i t m u s r e d , and p o s s e s s e d t h e .. odour o f o x i d e s o f n i t r o g e n . i n t h e f l a s k decreased  The q u a n t i t y o f s o l i d m a t e r i a l  slowly.  A f t e r one and o n e - h a l f  hours,  a f l o c c u l e n t p r e c i p i t a t e w h i c h s l o w l y i n c r e a s e d I n b u l k , was observed.  E v o l u t i o n o f gases c o n t i n u e d a t d e c r e a s i n g r a t e  f o r siixteen hours.  When e v o l u t i o n ceased, t h e s o l u t i o n was  e v a p o r a t e d a t room temperature  and d e c r e a s e d p r e s s u r e t o a  volume o f 10 m l . , c a u s i n g t h e s e p a r a t i o n o f a r e d o i l y and t h e p r e c i p i t a t i o n o f some s o l i d m a t e r i a l .  liquid  The m i x t u r e  was poured i n t o c o l d w a t e r ( 3 0 0 m l . ) , c a u s i n g t h e s e p a r a t i o n o f an orange o i l w h i c h r a p i d l y s o l i d i f i e d .  The s o l i d i f i e d  p r o d u c t was d r i e d t o a c o n s t a n t weight o f 5 . i f 7 & » m  a f t e r one r e c r y s t a l l i z a t i o n was i j . , 5 gm. ( 6 7 $ ) .  T  h  e  yield  The p r o d u c t  was r e c r y s t a l l i z e d t o a c o n s t a n t m e l t i n g p o i n t o f 8 0 - 8 l ° C . A mixed m e l t i n g p o i n t w i t h a sample o f m a n n i t o l p e n t a n i t r a t e p r e p a r e d by t h e method o f M a r s h a l l and Wigner gave a v a l u e of 8 0 - 8 l ° C . reported f V ] ,  -^6.5° 47.7°  (C I.O8I4., E t h a n o l , ^ = 1 ) .  Brown(iil)  (C if.ij.26).  N i t r i c Acid Red fuming n i t r i c a c i d was o b t a i n e d f r o m Baker and Adams, s.g.  1.59-1.50.  -22Chromium t r i o x i d e A n a l y t i c a l r e a g e n t grade chromium t r i o x i d e was  obtained  f r o m t h e B r i t i s h Drug Houses l i m i t e d , London, E n g l a n d . Acetone Acetone was d r i e d by r e f l u x i n g o v e r anhydrous magnesium s u l p h a t e , t h e n was d i s t i l l e d f r o m p o t a s s i u m permanganate t o remove t r a c e s o f r e a d i l y o x i d i z e d  impurities.  Pyridine P y r i d i n e was d r i e d by r e f l u x i n g over two s u c c e s s i v e ; , p o r t i o n s of B a r i u m o x i d e .  B. ANALYTICAL METHODS  Nitrogen N i t r o g e n was d e t e r m i n e d by a m o d i f i e d K j e l d a h l method as d e s c r i b e d by Brown and Purves (Zj.2). Chromium Chromium VT was d e t e r m i n e d as b a r i u m chromate by t h e method d e s c r i b e d by V o g e l (i|.3).  Chromium I I I was  precipitated  as green chromic h y d r o x i d e f r o m a s o l u t i o n j u s t b a s i c w i t h ammonia, and 0.125  m o l a r i n ammonium n i t r a t e .  The p r e c i p i -  t a t e was f i l t e r e d o u t , I g n i t e d , and weighed as Chromic  oxide.  Ketose Te3t  A q u a l i t a t i v e t e s t f o r feetoses has been d e s c r i b e d by Pacsu  A d d i t i o n o f sodium h y d r o x i d e t o an acetone  u t i o n of a k e t o s e y i e l d e d a b r i g h t y e l l o w s o l u t i o n .  The  sol-  - 23c o l o u r was d i s c h a r g e d on a c i d i f i c a t i o n w i t h s u l p h u r i c a c i d . The r e s u l t i n g s o l u t i o n d e c o l o u r i z e d aqueous permanganate. Diphenylamine  Reagent  The d i p h e n y l a m i n e r e a g e n t f o r n i t r a t e s was p r e p a r e d as d e s c r i b e d i n t h e "Manual o f t h e I d e n t i f i c a t i o n o f O r g a n i c Compounds" (lj.5)» Refractive  Index  The r e f r a c t i v e i n d e x was d e t e r m i n e d i n an Abbe r e f r a c t o meter connected t o a t h e r m o s t a t i c a l l y c o n t r o l l e d c o n s t a n t Readings were t a k e n a t 21°C»  temperature b a t h .  C.  NITRATION OP D-MANNITOL-1,2,3,5,6-PENTANITRATE  D - M a n n i t o l - l £ , 3 , 5 , 6 - p e n t a n i t r a t e ( 0 . 5 0 0 0 gm.) was n i t r a t e d by t h e method o f S o k o l o f f (1|0).  The crude y i e l d o f  t h e d r i e d w h i t e c r y s t a l l i n e p r o d u c t was 0.5>lj.07 gm. (96$).  The  p r o d u c t was r e c r y s t a l l i z e d f r o m w a t e r t o a c o n s t a n t m e l t i n g point of 112-113°C  A mixed m e l t i n g p o i n t w i t h D - M a n n i t o l  h e x a n i t r a t e gave 112-113°C.  D.  INVESTIGATION OP OXIDANTS POR D - M A N N I T O L - 1 , 2 , 3 , 5 , 6 PENTANITRATE.  I.  P o t a s s i u m Permanganate i n Acetone  Solution  D - M a n n i t o l - 1 , 2 , 3 , 5 , 6 - p e n t r a n i t r a t e ( 0 . 5 0 gm.) was d i s s o l v e d i n acetone  ( 1 0 m l . ) a t room t e m p e r a t u r e .  To t h e c l e a r  c o l o u r l e s s s o l u t i o n was added a s u s p e n s i o n o f p o t a s s i u m permanganate^.38  gm.) i n acetone  (25 m l . ) .  The p u r p l e c o l o u r o f t h e  -2k-  permanganate was d i s c h a r g e d a f t e r r e f l u x i n g t h e s o l u t i o n i n a hot water b a t h f o r f i f t e e n minutes. formed.  A d a r k brown p r e c i p i t a t e  The m i x t u r e was c o o l e d i n an i c e b a t h , f i l t e r e d and  the c o l o u r l e s s f i l t r a t e obtained evaporated t o dryness.  A  w h i t e , o d o u r l e s s c r y s t a l l i n e m a t e r i a l ( 0 . 3 5 gm.) m e l t i n g a t 78*5  -  79.5°0.  was o b t a i n e d .  Mixed m e l t i n g p o i n t w i t h D-  m a n n i t o l l , 2 , 3 , 5 » 6 - p e n t r a n i t r a t e was 7 8 . 5 - 8 0 . 0 ° C . The  c r y s t a l l i n e p r o d u c t ( O . 2 I 4 . 2 gm.) was d i s s o l v e d i n  2 0 $ aqueous e t h a n o l  ( 2 5 m l . ) and t h e s o l u t i o n was shaken w i t h  hydrogen f o r s i x t e e n h o u r s i n a P a r r h y d r o g e n a t o r i n t h e p r e sence o f p a l l a d i z e d - c h a r c o a l c a t a l y s t ( o . 0 5 gm.) a t an i n i t i a l pressure The  o f 1L1»7 p . s . i .  The f i n a l p r e s s u r e was i f l . I f p . s . i .  c a t a l y s t was removed by f i l t r a t i o n and t h e s o l u t i o n evap-  orated t o a pale yellow residue  (0.0198  gm.). T h e p r o d u c t  gave n e g a t i v e t e s t s w i t h t h e d i p h e n y l a m i n e r e a g e n t , r e a g e n t and P e h l i n g s s o l u t i o n .  Pacsu's  A f t e r one r e c r y s t a l l i x a t i o n ,  the p r o d u c t m e l t e d a t 1 6 0 - l 6 3 ° C .  A mixed m e l t i n g p o i n t w i t h  D - m a n n i t o l gave 1 6 0 - l 6 5 ° C . II.  P o t a s s i u m Permanganate i n P y r i d i n e S o l u t i o n To a s o l u t i o n o f D - m a n n i t o l - 1 , 2 , 3 * 5 * 6 - p e n t a n i t r a t e  (0.50  gm.) i n anhydrous p y r i d i n e ( 1 0 ml.) a t room t e m p e r a t u r e was added p o t a s s i u m permanganate ( 0 . 3 gm.) d i s s o l v e d i n p y r i d i n e (20 ml.).  The d a r k p u r p l e s o l u t i o n r a p i d l y changed c o l o u r t o  d a r k g r e e n i s h brown.  A f t e r t h i r t y m i n u t e s t h e brown s o l u t i o n  was poured I n t o w a t e r ( 1 0 0 ml.) and t h e p y r i d i n e n e u t r a l i z e d w i t h dilute hydrochloric acid.  A d a r k brown r e s i d u e p r e c i p i t a t e d .  -25-  The m i x t u r e was f i l t e r e d and t h e c l e a r c o l o u r l e s s f i l t r a t e was extracted with ether.  E v a p o r a t i o n of the d r i e d e t h e r e a l  solu-  t i o n y i e l d e d a y e l l o w o i l y r e s i d u e ( 0 . 0 5 gm.) h a v i n g t h e odour of mould.  The d a r k brown p r e c i p i t a t e f r o m t h e o x i d a t i o n was  also extracted with ether.  The e t h e r e a l s o l u t i o n t h u s o b t a i n e d  was e v a p o r a t e d l e a v i n g a p a l e cream c r y s t a l l i n e r e s i d u e ( 0 . 3 gm.) M.p. 68 - 7 l ° C T  A f t e r one r e c r y s t a l l i z a t i o n f r o m aqueous-  e t h a n o l t h e m e l t i n g p o i n t was 78 - 80°C.  A. mixed m e l t i n g p o i n t  w i t h D - m a n n i t o l - l , 2 , 3 , 5 » 6 - p e n t a n i t r a t e gave 78 - 80°C. The c r y s t a l l i n e p r o d u c t ( O . 2 6 0 8 gm.) was h y d r o g e n a t e d by the method d e s c r i b e d i n s e c t i o n D ( I ) .  The y e l l o w semi-  c r y s t a l l i n e s o l i d h y d r o g e n a t i o n p r o d u c t ( 0 . 1 6 3 7 gm.). gave negat i v e r e a c t i o n s w i t h t h e d i p h e n y l a m i n e r e a g e n t , Pacsu»s r e a g e n t and P e h l i n g s s o l u t i o n .  The p r o d u c t r e c r y s t a l l i z e d f r o m aqueous  ethanol melted a t l 6 l - l6if°C. m a n n i t o l gave l 6 l - l 6 5 ° C  A mixed m e l t i n g p o i n t w i t h D-  The y e l l o w s y r u p ( 0 . 0 3 0  gm.)  i s o l a t e d f r o m t h e o x i d a t i o n m i x t u r e was h y d r o g e n a t e d by t h e procedure d e s c r i b e d i n s e c t i o n D ( I ) . t i o n p r o d u c t (0.0134-  The syruppy  hydrogena-  ) gave n e g a t i v e t e s t s w i t h d i p h e n y l a -  mine r e a g e n t , Pacsu's r e a g e n t and P h l i n g s s o l u t i o n . e  III.  Sodium B l s m u t h a t e i n Acetone  Solution  D - m a n n i t o l - l , 2 , 3 » 5 » 6 - p e n t a n i t r a t e ( 0 . 5 0 gm.) was d i s s o l ved i n a m i x t u r e o f acetone (10 ml.) and a c e t i c a c i d (1 m l . ) . To t h i s s o l u t i o n was added a s u s p e n s i o n o f sodium b l s m u t h a t e ( 0 . 5 0 gm.) i n acetone (15 m l . ) .  The m i x t u r e was a l l o w e d t o  s t a n d o v e r n i g h t a t room t e m p e r a t u r e , t h e n was f i l t e r e d a Whatman No. 5 0 f i l t e r p a p e r .  Some w h i t e , f i n e l y  through  divided  -26-  m a t e r i a l s t i l l remained i n s u s p e n s i o n .  The m i x t u r e was  evap-  o r a t e d t o dryness and the d r i e d s o l i d e x t r a c t e d w i t h e t h e r . Evaporation odourless 8l°C.  o f the e t h e r e a l s o l u t i o n y i e l d e d a p a l e y e l l o w  c r y s t a l l i n e compound ( 0 . 3 7  ) m e l t i n g a t 79 *"  A mixed m e l t i n g p o i n t w i t h D - m a n n i t o l - l , 2 , 3 , 5 > 6 - p e n t a -  n i t r a t e gave 78 - 8l°C. The  c r y s t a l l i n e p r o d u c t ( 0 . 3 1 3 7 gm.)  was  hydrogenated  by the method d e s c r i b e d i n s e c t i o n D ( I ) . A y e l l o w s e r a i - c r y s t a l l i n e s o l i d (0.200ij. gm.) mixture.  was  The h y d r o g e n a t i o n  i s o l a t e d from the r e a c t i o n  p r o d u c t gave  negative t e s t s with  d i p h e n y l a m i n e r e a g e n t and Pacsu's r e a g e n t and a d o u b t f u l Fehling's test.  A f t e r two r e c r y s t a l l i z a t i o n s f r o m aqueous  ethanol the product melted at l 6 l p o i n t w i t h m a n n i t o l gave l 6 l IV.  -  - l63°C.  A mixed m e l t i n g  l63°C.  Hydrogen P e r o x i d e i n A c e t i c A c i d D-mannitol-l,2,3»5»6-pentanitrate  v e d i n g l a c i a l a c e t i c a c i d ( 1 . 5 ml.) t h i s s o l u t i o n was ( 1 . 3 ml.)  added a m i x t u r e  (0.28 gm.)  was  dissol-  a t room t e m p e r a t u r e .  of 30$ hydrogen  i n g l a c i a l a c e t i c a c i d (2 m l . ) .  To  peroxide  A f t e r standing  over-  n i g h t a t room t e m p e r a t u r e , the c l e a r c o l o u r l e s s s o l u t i o n was shaken w i t h a few grains«',of p a l l a d i u m c h a r c o a l c a t a l y s t t o remove the e x c e s s p e r o x i d e .  The  c a t a l y s t was  out and the s o l u t i o n e v a p o r a t e d t o d r y n e s s . l i n e compound (0.028 gm.), 82°C. was  obtained.  1,2,3,5,6-pentanitrate  having  then f i l t e r e d A white  crystal-  a m e l t i n g p o i n t of 81  -  A mixed m e l t i n g p o i n t w i t h D - m a n n i t o l gave 81 - 82°G.  -27-  V,  Chromium 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 - Sulphuric Acid Solution A mixture  o f a c e t i c a c i d (5> m l . ) , s u l p h u r i c a c i d (5> ml.)  and a c e t i c a n h y d r i d e (If? ml.) was c o o l e d i n a n i c e - s a l t D-mannitol-l,2,3,5»6-pentanitrate  bath.  ( 1 . 0 0 gm.) was d i s s o l v e d i n  5 m l . o f t h e a c i d m i x t u r e i n a 100 m l . f l a s k f i t t e d w i t h a dropping  f u n n e l , a condenser and a thermometer.  c o o l e d i n an i c e - s a l t b a t h .  Chromium t r i o x i d e  d i s s o l v e d i n t h e remainder o f t h e a c i d m i x t u r e added s l o w l y t h r o u g h t h e d r o p p i n g one h o u r .  The f l a s k was ( 1 . 0 0 gm.) ( 2 0 ml.) was  f u n n e l over a p e r i o d o f  On s t a n d i n g o v e r n i g h t I n t h e r e f r i g e r a t o r , t h e  c o l o u r of the r e s u l t i n g o x i d a t i o n mixture r e d t o dark green.  changed f r o m d a r k  The d a r k g r e e n s o l u t i o n was poured i n t o  water (300 ml.) and t h e a c i d n e u t r a l i z e d w i t h sodium b i c a r bonate.  The n e u t r a l 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 , t h e n  with chloroform.  Evaporation  of the d r i e d e t h e r e a l e x t r a c t  y i e l d e d 2 9 - 5 mg. o f p a l e cream c r y s t a l l i n e m a t e r i a l .  The sub-  s t a n c e gave a n e g a t i v e t e s t w i t h d i p h e n y l a m i n e r e a g e n t and when ashed l e f t a w h i t e r e s i d e u w h i c h t u r n e d r e d l i t m u s paper blue.  The r e s i d u e f r o m e v a p o r a t i o n  of the chloroform  extract  was e x t r a c t e d w i t h carbon t e t r a c h l o r i d e , w i t h e t h a n o l , t h e n a g a i n w i t h carbon t e t r a c h l o r i d e . E v a p o r a t i o n  of the ethanol  e x t r a c t y i e l d e d 2 6 . 9 mg. o f cream c o l o u r e d c r y s t a l l i n e m a t e r ial.  Evaporation  o f t h e two c a r b o n t e t r a c h l o r i d e e x t r a c t s  y i e l d e d !f9«6 mg. and 2 5 . 2 mg. r e s p e c t i v e l y o f brown semi crystalline residues.  The brown syruppy c h l o r o f o r m  a f t e r e x t r a c t i o n , weighed 39*4- rog*  T l l e  residue,  r e s i d u e gave a  negative t e s t w i t h diphenylamine reagent.  P o s i t i v e t e s t s were  -28 obtained, f o r t h e e t h a n o l and carbon t e t r a c h l o r i d e f r a c t i o n s . Analyses Ethanol extract Found; $N - 11.5, U.O F i r s t carbon t e t r a c h l o r i d e e x t r a c t $N - 9.o5„ 5.9 Second carbon t e t r a c h l o r i d e e x t r a c t $N * l4«05, 14.05 VI.  Chromium 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  Anhydride  D - M a n n i t o l - 1 , 2 , 3 , 5 , 6 - p e n t a n i t r a t e (0.50 gm, ) was d i s s o l v e d i n a c e t i c a c i d (10 m l . ) a t room t e m p e r a t u r e .  To t h i s  s o l u t i o n was added chromium t r i o x i d e (0.2 gm.) i n a c e t i c (15 ml.)  and a c e t i c a n h y d r i d e (10 m l . ) .  orange-red s o l u t i o n s l o w l y  acid  The r e s u l t i n g d a r k  changed c o l o u r t o a d a r k g r e e n on  s t a n d i n g f o r one and o n e - h a l f h o u r s a t room t e m p e r a t u r e . T h i s g r e e n s o l u t i o n was poured i n t o c o l d w a t e r (50 ml.) and s o l i d sodium b i c a r b o n a t e was added s l o w l y w i t h v i g o r o u s s t i r t i n g to n e u t r a l i z e the a c i d . extracted  The n e u t r a l s o l u t i o n was  w i t h e t h e r , w h i c h was t h e n d r i e d and e v a p o r a t e d ,  l e a v i n g a brown o i l y r e s i d u e (0.088 gm.) Found $N • l i f . 3 , l4«6  Analysi3£  Treatment o f D - M a n n i t o l - 1 , 2 , 3 , 5 ? 6 - p e n t a n i t r a t e w i t h A c e t i c - A c i d - A c e t i c Anhydride Sulphuric A c i d Mixture D - M a n n i t o l - 1 , 2 , 3 , 5 , 6 - p e n t a n i t r a t e (0.20 gm.) was d i s s o l v e d i n a m i x t u r e o f c h i l l e d a c e t i c a c i d (1 m l . ) s u l p h u r i c a c i d (1 m l . ) and a c e t i c a n h y d r i d e (5 m l . ) .  T h i s s o l u t i o n was  a l l o w e d t o s i t i n an i c e - s a l t b a t h f o r t h r e e h o u r s , the temperature of the mixture r i s i n g slowly. solution, smelling w a t e r (50 m l . ) .  A f t e r three hours, the  o f o x i d e s o f n i t r o g e n was poured i n t o i c e  The w h i t e f e a t h e r y  c r y s t a l s which p r e c i p i -  -29t a t e d s l o w l y from t h e aqueous s o l u t i o n were c o l l e c t e d on a f i l t e r and d r i e d t o a c o n s t a n t weight of 0.ll\. gm.  The  m e l t i n g p o i n t a f t e r one r e c r y s t a l l i z a t i o n f r o m e t h a n o l was 119.5  - 120.5°C  A: mixed m e l t i n g p o i n t w i t h an a u t h e n t i c  sample of D - m a n n i t o l - h e x a a c e t a t e VII.  was 119«5  - 120.5°C.  Chromium T r i o x i d e i n P y r i d i n e S o l u t i o n D-mannitol-1,2,3,5*6-pentanitrate  (0.50 gm.)  was  diss-  o l v e d i n anhydrous p y r i d i n e (10 ml.) a t room t e m p e r a t u r e . Chromium t r i o x i d e (0.2 gm.)  i n d r y p y r i d i n e (15 ml.) was  slowly to the p e n t a n i t r a t e s o l u t i o n .  The d a r k orange o x i d a -  t i o n m i x t u r e was a l l o w e d t o s t a n d o v e r n i g h t , t h e n was i n t o c o l d water  added  poured  (150 ml.) and the s o l u t i o n a c i d i f i e d w i t h  dilute hydrochloric acid. on a c i d i f i c a t i o n , was  A d a r k brown o i l w h i c h s e p a r a t e d  e x t r a c t e d i n e t h e r and combined w i t h  t h e e t h e r e x t r a c t s of t h e aqueous  layer.  E v a p o r a t i o n of the  d r i e d e t h e r e a l s o l u t i o n y i e l d e d a p a l e cream c r y s t a l l i n e residu© (0.27 gm.)  M.p. 75 - 77°C.  A mixed m e l t i n g p o i n t  w i t h a sample of D - m a n n i t o l - 1 , 2 , 3 , 5 , 6 - p e n t a n i t r a t e  was  75 -  oC 79  *  The o x i d a t i o n p r o d u c t (0.2015 gm.)  t h e method d e s c r i b e d i n s e c t i o n D ( l ) . p r o d u c t (O.IO2I4. gm.)  was hydrogenated  A white  crystalline  w h i c h gave n e g a t i v e t e s t s w i t h d i p h e n y -  l a m i n e r e a g e n t , pacsu's r e a g e n t and F e h l i n g s s o l u t i o n , obtained.  was  A f t e r one r e c r y s t a l l i z a t i o n from aqueous e t h a n o l  the p r o d u c t m e l t e d a t lbl\. - l 6 6 ° C . w i t h D-mannitol  by  gave I6I4. r-/166°C.  A mixed m e l t i n g p o i n t  -30-  VIII.  Chromium T r i o x i d e i n Acetone  Solution males  a.  D - m a n n i t o l - l , 2 , 3 , 5 * o - p e n t a n i t r a t e (0.50 gm. .00112M.)  was d i s s o l v e d i n d r y acetone (10 ml.) and a s o l u t i o n o f chromium t r i o x i d e (0.2 gm. .002 M.)' i n d r y acetone (15 ml.) was added. to  (Caution:  Chromium t r i o x i d e must be added  t h e acetone s l o w l y .  Chromium t r i o x i d e ) .  Acetone s h o u l d n o t be added t o  The r e s u l t i n g d a r k brown s o l u t i o n was  a l l o w e d t o s t a n d o v e r n i g h t a t room t e m p e r a t u r e , t h e n was poured i n t o c o l d w a t e r (200 m l . ) w i t h t h e f o r m a t i o n o f a pale yellow p r e c i p i t a t e . the  After f i l t r a t i o n  of t h e m i x t u r e ,  p r e c i p i t a t e was d i s s o l v e d i n e t h e r and t h e aqueous  filtrate  e x t r a c t e d s e v e r a l times w i t h ether.  The combined  e t h e r e a l s o l u t i o n s were d r i e d and e v a p o r a t e d t o y i e l d a p a l e pream s e m i - c r y s t a l l i n e r e s i d u e (0«2|l}-37 gm») M.p. 70 - 80 °C.  A mixed m e l t i n g p o i n t w i t h  D-mannitol-1,2,  3 , 5 , 6 - p e n t a n i t r a t e gave 6I4. - 75°C. Analysis:.  Pound:  $N. - 1 6 . 3 , 16.3  The o x i d a t i o n p r o d u c t O.2985 gm. was h y d r o g e n a t e d b y t h e u s u a l method y i e l d i n g O.I867 gm. o f a y e l l o w i s h syruppy compound.  The hydrogenated p r o d u c t gave n e g a t i v e t e s t s  w i t h d i p h e n y l a m i n e r e a g e n t , Pacsu's r e a g e n t and P e h l i n g s solution. b.  The p r e v i o u s p r o c e d u r e was r e p e a t e d u s i n g D - m a n n i t o l -  1 , 2 , 3 , 5 , 6 - p e n t a n i t r a t e (6.100 gm., 0.015 it'.*) and chromium t r i o x i d e (1.100 gm., 0.011 M.") i n a t o t a l volume o f 130 m l . acetone.  The p r e c i p i t a t e w h i c h formed i n t h i s aqueous  -31  s o l u t i o n was  d r i e d t o a c o n s t a n t weight of 3»66IL5  gm.  E v a p o r a t i o n of the e t h e r e x t r a c t y i e l d e d a l i g h t brown syrup  gm.).  (O.IL591  Repeated c r y s t a l l i z a t i o n o f the p r e -  c i p i t a t e y i e l d e d 3»lf660 gm. m e l t i n g a t 80 - 8 l ° C .  of a w h i t e c r y s t a l l i n e m a t e r i a l  A mixed m e l t i n g p o i n t w i t h a sample  of D - m a n n i t o l - l , 2 , 3 , 5 » 6 - p e n t a n i t r a t e mother l i q u o r was  gave 80 - 8 l ° C .  combined w i t h the syruppy p r o d u c t .  attempted r e c r y s t a l l i z a t i o n , the p r o d u c t  Pehlings  t  £-\).  The  In  continually oiled  o u t , p a r t i a l l y s o l i d i f y i n g o n l y on s t a n d i n g . Qc]^(C 1 . 2 6 6 , E t h a n o l  The  +lf3.2°  compound d i d not r e d u c e  solution.  A n a l y s i s Pound:  $N - 1 6 . 8 ,  16.9  A n a l y s i s of aqueous s o l u t i o n : Found: N.2I4-.6. 21L.1L  R e q u i r e d : 21L.1L meq»  Cr.III Cr.IV  meq.  0 . 0 2 3 6 , 0.021L5 0.0218, 0.0236  gm. gm.  I n f r a r e d a n a l y s i s showed v e r y l i t t l e as the sample would not m u l l s a t i s f a c t o r i l y i n N u j o l and an attempt t o d e p o s i t the substance d i r e c t l y on the p r i s m was  unsuccess-  ful. The  syrup  (O.hSbg gm.)  was  hydrogenated as d e s c r i b e d i n  s e c t i o n D ( I ) . A d i p h e n y l a m i n e t e s t of the r e s u l t i n g t i o n i n d i c a t e d t h a t n i t r a t e groups were s t i l l p r e s e n t . s o l u t i o n was  soluThe  f i l t e r e d and r e t u r n e d t o the h y d r o g e n a t o r w i t h  platinum oxide c a t a l y s t ( 0 . 1  gm.).  A f t e r shaking  with  hydrogen o v e r n i g h t , the s o l u t i o n gave no r e a c t i o n w i t h the  -32-  diphenylamine reagent.  The s o l u t i o n was f i l t e r e d and  evaporated t o a s l i g h t l y g r e e n i s h syrup (0.0533  gm.)  w h i c h d i d n o t c r y s t a l l i z e on s t a n d i n g . The o b s e r v e d opt i c a l r o t a t i o n was ( S O ^ O . 0  £ ^ 7 p '  s  1.4673.  (C  0.529,  K2°>^  =  )*  1  The syrup d i d n o t reduce F e h l i n g s s o l u t i o n  n o r d i d i t g i v e a p o s i t i v e t e s t w i t h Pacsu's r e a g e n t .  c.  D-mannitol-1,2,3,5,6-pentanitrate  (0.50gm.,  .00112  M.)  was d i s s o l v e d i n acetone (30 ml.) c o n t a i n e d i n a s t o p p e r e d f l a s k , f i t t e d w i t h a d r o p p i n g f u n n e l , connected by g l a s s t u b i n g t o a pneumatic samples over w a t e r .  t r o u g h a r r a n g e d f o r c o l l e c t i n g gas To t h e p e n t a n i t r a t e s o l u t i o n was  added s l o w l y from t h e f u n n e l Chromium t r i o x i d e ( 0 . 0 8 8 O.OOO88 M.) i n acetone (10 m l . ) .  gm.,  The s o l u t i o n was a l l o w e d  t o s t a n d a t room temperature u n t i l t h e c o l o u r changed t o p a l e g r e e n and i n d i c a t e d t h a t most o f t h e h e x a v a l e n t chromium had been reduced ( l 6 d a y s ) .  No e v o l u t i o n o f gas  was o b s e r v e d , and t h e water i n t h e c o l l e c t i n g tube r e m a i n ed n e u t r a l t o l i t m u s .  The r e a c t i o n m i x t u r e c o n t a i n e d a  d a r k g r e e n i s h - b r o w n p r e c i p i t a t e d e p o s i t e d on t h e w a l l s of the f l a s k .  The c l e a r , p a l e g r e e n acetone s o l u t i o n was  decanted i n t o w a t e r (200 ml.) c a u s i n g t h e f o r m a t i o n o f a bulky p r e c i p i t a t e resembling cotton wool.  The aqueous  m i x t u r e was e x t r a c t e d d i r e c t l y w i t h e t h e r and t h e d r i e d e t h e r e a l e x t r a c t was e v a p o r a t e d t o d r y n e s s i n a r o t a r y e v a p o r a t o r , l e a v i n g 0 . ^ 0 8 3 gm. of orange-brown s o l i d  resi-  -33due.  A f t e r s e v e r a l r e c r y s t a l l i z a t i o n s from  t e t r a c h l o r i d e , a white  ethanol-carbon  c r y s t a l l i n e p r o d u c t (O.III4.3 gm.)  m e l t i n g a t 73.5 - 7k»5°C. was o b t a i n e d . (C I4..82, e t h a n o l ^ = 1).  M j - + Ij-9.6 1  Further r e c r y s t a l l i z a t i o n  failed  to a l t e r the melting point or the o p t i c a l r o t a t i o n . mixed m e l t i n g p o i n t w i t h gave 71 - 78°G.  A  D-mannitol-l,2,3,5>6-pentanitrate  Reworking o f t h e mother l i q u o r s y i e l d e d  a f u r t h e r 0.1331 gm. o f p r o d u c t and 0.1539 g^* °£ brown semi-crystalline residue.  No m a n n i t o l p e n t a n i t r a t e was  recovered. Analysis:  Found:  $N - 1 9 . 0 , 18. 2, 1 8 . 6 , 1.8.0  184)  (av. The  I n f r a r e d spectrum o f t h i s compound showed t h e c h a r a  c t e r i s t i c peaks f o r n i t r a t e g r o u p s , b u t d i d n o t show t h e peak a t 3620 cm""-- f o r t h e h y d r o x y l group o f m a n n i t o l pent a 1  nitrate.  There was however a s m a l l p e a k a t 3520 c m . " l .  There was no a b s o r p t i o n a t 174-0 cm.""-- where t h e c a r b o n y l 1  s t r e t c h i n g band would appear. I n a b l a n k experiment t o determine t h e a c t i o n o f chromium t r i o x i d e i n a c e t o n e , t h e r e was no a p p a r e n t e v o l u t i o n o f gas, and e t h e r e x t r a c t i o n o f t h e aqueous s o l u t i o n y i e l d e d o n l y 2.8mg. o f c l e a r syruppy r e s i d u e . I n a s i m i l a r experiment D-mannitol h e x a n i t r a t e (O.Ij.0 gm. was  t r e a t e d l i n acetone s o l u t i o n (I4.O ml.) w i t h chromium t r i  oxide  (.088 gm.).  There was no apparent e v o l u t i o n of g a s .  When t h e s o l u t i o n was poured i n t o w a t e r , p r e c i p i t a t i o n occurred.  The p a l e , c r e a m y - w h i t e p r e c i p i t a t e was f i l t e r e d  -3kout and d r i e d t o a c o n s t a n t w e i g h t o f 0.3678 gm. M.p. 107 - 110°C.  The f i l t r a t e was e x t r a c t e d s e v e r a l t i m e s  w i t h e t h e r w h i c h was t h e n d r i e d and e v a p o r a t e d .  Y i e l d of  c r y s t a l l i n e m a t e r i a l 0.034- gnu M.p. 105 - 110°C. crude y i e l d was 0.4-036 gm. ( 1 0 1 $ ) .  lotal  A f t e r two r e c r y s t a l l i -  z a t i o n s t h e substance m e l t e d a t H I . 5 - 113°C.  A mixed  m e l t i n g p o i n t w i t h D-mannitol h e x a n i t r a t e gave 1 1 1 . 5  -  113°C Hydrogenation of the C r y s t a l l i n e O x i d a t i o n Product from S e c t i o n V I I I c. The c r y s t a l l i n e m a t e r i a l ( 0 . 0 5 2 5 gm.) was h y d r o g e n a t e d i n t h e u s u a l manner.  No p r e s s u r e drop was o b s e r v e d b u t  a f t e r n i n e h o u r s , a n e g a t i v e d i p h e n y l a m i n e t e s t showed t h e absence o f n i t r a t e n i t r o g e n .  The h y d r o g e n a t i o n m i x t u r e  contained a suspension of f i n e c o l o u r l e s s c r y s t a l s .  The  s o l u t i o n was f i l t e r e d and t h e s o l i d s were washed w i t h w a t e r . The combined f i l t r a t e and washings were e v a p o r a t e d t o d r y ness below 50°C. b a t h t e m p e r a t u r e .  The c o l o u r l e s s  syruppy  r e s i d u e ( 0 . 0 2 2 3 gm.) c r y s t a l l i z e d on s t a n d i n g o v e r n i g h t i n a vacuum d e s i c c a t o r and t h e crude p r o d u c t m e l t e d a t 14-0 155°C  A f t e r two r e c r y s t a l l i z a t i o n s f r o m aqueous e t h a n o l  the m e l t i n g p o i n t was I64. - 1 6 5 . 5 ° C .  A mixed m e l t i n g p o i n t  w i t h a u t h e n t i c D-mannitol was 164- - 1 6 5 ° C s p e c i f i c r o t a t i o n was foc}^ =  t  The o b s e r v e d  0 . 0 0 (C . 0 4 - 6 w a t e r 5  }  The i n f r a r e d spectrum o f t h e hydrogenated p r o d u c t c o r r e s ponded c l o s e l y t o t h a t o f D - m a n n i t o l .  Oxidant  Solvent  TABLE 1 Results of Oxidations Mannitol Pentanitrate Time Recovered  Other P r o d u c t s  70$  I  KWnOlj.  Acetone  1$ m i n .  II  KMnOlj.  Pyridine  30 m i n .  III  NaBi03  iii hrs.  IV  H2O2  Acetone-Acetic acid Acetic Acid  V  Cr03  G l a c i a l Acetic acid 2li hrs. A c e t i c Anhydride Sulphuric Acid  O i l , l o s s of Nitrogen  VI  CrO:  Glacial Acetic acid " 1-| h r s . A c e t i c anhydride  O i l , l o s s of Nitrogen  VII  GrOr  Pyridine  llf h r s .  V i l l a CrO 3  Acetone  lli hrs.  b Cr03  Acetone  llj. h r s .  c CrOo  Acetone  16  lli hrs.  days  Oil  7h%100%  $k% Syrup, s l i g h t l o s s of n i t r o gen  Wo  Syrup, s l i g h t l o s s of n i t r o gen. White crystalline compound.  -35-  P r e p a r a t i o n of Isomannide (1:4, Isomannide was D-mannitol (50 gm.) a c i d (300 ml.) gas  was  The  of gas  b u b b l e r was  72 h o u r s .  hydrochloric  tube.  a syrup.  t h a t the the  s o l u t i o n was  saturated.  s o l u t i o n was  c o l o u r of the  solution gradually  refluxed  was  added and  A clear colourless  b o i l i n g at 117  for  several  darkened.  e v a p o r a t e d t o a syrup under reduced p r e s s u r e , the  s o l u t i o n again evaporated to  crude syrup (1|2*5 gm. ) was  The  Dry  introduced from a c y l i n d e r u n t i l  Hydrogen c h l o r i d e fumes were e v o l v e d f o r  water (50 ml.)  vacuum.  was  indicated  s o l u t i o n was  •  l i t e r two-necked f l a s k f i t t e d w i t h a  t h e n removed and  h o u r s w h i l e the The  i n concentrated  a condenser p r o t e c t e d by a d r y i n g  hydrogen c h l o r i d e gas evolution  dissolved  - Dianhydromannitol) the method of W i g g i n s (46)  p r e p a r e d by  i n a one  b u b b l e r and  3:6  d i s t i l l e d under  f r a c t i o n (10.8  gm. ) was  - 12£°C. at a p r e s s u r e of 2 mm.  c r y s t a l l i z e d on s t a n d i n g o v e r n i g h t .  collected  Both f r a c t i o n s  F r a c t i o n one  was  re-  c r y s t a l l i z e d from e t h y l acetate - ethanol to a constant m e l t i n g p o i n t 85 M,  -  86°C.  [oG,  5  reported  86-87°G.  and m.p.  = *  W i g g i n s (46)  =-91.0°  N i t r a t i o n of Isomannide Isomannide ( 2 . 0 n i t r i c acid  (20 ml.)  added s l o w l y , acid  (4.0  ml.).  gm.)  was  i n an i c e b a t h .  To  i n cold red  the  solution  with s t i r r i n g , cold concentrated  fuming was  sulphuric  A f t e r s t a n d i n g f o r f i f t e e n m i n u t e s , the  ruppy r e d d i s h - o r a n g e s o l u t i o n was (500 m l . ) .  dissolved  sy-  poured i n t o i c e - w a t e r  No p r e c i p i t a t e formed i m m e d i a t e l y , however f i n e  -36c o l o u r l e s s n e e d l e s were d e p o s i t e d when t h e s o l u t i o n was a l l o w e d t o s t a n d a t room temperature f o r two h o u r s .  The p r o -  duct was r e c o v e r e d on a f i l t e n washed w i t h w a t e r and d r i e d i n a vacuum d e s i c c a t o r t o a c o n s t a n t weight o f I.I4. gm. (l|-6$). The m e l t i n g p o i n t a f t e r two r e c r y s t a l l i z a t i o n s f r o m c a r b o n t e t r a c h l o r i d e water was 6I1 - 65.5°C. (G. 1 . 2 1 3 ,  H 0, 2  =  EK3j  fc  =  f  319.2°  K r a n t z (1+7) r e p o r t e d a m e l t i n g p o i n t  of 6 5 . 5 ° c Analyses:  Pound: $N Required:  H y d r o g e n a t i o n o f Isomannide Isomannide  ( 0 . 1 2 8 5 gm.) was hydrogenated as des-  c r i b e d i n s e c t i o n D ( I ) , u s i n g platimum o x i d e c a t a l y s t ( o . l gm. ) a t an i n i t i a l p r e s s u r e o f 35»4- p . s . i .  There was  no d e t e c t a b l e p r e s s u r e drop d u r i n g t h e r e a c t i o n p e r i o d . A f t e r removal f r o m t h e h y d r o g e n a t o r , t h e s o l u t i o n was f i l t e r e d and e v a p o r a t e d i n a r o t a r y e v a p o r a t o r t o a c l e a r syrup ( 0 . 1 2 7 5 gm.) w h i c h d i d n o t c r y s t a l l i z e on s t a n d i n g i n a vacuum desiccator.  C r y s t a l l i z a t i o n o c c u r r e d i m m e d i a t e l y when t h e  s y r u p was seeded w i t h a c r y s t a l o f i s o m a n n i d e .  A f t e r one  r e c r y s t a l l i z a t i o n from ethanol-ethylacetate the m e l t i n g p o i n t o f t h e p r o d u c t was 85 - 86°C.  The mixed m e l t i n g  p o i n t w i t h an a u t h e n t i c sample o f isomannide was 85 - 8 6 » o C  H y d r o g e n a t i o n o f Isomannide Isomannide d i n i t r a t e  Dinitrate ( 0 . 1 2 1 3 gm. ) was h y d r o g e n a t e d  -37-  by t h e p r o c e d u r e g i v e n i n S e c t i o n D ( I ) , u s i n g o x i d e c a t a l y s t (0.1 p.s.i.  There was  gm.)  a t an i n i t i a l p r e s s u r e  of 39*5  no apparent p r e s s u r e d r o p , but a t t h e  of the h y d r o g e n a t i o n  end  p e r i o d a t e s t f o r n i t r a t e w i t h the d i -  phenylamine reagent was and  platinum  negative.  The  s o l u t i o n was  e v a p o r a t e d to a c o l o u r l e s s s y r u p ( 0 . 0 5 0 5 gm.)  filtered The  syrup c r y s t a l l i z e d a f t e r s e e d i n g w i t h a c r y s t a l o f isomannide.  A f t e r one r e c r y s t a l l i z a t i o n f r o m e t h a n o l - e t h y l  a c e t a t e the p r o d u c t m e l t e d a t 85 - 86°C. p o i n t w i t h isomannide was  The mixed m e l t i n g  85 - 86°C.  D I S C U S S I O N CHOICE OP OXIDANT The r e a c t i o n s  of hexoses and t h e i r d e r i v a t i v e s  w i t h a number of o x i d i z i n g s t u d i e d (48).  agents had p r e v i o u s l y been  S e v e r a l o f the r e a g e n t s  had been shown t o  be  s p e c i f i c f o r o x i d a t i o n a t t h e ends of t h e c a r b o n c h a i n , or at the p e n u l t i m a t e  positions.  However, i n v e s t i g a t i o n has  not r e v e a l e d an o x i d a n t w h i c h a c t s s p e c i f i c a l l y on a h y d r o x y l group a t the t h i r d p o s i t i o n .  I£ i s t h u s e v i d e n t t h a t t o  i n t r o d u c e a c a r b o n y l group a t the t h i r d c a r b o n o n l y of a h e x i ' t o l molecule i t i s necessary  to form s u i t a b l e i n e r t  v a t i v e s of a l l the o t h e r h y d r o x y l B a c t e r i a l o x i d a t i o n was been  shown t h a t 1:2,  5t6  deri-  groups.  n o t i n d i c a t e d because i t had  - d i i s o p r o p y l i d i n e - D - g l u c o s e , which  -38-  p o s s e s s e d an u n s u b s t i t u t e d h y d r o x y l group a t p o s i t i o n t h r e e , was  untouched by b a c t e r i a l a c t i o n (1+9)  •  O x i d a t i o n o f the same compound w i t h aqueous permangana t e was  a l s o attempted ($0),  t h e p o t a s s i u m s a l t of 1:2  f r o m the r e a t i o n was enexyluronic a c i d . f e r e n t i a l l y at  however the o n l y p r o d u c t i s o l a t e d - isopropylid-  This i n d i c a t e d that r e a c t i o n occurred  pre-  C5.  Oppenauer o x i d a t i o n of 1 , - 3 - d i b e n z o y l g l y c e r o l was u n s u c c e s s f u l l y attempted by White (lf-9), however he was t o p r e p a r e 1,  3-dibenzoyldihydro-xyacetone  able  by t r e a t m e n t of the  d i s u b s t i t u t e d g l y c e r o l w i t h chromium t r i o x i d e i n a c e t i c a c i d . S u l l i v a n (52)  a l s o u s i n g chromium t r i o x i d e and g l a c -  i a l a c e t i c a c i d p r e p a r e d an L-sorbosd. d e r i v a t i v e f r o m a sorbitol.  O x i d a t i o n of 6 - t o s y l - 1:3*  D-  2:l|.-diethylddene-  D - s o r b i t 0 l y i e l d e d l - t o s y l - 3 : 5 > l+t'6 - d i e t h y l l d e n e - k e t o - L sorbose. Chromium t r i o x i d e t h u s appeared t o be a s u i t a b l e o x i dant f o r h y d r o x y l groups i n s u b s t i t u t e d p o l y o l s .  The  of chromium t r i o x i d e and o t h e r u n s p e c i f i c o x i d a n t s ; p o t a s s i u m permanganate, hydrogen p e r o x i d e  and  muihate were i n v e s t i g a t e d i n v a r i o u s s o l v e n t s . s o l v e n t s were not c o n s i d e r e d  action e.g.  sodium b i s Alkaline  s i n c e n i t r a t e groups were  known t o be h y d r o l y z e d under b a s i c c o n d i t i o n s  (5)»  P y r i d i n e , known t o be an o r g a n i c base w h i c h i s capa b l e of removing the n i t r a t e e s t e r f r o m p o s i t i o n t h r e e  of  -39D-mannitol h e x a n i t r a t e  (3k-)*  produces a p e n t a n i t r a t e  i s r e l a t i v e l y s t a b l e t o f u r t h e r a t t a c k by p y r i d i n e  that  (lj.1).  Thus d e s p i t e i t s b a s i c c h a r a c t e r , p y r i d i n e appeared t o be suitable solvent.  To p r o v i d e  a  acid conditions, acetic acid-  a c e t i c anhydride mixtures, comparatively  stable to o x i d a t i o n ,  were used. I n the remainder of the o x i d a t i o n s , acetone was as the most c o n v e n i e n t n e u t r a l s o l v e n t .  used  Acetone i s known t o  be s u s c e p t i b l e t o a t t a c k by chromium t r i o x i d e i n the  hot  s o l u t i o n (53), however, a t room temperature experiment f a i l e d t o i n d i c a t e e v o l u t i o n of gas  o r the f o r m a t i o n  of a  signifi-  cant q u a n t i t y of p o l y m e r i c m a t e r i a l , when acetone was  allowed  t o stand i n the p r e s e n c e of chromium t r i o x i d e . RESULTS OF OXIDATIONS The  r e s u l t s of the a p p l i c a t i o n of the v a r i o u s  d i z i n g solutions to D-mannitol-l,2,3,5,6-pentanitrate summarized i n T a b l e I . u t i o n was  apparently  oxiare  Hydrogen p e r o x i d e i n a c e t i c a c i d  i n e f f e c t i v e as an o x i d a n t  sol-  f o r D-mannitol  p e n t a n i t r a t e , s i n c e the s t a r t i n g m a t e r i a l c o u l d be  recovered  quantitatively. In a l l i n t e r a c t i o n had  the o t h e r a t t e m p t s , i t was occurred,  n o t e d t h a t some  s i n c e the o r i g i n a l  pentanitrate  c o u l d not be r e c o v e r e d i n h i g h y i e l d s (Table I ) . Mien  chromium t r i o x i d e was  a c e t i c anhydride mixtures,  non  used i n a c e t i c a c i d -  c r y s t a l l i n e p r o d u c t s were  -39a-  TABLE I I N i t r o g e n C o n t e n t s o f Some P o l y o l N i t r a t e s ^NITROGEN FORMULA COMPOUND 0 0 N N 1 . D-mannitol H H.H 0 0 H • 18J hexanitrate °2N0-C-C-C-C-G-C-0N0 E 6 6 H H. H N N o o 2  2  2  2  2.  2  D-mannitol-1,2,3,  0 0 N N H H H 0 0 H * > * II* 02N0-C-C-C-C-C-C-0N0 . 2  5,6-pentanitrate  2  17.3$  2  11  1 • •<  H 0 0 H H H N H 0. 2  3.  -0—1  D-mannitan tetranitrate  15.5$  N 0 H  H H  H C-•C-C-C-C-C-ONO' 2  l  I  I  1  1  c  0 0 H H H N N °2°2  It.  N 0  Isomannide dinitrate  I  H C-C  2 0  5.  Dimer  3-C  LvJ  1  0 N 0  C-C-H . .  2  2  Mannitol pentanitrate 1 O I  Mannitol pentanitrate  17.1  -40-  obtained.  K j e l d a h l analyses  showed t h a t t h e n i t r o g e n c o n -  t e n t was c o n s i d e r a b l y l o w e r t h a n t h a t r e q u i r e d f o r a h e x i t o l p e n t a n i t r a t e on t h e c o r r e s p o n d i n g This could probably t y l a t e d products,  carbonyl d e r i v a t i v e .  be accounted f o r by t h e f o r m a t i o n  as i t was a l s o shown t h a t m a n n i t o l  n i t r a t e c o u l d be c o n v e r t e d  to mannitol  penta-  h e x a a c e t a t e i n an  a c e t i c a c i d - a c e t i c anhydride - sulphuric a c i d  mixture.  A s i m i l a r s o l v e n t m i x t u r e had been p r e v i o u s l y posed by Wolfrom (54) ^  o r  o f ace-  pro-  acetylative denitration.  I n most o t h e r cases t h e c r y s t a l l i n e m a t e r i a l i s o l a t e d was u n a l t e r e d m a n n i t o l  pentanitrate.  Only w i t h the use o f  a chromium t r i o x i d e - a c e t o n e o x i d a t i o n m i x t u r e was a p r o d u c t obtained  w h i c h l o w e r e d t h e m e l t i n g p o i n t of the o r i g i n a l  pentanitrate.  Treatment o f m a n n i t o l  pentanitrate with a  s l i g h t excess of chromium t r i o x i d e i n acetone f o r a s h o r t p e r i o d o f time y i e l d e d a s m a l l q u a n t i t y o f s e m i - c r y s t a l l i n e m a t e r i a l ; 55$ o f t h e p e n t a n i t r a t e was r e c o v e r e d unchanged. Chromium VI was p r e s e n t reaction 3 H2©»  3  i n excess o f t h a t r e q u i r e d by t h e  ^CHOH + 2 CrC-3  3  ^C-0  +  -CrgO^  More chromium (52$) was r e d u c e d t o t h e t r i v a l e n t  s t a t e t h a n was accounted f o r by t h e o x i d a t i o n o f t h e nonrecovered  p e n t a n i t r a t e to a h e x u l o s e d e r i v a t i v e .  Detection of  n i t r o g e n i n t h e aqueous s o l u t i o n suggested t h a t a p o r t i o n o f t h e p e n t a n i t r a t e was decomposed t o w a t e r s o l u b l e Since mannitol  h e x a n i t r a t e c o u l d be r e c o v e r e d  products.  unchanged  f r o m t r e a t m e n t i n a s i m i l a r o x i d a t i o n medium, i t seemed  -1*1that  a t t a c k on t h e p e n t a n i t r a t e m o l e c u l e  the s i t e  o f the f r e e h y d r o x l group.  o f t h e s y r u p p y p r o d u c t was l o w e r  occurred f i r s t at  The N i t r o g e n c o n t e n t  than that  required f o r the  d e s i r e d h e x u l o s e . The i n f r a r e d s p e c t r a , w h i c h was t e d l y poor,  showed no t r a c e  cm"-'-, t h e c h a r a c t e r i s t i c Denitration  lings  of the m a t e r i a l y i e l d e d reagent  treatment  chromium t r i o x i d e  frequency.  a syrup w h i c h gave a and d i d n o t r e d u c e  acetone mixture  quite different  determined  The  results.  f o r s i x t e e n days  A white  and o f t h e s t a r t i n g  compound showed no i n f r a - r e d  i t was n o t a c a r b o n y l  vative.  also  showed d i f f e r e n c e s f r o m  of t h e m a n n i t o l penta-and mannide  that  h e x a n i t r a t e s and from  derithose  iso-  dinitrate. Hydrogenation  stalline  as  a b s o r p t i o n a t o r near  that  The s p e c t r u m  com-  material.  I7I1O cm"--, i n d i c a t i n g 1  pro-  crystalline  b y t h e K j e l d a h l method was h i g h e r t h a n  the d e s i r e d hexulose  product  o f t h e compound y i e l d e d  apparently i d e n t i c a l  therefore the material isolated c o u l d n o t have r e s u l t e d nitol  Peh-  of mannitol pentanitrate with the  pound was o b t a i n e d , t h e n i t r o g e n c o n t e n t o f w h i c h ,  of  174-0  solution. The  duced  of a b s o r p t i o n a t or near  carbonyl stretching  n e g a t i v e t e s t w i t h Pacsu's  admit-  pentanitrate.  from  from  a  cry-  t o D-mannitol, the reaction  mixture  c h a i n d e g r a d a t i o n o f man-  Mannitol  hexanitrate  (see T a b l e  percentage of n i t r o g e n agreeing mentally  f o r the  crystalline  with  is  mannitol  different,  i t i s doubtful  chromium t r i o x i d e  w e l l as  an  hydride  formation  oxidant,  i t was  could  pentanitrate with prepared, The  dinitrate  the  limited red 1030  the  from treatment  i s o m a n n i d e was high  i s reported  synthesized  optical  f o r the  (1+$),  t o the m e l t i n g  cm.probably ether  point  an-  tetraniobtained  linkage  due (55)  cm""'" f r o m t h e  (ii|) and of  T h i s p e a k was A  similar  tetrahydrofuran  expected i n mannitan t e t r a n i t r a t e . In this region.  I t was  work. reported  q u o t e d were The  infra-  showed a b s o r p t i o n  to the presence of the •  nit-  been  solubility.  was  isomannide  time i n t h i s  compound had  and  as  mannitol  the p h y s i c a l constants  s p e c t r u m o f t h e unknown.  absorption  agent  (31)  of  rotation  first  p r e p a r a t i o n of the  literature  n e a r 1076  compound  possible that  Tichanowich  s p e c t r u m o f isomannaide d i n i t r a t e  cyclic  t h a t the  are  anhydrous;ammonia,although m a n n i t o n  unusually  Although the in  however,  spectra  to g i v e manniton  or isomannide d i n i t r a t e .  rated.  experi-  i s a dehydrating  considered  occur  some m a n n i t a n t e t r a n i t r a t e  not  infra-red  a  hexanitrate.  Since  trate  that found  o x i d a t i o n product,  s i n c e t h e p h y s i c a l p r o p e r t i e s and substantially  II) contains  The  not  peak,  at  strained present  in  probably  s t r u c t u r e would unknown showed  alos determined  that  be no  -43t r e a t m e n t of isomannide and i t s d i n i t r a t e under c o n d i t i o n s s i m i l a r t o those used i n h y d r o g e n a t i o n of the unknown y i e l d ed o n l y isomannide i n b o t h cases.. was  preserved  S i n c e the e t h e r  linkage  i n t h e s e compounds, i t i s d o u b t f u l t h a t h y d r o -  g e n o l y s i s of s i m i l a r m a t e r i a l s would y i e l d m a n n i t o l . therefore considered intramolecular  It is  improbable t h a t the compound i s an  anhydride.  Though the n i t r o g e n a n a l y s i s f a i l s t o c o n f i r m p o s t u l a t e , t h e p o s s i b i l i t y of f o r m a t i o n of an c u l a r anhydride,  the  intermole-  combining two m o l e c u l e s of p e n t a n i t r a t e  j o i n e d t h r o u g h an e t h e r l i n k a g e a t the t h r e e  positions,  would not be i n c o m p a t i b l e w i t h o t h e r d a t a o b t a i n e d . a compound might c o n c e i v a b l y y i e l d m a n n i t o l  Such  I n hydrogena-  tion. Another p o s s i b i l i t y , though  a l s o i n disagreement w i t h  the n i t r o g e n a n a l y s i s , i s the c o n v e r s i o n n i t r a t e i n t o a d i f f e r e n t molecular  form.  of m a n n i t o l  penta-  A structure  h a v i n g more i n t e r n a l hydrogen bonding would have a l o w e r m e l t i n g p o i n t and the s p e c t r a l bands c o u l d e x h i b i t  slight  shifts. No  s a t i s f a c t o r y s t r u c t u r e has been p o s t u l a t e d .  BI  1. 2.  B L I  O G R A P H Y  F e n t o n , H. and J a c k s o n , H. J . Chem. Soc. 7 5 : 1 .  99  l 8  G l a t t f e l d , J . and Gershan, S. J . Am. Chem. S o c . 6 0 : 2 0 1 3 . 1938  3.  B e r t r a n d , C.  Compt. r e n d . 1 2 6 : 7 6 2 .  4.  Hunter, J .  Iowa S t a t e C o l l . J . S c i . 1 5 : 7 8 . 1940  5.  C.A. 3 5 : 5 4 % .  I898  1941  V i g n o n , L. and B<&y, I . Compt. r e n d . 1 3 5 : 5 0 7 . 1 9 0 2  6.  Kuhn, L.P.  7.  L o b r y de Bruyn, C.A. and Van E k e n s t e i n , A.  8.  J r . Am. Chem. S o c . 6 8 : 1 7 6 l . 194& Rec.  t r a v . chim. l i j . : 2 0 3 . I896 '  L o b r y de B r u y n , C.A. and Van E k e n s t e i n , A. Rec. t r a v . chim. l 6 : 2 7 4 » ^ 9 7 L o b r y de B r u y n , C.A. and Van E k e n s t e i n , A. Rec. t r a v . chim. 1 6 : 2 6 2 . I 8 9 7 8  9. 10.  L o b r y de Bruyn, C.A. and Van E k e n s t e i n , A. 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