CN103114108B - Method for preparing D-panthenol 16 ether monopalmitate by using lipase as catalyst - Google Patents
Method for preparing D-panthenol 16 ether monopalmitate by using lipase as catalyst Download PDFInfo
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- CN103114108B CN103114108B CN201210320480.0A CN201210320480A CN103114108B CN 103114108 B CN103114108 B CN 103114108B CN 201210320480 A CN201210320480 A CN 201210320480A CN 103114108 B CN103114108 B CN 103114108B
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Abstract
The invention relates to a method for preparing D-panthenol 16 ether monopalmitate by using lipase as a catalyst, belonging to the technical field of biological catalysis. The method comprises the following steps: by using hexamethylene as a reaction medium, carrying out enzymatic reaction on D-panthenol 16 ether and palmitinic acid by using lipase as a catalyst, wherein the conditions of the enzymatic reaction are as follows: the concentration of the substrate palmitinic acid is 50-200 g/L, the mol ratio of palmitinic acid to D-panthenol 16 ether (1.5-3):1, the mass ratio of palmitinic acid to lipase is 100:2-100:8, the enzymatic reaction temperature is 20-60 DEG C, and the reaction time is 12-24 hours; and after the enzymatic reaction finishes, filtering to recover the lipase, carrying out rotary evaporation under reduced pressure to remove the hexamethylene, and separating and purifying by column chromatography to obtain the D-panthenol 16 ether monopalmitate pure product, wherein the volume ratio of n-hexane:aether:acetic acid in the eluate is 89:10:1. The invention has the advantages of mild reaction conditions, favorable reaction selectivity, single reaction product and high conversion rate.
Description
Technical field
The invention belongs to the preparation field of D-panthenol 16 ether palmitinic acid monoesters, particularly relate to the method for the synthetic D-panthenol 16 ether palmitinic acid monoesters of a kind of enzyme-catalyzed change, belong to biocatalysis technology field.
Background technology
D-panthenol (lower structure
1.), chemistry (D)-N-(2,4-dihydroxyl-β, β dimethyl butyryl)-beta-amino propyl alcohol by name, is a kind of
the B family thing of supporting one's family, is commonly called as the former B5 of the thing of supporting one's family, be the dextrorotatory isomer of panthenol, be the same effect thing of D-VB5.Its biological activity is mainly manifested in D-panthenol and enters in human body and can be converted into pantothenic acid, and then closes mucous membrane and the hair luster of skin surface, will cause dermatosis and physiological barrier and lack D-panthenol.Become coenzyme A, promote the metabolism of human body protein, fat, carbohydrate, mucous membrane and the hair luster of protection skin surface, will cause dermatosis and physiological barrier and lack D-panthenol.D-panthenol derivative (lower structure
2.chemistry (D)-N-(2,4-dihydroxyl-β, β dimethyl butyryl) amino cetyl ether of-β-the third by name) be the derivative that has changed its side chain of D-panthenol, keep the derivative molecular of the skeleton three-dimensional arrangement of D-panthenol.Its R1 group is natural palm acid product.Using D-panthenol derivative is that new sheath amine ol skeleton structure is to reach synthetic new N-acyl sheath amine alcohol series material (lower structure
3.)
N-acyl sheath amine alcohol product has natural and synthesizes two kinds.The large cosmetics companies such as the U.S., Japan, France all widely apply N-acyl sheath amine alcohol to make makeup.Natural N-acyl sheath amine alcohol is very low at animal and plant body intensive amount, extracts difficulty, has limited the popularization of its application.Once from ox brain, extracted N-acyl sheath amine alcohol matter, but since 1986 " mad cow disease ", substituted by vegetalitas N-acyl sheath amine alcohol, it is in only promising 0.01%-0.02% left and right of rice, wheat, corn content.Mainly rely in the world at present the synthetic method synthetic of biological chemistry can realize its market requirement widely.Some major company is as the makeup for the nursing of skin, hair and nail by the plan N-acyl sheath amine alcohol matter of chemical preparations of Unilever company.The synthetic work of intending N-acyl sheath amine alcohol of artificial bio-membrane is mainly divided into two parts: 1) fatty acid esterification part, mainly contain and change fatty acid ester number, the change carbon chain lengths of lipid acid and the local structure of lipid acid reach the object of different application demand such as side chain and degree of unsaturation etc. change its character.2) by changing the skeleton structure of sheath amine alcohol such as the directly plan N-acyl sheath amine alcohol molecular series material of synthesizing new such as number and locus of hydroxyl.More successfully having QUEST INTERNATIONAL AUSTRALIA PTY Ltd(company of Britain) the product QUEST H of exploitation is 2004 just by the SCCP of European Union test (numbering SCCP/0852/04), and current production rate has exceeded 400 tons/year.
At present at chemical field, comparatively conventional macromole esterification technique is first prepared to complete esterification after acyl chlorides by sulfur oxychloride or phosgene mostly, this old processing condition that generally use easily produce a large amount of exhaust emissions, the transformation efficiency of its reaction is simultaneously limited, also conventionally causes the hypergeometric example use of raw material thereby does not possess competitive capacity.
The present invention is mainly the three-dimensional arrangement that changes sheath amine alcohol by D panthenol derivative (D-panthenol 16 ethers, lower structure 2), then obtains a new plan N-acyl sheath amine alcohol series material by the directed esterification of biological activity fat enzyme.Its object can reduce the dependence of its product to natural product raw material, is more conducive to its large-scale industrial production and application; And screen directional catalyzing technology by biological enzyme, thereby the transformation efficiency that can improve target product reaches to reduce costs and improves the competitive power of product in market, also will aspect low pollution environmental protection, embody its competitive edge simultaneously.
。
Summary of the invention
The object of this invention is to provide the method for the synthetic D-panthenol 16 ether palmitinic acid monoesters of organic phase system enzyme-catalyzed change, synthetic method of the present invention improves the selectivity of esterification, the productive rate of D-panthenol 16 ether palmitinic acid monoesters reaches more than 75%, and reaction conditions gentleness, the method reaction conditions is safe, gentle, purifying is easy, and step is few, is convenient to suitability for industrialized production.Reaction equation:
Technical scheme of the present invention: a kind of lipase-catalyzed method of preparing D-panthenol 16 ether palmitinic acid monoesters, carry out according to following step: (1) is taking cyclohexane as reaction medium, carry out enzymatic reaction with lipase-catalyzed D-panthenol 16 ethers and palmitinic acid, synthetic D-panthenol 16 ether palmitinic acid monoesters; The condition of wherein said enzymatic reaction is that substrate palmitinic acid is 50 ~ 200g/L, the mol ratio of palmitinic acid and D-panthenol 16 ethers is 1.5 ~ 3:1, the mass ratio of palmitinic acid and lipase is that 100:2 ~ 100:8 enzymatic reaction temperature is 20 ~ 60 DEG C, 12 ~ 24 hours reaction times;
(2) after enzymatic reaction finishes, filtered and recycled lipase, decompression rotary evaporation is removed cyclohexane, and through column chromatographic isolation and purification, elutriant is normal hexane: ether: acetic acid=89:10:1, obtain D-panthenol 16 ether palmitinic acid monoesters sterlings, purity reaches more than 94%.
The present invention has reaction conditions gentleness, good reaction selectivity, and reaction product is single, and transformation efficiency is high, and product safety, subsequent purification are processed the plurality of advantages such as simple easy.Therefore, the present invention provides new approach for Biological preparation D-panthenol 16 ether palmitinic acid monoesters.
Brief description of the drawings
The HPLC figure of Fig. 1 D-panthenol 16 ether palmitinic acid monoesters, the mass spectrum of Fig. 2 D-panthenol 16 ether palmitinic acid monoesters.
Embodiment
Lipase of the present invention comprises that Novozym 435(derives from
candida antarctica); Purchased from Novozymes Company.With specific embodiment, technical scheme of the present invention is described further below.
The present invention adopts HPLC to analyze the content of product D-panthenol 16 ether palmitinic acid monoesters in assaying reaction, and chromatographic condition is OD-H chiral column, 30 DEG C of column temperatures, and moving phase is V (normal hexane): V (Virahol)=90:10, flow velocity is 1mL/min.Detector is light scattering detector (ELSD).
embodiment 1
Synthesizing of D-panthenol 16 ether palmitinic acid monoesters: in 50mL tool plug ground Erlenmeyer flask, add respectively 1.9g palmitinic acid, 2g D-panthenol 16 ethers (mol ratio of palmitinic acid and D-panthenol 16 ethers is 1.5:1) and 10mL cyclohexane, lipase 0.1g, be placed in 30 DEG C of constant-temperature tables, 120rpm, reaction result is followed the tracks of and is detected and sampling HPLC analysis by thin-layer chromatography TLC.React after 24 hours, productive rate reaches 85%.Remove by filter lipase, cyclohexane is removed in 40-50 DEG C of underpressure distillation, obtains D-panthenol 16 ether palmitinic acid monoesters crude products.
With 200-300 order silica gel wet method dress post, elutriant is normal hexane: ether: acetic acid=89:10:1, wet method loading, TLC follows the tracks of wash-out process, the elutriant that contains single product obtaining is merged to evaporate to dryness, obtain white or flaxen monoesters crystal, obtain D-panthenol 16 ether palmitinic acid monoesters sterlings (purity is more than 96%), mass spectroscopy molecular weight is that its theoretical molecular of 626.8(is 627).
Fig. 1 be D-panthenol 16 ether palmitinic acid monoesters HPLC figure (HPLC testing conditions: OD-H chiral column, 30 DEG C of column temperatures,
v (normal hexane) : V ( virahol) =90:10, flow velocity is 1mL/min, ELSD detector), retention time is 2.576min.
Fig. 2 is panthenol 16 ether palmitinic acid monoesters sterling LC-MS figure, and the molecular weight of tetradecyl alcohol serine ester is 626.8, conforms to theoretical molecular 627.
embodiment 2
Synthesizing of D-panthenol 16 ether palmitinic acid monoesters: in 50mL tool plug ground Erlenmeyer flask, add respectively 3.8g palmitinic acid, 10mL cyclohexane and 2g D-panthenol 16 ethers (mol ratio of palmitinic acid and D-panthenol 16 ethers is 3:1), lipase 0.1g, be placed in 30 DEG C of constant-temperature tables, 120rpm, reaction result is followed the tracks of and is detected and sampling HPLC analysis by thin-layer chromatography TLC.React after 24 hours, productive rate reaches 88%.Remove by filter lipase, cyclohexane is removed in 40-50 DEG C of underpressure distillation, obtains D-panthenol 16 ether palmitinic acid monoesters crude products.Cross silicagel column by embodiment 1 method, obtain tetradecyl alcohol serine ester sterling (purity is more than 95%).
embodiment 3
Synthesizing of D-panthenol 16 ether palmitinic acid monoesters: take respectively 2g palmitinic acid and 2g D-panthenol 16 ethers, add the solvent that 10mL is different (acetone, normal hexane, methylene dichloride and tetrahydrofuran (THF)), be placed in 4 50mL tool plug ground Erlenmeyer flasks, then add respectively lipase 0.1g, be placed in 30 DEG C of constant-temperature tables, 120rpm, reaction result is followed the tracks of and is detected and sampling HPLC analysis by thin-layer chromatography TLC.React after 24 hours, productive rate reaches respectively 23%, 67%, 45% and 22%, removes by filter lipase, and 40-50 DEG C of underpressure distillation, except desolventizing, obtains D-panthenol 16 ether palmitinic acid monoesters and palmitinic acid mixture.Cross silicagel column by embodiment 1 method, obtain tetradecyl alcohol serine ester sterling (purity is more than 95%).
Claims (1)
1. a lipase-catalyzed method of preparing D-panthenol 16 ether palmitinic acid monoesters, it is characterized in that carrying out according to following step: (1) is taking cyclohexane as reaction medium, carry out enzymatic reaction with lipase-catalyzed D-panthenol 16 ethers and palmitinic acid, synthetic D-panthenol 16 ether palmitinic acid monoesters; The condition of wherein said enzymatic reaction is that substrate palmitinic acid is 50 ~ 200g/L, the mol ratio of palmitinic acid and D-panthenol 16 ethers is 1.5 ~ 3:1, the mass ratio of palmitinic acid and lipase is 100:2 ~ 100:8, and enzymatic reaction temperature is 20 ~ 60 DEG C, 12 ~ 24 hours reaction times;
(2) after enzymatic reaction finishes, filtered and recycled lipase, decompression rotary evaporation is removed cyclohexane, and through column chromatographic isolation and purification, elutriant is that volume ratio is counted normal hexane: ether: acetic acid=89:10:1, obtains D-panthenol 16 ether palmitinic acid monoesters sterlings;
Wherein, the lipase-catalyzed reaction equation of preparing D-panthenol 16 ether palmitinic acid monoesters is:
;
Wherein, the lipase described in step (1) is Novozym 435.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1223300A (en) * | 1998-11-05 | 1999-07-21 | 无锡轻工大学发酵工程发展公司 | Process for synthesizing ester from Rhizopus chinensis by using enzyme method |
| CN102161683A (en) * | 2011-02-24 | 2011-08-24 | 浙江工业大学 | Method for synthesizing sucrose-6-palmitate by using lipase through catalytic selectivity |
| DE102010061270A1 (en) * | 2010-12-15 | 2012-06-21 | Bundesanstalt für Materialforschung und -Prüfung (BAM) | Enzymatically catalyzed esterification of fatty acid component with hydroxyl group-containing organic component, comprises performing esterification reaction in a solvent-free emulsion in presence of lipase A |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008053051A2 (en) * | 2006-12-15 | 2008-05-08 | Haering Dietmar | Panthenol esters of unsaturated carboxylic acids |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1223300A (en) * | 1998-11-05 | 1999-07-21 | 无锡轻工大学发酵工程发展公司 | Process for synthesizing ester from Rhizopus chinensis by using enzyme method |
| DE102010061270A1 (en) * | 2010-12-15 | 2012-06-21 | Bundesanstalt für Materialforschung und -Prüfung (BAM) | Enzymatically catalyzed esterification of fatty acid component with hydroxyl group-containing organic component, comprises performing esterification reaction in a solvent-free emulsion in presence of lipase A |
| CN102161683A (en) * | 2011-02-24 | 2011-08-24 | 浙江工业大学 | Method for synthesizing sucrose-6-palmitate by using lipase through catalytic selectivity |
Non-Patent Citations (2)
| Title |
|---|
| 杨广花等.脂肪酶法催化胆固醇合成胆固醇棕榈酸酯的研究.《安徽农业科学》.2010,第38卷(第25期),第13565-13566页. |
| 脂肪酶法催化胆固醇合成胆固醇棕榈酸酯的研究;杨广花等;《安徽农业科学》;20100901;第38卷(第25期);第13565-13566页 * |
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