CS274098B1 - Method of n-phenyl-d-manosilamine preparation from mixture of d-glucose and d-mannose - Google Patents

Abstract

The purpose of this method of preparation of N-phenyl-D-manosilamine from a mixture of D-glucose and D-mannose is reduction of costs and waste during production of D-mannose. The given purpose is achieved by subjecting a mixture of D-mannose and D-glucose in a molar ratio of 1 : 1 to 2 dissolved in a mixture of methanol and ethanol with a content of 5 to 10 % by volume water, to aniline, in a quantity of 50 to 80 % of theoretical quantity calculated to aldohexose, and the occurring N-phenyl-D-mannosyl amine is isolated by crystallisation. The invention can be used in organic chemistry.

Description

The present invention relates to a process for the preparation of N-phenyl-D-manozylamine from a mixture of D-mannose and □-glucose.

In many cases, the N-arylglycosylmines of aldoses are good crystallizing compounds / G. P. Cllis, 3. Honeyman: Advan. Carbohyd. Chem. 10, 95 (1955) J7 and their distinct crystallization ability is also used for the distribution of aldoses, respectively. aldoses from ketoses.

Of all aldopentoses, aldohexoses and aldoheptoses, ribose, lyxose, mannose, and manoheptosis have a very good crystallization capacity. If these aldoses are present in mixtures of aldoses resp. ketosis in sufficient quantities, they may be isolated as a crystalline N-ribose fenylglykozylaminov / 7 · ^R · ^L Whistler, W 3 BeMillers Methods Carbohyd. Chem., Vol. X, p. 79, Asademic Press, New York-London, 1962; V. Bilik, 3. Caplovich: Chem. Rumors 27, 547 (1973) J, Lyxoses Γ V. Bilik, 3rd Caplovich:

Chem. Rumors 27, 547 (1973) J, Mannose / T. Fujita, T, Sato; Bull. Chem. Sap, 3apan 33,

353 (1960) / V. Bilik, J. <. Chem. Rumors 28, 106 (1974) J, Manoheptoses / 7 V. Bilik, L. Petruš: Chem. Rumors 30, 359 (1976). These N-phenylglycosylamine properties of said aldoses have been utilized to isolate them from the corresponding ^C (2) -immediate acdoses. To isolate L-arabinose from a hemicellulose hydrolyzate, or isolate arabinose from xylose. A. Kramar: Chem. Rumors 33, 641 (1979) J7 may be isolated

D-glucose from sucrose hydrolyzate and D-mannose from mannan hydrolyzates / 3. Weygand, W. Perkov, P. Kuhner, Ber. 34, 594 (1951) 7 have proven to be good crystallizing 4-nitrophenyl-N-glycosylamines of erabinose, glucose and mannose. However, the quantitative yield of the aldose in the form of a good crystallizing N-phenyl- and / or N-phenyl is in no way achieved. 4-nitrophenyl-N-glycosylamine.

This disadvantage is substantially eliminated by the process of preparing N-phenyl-D-mannose amine from a mixture of D-glucose and D-mannose, which consists in the fact that the molar ratio of D-mannose and D-glucose in a molar ratio of 1: 1 to 2 is dissolved. in a mixture of methanol and ethanol containing 5 to 10 vol. % of water is treated with aniline in an amount of 50 to 80% of the theoretical amount calculated for aldohexoses, and the resulting N-phenyl-D-manozylamine is isolated by crystallization.

An advantage of the proposed process for the preparation of N-phenyl-D-manozylamine with a mixture of D-mannose and D-glucose is that using only 50-80% of the theoretical amount of aniline per aldohexose yields 89-100% of D-mannose as N-phenyl- D-manozylaminu. A further advantage is that the process of isolating D-mannose is unpretentious for technological equipment and the necessary chemicals.

Example 1

Mixtures 198 g (1 mol) of D-glucose monohydrate, 20 ml of a 6% aqueous solution of hexa-ammonium heptamolybdate tetrahydrate and 2 ml of 98 wt. % acetic acid is heated at 95-100 ° C for 3 h. To the reaction mixture cooled to 60-70 ° C, 100 ml of methanol and then 100 ml of 96 wt. % denatured ethanol. The solution was left to crystallize at 20-23 ° C for 48 h. Crystalline D-glucose 69 g (0.35 mol) was filtered off and washed with a small amount of a 1: 1 v / v mixture of methanol and ethanol. % ethanol to 400 ml volume and 29.6 ml (0.33 mol) of aniline (molar ratio of aldohexoses to aniline of 1: 0.5) is added. After 5 h of solution, 57.4 g of crystalline N-phenyl-D-manozylamine are filtered off. In this way, 22.5% yields of D-mannose are obtained in the form of N-phenyl / D-manozylamine calculated on the starting D-glucose.

Example 2

The procedure is as in Example 1 except that 35.5 ml (0.39 mol) of aniline (molar ratio of aldohexoses to aniline is 1: 0.6) is added, yielding 24.4% of the D-mannose yield in the the N-phenyl-D-manozylamine form calculated on the starting D-glucose.

Example 3

The procedure is as in Example 1 except that 41.9 ml (0.46 mol) of aniline (mole ratio of aldohexoses to aniline is 1: 0.7) is added to obtain 25.0% of D-mannose yield.

CG 274000 D1 in the form of N-phenyl-D-manozylamine calculated on the starting! D-glucose.

Example 4

The procedure is as in Example 1 except that 47.4 ml (0.02 mol) of aniline (the molar ratio of aldohexoses to aniline is 1: 0.8) is added to yield a 25.1% D-mannose extract in the N-phenyl-D-mannosylomine form calculated on the D-glucose starting material.

Example 5

A mixture of 14.85 g (75 mmol) of D-glucose monohydrate, 13.5 g (75 mmol) of D-mannose, 6 ml of water with 0.5 ml of 98 wt. % acetic acid and heated to 95-100 ° C. After cooling the solution to 60-70 [deg.] C., 40 ml of methanol, then 40 ml of 96% by weight of ethanol are added, with stirring, and finally 11 ml (0.12 mol) of aniline (molar ratio of aldohexoses to aniline is 1: 0.8). The solution is allowed to stand at 20 to 23 ° C for 5 h. Filtration gave 19.1 g of crystalline N-phenyl-D-manozylamine, which is 99.7% yield of the starting D-mannose in the form of N-phonyl-O-manozylamine.

Example 6

The procedure was as in Example 5 except that e prepared a mixture of 19.8 g (100 mmol) D-glucose monohydrate, 9.0 g (50 mmol) D-mannose, 5.5 ml water and 0.5 ml 98. wt. % acetic acid. Filtration yielded 12.55 g of crystalline N-phenyl-D-menozylamine, which represents 98.3% yield of the starting D-mannose as N-phenyl-D-manozylamine.

Comparing the effect of the reduced aniline additive by the excess amount of aniline used hitherto calculated by no aldohoxosis shows a noeled example;

Example 7

The procedure is as in Example 1 except that 65.6 ml (0.72 mol) of aniline (molar ratio of aldohoxoses to aniline is 1: 1.1) is added, yielding a 25.3% ϋ-mannose extract in the N-phenyl-D-manozylamine form calculated on the starting D-glucose.

A comparison of the effect of isolation of D-mannose in the formo N-phonyl-D-manozylamine with the isolation of D-mannose in the formo phenylhydrazone of D-mannose, which is a proven gravimetric method for the determination of D-mannose, shows a lead example:

Example O

The procedure is as described in Example 1, except that after the D-glucose has been crystallized to adjust the filtrate to 400 ml by volume of alcohol, 200 ml of water and 70.5 ml (0.72 mol) of phenylhydrazine (molar ratio of aldohoxoses to phonylhydrazine Jo 1: 1.1). After 20 h. After standing the solution, 68.0 g of crystalline phenylhydrazone D-methanose are filtered off. This yields a 25.2% yield of D-mannose in the form of phenylhydrazone D-mannose.

The invention can be used in the preparation of D-mannose which has utility in organic chemistry and biochemistry.

Claims (1)

A process for the preparation of N-phenyl-D-mannose amine from a mixture of D-glucose and D-mannose, characterized in that for a mixture of D-monose and D-glucose in a molar ratio of 1: 1 to 2 dissolved in methanol / ethanol containing 5%. up to 10 vol. % of water is treated with aniline in an amount of 50 to 80% of the theoretical amount of calcitonone to aldohoxoses of the resulting N-phonyl-D-manozylamine o and isolated by crystallization.