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UBC Theses and Dissertations

The action of pyridine on dulcitol hexanitrite McKeown, George Gordon 1952

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THE ACTION OP PYRIDINE ON DULCITOL HEXANITRATE by GEORGE GORDON MCKEQWN A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE In the Department of CHEMISTRY We accept t h i s t h e s i s as conforming to the standard r e q u i r e d from candidates f o r the degree of MASTER OF SCIENCE. Members o f the Department o f Chemistry T H E UNIVERSITY OP BRITISH COLUMBIA September, 1952. ABSTRACT D u l c i t o l h e x a n i t r a t e was prepared In 90% y i e l d by n i t r a t i n g d u l c i t o l w i t h n i t r i c and s u l p h u r i c a c i d . The o p t i c a l l y i n a c t i v e h e x a n i t r a t e c r y s t a l l i z e d from ethanol and water to give f i n e , c o l o r l e s s needles m e l t i n g a t 98-99°C. When the pure d u l c i t o l h e x a n i t r a t e was d i s s o l v e d i n anhydrous p y r i d i n e , an exothermic r e a c t i o n o c c u r r e d w i t h the e v o l u t i o n of a gas. On d i l u t i o n of the s o l u t i o n w i t h water, a c r y s t a l l i n e d u l c i t o l p e n t a n i t r a t e separated i n 65% y i e l d . The p e n t a n i t r a t e was r e -c r y s t a l l i z e d from ethanol and water as f i n e , c o l o r -l e s s n e e d l e s , which melted at 85-86°C; i t was o p t i c a l l y i n a c t i v e and d i d not reduce F e h l i n g ' s s o l u t i o n . The p e n t a n i t r a t e was methylated w i t h s i l v e r oxide and methyl i o d i d e , and then reduced with hydrogen over p a l l a d i z e d c h a r c o a l t o give an o p t i c a l l y i n a c t i v e monomethyl d u l c i t o l . T h i s product c r y s t a l l i z e d from e t h a n o l as heavy, c o l o r l e s s c r y s t a l s which melted at 149-150°C. P e r i o d a t e o x i d a t i o n of the monomethyl d u l c i t o l i n d i c a t e d t h a t i t was a racemic mixture of 3- and 4-methyl D - d u l c i t o l ( D - g a l a c t i t o l ) • Hence the a c t i o n of p y r i d i n e s e l e c t i v e l y removed a n i t r i c a c i d e s t e r group from the 3-(or c h e m i c a l l y e q u i v a l e n t 4-) p o s i t i o n i n the D - d u l c i t o l h e x a n i t r a t e molecule l e a v i n g a hydroxyl group. ACKNOWLEDGEMENTS The w r i t e r wishes to express h i s s i n c e r e thanks t o Dr. L.D. Hayward f o r h i s ready encouragement and sound advi c e i n the d i r e c t i o n o f t h i s i n v e s t i g a t i o n . G r a t e f u l acknowledgements are a l s o made to the Standard O i l Company o f B.C. f o r the award o f a f e l l o w s h i p , t o the N a t i o n a l Research C o u n c i l o f Canada f o r a summer grant, and to the Department of Veterans A f f a i r s . TABLE OP CONTENTS _____ GENERAL INTRODUCTION 1 HISTORICAL INTRODUCTION 2 DISCUSSION OP RESULTS 9 A. D u l c i t o l H e x a n i t r a t e 9 B. D u l c i t o l P e n t a n i t r a t e 9 C. Monomethyl D u l c i t o l P e n t a n i t r a t e 12 D. Monomethyl D u l c i t o l 13 EXPERIMENTAL 19 S p e c i a l P r e c a u t i o n s 19 A. M a t e r i a l s 19 N i t r i c A c i d 19 P y r i d i n e 19 D u l c i t o l 19 P a l l a d i z e d Charcoal C a t a l y s t 19 Sodium Metaperiodate 20 Diphenyiamine Reagent 20 S i l v e r Oxide 20 B. A n a l y t i c a l Methods 21 N i t r o g e n 21 Methoxyl 21 Oxid a t i o n s with P e r i o d a t e 21 C. D u l c i t o l H e x a n i t r a t e 23 P r e p a r a t i o n of D u l c i t o l H e x a n i t r a t e 23 Hydrogenolysis of D u l c i t o l H e x a n i t r a t e 24 TABLE OF CONTENTS (continued) Page D. D u l c i t o l P e n t a n i t r a t e 24 D e n i t r a t i o n of D u l c i t o l H e x a n i t r a t e 24 Hydrogenolysis of D u l c i t o l P e n t a n i t r a t e 26 M e t h y l a t i o n of D u l c i t o l P e n t a n i t r a t e 26 E. Monomethyl D u l c i t o l 27 Hydrogenolysis of Methyl D u l c i t o l P e n t a n i t r a t e 27 N i t r a t i o n of Monomethyl D u l c i t o l 28 Pe r i o d a t e O x i d a t i o n of Monomethyl D u l c i t o l 29 BIBLIOGRAPHY 31 GENERAL INTRODUCTION I t has l o n g been known t h a t D-mannitol h e x a n i t r a t e i s u n s t a b l e to p y r i d i n e and other bases. Prom the a c t i o n of p y r i d i n e on D-mannitol h e x a n i t r a t e , a product had been i s o l a t e d i n good y i e l d which a n a l y s i s had i n d i c a t e d t o be a D-mannitol p e n t a n i t r a t e . D u l c i t o l h e x a n i t r a t e had a l s o been t r e a t e d w i t h p y r i d i n e t o y i e l d a product b e l i e v e d t o be a d u l c i t o l p e n t a n i t r a t e . I n 1950, L.D. Hayward undertook t o determine the p o s i t i o n of the uns t a b l e n i t r a t e group i n the D-mannitol compound. He showed c o n c l u s i v e l y t h a t a n i t r a t e group was s e l e c t i v e l y removed from the 4 - p o s i t i o n (or 3- which i s I d e n t i c a l c h e m i c a l l y and o p t i c a l l y ) p r o d u c i n g 1,2,3,5,6, D-mannitol p e n t a n i t r a t e . The p r e s e n t work i s a s i m i l a r study on the op-t i c a l l y i n a c t i v e d u l c i t o l compound ( d u l c i t o l has a meso s t r u c t u r e and may be designated as D- or L-d u l c i t o l or g a l a c t i t o l ) . One might a n t i c i p a t e t h a t the c h e m i c a l l y e q u i v a l e n t 3- and 4 - p o s i t i o n s would be a t t a c k e d . However, i f such was the case, the two products would not be i d e n t i c a l , but would be o p t i c a l isomers. That i s , the product would be a racemic mixture of 1,2,3,5,6, D - d u l c i t o l p e n t a n i t r a t e and 1,2,3,5,6, L - d u l c i t o l p e n t a n i t r a t e . HISTORICAL INTRODUCTION In r e c e n t y e a r s , c o n s i d e r a b l e study has been made orf the s e l e c t i v e removal of n i t r i c a c i d e s t e r groups from carbohydrate molecules. Apart from the i n t r i n s i c i n t e r e s t , s e l e c t i v e d e n i t r a t i o n c o u l d be of great value i n s y n t h e s i s work r e q u i r i n g s p e c i f i c s u b s t i t u t i o n . N i t r a t e e s t e r groups have many q u a l i t i e s o f a good b l o c k i n g agent - i n t r o d u c t i o n Is r e l a t i v e l y easy, u s u a l l y by d i r e c t n i t r a t i o n , complete removal i s q u a n t i t a t i v e by a Kuhn h y d r o g e n a t i o n 1 and no wandering of the groups has 2 ever been r e p o r t e d . D e n i t r a t i o n f i r s t appeared as the u n d e s i r a b l e slow decomposition of guncotton. Guncotton, when s t o r e d f o r extended p e r i o d s , became very s e n s i t i v e to shock and, Indeed, detonated spontaneously. T e c h n i c a l l y , the problem was s o l v e d by Abel's process of d i s t i n t e g r a t i n g the n i t r a t e d f i b r e on H o l l a n d e r machines and washing thoroughly w i t h warm water. In" 1911, W a l t e r 4 i n v e s t i g a t e d the a c t i o n o f weak org a n i c bases on guncotton. D i m e t h y l a n i l i n e , phenylhy-d r a z i n e , o- and p - t o l u i d i n e and naphthylamine were employed. 5 ' Becker and Hunold r e p o r t e d d e g r a d a t i o n of guncotton by 6 7 diphenylamine. A n g e l i and l a t e r G i a n n i n i s t u d i e d the decomposition of guncotton by p y r i d i n e at room temperature. A n a l y s i s of the carbohydrate products showed d e g r a d a t i o n and o x i d a t i o n b u t o n l y a s m a l l d e g r e e o f d e n i t r a t i o n . 8 I n 1944, G l a d d i n g and P u r v e s f o u n d t h a t p u r e , d r y p y r i d i n e c a u s e d a v i g o r o u s d e c o m p o s i t i o n o f d i s s o l v e d , s t a b i l i z e d gunco.tton a t steam b a t h t e m p e r a t u r e . N i t r o g e n d i o x i d e was e v o l v e d as a v o l a t i l e p y r i d i n e complex t h a t r e a d i l y c r y s t a l l i z e d above t h e s o l u t i o n on c o o l i n g . S e g a l l , 9 i n 1946, was i n t e r e s t e d i n t h e r e l a t i v e r e a c t i v i t y o f t h e n i t r a t e g r o u p s i n c e l l u l o s e t r i n i t r a t e and s t u d i e d i t s b e h a v i o r when t r e a t e d w i t h p y r i d i n e i n t h e p r e s e n c e o f h y d r o x y l a m i n e , methoxyamine, and t h e i r c o r r e s p o n d i n g h y d r o c h l o r i d e s . P y r i d i n e w i t h e x c e s s h y d r o x y l a m i n e a t t a c k e d c e l l u l o s e t r i n i t r a t e a t room t e m p e r a t u r e l i b e r a t i n g one mole o f n i t r o g e n p e r g l u c o s e r e s i d u e . The p r o d u c t o b t a i n e d i n 98$ y i e l d , was a p p r o x i m a t e l y a d i n i t r a t e . The n i t r a t e g r o u p s a t t a c k e d were shown t o be s e c o n d a r y i n n a t u r e . T h i s c e l l u l o s e d i n i t r a t e was t h e f i r s t c e l l u l o s e n i t r a t e r e p o r t e d a s b e i n g s t a b l e i n p y r i d i n e and S e g a l l s u g g e s t e d t h a t t h e i n s t a b i l i t y o f c e l l u l o s e t r i n i t r a t e was due t o a s p e c i f i c n i t r a t e g r o u p . i n a d e f i n i t e p o s i t i o n i n t h e g l u c o s e r e s i d u e . A t t e m p t s t o l o c a t e t h e p o s i t i o n o f t h i s g r o u p were un-s u c c e s s f u l . Methoxyamine i n p y r i d i n e y i e l d e d t h e same d i n i t r a t e b u t t h e r e was no n o t i c e a b l e y i e l d o f n i t r o g e n . S e g a l l e x p l a i n e d t h i s on t h e b a s i s o f t h e weaker r e d u c i n g a c t i o n o f methoxyamine. S e g a l l a l s o t r e a t e d c e l l u l o s e t r i n i t r a t e w i t h e x c e s s h y d r o x y l a m i n e h y d r o c h l o r i d e i n p y r i d i n e . The gas _ 4 -l i b e r a t e d contained 85$ n i t r o u s o x i d e , the remainder b e i n g n i t r o g e n . The product o b t a i n e d i n 85$ y i e l d approx-imated a ketoxime d i n i t r a t e . I n 1949, L.D. Hayward 1 0 i n v e s t i g a t e d the a c t i o n of hydroxylamine i n p y r i d i n e on methyl -^-D-glucopyranoside t e t r a n i t r a t e t o see i f any l i g h t might be shed on S e g a l l ' s r e s u l t s w i t h c e l l u l o s e t r i n i t r a t e . Hayward found t h a t a s i m i l a r d e n i t r a t i o n proceeded v i g o r o u s l y , with the e v o l u t i o n of 1.26 moles of pure n i t r o g e n . The r e a c t i o n was h a l t e d a f t e r s e v e r a l hours by p o u r i n g the mixture i n t o water. E t h e r e x t r a c t i o n y i e l d e d a s i r u p i n 80% y i e l d which was shown to c o n t a i n methyl -fl -D-glucopyranoside -2,3,6 -t r i n i t r a t e (53$), methyl -D-glucopyranoside - 3,6 -d i n i t r a t e (33$) and u n i d e n t i f i e d methyl - 4-D-glucoside t r i n i t r a t e (14$). S i n c e 70$ of the n i t r a t e groups were removed from the 4 - p o s i t i o n , t h i s r e s e a r c h d i d not d i r e c t l y e x p l a i n the r e a c t i o n s o f c e l l u l o s e t r i n i t r a t e i n which the 4 - p o s i t i o n i s not a v a i l a b l e . C.S. R o o n e y 1 1 f o l l o w e d up the work of Hayward by t r e a t i n g methyl y S-D-glucopyranoside t e t r a n i t r a t e w i t h hydroxylamine h y d r o c h l o r i d e i n p y r i d i n e . A slow r e a c t i o n occurred with e v o l u t i o n of a gas composed of 70$ n i t r o u s oxide and 30$ n i t r o g e n . The carbohydrate products c o n s i s t e d of a complex mixture of p a r t i a l l y n i t r a t e d m e t h y l g l u c o s i d e s and completely d e n i t r a t e d polyoxime p r o d u c t s . Methyly$-D-glucopyranoside - 2 , 3 , 6 - t r i n i t r a t e and a substance b e l i e v e d - 5 -t o be methyl T ^ - D - g l u c o p y r a n o s i d e - 2 , 6 - d i n i t r a t e were i s o l a t e d , 12 E.P. Swan has shown t h a t methyl-#-D-glucopy-r a n o s i d e t e t r a n i t r a t e i s acted upon by q u i n o l i n e at 50°C with the e v o l u t i o n of a gas. A n g e l i s t u d i e d the d e n i t r a t i o n of methyl and e t h y l n i t r a t e with hydroxylamine. The corresponding a l c o h o l s were formed. 14 Ryan and Casey s t u d i e d the a c t i o n of primary, secondary and t e r t i a r y amines on v a r i o u s organic n i t r a t e e s t e r s . No analyses of the carbohydrate products were attempted. D i m e t h y l a n i l i n e r e a c t e d with mannitol h e x a n i t r a t e , a t an e l e v a t e d temperature t o evolve a gas c o n s i s t i n g of 70$ n i t r o u s oxide and 30$ n i t r o g e n . The study of p a r t i a l d e n i t r a t i o n of the n i t r i c a c i d e s t e r s of sugar a l c o h o l s began i n 1863, when 15 Ti c h a n o w l t s c h Passed dry ammonia gas through an e t h e r e a l s o l u t i o n of D-mannitol h e x a n i t r a t e ( I I ) . A dark, v i s c o u s l a y e r separated and n i t r o g e n was e v o l v e d . The supernatant l i q u i d y i e l d e d a s o l i d which proved to be a D-mannitol p e n t a n i t r a t e , together with a s i r u p y substance which appeared to be an anhydromannitol t e t r a n i t r a t e . The dark, v i s c o u s l a y e r y i e l d e d a product which appeared to be an anhydromannitol tetraamine. In 1903, W i g n e r 1 6 t r e a t e d mannitol h e x a n i t r a t e w i t h a l c o h o l i c p y r i d i n e , to o b t a i n a mannitol p e n t a n i t r a t e i n 80-90$ y i e l d s i m i l a r to t h a t obtained by T i c h a n o w l t s c h . No lower n i t r a t e s or amines were found. - 6 -WIgner showed that the p e n t a n i t r a t e d i d not reduce 17 F e h l i n g ' s s o l u t i o n as r e p o r t e d by e a r l i e r workers. N i t r a t i o n of mannitol by n i t r i c and s u l p h u r i c a c i d gave a small amount of p e n t a n i t r a t e along w i t h the h e x a n i t r a t e . 18 L.D. Hayward, i n 1950, s t u d i e d the d e n i t r a t i o n of mannitol h e x a n i t r a t e w i t h the o b j e c t of l o c a t i n g the p o s i t i o n of the u n s t a b l e n i t r a t e group. D-mannitol(I) was n i t r a t e d w i t h fuming n i t r i c a c i d and con c e n t r a t e d s u l p h u r i c a c i d t o produce D-mannitol h e x a n i t r a t e ( I I ) . The pure, dry h e x a n i t r a t e was d i s s o l v e d i n anhydrous p y r i d i n e at room temperature. The c o l o r l e s s s o l u t i o n soon turned t o a c l e a r , r e d c o l o r and a gas was ev o l v e d . E x t e r n a l c o o l i n g was necessary t o r e s t r a i n the r e a c t i o n . A f t e r s t a n d i n g s e v e r a l hours, the s o l u t i o n was poured i n t o c o l d water. A s i r u p p r e c i p i t a t e d which immediately c r y s t a l l i z e d i n t o the c o l o r l e s s D-mannitol p e n t a n i t r a t e ( I I I ) I n 73$ y i e l d . The p e n t a n i t r a t e was shown to be s t a b l e to f u r t h e r d e n i t r a t i o n by p y r i d i n e a t room temperature. Hayward methylated the p e n t a n i t r a t e w i t h s i l v e r oxide and methyl i o d i d e t o o b t a i n methyl-D-mannitol p e n t a n i -t r a t e ( I V ) . T h i s product was hydrogenated with hydrogen over p a l l a d i z e d c h a r c o a l t o g i v e the known 4-methyl-D-m a n n i t o l ( V ) . P e r i o d a t e o x i d a t i o n confirmed the p o s i t i o n of the methyl group. Hayward thus proved t h a t the 4 - p o s i t i o n n i t r a t e group(or 3, which i s i d e n t i c a l ) i s removed by the a c t i o n of p y r i d i n e t o leav e a hydroxyl group. 7 -CRgOH HO-C-H I HO-ChH I H-C-OH I H-C-OH I CHgOH I mo-. H2S04 CHg0N02 0 2 N O - C - H I O p N O - C - H * I H - C - 0 N 0 2 " H - C - O N O p I d CH20N<)2 I I p y r i d i n e \ CH 20N0 2 02N0-C-H I 02N0-C-H I H-C-OH I H-C-ONOo, I 2 CH2ONO2 II I CH3I, " A g i o ' J 2 . Pd C H p O H I 2 H o e e - H 1 H O - C - H . I H-C-0CH3 I H - C - O H I C H 2 0 H CH20N02 02N0-C-H I OpNO-C-H H-C-OCH3 H-C-0NO2 l CH 20N0 2 IV V 19 J.R. Brown, at pre s e n t , i s I n v e s t i g a t i n g the gases formed i n the mannitol h e x a n i t r a t e r e a c t i o n and the products found i n the f i l t r a t e from the p e n t a n i t r a t e s e p a r a t i o n . 16 WIgner a l s o n i t r a t e d d u l c i t o l ( V I ) t o o b t a i n d u l c i t o l h e x a n i t r a t e ( V I I ) . He found t h a t a l c o h o l i c p y r i d i n e had almost no e f f e c t on the h e x a n i t r a t e even a t the b o i l i n g p o i n t . Upon warming a s o l u t i o n of the h e x a n i t r a t e i n pure p y r i d i n e , however, a r e a c t i o n o c c u r r e d w i t h - 8 -the e v o l u t i o n o f a gas;. A product was obt a i n e d which a n a l y s i s i n d i c a t e d to be a p e n t a n i t r a t e . Wigner r e c r y -s t a l l i z e d t h i s product three times from a l c o h o l and water to o b t a i n c o l o r l e s s needle c r y s t a l s which " s i n t e r e d about 71° and melted at about 75°G." CH 20H CHgONOg H-G-OH H-C-ONO„ I i a HO-C-H OgNG-C-H D u l c i t o l I HNO,^ I p y r i d i n e HO-C-H HgSO^ OgNO-C-H " P e n t a n i t r a t e H-C-OH H-C-0N0« i i . d CHgOH CHgONOj VI VII No work on d u l c i t o l p e n t a n i t r a t e other than that of Wigner i s r e p o r t e d i n the l i t e r a t u r e DISCUSSION OP RESULTS A. D u l c i t o l h e x a n i t r a t e D u l o i t o l was n i t r a t e d w i t h a n i t r i c and s u l p h u r i c a c i d mixture. The product was p u r i f i e d by repeated r e c r y s t a l l i z a t i o n s from aqueous a l c o h o l to g i v e f i n e , c o l o r l e s s , n e e d l e l i k e c r y s t a l s which melted a t 98-99°C. ( W i g n e r 1 6 prepared the h e x a n i t r a t e and r e p o r t e d i t s m e l t i n g p o i n t at "about 95°C".) N i t r a t e e s t e r a n a l y s i s gave the c o r r e c t value f o r a h e x a n i t r a t e . Hydrogenolysis of a sample of the h e x a n i t r a t e produced d u l c i t o l q u a n t i t -a t i v e l y , thus p r o v i n g t h a t the n i t r a t i o n caused no con-f i g u r a t i o n a l change. The h e x a n i t r a t e was found to be o p t i c a l l y i n a c t i v e . A zero value was to be expected as d u l c i t o l has a meso s t r u c t u r e . The y i e l d of d u l c i t o l h e x a n i t r a t e from d u l c i t o l v a r i e d from 70-92$. B. D u l c i t o l p e n t a n i t r a t e In a p r e l i m i n a r y experiment, p y r i d i n e was found to a c t very s l o w l y on d u l c i t o l h e x a n i t r a t e at room temperature. At 50°C, however, the r e a c t i o n was q u i t e vigorous - a l l subsequent d e n i t r a t i o n s were conducted at t h i s temperature. The p u r i t y of the p y r i d i n e a l s o had a marked e f f e c t on the r e a c t i o n . P y r i d i n e from a f r e s h l y opened b o t t l e was n o t i c e a b l y more a c t i v e . The pure, dry h e x a n i t r a t e d i s s o l v e d immediately i n anhydrous p y r i d i n e to give a c l e a r , c o l o r l e s s s o l u t i o n . - 10 -An exothermic r e a c t i o n o c c u r r e d which d i s c o l o r e d the s o l u t i o n to a c l e a r , dark r e d and caused the e v o l u t i o n of a gas. A f t e r s e v e r a l hours the r e a c t i o n mixture was poured i n t o c o l d water. A c o l o r l e s s s i r u p separated which immediately heg&n to c r y s t a l l i z e . T h i s product was separated by f i l t r a t i o n , washed with water and d r i e d i n vacuo. The d r y i n g was necessary to remove t r a c e s of p y r i d i n e . R e c r y s t a l l i z a t i o n y i e l d e d f i n e , c o l o r l e s s , n e e d l e l i k e c r y s t a l s which melted at 85-86°C and were s i m i l a r to but l e s s p e r f e c t than the h e x a n i t r a t e c r y s t a l s . The p u r i f i e d product gave the c o r r e c t value f o r a penta-n i t r a t e w i t h n i t r a t e e s t e r a n a l y s i s , q u a n t i t a t i v e l y produced d u l c i t o l on h y d r o g e n o l y s i s and d i d not reduce P e h l i n g ' s s o l u t i o n . The y i e l d of d u l c i t o l p e n t a n i t r a t e from the h e x a n i t r a t e was 65-69$. The p e n t a n i t r a t e was o p t i c a l l y i n a c t i v e . The p e n t a n i t r a t e was found to be s t a b l e to f u r t h e r d e n i t r a t i o n under the c o n d i t i o n s which cause d e n i t r a t i o n of the h e x a n i t r a t e . A sample was d i s s o l v e d i n p y r i d i n e and l e t stand o v e r n i g h t . No gas was e volved but the s o l u t i o n d i s c o l o r e d to a c l e a r , dark r e d . The p e n t a n i t r a t e was r ecovered i n 94$ y i e l d . R e c r y s t a l l i z a t i o n of the p e n t a n i t r a t e was d i f f i c u l t . Aqueous ethanol u s u a l l y a f f o r d e d a s i r u p . However, a very concentrated s o l u t i o n of the p e n t a n i t r a t e i n s l i g h t l y aqueous ethanol would form c r y s t a l s at r e f r i g -e r a t o r temperatures. The c r y s t a l s thus obtained were - 11 -d r i e d i n a i r and showed v a r i o u s m e l t i n g p o i n t s from 65-85°C. Prolonged d r y i n g i n vacuo r a i s e d the m e l t i n g p o i n t t o a constant value of 85-86°C. A p p a r e n t l y , a semi-stable hydrate of the p e n t a n i t r a t e was p r e s e n t . R e c r y s t a l l i z a t i o n from ether and petroleum e t h e r 16 y i e l d e d c r y s t a l s m e l t i n g at 85-86°C. (Wigner r e p o r t e d the p e n t a n i t r a t e as having an i n d e f i n i t e m e l t i n g p o i n t about 71-75 6C.) C o n s i d e r a t i o n of the formula of d u l c i t o l h e x a n i t r a t e (VII) r e v e a l s t h a t the 1- and 6 - p o s i t i o n n i t r a t e groups are c h e m i c a l l y i d e n t i c a l , a l s o the 2-and 5- and the 3- and 4- p o s i t i o n s . I f one assumes, f o r example, that the n i t r a t e group on the 3 (or 4) p o s i t i o n i s the one u n s t a b l e to p y r i d i n e , then the d e n i t r a t i o n process w i l l s t a t i s t i c a l l y remove the 3-p o s i t i o n n i t r a t e group from h a l f of the molecules and the 4 - p o s i t i o n n i t r a t e group from the remainder. The r e s u l t i n g products w i l l be c h e m i c a l l y the same but d i f f e r e n t o p t i c a l l y . The product w i l l be a racemic mixture of 1 , 2 , 3 , 5 , 6 , - D - d u l c i t o l - p e n t a n i t r a t e (VIII) and 1 , 2 , 3 , 5 , 6 , - L - d u l c i t o l - p e n t a n i t r a t e (IX). The c o r r e c t nomenclature to be used at t h i s p o i n t seems to be q u i t e a r b i t r a r y . D u l c i t o l , D - d u l c i t o l , L - d u I c i t o l , D - g a l a c t i t o l , L - g a l a c t i t o l , and g a l a c t i t o l are a l l one and the same molecule. D u l c i t o l w i t h the D- and L-d e s i g n a t i o n s are used here with the o b j e c t of c a u s i n g the l e a s t c o n f u s i o n . 12 -CHgONO. I d H-C-0N0 o I * 02N0-G-H CH o0N0 CHgONO H - C - O N O g O o N O - C - H OgNO-C-H H-C-ONO_ OgNO-C-H HO-C-H + H-C-OH H-C-ONO, I H-C-ONO 2 OgNO-C-H CH 2ON0 2 VII V I I I IX A s i m i l a r s i t u a t i o n w i l l p r e v a i l i f the 1- and 6 - p o s i t i o n s or the 2- and 4 - p o s i t i o n s are a t t a c k e d . In any case, by the f a c t t h a t only one n i t r a t e group i s removed and t h a t the product i s o p t i c a l l y i n a c t i v e , the p e n t a n i t r a t e must be a racemic m i x t u r e . C. Monomethyl d u l c i t o l p e n t a n i t r a t e M e t h y l a t i o n o f d u l c i t o l p e n t a n i t r a t e with s i l v e r oxide and methyl i o d i d e gave a product which r e c r y s t a l l i z e d r e a d i l y from aqueous ethanol t o form c o l o r l e s s , n e e d l e l i k e c r y s t a l s m e l t i n g at 99-100*0. Methoxyl and n i t r a t e e s t e r analyses agreed wi t h the values f o r a monomethyl d u l c i t o l p e n t a n i t r a t e . S p e c i f i c r o t a t i o n was ze r o . The methylated p e n t a n i t r a t e was found t o be s t a b l e to p y r i d i n e . A sample was l e f t i n p y r i d i n e f o r two days. No gas was evolved but the s o l u t i o n became c o l o r e d as i n the case of the p e n t a n i t r a t e s t a b i l i t y t e s t . The methylated p e n t a n i t r a t e was re c o v e r e d i n 89$ y i e l d . - 13 -D. Monomethyl d u l c i t o l H ydrogenolysis o f the monomethyl d u l c i t o l p e n t a n i t r a t e gave a product which r e c r y s t a l l i z e d from absolute e t h a n o l i n t h i c k , c o l o r l e s s c r y s t a l s m e l t i n g a t 149-150°C. C r y s t a l l i z a t i o n from water and from isoamyl a l c o h o l w i t h petroleum ether y i e l d e d the same product. Methoxyl a n a l y s i s agreed w i t h the value c a l c u l a t e d f o r a monomethyl d u l c i t o l . The product was found t o be o p t i c a l l y i n a c t i v e . T e s t s w i t h F e t i l i n g ' s s o l u t i o n , bromine water, and a n i t r o g e n a n a l y s i s proved n e g a t i v e . N i t r a t i o n gave back the methyl d u l c i t o l p e n t a n i t r a t e i n 75$ y i e l d . The y i e l d o f r e c r y s t a l l i z e d monomethyl d u l c i t o l o b t a i n e d from the p e n t a n i t r a t e was 90$. A l i t e r a t u r e search showed that no monomethyl d e r i v a t i v e s of d u l c i t o l had been prepared. Apart from an independent s y n t h e s i s , p e r i o d a t e o x i d a t i o n o f f e r e d the o n l y means o f l o c a t i n g the p o s i t i o n of the methyl group. The monomethyl d u l c i t o l c o u l d be one of th r e e p o s s i b i l i t i e s - a racemate of D- and L- 1-methyl d u l c i t o l , D- and L- 2-methyl d u l c i t o l or D- and L- 3-methyl d u l c i t o l . The three p o s s i b i l i t i e s and t h e i r t h e o r e t i c a l b e havior towards p e r i o d a t e o x i d a t i o n are presented below. - 14 -Case 1 CH o0CH, , 2 3 CH-OH I CH-OH I CH-OH l CH-OH I CH 2-0H 4 NaI04 1 HCHO -4-3 HGOOH CH 20CH 3 CHO Case 2 CHp-OH I * CHOCH, I ^ CH-OH i CH-OH I CH-OH CHo-OH 3 NalOa 1 2 HCHO + HCOOH CH2OH / CHOCH3 \ CHO Case 3 CHg-OH CH-OH I CHOCH, I 0 CH-OH I CH-OH I CH 2-0H 3 NalO/t 2 1 HCHO + HCOOH + CHO / CHOCH, \ * CHO - 15 -An o x i d a t i o n w i t h aqueous NalO^ showed a consumption of 4.9 moles of oxidant with a p r o d u c t i o n of 2.1 moles of f o r m i c a c i d and 2.0 moles of formaldehyde. Subsequent o x i d a t i o n s with Nal.04 and with KIO. d i d not a p p r e c i a b l y 4. z a l t e r these f i g u r e s . Case 2 or case 3 c o u l d permit these r e s u l t s i f an a d d i t i o n a l o x i d a t i o n , r e q u i r i n g 2 moles of o x i d a n t , o c c u r r e d w i t h the f o r m a t i o n of an e x t r a mole of formaldehyde or of f o r m i c a c i d r e s p e c t i v e l y . The r a t e of p r o d u c t i o n of aldehyde and a c i d was s t u d i e d to see i f such was the case. F i g u r e 1 shows the values of oxidant consumption, aldehyde and a c i d p r o d u c t i o n i n r e l a t i o n t o the time of r e a c t i o n . The graph shows an r a p i d i n i t i a l consumption of 3 moles producing 2 moles of formaldehyde and approximately 1 mole of f o r m i c a c i d . These r e s u l t s conform o n l y to case 3. An hour l a t e r , the aldehyde value i s the same but the f o r m i c has r i s e n t o 2 w i t h the consumption at 5 moles. These o x i d a t i o n s were conducted at room temperature. Another o x i d a t i o n was r u n at 0°C i n order to slow or h a l t the i n t e r f e r i n g o x i d a t i o n . F i g u r e 2 c l e a r l y shows a r a p i d f o r m a t i o n of 1 mole of f o r m i c a c i d then a d i f f e r e n t r e a c t i o n begins which s l o w l y i n c r e a s e s the v a l u e . Only a f t e r 11 hours d i d the a c i d r e a c h a value of 2 moles. These f i n d i n g s i n d i c a t e t h a t case 3 i s i n v o l v e d and t h e r e f o r e the dialdehyde formed must be o x i d i z e d f u r t h e r t o produce a mole of a c i d . 2.0 MOLES 1.0 Pro d u c t i o n of Formic A c i d 1 0 20 30 TIME (MINUTES) 50 60 FIGURE 2. Peri o d a t e o x i d a t i o n of methyl d u l c i t o l at 0°C. 70 - 18 -20 Huebner, Ames and Bubl r e p o r t t h a t the dialdehyde of malonic a c i d (X) w i l l undergo o x i d a t i o n by p e r i o d a t e to form 3 moles of form i c a c i d with a 3 mole oxidant consumption. The f o l l o w i n g mechanism was o f f e r e d -CHO CHO HCOOH / / + H-C-H NalOa _, H-C-OH NaI0_u CHO \ ^ \ ^ " | NaI0_2HC00H CHO CHO CHO ^ Th i s mechanism i s a p p l i e d t o the s i m i l a r dialdehyde formed i n case 3. CHO CHO HCOOH / / + CH3O-C-H N a l O ^ CH3O-C-OH NalOa^ COOCH3 \ H 0 CHO CHO Two moles o f p e r i o d a t e produce 1 mole of fo r m i c a c i d and an e s t e r which may be assumed to be c o m p a r i t i v e l y s t a b l e to o x i d a t i o n . From the f o r e g o i n g evidence and c o n s i d e r a t i o n s , the methyl d u l c i t o l i n q u e s t i o n must indeed be a racemate o f 3- m e t h y l - D - d u l c i t o l and 3 - m e t h y l - L - d u l c i t o l with the p e n t a n i t r a t e b e i n g D-duleitol-1,2,4,5,6,-p e n t a n i t r a t e and L - d u l c i t o l - 1 , 2 , 4 , 5 , 6 , - p e n t a n i t r a t e . Absolute c o n f i r m a t i o n can only come from an Independent s y n t h e s i s . - 19 -EXPERIMENTAL S p e c i a l P r e c a u t i o n s In view of the e x p l o s i v e c h a r a c t e r of the n i t r a t e compounds, p r e c a u t i o n s were observed to minimize the danger of a d e t o n a t i o n . No more than 5 grams of the n i t r a t e s were handled at any one time. Larger amounts were s t o r e d i n s m a l l , i s o l a t e d samples. Ev a p o r a t i o n s were conducted at reduced p r e s s u r e with bath temperatures not exceeding 50°C. The d r y i n g of samples was accomplished at room temperature i n vacuo. A. M a t e r i a l s  N i t r i c A c i d Red fuming n i t r i c a c i d used i n a l l n i t r a t i o n s as s u p p l i e d by Baker and Adams, s.g. 1.59-1.60. P y r i d i n e A.R. grade by B r i t i s h Drug Houses was used d i r e c t l y f o r the d e n i t r a t i o n s . D u l c i t o l D u l c i t o l was s u p p l i e d by B r i t i s h Drug Houses. I t was r e c r y s t a l l i z e d from water to melt c o r r e c t l y P a l l a d i z e d Charcoal C a t a l y s t The p a l l a d i u m on c h a r c o a l c a t a l y s t f o r the h y d r o g e n o l y s i s of n i t r a t e groups was prepared by the (C, 5.40) HgO. method of Hartung. 21 When thoroughly dry i t i g n i t e d - 20 -spontaneously i n a i r and r e q u i r e d care i n h a n d l i n g t o a v o i d i g n i t i o n of the s o l v e n t and n i t r a t e . The same c a t a l y s t c o u l d be used s e v e r a l times and was regenerated by washing w i t h water, ethanol and anhydrous ether and d r y i n g i n vacuo. P a l l a d i u m was r e c o v e r e d from poisoned c a t a l y s t by i g n i t i o n t o remove the •carbon and treatment w i t h aqua r e g i a t o o b t a i n the c h l o r i d e of p a l l a d i u m . Hydrogen, the commercial product, was used d i r e c t l y from the storage tank of the Pa r r low-pressure hydrogenator. Sodium Metaperiodate NalO^ was s u p p l i e d by Brickman and Company. Dlphenylamine Reagent Dipheriylamine reagent f o r t e s t i n g f o r the presence 22 of n i t r a t e was prepared a f t e r the method of M u l l i k e n . S i l v e r Oxide F r e s h l y prepared s i l v e r oxide was used i n the me t h y l a t i o n s , as the commercial v a r i e t y gave u n s a t i s f a c t o r y r e s u l t s . P r e p a r a t i o n - Concentrated n i t r i c a c i d (100 ml.) was added slowly to 29.7 gm. of b l a c k s i l v e r o xide. The s o l u t i o n was d i l u t e d to 200 ml. and heated t o b o i l i n g . The s o l u t i o n was allowed to cool and then f i l t e r e d through a s i n t e r e d g l a s s f u n n e l . Potassium hydroxide s o l u t i o n was slow l y added w i t h vigorous mechanical s t i r r i n g , - 21 -The chocolate-brown p r e c i p i t a t e of s i l v e r oxide was washed with water, ethanol and e t h e r , then d r i e d at 80°C f o r 12 hours. The weight of s i l v e r oxide r e c o v e r e d was 27.5 grams. Irestored over CaClg and out of contact with l i g h t . The whole o p e r a t i o n was c a r r i e d out i n subdued l i g h t . B. A n a l y t i c a l Methods  N i t r o g e n N i t r a t e n i t r o g e n was determined by E l v i n g and McElroy's semi-micro m o d i f i c a t i o n of the Dupont n i t r o m e t e r . ^ Methoxyl Methoxyls were determined by the method of VIebock 24 and Schwappach as d e s c r i b e d by G l a r k . O x i d a t i o n s w i t h P e r i o d a t e 1O 2S 2fi 27 2ft The procedures used by s e v e r a l authors 9 9 9 9 were adapted and combined so t h a t a s i n g l e 50 mg. sample would r e v e a l the amount of p e r i o d a t e consumed and the amount of f o r m i c acid' and formaldehyde produced. The sample was d i s s o l v e d i n 90 ml. of water i n an erlenmyer f l a s k with a ground g l a s s stopper. Ten ml. of a 0.2 M s o l u t i o n of sodium metaperlodate was added. A blank s o l u t i o n was s i m i l a r l y prepared. The f l a s k s were s t o r e d out of contact w i t h l i g h t . - 22 At s u i t a b l e i n t e r v a l s , 10 ml. a l i q u o t s were withdrawn, the excess p e r i o d a t e destroyed by adding 5 drops o f pure ethylene g l y c o l , then t i t r a t e d w i t h 0.01 N NaOH s o l u t i o n u s i n g methyl r e d as I n d i c a t o r . (A t i t r a t i o n , f o l l o w e d with a c a l i b r a t e d Beckman pH meter, t i t r a t i n g t o the pH o f the blank s o l u t i o n gave r e s u l t s i d e n t i c a l t o those obtained with the i n d i c a t o r s o l u t i o n . ) When the t i t r a t i o n f o r a c i d reached a constant v a l u e , 10 ml. a l i q u o t s were withdrawn from the sample and the blank s o l u t i o n . To these s o l u t i o n s was added 10 ml. of HgO, 9 gm. of NaHCOg, 10 ml. of 0.1 N standard sodium a r s e n i t e s o l u t i o n and 2 ml. of 20$ K l s o l u t i o n . A f t e r s t a n d i n g 15 minutes at room temperature, the solutionswere t i t r a t e d with 0.1 N standard Iodine s o l u t i o n u s i n g f r e s h s t a r c h i n d i c a t o r . The d i f f e r e n c e i n t i t r e between the blank and the sample s o l u t i o n gave the consumption o f p e r i o d a t e . For the formaldehyde d e t e r m i n a t i o n , two 10 ml. a l i q u o t s were withdrawn, and t r e a t e d w i t h 10 ml. of 1.0 N HC1. Sodium a r s e n i t e s o l u t i o n (1.0 N) was added u n t i l the s o l u t i o n became c o l o r l e s s . One gm. of sodium acetate was added and the s o l u t i o n a d j u s t e d to a pH of 4-5 with a c e t i c a c i d u s i n g u n i v e r s a l pH paper. Two ml. of an 8$ a l c o h o l i c s o l u t i o n of d i m e t h y l d l h y d r o -r e s o r c i n o l (dimedon) was added and the s o l u t i o n allowed - 23 t o stand o v e r n i g h t . The p r e c i p i t a t e was r e c o v e r e d on an P P r e g l f i l t e r , washed wi t h water and d r i e d was weighed and I d e n t i f i e d by i t s sharp m e l t i n g p o i n t at 188-189°C. C. D u l c i t o l H e x a n i t r a t e Red fuming HN03 (33 ml.) i n a. 125 ml. beaker was cooled to -10°C i n an i c e - s a l t bath. F i n e l y powdered d u l c i t o l (3.95 gm.) was added i n small amounts over a p e r i o d of about 30 minutes. Concentrated s u l p h u r i c a c i d (54 m l . ) , a l s o cooled to -10°C, was added wi t h s t i r r i n g . A white, c r y s t a l l i n e p r e c i p i t a t e appeared. The mixture was allowed to stand f o r 20 minutes w i t h o c c a s s i o n a l s t i r r i n g , then poured i n t o 3 l i t r e s of i c e water. The p r e c i p i t a t e was r e c o v e r e d on a s i n t e r e d , g l a s s f u n n e l , washed n e u t r a l t o congo r e d with water and d r i e d i n vacuo over ^2^5* ^ e w e ^ S ^ °^ ^he h e x a n i t r a t e was 9.05 gm. (92$ y i e l d ) . The h e x a n i t r a t e r e c r y s t a l l i z e d r e a d i l y from aqueous ethanol i n c o l o r l e s s , n e e d l e l i k e c r y s t a l s , m.p. 98-99*0,L<; | 2 5 = 0 # 0 0 (c,4.01) i n vacuo over P o0 2 U5- The formaldehyde-dimedon complex P r e p a r a t i o n of D u l c i t o l h e x a n i t r a t e EtOH. A n a l y s i s : C a l c . f o r C 6 H 8 ( N 0 3 ) 6 - N = 18.6$ Found - N = 18.4, 18.8$ - 24 -Hydrogenolysis of D u l c i t o l H e x a n i t r a t e Hydrogenolysis of the h e x a n i t r a t e t o form d u l c i t o l was accomplished by the method of Kuhn^.^" The r e a c t i o n a c c o r d i n g to Kuhn-2 RONOg -f 5 Hg *- 2R0H + Ng -|- 4 HgO The h y d r o g e n o l y s i s was c a r r i e d out i n a 500 ml. pressure f l a s k a t t a c h e d t o the Parr low-pressure hydrogenatpr. 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 (0.5 gm,-) was added to a s o l u t i o n of 0.685 gm. of the h e x a n i t r a t e i n 50 ml. of e t h a n o l . A f t e r 2 hours r e a c t i o n time at 21 p . s . i . of hydrogen, a t e s t with diphenylamine reagent showed the s o l u t i o n to be n i t r a t e f r e e . The c a t a l y s t was removed by f i l t r a t i o n and washed, and the f i l t r a t e and washings were evaporated. A c o l o r l e s s c r y s t a l l i n e product weighing 0.286 gm. was obtained (103$ y i e l d ) . R e c r y s t a l l i z a t i o n from ethanol and water gave 0.189 gm. of s h o r t , t h i c k c r y s t a l s , m.p. 185-187°C. A mixed m e l t i n g p o i n t w i t h pure d u l c i t o l showed no d e p r e s s i o n . D. D u l c i t o l P e n t a n i t r a t e  D e n i t r a t i o n o f D u l c i t o l H e x a n i t r a t e A 500 ml. f l a s k c o n t a i n i n g 3.11 gm. of pure, dry h e x a n i t r a t e was immersed i n a water-bath a t 30°C. The h e x a n i t r a t e d i s s o l v e d immediately on a d d i t i o n of 25 ml. of p y r i d i n e to form a c l e a r , c o l o r l e s s s o l u t i o n . The s o l u t i o n became orange-colored i n 5 minutes but no gas - 25 -e v o l u t i o n was observed. A f t e r h e a t i n g the water-bath t o 50°C, the s o l u t i o n r a p i d l y e volved small bubbles of gas and f i n e , c o l o r l e s s c r y s t a l s appeared on the neck of the f l a s k . The s o l u t i o n was allowed to c o o l and l e t stand o v e r n i g h t . A f t e r 24 hours, the c l e a r , dark-red s o l u t i o n was poured with s t i r r i n g Into 300 ml. of water. A c o l o r l e s s s i r u p separated which immediately began t o c r y s t a l l i z e . The product was r e c o v e r e d on a weighed s i n t e r e d g l a s s f u n n e l , washed with water and d r i e d to constant weight i n vacuo over Pg^S* ^ e w e*-ght of the p e n t a n i t r a t e was 1.81 gm. (65$). Y i e l d s o b tained i n s i m i l a r d e n i t r a t i o n s were 63, 65 and 69$. R e c r y s t a l l i z a t i o n from aqueous ethanol or ether and petroleum ether y i e l d e d c o l o r l e s s , n e e d l e l i k e c r y s t a l s , m.p. 8 5 - 8 6 6 C , [ k J ^ 5 = 0.00(0,2.00) EtOH. The p e n t a n i t r a t e was s o l u b l e i n a l c o h o l , acetone, e t h e r , benzene and c hloroform and i n s o l u b l e i n water and petroleum e t h e r . The p e n t a n i t r a t e d i d not reduce P e h l i n g ' s s o l u t i o n . A n a l y s i s : C a l c . f o r C 6Hg(0H) ( N 0 3 ) & - N = 17.2$ Pound - N = 16.9, 17.0$ A sample of the pure p e n t a n i t r a t e (0.63 gm.) was t r e a t e d with p y r i d i n e (4.0 ml.) under the c o n d i t i o n s which cause d e n i t r a t i o n of the h e x a n i t r a t e . No e v o l u t i o n of gas was observed but the s o l u t i o n became a dark-red - 26 -c o l o r . The p e n t a n i t r a t e was r e c o v e r e d i n 94$ y i e l d , m e l t i n g c o r r e c t l y at 85-86°C and showing no d e p r e s s i o n w i t h a mixed m e l t i n g p o i n t . Hydrogenolysis of D u l c i t o l P e n t a n i t r a t e A sample of the p e n t a n i t r a t e (0.240 gm,) was d i s s o l v e d i n 50 ml. of e t h a n o l and 1.0 gm. of p a l l -a d i z e d c h a r c o a l was added. Reduction r e q u i r e d 1 hour at a pressure of 36 p . s . i . of hydrogen. F i l t r a t i o n and e v a p o r a t i o n y i e l d e d a c o l o r l e s s , c r y s t a l l i n e product weighing 0.110 gm. (100$ y i e l d ) . R e c r y s t a l l i z a t i o n from water and ethanol gave 0.60 gm. (56$) of c o l o r l e s s c r y s t a l s m e l t i n g at 185-188*0. Admixture with pure d u l c i t o l caused no d e p r e s s i o n i n the m e l t i n g p o i n t . M e t h y l a t i o n of D u l c i t o l P e n t a n i t r a t e The f i r s t m e t h y l a t i o n s gave very low y i e l d s w i t h much decomposition. Traces of p y r i d i n e on the p e n t a n i t r a t e and i n e f f e c t i v e s i l v e r o x i d e , seemed to cause the t r o u b l e . To o b t a i n s a t i s f a c t o r y y i e l d s , the p e n t a n i t r a t e was d r i e d i n vacuo over cone, s u l p h u r i c a c i d u n t i l "nose f r e e " of p y r i d i n e and the s i l v e r oxide was f r e s h l y prepared. The p e n t a n i t r a t e (0.730 gm.) was d i s s o l v e d i n 11 ml. of methyl i o d i d e and 4 ml. of methanol. F i v e gm. of " D r i e r i t e " and 5 gm. of s i l v e r oxide was added. The mixture was r e f l u x e d on a steam bath f o r 9 hours. The s o l u t i o n was f i l t e r e d and the s o l i d s washed wit h dry acetone. The f i l t r a t e and washings were evaporated to g i v e a 27 -c o l o r l e s s c r y s t a l l i n e r e s i d u e . R e c r y s t a l l i z a t i o n from aqueous ethanol gave 0.508 gm. (67$) of the monomethyl d u l c i t o l p e n t a n i t r a t e . Some d u l c i t o l p e n t a n i t r a t e was rec o v e r e d from the mother l i q u o r . The methyl d u l c i t o l p e n t a n i t r a t e forms l o n g , c o l o r l e s s , n e e d l e s , m.p. 99-100°C, [ < * ] 2 5 = 0.00 (C, 0.74) EtOH. I t was s o l u b l e i n a l c o h o l , e t h e r , acetone and dioxane but i n s o l u b l e i n water. A n a l y s i s : C a l c . f o r CgHg(0CH 3) ( N 0 3 ) 5 N « 16.6$ 0CH 3 = 7.37$ Pound - N = 16.6, 16.5$ 0CH 3 = 7.34, 7.37$ A sample of the methylated p e n t a n i t r a t e (0.457 gm.) was d i s s o l v e d i n p y r i d i n e (3.0 ml.) and l e t stand f o r two days. No gas e v o l u t i o n was observed but the s o l u t i o n became a dark-red c o l o r and c o l o r l e s s c r y s t a l s appeared on the neck of the f l a s k . A d d i t i o n of 30 ml. of water p r e c i p i t a t e d a c o l o r l e s s s i r u p which almost immediately c r y s t a l l i z e d . F i l t r a t i o n and r e c r y s t a l l i z a t i o n from aqueous et h a n o l y i e l d e d 89$ (0.407 gm.) of the methyl d u l c i t o l p e n t a n i t r a t e unchanged, I d e n t i f i e d by a mixed m e l t i n g p o i n t . E. Monomethyl D u l c i t o l Hydrogenolysis of Methyl D u l c i t o l P e n t a n i t r a t e A sample of the methylated p e n t a n i t r a t e (1.42 gm.) was d i s s o l v e d In 30 ml. dioxane and d i l u t e d w i t h \ - 28 -45 ml. of ethanol and 5 ml. of water. One gram of p a l l a d l z e d c h a r c o a l c a t a l y s t was added and the mixture hydrogenated at a pressure of 45 p . s . i . The r e a c t i o n was complete a f t e r 1 hour with the s o l u t i o n b e i n g f r e e of n i t r a t e by the diphenylamine t e s t . The s o l u t i o n was f i l t e r e d t o remove the c a t a l y s t , and the hydrogenator b o t t l e and the c a t a l y s t were washed with hot water. The f i l t r a t e and washings were evaporated at reduced pressure t o y i e l d a c o l o r l e s s , c r y s t a l l i n e product. The product d i s s o l v e d i n b o i l i n g a b s o l u t e ethanol and on c o o l i n g s l o w l y formed 0.552 gm. of t h i c k , c o l o r l e s s c r y s t a l s (83$ y i e l d ) m.p. 149-150°G. R e c r y s t a l l i z a t i o n from Isoamyl a l c o h o l and from water y i e l d e d the same product. Te s t s with P e h l i n g ' s s o l u t i o n and w i t h bromine water were n e g a t i v e . J j * j 2 5 ' = 0 , 0 0 (G» 1 ' 0 0 ^ H 2 ° * A n a l y s i s : C a l c . f o r CgHg(0CH 3)(0H) 5 - 0CH 3= 15 Pound - 0CH 3 = 16.1, 16.0$ N i t r a t i o n of Monomethyl D u l c i t o l A sample o f f i n e l y powdered methyl d u l c i t o l (68.8 m was added to 4 ml. of r e d fuming n i t r i c a c i d which was p r e v i o u s l y cooled to -10°C. S i x ml. of cone, s u l p h u r i c a c i d were added w i t h s t i r r i n g and a white c r y s t a l l i n e p r e c i p i t a t e appeared. A f t e r s t a n d i n g 15 minutes, the mixture was poured i n t o 300 ml. - 29 -of i c e water. A c o l o r l e s s s i r u p separated which immediately c r y s t a l l i z e d . T h i s product was separated by f i l t r a t i o n and washed w i t h water. R e c r y s t a l l i z a t i o n from aqueous ethanol gave 111.0 mg. (75$ y i e l d ) of f i n e , d o l o r l e s s n e e d l e s , m.p. 99-100°C. A mixed m e l t i n g p o i n t w i t h pure monomethyl d u l c i t o l p e n t a n i t r a t e showed no d e p r e s s i o n . Methoxyl a n a l y s i s (7.39, 7.20$) agreed with the value f o r the methylated p e n t a n i t r a t e . P e r i o d a t e O x i d a t i o n of Monomethyl D u l c i t o l A 50.3 mg. sample of methyl d u l c i t o l was o x i d i z e d by aqueous NaI0 4 at room temperature as d e s c r i b e d above under "Oxidations with P e r i o d a t e . " ' The values of f o r m i c a c i d o b tained per mole of methyl d u l c i t o l were 1.20, 1.30, 1.38, 1.51, 1.91, 2.06 and 2.11 moles a f t e r 1.5, 3, 5, 10, 38, 130 and 900 minutes (15 h o u r s ) . At 16 hours, a d e t e r m i n a t i o n r e v e a l e d a consumption of 4.93 moles of p e r i o d a t e . At 17 hours, the formaldehyde p r o d u c t i o n was found to be 1.98 moles. A 45,8 mg. sample was o x i d i z e d under the same c o n d i t i o n s i n order to f o l l o w the consumption of p e r i o d a t e per mole of methyl d u l c i t o l . The values were 2.76, 2.86, 3.86, 4.43 and 4.77 moles a f t e r 2, 5, 20, 40 and 55 minutes. - 30 -Another o x i d a t i o n w i t h 45.3 mg. of methyl d u l c i t o l was r u n i n order to f o l l o w the molar p r o d u c t i o n of formaldehyde. Values were 1.61, 1.81, 2.02, 1.92 and 1.98 a f t e r 1, 2, 5, 30 and 1020 minutes. An o x i d a t i o n on 42.8 mg. of methyl d u l c i t o l was conducted i n an i c e b a t h . T h e values of f o r m i c a c i d p r o d u c t i o n were 0.91, 1.04, 1.12, 1.20, 1.27, 1.40, 1.70, 2.06 and 2.12 moles a f t e r 2, 5, 10, 20, 45, 90, 300, 660 and 1440 minutes. A 46.6 mg. sample of pure d u l c i t o l was o x i d i z e d at room temperature under the same c o n d i t i o n s as the methyl d u l c i t o l o x i d a t i o n s . Formic a c i d values were 3.53, 3.63 and 3.68 moles a f t e r 5, 15 and 25 hours. At 25 hours, consumption was found to be 4.95 moles and formaldehyde p r o d u c t i o n was 1.98 moles. - 31 BIBLIOGRAPHY 1. Kuhn, L.P., J . Am. Chem. S o c , 68, 1761 (1946). 2. Bacon, J.S.D. and B e l l , D. J . , J . Chisiil. S o c , 1869 (1939). 3. A b e l , P., B r i t i s h Patent 1102 (1865); see a l s o Worden, E.G./"Technology of C e l l u l o s e E s t e r s " , V o l . I , Part 3, p 1604. 4. Walter, V.J.. Z. Angew. Chem., 24, 62, (1911) C.A., 5, 2950 (1911). " 5. Becker, P. and Hunold, G.A., Z. ges. S c h i e s s - u. Sprengstoffw., 33, 213, 244 (1938). 6. A n g e l i , A., Rend. Accad. L i n c e i , 28, 1, 20 (1919); 30, 259 (1921). 7. G i a n n i n i , C.G., Gazz. chim. i t a l . , 54, 79 (1924). 8. Gladding, E.K. and Purves, C.B., J . Am. Chem. S o c , 66, 76 (1944). 9. S e g a l l , G.H., Ph. D. D i s s e r t a t i o n , M c G i l l U n i v e r s i t y (1946). 10. Hayward, L.D., Ph. D. D i s s e r t a t i o n , M c G i l l U n i v e r s i t y (1949). 11. Rooney, C.S., Ph. D. D i s s e r t a t i o n , M c G i l l U n i v e r s i t y (1952). 12. Swan, E.P., B.A. T h e s i s , U n i v e r s i t y o f B r i t i s h Columbia (1952). 13. A n g e l i , A., Gazz. chim. i t a l . , 26, 17 (1896); A n g e l i , A. and A n g e l i c o , P., i b i d . , 33, 245 (1903); 34, 50 (1904). ~ ~ 14. Ryan, H. and Casey, M.T., S c i e n . Proc. Royal  D u b l i n Soc., 19, 101 (1928-30). ~ 15. Ti c h a n o w i t s c h , Th., Z. chem. Pharm., 482 (1864); J . P o r s c h r i t t e Chem., 582 (1864). 16. Wigner, J.H., Ber., 36, 794 (1903). 17. Vignon, L. and G e r i n , P., Compt. r e n d . , 133, 515 (1901). 18. Hayward, L.D., J . Am. Chem. S o c , 73, 1974 (1951). 32 -19. Brown, J.R., P r i v a t e Communication, U n i v e r s i t y of B r i t i s h Columbia (1952). 20. Huebner, C P . , Ames, S.R., and Bubl, E.C., J . Am. Chem. S o c , 68, 1621-8 (1946). 21. Hartung, W.H., i b i d . , 50, 3372 (1928). 22. M u l l i k e n - H u n t r e s s , "Manual of the I n d e n t i f i c a t i o n of Organic Compounds", M.I.T.,pl63 (1937). 23. E l v i n g , P.J. and McElroy, W.R., Ind. Eng. Chem., (Anal. E d . ) , 14, 84 (1942). 24. C l a r k , E.P., "Semimlcro Q u a n t i t a t i v e Organic A n a l y s i s " , Academic Press Inc., N.Y. (1943). 25. Reeves, R.E., J . Am. Chem. S o c , 63, 1476 (1941). 26. Head, F.S;,and Hughes, G., J . Chem. S o c , 2046 (1952). 27. H a l s a l l , H i r s t and Jones, i b i d . , 1427 (1947). 28. W i l l a r d and Greathouse, J . Am. Chem. S o c , 60, 2869 (1938). 29. Pigman, W.W. and Goepp, R.M. "Carbohydrate Chemistry", Academic Press Inc., N.Y. (1943). 

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