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The hydroformylation of 3,4-Di-O-acetyl-D-xylal Black, John David 1960

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THE HYDROFORMYLATION OF 3,i|--DI-O-ACETYL-D-XYLAL by JOHN DAVID BLACK B.Sc. ( H o n s . ) , U n i v e r s i t y o f L i v e r p o o l , 19f>7 A THESIS SUBMITTED I N PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE i n t h e Department o f CHEMISTRY We a c c e p t t h i s t h e s i s as c o n f o r m i n g t o t h e r e q u i r e d s t a n d a r d THE UNIVERSITY OF BRITISH COLUMBIA O c t o b e r , i960 I n p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t o f t h e r e q u i r e m e n t s f o r an advanced degree a t the U n i v e r s i t y o f B r i t i s h C o l u m b i a , I agree t h a t t h e L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r r e f e r e n c e and s t u d y . I f u r t h e r agree t h a t p e r m i s s i o n f o r e x t e n s i v e c o p y i n g o f t h i s t h e s i s f o r s c h o l a r l y purposes may be g r a n t e d by the Head o f my Department o r by h i s r e p r e s e n t a t i v e s . I t i s u n d e r s t o o d t h a t c o p y i n g o r p u b l i c a t i o n o f t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be a l l o w e d w i t h o u t my w r i t t e n p e r m i s s i o n . Department o f (J^wilfci The U n i v e r s i t y o f B r i t i s h Columbia Vancouver 8, Canada. Date i i ABSTRACT 3,U-Di - 0-acetyl-D-xylal was treated i n the presence of dicobalt octacarbonyl with carbon monoxide and hydrogen at elevated temperatures and pressures. From deacetylation of the reaction products, 1- oc(ory3)-hydroxymethyl-2-hydro-D-x y l a l and l - < v (or J3)-formyl-2-hydro-D-xylal were obtained; that i s , a hydroxymethyl group and a formyl group were added respectively at carbon one of the o r i g i n a l unsaturated sugar. Sodium borohydride reduction i n aqueous solution of 1- cx'(ory0)-forrayl -2-hydro-D-xylal produced 1 -c< (or p )-hydroxy-methyl -2-hydro-D-xylal. 1- cx(ory3)-Formyl -2-hydro-D-xylal gave an acetate which i s described. Periodate oxidation of the sugar alcohol gave the dialdehyde which on treatment with p-nltrophenylhydrazine hydrochloride yielded glyoxal-bis-p-nitrophenylhydrazone and 2- deoxy-D,L-tetrose p-nitrophenylhydrazone as major degradation products. i i i TABLE OF CONTENTS Page .No, I n t r o d u c t i o n 1 HISTORICAL INTRODUCTION 1. U n s a t u r a t e d Sugars ( G l y c a l s ) . . . 2 (a) S y n t h e s i s 2 (ta) R e a c t i o n s 2 2. H y d r o f o r m y l a t i o n (Oxo R e a c t i o n ) k 3. D e a c e t y l a t i o n . . . . . 8 i | . p - N i t r o p h e n y l h y d r a z o n e s 9 EXPERIMENTAL S y n t h e s i s o f 3 , h - D i - 0 - A c e t y l - D - X y l a l 11 S y n t h e s i s o f D I c o b a l t O c t a c a r b o n y l 12 H y d r o f o r m y l a t i o n No. 1 13 Hydrof o r r a y l a t i o n No. 2 15 D e a c e t y l a t i o n o f Product o f Hydrof o r r a y l a t i o n No. 1 15 Paper Chromatography o f Product A 16 Continuous Flow Chromatography o f Product A . . . 16 D e a c e t y l a t i o n o f Product o f H y d r o f o r m y l a t i o n No.2 17 Paper Chromatography o f Produc t E 18 Q u a l i t a t i v e T e s t s on P r o d u c t s . 20 Somogyi A n a l y s i s 20 Sodium B o r o h y d r i d e R e d u c t i o n 21 P e r i o d a t e O x i d a t i o n 23 p - N i t r o p h e n y l h y d r a z o n e o f O x i d a t i o n Product . . . 25 Chromatography o f O x i d a t i o n Product V 26 i v TABLE OF CONTENTS (cont'd) Page No. Chromatography of Oxidation Product III 27 Preparation of Glyoxal Bis-p-Nitrophenylhydrazone 29 Preparation of Derivatives 32 1. Acetylation of Fraction J 32 2 . Benzoylation of Fraction I 32 3 . Attempted preparation of 2 , 5-Dichloro-phenylhydrazone 3k V LIST OP TABLES Page No. Table I. Summary of Chromatography of Oxidation Products 30 Table I I . Summary of Products Obtained Prom Chromatography of Oxidation Products . . . 31 LIST OP FIGURES Page No. Figure I. Hydroformylation No. 1 Ik ACKNOWLEDGEMENT The writer wishes to express his sincere thanks to Dr. A. Rosenthal f o r guidance, patience, and f a i t h throughout t h i s i n v e s t i g a t i o n . INTRODUCTION The hydroformylation reaction has been applied to several types of o l e f i n l c unsaturated compounds to y i e l d homologous aldehydes or alcohols. It has been found (1, 2) that the carbon chain of carbo-hydrates can be lengthened by the addition of carbon monoxide and hydrogen to unsaturated sugars (3) to y i e l d sugar alcohols. Branched or straight-chain aldehydes and alcohols have been produced by the addition of carbon monoxide and hydrogen to o l e f i n s (k). It i s then possible that the hydroformylation of an unsaturated sugar would y i e l d one or a mixture of new branched or straight-chain sugars or sugar alcohols. Hydro-genation of the double bond to y i e l d a 1,2-dihydro carbohydrate i s also possible. In addition to the above method sugars having more carbon atoms than the sta r t i n g compounds have been prepared by several methods (5) involving the addition of hydrocyanic acid, n i t r o -methane, and the Grignard reagent to the appropriate sugar. The present work describes the hydroformylation of 3,4_di-0_-acetyl-D-xylal and the characterization of the reaction pro-ducts. -2 HISTORICAL INTRODUCTION 1. Unsaturated Sugars (glycals) (a) Synthesis Glycals were f i r s t reported by Fischer (6) i n 191k» 3 > 6 -Tri-O-acetyl-D-glucal was obtained by treating 2 , 3,k»6-tetra -0 -acetyl-<x-D-glucopyranosyl bromide with zinc dust i n f i f t y percent acetic a c i d . The method of g l y c a l synthesis has been changed l i t t l e . However i n 1954, H e l f e r i c h and co-workers (7) shortened the procedure. They acetylated D-glucose, brominated the acetate, and converted the r e s u l t i n g bromo compound to the corresponding unsaturated sugar without i s o l a t i n g the above intermediates. The method of reduction of the crude bromo sugar was similar to that employed by Fischer. However, sodium acetate was added to neutralize the excess hydrobromic acid formed i n the bromination procedure. Also, copper sulphate was added to catalyze the re-action. These modifications gave increased y i e l d s of the f i n a l product. (b) Reactions The reactions of the glycals have been summarized by Hel-f e r i c h (3). Because of t h e i r special properties, these compounds have found frequent use as intermediates i n further syntheses. Although glycals have been found to exhibit unique proper-t i e s , they also have been shown to undergo many reactions c h a r a c t e r i s t i c of o l e f i n i c compounds. Fischer, i n 191k (6), treated a solution of 3,k>6-tri-0-acetyl-D-glucal i n g l a c i a l acetic acid with hydrogen i n the -3-presence o f a platinum c a t a l y s t . l , 2 -Dihydro-3,h,6-tri-0-a c e t y l - D - g l u c a l was obtained. The a c t i o n of o x i d i z i n g agents on unsaturated sugars has been studied e x t e n s i v e l y . Levene and Tipson (8) treated D-g a l a c t a l w i t h perbenzoic a c i d and obtained D-galactose and another compound that was probably D-talose. The two sugars were not obtained i n equal amounts. The a d d i t i o n of hydroxyl groups to the double bond of a g l y c a l has been found to y i e l d only one sugar under c e r t a i n c o n d i t i o n s . Hockett and Millman (9) t r e a t e d D - g a l a c t a l w i t h hydrogen peroxide i n t-butanol i n the presence of a small amount of osmium t e t r o x i d e . Although they obtained D-galactose, no D-talose was found. Some cleavage of the double bond occur-r e d , w i t h the production of what was thought to be D-lyxonic a c i d . The double bond of a g l y c a l has been shown to migrate under f a i r l y m i ld c o n d i t i o n s . Lohaus and Widmaier (10) treated 3 , 4 , 6 - t r i - 0 - a c e t y l - D - g a l a c t a l w i t h b o i l i n g water. Prom the r e -a c t i o n mixture they i s o l a t e d h,6-di-0-acetyl-D-pseudogalactal (the double bond had s h i f t e d to the 2,3 p o s i t i o n ) . This com-pound gave t y p i c a l aldehyde r e a c t i o n s . I t reduced Pehling's s o l u t i o n and when i t was treated w i t h e t h y l orthoformate, the corresponding e t h y l a c e t a l was obtained. Water has been found to add across the double bond of an unsaturated sugar. I s b e l l and Pigman ( l l ) obtained 2-deoxy-D-galactose by t r e a t i n g D - g a l a c t a l w i t h water. -k-2. H y d r o f o r m y l a t i o n (Oxo R e a c t i o n ) The r e a c t i v i t y o f c a r b o n monoxide was n o t s t u d i e d u n t i l t h e t w e n t i e t h c e n t u r y . F i s c h e r and T r o p s c h formed s m a l l q u a n t i t i e s o f f o r m i c e s t e r s f r o m c a r b o n monoxide and m e t h y l a l c o h o l and e t h y l a l c o h o l i n 1921 ( 1 2 ) . I n 1926 F i s c h e r and T r o p s c h (13) announced t h a t h i g h e r homologues o f methane were f o r m e d when m i x t u r e s o f h y d r o g e n and c a r b o n monoxide were p a s s e d a t a t m o s p h e r i c p r e s s u r e o v e r a c a t a l y s t o f i r o n o r c o b a l t a t e l e v a t e d t e m p e r a t u r e s . S m i t h , Hawk and G o l d e n (li+)> i n 1930, t r e a t e d e t h y l e n e w i t h c a r b o n monoxide and h y d r o g e n i n t h e p r e s e n c e o f a c a t a l y s t . They o b t a i n e d h y d r o c a r b o n s p l u s a w a t e r s o l u b l e o x y g e n c o n t a i n -i n g o i l . I t was t h e i r o p i n i o n t h a t t h e o x y g e n c o n t a i n i n g compounds were fo r m e d f i r s t i n t h e r e a c t i o n and t h a t t h e y were n e x t , d e h y d r a t e d w i t h s u b s e q u e n t p o l y m e r i z a t i o n . I n 19h3> R o e l e n (15) d i s c l o s e d the f o l l o w i n g r e a c t i o n : RCH=CH 2 -f GO -+- H 2 90-200° , RCH 2CH 2CH0 125-200 atm. The c a t a l y s t s c o n t a i n e d c o b a l t , t h o r i u m o x i d e , k i e s e l g u h r , and sometimes c o p p e r . E t h y l e n e t r e a t e d a c c o r d i n g t o t h i s r e a c t i o n y i e l d e d f o r t y p e r c e n t p r o p i o n a l d e h y d e , t w e n t y p e r c e n t d i e t h y l k e t o n e and f o r t y p e r c e n t h i g h e r b o i l i n g a l d e h y d e s and k e t o n e s . An i m p o r t a n t s e r i e s o f s y n t h e s e s w i t h c a r b o n monoxide was d e v e l o p e d i n Germany d u r i n g the l a s t war and n o t d i s c l o s e d u n t i l a f t e r 19h.&. C a r b o n monoxide was shown t o r e a c t u n d e r p r e s s u r e (200 a t m o s p h e r e s ) a t e l e v a t e d t e m p e r a t u r e s (200-300 ) and i n t h e p r e s e n c e o f c a r b o n y l c a t a l y s t s ( e s p e c i a l l y n i c k e l o r c o b a l t carbonyls) with a variety of types of organic molecules. For example: (16) CH 2— CH2-f- CO-<-H20 > CH3CH2COOH With a r e v i v a l of carbonylation a f t e r the war several new poten t i a l f i e l d s have appeared. For example Tyson and Shaw (17) synthesised 3-indole carboxaldehyde by treating potassium indole with carbon monoxide at elevated pressures i n the pre-sence of N,N-dimethyl formaraide. I n i t i a l l y carbonylation and hydrofromylation reactions were catalyzed by a variety of heterogeneous c a t a l y s t s , but i n 191+Q Adkins and Krsek (18) concluded that the best r e s u l t s were obtained using a homogeneous ca t a l y s t , s p e c i f i c a l l y dicobalt octacarbonyl. For the reaction with an alkene they postulated the following mechanism: 150° Go(GO)^ 2 2 C o ( C 0 ) o C 0 H Co(CO) co(co)3 ^ H-4-co . 125° * 2 Co(CO) 2 In 19^-9, Adkins and Krsek (19) modified the hydroformylation -6-technique by using benzene instead of ether as the solvent. This allowed the reactions to proceed at lower temperatures and pressures. These workers subjected a number of unsaturated compounds to the hydroforraylation reactions. Hexene-1 was con-verted to a mixture of n-heptaldehyde and 2-methyl hexaldehyde. Compounds of the type RCH = CH"2 (where R was -C0 2C 2H£, -CH202CCH^ and -CH(02CCH-j)2 ) added the formyl group exclusively i n the terminal position. A further modification of the hydroforraylation reaction was introduced by Pino (20) i n 1951. By adding ethyl orthofor-mate to the reaction mixture, the aldehydes produced were sub-sequently converted to the corresponding ethyl acetals. In th i s way, secondary reactions of the carbonyl groups were i n h i b i t e d . In 1950, Wender, Levine and Orchin (21) found that croton-aldehyde, which Adkins and Krsek (19) found was converted to o n-butyraldehyde at 120-125 , was converted to n-butanol at 180-185 • These workers postulated the following mechanism f o r the reaction: 2Co -f-8C0 Co(CO)^ Co(CO) 2 2 -Co(CO) k . C o f C O j ^ - f H g - H- - j - C o t C O ^ C O H H- -f-RCHO •RCHOH RCHOH + Co(C0) 3C0H -7-This mechanism involves cobalt hydrocarbonyl, and various workers have sought evidence f o r the presence of th i s compound i n the oxo reaction. Wender, Mettin, and Orchin (22) treated pinacol under hydroformylation conditions. Among the reaction products obtained was pinacolone. As the pinacol-pinacolone rearrangement i s a known example of an acid catalyzed reaction, the presence of cobalt hydrocarbonyl was indicated. This com-pound was the only strong acid that could have been present i n the reaction mixture. Homologation of alcohols v i a the oxo reaction has also been found to take place. This too was thought to be catalyzed by the acid cobalt hydrocarbonyl. Wender, Levine and Orchin (23) subjected t-butyl alcohol to hydroformylation conditions at 160-loO and obtained a good y i e l d of isoamyl alcohol. By treating methanol s i m i l a r l y , Wender, Priedel and Orchin (21+) obtained ethanol as the major product. In 195>6 Rosenthal and Read (l) synthesized a new c r y s t a l -l i n e seven-carbon branched-chain carbohydrate by application of the oxo reaction to 3 , ! j->6-tri-0-acetyl-D-galactal. A hydroxy-methyl group was added to the unsaturated carbohydrate. In summary, many o l e f i n i c unsaturated compounds have been found to react with carbon monoxide and hydrogen i n the presence of a cobalt catalyst at elevated pressures and temperatures. - 8 -Aldehydes containing one more carbon atom than the o r i g i n a l compound were usually produced. However i n some instances they were not isolated, due to hydrogenation of the carbonyl group, polymerization, and other side reactions. Pino and E r c o l i (25) were the f i r s t to do a reaction of t h i s nature with a carbon-nitrogen double bond. In 1953 they hydroformylated pyridine with carbon monoxide and hydrogen i n the presence of cobalt catalysts to give several products of which N-formyl piperidine and N-methyl piperidine were the major portions. More recently, In 1958* the synthesis of 3-phenyl, 3-methyl, and 3-benzyl-phthalimidine was achieved by application of the oxo reaction to aromatic ketoximes by Rosenthal, Astbury,. and Hubscher (26). The most recent new applications of the oxo reaction i n the. f i e l d of natural products involve terpenes and steroids. In 1952 LoCicero and Johnson (27) hydroformylated camphene to give an aldehyde which was s t r u c t u r a l l y related to isocamphenilan-aldehyde. In 1957 Bordena (28) applied the oxo reaction to Oc-pinene, and /3 -pinene and obtained a product which was seventy per cent aldehyde. In 1959 Nussbaum et a l (29) hydroformylated 3 f3 ,20/3 -dihydroxy- .A -pregnene at 195° to obtain a 6<X-hydroxy-raethyl s t e r o i d . They concluded that the hydroformylation of complex molecules was st e r e o s p e c i f i c . Beal, Rebenstorf, and Pike (30) obtained a steroid having an added 60<-hydroxymethyl group by hydroformylation at l 8 0 ° . 3. Deacetylation For the deacetylation of sugar acetates the methods devel--9-oped by Zemplen and co-workers are s t i l l widely employed although other deacetylation procedures (31) have been found. Zemplen and Kunz ( 3 2 ) , 'In 1923, f i r s t effected deacetylation of a sugar acetate with sodium alkoxide. By treating D-glucose penta-acetate with an excess of sodium ethoxide dissolved i n absolute ethanol, they obtained a D-glucose-sodium ethoxide addition product. It was thought that the reaction involved t r a n s e s t e r i f i c a t i o n , since ethyl acetate was also i s o l a t e d . Three years l a t e r , Zemple'n (33) modified the reaction by using sodium methoxide i n methanol. Cellobiose octa-acetate was dissolved i n chloroform and a methanolic solution of excess sodium methoxide was added. The precipitated cellobiose-alkoxide addition product was decomposed with water, the a l k a l i neutral-ized with acetic acid, and the product, was c r y s t a l l i z e d from ethanol. The method was improved when Zemplen and Pascu (3k) found i t was s u f f i c i e n t f o r sodium methoxide to be present i n trace amounts to ef f e c t deacetylation. D-Mannitol hexa-acetate was dissolved i n absolute methanol containing a c a t a l y t i c amount of sodium methoxide. D-Mannitol was obtained i n good y i e l d . k.. p-Nitrophenylhydrazones of Sugars In 1922 Bergmann, Schotte and Lechinsky (35) obtained 2-deoxy-D-glucose-p-nitrophenylhydrazone from 2-deoxy-D-glucose using p-nitrophenylhydrazine as reagent. Canary yellow c r y s t a l s were obtained from alcohol. In 1930 B r i g l and Schinle (36) reacting 2-methyl-D-glucose with phenylhydrazine and a c a t a l y t i c amount of acetic acid ob--10-tained a phenylhydrazone i n good y i e l d . Heating the mixture f o r a further hour with more reagent produced a methoxyl free glucosazone. This observation was confirmed i n 1 9 3 1 by Haworth, Hi r s t and Teece ( 3 7 ) . The loss of methoxyl during the transform-ation was confirmed by analysis. -11-EXPERIMENTAL P r e p a r a t i o n o f 3 , l i - D i - 0 - a c e t y l - D - x y l a l 3 , h - D i - 0 - a c e t y l - D - x y l a l was s y n t h e s i z e d by a m o d i f i c a t i o n o f the method o f H e l f e r i c h and co-workers ( ? ) • To a s t i r r e d s o l u t i o n o f a c e t i c a n h y d r i d e (210 m l . ) , f r e s h l y d i s t i l l e d , and p e r c h l o r i c a c i d (QQ%, 2 m l . ) , D-xylose (50 gm.), d r i e d , was added s l o w l y i n a t h i r t y minute i n t e r v a l . D u r i n g t h i s time the temperature was kept between 50 and 60° by c o o l i n g i n a water b a t h . The m i x t u r e was s t i r r e d an a d d i t i o n a l f i f t e e n minutes a f t e r the a d d i t i o n and t h e n l e f t t o stand o v e r n i g h t a t room temperature i n a d a r k p l a c e . Red phosphorus (16 gm.) was added s l o w l y i n a t e n minute i n t e r v a l t o the s t i r r e d r e a c t i o n m i x t u r e , the. m i x t u r e c o o l e d t o 25-30° and t h e n bromine (96 gm.) was added dropwise f o r twenty minutes w h i l e the s t i r r e d r e a c t i o n was kept between 25 and 30°. A f t e r the a d d i t i o n o f the bromine the m i x t u r e was s t i r r e d f o r t e n minutes and t h e n water (19 mi.) added dropwise d u r i n g twenty-f i v e m i n u t e s . A f t e r the a d d i t i o n o f water s t i r r i n g was c o n t i n u e d f o r f o r t y m i n u t e s . The phosphorus was removed by f i l t r a t i o n and the r e s i d u e washed w i t h g l a c i a l a c e t i c a c i d (25 m l . ) . The r e s u l t i n g s o l u t i o n ofC<-bromo 2 , 3 , h ~ t r i - 0 - a c e t y l -D-xylose was c l e a r and dark r e d . Hydrated sodium a c e t a t e (200 gm.) was d i s s o l v e d i n water (150 ml.) and g l a c i a l a c e t i c a c i d (250 m l . , 95$) added. A f t e r c o o l i n g the s o l u t i o n t o - 1 5 ° w i t h a i c e - s a l t m i x t u r e , z i n c dust (110 gm.) and a s o l u t i o n o f h y d r a t e d copper s u l p h a t e (11 gm. i n 25 m l . o f wa t e r ) were added. When the b l u e c o l o r d i s a p p e a r e d - 1 2 -from the mixture the s o l u t i o n of -bromo 2 , 3 , i 4 - - t r l - 0 - a c e t y l - D -xylose was added dropwise over an i n t e r v a l of t h i r t y - f i v e minutes to the s t i r r e d s o l u t i o n . The mixture was maintained at -10° by adding small pieces of s o l i d carbon dioxide to the r e a c t i o n mixture, which was then s t i r r e d f o r a f u r t h e r three hours at -10°. On completion o f the r e a c t i o n the mixture was s u c t i o n -f i l t e r e d i n t o ice-water, the funnels being kept c o o l w i t h small pieces of s o l i d carbon d i o x i d e . The f i l t r a t e was extracted w i t h chloroform ( 3 x 300 ml.). The chloroform s o l u t i o n was washed w i t h s i x p o r t i o n s (600 ml. each) of ice-water, followed by washing w i t h cold bicarbonate s o l u t i o n , and f i n a l l y washing w i t h i c e - c o l d water u n t i l n e u t r a l to l i t m u s . A f t e r d r y i n g at 0 ° overnight over anhydrous calcium c h l o r i d e the s o l u t i o n was f i l t e r e d and the chloroform removed under reduced pressure (water a s p i r a t o r ) . Benzene was added and removed under reduced pressure as before. The product was a l i g h t y e llow syrup; y i e l d 2 2 gm. The crude mixture was subjected to vacuum d i s t i l l a t i o n . The f i r s t f r a c t i o n , which d i s t i l l e d at 8 2 - 8 U ° ( 0 . 2 5 m.m. pres-sure) was 3 , l 4 - - d i - 0 - a c e t y l - D - x y l a l . Y i e l d 9 . 8 gm. ( 1 5 $ ) . The product was c o l o r l e s s o i l . I ° * I = -310° ( c , l i n chloroform). r - l ' 1 L J j ) L i t . v a l u e : I - 3 1 4 ° ( c , 2 i n chloroform). ( 3 8 ) . Synthesis of D i c o b a l t Octaoarbonyl D i c o b a l t octacarbonyl was prepared by the method of Wender and co-workers ( 3 9 ) . Cobalt ( I I ) carbonate ( 3 0 gm.) suspended i n anhydrous t h i o -phene-free benzene ( 8 0 m l . ) , was placed i n a g l a s s l i n e r con--13-t a i n e d i n a s t a i n l e s s s t e e l bomb h a v i n g a v o i d o f 278 m l . (the S u p e r - P r e s s u r e a p p a r a t u s was made by the American I n s t r u m e n t Co.) Hydrogen and car b o n monoxide were a d m i t t e d t o a t o t a l p r e s s u r e o f 3200 p . s . i . ( 1 : 1 ) . The m i x t u r e was heated t o 160° and l e f t a t t h i s t emperature f o r one hour w i t h r o c k i n g . I t was the n c o o l e d t o room t e m p e r a t u r e ; the f i n a l p r e s s u r e was 26iu0 p . s . i . The dark m i x t u r e was f i l t e r e d and the r e s i d u e washed w i t h ben-zene. A r e d - b l a c k s o l u t i o n was o b t a i n e d . H y d r o f o r m y l a t i o n No. 1 The procedure was based on t h a t o f A d k i n s (18) and R o s e n t h a l ( 1 ) . 3 , i i - D i - 0 - a c e t y l - D - x y l a l ( 9 . 8 gm.) was added to an anhydrous t h i o p h e n e - f r e e benzene s o l u t i o n (50 ml.) t o g e t h e r w i t h preformed d i c o b a l t o c t a c a r b o n y l (a s o l u t i o n c o n t a i n i n g 13 gm.). The combined s o l u t i o n was p l a c e d i n the g l a s s l i n e r o f a h i g h p r e s -sure h y d r o g e n a t o r h a v i n g a v o i d o f 280 m l . The bomb was f l u s h e d t h r e e t i m e s v / i t h c a r b o n monoxide t o remove t r a c e s o f oxygen and th e n charged w i t h c a r b o n monoxide (15^-0 p . s . i . ) and hydrogen (15'ij-O p . s . i . ) . A f t e r the hy d r o g e n a t o r was r o c k e d f o r t h r e e minutes the combined gas p r e s s u r e was 2960 p . s . i . a t 2 1 ° . The bomb was heated w i t h r o c k i n g t o 1 2 5 - 1 3 5 ° f o r f o r t y - f i v e m i n u t e s . On c o o l i n g t o room temperature ( 2 1 ° ) . The observed p r e s s u r e drop was 250 p . s . i . The c o n t e n t s o f the l i n e r were removed and the l i n e r washed w i t h a b s o l u t e e t h a n o l (50 m l . ) . The s o l u t i o n was heated a t 7 5 ° f o r t h i r t y minutes and r u n t h r o u g h a mixed a b s o r b e n t column (20 cm. x 5 cm.) o f s i e v e d acid-washed a l u m i n a and c e l i t e 535 ( 2 : 1 by w e i g h t ) . A f t e r e l u t i o n w i t h benzene-3800'; 1.0 . - ' ' 10 ~~ To ~~~ : - - - ~~ 30 .• - ' ' . , kQ. - Time, (minutes)., r\j"r'• ~ " ' ' ' : 3800 10 Time (minutes). 30 - i 5 -ethanol (^:1 v/'v, 600 ml.) and removal of the solvent at 3 5 ° under reduced pressure (water aspirator) a l i g h t yellow syrup remained. The syrup was dried several times by azeotroping i t with small portions of anhydrous benzene. The product reduced Pehling's solution at room temperature; y i e l d 9.4- 8 m« (87%) • Hydroformylation No. 2 This was similar to hydroformylation No. 1. Identical amounts of 3,l|-di - 0-acetyl-D-xylal and preformed dicobalt octa-carbonyl were used. The i n i t i a l pressure of hydrogen was 1550 p . s . i . and that of carbon monoxide 1550 p . s . i . After heating for one hour at 1 2 5 ° the pressure drop on cooling was 260 p . s . i . After working the product as previously, the product was a l i g h t brown sweet smelling o i l ; y i e l d 8 . 6 gm. ( 8 2 % ) . The product gave a positive Pehling's test on warming. Deacetylation of Product of Hydroformylation No. 1 The method used was a modification of that developed by Zemplen and Pacsu (3k)• The product (9»k gm.), dried by repeated azeotroping with benzene, was dissolved i n a 0 . 0 5 N sodium methylate solution (200 ml.). The solution was stoppered to exclude moisture and l e f t at room temperature f o r three hours. After addition of water to dissolve s o l i d material the solution was passed successively through columns (22 cm. x 2 cm.) containing a cation exchange r e s i n (Amberlite IR - 1 2 0 , Rohm and Haas Co., Philadelphia, Penn.) (1+0) and an anion exchange r e s i n (Duolite A-ii, Chemical Process Co., Redwood City, C a l i f .)• (l+O). The -16-columns were washed with d i s t i l l e d water (1000 ml.) to remove the remaining material. The eluant was evaporated to a syrup under reduced pressure and the residual water removed by repeated d i s t i l l a t i o n with 100% ethanol under reduced pressure; y i e l d 2.6 gm. (60%). This brown syrup (product A) reduced Pehling's solution on warming. Paper Chromatography of Product A Paper chromatography, using a modification of the method described by Wolfrom and Schumacher (41) was employed to examine product A. A descending chromatogram (50 x 10 cm.) was prepared from Whatman No. 1 f i l t e r paper. The paper was spotted (0.5 mg. / spot) with a solution of product A i n water and then placed i n chromatographic chamber maintained at room temperature. The chromatogram was developed with n-butanol-water (saturated) ..(42) for f i f t e e n hours. After drying the paper was sprayed with sodium metaperiodate-alkaline permanganate reagent developed by Lemieux and Bauer (43) and a similar paper sprayed with p - a n i s i -dine trichloroacetate solution developed by Jones et a l (1+2). Spraying with the periodate-permanganate reagent produced three spots (R f 0.07; Rf 0.23; R f 0 . k 5 ) . Spraying with the p - a n i s i -dine reagent produced two spots (R^ 0.07; R^ 0 .45) . Continuous Flow Chromatography of Product A The method used was based on that of Flood, Hirst and Jones (44). Whatman No. 1 c e l l u l o s e (150 gm.) was used to prepare an absorbent column (400.-x 30 mm.). The column was prewet with -17-butanol-water (600 ml., saturated) and product A ( 0 • 8I4. gm. dissolved i n 3 ml. solvent) was added. Development was effected with butanol-water (600 ml. saturated). Fractions (h ml. each) were collected i n an automatic f r a c t i o n a l c o l -l e c t o r . Aliquots ( 0 . 5 ml.) from each f r a o t i o n were placed on f i l t e r paper and sprayed with periodate-permanganate reagent to ascertain whether or not carbohydrate was present, Fractions containing carbohydrate occurred i n three d i s t i n c t zones and these were combined and the solvent evaporated y i e l d i n g three yellow o i l s . R f Y i e l d $Yield Product B 0 . 0 7 0 . 0 5 6 gm. 8 Product C 0 . 2 3 0 . 3 8 7 55 Product D 0 . h 5 0.260 37 0 . 7 0 5 % recovery from the column: 8 l Optical rotaion measurements were performed on each of the products: Product B [o*]^  = + 2 3 ° (c, 3 . 8 i n water) Product C [ax]" «= + 2 2 ° (c, 1 .0 i n water) Product D [ « ] " = . +12° (c, 3 . 7 i n water) Deacetylation of Product of Hydroformylation No. 2 - 1 7 A -The p r o d u c t o f H y d r o f o r m y l a t i o n No. 2 was i m m e d i a t e l y p l a c e d o n a P l o r i s i l c o l u m n ( 20 x 7 cm. ) . No s o l i d c o b a l t was p r e s e n t i n t h e r e a c t i o n m i x t u r e . The col u m n was d e v e l o p e d w i t h p e t r o l e u m e t h e r ( $00 m l . , 30-60° ) t o t a k e o f f a p u r p l e band w h i c h was d i s c a r d e d . The col u m n was t h e n d e v e l o p e d w i t h b e n z e n e - e t h y l a c e t a t e ( 98:2, 500 m l . ). The e l u a t e was c o l l e c t e d ( P ) . The c o l u m n was t h e n d e v e l o p e d w i t h b e n z e n e - e t h a n o l ( 95*5, 500 m l . ) . The e l u a t e was c o l l e c t e d ( Q, ) . F r a c t i o n P was e v a p o r a t e d down t o g i v e an o i l w h i c h gave a p o s i t i v e F e h l i n g ' s t e s t . T h i s o i l ( 2.5 gm. ) was d e a c e t y l a t e d u s i n g i d e n t i c a l c o n d i t i o n s as p r e v i o u s l y . The p r o d u c t ( 0» 88 gm. ) was a c o l o u r l e s s o i l ( P r o d u c t E ) . A p o r t i o n ( 110 rag. ) was r u n down Whatman No. 3 p a p e r and t h e l o w e r zone ( l o c a t e d w i t h p - a n i s i d i n e s p r a y ) c u t o u t and e x t r a c t e d w i t h w a t e r t o y i e l d a w h i t e s o l i d ( J ) . J i s d i s c u s s e d l a t e r . F r a c t i o n Q was e v a p o r a t e d down t o an o i l ( 2.0k gm. ) w h i c h d i d n o t r e d u c e F e h l i n g ' s s o l u t i o n . D e a c e t y l a t i o n f o l l o w e d by d e i o n i z a t i o n p r o d u c e d an o i l ( 0.9k )• T h i s was combined w i t h p r o d u c t G. - 1 8 -Paper Chromatography of Product E Paper chromatography using the modification of the method of Wolfrom and Schumaker (hi) already described i n the examin-ation b'f product A was used to examine product E. The conditions were the same using a developer and butanol-water-ethanol-ammonium hydroxide (111) running f o r sixteen hours. After drying the paper was sprayed with sodium metaperiodate-alkaline permanganate reagent and a similar chromatogram was sprayed with p-anisidine trichloroacetate reagent. Spraying with p-anisidine produced three spots (Rf 0 . 0 7 ; Rf 0 . 3 2 ; Rf 0 . 5 2 ) . Spraying with periodate-permanganate reagent revealed f i v e spots (Rf 0 . 0 7 ; Rf 0 . 2 8 ; Rf 0 . 3 2 ; Rf 0 . 3 8 ; Rf 0 . 5 2 ) . A chromatographic separation of product E into i t s com-ponents was then attempted using Whatman No. 3 f i l t e r paper as adsorbent. Pour sheets of Whatman No. 3 f i l t e r paper (5$ x 4.6 cm.) were spotted (2 mg./spot) with product E (610 mg.) and the paper run as descending chromatograms i n a chromatocab using a butanol-water-ethanol-ammonium hydroxide ( l j . 0 : l 9 : l l ! l ) solvent (ij .1). The sheets were run f o r twenty-three hours and then s t r i p s were cut from the sheets and sprayed with perlodate-permanganate reagent. Five zones were v i s i b l e (Rf 0 . 0 7 ; Rf 0 . 2 8 ; Rf 0 . 3 2 ; Rf 0 . 3 8 ; Rf 0 . 5 2 ) . The papers were then cut up and parts bearing similar zones combined. The paper was then eluted with water. The solvent was removed and the products weighed. -19-i R f Y i e l d % Y i e l d Nature P r o d u c t X 0.07 0.036 2.9 Reducing P r o d u c t Y 0.28 0.037 2.9 Non Reducing P r o d u c t Z 0.32 0 .044 3 . 5 Reducing Product (G -f- Q) 0.38 0.923 72. Non Reducing P r o d u c t H 0 .52 0.200 . 18. Reducing 1.2^0 % r e c o v e r y from p a p e r : 8* f u r t h e r work was performed on p r o d u c t s X, Y, and Z because o f l a c k o f t i m e . P r o d u c t G [°< J ^rs +22.4° ( c , 0 .96 i n wa t e r ) Product H [ C<]y=: 4 1 2 . 8 ° ( c , 1.10 i n water) P r o d u c t s G and G were combined and d e s i g n a t e d as I . P r o d u c t s H and D were combined and d e s i g n a t e d as J . F r a c t i o n I c r y s t a l l i z e d on s t a n d i n g and was r e c r y s t a l l i z e d f r om m e t h a n o l - i s o p r o p y l e t h e r . I t was a whit e s o l i d ; m.p. 8o-S7° H j r + 2 5 . 3 0 1 , 2 l n w a t e r ) ' 1 d i d n o t reduce F e h l i n g ' s s o l u t i o n . A n a l . (45). G a l e f o r C 6 H l 2 0 ^ ; C, 48 .60; H, 8.10%. Found: C, 48.16; H, 7.86%. I.R. spectrum (SBr) o f I ( c m " 1 ) : 3bfeo(w), 3S0o(w), 3oao(s) , x^oO ( n n > J l tS2o(*S), >i4.1S(ui) , II+JLS(V/) , i % l O (.*)» 10-75(10), loi+sLxS) , S3o(w) , Soo ( w ) , sso(w/), eosOo). I h o ( r ^ ) , " 7 a s ( s A ) , F r a c t i o n J was a s w e e t - s m e l l i n g s y r u p . T h i s was r e -chromatographed'using Whatman No. 3 f i l t e r paper and i d e n t i c a l -20-procedure as f o r the chromatography of product E. Upon e x t r a c t -ing the paper w i t h water and evaporating the s o l u t i o n to dryness a white s o l i d was obtained. I t was r e c r y s t a l l i z e d from methanol-J reduced Fehling's s o l u t i o n and gave a p o s i t i v e S c h i f f ' s t e s t . C, L.9.19; H, 6 . 9 3 $ . I.R. spectrum (KBr) of J (cm" 1): 3hhO (ah),. 3320 (ah), 3220 ( s ) , 2960 (ah), 1725 (ah), 1665 (a), 1620 (w), 1580 ( s ) , lk.95 ( s ) , 1360 (w), 13h5 (ah), 1315 (w), 1285 ( s ) , 1250 (m), 1175 (in), 1155 (m), 1150 (ah), 1125 (ah), 1100 (m), 1075 (m), 1035 (w), 1015 (w), 975 (w), 950 (w), 900 (w), 875 (m), 820 (w), 800 (ah), 785 (a), 710 (w), 680 (m), 660 (m). Q u a l i t a t i v e Tests on Hydroformylation Products I n f r a - r e d Analyses - A Perkin-Elmer Model 21 double-beam record-ing spectrophotometer w i t h a sodium c h l o r i d e prism was used. The s o l i d samples were ground i n t o a di s c w i t h potassium bromide. F e h l l n g ' s Test - Carbonyl groups were detected w i t h Pehling's s o l u t i o n using the-j method reported by Shriner and Fuson (1+.6). Somogyi A n a l y s i s of F r a c t i o n J (1- (x(or / 3)-Formyl-2-Hydro-D-Xylal). F r a c t i o n J was subjected to a Somogyi a n a l y s i s (h7»h8). F r a c t i o n J (5»1 mg.) was d i s s o l v e d i n water (5 ml.) and added to the Somogyi reagent (5 ml.) i n a large t e s t tube. The tube was covered and l e f t i n a b o i l i n g water bath f o r f i f t e e n minutes. The s o l u t i o n was then cooled and sul p h u r i c acid added (5N, 1 ml. ) . The s o l u t i o n was then t i t r a t e d w i t h sodium t h i o -sulphate (0 . 0 0 5 3 8 N ) . i s o p r o p y l (c, 1.2 i n water). Anal. ( h 5 ) . C a l c . f o r C 6H 1 00^: C, h.9.36; H, 6.85%. Found: -21-Volume t h i o s u l p h a t e s o l u t i o n u s e d =. 11 .75 m l . A b l a n k t i t r a t i o n on the Somogyi r e a g e n t (5 ml.) was p e r f o r m e d a f t e r h e a t i n g w i t h a n e q u a l volume o f w a t e r . Volume o f t h i o s u l p h a t e s o l u t i o n used = 25.62 m l . A s t a n d a r d d e t e r m i n a t i o n u s i n g a known compound was p e r f o r m e d . 2 - D e o x y - D - g l u c o s e (1.1 mg.) was t r e a t e d i n t h e same manner as F r a c t i o n J . Volume o f t h i o s u l p h a t e r e q u i r e d f o r t i t r a t i o n = . 2 2 . 8 0 m l . Volume o f t h i o s u l p h a t e c o r r e s p o n d i n g t o 1 mg o f s t a n d a r d = 25.62'- 22 .80 _ 2 .55 m l . 1.1 Wt. o f F r a c t i o n J p r e s e n t = 25.62 - 11 .75 _ 5.1+4 mg. M o l e c u l a r w e i g h t o f 2 - d e o x y - D - g l u c o s e = l61|_ gm. M o l e c u l a r w e i g h t o f F r a c t i o n J ( a s s u m i n g C^H^QO^) = I/4.6 gm. $ s u g a r i n F r a c t i o n J = S.kk lh.6 100$ - 95$ 5Tl x I&T+ x Sodium B o r o h y d r i d e R e d u c t i o n o f F r a c t i o n J ( S u g a r ) The method was t h a t o f W r i g h t and Hayward (1|9)« F r a c t i o n J had b e e n shown p r e v i o u s l y t o be r e d u c i n g t o w a r d s F e h l i n g ' s s o l u t i o n . A p o r t i o n o f t h e compound (53 mg.) t o g e t h e r w i t h s o d i u m b o r o h y d r i d e (h.0 mg.) were d i s s o l v e d i n w a t e r ( o . 5 ml.) and a l l o w e d t o s t a n d a t room t e m p e r a t u r e f o r t w e n t y -f o u r h o u r s . To t h e s o l u t i o n 6N a c e t i c a c i d (0.1 ml.) was a d d e d . The m i x t u r e was d i l u t e d w i t h w a t e r t o 10 m l . and t h e n shaken w i t h a n i o n and c a t i o n exchange r e s i n s ( D u o l i t e A-k.. Chem. P r o c e s s Co., Redwood C i t y , C a l i f , and A m b e r l i t e IR-120. Rohn and Haas Co., P h i l a d e l p h i a , Penn. r e s p e c t i v e l y ) . The r e s i n s -22-were washed and t h e washings added t o the d e i o n i z e d . s o l u t i o n w h i c h was evaporated, t o a c o l o r l e s s o i l y p r o d u c t under reduced, p r e s s u r e . The o i l (46 mg.) f a i l e d t o s o l i d i f y a f t e r t r e a t m e n t w i t h e t h y l a c e t a t e o r i s o p r o p y l e t h e r . The o i l was non-red.ucing towards F e h l i n g ' s s o l u t i o n i n d i c a t i n g t h a t r e d u c t i o n was com-p l e t e . The o i l was p u r i f i e d , by a l l o w i n g i t t o r u n the l e n g t h o f a paper chromatogram u s i n g Whatman No. 1 paper and the s o l -v e n t n-butanol-water-ethanol-ammonium h y d r o x i d e ( 4 2 ) . The p r o -d u c t v/as eluted, o f f the paper w i t h water and the s o l v e n t evap-o r a t e d . The p r o d u c t was a w h i t e s o l i d . I t was r e c r y s t a l l i z e d . from m e t h a n o l - i s o p r o p y l ' e t h e r ; m.p. 86-87°. Using, Whatman No. 1 paper and s o l v e n t n-butanol-water-ethanol-amrnonium h y d r o x i d e , p o r t i o n s o f the p r o d u c t and f r a c t i o n I were r u n s i d e by s i d e on the same sheet o f paper f o r f o r t y - t w o h o u r s . On s p r a y i n g w i t h sodium metaperiod.ate s o l u t i o n i n w a t e r and p o t a s s i u m p e r -manganate (43) s p o t s were obtained, f o r each a t s i m i l a r d i s t a n c e s (33 cm.) from t h e o r i g i n . I.R. S-pectrum ( C H C l - ^ o f r e d u c t i o n p r o d u c t ( c m - 1 ) ; 3660 (w), 3580 (w), 3020 ( s ) , 2400 (m), 1520 (w), 1475 (w), 1425 (w), 1220 ( s ) , 1075 (w), 1045 (w), 930 (w), 900 (w), 850 (w), 805 (w), 760 (m), 7 2 5 ( s h ) , 670 (w). P r e p a r a t i o n o f 2-Deoxy-D-Glucose p-Nitrophenylhyd.razone 2-Deoxy-D-glucose p - n i t r o p h e n y l h y d r a z o n e was prepared, as a model. A p o r t i o n o f 2-deoxy-D-glucose (46 mg.), p - n i t r o p h e n y 1 -h y d r a z i n e h y d r o c h l o r i d e (47 mg.) and sodium a c e t a t e (105 mg.) were d i s s o l v e d i n wa t e r ( l ml.) and methanol ( l m l . ) . The s o l u t i o n was shaken f o r two minutes a.nd l e f t s t a n d i n g o v e r n i g h t . - 2 3 -A c a n a r y y e l l o w s o l i d was c o l l e c t e d by f i l t r a t i o n . R e c r y s t a l -l i z a t i o n f r o m m e t h a n o l y i e l d e d 50 mg.; m.p. 1 8 8-190°. L i t e r a t u r e v a l u e 1 9 0-191°. (35) I.R. S p e c t r u m (KBr) ( c m " 1 ) ; 3440 (m), 3340 (m), 3240 (m), 2920 (w), 1600 ( s ) , 1550 (w), 1495 (m), 1475 (m), 1325 ( s ) , 1280 (m), 1260 (m), 1185 (w), 1170 (w), 1110 (m), 1090 (m), 1075 (m), 1065 (m), 1045 (m), 1020 (m), 1030 (m), 995 (m), 945 (w), 880 (w), 835 (m), 8 l 5 (w), 750 (m), 695 (w). P e r i o d a t e O x i d a t i o n o f F r a c t i o n I Sodium m e t a p e r i o d a t e s o l u t i o n was made r o u g h l y IN and s t a n d a r d i s e d by a d d i n g e x c e s s o f a known s o l u t i o n (0.0101N) o f a r s e n i o u s o x i d e and b a c k - t i t r a t i n g w i t h s t a n d a r d i o d i n e s o l u t i o n ( 0.0107N). The method us e d was t h a t d e s c r i b e d by V b g e l ( 5 0 ) . The p e r i o d a t e was c a l c u l a t e d t o be 1 . 0 5 N . F r a c t i o n I (518 mg.) was d i s s o l v e d i n s o d i u m p e r i o d a t e s o l u t i o n (3.68 m l . , 10% e x c e s s ) . T h i s s o l u t i o n was k e p t 'in t h e d a r k a t room t e m p e r a t u r e f o r twenty h o u r s . A p o r t i o n o f t h e s o l u t i o n (0.9 ml.) s t o o d i n a c l o s e d p o l a r i m e t e r t u b e and r e a d -i n g s o f the o p t i c a l r o t a i o n were p e r f o r m e d p e r i o d i c a l l y : Time i n H o u r s 0 22° 0 .25 16° 0 . 5 1.0 -21*-3 . 0 7° 21|.o 7° 'The r e a c t i o n was assumed to be complete a f t e r twenty hours and an a l i q u o t from the f i n a l s o l u t i o n was withdrawn and t i t r a t e d w i t h iodine s o l u t i o n a f t e r f i r s t adding an excess of arsenious oxide s o l u t i o n . For the l a s t o p e r a t i o n 2 ml. of the s o l u t i o n were withdrawn and d i l u t e d w i t h water (2 ml.). Of the r e s u l t -i n g s o l u t i o n a p o r t i o n (1 ml.) was p i p e t t e d i n t o an excess (kO ml.) of arsenious oxide s o l u t i o n (0.0101N). Sodium bicarbonate (k gm.) was added and the mixture l e f t to stand f o r f i f t e e n minutes. On b a c k - t i t r a t i n g w i t h iodine s o l u t i o n ( 0 . 0 1 0 7 N ) using s t a r c h i n d i c a t o r 32.7k ml. of iodine were re quired. m. equivs. periodate s o l u t i o n present |(k0 x 0 . 0 1 0 1 ) - (32.7k x 0.0107)] x 8 = o.o55 x 8 = o.kko m. equivs. periodate present o r i g i n a l l y - 3.68 x 1.05 = 3.86 i m. equivs. periodate consumed = 3.86 - o.kko « 3 . k 2 m. equivs. of f r a c t i o n I used = 3 . 5 Number of moles of periodate consumed per mole of compound 3 . k 2 0 .98 " J i? The product was n e u t r a l i z e d w i t h barium c h l o r i d e (1 gm.) i n water ( 5 ml.). A white p r e c i p i t a t e was produced which was f i l t e r e d o f f and washed. Saturated sodium bicarbonate s o l u t i o n (20 ml.) was added to the f i l t r a t e . A white p r e c i p i t a t e formed -25-which was f i l t e r e d o f f and washed and the f i l t r a t e evaporated to dryness. The residue was extracted with three portions (1|0 ml. each) of methanol to remove organic materials. The extracts were evaporated to a s o l i d , white, water soluble residue (0.508 gm.) which gave a rapidly positive Pehling's t e s t . This residue was assumed to be the dialdehyde ( I I ) . I H-C CH,OH H O - C - H H - c - o H I H f H-C-K t>*C.-H p-Nitrophenylhydrazone Derivative of Oxidation Product (II) The oxidation product (0.508 gm.), sodium acetate (1.2 gm.) and p-nitrophenylhydrazine hydrochloride (1.1 gm.) were d i s -solved i n methanol (10 ml.) and water (3 ml.) and heated to 60° on a water bath f o r f i f t e e n minutes, shaken f o r t h i r t y minutes and then l e f t to stand overnight at room temperature. The product consisted of a yellow-red s o l i d (III) (0.73 gm.) and a red solution (IV). The solution was evaporated to dryness y i e l d i n g a red-brown s o l i d (1.1 gm.). This s o l i d was hardly soluble i n benzene but an appreciable amount dissolved i n chloroform to y i e l d a yellow solution (V). The re s i d u a l , chloroform insoluble, s o l i d was p a r t i a l l y soluble i n ethanol y i e l d i n g a red-brown solution which on evaporation gave a brown o i l (VIII) (0.074 gm.). The ethanol and chloroform insoluble portion (VII) (0.322 gm.) was a colorless c r y s t a l l i n e s o l i d - 2 6 -which showed c h a r a c t e r i s t i c inorganic properties i n refusing to melt or burn with an organic flame or give a Molisch t e s t . In addition an aqueous solution of VII produced a white precipitate with s i l v e r nitrate solution. VII was thought to be sodium chloride. Chromatography of Fraction V on P l o r l s l l Fraction V (O.67 gm.) was dissolved i n N,N-dimethylform-amide (0 .6 ml.) and added to the top of a f l o r i s i l column (2 x 15 cm.). Development with benzene: alcohol (99:1, 100 ml.) produced two orange-coloured zones. Further solvent (30 ml.) removed the lower band XI. The column was then allowed to dry and then extruded and the top part (IX) of the extended v i s i b l e upper zone and the rest of the upper zone (X) cut out and ex-tracted with ethanol. Upon evaporation of the solution containing the three zones to dryness three solids remained. m.p. y i e l d IX (top zone) 128-133° 0.05h gm. X (middle zone) 110-140° 0.585 XI (lower zone) Ih3-l50° 0.02h Zone IX was r e c r y s t a l l i z e d from ethanol-water; m.p. 133-135°• I.R. Spectrum (KBr) of IX (cm" 1): 3h50 (sh), 3260 (w), 2900 (w), I 6 h 5 (m), 1595 (s), 1525 (sh), 1510 (sh), 1500 (m), l h 9 0 (sh), 1325 (s), 1305 (sh), 1265 (m), 1175 (w), 1110 (m), 1000 (w), 8h5 (w), 81+0 (m), 7^0 (w), 692 (w). - 2 7 -T h i s was i d e n t i c a l w i t h t h a t o f an a u t h e n t i c sample o f 2-deoxy-D - t e t r o s e p - n i t r o p h e n y l h y d r a z o n e . Zone X (0.58 gm.) was d i s s o l v e d i n N,N-dimethylformamide (0 .5 ml.) and a p p l i e d t o the t o p o f a f l o r i s i l column (2 x l h cm.). Development w i t h b e n z e n e - e t h a n o l ( 9 8 : 2 , 100 ml.) s e p a r a t e d two zones (0 cm. and 5 cm. from the t o p o f the column). The column was a l l o w e d t o dry and then e x t r u d e d . The two zones were c u t out and e x t r a c t e d w i t h e t h a n o l . On e v a p o r a t i o n o f the s o l v e n t s two s o l i d s (XV and XVI) remained. m.p. y i e l d XV ( t o p zone) 128 -133° 0.530 gm. XVI (bottom zone) l i i . l - l l j . 9 0 0.038 XV was r e c r y s t a l l l z e d f r o m e t h a n o l - w a t e r ; m.p. 133 - 1 3 5 ° . I.R. spectrum (KBr) o f XV was i d e n t i c a l w i t h t h a t o f I X and w i t h t h a t o f an a u t h e n t i c sample o f 2-deoxy-D-tetrose p - n i t r o p h e n y l -hydrazone. F o r XV and I X |.C<Jjt>= °° (C . 1 . 0 8 i n e t h a n o l ) . Chromatography o f F r a c t i o n I I I on F l o r i s i l F r a c t i o n I I I (o . 7 3 gm.) was d i s s o l v e d i n N,N-dimethyl-formamide ( 0 . 8 ml.) and a p p l i e d t o the t o p o f a f l o r i s i l column (2 x 16 cm.). Development w i t h benzene (80 ml.) e l u t e d r a p i d l y a r e d - b l a c k band (XIV) wh i c h was c o l l e c t e d and t r e a t e d w i t h p e t r o l e u m e t h e r (30-60°, 20 ml.) to p r e c i p i t a t e a s c a r l e t r e d s o l i d ; m.p. 333-335°, y i e l d 0.195 gm. I.R. spectrum (KBr) o f XIV ( c m " 1 ) ; 3760 (w), 3h60 (w), 3270 (m), 3100 ( s h ) , 1655 ( s h ) , 1600 ( d b , s ) , -28-1565 (s), 1532 (m), 1505 (ah), 1500 (s), l k 8 0 (s), 1315 (db,s), 1290 (db,s), 1275 (db,s), 1175 (m), llkO (m), 1105 ( a ) , 1000 (sh), 998 (w), 920 (w), 885 (w), 8k0 (w), 835 ( a ) , 752 (s), 700 (sh), 692 (w). This was i d e n t i c a l with that of an authentic sample of glyoxal bis-p-nitrophenylhydrazone. Mixed m.p. of XIV with an authentic sample of glyoxal bis-p-nitrophenylhydrazone was undepressed. After e l u t i o n of XIV a band remained at the top of the column (XII) and an orange coloured zone (XIII) persisted throughout the length of the column. The column was allowed to dry and then extruded. Zone XII was cut o f f and eluted with N,N-dimethyIformamide and ethanol. Evaporation of the solvent yielded a yellow s o l i d ; m.p. >350° , y i e l d 0.08k. gm. Zone XIII was extracted with N,N-dimethyIformamide and ethanol, the solvent evaporated to y i e l d a red-orange s o l i d (0 .k9 gm.) which was dissolved i n N,N-dimethylformamide (O.k ml.) and added to the top of a f l o r i s i l column (2 x 17 cm.). Benzene (100 ml.) eluted a red-black band (XVIII) which, was collected and treated with petroleum ether (30-60°, 20 ml.) to precipitate a scarlet s o l i d ; m.p. 333-335°* y i e l d 0 . k l 8 gm. Mixed m.p. with an authentic sample of glyoxal bis-p-nitrophenyl hydrazone was undepressed. The I.R. spectrum (KBr) of XVIII was i d e n t i c a l with that of an authentic sample of glyoxal bis-p-nitrophenyl-hydrazone . After e l u t i o n of band XVIII a band XVII remained at the top of the column. Extrusion of the column, elu t i o n with ethanol, and evaporation of the solvent yielded a yellow s o l i d : m.p. > 3 5 0 ° , y i e l d 0.029 gm. -29-Preparation of Glyoxal Bis-p-Nltrophenylhydrazone Glyoxal (100 mg.), sodium acetate (450 mg.), and p-nitro-phenylhydrazine hydrochloride (510 mg.) were dissolved i n methanol (5 ml.) and water (2 ml.). A red precipitate formed immediately and was f i l t e r e d o f f and washed with water. The s o l i d was r e c r y s t a l l i z e d from N,N-dimethylformamide-petroleum ether (30-60°); m.p. 333-335°, y i e l d O.ij.2 gm. (68$) . I.R. Spectrum (KBr) (cm" 1): 3760 (w), 3460 (w), 3270 (m), 3100 (sh), 1655 (sh), 1600 (db,s), 1565 (s), 1532 (m), 1505 (sh), 1500 (s), 1480 (s), 1315 (db,s), 1290 (db,s), 1275 (db,s), 1175 (m), 1140 (m), 1105 (s), 1000 (sh), 998 (w), 920 (w), 885 (w), 840 (m), 835 (s), 752 (s), 700 (sh), 692 (w). - 3 0 -Summary of Treatment of Oxidation Product Preparation of p-nitrophenylhydrazpne of oxidation product (II) f i l t e r Residue III I XVII chromatography ~1 1 XII XIII XIV chromatography 1 XVIII 1 F i l t r a t e IV evaporate add chloroform I I Soluble V Insoluble VI ethanol I r IX r Insoluble VI Soluble VIII chromatography r XV 1 1 X XI chromatography XVI Table II Summary of Products Obtained Prom Chromatography of Oxidation Products Product Colour m.p. Weight (gm) Identity VII yellow-white >350° 0.322 Inorganic VIII yellow - 0.074 -IX XI red yellow 133-135° 143-150° 0.054 0.024 2-Deoxy-D,L-tetrose p-nitrophenylhydrazone . XV XVI red yellow 133-135° 141-149° 0.530 0.038 2-Deoxy-D,L-tetrose p-nitrophenylhydrazone XII brown >350° 0.084 -XIV XVII scar l e t yellow 333-335° >350° 0.195 0.029 Glyoxal b i s - p - n i t r o -phenylhydrazone XVIII scarlet 333-335° 0 . 4 l 8 1.734 Glyoxal b i s - p - n i t r o -phenylhydrazone Theoret i c a l t o t a l recovery = 1.93 gm. Weight of 2-deoxy-D, L-tetrose p-nitrophenylhydrazone «= 0.58 gm. Theoretical y i e l d «=• 0.83 gm. % Y i e l d BB 70% Weight of glyoxal bis-p-nitrophenylhydrazone = 0 . 6 l gm. Theoretical y i e l d 1.10 gm. % Y i e l d - 54$ - 3 2 -Preparation of Derivatives 1. Aoetylation of Fraction J (1-of (ory3)-Formyl-2-Hydro-D-Xylal) The method employed was e s s e n t i a l l y that described by V o g e l . ( S l ) . Fraction J (1+.8 mg.) was slowly added to a warm ($0°) solution of acetic anhydride (0 .3 ml.) and anhydrous zinc chloride (0 .1 gm.). The mixture was warmed (50°) for a further one hour on a water bath. On pouring into ice-water (25 ml.) an o i l separated. The o i l was separated from the rest of the solution using a separatory funnel. The o i l was dried by repeated azeotroping with small quantities of benzene. The o i l (h0 mg.) was dissolved i n benzene-petroleum ether (1 ml., 1:2) and placed on the top of a f l o r i s i l column (12 x 3 cm.) and the column developed with benzene-petroleum ether (i|_5 ml., 1 : 2 ) . Small f r a c t i o n s (5 ml.) were c o l l e c t e d . A small amount (8 mg.) of o i l was present aft e r evaporation of the eluant. No further product was eluted with benzene-petroleum ether (60 ml., 1 :1) . Using benzene-ethanol (70 ml., 99:1) as developer, a s o l i d white product (28 mg.) was obtained on evaporation of the eluant. This was recsrystallized from methanol-isopropyl ether; m.p. 55-5 7 ° , [ ° < ] j l 3 . 2 0 (c,1.3 i n water). Anal. Calc. f o r C^H^O^; C, 52.19; H, 6 . 0 8 $ . Found: C, 51 .63; H, 5 . 7 9 $ . 2. Benzoylation of Fraction I (1- «(oryff)-Hydroxymethy1-2- Hydro-D-Xylal The compound was benzoylated by a modification of the method of Smith and Van Cleve ( 5 2 ) . A portion of the compound (I4.6 mg.) was dissolved i n anhy--33-dous pyridine (2 ml.) i n a ground glass f l a s k , and benzoyl chloride (0.1+ ml.) added to the solution with a micro-pipette. The f l a s k was f i t t e d with a ground glass inverted drying tube, l e f t i n a water bath (90-100°) f o r f o r t y minutes, and then cooled to room temperature. Cooling brought about the formation of c r y s t a l s (probably a benzoyl choride-pyridine complex). When the mixture was poured into a saturated sodium bicarbonate solution (15 ml.) o i l y droplets formed. After i t was shaken for several minutes, the mixture was extracted twice with portions (20 ml. each) of chloroform. The combined chloroform extracts were washed with water ($0 ml.) and with three separate portions of ice-cold hydrochloric acid (3N, 30 ml. each), followed by four separate washes with water (1+0 ml. each). The solution was then neutral to litmus and was dried overnight over calcium chloride. After f i l t r a t i o n , the solution was concentrated (water aspirator) at room temperature to a syrup. Removal of the l a s t traces of pyridine was affected by drying the product over phosphorous pentoxide at reduced pressure at the b o i l i n g point of acetone for one day. The o i l y product (37 mg.) was dissolved i n benzene-petroleum ether (0.5 ml., 1:1) and added to the top of a f l o r i s i l column (10 x 1 cm.). Development with benzene-petroleum ether (1+0 ml., 1:1) f a i l e d to remove any s o l i d . After unsuccessful development with benzene-petroleum ether (50 ml., 2:1), benzene (5'0 ml.) and benzene-ethanol (30 ml., 0.5%) the column was developed with benzene-ethanol (80 ml., 1%). After evaporating the solvent a white s o l i d (26 mg.) was l e f t . .Jpiis was r e c r y s t a l l i z e d from ethanol-water; m.p. l59-l6l° , 21° c, 1.8 i n chloroform). Anal. Calc. f o r Cp 7H p.0 ?(three benzoyl -3k-g r o u p s ) : C, 7 0 . k l ; H , 5-25%. C a l c . f o r C2oH2o°6^ t w o D e n z o y l g r o u p s ) : C, 6 7 . 5 U H , 5.62%. Pound: C, 68 .55; H , 5 . 5 0 % . 3 . Attempted" P r e p a r a t i o n o f 2 , 5 - D i c h l o r o p h e n y l h y d r a z o n e o f  F r a c t i o n J ( 1 - o< ( o r y g ) - F o r m y l - 2 - H y d r o - D - X y l a l ) F r a c t i o n J (72 mg.) was d i s s o l v e d i n water (1 ml.) and added to a s o l u t i o n o f 2 , 5 - d i c h l o r o p h e n y l h y d r a z i n e (291 mg.) i n e t h a n o l (2 m l . ) . A c e t i c a c i d (8N, 2 ml.) was added t o g e t h e r w i t h sodium a c e t a t e ( s u f f i c i e n t t o g i v e pH o f about k ) • The s o l u t i o n was heated a t 100° f o r an hour and t h e n l e f t f o r two days. A s o l i d r e s i d u e appeared. T h i s was f i l t e r e d o f f ; y i e l d 6k mg. T h i s was r e c r y s t a l l i z e d from ethano 1 /water; m.p. 156-1 5 9 ° . A n a l . C a l c . f o r C - ^ H^ClgNgO^: C, k 7 - 2 0 ; H, k - 6 ; N, 9 . 2 % Found: C, k 3-91; H , 3 . 6 8 ; N, 1 0 . 9 6 % The f i l t r a t e was ev a p o r a t e d down to a s o l i d r e s i d u e ( 6 l mg.) whic h was d i s s o l v e d i n benzene ( l ml.) and a p p l i e d to the t o p o f a f l o r i s i l column ( 10 x 1 cm.). E l u t i o n w i t h b e n z e n e - a l c o h o l ( 9 9*1, 60 ml.) and e v a p o r a t i o n o f the s o l v e n t produced a l i g h t y e l l o w s o l i d (36 mg.). T h i s was t r e a t e d w i t h N o r i t e and r e -c r y s t a l l i z e d f r o m e t h a n o l - w a t e r ; m.p. 1 5 8 - 1 6 0 ° . A n a l . C a l c . f o r C ^ H - j ^ C ^ N ^ : C, k 7 . 2 0 ; H, 4 . 6 ; N, 9 . 2 % Found: C, k 3 . 8 6 ; B y 3 . 8 5 % C a l c . f o r N. a c e t y l d e r i v a t i v e o f 2 , 5 - D i c h l o r o p h e n y l -h y d r a z i n e ( C 8 H 9 C l 2 N 2 o ) : C, k 3.30; H , 3 . 5 0 - 3 5 -DISCUSSION 3,i4--Di-0-acetyl-D-xylal, synthesized by a modification of the method of H e l f e r i c h (7) was obtained i n lB% y i e l d . The compound was found to be stable over a period of a few days afte r d i s t i l l i n g i f kept at - 1 0 ° . Prolonged standing even at t h i s temperature caused deterioration and standing f o r short periods i n daylight at room temperature was found to be disasterous. It i s recommended that the x y l a l be used soon afte r preparation. The catalyst for the reaction, dicobalt octacarbonyl, was preformed by the action of carbon monoxide and hydrogen on cobalt (II) carbonate at elevated temperatures and pressures. Dicobalt octacarbonyl was found to be stable i f kept i n a stoppered f l a s k at - 1 0 ° . It i s extremely toxic and unpleasant to work with and precautions were taken to use a well v e n t i l l a t e d fume hood when working with i t . It has been shown that glycals react with water under certain conditions to form 2-deoxy sugars (11) or pseudoglycals ( 1 0 ) . It was noted ( 5 h ) that the amount of moisture present i n the carbon monoxide used was very small so that only negl i g i b l e amounts of these compounds could have been produced i n the reaction. The hydro£ormylations were carried out under the same conditions using a benzene solvent and equal concentrations of carbon monoxide and hydrogen. It was found that on an average between two and three moles of synthesis gas was consumed per mole of gas. Theoretically when an aldehyde i s formed from the -36-g l y c a l two moles o f gas a r e a b s o r b e d p e r mole o f g l y c a l . When an a l c o h o l i s f o r m e d t h e n t h e t h e o r e t i c a l c o n s u m p t i o n i s t h r e e m o l e s o f g a s . T h a t between two and t h r e e m o l e s o f g a s e s a r e consumed i s an i n d i c a t i o n t h a t a m i x t u r e o f a l d e h y d e and a l c o h o l i s p r e s e n t i n the p r o d u c t . One e x p l a n a t i o n i s t h a t an a l d e h y d e i s t h e p r i m a r y p r o d u c t w h i c h becomes h y d r o g e n a t e d t o t h e c o r r e s p o n d i n g a l c o h o l . H y d r o g e n a t i o n u n d e r t h e r e a c t i o n c o n -d i t i o n s i s a p p a r e n t l y o n l y p a r t i a l as a s i z e a b l e f r a c t i o n o f t h e p r o d u c t was a l d e h y d e . A s s u m i n g t h e t r u t h o f t h e p o s t u l a t e t h a t t h e p r i m a r y a l d e h y d e p r o d u c t i s r e d u c e d s u b s e q u e n t l y t o t h e a l c o h o l i s l e f t w i t h t h e c o n c l u s i o n t h a t t h e a l d e h y d e i s t h e p r e c u r s o r o f t h e a l c o h o l . T h i s was p r o v e d and i s d i s c u s s e d l a t e r . I t i s n o t a b l e t h a t t h e p r o d u c t s o b t a i n e d by Nussbaum e t a l (29) and B e a l (30) were s u g a r a l c o h o l s and t h e p r o d u c t o b t a i n e d by R o s e n t h a l (2) was m a i n l y s u g a r a l c o h o l . However t h e Nussbaum and B e a l w o r k e r s h y d r o f o r m y l a t e d a t 1 8 0 - 1 9 0 ° - a t e m p e r a t u r e a t l e a s t h0° above t h a t o f t h e p r e s e n t work. R o s e n t h a l i n o b t a i n i n g a q u a n t i t y o f a l d e h y d e worked a t a b o u t t h e same t e m p e r a t u r e ( 1 2 0 ° ) as t h e p r e s e n t work b u t a l l o w e d t h e r e a c t i o n t o go f o r a c o n s i d e r a b l e l e n g t h o f t i m e ( f i v e h o u r s ) as o p p o s e d t o t h e p r e s e n t one h o u r . S i n c e t h e a l d e h y d e has b e e n o b t a i n e d i n a b o u t t h e same y i e l d as the s u g a r a l c o h o l i t i s r e a s o n a b l e t o suppose t h a t m o d e r a t i n g the c o n d i t i o n s s t i l l f u r t h e r would a l l o w m a i n l y a l d e h y d e t o be i s o l a t e d . The h y d r o f o r m y l a t i o n p r o d u c t s a f t e r d e a c e t y l a t i o n were f r a c t i o n a t e d i n t o t h r e e components ( f r a c t i o n s B, C, D) u s i n g a b u t a n o l - w a t e r ( s a t u r a t e d ) d e v e l o p e r . F r a c t i o n s B and D were -37-sugars and C was a sugar alcohol. Using a butanol-water-ethanol-ammonium hydroxide developer f i v e components (X, Y, Z, G and H) were i s o l a t e d . Fractions X, Z and H were sugars while f r a c t i o n s Y and G were sugar alcohols. A l l the fractions were water-soluble. Fractions C, D, G and H were the major products. Fractions C and G were i d e n t i c a l as were fractions D and H. Fractions X, Y and Z were not characterized as they were minor components and also because of lack of time. Fraction C was eventually c r y s t a l l i z e d . Carbon and hydrogen analyses corresponded to those of a compound having an empirical formula P^H^O^. Fraction D when c r y s t a l l i n e gave carbon and hydrogen analyses corresponding to a compound having an empirical formula C6HloV A reduction of f r a c t i o n C with sodium borohydride gave a compound having i d e n t i c a l R^ value, melting point, and i n f r a -red spectrum to that of f r a c t i o n D. It has been shown (1+9, 55 ) that sodium borohydride i n aqueous solution w i l l reduce an aldehydo group to a hydroxy methyl group. Fractions C and D are thus relat e d . Fraction D i s the precursor of f r a c t i o n C and by hydrogenation i s converted into f r a c t i o n C during the course of the hydroformylation. Periodate oxidation of f r a c t i o n C was carried out. Periodate oxidation i s known to cleave adjacent hydroxyl groups ( 5 6 ) . It was shown by t i t r a t i o n data that approximately one mole of periodate was consumed per mole of carbohydrate (based on a formula C^H-^gO^). Therefore f r a c t i o n C contained one pair of adjacent hydroxyl groups. That cleavage had i n fact taken -38-place was shown by the fact that the product gave a positive Pehling's test, indicating the presence of the dialdehyde. Reaction of the oxidation product to form the p-nltrophenyl-hydrazone derivative produced as the major components 2-deoxy-D,L-tetrose p-nitrophenylhydrazone/^and glyoxal b i s - p - n i t r o -phenylhydrazone (II) c ( H , O H ) I jr—\ H C = N N H { ^ N O x These products could be produced from the dialdehyde (III) by cleavage of the ether linkage between and C^. c H , p H H C , I H - C - O 3 L T The fact that the 2-deoxy-D-tetrose p-nitrophenylhydrazone formed i n the reaction was found to be o p t i c a l l y inactive to sodium D l i g h t i s s i g n i f i c a n t . This would indicate that the C-j_ i s racemized i n the course of the cleavage so that the ether l i n k was severed between C-^  and the ether oxygen atom rather than between and the ether oxygen. A plausible mechanism would be: -39-HC H-C=Q cNiOH CM-H C -CH-* HceJ- , H C = N N H ^ ( y 0 i HxO £w,OH « - c © H C — N N H ^ ^ N O i CHjpK I H C = N N H ^ ^ N < V -40-A p l a n a r f o r m o f the c a r b o n i u m i o n i n t e r m e d i a t e would a l l o w r a c e r a i z a t i o n . The s t r u c t u r e o f compound G must f i t t h e c o n c l u s i o n s p r e v i o u s l y drawn. T h a t i s : 1. No c a r b o n y l g r o u p i s p r e s e n t . 2. The compound had one p a i r o f a d j a c e n t h y d r o x y l g r o u p s . 3 . I t had an e m p i r i c a l f o r m u l a G/^12®}+' 1}.. I t was formed by sodium b o r o h y d r i d e r e d u c t i o n o f a c a r b o n y l compound h a v i n g an e m p i r i c a l f o r m u l a C^H-^QO^. 5 . P e r i o d a t e o x i d a t i o n o f t h e compound f o l l o w e d by t r e a t m e n t w i t h p - n i t r o p h e n y l h y d r a z i n e r e a g e n t p r o d u c e d as m a j o r components 2 - d e o x y - D , L - t e t r o s e p - n i t r o p h e n y l -h y d r a z o n e and g l y o x a l b i s - p - n i t r o p h e n y l h y d r a z o n e . A compound f i t t i n g a i l t h e s e f a c t s i s I I * H C C M x O H - C I ^ I Ho-c-H I H - C - O M I o r i t s i s o m e r HO-c-H I H - c - o r i I T h i s i n d i c a t e s t h a t i n t h e c o u r s e o f t h e h y d r o f o r m y l a t i o n o f 3 , i | . - d i - 0 - a c e t y l - D - x y l a l a h y d r o x y m e t h y l g r o u p was added a t C^, On t h e e v i d e n c e o f the s o d i u m b o r o h y d r i d e r e d u c t i o n I t i s e v i d e n t t h a t t h e o t h e r m a j o r component o f the h y d r o f o r m y l a t i o n was t h e compound ( V I ) h a v i n g a f o r m y l g r o u p added a t C ^ . Any f o r m u l a t i o n o f compound D ( V I ) must f i t t h e f o l l o w i n g c o n c l u s i o n s : 1. A c a r b o n y l g r o u p i s p r e s e n t . 2. The compound has an e m p i r i c a l f o r m u l a C^H-^QO^. -41-3. It Is reduced by sodium borohydride i n aqueous solution to compound C. 4 . On acetylation a compound having empirical formula ^10^14^6 P r 0 ^ u c e d . A compound f i t t i n g a l l these facts is CHO H - C H O - C - W I H-C-OH or Its Isomer H I O H C - C I : i rio-c-H I H - c - o H In conclusion, a new six carbon polyol, l - c x ( o r p ) -hydroxymethyl -2-hydro-D-xylal, has been prepared by the hydro-formylation of 3 , 4-di-O-acetyl-D-xylal. A new six carbon sugar, 1-cy (or y3)-f ormyl -2-hydro-D-xylal, was also formed and must have been hydrogenated to the corresponding alcohol i n the reaction mixture. BIBLIOGRAPHY 1. R o s e n t h a l , A. and Read, D., Can. J . Chem., 35: 7 8 8 . 1957. 2. 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