CS260393B1 - A method of preparing aldoses - Google Patents

Abstract

The purpose of the method of preparing aldoses is to improve the methods of preparing aldoses, i.e. to simplify and save money on these methods of preparation. The stated purpose is achieved by adding spavelic acid to N-phenylglycosylamine, formaldehyde, ethanol, water and a molybdenum compound in a mole ratio of molybdenum with oxidation state VI to oxalic acid of 1: at least 4 and allowing it to react at a temperature of up to 90°C. The method of preparing aldoses is used in organic chemistry.

Description

The invention relates to a process for the preparation of aldoses.

In some methods of isolating one aldose from the aldose mixture, the reaction of the aldoses with anilines, which utilizes the different crystallization capacity of the resulting N-phenylglycosylamines, has been used. N-phenylribozylamine is isolated from arabinose-ribose mixture, and N-phenyllyxozylamine from V. a mixture of xylose and lyxose [V. Bilik, J. Caplovic: Chem. Legends 27, 547 (1973)], fructose, glucose and mannose N-phenylmanozylamine (V. Bilik, K. Tihlárik: Chem. Legends 28, 106 (1984)), from D-glycero-L-glucoheptose and D-glycero- L-manoheptoses N-phenyl-D-glycero-L-manoheptozylamine [V. Bílik, L. Petruš: Chem. Zvěsti 30, 359 (1976)] and from a mixture of L-arabinose and D-xylose N - (4-nitrophenyl) -L-arabinozylamine [V. Bílik A. Kramar: Chem. Annals 33, 641 (1979)].

Aldoses can be released from formaldehyde from N-phenylglycosylamines [T. Fujita, T. Šate: Bull. Chem. Soc. Japan 33, 353 (1960)], benzaldehyde [R. L. Whistler, J. N. BeMiller: Methods Carbohydr. Chem. 1, 81 (1962)], by hydrolysis by the water vapor bleeding technique [V. Bílik, j. Caplovic: Chem. Rumors 27, 547 (1973); V. Bílek, L. Petruš: Chem. Rumors 30, 359 (1976)], by strong acid ion exchanger hydrolysis (CS AO No. 198 996 i.

In all of these reactions, molybdate ions need not be present in the depletion procedures. Therefore, aldose solutions had to be deionized prior to appropriate derivatization to the corresponding N-phenylglycosylamines, which increases laboriousness and makes the prepared aldoses more expensive. Aldoses are epimerized in weakly acidic aqueous solutions in the presence of molybdenum ions to form an equilibrium mixture of C-2-epimeric aldoses [V. Bilik: Chem. 77, 496 (1983)].

The above-mentioned disadvantages are substantially eliminated by the process for preparing aldoses according to the invention, which comprises adding to the N-phenylglycosylamine, formaldehyde, ethanol, water and molybdenum compound a molar ratio of molybdenum having an oxidation degree of VI to oxalic acid of 1: at least 4 and allowed to react at a temperature of <100 ° C.

The advantage of the proposed process for the preparation of aldoses is that there is no need to remove molybdenum ions, most often by anion exchange resins, followed by concentration of the solutions, thus saving on wages, materials, energy, and substantially saving the use of some devices (evaporators, columns).

Example 1

A mixture of 25.5 g (0.1 mol) of N-phenyl-D-manozylaminu, 0.25 g (2.10 mmol ~ ⁴⁾ Hexaammonium heptamolybdate tetrahydrate, 0.71 g (5,6.10 ^-3 mol) šťaveiovej acid dihydrate (the mole the ratio of oxalic acid to molybdenum in oxidation stage VI is 4: 1, 15.8 ml (0.2 mol) 35% by weight. % aqueous formaldehyde solution, 35 ml 96 wt. of ethanol and 190 ml of water are heated at 90 ° C for 3 hours. Inhibition of D-mannose epimerization was determined by paper chromatography (Whatman No 1) using A: acetone 1-butanol / water (7: 2: 1 by volume) and B: 1-butanol, ethanol: water (5 by volume) : 1: 4, with a flow time of the elution systems of 18 to 20 h and subsequent detection with aniline hydrogen phthalate. Chromatography shows the presence of D-mannose and, in trace amounts, the presence of D-glucose. Glucose-related mobility of 1.00 is for mannose in the elution system A: 1.31 and in the elution system B: 1.30.

Example 2

The procedure is as in Example 1 except that the mixture is heated at 100 ° C for 2 h. Chromatography shows the presence of D-mannose and trace amounts of D-glucose.

Example 3

The procedure was as in Example 1 except that a mixture of 22.5 g (0.1 mol) of N-phenyl-D-ribozylamine, 25 mg (2.10 ^-5 mol) of bexaammonium heptamolybdate tetrahydrate, 71 mg ( 5,6.10 ⁴ moles) of oxalic acid dihydrate (molar ratio of oxalic acid] to molybdenum in oxidation stage VI is 4: 1], 15.8 ml (0.2 mol) of 35% by weight aqueous formaldehyde solution, 35 ml 96 % by weight of ethanol and 190 ml of water.

Chromatography shows the presence of D-ribose and trace amounts of D-arabinose. Mobility related to D-glucose 1.00 is for D-ribose in elution system A: 2.13 and in elution system B: 1.90 and for D-arabinose in elution system A: 1.41 and in elution system B: 1 30.

Example 4

The procedure is as in Example 3 except that N-phenyl-L-lyxozylamine is used. Chromatography shows the presence of L-xylose and trace amounts of L-xylose. The mobility related to D-glucose is for L-lyxose in elution system A: 1.82 and in elution system B: 1.66 and for L-xylose in elution system A: 1.72 and in elution system B: 1.54.

Example 5

To a solution containing 3 g of hexaammonium heptamolybdate tetrahydrate, 2 ml of 99 wt. of acetic acid and 25 ml of water are added 250 g of D-glucose monohydrate. Heat the mixture at 90 ° C for 50 min, then add 120 mL of methanol, 120 mL of 96 wt. ethanol and crystallized at 23 ° C for 3 days.

Then 105 g of D-glucose is filtered off (yield of regenerated D-glucose is 42%). The filtrate was supplemented with a mixture of methanol and 96 wt. of ethanol in a 1: 1 by volume ratio to a volume of 500 ml, to which 100 ml of aniline was added and allowed to stand at 23 ° C for 20 h. 80 g of N-phenyl-D-banozylamine are filtered off (yield of D-mannose in the form of N-phenyl-D-manozylamine is 25% relative to the starting D-glucose, or the yield is 43% relative to regenerated D-glucose) ). A mixture of 80 g of N-phenyl-D-mannose laminate, 0.5 g of oxalic acid dihydrate, 50 ml of 35% w / w. aqueous formaldehyde solution, 600 ml water and 100 ml 96% w / w. of ethanol was heated at 90 ° C for 3 h.

The solution is filtered, concentrated and the residue is dissolved in 150 ml of methanol and left to crystallize for 24 h at ° C. 47.5 g of D-mannose are filtered off. The mother liquor is concentrated and the residue is dissolved in 30 ml of methanol to give a second crystalline portion of 7.5 g of D-mannose. The total yield of crystalline D-mannose is% relative to the starting D-glucose and d-glucose, respectively. is 41.5% based on regenerated D-glucose.

Example 6

A solution of 100 g of D-xylose, 1 g of hexaainonic heptamolybdate tetrahydrate and 4 ml. of acetic acid in 400 mL of water was heated at 90 ° C for 4 h. The solution is treated with charcoal, filtered, concentrated and the residue is dissolved in

100 ml of methanol and allowed to crystallize for 24 h. Filter 46 g of D-xylose (46% yield). Adjust the filtrate to 200 ml with methanol, add 40 ml of aniline and allow to stand at 23 ° C for 2 h. Filter 32 g of N-phenyl-D-, lyxozylamine (yield of D-lyxose is 21% by weight based on the starting D-xylose) Mixture of 32 g of N-phenyl-D-lyxozylamine, 270 ml of water, 50 ml of 96 wt% ethanol, 22.5 ml of 35 wt% The aqueous formaldehyde solution and 0.2 g of oxalic acid dihydrate are heated at 90 ° C for 3 h. The solution is filtered, treated with charcoal, filtered and concentrated again, and the residue is dissolved in 20 ml of 96% ethanol and left to stand. crystallize at 23 ° C for 24 h to yield 13.8 g of D-lyxose (14% yield based on the starting D-xylose and 25.5% relative to the recovered D-xylose, respectively).

Example 7

To a mixture of 100 g of L-arabinose, 100 ml of dimethylsulfoxide, 300 ml of methanol, 200 ml of n-tromethane is added with stirring over 1 hour 800 ml of methanolic sodium methoxide solution (24 g of sodium in 800 ml of methanol) and stirred for 7 h then stand for 20 h. The sodium salts of 1-deoxy-1-nitrohexitols are filtered off and added portionwise over 15 min to a solution containing 4 g of hexaammonium heptamolybdate tetrahydrate, 2 g of sodium hydroxide, 200 ml of 30% by weight. hydrogen peroxide and 1000 ml water. The reaction mixture is maintained in the oxidative decomposition by cooling at a temperature of from 20 to 30 ° C for the first three hours (exothermic reaction). The reaction mixture was then allowed to stand at 23 ° C for 20 hours. After addition of 0.1 g of 5 wt. The palladium on activated carbon is allowed to stand at 23 ° C for a further 20 h. The distillation residue was dissolved in 350 ml of methanol, 40 ml of aniline was added and the mixture was allowed to stand at 23 ° C for 5 h.

Filter 70 g of N-phenyl-L-manozylamine (L-mannose yield 41%) in the form of N-phenyl-L-manozylamine referring to the starting L-arabinose). A mixture of 70 g of N-phenyl-L-mannose amine, 600 ml of water, 100 ml of 96 wt. ethanol, 50 ml 35 wt. of formaldehyde and 1 g of oxalic acid dihydrate are heated at 90 ° C for 3 h.

The solution is filtered, the filtrate is concentrated and the distillation residue is crystallized from 100 ml of methanol to give 40 g of L-mannose (L-mannose yield 33.5% based on the starting L-arabinose).

In the examples, epimerization inhibition temperatures of 90 and 100 ° C are reported, but epimerization is inhibited α1 at substantially lower temperatures, for example, when the aldose solutions are concentrated. The oxalic acid forms a stable complex with molybdate cyanides, which inhibits the epimerization of aldoses even over a substantial period of time, as exemplified in the examples. However, it is not efficient to store aldose solutions for longer periods of time at lower temperatures, since aldose solutions are good nutrients for some microorganisms that can destroy them.

The process for preparing aldoses can find widespread use in organic chemistry in the preparation of both the D- and L-series aldoses.

Claims (1)

260393 milliliters 96 wt. ethanol and allowed to crystallize at 23 ° C for 3 days. 105 g of D-glucose are then filtered off (yield of regenerated D-glucose is 42%) and the filtrate is made up with a mixture of methanol and 96% by weight. of ethanol at a volume ratio of 1: 1 to 500 ml, to which 100 mlaniline is added and left to stand at 23 ° C for 20 h. 80 g of N-phenyl-D-banosyl-amine (D-mannose yield in N- Phenyl-D-manozylamine is 25% relative to sana starting D-glucose, and the yield is 43% relative to regenerated D-glucose). A mixture of 80 g of N-phenyl-D-manozylamine, 0.5 g of oxalic acid dihydrate, 50 ml of 35% w / w. aqueous formaldehyde solution, 600 ml water and 100 ml 96% w / w. the ethanol is heated for 3 h at 90 ° C. The solution is filtered, concentrated and the residue is dissolved in 150 ml of methanol and crystallized for 24 h at 23 ° C. 47.5 g of D-mannose are filtered off. The master solution is concentrated and the residue is dissolved in 30 ml of methanol to give a crystalline fraction of 7.5 g of D-mannose. The total yield of crystalline D-mannose is 24% based on the starting D-glucose, respectively. is 41.5% based on regenerated D-glucose. Example 6 A solution of 100 g of D-xylose, 1 g of heptamolybdate tetrahydrate and 4 ml of 99% w / w. Acetic acid in 400 mL of water is heated at 90 ° C for 4 h. The solution is purified with activated carbon, filtered, concentrated and the residue is dissolved in 100 mL of methanol and crystallized for 24 h. -xylose (46% yield). The filtrate is adjusted to 200 ml with methanol, 40 ml of aniline are added and left to stand at 23 DEG C. for 2 h. 32 g of N-phenyl-D-, lyxozylamine (D-lyxose yield is 21 θ / o relative to the starting D-xylose). A mixture of 32 g of N-phenyl-D-lyxozylamine, 270 ml of water, 50 ml of 96 wt. ethanol, 22.5 ml 35 wt. The aqueous solution of formaldehyde and 0.2 g of oxalic acid dihydrate are heated at 90 ° C for 3 h. The solution is filtered, washed with activated carbon, filtered and concentrated. The distillation residue was dissolved in 20 ml of 96 wt. ethanol and allowed to crystallize at 23 ° C for 24 h to give 13.8 g of D-lyxose (yield 14% based on starting D-xylose, respectively 25.5% on regenerated D--). xylose). EXAMPLE 7 800 ml of a sodium methanolate metariol solution (24 g of sodium in 800 ml of methanol) are added to a mixture of 100 g of L-arabinose, 100 ml of dimethylsulfoxide, 300 ml of methanol, 200 ml of nitromethane while stirring, and 24 g of sodium in 800 ml of methanol are added. the mixture is stirred for 7 h and then dried for 20 h. The 1-deoxy-1-nitrohexitols sodium salt is filtered off and added in portions over 15 min to a solution containing 4 g of heptamolybdate hexammonium hexahydrate, 2 g of hydroxide of sodium, 200 ml of 30 wt. hydrogen peroxide and 1000 ml water. The reaction mixture is maintained by oxidation decomposition by cooling to a temperature of from 20 to 30 ° C in the first three hours (exothermic reaction). The reaction mixture was then allowed to stand at 23 ° C for 20 hours. After the addition of 0.1 g of 5 wt. The charcoal is left at 23 DEG C. for a further 20 h. The distillation residue is dissolved in 350 ml of methanol, 40 ml of aniline are added and the mixture is allowed to stand at 23 DEG C. for 5 h. phenyl-L-manozylamine (L-mannose yield 41 ° / o in the form of N-phenyl-L-manozylamine relative to the starting L-arabinose). A mixture of 70 g of N-phenyl-L-manozylamine, 600 ml of water, 100 ml of 96% wt. ethanol, 50 ml of 35% formaldehyde and 1 g of oxalic acid dihydrate are heated at 90 DEG C. for 3 hours. The solution is filtered, the filtrate is concentrated and the distillation residue is crystallized from 100 ml of methanol to give 40%. g of L-mannose (Y-mannose yield is 33.5% based on starting L-arabinose). In the Examples, epimerization inhibition temperatures of 90 and 100 ° C are reported, but epimerization is inhibited even at substantially lower temperatures, for example, when concentrating aldose solutions. The oxalic acid formed with the molybdenum inorganic stable complex, which inhibits epimerization of the liposomes as well as substantial longer time, as exemplified. However, it is not effective to store aldose solutions at lower temperatures for a longer period of time, as aldose solutions are good nutrient stages for some microorganisms that can degrade them. The process for preparing aldoses can find widespread use in organic chemistry in the preparation of D- and L-series aldoses. SUBJECT A method of preparing aldoses from the corresponding N-phenylglycosylamine by the action of formaldehyde characterized in that N-phenylglycosylamine, formaldehyde, ethanol, water amolybdenum acid is added to the oxalic acid in moles of molybdenum by oxidation step VI to oxalic acid. 1: at least 4 and allow to react to 100 ° C. * rz