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Some Fatty Acid Derivatives of D-Glucosamine BY YOSHIYUKIINOUYE, KOXOSHIN ONODERA, SHOZABURO KITAOKA AND SHIGEIIIRO HIRANO RECEIVED APRIL 24, 1936 Sornc N-acyl and S-acyl-tetra-0-acyl-derivatives and some mixed acyl conipounds of D-glUCOSanline (2-ainino-d-deox)-Dglucose) were prepared by the action of the acid anhydrides and acid chlorides. The acyl groups used were those of t h e even-numbered saturated fatty acids. The rur-acyl-D-glucosamines prepared exhibited the identical ab3orption inasilna in the Morgan and Elson reaction.
The isolation from biological materials of a com- found that a supersaturated solution of D-glUC0pound composed of amino sugar and higher fatty samine is obtained when a suspension of D-glucoacid has not been reported, but this group of amino samine in an adequate volume of methanol is sugar derivatives is of great interest because amino treated with an equivalent amount of sodium methsugars are sometimes found in combination with oxide. The supersaturated, methanolic solution fatty acids, e.g., in the lipopolysaccharides of some of D-glUCOSamine so formed can be maintained for microorganisms. The present work was under- some time a t room temperature in concentrations as taken for the purpose of investigating the prepara- high as 10% or more, and upon the addition of a tion and properties of some X a c y l and -V-acyl- slight excess of an acid anhydride a t room temtetra-0-acyl derivatives of D-glucosamine (2-amino- perature an almost quantitative yield of quite pure 2-deoxy-~-glucose), in which the acyl group was de- ,V-acyl-D-glucosamine is precipitated. N-Benzoylrived from even-numbered saturated fatty acids. D-glucosamine which was previously preparedlo by Some acyl derivatives of this amino sugar with the action of benzoyl chloride was also prepared by lower fatty acids have been previously reported in this method from benzoic anhydride. This procedure offers a simplified method for the the literature. Wholly and partially acetylated D-glucosamines have been extensively investi- preparation of ;Vi-acetyl-D-glucosamine.l1 This imand de- portant derivative of D-glucosamine has hitherto gated, and ~V-propionyl-~-glucosamine~ rivatives of iY-formyl-, N-propionyl- and N- been prepared from D-glucosamine hydrochloride butyroyl-D-glucosamine5 have been prepared. in methanol by the action of acetic' anhydride and There is only one report, by Jones, Kaye and Sta- silver acetate'?; or with acetic anhydride and ancey,6 concerning the preparation of a higher fatty hydrous sodium acetatel'j ; in IV,AV-dimethylformacid derivative of D-glucosamine, namely, S- amide with acetic anhydride a t low temperature, stearoyl-tetra-O-stearoyl-D-glucosamine. Some and in aqueous methanol with acetic anhydride in fatty acid derivatives of D-glucose have been syn- the presence of Dowex-1.l 4 The present method needs no catalyst and no particular treatment, but thesized.? The N-acylation and polyacylation of D-glUC0- gives preparations of high purity in good yield. samine were carried out with fatty acid anhydrides The crude N-acetyl-D-glucosamine that inimediand chlorides.. Treatment of D-glucosamine with ately starts to crystallize from the methanolic the acid anhydrides in anhydrous methanol or with supersaturated solution of D-glucosamine on the adthe acid chlorides in water (with alternate addition dition of acetic anhydride with completion oi of sodium hydroxide) gave rise to the N-acylated crystallization overnight in the refrigerator has D-glucosamines, and treatment of D-glucosamine m p . 200 to 204O, being sufficiently pure for ordiwith acid anhydrides in pyridine or with acid nary purposes. One recrystallization raised the chlorides in a mixture of chloroform and pyridine melting point to 208" (uncorrected). produced the iT-acyl-tetra-0-acyl-D-glucosamines. The action of fatty acid chlorides on D-glucoThe N-acylation was most effectively carried out saniine resulted in smaller yields and lower purity by the addition of the respective acid anhydrides of the obtained Ali-acylated-D-glucosamines than to a supersaturated, methanolic solution of D-gluco- did the action of the acid anhydrides on D-glucosamine. It is known that D-glucosamine is lib- samine, and the chlorides of lower fatty acids gave crated from its salts by treatment with strong variable yields of the corresponding X-acyl-Dbasesss9and that i t is slightly soluble in alcohol (1 glucosamines. Concerning the higher homologs, part in 38 of boiling methanol8). However, it was the preparations from the acid chlorides showed physical constants identical with those from the (1) \V. I H a v m r t h . P \V K e n t a n d hI Stacey, J C h e m S o c . , 1220 (1948); X f . I k a w a . J. B. Koeyfli, S G. h f u d d a n d C. Niemann. THIS corresponding acid anhydrides. J O L ~ R N A I , 75, , 3439 (19.53): cf 0 \Vestghal a n d 0 Liideritz, iliigeru ~~-A~cy~-tetra-O-acy~-D-g~ucosamines were prer'hein , 66, 407 (1954). pared by either one or both methods in which the f ? ) .4. R . Foster and h i S t a c e y , acid anhydride or acid chloride was allowed to re247 ( I W ) (:%I P. \V. Kent and .\I \\-. IVhitehousr, "Biochemistry of thi, act with D-glucosamine, D-glucosamine hydro.4minosugars," Butterworths. I,ondon, 1933. chloride or ~!'-ac~-l-D-glucosamine. Preparations (4) R . Kuhn and I:. Haber. Cheni. H e i . , 86, 7 2 2 ( 1 Y . X ) t.5) .4. Neuberger a n d R . 1'. Pitt Rivers, Biochem. J . , 33, 1380 (l!l:w). l S t a c e y , J . C h c w Sot., X I ( j (6) A . S. Jonrs, I T . A . (;. K;IW i l n ~ \I.
(10) hl. Bergmann and I,. Zervas, ibid., 64, 975 (1931); 65, 1201 (1932). T
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