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The hydroformation of 3,4,6-Tri-O-acetyl-D-galactal Read, Dale Welton 1956

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THE HYDBQFGRMYLATION OP 3,M-,6-TEI«Q-iCETYL P~GALACTA1 by DALE WELTON READ A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN THE DEPARTMENT OF CHEMISTRY. We accept this thesis as conforming to the standard required from candidates for the Degree of MASTER OF SCIENCE Members of the Department of Chemistry THE UNIVERSITY OF BRITISH COLUMBIA Ap r i l , 1956. ABSTRACT 3,U,6-Tri-Q-acetyl-P-galactal was treated in the presence of dicohalt octacarbonyl with carbon monoxide and hydrogen at elevated temperatures and pressures. From deacetylation of the reaction products, a seven carbon homologuo of a deoxy anhydride of P-galactitol was obtained. That i s , a hydroxy methyl group was added to either carbon one or two of the original unsaturated sugar. ACKNOWEBDGMEHQ?S The writer wishes to express bis sincere thanks to Sr. A. Rosenthal for his encouragement and guidance throughout this investigation. Grateful acknowledgments are made to the Powell River Company Limited for the award of a scholarship, and to the National Research Council of Canada for a scholarship and a summer grant. Thanks are also due Dr.BR. Idler of the Fisheries Experimental Station, Vancouver, for performing elemental analyses. TABLE OF CONTENTS Page No. Introduction l a HISTORICAL INTRODUCTION 1. Unsaturated Sugars (Glycals)... 1 (a) Synthesis 1 (t>) Reactions 1 2. Hydroformylation (Oxo Reaction) 3 3. Deacetylation 6 DISCUSSION OF RESULTS S EXPERIMENTAL Instrumentation 15 Synthesis of 3,U,6-Tri-©-Acetyl-D-Galactal 15 Synthesis of Dicohalt Octacarbonyl l 6 Hydroformylation No. 1. IS Hydroformylation No. 2 18 Hydroformylation No. 3 19 Continuous Flow Chromatography of Hydroformylation Product No. 1 19 Chromatography of Hydroformylation Product No. 2 . . . 21 Qualitative tests on Products 22 Attempted Crystallizations of Fractions 23 Deacetylation : 23 Attempted Hydrolysis of Compound G 25 Qualitative Tests on Compound G 26 Periodate Oxidation 26 TABLE OS* CONSENTS (Cont.) Page No. EXPERIMENTAL (Cont.) Preparation of Derivatives 28 (1) Acetylation 28 (2) Attempted Preparation of a Benzylidene Derivative 29 (•5) Benzoylation 29 (4) P-Nitrobenzoylation 31 BIBLIOGRAPHY 32 LIST OF TABLES Table I. Chromatography of Product froml.Run.l... 20 Table II. Chromatography of Product from Hun 2... 21 Table III. Results of Qualitative Tests on Hydroformylation Products 22 Table IV. Periodate Oxidation of Compound ft 27 Table V. Chromatography of Benzoate 30 LIST OF FIGURES Figure 1. Infra Red Spectra of Hydroformylation Products 22a Figure 2. Periodate Oxidation of Compound G 27a - l a « INTRODUCTION The hydroformylation r e a c t i o n has "been applied to several types of o l e f i n i c unsaturated compounds to y i e l d homologous aldehydes or alcohols. Hydroformylation of an unsaturated sugar might he expected to y i e l d one or a mixture of new branched or s t r a i g h t chain sugars or sugar a l c o h o l s . Hydrogenation of the double bond to y i e l d a 1,2-dihydro carbohydrate i s also p o s s i b l e . Branched chain sugars are rare i n nature. Their occurrence i s u s u a l l y associated with p h y s i o l o g i c a l a c t i v i t y . U n t i l now, the cnly synthetic branched chain carbohydrates known are sugar acids produced from the r e a c t i o n of hydrogen cyanide with ketoses^ 3-?). The present work describes the hydroformylation of 3,U,6-tri-©-acetyl-D-galactal and the c h a r a c t e r i z a t i o n of a r e a c t i o n product. HISTORICAL INTRODUCTION 1. Unsaturated Sugars (Slycals). (a) Synthesis. Glycals were f i r s t reported "by Fischer^) i n 191U. 3,H,6-Tri--jfl|-acetyl-S-glucal was obtained "by treating 2,3.^.6-tetra-Jg-acetyl- oC-D glucopyranosyl bromide with zinc dust i n f i f t y percent acetic acid. Crystalline 3,U,6-tri-©-acetyl-D^galactal was f i r s t synthesized by levene and Tipson^ 2 0^ in 1931. The procedure of Fischer(5) was used. The method of glycal synthesis has been changed l i t t l e . However, in 195*+» Helferich and/co-workers(1 2) shortened the procedure. They ace-tylated D-glucose, brominated the acetate, and converted the resulting bromo compound to the corresponding unsaturated sugar without isolating 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 hydro bromic acid formed in the bromination procedure. Als.o, copper sulphate was added to catalyze the reaction. These modifications gave increased yields of the f i n a l product. (b) Reactions. Although glycals have been found to exhibit unique properties, they also have been shown to undergo many reactions characteristic of olefinic compounds. Fischer, i n I9l4(5>, treated a solution of 3» .^6-tri-^»acetyl-Pj-glucal i n glacial acetic acid with hydrogen in the presence of a platinum catalyst. l,2-Dihydro-3.M-,&-tri^-acetyl-Dj-glucopyranose was obtained. - 2 -The action of oxidizing agents on unsaturated sugars has been studied extensively. levene and Tipson^ 2 0^ treated JX-galactal with perbenzoic acid and obtained galactose and another compound that was probably S-talose. The two sugars were not obtained i n equal amounts. The addition of hydroxyl groups to the double bond of a glycal has been found to yi e l d only one sugar under certain conditions. Hockett and Millman^ 13) treated frgalactal with hydrogen peroxide i n tert-butanol in the presence of a small amount of osmium tetraoxide. Although they obtained ^ -galactose, no JVtalose was found. Some cleavage of the double bond occurred, with the production of what was thought to be D~lyxonic acid. The double bond of a glycal has been shown to migrate under f a i r l y mild conditions. Lohaus and Wldmaier^21^ treated 3,U,6~tri-£-acetyl-Jfc. galactal with boiling water. From the reaction mixture they isolated h ,6-di-^acetyl-Dwpseudogalactal. (The double bond had shifted to the 2,3 position.) This compound gave typical aldehyde reactions. It reduced Fehling' s solution and when i t was treated with ethyl ortho formate, the corresponding ethyl acetal was obtained. Water has been found to add across the double bond of an unsatura-ted sugar. Isbell and Pigman^) obtained 2-deoxy-P-galactose by treating Pj-galactal with water. The reactions of the glycals have been summarized by H e l f e r i c h ^ 1 1 ^ . Because of their special properties, these compounds have found frequent use as intermediates i n further syntheses. - 3 -2. Hydroformylation (Oxo Reaction). In 1926, Fischer and Tropsch^) announced that higher homologues of methane were formed when mixtures of hydrogen and carbon monoxide were passed at atmospheric pressure over a catalyst of iron or cobalt at elevated temperatures. Further investigation^ 7) showed the existence of traces of oxygen containing compounds i n the crude product. This oxygenated mixture consisted of acetone and aldehydes. Smith, Hawk and G o l d e n ^ ) , i n 1930, treated ethylene with carbon monoxide and hydrogen in the presence of a catalyst. They obtained hydro-carbons plus a water soluble oxygen containing o i l , which made up twenty -five to thirty-five percent of the total product. It was their opinion that the oxygen containing compounds were formed f i r s t i n the reaction, and that these were next dehydrated with subsequent polymerization. In 19U3, Hoelen^ 2^ disclosed the following reaction: RCH = CH P i 00 * Ho -9.Pr2PP° . RCHpCHoCHO 2 d 125-200 atm. * * The catalysts contained cobalt, thorium oxide* kieselguhr, and sometimes copper. Ethylene treated according to this reaction yielded forty percent propionaldehyde, twenty percent diethyl ketone and forty percent higher boiling aldehydes and ketones. -The method was modified i n 19*4-8 by Adkins and Krsek^ 1). By dissolving an alkene i n ether, adding a cobalt catalyst, and treating the mixture with carbon monoxide and hydrogen at a high pressure, they obtained the corresponding aldehyde(s) i n good yield. Diethyl fumarate gave diethyl- x-formyl succinate, while ; pentene-2 yielded what was assumed to be a mixture of the two possible isomeric aldehydes. It - 4 -was also noted by these workers that the use of preformed dicohalt octa-carbonyl as catalyst allowed the reaction to proceed more readily and at lower temperatures. They therefore postulated the following mechanism to account for the reaction: technique "by using benzene instead of ether as solvent. This allowed the reactions to proceed at lower temperatures and pressures. These workers subjected a number of unsaturated compounds to the hydroformylation reactions. Hexene-l was converted to a mixture of n-heptaldehyde and 2-niethyl hexaldehyde. A l l y l acetate and allylidene diacetate were converted i n good yields to 8* -acetoxybutyraldehyde and succindialdehyde-1,1-diacetate respectively. Compounds of the type RCHeCHg (where R was - COpCpH^, ~ CHpOpCCH^ and - CH(OgC CH^)2) added the formyl group exclusively i n the terminal position. Certain oc ,@ unsaturated carbonyl compounds, e.g. crotonaldehyde and acrolein, were reduced to butyraldehyde and propionalde-hyde respectively. 2Co + SCO 150© f}o(CO)k] 2 In ISkS, Adkins and Krsek^ 2) modified the hydroformylation A farther modification of the hydroformylation reaction was introduced by Pino<23) in 1951. By adding ethyl orthoformate to the reaction mixture, the aldehydes produced were subsequently converted to the corresponding ethyl acetals. In this way, secondary reactions of the carbonyl groups were inhibited. Keulemans and co-workers^), i n 19*18, found that aldehydes produced i n the oxo reaction could he reduced to the corresponding alcohols by the use of the Pischer-Tropsch catalyst with water gas replaced by pure hydrogen. Propene was converted to a mixture of n-and iso-butyraldehvde and then reduced to the corresponding alcohols. Isobutene was similarly reacted to yi e l d iso-amyl alcohol. In 1950, Wender, Levine and Orchin^33) found that cro ton-aldehyde, which Adkins and K r s e k ^ found was converted to n-butyr-aldehyde at 120-125°, was converted to n-butanol at 180-185°. These workers postulated the following reaction mechanism: 2Co + 800. '^o(00)u]2 [0o(C0)j.g 1 2 . 00(00)4 .0o(00)u * Hg- > H m + 0o(C0)3C0H H . + ECHO . BCHOH EC HOH * 0o(00)300H^± BOHgOH + . Co(C0)u This mechanism involves cobalt hydro carbonyl, and various workers have sought evidence for the presence of this compound i n the oxo reaction. Wender, Metlin and Qrchin(3*0 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 hydro-carbonyl was Indicated. This compound was the only strong acid that could have been present i n the reaction mixture. Other workers^35) have furnished further evidence for the presence of this compound. Homologation of alcohols via 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 0rchin^32) subjected i-butyl alcohol to hydroformylation conditions at 160-180° and obtained a good y i e l d of iso-amyl alcohol. Benzyl alcohol gave toluene and Q-phenyl ethyl alcohol. By treating methanol similarly, Wender, Priedel and Orchin^i) obtained ethanol as the major product. Other compounds obtained from this reaction were ethyl acetate, methyl acetate, propanol, and smaller amouats of other esters and alcohols. In summary, many ole 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. Aldehydes containing one more carbon atom than the original 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. 3 . Deacetylation. Zemplen andKunz(39), i n 1923, f i r s t effected deacetylation of a sugar acetate with sodium alkoxide. By treating ^ g l u c o se penta-acetate with an excess of sodium ethoxide dissolved i n absolute ethanol, they obtained a ^ -glucose-sodium ethoxide addition product. It was thought that the reaction involved transesterification, since ethyl acetate was also isolated. Three years later, Zemplien^37) modified the reaction "by using sodium methoxide i n methanol. Cellobiose octaacetate was dissolved i n chloroform and a methanol i c solution of excess sodium methoxide was added. The precipitated cellobiose-alkoxide addition complex was decomposed with water, the a l k a l i neutralized with acetic acid, and the product was crystallized from ethanol. The method was improved when Zemplen and P a c s u ^ ^ found that i t was sufficient for sodium methoxide to be present i n trace amounts to effect deacetylation. Dj-Mannitol hexaacetate was dissolved i n absolute methanol containing a catalytic amount of sodium methoxide. S-Mannitol was obtained i n good yield. Although other deacetylation methods have been found^1^»38) f the procedures developed by Zemp&en and co-workers are s t i l l widely employed. DISCUSSION OF RESULTS. 3,k,6~Tri-|Hwetyl-D~galactal, synthesized "by a modification of the method of Helferich et a l ^ 1 J , \ was obtained without d i f f i c u l t y . Dicobalt octacarbonyl was prepared by treating f i n e l y divided metallic cobalt with carbon monoxide at high temperatures and pressures. As the carbonyl was both volatile and unstable, precautions were taken to use a well ventilated fume hood when working with i t . Before subjecting the unsaturated sugar to hydroformylation, i t was necessary to determine the amount of moisture present i n the carbon monoxide used. It has been shown that glycals react with water under certain conditions to form 2-»deoxy sugars^5) o r pseudoglycals^ 2"^ . However, the water content was low, so that only small amounts of these compounds could have been produced in the reaction. Hydroformylations were carried out under different conditions. Dicobalt octacarbonyl, i n a benzene solution, was present i n a l l three syntheses. In the f i r s t and third run, high pressures of carbon monoxide and hydrogen in equal concentrations were employed, while i n the second t r i a l , the par t i a l pressures of the gases were much lower and much less carbon monoxide than hydrogen was used. Trie thylor tho formate waB added in the f i r s t two reactions. It was hoped this compound would convert any aldehyde formed to the corresponding acetal, thus protecting the carbonyl group from further reactions. I f an aldehyde containing one carbon more than the original compound was formed, then two moles of synthesis gas per mole of glycal would have been consumed. However, in both of these runs, three moles of gas were used up. The third synthesis was carried out without the presence of triethylorthoformate. The gas consumption corresponded to that observed i n the f i r s t two reactions. - 9 -One explanation of these findings was that any aldehyde formed was hydrog-enated to the corresponding alcohol before acetal formation could have occurred. Column chromatography, using alumina as the adsorbent, was employed to fractionate the products of the f i r s t two oxo reactions. The material from the f i r s t run was separated into three components (fractions A,B andC)» The f i r s t of these, being very small, was not investigated extensively. From the second hydroformylation product, two fractions (D and E) were obtained. The latt e r of these was also too small for thorough study. Since zones C and E required more polar solvents to remove them from the columns than did B and D, i t was concluded that the former two contained more polar groups than did the l a t t e r fractions. The product from the third hydroformylation (fraction F) was not chromatographed. Qualitative tests were carried out on the various fractions. One ofl the tools employed was infrared analysis. The spectra obtained are shown i n figure 1, page 22a. The spectrum of 3,U,6-tri-o_-acetyl-p-galactal was essentially the same as that reported by Kuhn (18a) for 3tk,6-tri-p-acetyl-D-glucal. A peak at approximately 1750 cm.""1 was assumed to be due to the presence of ester groups (10a). A second smaller peak at 165>0 wave no.'s was due -1 to unsaturation (10a). The bands at 1375> and 12J?0 cm. were the result of C-C single bond stretching and C-O-R (ester group) bond stretching re spe c tively {Z 3 a). As the spectra of fractions B, C and D were essentially the same, they were considered together. The bands at 3^00 wave no. 's were due to hydrogen bonded hydroxyl groups and the ones at approximately 2900 wave no.'s were the result of free alcoholic groups (l£a). The remainder of - o a -the spectra were identical with that of the original unsaturated sugar except that no peaks were present at 16$) cm.""-1-. That i s , olefinic double bonds could not be detected i n these components. Compound G, which was deacetylated fraction B, C,^or 1? (this will be explained more fully later in the discussion), showed a band at 3300 wave no."s, and a smaller peak at 2900 cm.""\ Again, these were due to hydroxyl groups (lf?a)» As there was no band at 17$) wave no.'s, noAcarbonyl group was present (10a). The smaller peaks below 15>00 wave no.'s were due to carbon-carbon single bond stretching and other factors too complex to determine (23a). Further qualitative tests were carried out on the various fractions. Fraction A did not decolorize a bromine solution so i t did not contain any olefinic double bond. It gave a weakly positive reaction to Fehling's S o l -vere ution both before and after i t was subjected to dilute acid. There]^, i t con-tained traces of one or more unsubstituted aldehydes. Fractions B, C and D did not discolor bromine solutions. This, together with the fact that the infra red spectra of these components showed no peaks at 16^0 cm.""'"(see above), proved that no olefinic double bonds were present. Before treatment with dilute acid, these fractions did not reduce Fehling's solution, but after attempted hydrolysis, weak to moderate aldehyde reactions were obtained.This reducing power may have been due to the presence of one or more aldehydes resulting from hydrolysis of their corresponding ethyl acetals. Another possibility was that the hot dilute hydrochloric acid may have part-i a l l y degraded the product to one or more reducing artifacts.The fact that the aldehyde reactions were not in any instance strong suggested that the main components of these zones did not consist of carbonyl containing - 10 -compounds. Infrared analyses detected hydroxyl groups i n these fractions (see page 9). The presence of these functional groups could have been explained by the formation of new aldehydes thatjrere subsequently hydrogenated. Partial deacetylation i n the chromatographic separations also could have accounted for their presence,. As was mentioned earlier, the infrared spectra of the three zones were essentially the same, so these products must have been similar. Fraction E, as shown by the weak bromine reaction, contained small amounts of unsaturated sugar. The slightly positive aldehyde reaction was probably due to the presence of a small amount of pseudo-glycal, which would have resulted from the heating of the glycal-con-taminated product i n Fehling's solution. Fraction F, which gave a negative bromine test and a sli g h t l y positive Fehling's reaction, contained no olefinic double bond but a small amount of one or more aldehydes was present. A l l fractions were tested for their s o l u b i l i t i e s i n polar and non-polar solvents. As was expected, none dissolved i n water. Since zones C and E were only slightly ether soluble, i t was l i k e l y that they each contained more than one polar group. Each of the other fractions, being ether soluble, probably had one free polar group. - 11 -Deacetylation of fraction B gave a crystalline compound that, when purified, had physical constants differing from those of any previously reported derivative of ^ -galactose. Hydroxyl, carton, and hydrogen analyses corresponded to those of a compound containing four hydroxyl groups and having the empirical formula CyB^O^. Tractions C, D and F were similarly deacetylated and purified. They had essentially the same melting points and optical rotations as did fraction B, and mixed melting points with that compound were not depressed. This, together with the fact that a l l these components had the same R.f. values when run on paper chromatograms i n two different solvent systems, proved that they were identical to one another. The fact that fractions B and C were the same was p a r t i a l l y explained previously. The reaction product must have been p a r t i a l l y deacetylated, probably during the attempted separation on the alumina chromatographic column. It was, therefore, concluded that 31 6 - t r i - f i - a c e t y l - P - g a l a c t a l could be subjected to the oxo reaction under different conditions to yi e l d the same crystalline product. However, since no unsaturated compounds were detected i n the products of the f i r s t and third oxo reaction, the conditions of these syntheses were preferred over those employed i n the second hydroformylation. (Reaction product No. 2 contained traces of unsaturated sugar, as shown by bromine tests.) The fact that the results from the third t r i a l ( in which t r i e t h y l -orthoformate was absent) were the same as those from the f i r s t synthesis (in which the ortho ester was present) showed that the presence of t r i e t h y l -orthoformate was not necessary for the hydroformylation of ^th,6-tTirSir acetyl-Dj-galactal under the conditions described. It was also concluded that chromatographic fractionation was unnecessary for these reaction - 12 -products. This was demonstrated "by working up the product from the third hydroformylation without employing chromatography and obtaining the same compound as before. The deacetylated purified hydroformylation product, now designated compound Or, was subjected to several qualitative tests. The sugar gave a negative Fehling's reaction and i t s infra red spectrum did not show a peak at 1700 wave no.'s. A portion of the compound was subjected to hot dilute acid for a short time to attempt hydrolysis of any acetal that may have been present. The product thus obtained had a lower melting point than did the original sugar and gave a slightly positive aldehyde reaction. However, subsequent purification yielded a product which did not reduce Fehling's solution and which was identical to the starting material. From this i t was concluded that the weak alde-hyde tests given by the crude acid treated product were due only to the presence of artifac t s . (This indicated that the weak reducing power detected in the "hydro l y zed" fractions before deacetylation was also the result of artifacts produced by acid degradation.) It was, therefore, concluded that the compound was not an aldehyde. Periodate oxidation of compound & was carried out. Besides cleaving adjacent hydroxyl groups, periodate has been shown to oxidize other groups at a slower r a t e ^ . However, a rate study of the reaction showed that approximately one mole of periodate was consumed per mole of carbohydrate (based on a formula of CjH^O^ and a molecular weight of 178). Therefore, the compound contained one pair of adjacent hydroxyl groups. It was next attempted to prepare derivatives of compound Cr. Although an acetate was prepared, i t could not be induced to crystallize. - 13 -The preparation of a benzilidene derivative was next attempted. No reaction product could he obtained. Since the isolation of the derivative depended on its water insolubility, it is possible that a water-soluble monobenzilidene derivative was formed. This would have been very difficult to separate from the other water soluble components of the mixture without hydrolysis of the acetal. The benzoate and jfc-nitrobenzoate of the carbohydrate were prepared. The elemental analyses of these derivatives gave values corresponding to those expected i f compound G had four hydroxyl groups and the empirical formula CyHj^Otj. The structure of compound G must f i t the conclusions previously drawn. That i s : (1) Unless side reactions involving large gas consumption occurred, the structure of the molecule must have accounted for the reaction of three moles of gas with each mole of glycal. (2) No carbonyl group was present. (3) It did not contain a double bond. (h) The compound had one pair of adjacent hydroxyl groups. (5) It contained four alcohol groups and had the empirical formula of CjH^O^. 2-Deoxy-JJ-galactose was ruled out as a possibility because: (1) Its melting point^) was approximately thirty degrees lower than that of the compound obtained. (2) Sufficient water for its formation in the amount isolated was not present in the reaction. (3) It would have given positive aldehyde tests. (If) The formation of the 2-deoxy sugar did not account for the amount of gas consumed. 1,2-Bihydro-B-galactopyranose was ruled out since: Its melting point v was 30° too low. (2) It would have had only three hydroxyl groups. (3) Only one mole of gas would have been consumed i n i t s formation. The only possible compounds that f i t a l l the data are: CH.CHgOH CH,CHP0H EOGH HOCH HC-Four isomers were possible. It was not known why only one was obtained. Other isomers may have been present i n smaller amounts. Some unsaturated compounds, as shown by other workers^, preferentially formed only one isomer even though others were theoretically possible. In conclusion, a new seven carbon polyol has been prepared by the hydroformylation of 3 » ^ i 6-tri-gt.acetyl-D^-galactal. A seven carbon aldehyde must have been formed which was hydrogenated to the correspond-ing alcohol i n the reaction mixture. EXPERIMENTAL. Instrument at ion. Optical rotations were determined in a 1 dm. polarimeter tube of about 0.5 ml. capacity. The solutions were made up in a 1 ml. volu-metric flask. The melting points were uncorrected. Synthesis of ^.U.6-»Tri-e-acetyl-D-galactal. 3,4,6-Tri-g-acetyl-p-galactal was synthesized by a modification of the method of Helferich and co-workers^12). To a stirred solution of acetic anhydride (200 ml., 2.0 moles) and perchloric acid (6o#, l.h ml.) , D-galactose (55 gm., 0*30 mole) was added slowly in a thirty minute interval. During this time, the temperature was kept between 30° and Uo° by cooling the reaction flask in an ice bath. After the resulting solution was allowed to stand twenty minutes, red phosphorus (15 gm.) was added, the mixture cooled to 0° , and then bromine (90 gm.) was added dropwise while the stirred mixture was kept below 20°. Water (15 ml.) was then added slowly and again the temperature of the agitated mixture was kept below 20°. Following this, the reaction flask was wrapped in aluminum f o i l and left at room temperature three hours. Hydrated sodium acetate (200 gm.) was dissolved in water ( 2 9 0 m l . ) and glacial acetic acid (200 ml.) was added. After cooling the solution below - 1 0 ° , zinc dust (llO gm.), and a solution of hydrated copper sulfate ( l l gm. in Uo ml. of water) were added. When the blue colour disappeared from the mixture, the crude solution of o<-bromo, 2,3,4,6-tetra-d-acet3i-D-galactose (previously filtered) was added during an interval of one hour. - 16 -Daring this time the mixture was stirred vigorously and the temperature was maintained "between -10° and -20° with a dry ice-acetone hath. When the addition was complete, the mixture was stirred an additional three hours at 0°, then suction-filtered into ice water (500 ml.). The f i l t r a t e was extracted five times with portions (lOO mi. each) of chloroform, and the combined chloroform solution washed with portions of 5$ sodium bicar-bonate unt i l carbon dioxide ceased to be evolved. After the extract wss checked for acidity (moistened litmus paper), and washed with a portion (lOO ml.) of water, i t was dried overnight over anhydrous sodium sulphate. The dried solution was f i l t e r e d , and the chloroform removed at U50 (bath temperature) under reduced pressure (water aspirator) while an atmosphere of nitrogen was maintained. Benzene (75 ml.) was added and this mixture was evaporated using the same conditions as before. The crude product (58 goO was subjected to a vacuum d i s t i l l a t i o n under an atmosphere of nitrogen. The f i r s t fraction (32 gm.) d i s t i l l e d at 122-125° and 0.05-0.08 mm.. A second fraction (5 gm.) d i s t i l l e d at 125-140°, and essentially the same pressure as before. Total y i e l d of d i s t i l l a t e : 37 gm., O.lk mole, 47# yield. Crystallization of the f i r s t fraction was effected by dissolving i t in an excess of ether - petroleum ether (b.p. 3O-600) and evaporating the solvent slowly under reduced pressure (water aspirator) in a nitrogen atmosphere at approximately -20°. lecrystallization yielded a product (23 gm.) with m.p. 29-30°, [<*] JJ20 - 13.5 (C,l i n chloroform). Constants reported by Levene and T i p s o n ^ ) ; m.p. 30°, [o<] ^ - 12.H (C.2.5 i n chloroform). Synthesjtft pf, D^pobaljb. Octacarbonyl,. "Co-OlOl-P" catalyst, supplied by the Harshaw Chemical Co., Cleveland 6, Ohio, was the cobalt containing starting material. - 17 -Co-0101-P powder (15 gm.), suspended in 35 ml. of anhydrous thiophane-free "benzene, was placed i n a glass l iner contained in a stainless steel hydrogenator having a void of 278 ml.. (The Super-Pressure apparatus was made by The American Instrument Co. . ) Hydrogen was admitted to a pressure of HlO p . s . i . at 17°. The temperature was raised to 425° over a period of three hours and maintained at that temperature for f ive hours. After the reaction vessel had cooled, the f ina l pressure was 200 p . s . i . at 19°. Water was removed from the benzene-catalyst mixture by azeotropic d i s t i l l a t i o n under reduced pressure In a nitrogen atmosphere. At a l l times the reduced catalyst was kept covered with benzene. The cobalt mixture, together with a small amount of anhydrous benzene, was returned to the hydrogenator and treated with carbon monoxide at 2900 p . s . i . (temp. 19°). The mixture was heated to 150°, l e f t at th is temperature six hours, and then cooled to room temperature ( 1 8 ° ) . Pinal pressure: 2480 p . s . i . . When the dark mixture was f i l t e red and the residue washed with benzene, a red-black solution was obtained. A second batch of dicobalt octacarbonyl was prepared as before, except that Baney cobalt, prepared by the method used by Adkins and K r s e k ^ , was employed as the start ing material . The concentration of dicobalt octacarbonyl i n the above solutions was determined by the method of Sternberg, Wender and O r c h i n ^ 2 ^ , and found to be 2.5 gm./lOO ml. i n both cases. The water content of the carbon monoxide used was determined by passing the gas slowly through a tube containing Dr ier i te . This tube was weighed at the start and at the end of the experiment, and the volume of carbon monoxide passed through was measured with a gas meter. The gas was found to contain 0.2 gvuwater/lOO l i t r e s a t standard conditions. Hydroformylation No. 1. 3.1+.6-!Pri-d-acetyl-g-galactal was reacted with carbon monoxide and hydrogen according to the method of Adkins and Krsek % '. 3 ,U ,6-Tri-fi-acetyl-P-galactal (13.5 gP" 0.0h9 mole) was added to an anhydrous thiophene-free benzene solution (25 ml.) of dicobalt oct a-carbonyl (0.6 gm.), together with ethyl ortho formate (9.2 ml., O.O58 mole). Benzene (lO ml.) was added to complete solution of the unsaturated sugar. This combined solution was placed i n a glass l i n e r i n the high pressure hydrogenator having a void of 278 ml.. After the bomb was flushed twice to remove traces of oxygen, i t was charged with carbon monoxide (15OO p.s.i.) and hydrogen (15OO p . s . i . ) . After the hydrogenator was rocked for five minutes, the pressure stabilized at 2930 p . s . i . at 22° . The bomb was heated with rocking to 125-135° over a two hour period, rocked an additional four hours at this temperature, and allowed to cool overnight to room temperature (22°). A pressure drop of 2^0 p . s . i . was observed. The dark red solution recovered from the hydrogenator l i n e r was heated on a steam bath in a fume hood twenty minutes to decompose the dicobalt octacarbonyl present. Following this, the cobalt was removed by f i l t r a t i o n and the solution was evaporated under reduced pressure (water aspirator) under a nitrogen atmosphere at 60° to yi e l d a straw coloured syrup. Yield: l h gm„ Hydroformylation No. 2. A modification of the method of Natta and co-workers^ 2 2) was used. 3,h,&-Tri~fl^acetyl~P-galactal (8.5 gm., 0.038 mole) and ethyl orthoformate (5.8 ml., 0.038 mole), together with a solution of dicobalt octacarbonyl (O.U gm. in 20 ml. of benzene), were placed i n a glass l i n e r . - 19 -This container was placed in the hydrogenator having a void of 278 ml.. After the bomb was charged with carbon monoxide (200 p.s.i.) and hydrogen (1670 p . s . i . ) , i t was allowed to stand ten minutes, by which time the pressure guage read a constant I8U0 p . s . i . at 20°. The pressure increased to 2250 p . s . i . while the hydrogenator was heated with rocking to 125-135° during a half hour period. After rocking at this temperature was continued two and one-half hours, the guage reading was 2200 p. s . i . . When the hydro-genator cooled overnight to room temperature (21°), the pressure dropped to 1670 p . s . i . . The gas was expelled from the bomb and the dark red solution from the li n e r was placed on a water bath at 70° for half an hour to decompose the dicobalt octacarbonyl. Then the resulting cobalt was removed by f i l t r a t i o n . By evaporating the solution under reduced pressure (same conditions as before), 9.^  gm. of a light orange coloured syrup was obtained. Hydroformylation Ho. 1, This was a repetition of the f i r s t synthesis except that the addition of triethyl orthoformate was omitted. The consumption of synthesis gases corresponded to that observed i n the f i r s t hydroformyla-tion. The product was worked up as before. Continuous Plow Chromatography of Hydroformylatlon.Product Wo. 1. Aluminum oxide (special grade for chromatography, product of the B r i t i s h Drug Houses Ltd., Poole, England) was stirred for one-half hour with ten percent acetic acid. It was then washed several times with water, dried in a vacuum drying oven at 180°, and passed through a number eighty mesh screen. M 20 — Treated aluminum oxide (1700 gm.) was used to prepare an adsorbent column (75 x 400 mm.). This column was prewet with benzene (l.5 l.)» and a solution of the product (6.3 gm. in 50 ml. of benzene) was added. Development was effected with the following: benzene (10.5 1.). 1$ absolute ethanol i n benzene ( 5 1.), 5$ absolute ethanol i n benzene ( 6 l . ) and 10$ absolute ethanol i n benzene (6 1.). A dark band remained at the top of the column during the development. To test for complete-ness of product removal, the column was extruded, the alumina extracted exhaustively with ethanol, and the ethanol extract evaporated to dryness. No organic product was obtained. The effluent, except the f i r s t 1.5 1., was collected in a Technicon T/P Fraction Collector, (manufactured by Technicon Chromato-graphy Corp., New Tork, N.Y.). Evaporation, i n half l i t r e portions, was carried out at reduced pressure (water aspirator) at a bath temperature of 70°• TABLE I. Chromatography of Product from Bun 1. Effluent fractions Wt. of fractions (in l i t r e s ) (in grams)  0-7.5 0 .) , 7.5-16 0.4} A 16 -16.5 0.9' 16.5-17. o.g; 17 -17.5. 0.7> B 17-5-18 0.4; 18 -18.5 0.3! 18.5-19 0.2; Effluent Wt. of fractions fractions 19 -19.5 0.1 19.5-20 0.1 20 -20.5 0.1) 20.5-21 0.7) 21 -21.5 °-3i C 21.5-22 O.lj 22 -23.5 0.2J 23.5-27.5 0 ) Total Recovery: 5.4 gm. (86# yield). - 21 -The fraction from 7«5-l6 1« was called fraction-A , the one from 16.5-20 1. was designated fraction B, and that from 20-23.5 l.» fraction 0. Chromatography of Hydroformylation Product No. 2. A column (75 * 550 mm.) containing aluminum oxide (2*400 gm.) was prepared by the method described above. This column was prewet with benzene (1.6 1.) and the hydroformylation product (9.4 gm. in 35 ml. of benzene) was added. Development was effected with: benzene (4.8 1.). then 1$ absolute ethanol in benzene (9 1.), and f i n a l l y with 10$ absolute ethanol i n benzene (9 ! • ) • The f i r s t l i t r e of effluent was discarded. The remainder was treated as before. TABLE II. Chromatography of Product from Run 2. Effluent fractions w t . of fractions (in l i t r e s ) \ (in grams)  0 - 1 . 5 0 ) & 1.5-11 * 8.3> » 11 -16.5 0 ) 16.5-18.5 0.4} E 18.5-23 0 ) Z One continuous zone. Total yield: 8.7 gm. (93$). The fraction from 1.5 ~ 11 1. was designated fraction D and that from 16.5 - 18.5 1. was called fraction E. Hydroformylation Product No. 1. The product from the third oxo reaction (fraction P,) was not subjected to column chromatography. - 22 -Qualitative Tests on Hydroformylation Products. Infra Bed Analyses. A PerkinJBlmer Model 21 double-beam recording spectrophotometer with a sodium chloride prism was used. Dr. R. Wright, of the B r i t i s h Columbia Research Council, Vancouver, performed the analyses. The spectra obtained were used in the detection of hydroxyl groups and olefinic double bonds. Bromine i n Carbon Tetrachloride. Unsaturation was also detected by treating portions of each sample (lO mgm.) with 2.5$ bromine in carbon tetrachloride (2 ml.). Fehling's Testa. ' . Carbonyl groups were detected with Fehling's solution using the method reported by Shriner and Fuson^25). The fractions that may have existed as acetals were tested for the presence of a carbonyl group both before and after they were subjected to 0.5 N. hydrochloric acid for one-half hour at 90-100°. TABLE III. Hesults of Qualitative Tests  on Hydroformylation Products Unsaturatipn Carbonyl Group (Fehling's) Infra Before After Hydroxyl Group Fraction Bromine Bed D i l . Hcl. D i l . Hcl. (By Infra Red) A 0 weak weak — B 0 0 0 moderate strong C 0 0 0 weak strong D 0 0 . 0 moderate strong E weak - weak weak — F 0 - weak - -- 22a -Figure 1. Infra Hed Spectra of Hydroformylajrion Products Curves 1 - Triacetyl-&*galactal. 2 - Fraction B -> Fraction C - Fraction D 5 - Compound 0 (Deacetylated Fraction E$,C Gb,r D or F)1 - 23 -Attempted Crystallizations of Fractions. A l l fractions f a i l e d to crystallize before deacetylation. A l l dissolved i n methanol and ethanol. C and E were only moderately soluble i n ethyl acetate and f a i r l y insoluble i n ether. The others were soluble in both these solvents. A l l products were insoluble i n water and i n petroleum ether (b.p. 3O -60 0 ) . To attempt crystallization the following solvents and solvent pairs were tried: methanol, ethanol, ethyl acetate -petroleum ether (3O~60°), and ethanol-water. In every case the product came down as an o i l . The syrups were scratched frequently and l e f t over phosphorus pentoxide in a vacuum desiccator for four months. S t i l l no c r y s t a l l i z a -tion occurred. Deacetylation. Although the fractions did not crystallize, they were deacety-lated in the hope that the unsubstituted products would be crystalline. The method used-was a modification of that developed by Zemplen and Pacsu ( l t 0\ Fraction B (1.5 gm.) was dried by repeated evaporation i n vacuo (anhydrous nitrogen atmosphere) of a methanol-benzene solution of the compound. Following this, 0.05 N. sodium methylate i n anhydrous methanol (25 ml.) was added and the resulting solution was protected from moisture with an inverted calcium chloride drying tube. After standing two hours at room temperature, the solution was l e f t i n a refrigerator overnight, diluted with water and passed.through a column (dim. 220 x 20 mm.) containing a cation exchange resin (Amberlite 1H-120). The column was washed with d i s t i l l e d water (600 ml.) and the combined solution was evaporated i n vacuo (water aspirator) at 40° to a syrup, - 2H -weight 1 . 2 gm.. This product was dried over phosphorus pentoxide in a vacuum desiccator for several days, after which time crystallization occurred (m.p. 1 3 0 - 1 3 5 ° ) . Three recrystallizations from methanol-iso-propyl ether raised the melting point to a constant 1 5 8 . 5 - 1 5 9 . 5 ° , j) + 37.6° ( 0 , 1 . 3 in water). Calc. for C y K ^ 0 , 4 6 . 9 1 ; H, S . U 3 ; Hydroxyl, 3 7 . 9 # . Pound: 0,47.1+3. H,g.l6; Hydroxyl,37.3$. Fraction C was deacetylated and recrystallized by the method used for fraction B. M.p. 1 5 7 - 1 5 8 0 ; mixed m.p. with faaction B, 1 5 7 - 1 5 9 ° ' Fractions D and F were worked up similarly, except that the methanol solution of fraction F had to be f i l t e r e d after deacetylation to remove a dark precipitate which was assumed to be a polymer (wt. 0.3 gm.). After purification, these fractions had essentially the same constants as those of fractions B and C. Again, mixed melting points were identical to those of either component alone. Paper chromatography, using a modification of the method described by Wolfrom and Schumacher^3^) t W a s e mp]_ 0y ea t 0 compare the B.f. values of the different fractions. A descending chromatogram ( 5 0 x 2 0 cm.) was prepared from Whatman no. 1 f i l t e r paper. The paper was spotted ( l mgm./spot; diam.: 1 cm.) with solutions of fractions B, C, D and F, and then placed i n a chromatographic chamber . maintained at a constant temperature ( 2 2 ° ) . The chromatogram was developed with butanol-ethanol-water (4:i.1 : 1 . 9 ) for sixteen hours. After drying the paper was sprayed with the sodium metaperiodate-alkaline permanganate reagent developed by Lemieux and Bauer^9). - 25 -A l l components produced only one spot each, with identical H.f. values (0.42) . A chromatogram was run similarly with water-saturated s-collidine as the solvent. Again, the fractions showed one spot each, with the same R.f. values (0 .50) . Detection i n this case was also with metaperiodate-alkaline permanganate reagent. It was then concluded that deacetylated fractions B, C, D and F were identical. The carbohydrate was designated compound 0-. Attempted Hydrolysis of Compound Gf. A portion of the sugar (lOO mgm.) was dissolved i n 1$ hydrochloric acid (20 ml.) and allowed to stand i n a water bath at 100° for three-quarters of an hour. After the solution had cooled to room temperature, l t was passed through a column (dim. 220 x 20 mm.) containing an anion exchange resin (Duolite A~4). The column was washed with water (500 ml.) and the total solution was evaporated as before. A syrup (98 mgm.) was obtained which crystallized after seeding with crystals of the "unhydrolized" compound. M.p. of product: 120-1350* Recrystallization from methanol-ethyl acetate did not raise the melting point appreciably. Paper chromatography was then employed to determine whether or not the compound had been changed by attempted hydrolysis. A descending chromatogram was prepared as previously described. It was spotted with both acid-treated and unaltered compound. To effect development, the previously described butanoL-ethanol-water mixture was used. The components showed one spot each, with identical (0.U2) R.f. values. By modifying the previous technique, a portion of the "hydrolized" compound was purified. Six paper chromatograms (18 x 5° cm.) were prepared. Spots (diam. 1 cm.) containing 1 mgm. of compound - 26 -each were placed along a line 10 cm. from one end. There was a space of 0.5 cm. between the perimeters of each spot. 66 Mgm. of product was used altogether. The chromatograms were run under the conditions described above for sixteen hours, then dried and rerun again for the same length of time. A strip 1 cm. wide was cut from each paper and the position of the compound was ascertained using the same detecting reagent as was employed before. The carbohydrate - containing zones of the chromatograms were then removed and the resulting strips suspended above a beaker. 1 ml. of d i s t i l l e d water was allowed to tricicle slowly down each. The eluate, collected i n the beaker, was evaporated (water aspirator) at Uo° to a syrup (wt. 5^ mgm.). One recrystallization (methanol-isopropyl ether) yielded a product (wt. UO mgm.) with m.p. 158-159°. Mixed m.p. with unhydrolized compound G : 158-159°. [ex] 2£ + 35.9 ( C I i n water). ^Qualitative Tests on Compound G. Fehling's tests were run as before. The sugar gave a negative reaction before i t was subjected to hydrolytic treatment, but when the crude product was recovered from the acid, i t gave a weakly positive test. However, after purification (by the previously described paper chromatography method) the carbohydrate gave a negative aldehyde reaction. An in f r a red spectrum of the compound was obtained as before. No carbonyl group or olefinic bond was detected. Periodate Oxidation. A modification of the method used by Edington et a l was employed. A buffer solution (pH 4.65) was made up according to Vogel^O) - 27 -u s i n g a s o l u t i o n 0.1 IT i n sodium a c e t a t e and 0.1 N i n a c e t i c a c i d . S o l u t i o n s o f 0.0987 N sodium a r s e n i t e and 0.0439 N i o d i n e were a l s o p r e p a r e d "by the method o f Vogel ^ 2 9 \ The compound (1O.3 mgm.) was d i s s o l v e d i n "buffer s o l u t i o n and c o o l e d to 1 3 ° . 0.120 M sodium metaperiodate ( 5 m l . ) was added, the volume made up to 50 m l . w i t h b u f f e r s o l u t i o n , and the f l a s k was wrapped i n aluminum f o i l and p l a c e d i n a constant temperature h a t h a t 13~lU°. At s u i t a b l e i n t e r v a l s , a l i q u o t s o f 5 1 1 1 1 • w e r e s a t u r a t e d w i t h sodium b i c a r b o n a t e . 0.0987 N sodium a r s e n i t e (5 m l . ) and p o t a s s i u m i o d i d e (0.5 gm.) were s u b -s e q u e n t l y added. T h i s m i x t u r e was set a s i d e f i f t e e n minutes and then t i t r a t e d w i t h 0.0439 N i o d i n e ( s t a r c h ) u n t i l a d d i t i o n o f 1 drop o f i o d i n e gave a b l u e c o l o u r w h i c h p e r s i s t e d f o r 5 s e c . w i t h s h a k i n g . A c o n t r o l experiment was conducted s i m i l a r l y . The r e s u l t s are t a b u l a t e d below. TABLE IV. P e r i o d a t e O x i d a t i o n o f Compound Gr. Amount 0.0^39 N Moles P e r i o d a t e Time (Hours) , I o d i n e ( m l . ) Consumed (x-10?) 0.5 8.63 1.8 1 S . 6 9 3 . 1 2 8.77 4.8 ? 8 . 8 1 5.7 4 8 . 8 2 5.9 7 . 8.85 6.6 20 8.90 7.7 30 8.94 8.3 40 8^26. i i O I o d i n e t i t r a t i o n o f c o n t r o l : 8.55 mL** ( T h i s v a l u e remained constant w i t h r e p e a t e d t i t r a t i o n s . ) I f the sugar had the f o r m u l a C y H ^ O ^ , then 5.8 x 10~5 moles were u s e d . The r e s u l t s above were graphed (see next page) and by FIGUREZ PERIQDn TE OXIDRTION of COMPOUND G £ TIME (HOURS) - 28 -extrapolation to zero time, the amount of periodate consumed was found to he 6.2 x 10~5 moles. The reaction was duplicated with essentially the same results. Preparation of Derivatives. ( l ) Acetylation. An attempt was made to characterize the sugar by synthesizing the acetate using a modification of the method of Behrend and E o t h ^ \ A portion of the compound (15 mgm.) was added to a 2:1 solution of pyridine and acetic anhydride (l.5 nil.) and the mixture was allowed to stand at room temperature. The substance dissolved completely within four hours but the reaction mixture was allowed to stand an additional -'. forty-four hours. Following this, the solution was evaporated to one-fourth i t s original volume (water aspirator) at room temperature, then the syrupy solution was cooled in an ice bath and ice water (0.5 ml.) was added. After i t was stirred well, the water was removed with a capillary tube. Crystallization was attempted from ethanol-water, but the product came down as a syrup. To remove traces of pyridine, the acetate was dissolved in chloroform and shaken in a separatory funnel with 5$ hydrochloric acid. The solution was then shaken once with 5$ sodium bicarbonate. Traces of inorganic matter were removed by washing twice with d i s t i l l e d water. The chloroform solution was evaporated and the resulting syrup was dried i n a vacuum desiccator over phosphorus pentoxide, but crystallization s t i l l f a i l e d to occur. Further attempts were made to crystallize the compound from ethanol-water and also from ether-petroleum ether (30-600), but no solid product was obtained. - 29 -(2) Attempted preparation of a benzylidene derivative. A synthesis of the benzylidene derivative of the compound was attempted by the method of Freudenberg and co-workers^9). A. portion of the compound (22 mgm.) and zinc chloride (20 mgm.) were placed i n a flask made by sealing the end of a short length of 8 mm. glass tubing. Freshly d i s t i l l e d benzaldehyde (0.080 ml.) was added with a micro pipette. After the mixture was stirred four hours i n an atmosphere of nitrogen, solution was complete. The reaction vessel was cooled to 0° and an equal volume of ice water was added. The mixture was shaken, the water removed (micro pipette) and the remaining l i q u i d was treated with an equal volume of petroleum ether (3O-600). However, no product precipitated and none could be isolated from the solution. (3) Benzovlation. The sugar was benzoyl ate d by a modification of the method employed (27) by Smith and Van Cleve x A portion of the compound (60 mgm.) was dissolved i n anhydrous pyridine ( l ml.) i n a 25 ml. ground glass flask, then benzoyl chloride (0.2 ml.) was added to the solution with a micro pipette. The flask 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°) for forty minutes, and then cooled to room temperature. Cooling brought about formation of crystals (probably a benzoyl chloride-pyridine complex). When the mixture was poured into saturated sodium bicarbonate solution (15 ml.), o i l y droplets formed. After i t was shaken several minutes, the mixture was extracted twice with portions (lO ml. each) of chloroform. The combined chloroform extract was washed several times with copious amounts of water and then - 30 -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 last traces of pyridine was affected "by drying the product over phosphorus pentoxide in a vacuum at the boiling point of acetone for one day. Yield: 122 mgm. The product was purified by chromatography. An adsorbent column (dim. 20 x 170 mm.) was packsd with acid washed alumina. Prewetting was effected with low boiling petroleum ether (50 ml.) and a solution of the benzoate (122 mgm. i n 2 ml. of 50$ benzene-low boiling petroleum ether) was added. Development was accomplished with low boiling petroleum ether-benzene. The results are given below. TABLE V. Chromatography of Benzoate. D E V E L 0 P E R Composition y> petroleum Volume Product $ Benzene ether (in ml.) (in mgm.) 0 : 100 150 0 150 0 4o 60 150 0 60 Ho 150 70 30 150 trace go 20 4oo 61 100 0 500 The product from the f i r s t zone (50 mgm.) crystallized (m.p. 80-85°). After three recrystallizations from methanol»water, the compound melted at 106-107°. [oC] | 2 - * 43.50 (0,1 in chloroform). Calc. for °35H3o°9 : 0.70,70? H,5.0l$; Mol. wt. 594. Pound: 0,70.86; H.4.94& Mol. wt. 545. - 31 -(4) P-Mtrpbenzoylat Ion. The p-nitrobenzoate of the carbohydrate was synthesized as above. A portion of compound G- (56 mgm.) was dissolved in anhydrous pyridine (2 ml.) and freshly d i s t i l l e d p-nitrobenzoyl chloride (330 mgm.) was added. The reaction mixture was worked up as before, giving a crystalline product. (Yield: 165 mgm.) M.p. 195-205°. Three re-crystallizations from chloroform-petroleum ether (3O-600) gave a product - 32 -BIBLIOGRAPHY: 1. Adkins, H. and Krsek, G . J . Am. Chem. Soc. 70 : 383. 1948. 2i Adkins, H. and Krsek, G. J . Am. Chem. Soc. 71: 305l. 1949. 3. Behrend, R. and Roth, P. Ann. 331: 362# 1904. 4. Edington, R.A. Hirst, E.L. and Percival, E.E. J . Chem. Soc. 2281. 1955. 5. Fischer, E. Ber. 47:196. 1914. 6. Fischer, F. and Tropsch, H. Ber. $9: 830. 1926. 7. Fischer, F. and Tropsch, H. Brenstoff-Cham. 9:21. 1928. Chem. Abstr. 22: 2657. 1928. . 8. Foster, A.B., Overend,W.G. and Stacey, M. J . Chem. Soc. 974. 1951. 9. Freudenberg, K., Toepffer, H. and Andersen, C.C. Ber. 61: 1750. 1928. 10. Gakhokidae, A.M. J . Gen. Chem. (U.S.S.B.) 10:497. 1940. Chem. Abstr. 34: 7857. 1940. 10a. Harley, J.H. and Wiberley, S.E. Instrumental Analysis. John Wiley and Sons. London. 1954. p. 86. 11. Helferich, B. Advances i n Carbohydrate Chemistry, Vol. 7. Academic Press Inc. New York. 1952. p. 209. 12. Helferich, B., Mulcahy, E. and Ziegler, H. Ber. 87s 233. 1954. 13. Hockett, R.C. and Millman, S.R. J . Am. Chem. Soc. 63: 2587. 1941. 14. Isbell, H.S. J . Research Natl. Bur. Standards. 5: 1185. 1930. 15. Isbell, H.S. and Pigman, W.W. J . Research Natl. Bur. Standards 20: 97. 1938. 15a. Ketelaar, J.A.A. Chemical Constitution. Elsevier Publishing Co. Amsterdam. 1953. p. 374. 16. Keulemans, A.I.M., Kwantes, A. and van Bavel, Th. Rec. trav. chim. 67:298. 1948. Chem. Abstr. 42: 8152. 1948. 17. K i l i a n i , H. Ber. 18:3066. 1885. 18. Kruger, D. and Roman, A. Ber. 69: 1830. 1936. 18a. Kuhn, L.P. Anal. Chem. 22:276. 1950. 19. Lemieux, R.U. and Bauer, H.F. Anal. Chem. 26* 920. 19$k. 20. Levene, P.A. and Tipson, R.S. J. B i o l . Chem. 93:631. 1931. 21. Lohaus, H. and Widmaier, 0. Ann. $20s 301. 1935. 22. Natta, G., E r c o l i , R., Castellano, S. and Barbieri, F.H. J. Am. Chem. Soc. 76: U0k9. 195k. 23. Pino, P. Gazz. chim. i t a l . 81* 625. 1951. 23a. Reid, C. Private Communication. 2k. Roelen, 0. U.S. 2,327,066. Chem. Abstr. 38: 550. 19UU. 15. Shriner, R.L. and Fuson, R.C. The Systematic Identification of Organic Compounds. John Wiley and Sons Inc. New York. 19l|8. p.98. 26. Smith, D.,Hawk, C. and Golden, P. J. Am. Chem. Soc. 52: 3221.1930. 27. Smith, F. and Van Cleve, J.W. J.Am. Chem. Soc. 77:3091. 1955. 28. Sternberg, A., Wender, I. and Orchin, M. Anal. Chem. 2h: 17k. 1952. 29. Vogel, A.I. Quantitative Inorganic Analysis. Longmans, Green and Co. London. 1951. p. 3U0. 30. Vogel, A.I. Quantitative Inorganic Analysis. Longmans, Green and Co. London. 1951. p. 868. 31. Wender, I., Friedel, R.A. and Orchin, M. Science. 113:206. 1951. 32. Wender, I., Levine, R . and 0rchin,M. ' J.Am. Chem. Soc. 71:iil60.19U9. 33. Wender, I., Levine, R. and Orchin, M, J.Am. Chem. Soc. 72:li375.1950. 3U. Wender, I., Metlin, S. and 6rchin, M. J. Am. Chem. Soc. 73:570ii. 1951. 35. Wender, I., Sternberg, H.W. and Orchin, M. J . Am. Chem. Soc. 75: 30U1. 1953. 36. Wolfrom, M.L. and Schumaker, J.N. J. Am. Chem. Soc. 77:3318. 1955. - 3k -37. Zemplln, G. Ber. 59: 1258.. 1926. . 38. Zemplen, G. Ber. 60:1555, 1927. 3 9 . Zemplen, G. and Kunz, A. Ber. 56: 1705. 1923. UO. Zemplen, G. and Pacsu, E. Ber. 62:l6l3. 1929. 

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