Method for separation purification of polyhydroxy-alkyl-pyrazine from suger amine reaction liquid

Abstract

This invention discloses a method of separately purifying caoboxyl alkyl pyrazine from sugar ammonium reaction liquor. Compound got by reaction of sugar and ammonia is pressed let in acceptable filtration membrane (retention molecular weight is more than 200) or exceed filtration membrane (retention molecular weight is more than 1000) from material storage tank. Macromolecule matter is entrapped by membrane module, parts feed liquids penetrate the two membranes (there is multi-caoboxyl alkyl pyrazine, and macromolecule matter content is low or absence because of entrapped by membrane module), the material liquid that don't penetrate the membrane module is sent back to material storage tank through tubes and then sent to membrane modules to be separated. Pure water can be added to material storage tank for dilution at the later stage of separation, then acceptable filtration or exceed filtration is kept on to make the multi-caoboxyl alkyl pyrazine penetrate the module along with the penetration liquid at the best. All penetration liquids are collected and pure multi-caoboxyl alkyl pyrazine category matter can be got after concentration, extraction, decoloration, crystallization or using chromatogram etc. technologies. It can be used as spice or medicine materials. The material liquid can be directly used to perfuming and charging of cigarette to improve taste of cigarette and other aspects.

Description

technical field

[0001] The invention relates to a method for separating and purifying polyhydroxyalkylpyrazines from sugar ammonium reaction liquid. Background technique

[0002] Polyhydroxyalkylpyrazines exist in plants such as Panax notoginseng and tobacco. The polyalkylpyrazines in plants are obtained from reducing sugars in plants such as glucose and amino compounds through Amadori rearrangement and a series of complex reactions, and these substances can be used as cigarette additives to enhance flavor. Li Qi et al reported the isolation of 2-(1′,2′,3′,4′-tetrahydroxybutyl)-6-(2″,3″ from Panax notoginseng in the 2001 Vol. , 4 "-trihydroxybutyl)-pyrazine and confirm its structure with synthetic method, and find that it has better anticancer activity. U.S. Patent No. 6,392,042 discloses a class of polyalkylpyrazines for the treatment of diabetes Previous studies have shown that the reaction of sugar and amino compounds often produces more macromolecular substances, calle...

Examples

Embodiment 1

[0027] Separation and purification of 2,5-bis(1',2',3',4'-tetrahydroxybutyl)pyrazine from the reaction mixture of glucosamine and ammonia by nanofiltration

[0028]20,000 grams of glucosamine hydrochloride was dissolved in 20,000 milliliters of 28% ammonia water, and stirred at room temperature for 2 days. Under the operating pressure of 3.5MPa, the mixture obtained by the reaction is passed into the tubular nanofiltration membrane module with a molecular weight cut-off of 500 from the raw material storage tank with pressure, 2,5-two (1 ', 2 ', 3 ', 4 '-Tetrahydroxybutyl)pyrazine aqueous solution is collected through the nanofiltration membrane to the permeate tank, and the macromolecular substances are intercepted by the membrane module and sent back to the raw material storage tank along with the feed liquid that has not passed through the membrane module, and then sent to The inlet membrane module is separated, and the separation is carried out in such a cycle. Membrane fl...

Embodiment 2

[0033] Separation and purification of the mixture of 2-hydroxymethyl-5-methylpyrazine and 2-hydroxymethyl-6-methylpyrazine from the reaction mixture of 1,3-dihydroxyacetone and ammonium acetate by ultrafiltration

[0034] 46 grams of 1,3-dihydroxyacetone was dissolved in absolute ethanol, added dropwise to 58 grams of ammonium acetate, and kept reflux during the dropwise addition, and refluxed for 3 hours after the dropwise addition. After the reaction, the reaction mixture was ultrafiltered in an ultrafiltration cup with an ultrafiltration membrane with a molecular weight cut-off of 1500, and compressed air was used as power to adjust the pressure to 0.3 MPa to collect the ultrafiltrate. This operating temperature is 20-30°C. In the later stage of ultrafiltration, add absolute ethanol repeatedly to dilute and continue ultrafiltration, 100 ml each time, until 2-hydroxymethyl-5-methylpyrazine and 2-hydroxymethyl-6-methylpyrazine in the ultrafiltrate are detected by GC-MS. The ...

Embodiment 3

[0037] Preliminary Purification of 2-(1', 2', 3', 4'-tetrahydroxybutyl)-5-(2", 3", 4" from the reaction mixture of glucose, fructose and diammonium hydrogen phosphate by ultrafiltration -trihydroxybutyl)-pyrazine and 2-(1′,2′,3′,4′-tetrahydroxybutyl)-6-(2″,3″,4″-trihydroxybutyl)-pyridine Zinc

[0038] 360 grams of glucose, 360 grams of fructose and 540 grams of diammonium hydrogen phosphate were dissolved in 2000 milliliters of water and reacted for 3 hours at 90-95°C. The mixture obtained by the reaction is passed through the hollow fiber ultrafiltration membrane module with a molecular weight cut off of 5000 from the raw material storage tank under pressure, the operating pressure is 0.3MPa, and the temperature is controlled at 30 to 40°C. Containing 2-(1', 2', 3', 4'-tetrahydroxybutyl)-5-(2", 3", 4"-trihydroxybutyl) pyrazine and 2-(1', 2' , 3′, 4′-tetrahydroxybutyl)-6-(2″, 3″, 4″-trihydroxybutyl) the aqueous solution of pyrazine is collected into permeate liquid tank thro...

technical field

[0001] The invention relates to a method for separating and purifying polyhydroxyalkylpyrazines from sugar ammonium reaction liquid. Background technique

[0002] Polyhydroxyalkylpyrazines exist in plants such as Panax notoginseng and tobacco. The polyalkylpyrazines in plants are obtained from reducing sugars in plants such as glucose and amino compounds through Amadori rearrangement and a series of complex reactions, and these substances can be used as cigarette additives to enhance flavor. Li Qi et al reported the isolation of 2-(1′,2′,3′,4′-tetrahydroxybutyl)-6-(2″,3″ from Panax notoginseng in the 2001 Vol. , 4 "-trihydroxybutyl)-pyrazine and confirm its structure with synthetic method, and find that it has better anticancer activity. U.S. Patent No. 6,392,042 discloses a class of polyalkylpyrazines for the treatment of diabetes Previous studies have shown that the reaction of sugar and amino compounds often produces more macromolecular substances, calle...

Examples

Embodiment 1

[0027] Separation and purification of 2,5-bis(1',2',3',4'-tetrahydroxybutyl)pyrazine from the reaction mixture of glucosamine and ammonia by nanofiltration

[0028]20,000 grams of glucosamine hydrochloride was dissolved in 20,000 milliliters of 28% ammonia water, and stirred at room temperature for 2 days. Under the operating pressure of 3.5MPa, the mixture obtained by the reaction is passed into the tubular nanofiltration membrane module with a molecular weight cut-off of 500 from the raw material storage tank with pressure, 2,5-two (1 ', 2 ', 3 ', 4 '-Tetrahydroxybutyl)pyrazine aqueous solution is collected through the nanofiltration membrane to the permeate tank, and the macromolecular substances are intercepted by the membrane module and sent back to the raw material storage tank along with the feed liquid that has not passed through the membrane module, and then sent to The inlet membrane module is separated, and the separation is carried out in such a cycle. Membrane fl...

Embodiment 2

[0033] Separation and purification of the mixture of 2-hydroxymethyl-5-methylpyrazine and 2-hydroxymethyl-6-methylpyrazine from the reaction mixture of 1,3-dihydroxyacetone and ammonium acetate by ultrafiltration

[0034] 46 grams of 1,3-dihydroxyacetone was dissolved in absolute ethanol, added dropwise to 58 grams of ammonium acetate, and kept reflux during the dropwise addition, and refluxed for 3 hours after the dropwise addition. After the reaction, the reaction mixture was ultrafiltered in an ultrafiltration cup with an ultrafiltration membrane with a molecular weight cut-off of 1500, and compressed air was used as power to adjust the pressure to 0.3 MPa to collect the ultrafiltrate. This operating temperature is 20-30°C. In the later stage of ultrafiltration, add absolute ethanol repeatedly to dilute and continue ultrafiltration, 100 ml each time, until 2-hydroxymethyl-5-methylpyrazine and 2-hydroxymethyl-6-methylpyrazine in the ultrafiltrate are detected by GC-MS. The ...

Embodiment 3

[0037] Preliminary Purification of 2-(1', 2', 3', 4'-tetrahydroxybutyl)-5-(2", 3", 4" from the reaction mixture of glucose, fructose and diammonium hydrogen phosphate by ultrafiltration -trihydroxybutyl)-pyrazine and 2-(1′,2′,3′,4′-tetrahydroxybutyl)-6-(2″,3″,4″-trihydroxybutyl)-pyridine Zinc

[0038] 360 grams of glucose, 360 grams of fructose and 540 grams of diammonium hydrogen phosphate were dissolved in 2000 milliliters of water and reacted for 3 hours at 90-95°C. The mixture obtained by the reaction is passed through the hollow fiber ultrafiltration membrane module with a molecular weight cut off of 5000 from the raw material storage tank under pressure, the operating pressure is 0.3MPa, and the temperature is controlled at 30 to 40°C. Containing 2-(1', 2', 3', 4'-tetrahydroxybutyl)-5-(2", 3", 4"-trihydroxybutyl) pyrazine and 2-(1', 2' , 3′, 4′-tetrahydroxybutyl)-6-(2″, 3″, 4″-trihydroxybutyl) the aqueous solution of pyrazine is collected into permeate liquid tank thro...

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