CS225315B1 - The preparation of the glycosylmethylamine beta-d-galactopyranosylemethylamine and beta-d-glucopyranosylemethylamine - Google Patents

Description

The present invention relates to a process for the preparation of glycosylmethyl amine β-D-galactopyranosylmethylamine and β-D-glucopyranosylmethylamine.

The conversion of the glycosyl derivatives of nitromethane to the corresponding amino derivatives has hitherto been accomplished only by catalytic hydrogenation. Reduction of nitrosaccharides with hydrogen gas using Raney nickel catalyst in aqueous medium for several hours yielded the desired product in ca 70% yields [j.C. Sowden and R. Schaffer, J. Amer. Chem., Soc. 73 * 4662 (1951); J.C. Sowden and M.L. Oftedahl: J. Org. Chem., 26, 1974 (1996); L. Hough and S.H. Shute: J. Chem. Soc. 4633 (1962)] · Applying Adams catalyst to provide several hours of hydrogenation of carbohydrate nitroderivatives in an aqueous environment resp. in 1'-glacial acetic acid, 72-90% yield of the corresponding amines [j.C. Sowden and M.L. Oftedahl: J. Org. Chem., 26, 1974 (1961); J.C. Sowden, C.H. Bowers and K.O. Lloyd: J. Org · Chem ·

29, 130 (1964)}. S.W. Gunner, R.D. King, W.G. Overend and N.R. Williams, J. Chem. Soc. (C) 1954 (1970)].

The proposed method is an alternative procedure, is simpler and provides glycosylmethylamines in high, almost quantitative yields. SUMMARY OF THE INVENTION The present invention is characterized in that the starting glycosylnitromethane of formula R-CH ₂ -NO ₂ , where R is preceded by β-D-galactopyranosyl or β-D-glucopyranosyl, is reduced in an aqueous solution of ferrous sulfate and a base, with preferably ammonia, at a temperature of 90 to 100 ° C and a pH> 8 for 5 to 20 minutes. The resulting corresponding pure glycosylmethylamine / SD-galactopyranosylmethylamine or β-D-glucopyranosylmethylamine of the general formula R-CH ₂ -NH ₂ , wherein R represents β-D-galact, i.e. pyrazyl or β-D-glucopyranosyl, is preferably from the reaction mixture. It is recovered by filtration of ferric oxide hydrate, removal of ammonia by evaporation of half of the liquid from the suspension of the filtrate and the anion exchange resin in reduced pressure while removing the sulphate ions by attaching them to the anion exchange resin, filtering the anion exchange resin and crystallizing the filtrate.

An advantage of the proposed process for the preparation of glycosylmethylamines of β-D-galactopyranosylmethylamine and β-D-glucopyranosylmethylamine is that it does not require the preparation of special catalysts and the work with hydrogen is eliminated. The method of preparation allows a simple and quantitative isolation of the product. The isolated product is of high purity because any unreacted starting glycosylnitromethane is removed in the penultimate step with an anion exchange resin in the hydroxide form [L. Petruš and V. Bílik, A.O. 216,437]. The procedure is simple and easy on the chemicals and equipment used.

The method of reducing nitro compounds to amino compounds by the ferrous hydroxide in the nascent state is very selective for this type of reduction and has been applied to the preparation of various aromatic amines [r. Schroter, Methoden der Organischen Chemie (Houben-Weyl), Bd. XI / 1, S. 443 »Georg Thieme Verlag, Stuttgart (1957)]

Example 1

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To a boiling solution of ferrous sulfate heptahydrate (26.4 g) in water (60 mL) was added a solution of β-D-galactopyranosylnitromethane (3 g) in hot water (30 mL) with stirring. Concentrated aqueous ammonia solution (3 3 to 5 ml) was then added in portions immediately with stirring so that the boiling solution was still significantly alkaline (pH> 8). Finally, the reaction mixture was boiled for 10 min (alkalinity was still ensured by the addition of ammonia). The precipitate was filtered off and washed with a 2% aqueous ammonia solution (100 ml). Anion exchanger in caustic form (ca 100 g) was added to the cooled filtrate, and about half the volume of the liquid was distilled off from the slurry under reduced pressure (ca 5 kPa) on a rotary evaporator. The anion exchanger was filtered off and washed with water (3 x 100 mL). Concentration of the filtrate gave pure N-D-galactopyranosylmethylamine (2.5 g · 96%), which after two crystallizations from methanol had m.p. Mp 191-192 ° C and + 29 ° 0.5 ° (water, c 2). Lit. [P. Coxon and H.G. Fletcher, J. Amer. Chem. Soc. 86, 922 (1964), reports β-D-galactopyranosylmethylamine m.p. 191 DEG -192 DEG C. and [.alpha.] D @ 20 +30.0 DEG (water, c = 1.6).

Example 2

Following the same procedure as in Example 1, β-D-glucopyranosylmethylamine of mp 142-143 ° C and [α] ¹ + 2.7 + 0.2 ° (water, c 5) was prepared from β-D-glucopyranosylnitromethane. Pne C _? H ₁₅ N0 ₅ Calculated 43.52% C, 7.83% H 7.25% N Found 43.35% C, 8.03% H, 7.22% N.

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The invention is of importance in the preparation of pure carbohydrate amines having utility in organic synthesis as reactive intermediates, some of which are biologically active substances.

Claims (1)

A process for the preparation of glycosylmethylamines of β-D-galactopyranosylmethylamine and β-D-glucopyranosylmethylamine of the general formula R-Cl-NHH, wherein R represents β-D-galactopyranosyl or β-D-glucopyles in the morning, characterized in that the starting glycosylnitromethane R-CHg-NOg, where R is ρ, -D-galactopyranosyl or β-D-glucopyranosyl, is reduced with an aqueous solution of ferrous sulfate and a base, preferably ammonia, at a temperature of 90-100 ° C and a pH> 8 for 5-5 20 min, whereby the corresponding pure glycosylmethylamine formed is advantageously obtained from reaction mixture 8 by crystallization after filtering out ferric oxide hydrate, removing ammonia by evaporating half of the liquid from the filtrate and anion exchange slurry in hydroxide form at 5-10 kP® while removing the sulphate ions by binding them anion exchange, filtration of the anion exchange material and concentration of the filtrate.