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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 of 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 the Department of Chemistry We accept t h i s t h e s i s as conforming to the r e q u i r e d standard THE UNIVERSITY OF BRITISH COLUMBIA August, 1956 A. C K N O W L E D G E M E N T I would l i k e to express my thanks and a p p r e c i a t i o n to Doctor L.D. Hayward f o r help and encouragement during the course of t h i s work. Thanks are a l s o due to the Powell 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 which was extended f o r a second year. ABSTRACT The o x i d a t i o n 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 by a s e l e c t i o n of n o n - s p e c i f i c oxidants 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 . Results of p r e l i m i n a r y experiments l e d to f u r t h e r study of the a c t i o n of chromium t r i o x i d e i n acetone 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 syrupy product which on hydrogenation 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 ketose reagent or w i t h F e h l i n g ' s s o l u t i o n . When the r e a c t i o n was allowed t o go to completion, a white c r y s t a l l i n e compound, which d i d not reduce 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 from the o x i d a t i o n mixture. This compound, which was not i d e n t i f i e d , y i e l d e d D-mannitol on hydrogenation 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 , D-Mannitol h e x a n i t -r a t e and isomannide d i n i t r a t e . TABLE OF CONTENTS INTRODUCTION 1 HISTORICAL 3 EXPERIMENTAL 20 DISCUSSION 37 BIBLIOGRAPHY kk LIST OF TABLES I . R e s u l t s o f Oxidations 34a I I . Nitrogen Contents of Some P o l y o l N i t r a t e s 39a - 1 -INTRODUCTlON A number of the p o s s i b l e a l d o - and 2-ketohexoses have been found widely d i s t r i b u t e d i n nature. 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 isomers have a l l been synthesized and ex-t e n s i v e l y s t u d i e d . Such has not been the case w i t h the 3 -ketohexose isomers. Although t h e i r e xistence has been pos-t u l a t e d , and has been the subject of controversy, as yet no 3-ketose has been i s o l a t e d from n a t u r a l sources. Por many yea r s , two substances, ' g l u t o s e 1 and • g a l t o s e ' , were b e l i e v e d to be 3-ketoses. Despite the f a c t t h a t t h e i r i d e n t i t y was l a t e r disproved, the great amount of specula-t i o n which was aroused concerning the formation 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 to study of p o s s i b l e un-equivocal s y n t h e t i c routes t o authentic samples of these sugars. The present work de s c r i b e s an attempt t o prepare D-arabino - 3-hexulose which has the s t r u c t u r e t o which Lobry de Bruyn and Alberda van Ek e n s t e i n assigned the name c<-glutose. Oxid a t i o n of 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. Normally, o x i d a t i o n of an u n s u b s t i t u t e d sugar a l c o h o l occurs at the ends of the carbon c h a i n to y i e l d aldohexoses or hydroxy a c i d s ( 1 , 2 ) , although i t i s p o s s i b l e by some methods, to o b t a i n 2-ketohexoses (3,l\.)» No oxidants 2 s p e c i f i c f o r the hydroxyl at carbon three of the 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 discovered. I f , however, a l l other h y d r o x y l groups could be blocked, by s u i t a b l e s u b s t i t -uents, o x i d a t i o n might be induced at p o s i t i o n three on the carbon chain w i t h the formation of a ketonic group at t h i s s i t e . Removal of the b l o c k i n g s u b s t i t u e n t s should y i e l d a compound isomeric w i t h the known hexoses. Since i t possessed a f r e e hydroxyl group at the d e s i r e d p o s i t i o n , D-mannitol-1,2,1}.,5>,6-pentanitrate appeared to pro-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 to be r e l a t i v e l y s t a b l e to n e u t r a l and a c i d c o n d i t i o n s (£.) and to o x i d a t i o n , yet c o u l d 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 t h e r e f o r e p o s t u l a t e d that s e l -e c t i v e o x i d a t i o n of the f r e e hydroxyl 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 of the n i t r a t e e s t e r groups, would complete the s y n t h e s i s of D-arabino - 3-hexulose, HISTORICAL INTRODUCTION GLUTOSE I n t h e i r study of the i n t e r c o n v e r s i o n of D-glucose ( I ) , f r u c t o s e (IV) said D-mannose ( I I I ) I n aqueous s o l u t i o n s under the i n f l u e n c e of i n o r g a n i c bases (potassium, sodium, calcium and l e a d hydroxides, sodium acetate and sodium carbonate), Lobry de Bruyn and Alberda van E k e n s t e i n (7) found t h a t a non-fermentable, apparently homogeneous syrup could be obtained i n y i e l d s v a r y i n g from one t o twenty percent. This syrup, which could be n e i t h e r c r y s t a l l i z e d nor 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 hexulose »glutose» ( V I , V I I I ) , i n which the carbonyl group was i n p o s i t i o n three on the carbon c h a i n . They p o s t u l a t e d that a 3-hexulose could be formed by a con-t i n u a t i o n down the carbon c h a i n of the eplmeric s h i f t s which r e s u l t e d i n the conversion of aldoses t o 2-ketoses through e n e d i o l forms ( I I , V , V I I ) . Though e i t h e r I , I I I , or IV co u l d be used as s t a r t i n g m a t e r i a l s f o r the p r e p a r a t i o n of " g l u t o s e * , Lobry de Bruyn and van Ek e n s t e i n found t h a t the best y i e l d s could be obtained by hea t i n g an aqueous s o l u t i o n of IV w i t h l e a d hydroxide ( 8 ) . The conversion to *gl 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 to y i e l d any t r a c e of I , I I I or IV. H - C I H - C - O H » HO C H Ii H C OH I H C OH . I C H 20H H - C - O H II C - O H I H O - C - H I H - C - O H I H - C - O H I C H 20H I I H-0*° I H O - C - H I H O - C - H I H - C - O H . I H - C - O H I C H 20H I I I C H 20H C=0 I H O - C - H I — H - C - O H I H - C - O H I C H 20H C H 20H I C - O H II H O - C I H - C - O H I H - C - O H I C H 20H C H 20H I H - C - OH I C=0 1 H - C - O H I H - C - O H I C H 20H I V CHpOH 1 . H O - C II H O - C I H - C - O H I H - C - O H - I C H 20H V I CH«OH I. . H O - C - H I -C=0 I H - C - O H I H - C - O H I C H 20H V I I V I I I 'Galtose', another non-fermentable syrup, a l s o thought t o be a 3"hexulose, was prepared i n a s i m i l a r manner from D-galact-ose (9)» Prom the r e s i d u e which remained as a by-product of the commercial p r o d u c t i o n of a l c o h o l from cane molasses by fermentation, up t o s i x percent of a syrup apparently i d e n t i -c a l to *glutose' could be i s o l a t e d (10). Nef (11) questioned the i d e n t i t y of t h i s ' g l u t o s e ' , sug-g e s t i n g that 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 product of D-glucose (1), D-glucosone ( I X ) . IX could not be r e c o n v e r t -ed to hexoses, but would y i e l d organic a c i d s a l t s on f u r t h e r 0— i O H I I H - C - C = C - C - C - C H p O H I I I I I 2 . 0 0 0 H H H H H r IX treatment w i t h base i n the presence of atmospheric oxygen. Nef then prepared another syrup which he termed 'authentic g l u t o s e * , by treatment of I w i t h aqueous calcium hydroxide i n the c o l d w i t h the e x c l u s i o n of a i r . L a t e r , Spoehre and Wilbur (12), i n 19^ 1)., claimed that I and IV were i n t e r c o n v e r t i b l e at 38° i n the presence of d i -sodium a c i d phosphate. Formation of some 'glutose' was r e -ported. None of the products were i s o l a t e d , conclusions being based on reducing power, o p t i c a l r o t a t i o n , a l k a l i n i t y and s u s c e p t i b i l i t y t o fermentation. Benedict, Dakin and West (13), r e p o r t e d a t h i r t y - e i g h t - 6 -percent y i e l d of 'glutose' prepared by shaking a s o l u t i o n of i n v e r t sugar w i t h calcium hydroxide f o r s e v e r a l hours. Wlfch regard to 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 contrast to the other hexoses, was n e i t h e r absorbed nor u t i l i z e d by the human body. Spoehr and S t r a i n (li{.) b e l i e v e d that the 'glutoses' prepared by d i f f e r e n t methods were not 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 to the presence of i m p u r i t i e s which v a r i e d w i t h the method of p r e p a r a t i o n . They found that the reported 'glutose phenylosazone" could be separated i n t o s e v e r a l components by solvent e x t r a c t i o n and that there was no evidence f o r the presence of a 3-hex-u l o s e . Spoehr and S t r a i n then obtained evidence t h a t ' g l u t o s e ' could not be a 3-hexulose. 'Glutose' formed a cyanohydrin (X) which by h y d r o l y s i s and r e d u c t i o n could be converted to 2-methylcaproic 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, since a true 3-keto-hexose H O - C - C s N H - C - C 0 0 H H - C - O - H 1. HOH 2. Ppeailg H - C - H H - C - O - H > H - C - H H - C - O - H H - C - H C H 20H X XI would y i e l d 2 - e t h y l v a l e r i c a c i d ( X I I ) . C H o O H i c -H 0-8 - H I C=0 I H - C - O H i H - C - O H l C H 2 0 H 1 . HON, HOH 2* p r e d , l 2 CH-, H-C-H I H-C-COOH I H-C-H i . H-C-H i CH, VI X I I S'attler and Zerban ( 1 5 » 1 6 ) i n 194-5* i s o l a t e d the u n f e r -mentable reducing substances i n cane molasses and proved them i d e n t i c a l to the h e t e r o l e v u l o s a n ( X I I I ) , probably 1 , 2 -anhydro-D-fructopyranose, and the d i h e t e r o l e v u l o s a n (XIV) reported by P i c t e t and Chavan ( 1 7 ) . The l a t t e r was shown to be a d i f r u c t o s e anhydride by Schulbache and Behre ( 1 8 ) . S a t t l e r and Zerban al s o demonstrated that the »glutosazone* reported by previous workers was i d e n t i c a l to D-glucosazone (XV). HOPC-H I H-C-OH I H-C-OH H-C-. H H C-K=K-H0 6H^ C -N=NHC^Hr^ HO-C-H I H-C-OH I H-C-OH I CH^OH X I I I XV -8-92 H H H 0 0 f l I Ho - c - c - c - c - c : \j-c- C-C-C-Hp 2 . . . ^Q.q' ... tL H H H 0 I I I -O—i I 1 1 0 0 H H H . CH I I I Hp 0 H H H . XIV Evans and coworkers (19), n e v e r t h e l e s s , showed t h a t 2,3" enediols were a c t u a l l y formed I n the course of a r e a c t i o n by i s o l a t i n g formic a c i d ( X V I I ) , l a c t i c a c i d (XXI) and the l a c t -one of D-galacto- ©< -metasaccharinic a c i d (XIX) from an a l k -a l i n e s o l u t i o n of ga l a c t o s e . They p o s t u l a t e d t h a t formic and l a c t i c a c i d s were formed through a i r - o x i d a t i v e cleavage of the double bonds of the 1,2- and 3 , i i - enediols r e s p e c t -i v e l y (XVI}'XX),, w h i l e the la c t o n e was formed, by a s e r i e s of steps, from the 2,3-enediol,(XVIII). H-C-OH II C-OH I HO-C -H I OH-C -H I H-C-OH I CHpOH 0 II HO-C-OH H0-C=0 I HO-C-H I HO-C-H I H-C-OH I CH 20H XVI XVII -9-CHoOH HO-C I I C-OH H-C-OH It I C-OH H-C-H I V - - I HO-C-H HO-C-H I I H-C-OH H-C-OH I I C H 2 0 H CH2OH X V I I I XIX CH 2 0 H H-C-OH I C-OH I) C-OH I H-C-OH CH 2 0 H to] CH, I * H-C-OH I HO-C=0 HO-C=0 I H-C-OH I CBL XX XXI The existence of a 2 , 3 - e n e d i o l gained f u r t h e r support from the f i n d i n g s of Wolfrom and coworkers ( 2 0 ) , who i n 19^-6 obtained evidence that V must have been present i n a glucose s o l u t i o n at pH 10 to 13» Prom the products of e l e c t r o l y t i c r e d u c t i o n of D-glucose I n b a s i c s o l u t i o n they i s o l a t e d D-s o r b i t a l (XXII) the expected product, i n t h i r t y percent y i e l d , but a l s o found 2-desoxy-D-sorbltol (XXV), ( 0 . 3 4/0; D-mannitol (XXIV), ( 2 . 2 7 $ ) ; and 1-desoxy-D-mannitol,(XXIII), ( 0 . 9 5 $ ) ; formed from the 1 , 2 - e n e d i o l s h i f t ( i l , I V ) . -10-D - a l l i t o l ( X X V I I I ) , (0 .5$ y i e l d ) , and an unknown 2-desoxy hexose thought to be 2 - d e s o x y - D - a l l l t o l (XXVII), {0.1$ y i e l d ) , which were al s o i s o l a t e d , c ould have formed only as a r e s u l t of a 2 , 3-enediol s h i f t (V,XXVI). D - t a l i t o l (XXIX), which could a l s o have been formed, was not obtained. H-C-OH CHpOH CHoOH II I . I C-OH 0=0 H-C-OH I I I HO-C-H ^ HO-C-H r,n HO-C-H H-C-OH H-C-OH H-C-OH I I I H-C-OH H-C-OH H-C-OH I I I CH 20H CH 20H CH2OH I I IV X l H l XXII C H , C H o 0 H CHoOH I 3 I \ d HO-C-H HO-C-H H-C-H I | l HO-C-H HO-C-H HO-C-H I I I H-C-OH H-C-OH H-C-OH I I I H-C-OH H-C-OH H-C-OH I I I C H 2 0 H C H 2 0 H C H 2 0 H X X I I I XXIV XXV -11 CHpOH I 2 C-OH II HO-C I H-C-OH I H-C-OH CH 20H CHpOH I C=0 I H-C-OH I . H-C-OH I H- C-OH I CH 20H CH-OH I 2 H-C-OH I H-C-OH I H-C-OH I H-C-OH CHpOH [H] CHpOH I H-C-H I H-C-OH I H-C-OH - I H-C-OH I CHgOH XXVII CH20H I HO-C-H I H-C-OH I H-C-OH I H-C-OH I CH 20H XX V I I l XXIX Only one 3-pentulose has been des c r i b e d i n the l i t e r a -t u r e . A3hwell and Hickman (21) i n 1954- i s o l a t e d from sploen e x t r a c t s a micromolar q u a n t i t y of a compound which they t e n -t a t i v e l y i d e n t i f i e d as erythro - 3-ketopentose (XXXI). They p o s t u l a t e d t h a t ^  the compound was formed from r i b o s e (XXX) through an ene d i o l i n t e r m e d i a t e . •12-H-C CH 20H HO-C-H H-C-OH H-C-OH C=0 H-C-OH H-C-OH XXX XXXI Other compounds r e l a t e d t o the sugars which c o n t a i n the 3-keto group are k o j i c a c i d (XXXII and XXXIII) (22), the as-co r b i c a c i d s (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 the a c t i o n of c e r t a i n mold3 on hex' oses and va r i o u s saccharides. I t s s t r u c t u r e i s tha t of an unsaturated 3-hexulose anhydride. B e e l i k and Purves (26) po s t u l a t e d t h a t the a c i d assumes an open ch a i n s t r u c t u r e (XXXIII) i n b a s i c s o l u t i o n s as a 3-keto-enediol which recy-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 II 9-CH 20H 0 H H XXXII XXXIII L-ascorbic a c i d (XXXIV) (Vitamin C ) , an e n e d i o l , was found to e x i s t I n an e q u i l i b r i u m mixture w i t h a 3-keto-a c i d (XXXV), which was i s o l a t e d only as a hydrazone d e r i v a -- 1 3 -t i v e . The e q u i l i b r i u m mixture i t s e l f was u n s t a b l e , s u f f e r -i n g r a p i d o x i d a t i o n to 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), )-C I II 0 ' J T-n—I 0=C H0-HO-C I H-C-I HO-C-H CH2OH XXXIV 0=C I H-C-OH I C=0 I H-C I HO-C-H I CH2OH XXXV HO-C=0 I HO-C=0 H0-C=0 I H-C -OH I HO-C-H I CH 20H XXXVI 2 , 3-Diketo-D-gluconic a c i d was reported as a product of low temperature o x i d a t i o n of D-glucose w i t h hydrogen per-oxide i n the presence of f e r r o u s sulphate ( 2 £ )• The compound decomposed r e a d i l y on heating y i e l d i n g carbon d i o x i d e , o x a l i c 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-keto-D-gluconic a c i d has a l s o been p o s t u l a t e d t o occur at one stage of the Warburg-Dickens-Harecker b i o l o g i c -a l c y c l e (27)• Wilson and C a l v i n (28) have p o s t u l a t e d the existence of a 3-pentulose as an intermediate i n the b i o l o g -i c a l f i x a t i o n of carbon d i o x i d e . Recently, J.K.N. Jones (29) has reported the p r e p a r a t i o n of 2 - 0-methyl-L-xylo - 3-hexulose (XL) from L - a s c o r b i c a c i d (XXXV). By rearrangement of the 2 - 3-di - 0-methyl ether (XXXVII), of L - ascorbic a c i d , he prepared the methyl g l y c o s i d e of a 3 --34-hexulonie a c i d , I s o l a t e d as the amide. The r e d u c t i o n of the lacto n e of t h i s a c i d (XXXVIII) w i t h l i t h i u m aluminum hydride y i e l d e d a g l y c o s i d e of the 3-hexulose (XXXIX). Upon a c i d h y d r o l y s i s the f r e e sugar (XL) was obtained, a i d was char-a c t e r i z e d as the c r y s t a l l i n e 2 , 5-dlchlorophenylhydrazone. Oxid a t i o n of the 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 formic a c i d and an e s t e r ( X L I ) . Since glycolamide and 2,3-di-0--Methyl-D-glyceronic a c i d amide (XLTI) were obtained through treatment of the e s t e r w i t h methyl Iodide and s i l v e r oxide, f o l l o w e d by a l c o h o l i c ammonia, the s t r u c t u r e of the sugar was confirmed as XL, probably i n the alpha form. Jones a l s o reported that 3-hexuloses as yet u n c h a r a c t e r i z e d , may be obtained from D-arabo-ascorbie a c i d and D-gluco-as-c o r b i c a c i d . 0=C~i CH30-0 I CH3O-C I H-C—' I HO-C -H CH 20H RATC , o=c— I CHoO-C-H * I CH3O-C -O— 1 v. I L'IAIH. -C-0 - 4 J H I 0 HO-C-H I H-C 1 H CH 20H CH,0-C-H 3 1 CH3O-C I H-C -OH I HO-C -H H-C . H XXXVII XXXVIII XXXIX -15-CH9OH I. V CH3O-C-H HO-C I H-C-OH I HO-C-H 0 H - C -H CH 20H CHqO-C-H J I HIO^ o=c-HCOOH H-C-0 I H-C H CHpOH I 1. C H 3 r - f n3io NHo-C=0 N H 2 " f H - C - O C H o I * CHgOCH^ XL XLI X L I I D-MANNITOL PENTANITRATE The n i t r a t i o n of D-mannltol to the h e x a n i t r a t e ( X L I I I ) was f i r s t accomplished i n 181^7 hy Domante and Menard (30). No Products of lower degree of n i t r a t i o n were i s o l a t e d . °2 °2 N N H H 9 9 OpKOHpC — C — C — C C CHoONOp . 6 6 H H N N X L I I I - 1 6 -I t was not u n t i l I86I4. when Tichanowich ( 3 1 ) , i n v e s t i g a t i n g the a c t i o n of anhydrous ammonia on an e t h e r e a l s o l u t i o n of 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 white 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 ether 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 , prepared the same D-mannitol p e n t a n i t r a t e i n good y i e l d by the a c t i o n of c o l d dry p y r i d i n e on the corresponding h e x a n i t r a t e . Wigner ( 3 3 ) a l s o obtained the 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 of D-raannitol. Although the main product of 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 sm a l l q u a n t i t y of the lower n i t r a t e was i s o l a t e d by co n c e n t r a t i o n of the mother l i q u o r s . The s t r u c t u r e of Wigner 1s p e n t a n i t r a t e was not de t e r -mined u n t i l 1952 when Hayward ( 3 4 ) proved that the u n e s t e r i -f i e d hydroxyl was l o c a t e d on the t h i r d (or equivalent f o u r t h ) carbon of the h e x i t o l c h a i n . M e t h y l a t i o n and subsequent de-n i t r a t i o n of 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 period a t e o x i d a t i o n of t h i s compound, r e s u l t -i n g i n the formation of two moles of formaldehyde and one of 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 of the o r i g i n a l f r e e hydroxyl group. Tichanowich*s compound was t h e r e f o r e c o r r e c t l y term-ed D-mannitol-l , 2 , 3 » 5 » 6-pentanitrate (XLIV). -17-CHo0N0 I 2 > 0oN0-C-H 2 HO-C-H H-C CH20 HO-C-H C H o O - C - H CHoO-C-H H-C-ONO_ 1 H-C-OH H-C-ONO-I * CHoOHO H-C—OH XLIV XLV XLVI Recently, E l r i c k , Marana and Pr e c k e l (35) prepared (XLIV) I n seventy percent y i e l d by treatment of the corresponding 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 carbon-ate. DENITRATTON OP NITRIC ACID ESTERS Complete removal of n i t r a t e groups from D-mannitol h e x a n i t r a t e has been accomplished by a l k a l i n e h y d r o l y s i s . Tichanowich (31) found t h a t treatment of the n i t r a t e d com-pound w i t h a l c o h o l i c potassium hydroxide regenerated the parent a l c o h o l , but als o y i e l d e d an anhydride, D-mannitan (1,4-anhydro-D-mannitol). He a l s o observed that the a c t i o n of sodium amalgam on the 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 oxides gave ' n i t r o m a n n i t a n , , -18-apparently a mannitan t e t r a n i t r a t e . D-mannitol could a l s o be regenerated by treatment of the n i t r a t e w i t h the weak base ammonium sulp h i d e . M i l l s (36), regenerated D-mannitol i n undetermined y i e l d by warming the 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 the a c t i o n of » metaphenylenediamine', a n i l i n e , water and f i v e percent s u l -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 n i t -r a t e s . They found that both n i t r a t e and n i t r i t e i o n s were produced, while the a l c o h o l s were completely 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 occurred upon heating the n i t r a t e s w i t h water i n a sealed tube. Removal of the e s t e r groups could be ac-complished by r e f l u x i n g the 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 , but some decomposition of the a l c o h o l r e -s u l t e d . Oldham (37) d e n i t r a t e d carbohydrate 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 parent carbohydrates were recovered from the r e a c t i o n mixtures i n approximately 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 of n i t r a t e e s t e r groups, h i g h pressure hydrogenation of the n i t r a t e s w i t h a palla d i u m c a t a l y s t , was developed by Kuhn (6) who obtained almost q u a n t i t a t i v e y i e l d s of the parent a l c o h o l s . This method was modified by Hayward (3l\.) who obtained low hydro-gen pressures i n a Paicrhydrogenator. Kuhn (38) a l s o proposed - 1 9 -the use of methanolic hydrazine 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 , since the reagent would not reduce carbonyl groups or double bonds. However, i t was found ( 3 9 ) t h a t the use of hydrazine was not s u c c e s s f u l f o r carbohydrate n i t r a t e s because, due to i t s b a s i c c h a r a c t e r , the reagent caused decomposition of the s e n s i t i v e sugars. -20 EXPERIMENTAL S p e c i a l Precautions Due to the ex p l o s i v e nature of the h e x i t o l n i t r a t e s , no more than 3 e v e n grams were handled or st o r e d i n the dry s t a t e . A. MATERIALS D-Mannitol Hexanitrate D-Mannitol was n i t r a t e d by the method of S o k o l o f f (I|.0), i n 82$ y i e l d . The product was r e c r y s t a l l i z e d from aqueous ethanol. M.p. 112-113°C. (uncorr.) tKJ**4-2.9° (C 1.027, Ethanol, 1=1). D-Mannitol 1,2,3,5,6-pentanitrate 1. Method of 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 prepared by the method of M a r s h a l l and Wigner i n 68.5$ y i e l d . 2. Method of 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.) at 22°C. i n a 100 ml. f l a s k f i t t e d w i t h a condenser and a thermometer. Ammonium carbonate (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 acetone (8 m l . ) . W i t h i n f i f t e e n minutes a f t e r the a d d i t i o n of the carbonate, the co l o u r of the s o l u t i o n darkened to a b r i g h t orange. The temperature of the r e a c t i n g mixture rose to - 2 1 -3^ 0C., then f e l l to 25°C. over a p e r i o d of two hours. Rapid e v o l u t i o n of gases from the warm s o l u t i o n was observed. I n i t i a l l y , the gas turned moist l i t m u s paper blue and pos-sessed the c h a r a c t e r i s t i c .odour of ammonia. A f t e r one hour, the gas evolved turned blue l i t m u s r e d , and possessed the .. odour of oxides of n i t r o g e n . The q u a n t i t y of s o l i d m a t e r i a l i n the f l a s k decreased s l o w l y . A f t e r one and one-half hours, a f l o c c u l e n t p r e c i p i t a t e which slowly i n c r e a s e d I n bul k , was observed. E v o l u t i o n of gases continued at decreasing r a t e f o r siixteen hours. When e v o l u t i o n ceased, the s o l u t i o n was evaporated at room temperature and decreased pressure to a volume of 10 ml., causing the se p a r a t i o n of a red o i l y l i q u i d and the p r e c i p i t a t i o n of some s o l i d m a t e r i a l . The mixture was poured i n t o c o l d water (300 m l . ) , causing the se p a r a t i o n of an orange o i l which 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 product was d r i e d to a constant weight of 5 . i f 7 & m » T h e y i e l d a f t e r one r e c r y s t a l l i z a t i o n was ij . , 5 gm. ( 6 7 $ ) . The product was r e c r y s t a l l i z e d to a constant m e l t i n g p o i n t of 8 0 - 8 l°C. A mixed me l t i n g p o i n t w i t h a sample of mannitol p e n t a n i t r a t e prepared by the method of M a r s h a l l and Wigner gave a value of 8 0 - 8 l°C. - ^ 6 . 5 ° (C I.O8I4., E t h a n o l , ^ = 1 ) . Brown(iil) reported f V ] , 4 7 . 7 ° (C if.ij.26). N i t r i c A c i d Red fuming n i t r i c a c i d was obtained from Baker and Adams, s.g. 1 . 5 9 - 1 . 5 0 . - 2 2 -Chromium t r i o x i d e A n a l y t i c a l reagent grade chromium t r i o x i d e was obtained from the B r i t i s h Drug Houses l i m i t e d , London, England. Acetone Acetone was d r i e d by r e f l u x i n g over anhydrous magnesium sulphate, then was d i s t i l l e d from potassium permanganate to remove t r a c e s of r e a d i l y o x i d i z e d i m p u r i t i e s . P y r i d i n e 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 successive ; , p o r t i o n s of Barium oxide. B. ANALYTICAL METHODS Nitrogen Nitrogen was determined by a modified K j e l d a h l method as described by Brown and Purves (Zj.2). Chromium Chromium VT was determined as barium chromate by the method des c r i b e d by Vogel (i | . 3 ) . Chromium I I I was p r e c i p i t a t e d as green chromic hydroxide from 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 molar 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 out, 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 described by Pacsu A d d i t i o n of sodium hydroxide to an acetone s o l -u t i o n of a ketose 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 - 2 3 -colour was discharged 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 diphenylamine reagent f o r n i t r a t e s was prepared as described i n the "Manual of the I d e n t i f i c a t i o n of Organic  Compounds" (lj.5)» R e f r a c t i v e Index The r e f r a c t i v e index was determined i n an Abbe r e f r a c t o -meter connected to 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 constant temperature bath. Readings were taken at 21°C» 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 the method of S o k o l o f f (1|0). The crude y i e l d of the d r i e d white c r y s t a l l i n e product was 0.5>lj.07 gm. (96$). The product was r e c r y s t a l l i z e d from water to a constant m e l t i n g poin t of 1 1 2 - 1 1 3°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 112-113°C. D. INVESTIGATION OP OXIDANTS POR D-MANNITOL-1,2,3,5,6-PENTANITRATE. I . Potassium Permanganate i n Acetone S o l u t i o n 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 lved i n acetone (10 ml.) at room temperature. To 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 added a suspension of potassium perman-g a n a t e ^ . 3 8 gm.) i n acetone (25 m l . ) . The purple colour of the - 2 k -permanganate was discharged a f t e r r e f l u x i n g the s o l u t i o n i n a hot water bath f o r f i f t e e n minutes. A dark brown p r e c i p i t a t e formed. The mixture was cooled i n an i c e bath, 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 white, odourless c r y s t a l l i n e m a t e r i a l ( 0 . 3 5 gm.) melt i n g at 7 8 * 5 - 7 9 . 5 ° 0 . was obtained. Mixed m e l t i n g p o i n t w i t h D-mannitol 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 product ( O . 2 I 4 . 2 gm.) was d i s s o l v e d i n 2 0 $ aqueous ethanol ( 2 5 ml.) and the 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 hours i n a Parr hydrogenator i n the pre-sence of 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.) at an i n i t i a l pressure of 1L1»7 p . s . i . The f i n a l pressure was i f l . I f p . s . i . The c a t a l y s t was removed by f i l t r a t i o n and the s o l u t i o n evap-orated to a pale y e l l o w residue ( 0 . 0 1 9 8 gm.). Theproduct gave negative t e s t s w i t h the diphenylamine reagent, Pacsu's reagent and Pehlings s o l u t i o n . A f t e r one r e c r y s t a l l i x a t i o n , the product melted at 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-mannitol gave 1 6 0 - l 6 5°C. I I . Potassium 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 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 ( 0 . 5 0 gm.) i n anhydrous p y r i d i n e ( 1 0 ml.) at room temperature was added potassium permanganate ( 0 . 3 gm.) d i s s o l v e d i n p y r i d i n e ( 2 0 ml.). The dark purple s o l u t i o n r a p i d l y changed c o l o u r to dark greenish brown. A f t e r t h i r t y minutes the brown s o l u t i o n was poured Into water ( 1 0 0 ml.) and the p y r i d i n e n e u t r a l i z e d 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 . A dark brown residue p r e c i p i t a t e d . - 2 5 -The mixture was f i l t e r e d and the c l e a r c o l o u r l e s s f i l t r a t e was ex t r a c t e d w i t h ether. Evaporation 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 y e l l o w o i l y r e s i d ue ( 0 . 0 5 gm.) having the odour of mould. The dark brown p r e c i p i t a t e from the o x i d a t i o n was a l s o e x t r a c t e d w i t h ether. The e t h e r e a l s o l u t i o n thus obtained was evaporated l e a v i n g a pale cream c r y s t a l l i n e r e s i d ue ( 0 . 3 gm.) M.p. 68 - 7 l T°C 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-ethanol the 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 product(O . 2 6 0 8 gm.) was hydrogenated by the method described 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 hydrogenation product ( 0 . 1 6 3 7 gm.). gave nega-t i v e r e a c t i o n s w i t h the diphenylamine reagent, Pacsu»s reagent and Pehlings s o l u t i o n . The product r e c r y s t a l l i z e d from aqueous ethanol melted at l 6 l - l6 i f°C. A mixed m e l t i n g p o i n t w i t h D-mannitol gave l 6 l - l 6 5 ° C The y e l l o w syrup ( 0 . 0 3 0 gm.) i s o l a t e d from the o x i d a t i o n mixture was hydrogenated by the procedure described i n s e c t i o n D ( I ) . The syruppy hydrogena-t i o n product (0.0134- ) gave negative t e s t s w i t h d i p h e n y l a -mine reagent, Pacsu's reagent and P e h l i n g s s o l u t i o n . I I I . Sodium Blsmuthate i n Acetone S o l u t i o n D-mannitol-l , 2 , 3 » 5 » 6-pentanitrate ( 0 . 5 0 gm.) was d i s s o l -ved i n a mixture of 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 suspension of sodium blsmuthate ( 0 . 5 0 gm.) i n acetone (15 m l . ) . The mixture was allowed t o stand overnight at room temperature, then was f i l t e r e d through a Whatman No. 50 f i l t e r paper. Some white, f i n e l y d i v i d e d - 2 6 -m a t e r i a l s t i l l remained i n suspension. The mixture was evap-orated 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 ether. Evaporation of 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 pale y e l l o w odourless c r y s t a l l i n e compound (0 . 3 7 ) melting at 79 *" 8l°C. A mixed mel t i n g p o i n t w i t h D-mannitol-l,2 , 3 , 5 > 6-penta-n i t r a t e gave 78 - 8l°C. The c r y s t a l l i n e product (0 . 3 1 3 7 gm.) was hydrogenated by the method described i n s e c t i o n D ( I ) . A y e l l o w serai-crys-t a l l i n e s o l i d (0.200ij. gm.) was i s o l a t e d from the r e a c t i o n mixture. The hydrogenation product gave negative t e s t s w i t h diphenylamine reagent and Pacsu's reagent and a d o u b t f u l F e h l i n g ' s t e s 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 from aqueous ethanol the product melted at l 6 l - l63°C. A mixed mel t i n g p o i n t w i t h mannitol gave l 6 l - l 6 3°C. IV. Hydrogen Peroxide i n A c e t i c A c i d D-mannitol-l,2 , 3 » 5 » 6-pentanitrate (0.28 gm.) was d i s s o l -ved i n g l a c i a l a c e t i c a c i d (1 . 5 ml.) at room temperature. To t h i s s o l u t i o n was added a mixture of 30$ hydrogen peroxide ( 1 . 3 ml.) i n g l a c i a l a c e t i c a c i d (2 ml.). A f t e r standing over-n i g h t at room temperature, 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 palladium c h a r c o a l c a t a l y s t to remove the excess peroxide. The c a t a l y s t was then f i l t e r e d out and the s o l u t i o n evaporated to dryness. A white c r y s t a l -l i n e compound (0.028 gm.), having a m e l t i n g p o i n t of 81 -82°C. was obtained. 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 81 - 82°G. - 2 7 -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 Anhydride - Sulp h u r i c A c i d S o l u t i o n A mixture of 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 anhydride (If? ml.) was cooled i n an i c e - s a l t bath. 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 ( 1 . 0 0 gm.) was d i s s o l v e d i n 5 ml. of the a c i d mixture i n a 100 ml. 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. The f l a s k was cooled i n an i c e - s a l t bath. Chromium t r i o x i d e ( 1 . 0 0 gm.) d i s s o l v e d i n the remainder of the a c i d mixture (20 ml.) was added slo w l y through the dropping f u n n e l over a p e r i o d of one hour. On standing overnight I n the r e f r i g e r a t o r , the colour of the r e s u l t i n g o x i d a t i o n mixture changed from dark red t o dark green. The dark green s o l u t i o n was poured i n t o water (300 ml.) and the 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 ether, then w i t h 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. of pale cream c r y s t a l l i n e m a t e r i a l . The sub-stance gave a negative t e s t w i t h diphenylamine reagent and when ashed l e f t a white r e s i d e u which turned r e d l i t m u s paper b l u e . The residue from evaporation of the chloroform e x t r a c t was extracted 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 , then again w i t h carbon t e t r a c h l o r i d e . Evaporation of the ethanol e x t r a c t y i e l d e d 2 6 . 9 mg. of cream coloured c r y s t a l l i n e mater-i a l . Evaporation of the two carbon 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 of brown semi c r y s t a l l i n e r e s i d u e s . The brown syruppy chloroform r e s i d u e , a f t e r e x t r a c t i o n , weighed 39*4- rog* T l l e residue 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 the ethanol 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 V I . 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-Mannitol - 1 , 2 , 3 , 5 , 6-pentanitrate (0.50 gm, ) was d i s s -olved i n a c e t i c a c i d (10 ml.) at room temperature. 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 a c i d (15 ml.) and a c e t i c anhydride (10 m l . ) . The r e s u l t i n g dark orange-red s o l u t i o n slowly changed col o u r to a dark green on standing f o r one and one-half hours at room temperature. This green s o l u t i o n was poured i n t o c o l d water (50 ml.) and s o l i d sodium bicarbonate was added slowly w i t h vigorous s t i r t i n g to n e u t r a l i z e the a c i d . The n e u t r a l s o l u t i o n was ext r a c t e d w i t h ether, which was then d r i e d and evaporated, l e a v i n g a brown o i l y r e s i d u e (0.088 gm.) Analysi3£ Found $N • l i f . 3 , l4«6 Treatment of D-Mannitol - 1 , 2 , 3 , 5 ? 6-pentanitrate w i t h  A c e t i c - A c i d - A c e t i c Anhydride S u l p h u r i c A c i d Mixture D-Mannitol - 1 , 2 , 3 , 5 , 6-pentanitrate (0.20 gm.) was d i s s -olved i n a mixture of c h i l l e d a c e t i c a c i d (1 ml.) s u l p h u r i c a c i d (1 ml.) and a c e t i c anhydride (5 m l . ) . This s o l u t i o n was allowed to s i t i n an i c e - s a l t bath f o r three hours, the temper-ature of the mixture r i s i n g s l o w l y . A f t e r three hours, the s o l u t i o n , s m e l l i n g of oxides of n i t r o g e n was poured i n t o i c e water (50 m l . ) . The white f e a t h e r y c r y s t a l s which p r e c i p i -Ethanol e x t r a c t 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 Second carbon t e t r a c h l o r i d e e x t r a c t Found; $N - 11.5, U.O $N - 9.o5„ 5.9 $N * l4«05, 14.05 -29-t a t e d slowly from the 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 to a constant weight of 0.ll\. gm. The m e l t i n g point 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 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 authentic sample of D-mannitol-hexaacetate was 119«5 - 120.5°C. V I I . 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 d i s s -olved i n anhydrous p y r i d i n e (10 ml.) at room temperature. Chromium t r i o x i d e (0.2 gm.) i n dry p y r i d i n e (15 ml.) was added slowly to the p e n t a n i t r a t e s o l u t i o n . The dark orange o x i d a -t i o n mixture was allowed to stand overnight, then was poured i n t o c o l d water (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 d i l u t e h y d r o c h l o r i c a c i d . A dark brown o i l which separated on a c i d i f i c a t i o n , was e x t r a c t e d i n ether and combined w i t h the ether e x t r a c t s of the aqueous l a y e r . Evaporation 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 pale cream c r y s t a l l i n e residu© (0.27 gm.) M.p. 75 - 77°C. A mixed me l t i n g p o i n t w i t h a sample of D-mannitol-1,2,3,5,6-pentanitrate was 75 -oC 79 * The o x i d a t i o n product (0.2015 gm.) was hydrogenated by the method described i n s e c t i o n D ( l ) . A white c r y s t a l l i n e product (O.IO2I4. gm.) which gave negative t e s t s w i t h dipheny-lamine reagent, pacsu's reagent and F e h l i n g s s o l u t i o n , was obtained. 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 ethanol the product melted at lbl\. - l66°C. A mixed me l t i n g p o i n t w i t h D-mannitol gave I6I4. r-/166°C. - 3 0 -V I I I . Chromium T r i o x i d e i n Acetone S o l u t i o n males a. D-mannitol-l , 2 , 3 , 5*o-pentanitrate (0.50 gm. .00112M.) was d i s s o l v e d i n dry acetone (10 ml.) and a s o l u t i o n of chromium t r i o x i d e (0.2 gm. .002 M.)' i n dry acetone (15 ml.) was added. (Caution: Chromium t r i o x i d e must be added to the acetone slowly. Acetone should not be added to Chromium t r i o x i d e ) . The r e s u l t i n g dark brown s o l u t i o n was allowed to stand overnight at room temperature, then was poured i n t o c o l d water (200 ml.) w i t h the formation of a pale y e l l o w p r e c i p i t a t e . A f t e r f i l t r a t i o n of the mixture, the p r e c i p i t a t e was d i s s o l v e d i n ether and the aqueous f i l t r a t e 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 evaporated to y i e l d a pale pream s e m i - c r y s t a l l i n e residue (0«2|l}-37 gm») M.p. 70 - 80 °C. A mixed melting 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. - 16.3, 16.3 The o x i d a t i o n product O.2985 gm. was hydrogenated by the us u a l method y i e l d i n g O.I867 gm. of a y e l l o w i s h syruppy compound. The hydrogenated product gave negative t e s t s w i t h diphenylamine reagent, Pacsu's reagent and P e h l i n g s s o l u t i o n . b. The previous procedure was repeated using D-mannitol-1 , 2 , 3 , 5 , 6-pentanitrate (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 of 130 ml. acetone. The p r e c i p i t a t e which formed i n t h i s aqueous - 3 1 s o l u t i o n was d r i e d to a constant weight of 3»66IL5 gm. Evaporation of the ether e x t r a c t y i e l d e d a l i g h t brown syrup ( O . I L 5 9 1 gm.). Repeated c r y s t a l l i z a t i o n of the pre-c i p i t a t e y i e l d e d 3»lf660 gm. of a white c r y s t a l l i n e m a t e r i a l m e l t i n g at 80 - 8 l°C. A mixed mel 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 gave 80 - 8 l°C. The mother l i q u o r was combined w i t h the syruppy product. I n attempted r e c r y s t a l l i z a t i o n , the product c o n t i n u a l l y o i l e d out, p a r t i a l l y s o l i d i f y i n g only on standing. Qc]^- +lf3.2° (C 1 . 2 6 6 , Ethanol t £ - \ ) . The compound d i d not reduce Pe h l i n g s s o l u t i o n . A n a l y s i s Pound: $N - 1 6 . 8 , 1 6 . 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 meq. Required: 21L.1L meq» C r . I I I 0 . 0 2 3 6 , 0.021L5 gm. Cr.IV 0 . 0 2 1 8 , 0 . 0 2 3 6 gm. I n f r a red a n a l y s i s showed very 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 to deposit the substance d i r e c t l y on the prism was unsuccess-f u l . The syrup (O.hSbg gm.) was hydrogenated as described i n s e c t i o n D ( I ) . A diphenylamine t e s t of the r e s u l t i n g s o l u -t i o n i n d i c a t e d that n i t r a t e groups were s t i l l present. The s o l u t i o n was f i l t e r e d and returned to the hydrogenator w i t h platinum oxide c a t a l y s t ( 0 . 1 gm.). A f t e r shaking w i t h hydrogen overnight, the s o l u t i o n gave no r e a c t i o n w i t h the - 3 2 -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 . 0 5 3 3 gm.) which d i d not c r y s t a l l i z e on standing. The observed op-t i c a l r o t a t i o n was ( S O ^ O 0 . (C 0 . 5 2 9 , K2°>^= 1)* £ ^ 7 p ' s 1 .4673. The syrup d i d not reduce F e h l i n g s s o l u t i o n nor 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 reagent. c. 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 . 5 0 g m . , .00112 M.) was d i s s o l v e d i n acetone (30 ml.) contained i n a stoppered f l a s k , f i t t e d w i t h a dropping f u n n e l , connected by g l a s s tubing to a pneumatic trough arranged f o r c o l l e c t i n g gas samples over water. To the p e n t a n i t r a t e s o l u t i o n was added slo w l y from the funnel Chromium t r i o x i d e ( 0 . 0 8 8 gm., O.OOO88 M.) i n acetone (10 m l . ) . The s o l u t i o n was allowed to stand at room temperature u n t i l the co l o u r changed to pale green and i n d i c a t e d t h a t most of the hexavalent chromium had been reduced ( l 6 days). No e v o l u t i o n of gas was observed, and the water i n the c o l l e c t i n g tube remain-ed n e u t r a l to l i t m u s . The r e a c t i o n mixture contained a dark greenish-brown p r e c i p i t a t e deposited on the w a l l s of the f l a s k . The c l e a r , p ale green acetone s o l u t i o n was decanted i n t o water (200 ml.) causing the formation of a bulky p r e c i p i t a t e resembling cotton wool. The aqueous mixture was e x t r a c t e d d i r e c t l y w i t h ether and the d r i e d e t h e r e a l e x t r a c t was evaporated to dryness i n a r o t a r y evaporator, l e a v i n g 0 .^083 gm. of orange-brown s o l i d r e s i --33-due. 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 ethanol-carbon t e t r a c h l o r i d e , a white c r y s t a l l i n e product (O.III4.3 gm.) melti n g at 73.5 - 7k»5°C. was obtained. M j 1 - + Ij-9.6 (C I4..82, e t h a n o l ^ = 1). F u r t h e r r e c r y s t a l l i z a t i o n f a i l e d to a l t e r the me l t i n g p o i n t or the o p t i c a l r o t a t i o n . A mixed m e l t i n g p o i n t w i t h D-mannitol-l , 2 , 3 , 5 > 6-pentanitrate gave 71 - 78°G. Reworking of the 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. of product and 0.1539 g^* °£ brown s e m i - c r y s t a l l i n e r e s i d u e . No mannitol p e n t a n i t r a t e was recovered. A n a l y s i s : Found: $N - 19.0, 18. 2, 18.6, 1.8.0 (av. 184) The I n f r a red spectrum of t h i s compound showed the chara c t e r i s t i c peaks f o r n i t r a t e groups, but d i d not show the peak at 3620 cm""-1- f o r the hydroxyl group of mannitol pent a n i t r a t e . There was however a small peak at 3520 cm."l. There was no abso r p t i o n at 174-0 cm.""-1- where the carbonyl s t r e t c h i n g band would appear. I n a blank experiment to determine the a c t i o n of chrom-ium t r i o x i d e i n acetone, there was no apparent e v o l u t i o n of gas, and ether e x t r a c t i o n of the aqueous s o l u t i o n y i e l d e d only 2.8mg. of 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 gas. When the s o l u t i o n was poured i n t o water, p r e c i p i t a t i o n occurred. The pale,creamy-white p r e c i p i t a t e was f i l t e r e d -3k-out and d r i e d to a constant weight of 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 times w i t h ether which was then d r i e d and evaporated. 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. l o t a l crude y i e l d was 0.4-036 gm. ( 1 0 1 $ ) . A f t e r two r e c r y s t a l l i -z a t i o n s the substance melted at 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 -1 1 3°C Hydrogenation of the C r y s t a l l i n e O xidation 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 hydrogenated i n the u s u a l manner. No pressure drop was observed but a f t e r nine hours, a negative diphenylamine t e s t showed the absence of n i t r a t e n i t r o g e n . The hydrogenation mixture 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 the s o l i d s were washed w i t h water. The combined f i l t r a t e and washings were evaporated t o dry-ness below 50°C. bath temperature. 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 standing overnight i n a vacuum d e s i c c a t o r and the crude product melted at 14-0 -1 5 5°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 from aqueous ethanol the m e l t i n g p o i n t was I64. - 165.5°C. A mixed melting p o i n t w i t h authentic D-mannitol was 164- - 1 6 5°C The observed s p e c i f i c r o t a t i o n was foc}^ = t 0 . 0 0 (C . 0 4 - 6 5water } The i n f r a red spectrum of the hydrogenated product c o r r e s -ponded c l o s e l y to that of D-mannitol. TABLE 1 Res u l t s of Oxidations Oxidant I KWnOlj. I I KMnOlj. I I I NaBi03 IV H 2 O 2 V Cr03 VI CrO: V I I GrOr V i l l a CrO 3 b Cr03 c CrOo Solvent Time Acetone 1$ min. P y r i d i n e 30 min. Acetone-Acetic i i i h r s . a c i d A c e t i c A c i d l l i h r s . G l a c i a l A c e t i c a c i d 2 l i h r s . A c e t i c Anhydride Sulphuric A c i d G l a c i a l A c e t i c a c i d " 1-| h r s . A c e t i c anhydride P y r i d i n e Acetone Acetone Acetone l l f h r s . l l i h r s . ll j . h r s . 16 days Mannitol P e n t a n i t r a t e Recovered 70$ 7h%-100% $k% Wo Other Products O i l O i l , l o s s of Nitrogen O i l , l o s s of Nitrogen Syrup, s l i g h t l o s s of n i t r o -gen Syrup, s l i g h t l o s s of n i t r o -gen. White c r y s t a l l i n e compound. - 3 5 -P r e p a r a t i o n of Isomannide (1:4, 3 : 6 - Dianhydromannitol) Isomannide was prepared by the method of Wiggins (46) • D-mannitol (50 gm.) was d i s s o l v e d i n concentrated h y d r o c h l o r i c a c i d (300 ml.) i n a one l i t e r two-necked f l a s k f i t t e d w i t h a gas bubbler and a condenser protected by a d r y i n g tube. Dry hydrogen c h l o r i d e gas was introduced from a c y l i n d e r u n t i l e v o l u t i o n of gas i n d i c a t e d that the s o l u t i o n was s a t u r a t e d . The bubbler was then removed and the s o l u t i o n was r e f l u x e d f o r 72 hours. Hydrogen c h l o r i d e fumes were evolved f o r s e v e r a l hours wh i l e the colour of the s o l u t i o n g r a d u a l l y darkened. The s o l u t i o n was evaporated to a syrup under reduced pressure, water (50 ml.) was added and the s o l u t i o n again evaporated to a syrup. The crude syrup (1|2*5 gm. ) was d i s t i l l e d under vacuum. A c l e a r c o l o u r l e s s f r a c t i o n (10.8 gm. ) was c o l l e c t e d b o i l i n g at 117 - 12£°C. at a pressure of 2 mm. Both f r a c t i o n s c r y s t a l l i z e d on standing overnight. F r a c t i o n one was r e -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 point 85 - 86°C. [ o G , 5 = - 9 1 . 0 ° Wiggins (46) r e p o r t e d M , = * and m.p. 86-87°G.  N i t r a t i o n of Isomannide Isomannide ( 2 . 0 gm.) was d i s s o l v e d i n c o l d red fuming n i t r i c a c i d (20 ml.) i n an i c e bath. To the s o l u t i o n was added s l o w l y , w i t h s t i r r i n g , c o l d concentrated s u l p h u r i c a c i d (4.0 ml.). A f t e r standing f o r f i f t e e n minutes, the sy-ruppy reddish-orange s o l u t i o n was poured i n t o ice-water (500 m l . ) . No p r e c i p i t a t e formed immediately, however f i n e -36-c o l o u r l e s s needles were deposited when the s o l u t i o n was allowed to stand at room temperature f o r two hours. The pro-duct was recovered on a f i l t e n washed w i t h water and d r i e d i n a vacuum d e s i c c a t o r to a constant weight of I.I4. gm. (l|-6$). The melting 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 from carbon-t e t r a c h l o r i d e water was 6I1 - 65.5°C. EK3jfc = f 3 1 9 . 2 ° (G. 1 . 2 1 3 , H 2 0 , = Krantz (1+7) reported a m e l t i n g p o i n t of 6 5 . 5°c Hydrogenation of 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 oxide c a t a l y s t ( o . l gm. ) at an i n i t i a l pressure of 35»4- p . s . i . There was no detectable pressure drop during the r e a c t i o n p e r i o d . A f t e r removal from the hydrogenator, the s o l u t i o n was f i l t -ered and evaporated i n a r o t a r y evaporator to a c l e a r syrup ( 0 . 1 2 7 5 gm.) which d i d not c r y s t a l l i z e on standing i n a vacuum d e s i c c a t o r . C r y s t a l l i z a t i o n occurred immediately when the syrup was seeded w i t h a c r y s t a l of isomannide. A f t e r one r e c r y s t a l l i z a t i o n from e t h a n o l - e t h y l a c e t a t e the m e l t i n g po i n t of the product was 85 - 86°C. The mixed m e l t i n g po i n t w i t h an authentic sample of isomannide was 85 - 8 6 o C » Hydrogenation of Isomannide D i n i t r a t e Isomannide d i n i t r a t e ( 0 . 1 2 1 3 gm. ) was hydrogenated Analyses: Pound: $N Required: - 3 7 -by the procedure given i n S e c t i o n D ( I ) , u s i n g p l a t i n u m oxide c a t a l y s t (0.1 gm.) at an i n i t i a l pressure of 39*5 p . s . i . There was no apparent pressure drop, but at the end of the hydrogenation 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 negative. The s o l u t i o n was f i l t e r e d and evaporated to a c o l o u r l e s s syrup ( 0 . 0 5 0 5 gm.) The syrup c r y s t a l l i z e d a f t e r seeding w i t h a c r y s t a l of isoman-nide. 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- e t h y l acetate the product melted at 85 - 86°C. The mixed mel t i n g p o i n t w i t h isomannide was 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 agents had p r e v i o u s l y been st u d i e d (48). Several of the reagents had been shown to be s p e c i f i c f o r o x i d a t i o n at the ends of the carbon c h a i n , or at the penultimate p o s i t i o n s . However, i n v e s t i g a t i o n has not revealed an oxidant which ac t s s p e c i f i c a l l y on a hydr-o x y l group at the t h i r d p o s i t i o n . I£ i s thus evident that to introduce a carbonyl group at the t h i r d carbon only of a hexi' t o l molecule i t i s necessary to form s u i t a b l e i n e r t d e r i -v a t i v e s of a l l the other hydroxyl groups. B a c t e r i a l o x i d a t i o n was not i n d i c a t e d because i t had been shown that 1:2, 5 t 6 - 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 - 3 8 -possessed an u n s u b s t i t u t e d hydroxyl group at 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) • Oxidation of the same compound w i t h aqueous permangan-ate was a l s o attempted ($0), however the only product i s o l a t e d from the r e a t i o n was the potassium s a l t of 1 :2 - i s o p r o p y l i d -enexyluronic a c i d . This i n d i c a t e d that r e a c t i o n occurred pre-f e r e n t i a l l y at C 5 . 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 able to prepare 1 , 3-dibenzoyldihydro-xyacetone by treatment 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 using 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 prepared an L-sorbosd. d e r i v a t i v e from a D-s o r b i t o l . O xidation of 6 - t o s y l - 1:3* 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 thus appeared to be a s u i t a b l e o x i -dant f o r hydroxyl groups i n s u b s t i t u t e d p o l y o l s . The a c t i o n of chromium t r i o x i d e and other u n s p e c i f i c oxidants; e.g. potassium permanganate, hydrogen peroxide and sodium b i s -muihate were i n v e s t i g a t e d i n various s o l v e n t s . A l k a l i n e solvents were not considered since n i t r a t e groups were known to be hydrolyzed under b a s i c conditions (5)» P y r i d i n e , known to be an organic base which i s cap-able of removing the n i t r a t e e s t e r from p o s i t i o n three of -39-D-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 that i s r e l a t i v e l y s t a b l e to f u r t h e r a t t a c k by p y r i d i n e (lj .1). Thus despite 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 to be a s u i t a b l e s o l v e n t . To provide a c i d c o n d i t i o n s , a c e t i c a c i d -a c e t i c anhydride mixtures, comparatively s t a b l e 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 used as the most convenient n e u t r a l s o l v e n t . Acetone i s known to be s u s c e p t i b l e to 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, at room temperature experiment f a i l e d to i n d i c a t e e v o l u t i o n of gas or the formation of a s i g n i f i -cant q u a n t i t y of polymeric m a t e r i a l , when acetone was allowed to stand i n the presence 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 various o x i -d i z i n g s o l u t i o n s t o D-mannitol-l,2,3,5,6-pentanitrate are summarized i n Table I . Hydrogen peroxide i n a c e t i c a c i d s o l -u t i o n was apparently i n e f f e c t i v e as an oxidant f o r D-mannitol p e n t a n i t r a t e , since the s t a r t i n g m a t e r i a l could be recovered q u a n t i t a t i v e l y . I n a l l the other attempts, i t was noted t h a t some i n t e r a c t i o n had occurred, since the o r i g i n a l p e n t a n i t r a t e could not be recovered 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 used i n a c e t i c a c i d -a c e t i c anhydride mixtures, non c r y s t a l l i n e products were -39a-TABLE I I Nitrogen Contents of Some P o l y o l N i t r a t e s COMPOUND 1 . D-mannitol h e x a n i t r a t e FORMULA 0 2 0 2 N N H H.H 0 0 H • °2N0-C-C-C-C-G-C-0N02 E 6 6 H H. H N N o 2o 2 ^NITROGEN 1 8 J 2 . D-mannitol - 1 , 2 , 3 , 5,6-pentanitrate 3. D-mannitan t e t r a n i t r a t e It. Isomannide d i n i t r a t e 5. Dimer 0 2 0 2 N N H H H 0 0 H * > * I I * 1 7 . 3 $ 02N0-C-C-C-C-C-C-0N02. 11 1 • • < H 0 0 H H H N H 02. N 0 H H2C--0— 1 H H •C-C-C-C-C-ONO' l I I 1 1 c 0 0 H H H N N 15.5$ ° 2 ° 2 3-C . . LvJ H0C-C 2 1 0 N 0 I C-C-H 2 N 0 2 Mannitol p e n t a n i t r a t e 1 O I Mannitol p e n t a n i t r a t e 17 .1 - 4 0 -obtained. K j e l d a h l analyses showed that the n i t r o g e n con-tent was considerably lower than that 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 the corresponding carbonyl d e r i v a t i v e . This could probably be accounted f o r by the formation of ace-t y l a t e d products, as i t was a l s o shown that mannitol penta-n i t r a t e could be converted to mannitol hexaacetate i n an a c e t i c a c i d - a c e t i c anhydride - s u l p h u r i c a c i d mixture. A s i m i l a r solvent mixture had been p r e v i o u s l y pro-posed by Wolfrom (54) ^ o r a c e t y l a t i v e d e n i t r a t i o n . I n most other cases the 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 mannitol p e n t a n i t r a t e . Only w i t h the use of 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 mixture was a product obtained which lowered the mel t i n g p o i n t of the o r i g i n a l p e n t a n i t r a t e . Treatment of mannitol p e n t a n i t r a t e w i t h 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 short p e r i o d of time y i e l d e d a small q u a n t i t y of s e m i - c r y s t a l l i n e m a t e r i a l ; 55$ of the p e n t a n i t r a t e was recovered unchanged. Chromium VI was present i n excess of that r e q u i r e d by the r e a c t i o n 3 ^CHOH + 2 CrC-3 3 ^ C - 0 + -CrgO^ 3 H2©» More chromium (52$) was reduced to the t r i v a l e n t s t a t e than was accounted f o r by the o x i d a t i o n of the non-recovered p e n t a n i t r a t e to a hexulose d e r i v a t i v e . D e t e c t i o n of n i t r o g e n i n the aqueous s o l u t i o n suggested that a p o r t i o n of the p e n t a n i t r a t e was decomposed to water s o l u b l e products. Since mannitol h e x a n i t r a t e could be recovered unchanged from treatment i n a s i m i l a r o x i d a t i o n medium, i t seemed -1*1-t h a t a t t a c k on the p e n t a n i t r a t e molecule o c c u r r e d f i r s t at the s i t e of the f r e e h y d r o x l group. The N i t r o g e n content of the syruppy product was lower than t h a t r e q u i r e d f o r the d e s i r e d hexulose. The i n f r a r e d s p e c t r a , which was admit-t e d l y poor, showed no t r a c e of a b s o r p t i o n at or near 174-0 cm"-'-, the c h a r a c t e r i s t i c c a r b o n y l s t r e t c h i n g frequency. D e n i t r a t i o n of the m a t e r i a l y i e l d e d a syrup which gave a ne g a t i v e t e s t w i t h Pacsu's reagent and d i d not reduce Peh-l i n g s s o l u t i o n . The treatment of mannitol p e n t a n i t r a t e w i t h the chromium t r i o x i d e acetone mixture f o r s i x t e e n days p r o -duced q u i t e d i f f e r e n t r e s u l t s . A white c r y s t a l l i n e com-pound was obtained, the n i t r o g e n content of which, as determined by the K j e l d a h l method was h i g h e r than t h a t of the d e s i r e d hexulose and of the s t a r t i n g m a t e r i a l . The compound showed no i n f r a - r e d a b s o r p t i o n at or near I7I1O cm"-1-, i n d i c a t i n g t h a t i t was not a ca r b o n y l d e r i -v a t i v e . The spectrum a l s o showed d i f f e r e n c e s from those of the m a n n i t o l penta-and h e x a n i t r a t e s and from i s o -mannide d i n i t r a t e . Hydrogenation of the compound y i e l d e d a c r y -s t a l l i n e product a p p a r e n t l y i d e n t i c a l to D-mannitol, t h e r e f o r e the m a t e r i a l i s o l a t e d from the r e a c t i o n mixture c o u l d not have r e s u l t e d from c h a i n d e g r a d a t i o n of man-n i t o l p e n t a n i t r a t e . M a n n i t o l h e x a n i t r a t e (see T a b l e I I ) c o n t a i n s a percentage of n i t r o g e n agreeing w i t h t h a t found e x p e r i -m e n t a l l y f o r the c r y s t a l l i n e o x i d a t i o n product, however, s i n c e the 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 are s u b s t a n t i a l l y d i f f e r e n t , i t i s d o u b t f u l t h a t the compound i s mannitol h e x a n i t r a t e . S i n c e chromium t r i o x i d e i s a dehydrating agent as w e l l as an oxidant, i t was c o n s i d e r e d p o s s i b l e t h a t an-h y d r i d e f o r m a t i o n c o u l d occur to g i v e manniton t e t r a n i -t r a t e or isomannide d i n i t r a t e . Tichanowich (31) o b t a i n e d some mannitan t e t r a n i t r a t e from treatment of mannitol p e n t a n i t r a t e w i t h anhydrous;ammonia,although manniton was not prepared, isomannide was s y n t h e s i z e d (ii|) and n i t -r a t e d . The u n u s u a l l y h i g h o p t i c a l r o t a t i o n of isomannide d i n i t r a t e i s r e p o r t e d f o r the f i r s t time i n t h i s work. Although the p r e p a r a t i o n of the compound had been r e p o r t e d i n the l i t e r a t u r e ( 1 + $ ) , the p h y s i c a l constants quoted were l i m i t e d t o the m e l t i n g p o i n t and s o l u b i l i t y . The i n f r a -r e d spectrum of isomannaide d i n i t r a t e showed a b s o r p t i o n at 1030 c m . p r o b a b l y due to the presence of the s t r a i n e d c y c l i c e ther l i n k a g e (55) • T h i s peak was not p r e s e n t i n the spectrum of the unknown. A s i m i l a r peak, probably near 1076 cm""'" from the t e t r a h y d r o f u r a n s t r u c t u r e would be expected i n mannitan t e t r a n i t r a t e . The unknown showed no a b s o r p t i o n I n t h i s r e g i o n . I t was a l o s determined t h a t -43-treatment 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 to those used i n hydrogenation of the unknown y i e l d -ed only isomannide i n both cases.. Since the ether l i n k a g e was preserved i n these compounds, i t i s d o u b t f u l that hydro-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 . I t i s t h e r e f o r e considered improbable t h a t the compound i s an i n t r a m o l e c u l a r anhydride. Though the n i t r o g e n a n a l y s i s f a i l s to confirm the p o s t u l a t e , the p o s s i b i l i t y of formation of an i n t e r m o l e -c u l a r anhydride, combining two molecules of p e n t a n i t r a t e j o i n e d through an ether l i n k a g e at the three p o s i t i o n s , would not be incompatible w i t h other dataobtained. Such a compound might conceivably y i e l d mannitol I n hydrogena-t i o n . 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 conversion of mannitol penta-n i t r a t e i n t o a d i f f e r e n t molecular form. A s t r u c t u r e having more i n t e r n a l hydrogen bonding would have a lower m e l t i n g p o i n t and the s p e c t r a l bands could e x h i b i t s l i g h t s h i f t s . 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 . B I B L I O G R A P H Y 1 . Fenton, H. and Jackson, H. J. Chem. Soc. 7 5 : 1 . l 8 9 9 2 . G l a t t f e l d , J . and Gershan, S. J. Am. Chem. Soc. 6 0 : 2 0 1 3 . 1938 3 . Bertrand, C. Compt. rend. 1 2 6 : 7 6 2 . I 8 9 8 4 . Hunter, J . Iowa State C o l l . J . S c i . 1 5 : 7 8 . 1940 C.A. 3 5 : 5 4 % . 1941 5 . Vignon, L. and B<&y, I . Compt. rend. 1 3 5 : 5 0 7 . 1902 6 . Kuhn, L.P. J r . Am. Chem. Soc. 6 8 : 1 7 6 l . 194& 7. Lobry de Bruyn, C.A. and Van Ekenstein, A. Rec. t r a v . chim. l i j . : 2 0 3 . I896 ' 8 . Lobry de Bruyn, C.A. and Van Ekenstein, A. Rec. t r a v . chim. l 6 : 2 7 4 » ^ 8 9 7 9 . Lobry de Bruyn, C.A. and Van Ekenstein, A. Rec. t r a v . chim. 1 6 : 2 6 2 . I 8 9 7 1 0 . Lobry de Bruyn, C.A. and Van Ekens t e i n , A. Rec. t r a v . chim. 1 6 : 2 5 7 • 1897 1 1 . Nef, J.U. Ann. 4 0 3 : 2 0 4 . 1 9 1 4 1 2 . Spoehr, H.A. and Wilbur, R.C.-J . B i o l . Chem. 6 9 : 2 i f l . I 9 2 6 1 3 . Benedict, E . M . , Dakin, H.D. and West,. R. J. B i o l . Chem. 6 8 : 1 . I 9 2 6 l i j . . Spoehr, H.A. and S t r a i n , H.H. J. B i o l . Chem. 8 5 : 3 6 5 . 1 9 2 9 - 3 0 15« S a t t l e r , L. and Zerban, F.W. Ind. Eng. Chem. 3 7 : H 3 3 . 1945 1 6 . S a t t l e r , L. i n Advances i n Carbohydrate Chemistry 3:113. W 1 7 . P i c t e t , A. and Chavan, J . Helv. Chim Acto. 9 : 8 0 9 . I 9 2 6 -45-1 8 . Schulbach, H.H. and Behre, C. . Ann. 5 0 8 : 1 6 . 1933 19. Evans, W.L., Edgar, R.F. and Hoff, G.P. J. Am. Chem. Soc. 4 8 : 2 6 6 5 . 1926 2 0 . Wolfrom, M.L. e t . a l . J . Am. Chem. 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