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Polymer-analogous denitration, a study of certain hexitol, disaccharide and cellulose nitrates Swan, Eric Paterson 1954

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POLIMER-ANALOGOUS DENTTRATION. A STUDY OF CERTAIN HEXTTOL, DISACCHARIDE AND CELLULOSE NITRATES by ERIC PATERSON SWAN 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 t o the standard r e q u i r e d from candidates f o r the degree of MASTER OF SCIENCE Members of the Department of Chemistry THE UNIVERSITY'OF BRITISH COLUMBIA APRIL, 1954 ABSTRACT The action of methanolic hydrazine with palladium catalyst, methyl magnesium iodide, and hydrogen with cupric acetate catalyst in pyridine solution, on certain hexitol and disaccharide polynitrates were found to be unsuitable methods for complete denitration of these carbohydrate polynitrates. Lithium alurninium hydride was shown to denitrate successfully D-mannitol hexanitrate. The foregoing methods were found to be unsuitable for complete denitration of polysaccharide polynitrates. Hydrogen with palladium-carbon catalyst was shown to denitrate successfully a l l the carbohydrate poly-nitrates studied, with good yields of the parent polyol. The use of hydrogen was extended to denitration of cellulose nitrates. In the presence of Raney nickel catalyst a cellulose nitrate containing 13.4$ N was reduced to a cellulose nitrate containing 12.1$ N. The reduction with hydrogen and Raney nickel catalyst of a heterogeneous cellulose nitrate, containing approximately equal amounts of a cellulose nitrate containing U.5% N and one containing 12.6% N, was found to yield a cellulose nitrate containing 2.7% N and one containing 12.5$ N. ACKNOWLEDGEMENTS The w r i t e r wishes t o express h i s s i n c e r e thanks t o D r . L . D. Hayward f o r h i s encouragement and guidance 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 . Gratefulacknowledgements are made a l s o t o the B r i t i s h Columbia Sugar R e f i n i n g Co. L t d . f o r the award o f a s c h o l a r s h i p , and 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 g r a n t . TABLE OF CONTENTS Page I n t r o d u c t i o n . . . . • • . . . . . . • •« • • • • * « . . . « • • • I H i s t o r i c a l I n t r o d u c t i o n . . . . . . . . . . . . . . . . . . . . . 3 D i s c u s s i o n o f R e s u l t s A . The P r e p a r a t i o n o f the Carbohydrate P o l y n i t r a t e Model Compounds 9 B . Hydrogenolys i s w i t h Pa l l ad ium-Carbon C a t a l y s t 12 C. Reduct ion w i t h Hydraz ine . . . . . . 15 D . Reduct ion w i t h M e t h y l Magnesium Iod ide . . . . . . .. 16 E . Reduc t ion w i t h L i t h i u m Aluininium Hydr ide . . . 17 F . Reduct ion w i t h Hydrogenj C u p r i c Ace ta t e i n P y r i d i n e C a t a l y s t 18 G . Reduc t ion o f the C e l l u l o s e N i t r a t e s . . . . . . . . . . . . 20 Conclusxons . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 Expe r imen ta l S p e c i a l P recau t ions . . . . . . . . . . . . . 24 A . M a t e r i a l s C e l l o b i o s e . . . . . . . . . . . . . . . . . . . . . . . . 24 C e l l o b i o s e O c t a n i t r a t e . . . 24 Methyl-(3 - C e l l o b i o s i d e H e p t a n i t r a t e . . . 25 Mal tose O c t a n i t r a t e . . . . . . . . . 26 D - M a n n i t o l H e x a n i t r a t e . . . . . . . . . . . . 26 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 . . . . . . . . . . . . 27 Methyl- j3>-D-Glucopyranoside T e t r a n i t r a t e 27 C e l l u l o s e N i t r a t e 28 B . Reduc t ion w i t h Hydrazine . . . . . . . . . . 29 Page c. Reduc t ion w i t h M e t h y l Magnesium I o d i d e . . . 30 D. Reduct ion w i t h L i t h i u m Aluminium Hydr ide 31 E . Reduct ion w i t h Hydrogen; C u p r i c Ace ta t e i n P y r i d i n e C a t a l y s t 32 F . Reduc t ion o f the C e l l u l o s e N i t r a t e s . . . . . . 33 G . A n a l y t i c a l Methods 34 B i b l i o g r a p h y . . . . . . . . . . . . - 37 INTRODUCTION In recent years t h e r e has been much i n t e r e s t i n the s t r u c t u r e of polysaccharides found i n nature. S t r u c t u r e s have been determined f o r many pure polysaccharides which are e a s i l y i s o l a b l e . The carbohydrate polymers i n wood, apart from c e l l u l o s e , however, remain comparatively unknown due t o the l a c k of s u i t a b l e methods of i s o l a t i o n and p u r i f i c a t i o n . These p o l y -saccharides are termed h e m i c e l l u l o s e s and are known t o be composed of chains of monosaccharides other than D-glucose l i n k e d t o g e t h e r i n s e v e r a l d i f f e r e n t f a s h i o n s . Strong bonding, probably of the hydrogen type, between these substances and the l i g n i n - c e l l u l o s e s t r u c t u r e prevents the u s u a l i s o l a t i o n by e x t r a c t i o n w i t h i n e r t s o l v e n t s . Hemicelluloses are obtained from wood g e n e r a l l y by e x t r a c t i o n w i t h aqueous a l k a l i and thus the i s o l a t e d product may not have the same s t r u c t u r e and c o n f i g u r a t i o n as i n nature s i n c e a l k a l i i s known t o cause extensive changes i n sugar molecules. Chemical pretreatment of the wood, before s e p a r a t i o n i n t o component p a r t s , t o form an ether or an e s t e r of the f r e e hydroxyl groups of the polysaccharides present, would g r e a t l y a s s i s t i n t h e i r i s o l a t i o n . The formation of the n i t r i c a c i d e s t e r s i s a most promising method of chemical pretreatment. N i t r a t i o n i s advantageous because the products, which are v e r y n e a r l y q u a n t i t a t i v e l y formed i n one n i t r a t i n g o p e r a t i o n , are s o l u b l e i n a v a r i e t y of organic s o l v e n t s , and the presence of the n i t r a t e groups strengthens the g l y c o s i d i c l i n k a g e s . F r a c t i o n a t i o n of the f u l l y - n i t r a t e d p l a n t t i s s u e f o l l o w e d by polymer analogous d e n i t r a t i o n of the separated polysaccharide n i t r a t e s would complete the c y c l e of operations through which p l a n t polysaccharides could be obtained i n s u i t a b l e form f o r s t r u c t u r a l s t u d i e s by the w e l l e s t a b l i s h e d methylation and periodate techniques. -2-The use of e s t e r i f y i n g agents other than n i t r i c a c i d , such as a c e t y l or benzoyl c h l o r i d e s , i s not d e s i r a b l e because of the d i f f i c u l t y encountered i n f o r c i n g complete e s t e r i f i c a t i o n without degradation of the polymer. M e t h y l a t i o n has been used as a method of chemical pretreatment of wood, and the technique has been employed t o determine the s t r u c t u r e of v a r i o u s p l a n t gums. M e t h y l a t i o n i s u n d e s i r a b l e f o r i s o l a t i o n purposes, however, s i n c e repeated treatments of the carbohydrate m a t e r i a l w i t h d i -methyl sulphate and sodium hydroxide are necessary t o approach the theo-r e t i c a l s u b s t i t u t i o n of methoxyl groups and a l k a l i n e c o n d i t i o n s are again i n v o l v e d . N i t r a t i o n , on the other hand, i s g e n e r a l l y complete upon one treatment w i t h the n i t r a t i n g agent, the product i s f u l l y n i t r a t e d and the y i e l d n e a r l y q u a n t i t a t i v e . Furthermore, n i t r a t e groups have been e a s i l y removed by hydrogenolysis from monosaccharide p o l y n i t r a t e s w i t h good y i e l d of the parent carbohydrate, whereas methoxyl groups have been extremely d i f f i c u l t t o remove from methylated monosaccharides t o y i e l d the parent carbohydrate. The ease of removal of n i t r a t e groups from simple sugars suggests t h a t methods may be found t o completely remove n i t r a t e groups from more complex carbohydrate m a t e r i a l s such as n i t r a t e d p o l y s a c c h a r i d e s . The purpose of the present research was t o study s e v e r a l methods of d e n i t r a t i o n of p o l y o l n i t r a t e s u s i n g simple carbohydrate n i t r a t e s as model substances and then t o apply the most s u c c e s s f u l of these methods t o c e l l u l o s e n i t r a t e i n the hope of a c h i e v i n g polymer analogous d e n i t r a t i o n of the carbohydrate polymer. HISTORICAL INTRODUCTION The discovery of nitrocellulose was made by Schonbein (51) i n 1846. Attempts by subsequent workers to remove completely the nitrate groups, i n order to regenerate the original cellulose, were unsuccessful. The problem of complete denitration of a polysaccharide polynitrate without alteration i n the structure of the parent substance has not yet been solved. By analogy with the saponification of carboxylic acid esters, i t would appear that one should be able to hydrolyze n i t r i c acid esters with solutions of metal hydroxides. Even with simple alkyl nitrates such i s not the case. Kenyon and Gray (28), reviewing the situation i n 1936, noted that various nitrates on alkaline hydrolysis have given a wide range of oxidized products of the parent alcohol. The formation of such products was considered to be due to the reduction of the nitrate groups to n i t r i t e with simultaneous oxidation of the alcohol. Further, the presence of oxygen i n alkaline solution has been shown to oxidize carbohydrate materials, the nature of the products depending upon the severity of the reaction. The racemization and degradation of sugars by a l k a l i has been known since the work of de Bruyn and van Ekenstien (8). This method of complete denitration therefore i s not useful for structural studies i n the carbohydrate f i e l d . Another possibility would be to attempt complete denitration using weaker bases. Thus sodium hydrosulphide reduced n-butyl nitrate to the parent alcohol (35). Similarly pentaerythritol tetranitrate when treated with sodium sulphide gave pentaerythritol (42). Cellulose t r i n i t r a t e , however, upon treatment with sodium or ammonium hydrosulphide yielded a cellulose nitrate s t i l l containing one to two percent of nitrogen (19) ( the theoretical value for cellulose t r i n i t r a t e i s 14.14$ N.). This was p o s s i b l y due to the f a c t that the product was ins o l u b l e i n the reac t i o n mixture and was not f u l l y reacted due t o t h i s heterogeneity. Denitration studies on sugar n i t r a t e s using sodium methylate have been c a r r i e d out by Gladding and Purves (16). These authors considered the foll o w i n g reactions may occur upon d e n i t r a t i o n . In the presence of sodium methylate there may be s c i s s i o n of the C-0 bond leading to anhydro r i n g formation, or al k o x y l s u b s t i t u t i o n , with or without Walden i n v e r s i o n , or double bond formation: X 1 1 1 H-C-ONOo H-Cv H-C-OCH„ H-C | * NaOCHp [;0 or I i or || OgNO-^-H CH^OiT y CH^O-C-H C-0N02 Another possible r e a c t i o n could be s c i s s i o n of the 0-N bond to give the parent a l c o h o l and sodium n i t r a t e : H-|^0-fN02 + NaOH H-(j-OH «f NaNO^ F i n a l l y , i t was suggested that a redox re a c t i o n might occur leading to a carbonyl group and sodium n i t r i t e , the carbonyl group would then undergo f u r t h e r changes i n the a l k a l i n e medium: H-([-0N02 + NaOH (JzO •+- NaNOg H~ H 20 Gladding and Purves were attempting t o show the s i m i l a r i t y between the reactions of a n i t r a t e group and those of the p-toluenesulphonate ( t o s y l ) group. The reactions of the t o s y l group had been studied by Peat (37), who had shown that when a t o s y l group i s attached t o a secondary carbon atom and adjacent, but trans, to a free or p o t e n t i a l l y f r e e hydroxyl group, a l k a l i n e hydrolysis of the t o s y l group r e s u l t s i n anhydro r i n g formation with i n v e r s i o n of configuration of the carbon o r i g i n a l l y carrying the group: - 5 -2-acetyl - 3-tosyl- 2,3-anhydro-4,6-benzylidine--4,6-benzylidine- -methyl- OC-D-alloside -methyl-C^-D-glucoside From the reactions studied, Gladding and Purves concluded that hydrolysis of a nitrate group proceeded in a similar manner to the hydrolysis of a tosyl group; that i s , with inversion of configuration when the nitrate group was adjacent but trans, to a free or potentially free hydroxyl group^' Ansell and Honeyman (1) have shown more recently that the nitrates are more stable to a l k a l i than the tosyl derivatives and inversion does not occur to such a large extent„ Ansell and Honeyman, i n the same work, also demonstrated that methyl--D-glucoside nitrates are more resistant to a l k a l i than the methyl-Q^-D-glucoside nitrates. The denitration method of Oldham (36), involving treatment of the carbohydrate nitrate with iron and zinc powder i n gl a c i a l acetic acid, caused degradation of the sugar molecule as indicated by the low yields of nitrate-free product. For example, the denitration by Dewar and co-workers (11) of methyl-2,4-dimethyl-^>-D-glucoside-3,6-dinitrate by this method to methyl-2,4-dimethyl-jJ-D-glucoside gave only a 31$ yield of the trimethyl-glucose. Consideration of the above techniques shows that none are satis-factory for carbohydrate structure studies. They are unsatisfactory because the carbohydrates are unstable i n a l k a l i and yield a variety of oxidized and degraded products, depending upon the severity of the reaction conditions, or the denitration i s not complete, or the carbohydrates isolated after reaction may have different configurations, or the yield of the reaction i s low. A study of those methods which may be satisfactory for complete denitration must therefore preclude those techniques involving the use of a l k a l i . A search of the literature showed that, i n general, such techniques involve reduction rather than hydrolysis. These reductions have involved catalytic hydrogenolysis, hydrolysis of Grignard adducts, and reaction with hydrazine and a catalyst, a l l leading to replacement of -0N0 2 by -GH. The most elegant treatment was the catalytic hydrogenolysis of Kuhn (3D: 2R0N02 -f 5 H 2 F d > 2R0H + N 2 + 4H 2 0 Kuhn's method has been checked by other workers (20)(40), and has been shown to give high yields of completely denitrated monosaccharide derivatives. Kuhn (32) also proved that methanolic hydrazine denitrated hexanol and cyclohexanol n i t r i c acid esters, i n the presence of palladium-carbon catalyst, with high yields of the parent alcohol: 2 0 ^ 0N02 4- 2N 2H 4 2C 6H 1 30H + 2N 2 -f- N 20 -f 3 ^ 0 Another interesting reaction was that between alkyl nitrates and a Grignard reagent. Hepworth (22) i n 1921 showed that when ethyl nitrate reacted with methyl magnesium iodide the products formed were ethanol and N,N-dimethylhydroxylamine, although only the l a t t e r was isolated: C 2 H 5OM0 2 +3CH 3 M g I -OMgl C 2 H 5 O M ( C H 3 ) 2 2H 2 0 M g l ^ _ | l y -h MgO + CH^I 2Mg(0H) l -f-OH C 2 H 5 O N ( C H 3 ) 2 C 2 H 5 OH -+- (CH 3 ) 2N0H A f o u r t h method o f d e n i t r a t i o n was t h a t o f S o f f e r e t a l , ( 4 4 ) i n v o l v i n g the a c t i o n o f l i t h i u m aluminium h y d r i d e on a l k y l n i t r a t e s . Thus h e x y l n i t r a t e reac ted w i t h an e t h e r e a l s o l u t i o n o f l i t h i u m aluminium hydr ide t o g i v e hexanol i n 90$ y i e l d . A r e d u c t i o n method which might be a p p l i c a b l e t o d e n i t r a t i o n was t h a t o f C a l v i n (10), W e l l e r and M i l l s (47). These authors have shown t h a t s o l u t i o n s o f cuprous o r c u p r i c ace ta t e i n p y r i d i n e c a t a l y z e d the hydro-gena t ion o f quinone t o hydroquinone. Al though p y r i d i n e was known t o r eac t w i t h carbohydrate p o l y n i t r a t e s (20), i t was f e l t t h a t the presence o f hydrogen would prevent any o x i d a t i o n which might o therwise o c c u r . I t was hoped t h a t t h i s r e a c t i o n would be a p p l i c a b l e t o carbohydrate p o l y n i t r a t e d e n i t r a t i o n , s i n c e the c a t a l y s t would be homogeneously mixed w i t h the carbohydrate p o l y n i t r a t e . The u s u a l c a t a l y t i c r e d u c t i o n o f c e l l u l o s e n i t r a t e s cannot go t o comple t ion because as the r e a c t i o n proceeds the p a r t i a l l y n i t r a t e d c e l l u l o s e p r e c i p i t a t e s out and the heterogeneous c a t a l y s t , such as p a l l a d i u m suspended on carbon , cannot pene t ra te the f i b e r s . Wi th , an homo-geneous' catalyst*, however, the r e a c t i o n might be expected t o go t o comple t ion because the c a t a l y s t cou ld pene t ra te the f i b e r s even though the r e a c t i o n mix tu re was heterogeneous. Fur thermore , i t was hoped t h a t t h i s r e a c t i o n would comple te ly d e n i t r a t e the ca rbohydra te . Thus c e l l u l o s e t r i n i t r a t e has been shown t o r eac t w i t h p y r i d i n e , i n the presence o f hydroxylamine , - 8 -t o g i v e a c e l l u l o s e d i n i t r a t e which was s t a b l e t o f u r t h e r a t t a c k by the reagents (43). D - M a n n i t o l h e x a n i t r a t e has a l s o been shown t o r eac t w i t h p y r i d i n e t o g i v e D-n ia ru i i to l - l ,2,3,5,6 -pen tan i t r a t e (21). S i m i l a r l y , D - g a l a c t i t o l ( d u l c i t o l ) h e x a n i t r a t e has been shown by McKeown (34) t o r eac t w i t h p y r i d i n e t o g i v e the racemic m i x t u r e o f d u l c i t o l -1 ,2 ,3,5,6, - p e n t a -n i t r a t e and d u l c i t o l - 1 , 2 , 4 , 5 , 6 7 p e n t a n i t r a t e . The f a t e o f the p y r i d i n e i n these r e a c t i o n s i s not known w i t h c e r t a i n t y , but Brown (7) has shown t h a t a t l e a s t one mole o f p y r i d i n e s u f f e r s r i n g opening w i t h l o s s o f n i t r o g e n and the probable fo rma t ion o f g lu taconaldehyde which may undergo f u r t h e r changes i n the a l k a l i n e s o l u t i o n . I n summary, i t has been shown t h a t the use o f i n o r g a n i c bases f o r q u a n t i t a t i v e d e n i t r a t i o n o f carbohydrate n i t r a t e s was not f e a s i b l e s i n c e t h e y caused changes i n c o n f i g u r a t i o n , degrada t ion and o x i d a t i o n o f the parent p o l y o l . Those methods i n v o l v i n g r e d u c t i o n w i t h hydrogen are v e r y u s e f u l f o r s imple p o l y o l s but r e d u c t i o n o f p o l y s a c c h a r i d e s w i t h a heterogeneous c a t a l y s t may not be f e a s i b l e . The r e d u c t i o n r e a c t i o n s .appeared t o ? be the most p romis ing and these were s t u d i e d , i n t h i s r e s e a r c h , w i t h s e v e r a l mono- and d i s a c c h a r i d e n i t r a t e s w i t h the ob jec t o f e x t r a p o l a t i n g t he use o f these r e d u c t i o n r e a c t i o n s t o the complete d e n i t r a t i o n o f c e l l u l o s e n i t r a t e and t o p o l y s a c c h a r i d e n i t r a t e s i n g e n e r a l . DISCUSSION OF RESULTS A. The Preparation of the Carbohydrate Polynitrate Model Compounds. The carbohydrate polynitrates prepared are listed -in Table I together with their physical constants. The criteria for the selection of the carbohydrate polynitrates studied were the presence of certain character-i s t i c linkages in the parent carbohydrate, the abundance of the parent carbohydrate or its ease of preparation, and the absence of complication in the structure of the parent carbohydrate so that the products of a reaction would be easily identified. Thus cellobiose and maltose octa-nitrates were selected for study because of their relationships to cellulose nitrate and starch nitrate respectively. These octanitrates, however, contain a hemi-acetal nitric acid ester group and methyl-ji-cellobioside heptanitrate was included in the study as a more accurate model of a poly-saccharide nitrate in which this labile nitrate group would be present in negligible proportions. The ease of isolation and identification of the carbohydrate product of a reaction was one of the main reasons why the reduction reactions of the simple carbohydrate polynitrates was studied before attempting any reactions involving polysaccharide nitrates. Thus D-mannitol hexanitrate was generally studied first with any reagent because the molecule was a true polyol nitric acid ester and because the products from a reaction would be easier to isolate and characterize than those resulting from the use of a more complex carbohydrate polynitrate. The presence of an aglycon nitrate group made the purification of cellobiose and maltose octanitrates difficult. Apparently this aglycon nitrate group was labile for when ethanol solutions of the octanitrates, especially cellobiose octanitrate, were heated above 50°C., to effect T A B L E I PHYSICAL CONSTANTS OF THE CARBOHYDRATE POLYNITRATES P2EPAHED AS MODEL SUBSTANCES Carbohydrate Nitrate Constants Found m.p. °c IjY^ B0 Cono. and Solvent Literature Values m.p. °0 rorJn C o n o # a M  J V Solvent Sefer--enoe Cellobiose Ootanitrate 150 + 88.92° 5% 0ln 140 + 22.2° 6$ in 16) adetone acetone 154 - - — (2) Maltose Ootanitrate 164-5 + 8.53° 1% in 163-4 + 128.6° rc35£ in (49) dioxane aoetio aoid 164^5 - (2) D-Mannitol Hexanitrate 111 + 43.03y 2% i n 111-2 + 43.1° Z% in (21) - .. - • - ethanol =- • ethanol D-Mannitol-1,2,3,5,6- 80 + 47.16° 4$ in 81-2 + 47.7?* 4% in (21) pentanitrate ethanol ethanol Methyl-p>-Cellobi08ide 136 + .16.19° 1.25$ in 134 + 20.3° 4$> in 113) Heptanitrate acetone • acetone s Hayoard, L.D. Private Comnonloation. - 1 1 -r e c r y s t a l l i z a t i o n s , the s o l u t i o n became y e l l o w and a syrup r e s u l t e d upon c o o l i n g . The p u r i f i c a t i o n o f these o c t a n i t r a t e s was f i n a l l y ach ieved by the method o f Hibber t et aJU (2), t h a t i s , by t a k i n g up the crude n i t r a t e i n warm methanol , t r e a t i n g w i t h carbon and anhydrous sodium su lpha te , f i l t e r i n g and e f f e c t i n g subsequent r e c r y s t a l l i z a t i o n s from e ther -methanol , by evapo ra t i on . I t was no ted , as H ibbe r t r e p o r t e d , t ha t d i s s o l u t i o n o f crude c e l l o b i o s e o c t a n i t r a t e was much e a s i e r than the d i s s o l u t i o n o f the pure compound, i n f a c t , t he pure c e l l o b i o s e o c t a n i t r a t e needed about t e n t imes more so lven t f o r r e c r y s t a l l i z a t i o n than the crude p roduc t . The s p e c i f i c r o t a t i o n o f these d i s a c c h a r i d e n i t r a t e s d i f f e r e d from those repor ted i n the l i t e r a t u r e . T h i s cou ld have been due t o the presence o f bo th the d -and | i - forms o f the o c t a n i t r a t e s i n p r o p o r t i o n s d i f f e r i n g from those ob ta ined by o ther workers (2), (6)., (49), and i n the case o f the mal tose o c t a n i t r a t e might a l s o have been due t o the use o f dioxane i n s t e a d o f g l a c i a l a c e t i c a c i d as the so lven t f o r the de t e rmina t i on o f the s p e c i f i c r o t a t i o n . I t was unfor tuna te t h a t the m e t h y l - ^ - c e l l o b i o s i d e h e p t a n i t r a t e was prepared from a syrup o f m e t h y l - | 3 - c e l l o b i o s i d e r a t h e r than the c r y s t a l -l i n e form, but the h e p t a n i t r a t e was p u r i f i e d e a s i l y by r e c r y s t a l l i z a t i o n from e thanol -wate r and d i d not appear t o be a f f e c t e d by hea t i ng e t h a n o l i c s o l u t i o n s o f i t t o the b o i l i n g p o i n t . A l l o ther n i t r a t e s were prepared e a s i l y and t h e i r p h y s i c a l cons tants agreed w i t h those r epor t ed i n the l i t e r a t u r e . The p r e p a r a t i o n o f c e l l u l o s e t r i n i t r a t e was at tempted f i r s t u s i n g o a s o l u t i o n o f n i t r o g e n pentoxide i n ch lo r o f o r m . I t was f e l t t ha t t h i s s o l u t i o n would g i v e l e s s degrada t ion and o x i d a t i o n o f the c e l l u l o s e molecu le - 1 2 -than would the conventional method of n i t r a t i o n w i t h mixtures of concen-t r a t e d n i t r i c and s u l p h u r i c a c i d s . The product i s o l a t e d from t h i s r e a c t i o n , however, had a degree of s u b s t i t u t i o n approximating two n i t r a t e groups per glucose residue i n the c e l l u l o s e molecule, and upon f u r t h e r examination i t was found t h a t the product could be separated i n t o two f r a c t i o n s by-e x t r a c t i o n w i t h ethylene g l y c o l monomethyl ether. This r e s u l t was probably due t o the high degree of d i l u t i o n of the n i t r o g e n pentoxide i n the c h l o r o -form (1%), r e s u l t i n g in n i t r a t i o n of a topochemical c h a r a c t e r . For f u t u r e work, i t i s suggested t h a t i t would be more convenient t o use a c e l l u l o s e n i t r a t e rendered more t r u l y homogeneous by a s e r i e s of c a r e f u l f r a c t i o n a t i o n s . N i t r a t i o n of c e l l u l o s e was then attempted u s i n g f r e s h l y d i s t i l l e d n i t r i c a c i d (lOO/o) c o n t a i n i n g phosphorus pentoxide as the dehydrating agent. Although these reagents may have given r i s e t o a small amount of o x i d a t i o n and degradation of the c e l l u l o s e molecule, i t was known th a t t h i s reagent gave products approximating t o a t r i n i t r a t e ( 4 3 ) . The product of t h i s r e a c t i o n was a c e l l u l o s e n i t r a t e w i t h a degree of s u b s t i t u t i o n of 2 . 7 2 n i t r a t e groups per glucose residue i n the c e l l u l o s e molecule, and appeared t o be reasonably homogeneous. No e x p l a n a t i o n can be found f o r t h i s comparatively low degree of substitution,-. • • ' ... -• • . .'.t B. Hydrogenolysis with Palladium-Carbon Catalyst. could be hydrogenated w i t h palladium-carbon c a t a l y s t t o give high y i e l d s of the parent carbohydrate. Since then other workers ( 2 0 ) , ( 2 1 ) , ( 3 4 ) have shown t h a t the r e a c t i o n was a p p l i c a b l e t o a v a r i e t y of monosaccharide p o l y n i t r a t e d e r i v a t i v e s . As t h i s r e a c t i o n has been w e l l worked out, t h i s In 1 9 4 6 Kuhn ( 3 1 ) had shown t h a t the o(- and o -13-technique was i n c l u d e d w i t h the n i t r a t e n i t r o g e n analyses of the n i t r a t e s prepared i n t h i s research as a proof of s t r u c t u r e (see a l s o Table I I ) . I n g e n e r a l the y i e l d s of d e n i t r a t e d carbohydrate from t h i s r e a c t i o n were g r e a t e r than 95$ and. these products were reasonably pure. The high y i e l d s were due t o the f a c t t h a t the hydrogenolysis product of the -NO2 group was n i t r o g e n and not ammonia and thus, as Kuhn (31) s t a t e d , t h ere can be no side r e a c t i o n s . Another reason f o r the high y i e l d s was the f a c t t h a t the s t a r t i n g m a t e r i a l and the f i n a l product were both s o l u b l e i n the solvent (ethanol) used f o r the hydrogenations; i t would be expected t h a t i f a p a r t i a l l y d e n i t r a t e d carbohydrate was i n s o l u b l e i n the r e a c t i o n s olvent then the r e a c t i o n would probably not go t o completion. Thus i t was a n t i c i p -ated t h a t one may not be able t o completely d e n i t r a t e c e l l u l o s e t r i n i t r a t e , but t h a t the r e a c t i o n might stop when the p a r t i a l l y d e n i t r a t e d c e l l u l o s e n i t r a t e became i n s o l u b l e i n the r e a c t i o n s o l v e n t . This research showed f u r t h e r the g e n e r a l i t y of the r e a c t i o n , the importance of the s o l u b i l i t y of both the reactant and the product, and the importance of having the reactants pure and f r e e from c a t a l y t i c poisons. Thus some d i f f i c u l t y was encountered when hydrogenating m e t h y l - ^ - c e l l o b i o -s i d e h e p t a n i t r a t e and maltose o c t a n i t r a t e . The methyl- ^ - c e l l o b i o s i d e h e p t a n i t r a t e was f i n a l l y hydrogenated when the solvent was p u r i f i e d and the rubber connections were cleaned w i t h hot sodium hydroxide s o l u t i o n ; the f i r s t f a i l u r e t o hydrogenate was t h e r e f o r e a t t r i b u t e d t o a t r a c e of p y r i d i n e l e f t i n the rubber connection from previous r e a c t i o n s . The hydrogenation of maltose o c t a n i t r a t e was achieved when the o r i g i n a l sample of maltose o c t a n i t r a t e was thrown out and more synthesized from p u r i f i e d maltose. I t was p o s s i b l e t h a t the o r i g i n a l sample of maltose o c t a n i t r a t e was decomposed TABLE II REACTIONS OF TH£ MODEL OASBOHZDSAIE POLYNITRATES Beduoing Agent 2ef« Nitrates Used Products Isolated Yield D.F.*Pest Methanolio Hydrazine Pd-C Catalyst (32) Cellobiose Octanitrate l l * 0 g») D-Mannitol Hexanitrate (0*97 g.) Orange Syrap 10«80 g.) Orange Syrup (0.77 g.) + + Methyl "?  Magn.es lum Iodide (22) Cellobiose Oota-nitrate i0.?5 g«) Ether layer-syrup (0.17 g.) Water layer-syrup-Oellobiose Ootaaoetate (0.1 g.) 10.956 + Hydrogen} Cuprio Aoetate in Pyridine (10) (47) D-Mannitol Hexanitrate 10.93 g.) D^aiannitol-1,2,3,5,6-Fentanitrate (2 runs. 0.97 & 0*92 g. Ether iayer-*syrup (0»21 g.) Water layer*«yrup 10.30 g.)-D-Mannitol Hezaaoetate Froduots not identified, did not appear to be carbohydrate 34.1> 4-LiAlH. 4 (44) D-41annItol Hexanitrate (0*95 g.) Bther layer-syrup (0.05 gi) Water layer, D*Mannitol Hezaaoetate (0.79 g.) 83.0% -f * Diphenylamiae-Sulplmris Apid. A ^ puitStue test indicated the pr«ssme« of nitrate nitrogen. oontinued on next page TABLE: I I continued Seducing Agent 3ef. Nitrates Used Products Isolated Yield D.P. Test Hydrogen Pd/C Catalyst (31) Cellobiose Ootanitrate (0*98 g.) Maltose Ootanitrate (1*22 g*) Methyl** P **Ceilobioside Heptanitrate (0.125 g.) V ' D-Mannitol Hexanitrate (0*97 g.) Methyl-/* *C-Gluoopyranos id e Tetranltrate (0*998 g.) Cellobiose (0.47 g.) Maltose (0.59 g.) Methyl* (J-Cellobioside (0.05 g.) D-Mannitol (0.39 g.) Methyl- (i*D« Gluoopyranoside (0.515 g.) 99.2$ 99.5$ 75.2?g 97.5% 99;«5jg -15-s l i g h t l y due t o s t and ing too l o n g a t room tempera ture . C . Reduc t ion w i t h Hydraz ine . I n 1951 Kuhn (32) showed t h a t methanol ic hyd raz ine i n the presence o f pa l l ad ium-ca rbon c a t a l y s t would reduce a l k y l e s t e r s o f n i t r i c o r n i t r o u s a c i d s t o the parent a l c o h o l . The r e a c t i o n s took p l a c e a t room temperature but the reagents would not reduce c a r b o n y l o r o l e f i n i c compounds showing t h a t the hydraz ine on p a l l a d i u m was a weaker r educ ing agent than hydrogen on p a l l a d i u m . T h i s r e a c t i o n was s t u d i e d because the r educ ing agent was i n the l i q u i d phase and t h e r e f o r e a v a i l a b l e t o the c a t a l y s t and the sugar n i t r a t e . Some apprehension, however, was f e l t concern ing the b a s i c cha r -a c t e r o f the hydraz ine which might have g i v e n r i s e t o i n v e r s i o n o f c o n f i g -u r a t i o n . The attempted r educ t ions o f c e l l o b i o s e o c t a n i t r a t e and D-manni to l h e x a n i t r a t e were u n s u c c e s s f u l . The weights o f the syrups ob ta ined a f t e r r e a c t i o n and the e v o l u t i o n o f gas i n d i c a t e d t h a t some d e n i t r a t i o n had taken p l a c e . The p roduc t s , however, c o u l d not be c r y s t a l l i z e d and were ob ta ined as orange co loured sy rups . These r e s u l t s may have been due t o the b a s i c na ture o f the h y d r a z i n e , but the hydraz ine may a l s o have a t t acked c e r t a i n carbon atoms t o form ca rbon-n i t rogen bonds w i t h the s p l i t t i n g out o f n i t r i c a c i d o r wate r , an ag lycon n i t r a t e group may have s p l i t o f f w i t h opening o f the pyranose r i n g t o form an aldehyde group which would then r eac t w i t h the hydraz ine t o form a hydrazone, o r the r e a c t i o n may have been s t e r i c a l l y h inde red , a l l l e a d i n g t o incomple te d e n i t r a t i o n o r u n d e s i r a b l e s i d e r e a c t i o n s . From the r e s u l t s ob ta ined (Table I I ) the r e a c t i o n was cons idered u s e l e s s f o r complete d e n i t r a t i o n o f carbohydrate p o l y n i t r a t e s and was not i n v e s t i g a t e d f u r t h e r . - 1 6 -D . Reduc t ion w i t h M e t h y l Magnesium I o d i d e . Hepworth (22) i n 1924 showed t h a t e t h y l n i t r a t e reac ted w i t h me thy l magnesium i o d i d e t o form e thano l and N,N-d ime thy lhydroxy lamine , a l t hough o n l y the l a t t e r was i s o l a t e d . T h i s r e a c t i o n was i n v e s t i g a t e d because the n i t r o g e n r e d u c t i o n product would have been d imethylhydroxylamine which was not expected t o r eac t w i t h any r e s i d u a l n i t r a t e groups present and thus g i v e u n d e s i r a b l e s i d e r e a c t i o n s . Fur thermore , the r e a c t i o n d i d not depend on a d s o r p t i o n on a c a t a l y t i c sur face but was e n t i r e l y homogeneous. The disadvantage t o the r e a c t i o n was the f a c t t ha t the n i t r a t e s were not v e r y s o l u b l e i n d i e t h y l e ther and t h e r e f o r e o the r e ther type compounds were r e q u i r e d as s o l v e n t s f o r the r e a c t i o n . The use o f dioxane was i n v e s t i g a t e d but i t was found t h i s so lven t forms an a d d i t i o n complex w i t h G r i g n a r d ' s reagent . Thus Schlenk and Schlenk (41) found t h a t from the e q u i l i b r i u m 2EMgX ^ + M g X 2 the RMgX and the MgX 2 may be q u a n t i t a t i v e l y p r e c i p i t a t e d as complexes w i t h d ioxane , l e a v i n g o n l y the R^Ig component i n the s o l u t i o n . The problem was s o l v e d by forming the G r i g n a r d reagent i n anhydrous e the r , and then adding a s o l u t i o n o f the n i t r a t e t o be reduced i n t e t r ahyd ro fu rane , i n which so lven t the carbohydrate n i t r a t e s were r e a d i l y s o l u b l e . The r educ t ions o f c e l l o b i o s e o c t a n i t r a t e and D-manni to l h e x a n i t r a t e w i t h methyl magnesium i o d i d e were shown t o g i v e low y i e l d s o f the parent a l c o h o l (Table I I ) . The a d d i t i o n complex between the G r i g n a r d reagent and the n i t r a t e was broken up by the a d d i t i o n o f water w i t h the subsequent fo rma t ion o f magnesium h y d r o x i d e s . The fo rmat ion o f t h i s base compl ica ted the i s o l a t i o n o f the carbohydrate produced i n the r e a c t i o n s i n c e the presence o f t h i s base might cause i n v e r s i o n of the sugar c o n f i g u r a t i o n . -17-There fo re , the magnesium hydroxides were t r e a t e d w i t h a c e t i c a c i d , and the wate r l a y e r , i n wh ich the f ree sugars would be found, was evaporated t o dryness and the res idue ob ta ined was t r e a t e d w i t h a c e t i c anhydride and p y r i d i n e t o a c e t y l a t e any carbohydrates p resen t . The carbohydrate ace ta tes thus formed were e a s i l y separated from the i n o r g a n i c r e s idues by v i r t u e o f the s o l u b i l i t y o f the former i n o rgan ic so lven t s such as ch lo ro fo rm . S ince the exper imenta l c o n d i t i o n s r e q u i r e d t h a t the carbohydrates be i s o l a t e d i n the form o f t h e i r a c e t a t e s , t h i s f a c t p rec luded the p o s s i b i l i t y o f u s i n g t h i s r e a c t i o n as a gene ra l means o f d e n i t r a t i o n o f p o l y s a c c h a r i d e n i t r i c a c i d e s t e r s . Fur thermore, the cos t o f the chemica ls i n v o l v e d would be p r o h i b i t i v e f o r a p p l i c a t i o n o f t h i s method on a l a r g e s c a l e . E . Reduct ion w i t h L i t h i u m Aluminium H y d r i d e . I n 1 9 5 2 S o f f e r et a l . ( 4 4 ) demonstrated t h a t v a r i o u s a l k y l n i t r a t e s and n i t r i t e s cou ld be reduced t o the parent a l c o h o l by an e t h e r e a l s o l u t i o n o f l i t h i u m aluminium h y d r i d e . N i t r a t e r e d u c t i o n products were n i t r o u s ox ide and ammonia. C e l l u l o s e n i t r a t e s were a l s o comple t e ly reduced but v i s c o s i t y measurements showed t h a t ex t ens ive degrada t ion o f the molecu le had o c c u r r e d . T h i s r e a c t i o n was s t u d i e d , however, i n o rder t o note the e f f e c t o f l i t h i u m aluminium hydr ide on s imple carbohydrate p o l y n i t r a t e s . The disadvantages to. the r e a c t i o n were the fo rma t ion o f ammonia and n i t r o u s ox ide which may form by-produc ts w i t h unreac ted sugar n i t r a t e . Bes ides the f a c t t ha t the c e l l u l o s e molecule i s degraded, another reason why t h i s r e a c t i o n p robab ly would not be a p p l i c a b l e t o p o l y s a c c h a r i d e d e n i t r a t i o n i s t h a t i f t h e r e were any u r o n i c a c i d u n i t s i n the polymer these would be reduced t o the a l c o h o l , and t h e r e f o r e cou ld not be d i s t i n g u i s h e d from o the r monomer u n i t s , i f bo th were d e r i v a t i v e s o f the same monosaccharide. o -18-The r e d u c t i o n of D-mannitol h e x a n i t r a t e w i t h l i t h i u m aluminium hydride was s u c c e s s f u l as evidenced by the h i g h y i e l d of D-mannitol hexa-acetate from the r e a c t i o n . The product was i s o l a t e d as the hexaacetate r a t h e r than the f r e e carbohydrate because of the presence of l i t h i u m alumin-ate upon h y d r o l y s i s of the a d d i t i o n product. Again the i s o l a t i o n of the acetate d e r i v a t i v e precluded the use of t h i s r e a c t i o n as a g e n e r a l method of complete d e n i t r a t i o n . T h i s r e a c t i o n may, however, be u s e f u l f o r the formation of the acetate d e r i v a t i v e from the n i t r a t e d e r i v a t i v e of a simple carbohydrate. Thus a carbohydrate could be c h a r a c t e r i z e d by forming i t s n i t r a t e d e r i v a t i v e and from the n i t r a t e the acetate could be produced. Wolfrem and co-workers (50) have t r a n s e s t e r i f i e d n i t r a t e e s t e r s w i t h mixtures of c o l d a c e t i c anhydride and s u l p h u r i c a c i d t o form the acetate e s t e r . The presence of the s u l p h u r i c a c i d , however, may l e a d t o h y d r o l y s i s of g l y c o s i d i c l i n k a g e s . The main disadvantage t o the r e d u c t i o n of carbohydrate n i t r a t e s w i t h l i t h i u m aluminium hydride was the f a c t t h a t the r e a c t i o n was dangerous, due t o the presence of two such s e n s i t i v e molecules as the n i t r a t e and the l i t h i u m aluminium hydride. F. Reduction w i t h Hydrogen; Cupric Acetate i n P y r i d i n e C a t a l y s t . The r e d u c t i o n of quinone t o hydroquinone by means of hydrogen a c t i v -ated by a cuprous or c u p r i c acetate c a t a l y s t i n p y r i d i n e s o l u t i o n has been st u d i e d by C a l v i n (10), W e l l e r and M i l l s (47). This method of r e d u c t i o n was chosen f o r study because the hydrogenation c a t a l y s t was homogeneous. Thus i f c e l l u l o s e t r i n i t r a t e were t o be reduced the r e a c t i o n may stop at a stage at which a c e l l u l o s e n i t r a t e begins t o separate out from the r e a c t i o n mixture. An heterogeneous c a t a l y s t , being unable t o penetrate the f i b e r s of the c e l l u l o s e n i t r a t e , would not c a t a l y z e any f u r t h e r r e d u c t i o n , however, an homogeneous - 1 9 -hydrogenation c a t a l y s t would s t i l l be able t o penetrate the f i b e r s of the p r e c i p i t a t e d c e l l u l o s e n i t r a t e . I t was unfortunate t h a t the solvent f o r the r e a c t i o n was p y r i d i n e s i n c e t h i s weak base was kwown t o a t t a c k carbo-hydrate p o l y n i t r a t e s . I t " was f e l t , however, t h a t the presence of hydrogen would prevent any o x i d a t i o n from t a k i n g p l a c e . Hayward (21) had shown t h a t D-mannitol h e x a n i t r a t e r e a c t s w i t h p y r i d i n e at room temperature t o form 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 which was i s o l a t e d by pouring the r e a c t i o n mixture i n t o water. The D-mannitol p e n t a n i t r a t e must t h e r e f o r e react r a t h e r s l o w l y w i t h p y r i d i n e a t room temperatures and t h i s n i t r a t e xiras chosen as the one t o be s t u d i e d w i t h the homogeneously c a t a l y z e d hydrogen-ation„(Table I I ) . In blank runs us i n g f i r s t c u p r i c acetate i n p y r i d i n e and secondly D-niannitol - 1 , 2 , 3 <> 5 , 6 - p e n t a n i t r a t e i n p y r i d i n e t h e r e was no hydrogen consumed. I n the a c t u a l experiment w i t h the p e n t a n i t r a t e and the c a t a l y s t present, there was a l i t t l e hydrogen consumed, although i n an i r r e g u l a r manner. The main product of the r e a c t i o n appeared t o be the copper s a l t of some strong organic a c i d . The s t r u c t u r e of t h i s a c i d was not examined f u r t h e r . The determination of the s t r u c t u r e of t h i s a c i d , however, may i l l u m i n a t e f u r t h e r the mechanism of the r e a c t i o n and the f a t e of the p y r i d i n e i n the p a r t i a l d e n i t r a t i o n of D-mannitol h e x a n i t r a t e t o 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 . So f a r the o n l y research i n t o the mechanism of t h i s r e a c t i o n has been reported from t h i s l a b o r a t o r y by Brown ( 7 ) . He found t h a t , besides n i t r o u s oxide, n i t r i c oxide, n i t r o g e n , p y r i d i n i u m n i t r a t e , and the D-mannitol p e n t a n i t r a t e , there were at l e a s t twelve other non-nitrogenous products formed which could be i s o l a t e d by p a p e r - p a r t i t i o n chromatography. I n a d d i t i o n t o some decomposition of the D-mannitol s k e l e t o n there must a l s o -20-have been r i n g opening of the p y r i d i n e . G. Reduction of the C e l l u l o s e N i t r a t e s . , Once i t had been shown t h a t the r e d u c t i o n w i t h hydrogen o f f e r e d the most elegant method f o r complete d e n i t r a t i o n of simple carbohydrate p o l y n i t r a t e s , the l o g i c a l procedure was t o study t h i s r e d u c t i o n method w i t h c e l l u l o s e n i t r a t e s . The choice of c a t a l y s t , however, was extremely import-ant. The c a t a l y s t must be e a s i l y removed; s o l u t i o n s of c e l l u l o s e n i t r a t e s form g e l s and cannot be f i l t e r e d and i f any d e n i t r a t i o n should occur, l e a d i n g t o a suspension of c e l l u l o s e n i t r a t e , the c a t a l y s t could not be separated by c e n t r i f u g a t i o n . Thus palladium-carbon and the more powerful platinum b l a c k , could not be used as c a t a l y s t s s i n c e t h e i r s e p a r a t i o n must have n e c e s s a r i l y i n v o l v e d use of reagents which would have degraded the c e l l u l o s e or c e l l u l o s e n i t r a t e . Kuhn (31) d i s c o v e r e d the hydrogenolysis of simple carbohydrate p o l y n i t r a t e s and st u d i e d the use of v a r i o u s c a t a l y s t s . He i n v e s t i g a t e d the r e d u c t i o n of these n i t r a t e s w i t h Raney n i c k e l , platinum b l a c k , palladium suspended on calcium carbonate and pa l l a d i u m suspended on ch a r c o a l c a t a l y s t s a t a hydrogen pressure of 1500 p . s . i . . He found t h a t a l l these c a t a l y s t s , except palladium-carbon, reduced the n i t r o g e n t o ammonia t o which unreacted n i t r a t e groups may be s e n s i t i v e . Therefore Kuhn used palladium-carbon c a t a l y s t a t lower pressures even though he showed t h a t palladium-calcium carbonate gave o n l y elemental n i t r o g e n as the n i t r a t e r e d u c t i o n product below pressures of 1500p.s.i.. At t h i s pressure he found i t i mpossible t o stop the r e d u c t i o n a t the elemental n i t r o g e n stage i n the case of Raney n i c k e l and platinum b l a c k and furthermore a temperature of 65°C. was necessary i n the case of the Raney n i c k e l . Raney n i c k e l was chosen, however, f o r the c a t a l y s t i n t h i s research. -21-Kuhn d i d not demonstrate t ha t Raney n i c k e l would not c a t a l y z e the r e a c t i o n below 1500p .s.i , o f hydrogen. The sample o f Raney n i c k e l used i n t h i s r e s e a r c h was known t o c a t a l y z e the hydrogena t ion o f o l e f i n i c double bonds a t room temperature and a t v e r y low pressures o f hydrogen. The main reason f o r the use o f the Raney n i c k e l was i t s e legant s e p a r a t i o n from s o l u t i o n s o f c e l l u l o s e n i t r a t e by means o f a magnetic f i e l d which a t t r a c t e d the c a t a l y s t t o the bottom o f the r e a c t i o n v e s s e l . T h i s s e p a r a t i o n l e f t v e r y l i t t l e Raney n i c k e l suspended i n s o l u t i o n as evidenced by the low ash content o f the c e l l u l o s e n i t r a t e s a f t e r hydrogena t ion . The r e s u l t s ob ta ined a t room temperature and about f o u r atmospheres pressure o f hydrogen showed ' t h a t v e r y l i t t l e d e n i t r a t i o n took p l a c e ; the r e a c t i o n was p robab ly t o p o -chemica l i n c h a r a c t e r . The amount o f r e d u c t i o n i n such r e a c t i o n s i s known t o v a r y w i t h the so lven t used , the temperature o f the r e a c t i o n and the pressure o f hydrogen. Thus i t i s p o s s i b l e t ha t more r e d u c t i o n may take p l a c e i f the exper imenta l c o n d i t i o n s are v a r i e d , keeping i n mind the l i m i t a t i o n found by Kuhn t h a t the n i t r a t e group may be reduced t o ammonia thus g i v i n g r i s e t o a l k a l i n e h y d r o l y s i s . - 2 2 -CONCLUSIONS 1. The complete d e n i t r a t i o n of D-mannitol h e x a n i t r a t e , methyl-(i>-D-gluco-p y r a n o s i d e ; t e t r a n i t r a t e , c e l l o b i o s e o c t a n i t r a t e , maltose o c t a n i t r a t e and m e t h y l - j ^ - c e l l o b i o s i d e h e p t a n i t r a t e , was accomplished by u s i n g hydrogen, at pressures of approximately 55 p . s . i . , w i t h palladium-carbon c a t a l y s t . I n each case the y i e l d of the parent carbohydrate was good and the product was e a s i l y i d e n t i f i e d a f t e r i s o l a t i o n , • care was-required*, however, t o ensure t h a t the s t a r t i n g m a t e r i a l s were pure and f r e e from t r a c e s of p y r i d i n e o r other c a t a l y s t poisons. 2. I n an e f f o r t t o f i n d an homogeneous hydrogenation c a t a l y s t f o r the r e d u c t i o n of carbohydrate p o l y n i t r a t e s , the r e d u c t i o n o f D-mannitol-1,2,3,5,6-p e n t a n i t r a t e w i t h hydrogen u s i n g c u p r i c acetate i n p y r i d i n e c a t a l y s t was st u d i e d . The product of the r e a c t i o n appeared t o be the copper s a l t of a strong organic a c i d and was not i n v e s t i g a t e d f u r t h e r . 3. The use of methanolic hydrazine w i t h palladium-carbon c a t a l y s t was a l s o shown t o be i n e f f e c t i v e f o r complete d e n i t r a t i o n of carbohydrate p o l y n i t r a t e s , the probable reason f o r t h i s being the b a s i c i t y of the hydrazine g i v i n g r i s e t o u n d e s i r a b l e side r e a c t i o n s . 4. The use of methyl magnesium i o d i d e as a reducing agent was s t u d i e d . The parent carbohydrate had t o be i s o l a t e d from the r e a c t i o n as i t s a c e t i c a c i d e s t e r t o prevent degradation by bases formed upon h y d r o l y s i s of the a d d i t i o n complex and the y i e l d s from the r e a c t i o n were low. 5. L i t h i u m aluminium hydride was found t o reduce D-mannitol h e x a n i t r a t e t o the parent p o l y o l but again the p o l y o l was i s o l a t e d as -i t s ; ' a c e t i c a c i d e s t e r . The y i e l d of D-mannitol hexaacetate from the r e a c t i o n , however, was high and i f i t were not f o r the dangerous nature of t h i s r e a c t i o n t h i s method c o u l d f i n d use as a means o f c o n v e r t i n g n i t r i c a c i d e s t e r s o f carbohydrates t o the a c e t i c a c i d e s t e r s . 6 . The use o f hydrogen as a d e n i t r a t i n g agent was extended t o c e l l u l o s e n i t r a t e s . Raney n i c k e l was chosen as the hydrogenat ion c a t a l y s t because i t cou ld be separated m a g n e t i c a l l y from the r e a c t i o n p roduc t . There was" evidence o f a s l i g h t amount o f d e n i t r a t i o n and f u r t h e r s tudy o f t h i s r e a c t i o n seems j u s t i f i e d . 7. F i n a l l y , n i t r a t i o n o f c e l l u l o s e w i t h a d i l u t e s o l u t i o n o f n i t r o g e n pentoxide i n ch loroform was found t o g i v e an heterogeneous c e l l u l o s e n i t r a t e , a l though n i t r a t i o n w i t h n i t r i c a c i d - phosphorus pentoxide appeared t o g i v e a reasonably homogeneous p roduc t . I n f u tu r e work i t would be d e s i r a b l e t o p u r i f y t he c e l l u l o s e n i t r a t e by c a r e f u l so lven t f r a c t i o n a t i o n . - 2 4 -EXPERIMENTAL S p e c i a l P r e c a u t i o n s . To ndji imize the ever -presen t danger o f e x p l o s i o n no more than f i v e grams o f any n i t r a t e was s t o r e d , i n a d r y c o n d i t i o n , a t any t i m e . A l l temperatures were determined i n Cent igrade degrees and were c o r r e c t e d . A . M a t e r i a l s . C e l l o b i o s e . C e l l o b i o s e oc taace ta te was prepared by the method o f Brauns (5) and t h a t o f Gatterman (14), from c o t t o n w o o l . The former method gave the b e t t e r y i e l d and the pu re r p roduc t . The oc taace ta te was p u r i f i e d t o m.p.= 229.5? \P(\B°- + 4 1 . 1 3 ° ( C =4 i n CHCI3). Hudson (24) gave m.p. = 2 2 9 . 5 ° . [ # ] p 0 = + 4 2 ° ( c =10 i n CHCT )'. C e l l o b i o s e was prepared from the oc taace ta te by the method o f Zempl in (52) i n 82$ y i e l d . T h i s was p u r i f i e d by f o u r r e c r y s t a l l i z a t i o n s from methanol-water t o m.p..=i242 0, J G / ] D ° f l *om+.22.29° t o + 3 4 . 4 5 ° ( c =4 i n H 2 0 ) . Pe te rson and Spencer (38) gave m.p . = 225° u n c o r r . , £ O / ] D 0 » + 3 5 . 2 0 f i n a l . WlrLs t l e r and Smart (48) gave m . p . = 230° and Smi th (15) r epor ted m.p. = 2 1 8 ° . C e l l o b i o s e O c t a n i t r a t e . The p r e p a r a t i o n o f t h i s compound was attempted ' f i v e t i m e s . The syn theses gave l ow y i e l d s due t o a l l o w i n g s o l u t i o n s o f the crude o c t a n i t r a t e t o heat above 50°. The s y n t h e s i s was f i n a l l y achieved i n the f o l l o w i n g manner. C e l l o b i o s e (5.04 g . ) was n i t r a t e d by the method o f W i l l and Lenze (49). The product was p u r i f i e d by the method o f H ibbe r t et a l ( 2 ) , keeping the temperature below 30° a t a l l t imes d u r i n g evapora t ion o f the mother l i q u o r s , t o g i v e c e l l o b i o s e o c t a n i t r a t e (6.67 g . ) , 64.2$ o f t h e o r y . A l l samples o f the o c t a n i t r a t e vrere then p u r i f i e d t o constant s p e c i f i c r o t a t i o n and m e l t i n g p o i n t . Values found were m.p. = 1 5 0 ° , [o^Jf^ +88.92° J (c - 5 i n a ce tone ) . B r i s s a u d ( ; 6 : ) gave m .p .= 1 4 0 ° , jpCjD + - 2 2 ° . 1 1 ' (c = 6 i n acetone) and Hibbe r t (2) gave m.p. = 1 5 4 ° . C e l l o b i o s e o c t a n i t r a t e (0 .98 g . ) was d i s s o l v e d i n e t h a n o l , then hydrogenated a t 5 3 p . s . i . f o r one hour i n the presence o f p a l l a d i u m -carbon c a t a l y s t ( 0 . 3 0 g . ) . The c a t a l y s t was prepared by the method o f Hartung ( 1 8 ) . The product was c e l l o b i o s e ( 0 . 4 7 g . ) , (99.2%). The product mel ted a t 2 4 2 ° and the mix tu re w i t h an a u t h e n t i c sample mel ted at 2 4 1 ° . Met h y l - j 3 , - c e l l o b i o s i d e H e p t a n i t r a t e . C e l l o b i o s e ( 3 3 . 0 g . ) was a c e t o -brominated by the method o f B a r c z a i - M a r t o s and Korosy ( 3 ) , u t i J . i z i n g the p roduc t ion o f hydrogen bromide i n s i t u . C e l l o b i o s e oc taace ta te p r e c i p i t -a ted from the r e a c t i o n m i x t u r e , and i t was found necessa ry t o add a volume o f g l a c i a l a c e t i c a c i d , equa l t o the volume o f a c e t i c anhydride p resen t , t o r e d i s s o l v e the o c t a a c e t a t e . 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 e the r -pe t ro leum e the r the ace tobromce l lob iose (50.5 g . ) gave m.p. = 1 7 6 ° ( d e c o m p . ) . The y i e l d was 7 4 . 5 $ o f t h e o r y . Brauns ( 5 ) gave m.p. = 1 8 0 ° ( d e c o m p . ) . The ace tobromce l lob iose (50.5 g . ) was r eac t ed w i t h anhydrous methanol i n a t y p i c a l Koenigs - Knor r (29) synthesis , - m o d i f i e d by the use o f a c a t a l y t i c amount o f i o d i n e ( 3 3 ) and by t he use o f anhydrous c a l c i u m su lpha te ( D r i e r i t e , -20 mesh) as an i n t e r n a l de s i ccan t (30) . The product was r e c r y s t a l l i z e d t w i c e from e thanol -wate r and t w i c e from c h l o r o f o r m - l i g r o i n t o g i v e m e t h y l - ^ - c e l l o b i o s i d e heptaace ta te (18.9 g . ) , ( 39 .1$ ) , m . p . = 1 8 5 ° . Hudson and Sayre (25) r epor t ed m.p. = 1 8 7 ? M e t h y l - { 3 - c e l l o b i o s i d e heptaaceta te ( 1 8 . 9 g . ) was d i s s o l v e d i n anhydrous methanol (250 m l . ) and a methano l i c s o l u t i o n o f bar ium methyla te (10 m l . , 5M) was added, a c c o r d i n g t o the d e a c e t y l a t i o n procedure o f I s b e l l ( 2 6 ) . - 2 6 -The p roduc t , m e t h y l - ^ - c e l l o b i o s i d e (9.6 g . ) , was a syrup which c o u l d not be induced t o c r y s t a l l i z e . The y i e l d was 96,9% o f t h e o r y . A n i t r a t i o n o f t h i s syrup (0.42 g . ) by the method o f W i l l and Lenze (49) gave me thy l -|B - ce l l ob ios ide h e p t a n i t r a t e (0.29 g . ) 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 e thano l -wa te r . The product gave m.p. = 1 3 4 ° , [o^^=+16.19° (c = 1.25 i n ace tone ) . B r i s s a u d (13) gave m.p. = 1 3 4 ° , [p(]i)0 = + 2 0 » 3 ° (c = 4 i n ace tone ) . M e t h y l - J i - c e l l o b i o s i d e h e p t a n i t r a t e (0.125 g . ) was d i s s o l v e d i n e thano l (20 m l . ) and hydrogenated a t 55 p . s . i . f o r one day i n the presence o f pa l l ad ium-ca rbon c a t a l y s t (0.5 g . ) . The product was a green c r y s t a l l i n e mass (0.05 g . ) w i t h m.p . =89 - 9 8 ° , y i e l d =75.2%. Raymond and Schroeder (39) r epo r t ed m.p . = 104 - 106° f o r methyl-JJ -ce l lobios ide hemihydrate . I t was p o s s i b l e t h a t the c a t a l y s t may have been poisoned thus caus ing a low y i e l d and m e l t i n g p o i n t . Ma l tose O c t a n i t r a t e . Ma l tose (1.91 g . ) was n i t r a t e d by the method o f W i l l and Lenze (49) w i t h n i t r i c a c i d (40 m l . , 100$) and concent ra ted s u l p h u r i c a c i d (80 m l . ) . The p roduc t , p u r i f i e d by the method o f H i b b e r t ( 2 ) , was mal tose o c t a n i t r a t e (1.55 g . ) , (39.7%'). The product had m . p . - 164 - 1 6 5 ° , ( _ 0 ^ ° — +8.53°(c = 1 i n d i o x a n e ) . W i l l and Lenze gave m.p. =164 - 1 6 5 ° , [(X ] Q 0 = +128 .6°(c = 35 i n g l a c i a l a c e t i c a c i d ) . Mal tose o c t a n i t r a t e (1.22 g . ) was d i s s o l v e d i n e thano l (50 m l . ) and hydrogenated a t 57 p . s . i . f o r one day i n the presence o f p a l l a d i u m -carbon, c a t a l y s t (0 . 40 g . ) . The product was mal tose (0.59 g . ) , (99.5$), w i t h m.p. =98 - 100° and when i n admixture w i t h an a u t h e n t i c sample o f mal tose the m.p . was 98 - 100°. I s b e l l and Pigman repor t ed m.p . 1 0 2 - 1 0 3 ° . D - M a n n i t o l H e x a n i t r a t e . D - M a n n i t o l (2.06 g . ) was n i t r a t e d by the method - 2 7 -o f W i l l and Lenze (49) t o g i v e D-manni to l h e x a n i t r a t e , crude y i e l d was 91$. The h e x a n i t r a t e was r e c r y s t a l l i z e d t w i c e from e thano l -wa te r t o m.p . = 1 1 1 ° , [ c ^ ° = + 4 3 . 0 3 ° ( c - 2 i n e t h a n o l ) . Hayward (21) r epo r t ed m.p. = 1 1 1 - 1 1 2 ° , [(yJD°= + 4 3 . l ( c = 2 i n e t h a n o l ) . D - M a n n i t o l h e x a n i t r a t e (0 .97 g . ) was d i s s o l v e d i n e thano l (50 m l . ) and hydrogenated a t 53 p . s . i . f o r one hour , w i t h pa l l ad ium-ca rbon c a t a l y s t (0 .5 g . ) . The p roduc t , D-mann i to l (0 .39 g . ) , ( 9 7 . 5 $ ) , gave m . p . = l 6 l - 1 6 4 ° , mixed m.p . = 1 6 1 - 1 6 3 ° . 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 . T h i s m a t e r i a l , prepared by the a c t i o n o f p y r i d i n e on D-manni to l h e x a n i t r a t e by the method o f Hayward (21 ) , was k i n d l y s u p p l i e d by M i s s . S . S u t h e r l a n d . B . A . , f o r which g r a t e f u l acknowledgement i s made. The 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 was r e c r y s t a l l i z e d once from ether-petroeum e the r t o g i v e m . p . = 8 0 ° , 0( (X 20 D =- + 4 7 . l 6 ° ( c =4 i n e t h a n o l ) . Hayward (21) r epor t ed m.p .= 8 2 ° , 2 ° = + 4 7 . 7 ° ( c = 4 i n e t h a n o l ) . -ID Methyl-1% -D-Glucopyranoside T e t r a n i t r a t e . T h i s m a t e r i a l was prepared i n a p rev ious r e sea rch (45) by r e a c t i n g m e t h y l - ^ - D - g l u c o p y r a n o s i d e w i t h n i t r i e a c i d , a c e t i c a c i d and a c e t i c anhydr ide a t - 1 0 ° f o r two hou r s . The methyl-13-D-glucoside t e t r a n i t r a t e had m.p. — 1 1 5 - 1 1 6 ° , JCXJp°=+11.62c (c = 4 i n C H C 1 3 ) . B r i s s a u d (6) r epo r t ed m.p .- 1 1 6 . 5 ° , [0^°=+11.6° (c =4 i n C H C 1 3 ) . Methyl - jJ -D-glucopyranos ide t e t r a n i t r a t e (0.998 g . ) was d i s s o l v e d i n e thano l (50 m l . ) and hydrogenated a t 54 p . s . i . f o r f i v e hours , i n the presence of pa l l ad ium-ca rbon c a t a l y s t (0.50 g . ) . The product was me thy l -p -D-g lucopyranos ide (0.515 g . ) , (99.5$), m .p .= 1 0 4 - 1 0 7 ° , and mixed w i t h an a u t h e n t i c specimen m.p . was 1 0 4 - 1 0 6 ° . -28-C e l l u l o s e N i t r a t e . Absorbent c o t t o n ( Johnson and Johnson Red Chain) was e x t r a c t e d w i t h a mix tu re o f e thano l one p a r t , benzene two p a r t s , i n a Soxh le t f o r two days . The c o t t o n was then e x t r a c t e d i n a Soxh le t w i t h l i g r o i n f o r two days . The product was found t o have 0.162$ ash and a copper number o f 0.247 based on bone d r y c e l l u l o s e . The c e l l u l o s e was then d r i e d i n an Abderhalden d r y i n g p i s t o l f o r one month over phosphorus pentoxide a t the temperature o f r e f l u x i n g ace tone . Dry c e l l u l o s e (1.912 g . ) was added t o a s o l u t i o n o f pure d r y ch lo ro fo rm (100 m l . ) c o n t a i n i n g n i t r o g e n pentoxide (7 g . ) . The n i t r o g e n pentoxide was prepared by the method o f Volmert (46) by r e a c t i n g n i t r i c a c i d (100$, f r e s h l y d i s t i l l e d ) w i t h phosphorus pen tox ide under vacuum a t room temperature . The n i t r a t i o n method used was t h a t o f Caesar and Goldf rank ( 9 ) . The r eac t an t s were a l l owed t o s tand a t 1 0 ° f o r one hour and the p r e c i p i t a t e d c e l l u l o s e n i t r a t e was recovered on a f i l t e r . The n i t r a t e was washed w i t h c o l d ch lo ro fo rm (100 m l . ) , f o l l o w e d by c o l d e thano l (50$, 1 l i t r e a t - 2 5 ° ) . The product was then b o i l e d t h ree t imes f o r f i v e minutes each w i t h e thano l (95$) and d r i e d i n vacuo w i t h phosphorus pen tox ide , a c c o r d i n g t o the s t a b i l i z a t i o n procedure o f B e r l ( 4 ) . The y i e l d o f product based on n i t r o g e n ana lyses was 91 .5$. Percent n i t r o g e n va lues found were 10.72, 10.65; t h e o r e t i c a l 14.14. The low n i t r a t e content was p robab ly due t o the h i g h degree o f d i l u t i o n o f the n i t r o g e n pentoxide i n the ch lo ro fo rm. I n another experiment bone d r y c e l l u l o s e (0.60 g . ) was n i t r a t e d by the method o f Hayward and Purves ( 2 0 ) . The c e l l u l o s e was immersed two hours a t 5 ° i n n i t r i c a c i d (100$, f r e s h l y d i s t i l l e d , 27 m l . ) and phosphorus pentoxide (11.4 g . ) . The product was f i l t e r e d and washed -29-w i t h c o l d a c e t i c a c i d (50$, 1 l i t r e a t - 1 0 ° ) f o l l o w e d by c o l d e thanol (50$, 1 l i t r e at - 1 0 ° ) . The f i b e r s were then suspended i n ethanol (250 ml.) and s t a b i l i z a t i o n completed by b o i l i n g the suspension under r e f l u x f o r twelve hours. The y i e l d of the d r y c e l l u l o s e n i t r a t e (1.25 g . ) was 106$ based on n i t r o g e n analyses. Percent n i t r o g e n found was 13.37, 13.24; t h e o r e t i c a l 14.14. B. Reduction w i t h Hydrazine. Hydrazine sulphate of reagent grade (2 moles, 260 g.) was d i s s o l v e d i n water (400 ml.) and the s o l u t i o n cooled i n an i c e bath. Barium oxide (2 moles, 307 g.) was added s l o w l y t o the hydrazine sulphate s o l u t i o n , keeping the temperature below 20°. The barium sulphate formed was f i l t e r e d o f f and the f i l t r a t e d i s t i l l e d under vacuum. The d i s t i l l a t e was r e d i s t i l l e d over potassium hydroxide, at atmospheric pressure, through a Vigreaux column. The f r a c t i o n b o i l i n g at 118° was c o l l e c t e d and corresponded t o hydrazine hydrate which was then d i s s o l v e d i n s u f f i c i e n t anhydrous methanol, such t h a t the r e s u l t i n g s o l u t i o n was two molar w i t h respect t o hydrazine. * A r e d u c t i o n of c e l l o b i o s e o c t a n i t r a t e (1.02 g.) w i t h methanolic hydrazine (10 ml., 2M) and palladium-carbon c a t a l y s t (0.5 g . ) , by the method of Kuhn (32), was attempted. Gas e v o l u t i o n waB noted and the s o l u t i o n was s t i r r e d by means of a magnetic s t i r r e r . The s o l u t i o n was r e f l u x e d f o r one hour a f t e r gas e v o l u t i o n had ceased and was then f i l t e r e d and the recovered c a t a l y s t was washed w i t h warm methanol. Removal of the methanol under vacuum from the combined f i l t r a t e and washings l e f t an orange v i s c o u s syrup which gave a -positive diphenylamine-sulphuric a c i d t e s t f o r the presence of n i t r a t e groups. Another r e d u c t i o n u s i n g D-mannitol h e x a n i t r a t e w i t h methanolic - 3 0 -hydraz ine (10 m l . , 2M.) and pa l l ad ium-ca rbon c a t a l y s t was a t tempted . Gas e v o l u t i o n was no ted . A f t e r gas e v o l u t i o n had ceased the s o l u t i o n was r e f l u x e d f o r one hour and then a l l owed t o stand two hours a t room temper-a t u r e . The s o l u t i o n was f i l t e r e d and the f i l t r a t e evaporated t o dryness under reduced p r e s su re . The product was an orange syrup (0.77 g . ) which gave a p o s i t i v e diphenylamine t e s t . C . Reduct ion w i t h M e t h y l Magnesium I o d i d e . The r e d u c t i o n o f D-manni to l h e x a n i t r a t e w i t h G r i g n a r d ' s reagent , by the method o f Hepworth (22) , was a t tempted. The reagent was prepared by r e a c t i n g methy l i o d i d e (6.6 g . ) i n anhydrous e the r (25 m l . ) w i t h magnesium (1.13 g . ) covered w i t h anhydrous e the r (25 ml , - ) . To the c o l d s o l u t i o n o f G r i g n a r d ' s reagent was added D-mann i to l h e x a n i t r a t e (0.93 g . ) i n t e t r a -hydrofurane (20 m l . ) . The t e t rahydrofurane was p u r i f i e d by a l l o w i n g i t t o remain over sodium me ta l f o r s i x months, f o l l o w e d by d i s t i l l a t i o n . The r e a c t i o n mix tu re was a l l owed t o s tand a t room temperature f o r 24 hour s . Water (50 m l . ) and g l a c i a l a c e t i c a c i d (5 m l . ) were then added and the water was e x t r a c t e d t w i c e w i t h e t h e r . The combined e the r e x t r a c t s were evaporated under reduced pressure t o l e ave a y e l l o v ; syrup (0.21 g . ) which gave a p o s i t i v e diphenylamine t e s t . The water l a y e r was evaporated , under reduced p res su re , t o d ryness . To the s o l i d r e s idue o b t a i n e d , p y r i d i n e (25 m l . ) and a c e t i c anhydride (25 m l . ) were added, a c c o r d i n g t o the carbohydrate a c e t y l a t i o n method o f Hudson and Dale (23). Thus any carbohydrates present i n the res idue ob ta ined would be a c e t y l a t e d and should then have been separated e a s i l y from any i n o r g a n i c s a l t s p re sen t . Upon the a d d i t i o n o f p y r i d i n e and a c e t i c anhydride t he r e was an exothermic r e a c t i o n and the s o l u t i o n tu rned brown i n c o l o u r , due t o the l i b e r a t i o n o f f r ee i o d i n e . -31-The r e a c t i o n mix tu re was coo led and a l l o w e d t o s tand f o r e igh t hours . I t was then poured i n t o i c e - w a t e r (100 m l . ) and the mix tu re was a l l owed t o s tand f o r a f u r t h e r t h r ee hours . Sodium t h i o s u l p h a t e s o l u t i o n (10$) was then added u n t i l the i o d i n e c o l o u r d i s sappea red . The aqueous s o l u t i o n was e x t r a c t e d t w i c e w i t h ch lo ro fo rm (50 m l . ) and the ch lo ro fo rm e x t r a c t was washed t w i c e w i t h d i l u t e h y d r o c h l o r i c a c i d ( 6 N . ) , t w i c e w i t h potass ium hydroxide s o l u t i o n (10$) and t w i c e w i t h w a t e r . The ch lo ro fo rm e x t r a c t was d r i e d over anhydrous sodium sulphate and sodium b i c a r b o n a t e . Removal o f the ch lo ro fo rm under reduced pressure gave a s e m i - c r y s t a l l i n e syrup (0.30 £ which 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 e thano l -wa te r mel ted a t 1 1 4 - 1 1 6 ° and when mixed w i t h an a u t h e n t i c sample o f D-mann i to l hexaaceta te mel ted a t 1 1 3 - 1 1 6 ° . The D-mann i to l hexaacetate was prepared from D-manni to l b y the a c e t y l a t i o n method o f Hudson and Dale (23) . C e l l o b i o s e o c t a n i t r a t e (0.95 g . ) was reac ted w i t h the G r i g n a r d reagent i n a s i m i l a r manner. The e the r l a y e r y i e l d e d a syrup (0.17 g.) which gave a p o s i t i v e diphenylamine t e s t . The water l a y e r was evaporated, the r e s idue ob ta ined a c e t y l a t e d and t he a c e t y l a t i o n mix tu re e x t r a c t e d w i t h c h l o r o f o r m , the ch lo ro fo rm b e i n g washed as b e f o r e . Removal o f the ch lo ro fo rm under reduced pressure gave a syrup which was r e c r y s t a l l i z e d t w i c e from e thanol -wate r and was shown t o be c e l l o b i o s e oc taace ta te (0.1 g m.p. = 207-214° and mixed m.p . = 219° when i n admixture w i t h an a u t h e n t i c sample o f c e l l o b i o s e o c t a a c e t a t e . D. Reduc t ion w i t h L i t h i u m Aluminium H y d r i d e . A s o l u t i o n o f l i t h i u m aluminium hydr ide i n e ther (20 m l . , c=98.3 grams per l i t r e ) was p l aced i n a two necked ground g l a s s f l a s k (200 m l . ) , f i t t e d w i t h a r e f l u x condenser, d ropping f u n n e l and magnetic s t i r r e r . The - 3 2 -s o l u t i o n had been s t anda rd ized by measuring the , volume o f hydrogen gas evo lved when a g i v e n volume o f the s o l u t i o n was r e a c t e d w i t h wa te r . The e t h e r e a l s o l u t i o n was coo led and a stream o f n i t r o g e n gas passed con t inuous -l y over i t . D - M a n n i t o l h e x a n i t r a t e (0.95 g . ) i n d ioxane (20 m l . ) was added s l o w l y w i t h s t i r r i n g . The r e a c t i o n was exothermic and the temperature was c o n t r o l l e d by e x t e r n a l c o o l i n g . A f t e r the a d d i t i o n was complete the mix tu re was s t i r r e d f o r t h r ee hours a t 0° and r e f l u x e d f o r one h a l f hour . A t the end o f t h i s t i m e , e t h y l ace ta t e (10 m l . ) was added -to reac t w i t h any remaining l i t h i u m aluminium h y d r i d e , f o l l o w e d by wet e the r and then wa te r . The e the r l a y e r was t h e n washed w i t h water and v i c e - v e r s a . The combined e ther s o l u t i o n s were evaporated under vacuum t o g i v e a brown syrup (0.05 g . ) which gave a p o s i t i v e diphenylamine t e s t . The water l a y e r was t r e a t e d w i t h a c e t i c a c i d (5 m l . ) and the water removed under vacuum. The r e s idue was then t r e a t e d w i t h p y r i d i n e (25 m l . ) and a c e t i c anhydr ide (25 m l . ) t o a c e t y l a t e any f r e e h y d r o x y l groups p re sen t . A f t e r evapora t ion o f the ch lo ro fo rm e x t r a c t t he r e was l e f t a l i g h t y e l l o w syrup (0.79 g . ) , which c r y s t a l l i z e d on s t a n d i n g . A f t e r r e c r y s t a l l i z a t i o n from e thano l -wa te r t he product mel ted a t 1 1 9 ° . T h i s m.p . was not depressed when the product was mixed w i t h an a u t h e n t i c sample o f D-manni to l hexaace ta te . The y i e l d o f D-manni to l from the de-n i t r a t i o n r e a c t i o n was 88$. E . Reduct ion w i t h Hydrogen; C u p r i c Ace t a t e i n P y r i d i n e C a t a l y s t . D - M a n n i t o l - l , 2 , 3 , 5 , 6 - p e n t a n i t r a t e (0.97 g . ) and c u p r i c ace ta te (0.1+1+ g . ) were d i s s o l v e d i n p y r i d i n e (100 m l . ) and the s o l u t i o n shaken a t room temperature w i t h hydrogen a t 55 p . s . i . f o r one day . At the end o f t h i s t ime b l u e , w a t e r - s o l u b l e c r y s t a l s were found on the w a l l s o f the r e a c t i o n v e s s e l . These were washed i n t o the p y r i d i n e s o l u t i o n and the s o l u t i o n was evaporated t o dryness i n vacuo. The r e s idue was t aken up i n e thano l -wa te r and sa tu ra t ed w i t h hydrogen s u l p h i d e . The copper su lph ide formed was f i l t e r e d o f f and the f i l t r a t e aga in evaporated t o dryness i n vacuo. The r e s idue was t aken up w i t h water and e x t r a c t e d th ree t imes w i t h e t he r , the e ther l a y e r then b e i n g washed w i t h w a t e r . E v a p o r a t i o n o f the e ther l a y e r gave a brown syrup (0.27 g . ) which would not c r y s t a l l i z e and gave a p o s i t i v e d i p h e n y l a m i n e - s u l p h u r i c a c i d t e s t f o r the presence o f n i t r a t e groups . E v a p o r a t i o n of the water l a y e r gave a y e l l o w syrup (0.32 g . ) which c r y s t a l l i z e d i n t o needles m e l t i n g a t 7 5 - 9 1 ° . T h i s c r y s t a l l i n e product xuas shown t o r eac t w i t h sodium b ica rbona te s o l u t i o n w i t h the e v o l u t i o n o f carbon d i o x i d e , a s o l u t i o n o f •'. i t ' was a c i d t o Congo r e d , and i t gave a p o s i t i v e diphenylamine t e s t . The experiment was repeated and aga in the same c r y s t a l s were ob ta ined from the water l a y e r . S i n c e the 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 should not be a c i d i c upon removal o f the n i t r a t e groups the r e a c t i o n was not s t u d i e d f u r t h e r . F . Reduct ion o f the C e l l u l o s e N i t r a t e s . The hydrogenat ion o f c e l l u l o s e n i t r a t e • ( 0 . 5 3 g . , 13.4$ N) d i s s o l v e d i n e thylene g l y c o l monomethyl e ther (50 m l . ) was a l l o w e d t o run f o r 46 hours a t a pressure o f 56 p . s . i . o f hydrogen w i t h Raney n i c k e l c a t a l y s t (0.5 g . ) . The product was a b l a c k suspension t o which was added acetone (150 m l . ) . The s o l u t i o n was s t i r r e d f o r one hour over a magnet ( f i e l d s t r e n g t h o f 4&45 gauss) and the Raney n i c k e l was a t t r a c t e d t o the bottom o f the r e a c t i o n v e s s e l . The c l e a r s o l u t i o n was decanted from the Raney n i c k e l w h i l e the bottom o f the v e s s e l was kept i n contac t w i t h the magnet. The Raney n i c k e l was washed th ree t imes w i t h acetone (25 m l . ) and the washings -34-added to the original solution. The solution was then poured with s t i r r i n g into cold water (1000 ml.) and the cellulose nitrate was reprecipitated. The fibers were recovered on a Buchner funnel without the aid of f i l t e r paper and washed with cold water (200 ml.). The remaining moisture was pressed out of the fibers of cellulose nitrate and they were allowed to dry i n vacuo, for three days at room temperature, over phosphorus pentoxide. The product was a white mass of coarse fibers (0.40 g.), $N found was 12.11, 12.15; ash 0.075$. In a second experiment, cellulose nitrate (0.66 g., 10.7$N) was dissolved i n ethylene glycol monomethyl ether (50 ml.) and Raney nickel (0.5 g.) was added. The reaction was all.owed to proceed for one day at a pressure of 57 p.s.i. of hydrogen. The resulting suspension was treated as before, the Raney nickel being separated i n the same manner. The product was a suspension of cellulose nitrate i n a solution of a more highly substituted cellulose nitrate i n the solvent. The suspended fibers were centrifuged and washed three times with acetone (25 nil.), the washings being added to the centrifugate. These fibers were set aside to dry i n  vacuo, for three days at room temperature, over phosphorus pentoxide. The product (0.26 g.) was slightly gray, $N found was 2.73, 2.77; ash was 2.1$. The centrifugate was poured into cold water (1000 ml.) and a cellulose nitrate was precipitated. This was worked up as before, to yield white fibers (0.31 g.), $N found was 12.40, 12.54; ash was 0.053$. To test the homogeneity of the original sample of cellulose nitrate the following experiment was performed: cellulose nitrate (0.52 g., 10.7$N) was shaken overnight with ethylene glycol monomethyl ether (50 ml.). The product appeared as a suspension of fibers in a viscous solution. These -35-f i b e r s were c e n t r i f u g e d , washed and d r i e d as be fo re ; y i e l d 0.25 g.> zoN: 4 . 5 0 , 4.53« The washings and c e n t r i f u g a t e were combined and the d i s s o l v e d c e l l u l o s e n i t r a t e was p r e c i p i t a t e d w i t h water and d r i e d as b e f o r e . The product was a wh i t e mass o f f i b e r s (0.26 g . ) , $N: 12.10, 12.64. I t was concluded t ha t t h i s sample o f c e l l u l o s e n i t r a t e was not homogeneous. G . A n a l y t i c a l Methods. The ana lyses f o r n i t r a t e n i t r o g e n , i n the case o f c e l l o b i o d e o c t a -n i t r a t e , D-manni to l h e x a n i t r a t e , 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 , and the c e l l u l o s e n i t r a t e prepared by the a c t i o n o f n i t r o g e n pentoxide i n c h l o r o f o r m , were performed u s i n g a semi-micro Dupont n i t r o m e t e r a c c o r d i n g t o the method o f E L v i n g and M c E l r o y (12). A l l o the r n i t r o g e n ana lyses were performed u s i n g the semi-micro adap ta t i on o f the Gunning m o d i f i c a t i o n o f t he K j e l d a h l procedure (17) f o r n i t r a t e n i t r o g e n . The n i t r o g e n ana lyses o f the carbohydrate p o l y n i t r a t e s are recorded i n Table I I I . - 3 6 -TABLE I I I NTTROGEM ANALYSES OF CARBOHYDRATE POLYNITRATES Carbohydrate Nitrate Values %"N Found Pheoretical Value $N Method Reference Cellobiose Octanitrate 1 . 15.78, 15.82 15.92 (12) Maltose Octanitrate 15.72, 16.46 15.92 (17) D-Mannitol Hexanitrate 18.30, 18.57 18.55 (12) D~Mannitol-l,2,3,5,6-Pentanitrate 17.28, 16.79 17.23 (12) Methyl- (3 -Cellobioside : Heptanitrate 14.48, 14.71 14.58 (17) Methyl- £-D-Glucoside Tetranitrate i ' 14.53, 14.59 14.56 (17) \ - 3 7 -BIBLICGRAPHY 1. A n s e l l , E . G . , and Honeyman, J . J . Chem. S o c . 2778. 1952. 2 . A s h f o r d , ¥ . , Evans , T., and H i b b e r t , H . Can. J . Res . 25B : 155 . 1947. 3 . B a r c z a i - M a r t o s , M . , and Korosy , F . Na tu re . 165 369. 1950. 4 . B e r l , E . I n d . Eng . Chem. ( A n a l . E d . ) . 13 : 322. 1941. 5. Brauns , G . i n Organic Syntheses , ed. by A . H . B l a t t . 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