CS263174B1 - Method of D-glycero-D-galacto-heptose and D-glycero-D-taloheptose Preparation - Google Patents

Abstract

The purpose of the solution is to improve the method of preparing D-glycero-D-galactoheptose and D-glycero- -D-taloheptose. The stated purpose is achieved by decomposing solid sodium salts of 1-deoxy-1-nitroheptitols with hydrogen peroxide under the catalysis of molybdenum ions to the corresponding aldoheptoses. The method of preparing D-glycero-D-galactoheptose and D-glycero- -D-taloheptose has applications in organic chemistry and biochemistry in the preparation of carbohydrates.

Description

263174 2

The invention relates to a process for the preparation of D-glycero-D-galacto-heptose and D-glycero-D-taloheptose.

For the preparation of D-glycero-D-galactoheptose and D-glycero-D-taloheptose, the reaction based on the extension of the D-mannose carbon chain is utilized. The cyanohydrin synthesis and subsequent hydrolysis of the C-epimeric heptonic acids obtained are resolved in the form of their calcium or barium salts which, upon reduction, yield D-glycero-D-galacto-heptose, respectively. D-glycero-D-taloheptose [h. S. Isbell, J. Res. Nat. Bur. Stand. 20, 97 (1938), EM Montgomery, CS Hudson, J. Amer. Chem. Soc. 64, 247 (1942) 3- Nitromethane synthesis is carried out in a methanolic sodium methanolate solution C. Sowden, R. Schaffer: J. Amer.

Chem. Soc. 73, 4,662 (1951)], or an aqueous solution of sodium hydroxide. C. Sowden, RR Thomson: J. Amer. Chem. Soc. 80, 2236 (1958)], the obtained C (2) -epimeric 1-deoxy-1-nitro-heptitols are separated by fractional crystallization, and finally the isolated nitroheptitoly in the form of their sodium salts is decomposed by the Neff reaction (sulfuric acid) to the corresponding deheptoses. Also, the reaction of nitromethane and L-mannose in methanolic solution in the presence of methanolic sodium was used for the preparation of L-glycero-L-galacto-heptose and L-glycero-L-taloheptose, and the obtained sodium nitroheptitols were dissolved in water and the hydrogen peroxide decomposed to the corresponding molybdenum ions. aldoheptoses which are isolated by chromatography on an ion exchanger with functional sulfo groups in the barium ring [v. Bilik, D. Anderle, J. Alfoldi: Chem. rumors 28, 668 (1974)]. In nitromethane synthesis, the sodium salts of nitroheptitols in aqueous solution decompose to the starting materials, thereby reducing the yield of the desired aldoheptides.

The principle of the preparation of D-glycero-D-galacto-heptose and D-glycero-D-taloheptose by reaction of D-mannose and nitromethane in methanolic sodium hydroxide solution, oxidative decomposition of the aqueous solution, deionization of the solution by ion exchangers, fermentation of D-mannose, crystallization of D-glycero-D -galaktoheptose from a solution of methanol and acetic acid and by separation of the parent solution by ion exchange chromatography with functional sulfo groups in the calcium or barium ring, the solid sodium salts of 1-deoxy-1-nitro-D-glycero-D-galactoheptitol and 1-deoxy-- 1-nitro-D-glycero-D-taloheptitol is decomposed by hydrogen peroxide under the catalysis of molybdenum aniones. The advantage of the proposed method of preparing D-glycero-D-galacto-heptose and D-glycero-D-taloheptose is that it is very simple in technical terms, all the necessary chemicals are unavailable and low-tech. A further advantage is that when using solid sodium salts of 1-deoxy-1-nitroheptitols, the extracts are higher. The added acetic acid decomposes the nitrites to nitrogen oxides, which are released and removed, thereby avoiding the life of the ion exchangers used. EXAMPLE 1 100 g of D-mannose are dissolved in 500 ml of methanol, 200 ml of nitromethane is added, and 750 ml of 1.3 mol / L methanolic sodium hydroxide solution is added in portions (30 ml each) with stirring. hours and then allowed to stand for 20 hours at 23 ° C. The precipitated sodium salts of 1-deoxy-1-nitro-D-glycero-D-galacto-heptitol and 1-deoxy-1-nitro-D-glycero-D-taloheptitol were filtered and washed with methanol. To a mixture of 1000 ml of 0.05 mol / l aqueous sodium hydroxide solution, 100 ml of 30 wt. The aqueous solution of hydrogen peroxide and 2 g of molybdenum ammonium are added with sodium solitonitriles over a period of 7 minutes with stirring in portions (ie, 1 g). The oxidative decomposition of nitroheptitols to aldoheptose is a mildly axotarmic reaction and therefore the reaction mixture was cooled to a temperature not exceeding 30 ° C. The reaction mixture was allowed to stand at 23 ° C for 20 hours. Then 10 ml of 100 wt. acetic acid and solution bubbled through the air. The solution is then allowed to stand for 20 hours and after the addition of 0.1 g of 5 wt. Palladium on carbon is allowed to stand for another 20 hours. The solution is filtered and de-ionized by the addition of 500 ml of an ion exchanger with functional sulfo groups (Ostion KS 210) and then a 500-ion tertiary amine-functional ion exchanger (Ostion AT 0 209) in the carbonate ring. Concentrate the deionized solution to 1 000 ml of volume, add 1000 ml of drinking water,

10 g of baker's yeast (Saccharpmyces cerevisiae) and allow to stand at 23 ° C

Claims (1)

3 263174 for 1-2 days until complete D-mannose fermentation. The solution is filtered, concentrated and the residue is dissolved in a mixture of 30 ml of 100 wt. acetic acid and 90 ml of methanol and crystallize to give 36 g of D-glycero-D-galacto-heptose. The mother liquor is chromatographed on a column of an ion exchanger with a functional sulfo group in a calcium cycle of 3.6 cm and a length of 110 cm eluting with water at a flow rate of 150 ml.h -1 of the first 1000 ml and then at a flow rate of 250 ml.h 1. Fraction I (480 elution volume) up to 940 ml) contains 16 g of D-glycero-D-galacto-heptose and fraction II (elution volume 1000-2000 ml) of 19 g of D-glycero-D-taloheptose. The total yield of D-glycero-D-galacto-heptose is 44.5% and D-glycero-D-taloheptose is 16.2% calculated on starting D-mannose. Crystallization resp. the recrystallization is carried out in a 2: 1 mixture of methanol and 100% acetic acid to yield D-glycero-D-galactoheptose at temperatures of 139-141 ° C and optical rotation of [α] D + 67.5 ° (c). 1.5, water) and D-glycero-D-talo-heptose, m.p. 106-108 ° C and optical rotation + 13.5 ° (c 1.5, water). JC Sowden and R. Schaffer report for alpha-D-glycero-D-galacto-heptose a melting point of 135-137 ° C and a specific rotation of + 68.1 ° (c 3.5, water) and for D-glycero-D-talo- Heptose monohydrate mp 83-84 ° C and optical rotation [α] D + 15.8 ° (c 3.5, water). C. Sowden, R. Schaffer: J. Amer. Chem. Soc. 80, 2236 (1958) J. The composition of the reaction mixtures as well as the purity of the isolated aldoheptoses was monitored by chromatography on a chromatography paper (Whatman No 1) eluting with n-butanol: ethanol: water in a 5: 1: 4 volume ratio (detection with aniline acid phthalate) at 18-22h where mobility D-glucose drawn in 1.00 (brown) is 1.36 (brown) for D-mannose, D-glycero-D-galactoheptide is 0.63 (brown-red) and 1.29 (brown-red) for D-glycero-D-taloheptose . The invention can be widely used for the preparation of D-glycero-D-galacto-heptose and D-glycero-D-taloheptose, which are simultaneously starting compounds for the preparation of naturally-occurring carbohydrates ie D-pesitol, D-volemitol, D-manoheptulosis , D-altroheptuloses, L-galactoheptuloses and also as standard compounds for the monitoring of carbohydrates in natural material. OBJECT OF THE INVENTION A process for preparing D-glycero-D-galacto-heptose and D-glycero-D-taloheptose by reacting D-mannose and nitromethane in methanolic sodium hydroxide solution, by oxidative decomposition in aqueous solution, deionizing the solution by ion exchange, fermenting D-mannose in solution, crystallizing parts of D-glycero-D-galactoheptose from a solution of methanol and acetic acid and dividing the mother liquor by ion exchange chromatography with functional sulfo groups in calcium or barium cycles, characterized in that the solid sodium salts of 1-deoxy-1-nitro-D-glycero-D-galacto-heptitol a1 -deoxy-1-nitro-D-glycero-D-talogeptitol decompose in aqueous solution of hydrogen peroxide under catalysis with molybdenum ions.