CN100427608C - Process for resolution preparation of allyl furfural alcohol with optical activity by enzyme method - Google Patents
Process for resolution preparation of allyl furfural alcohol with optical activity by enzyme method Download PDFInfo
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- CN100427608C CN100427608C CNB2006101545769A CN200610154576A CN100427608C CN 100427608 C CN100427608 C CN 100427608C CN B2006101545769 A CNB2006101545769 A CN B2006101545769A CN 200610154576 A CN200610154576 A CN 200610154576A CN 100427608 C CN100427608 C CN 100427608C
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- furfuralcohol
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Abstract
The invention discloses a method for preparing allyl-furfurl alcohol with optical activity through enzymatic resolution. The method comprises the following steps: adding 0.065-0.800mol/L racemic allyl-furfurl, 0.2-1.0mmol acyl donor reagent and 3-10ml organic solvent into a reaction container, adding 0.03-0.55g enzyme, stirring for reaction at 20DEG C-50DEG C for 8-80h to obtain R-allyl-furfurl and S-allyl-furfurl. The invention has the advantages of mild reaction conditions, high converting rate, good reaction selectivity, highly pure product of S-allyl-furfurl, wide suitable reaction temperature (can bring out a reaction at normal temperature), simple operation, and simple equipments. The invention is carried out in organic solvent, thus, the enzyme activity is stable, not easy to lose, and can be used repeatedly.
Description
Technical field
The present invention relates to a kind of method of process for resolution preparation of allyl furfural alcohol with optical activity by enzyme.
Background technology
Optical activity allyl group furfuralcohol is a kind of chiral intermediate with significant application value, and it can synthesize multiple important compound, and (Tashiro, Kazuo are with a wide range of applications in fields such as medicine, agricultural chemicals and spices; Tanaka, Kunihiko.JP 63035569; Tashiro, Kazuo; Tanaka, Kunihiko.JP63030480; Tashiro, Kazuo; Tanaka, Kunihiko.EP 247589).
According to reaction process, the method for preparing optical activity allyl group furfuralcohol at present mainly is to utilize the direct synthesis of optically active allyl group of chirality chemical catalyst catalysis asymmetric catalysis synthesis furfuralcohol.The chiral catalyst of having reported have (salen) Cr (III) (as Kwiatkowski, Piotr; Chaladaj, Wojciech; Jurczak, Janusz.Tetrahedron (2006), 62 (21), 5116-5125 and Kwiatkowski, Piotr; Jurczak, Janusz.Synlett (2005), (2) are reported among the 227-230), In (OTf) 3 and chirality PYBOX ligand complex (as Lu, Jun; Ji, Shun-Jun; Loh, Teck-Peng.Chemical Communications (2005), (18), and Lu, Jun; Ji, Shun-Jun; Loh, Teck-Peng.Organic Letters (2005), 7 (1), 159-161.2345-2347 middle report), often reaction conditions is comparatively harsh yet utilize above-mentioned chemical chiral catalyst to prepare single enantiomer, and chiral catalyst costs an arm and a leg, so production difficulty and cost are higher.
Summary of the invention
The purpose of this invention is to provide a kind of enzyme catalysis transesterification and split the method for preparing optical activity allyl group furfuralcohol.
Method is the allyl group furfuralcohol with the 0.065-0.800mol/L racemization; 0.2-1.0mmol acry radical donor class reagent and 3-10ml organic solvent join in the reaction vessel; add the 0.03-0.55g enzyme then; under 20 ℃-50 ℃ temperature of reaction; stirring reaction 8-80h obtains R-allyl group furyl methyl ester and S-allyl group furfuralcohol.
The present invention be by with allyl group furfuralcohol and acry radical donor class agent dissolves in organic solvent; add enzyme then, under the katalysis of enzyme, asymmetric transesterification takes place in allyl group furfuralcohol and acry radical donor class reagent; acquisition has the S-allyl group furfuralcohol of high optical activity; this reaction conditions gentleness, transformation efficiency height, good reaction selectivity; the reaction broad application temperature range; and can carry out at normal temperatures, easy to operate, equipment is simple.The present invention realizes that in organic solvent enzyme activity is stable, is difficult for running off, and is reusable.Utilize enzyme process catalysis to split the method for preparing optical activity allyl group furfuralcohol at present and still do not have report.
Embodiment
Used acry radical donor reagent is fatty acid ester, acid anhydrides etc. among the present invention.Organic solvent is the mixed organic solvents that a kind of or wherein multiple mutual mixing in normal hexane, toluene, benzene, isopropyl ether, vinyl-acetic ester, methylene dichloride, chloroform, dioxane, hexanaphthene, normal heptane, tetrahydrofuran (THF) or the methyl tertiary butyl ether obtains.Used lipase can be commercial enzyme, such as deriving from pure enzyme or the immobilized enzyme that Alcaligenes sp., Pseudomonas sp. and Novozym 435 etc. have the highly selective catalytic capability; After also can being the microorganism or process microorganism culturing of fermentation culture, through the thick enzyme of initial gross separation purifying, such as the homemade thick enzyme that derives from candiyeast Candida in laboratory.Can contain minor amount of water in the organic solvent of the present invention, the water that contains 0%-2% weight usually in the organic solvent can react, but may influence the optical purity and the transformation efficiency of product.
The reaction implementation process is as follows:
In order to prevent the volatilization of reactant and solvent, be reflected in the airtight container and carry out.Allyl group furfuralcohol, acry radical donor reagent, organic solvent and enzyme with racemization during reaction successively join in the reactor; as previously mentioned; used acry radical donor reagent is fatty acid ester, acid anhydrides; the acry radical donor reagent of other structures also can be used as reaction substrate; but speed of reaction is slower, enumerates no longer one by one at this.Used organic solvent can be common solvent such as aromatic hydrocarbons, substituted arene, alkane, halogenated alkane, ether or ketone, comprises that above-mentioned solvent mixes the mixed solvent of gained mutually, as long as used organic solvent is an inert to reaction.Used lipase can be commercialization free-fat enzyme or commercial immobilized lipase; After also can being the microorganism or process microorganism culturing of fermentation culture, through the thick enzyme of initial gross separation purifying.Earlier allyl group furfuralcohol, acry radical donor reagent and enzyme are added according to the mol ratio of predefined allyl group furfuralcohol and acry radical donor reagent and the amount ratio of allyl group furfuralcohol and enzyme before the reaction; add solvent then; reactor is sealed; control reaction temperature finishes reaction 0 ℃-70 ℃ (recommending to use 20 ℃-50 ℃) behind the stirring reaction 8-80h.When temperature of reaction was higher, speed of reaction was very fast, but the selectivity of the enzymic catalytic reaction of part kind slightly reduces.The transformation efficiency of product and enantiomeric purity gas Chromatographic Determination, mark in n-dodecane is done.Transformation efficiency is defined as the per-cent of the mole number of the substrate that adds when the product mole number that obtains after reaction finishes begins with reaction; The calculation formula of the enantiomeric purity of product R-allyl group furyl methyl ester is: e.e.%=(R-S)/(R+S) * 100%, and wherein S represents the quality of S-allyl group furyl methyl ester, and R-represents the quality of R-allyl group furyl methyl ester.
Embodiment 1: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.065mol/L (39.52mg) allyl group furfuralcohol, the 4ml vinyl-acetic ester joins in the reactor of 5ml, add 0.048g lipase (deriving from Alcaligenes sp.) then, stirring reaction 8h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 49.5%, the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%, and the e.e.% value of S-allyl group furfuralcohol is 97.8%; Stirring reaction 10h, the transformation efficiency of reaction are 51.2%, and this moment, the e.e.% value of S-allyl group furfuralcohol was 99.9%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 95.1%.
In this reaction, vinyl-acetic ester had not only been done acry radical donor but also the double solvent of doing.
Embodiment 2: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 50 ℃ with 0.453mol/L (206.57mg) allyl group furfuralcohol, the 3ml vinyl-acetic ester joins in the reactor of 5ml, add 0.050g lipase (deriving from Alcaligenes sp.) then, stirring reaction 48h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 49.0%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 97.0%.
In this reaction, vinyl-acetic ester had not only been done acry radical donor but also the double solvent of doing.
Embodiment 3: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 45 ℃ with 0.800mol/L (1216.00mg) allyl group furfuralcohol, the 10ml vinyl-acetic ester joins in the reactor of 25ml, add 0.069g lipase (deriving from Alcaligenes sp.) then, stirring reaction 46h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 48.4%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%.
In this reaction, vinyl-acetic ester had not only been done acry radical donor but also the double solvent of doing.
Embodiment 4: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 20 ℃ with 0.316mol/L (144.10mg) allyl group furfuralcohol, the 3ml vinyl-acetic ester joins in the reactor of 5ml, add 0.051g lipase (deriving from Alcaligenes sp.) then, stirring reaction 49h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 49%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 61.0%.
In this reaction, vinyl-acetic ester had not only been done acry radical donor but also the double solvent of doing.
Embodiment 5: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.108mol/L (49.25mg) allyl group furfuralcohol, 0.200mmol vinyl-acetic ester (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 1.6/1), 3ml methylene dichloride join in the reactor of 5ml, add 0.033g lipase (deriving from Alcaligenes sp.) then, stirring reaction 66h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 49.1%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%.
Embodiment 6: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 45 ℃ with 0.065mol/L (39.52mg) allyl group furfuralcohol, the 4ml vinyl-acetic ester joins in the reactor of 5ml, add 0.032g lipase (the homemade thick enzyme in laboratory then, derive from Candidarugosa), stirring reaction 26h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 49.8%, the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%.
In this reaction, vinyl-acetic ester had not only been done acry radical donor but also the double solvent of doing.
Embodiment 7: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.073mol/L (33.56mg) allyl group furfuralcohol, 0.552mmol vinyl-acetic ester (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 2/5), the 3ml normal hexane joins in the reactor of 5ml, add 0.040g lipase (the homemade thick enzyme in laboratory then, derive from Candidarugosa), stirring reaction 80h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 47.6%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%.
Embodiment 8: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 35 ℃ with 0.071mol/L (32.37mg) allyl group furfuralcohol, 0.426mmol vinyl-acetic ester (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 1/2), 3ml toluene joins in the reactor of 5ml, add 0.040g lipase (the homemade thick enzyme in laboratory then, derive from Candida rugosa), stirring reaction 50h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 48.6%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%.
Embodiment 9: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.091mol/L (41.27mg) allyl group furfuralcohol, 0.543mmol vinyl-acetic ester (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 1/2), the 3ml isopropyl ether joins in the reactor of 5ml, add 0.059g lipase (the homemade thick enzyme in laboratory then, derive from Candidarugosa), stirring reaction 47h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 46.6%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%.
Embodiment 10: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.647mol/L (984.50mg) allyl group furfuralcohol, the 10ml vinyl-acetic ester joins in the reactor of 25ml, (resolvase is the homemade thick enzyme in laboratory to add the 0.550g immobilized lipase then, derive from Candida rugosa), stirring reaction 72h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 45.6%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.1%.
In this reaction, vinyl-acetic ester had not only been done acry radical donor but also the double solvent of doing.
Embodiment 11: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 45 ℃ with 0.065mol/L (39.52mg) allyl group furfuralcohol, 1.250mmol vinyl-acetic ester and 4ml hexanaphthene join in the reactor of 10ml, add 0.045g lipase (the homemade thick enzyme in laboratory then, derive from Candida rugosa), stirring reaction 68h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 46.0%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 94.9%.
Embodiment 12: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.073mol/L (33.56mg) allyl group furfuralcohol, 0.552mmol vinyl-acetic ester (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 2/5), 3ml benzene joins in the reactor of 5ml, add 0.040g lipase (the homemade thick enzyme in laboratory then, derive from Candida rugosa), stirring reaction 80h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 47.6%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 99.0%.
Embodiment 13: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.083mol/L (31.40mg) allyl group furfuralcohol, 0.817mmol butylacetate (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 1/4), 2.5ml methyl tertiary butyl ether joins in the reactor of 5ml, add 0.0876g lipase (the homemade thick enzyme in laboratory then, derive from Candidarugosa), stirring reaction 20h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 47.6%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 98.8%.
Embodiment 14: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 35 ℃ with 0.065mol/L (39.52mg) allyl group furfuralcohol, 1.000mmol vinyl-acetic ester (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 1/5), 3ml normal heptane join in the reactor of 5ml, add 0.051g lipase (deriving from Pseudomonas sp.) then, stirring reaction 30h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 49%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 94.0%.
Embodiment 15: the enzyme catalysis transesterification split preparation S-allyl group furfuralcohol under 40 ℃ with 0.072mol/L (27.50mg) allyl group furfuralcohol, 0.775mmol diacetyl oxide and 2ml tetrahydrofuran (THF) join in the reactor of 5ml, add 0.0457g lipase (deriving from Novozym 435) then, stirring reaction 26h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 47.3%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 95.3%.
Embodiment 16: the enzyme catalysis transesterification splits preparation S-allyl group furfuralcohol
Under 40 ℃ with 0.072mol/L (27.50mg) allyl group furfuralcohol, 0.904mmol vinyl-acetic ester (mol ratio of allyl group furfuralcohol and vinyl-acetic ester is 1/5) and 2.5ml chloroform join in the reactor of 5ml, add 0.0457g lipase (deriving from Novozym 435) then, stirring reaction 46h, the content gas chromatographic analysis of R-allyl group furfuralcohol acetic ester in the reaction solution and S-allyl group furfuralcohol acetic ester, the transformation efficiency of reaction is 47.3%, and the e.e.% value of R-allyl group furfuralcohol acetic ester is 95.3%.
Claims (2)
1. an enzyme catalysis splits the method for preparing optical activity allyl group furfuralcohol, it is characterized in that: with the allyl group furfuralcohol of 0.065-0.800mol/L racemization, 0.2-1.0mmol vinyl-acetic ester and 3-10ml organic solvent join in the reaction vessel, add 0.03-0.55g lipase then, under 20 ℃-50 ℃ temperature of reaction, stirring reaction 8-80h obtains R-allyl group furyl methyl ester and S-allyl group furfuralcohol.
2. a kind of enzyme catalysis according to claim 1 splits the method for preparing optical activity allyl group furfuralcohol, it is characterized in that described organic solvent is normal hexane, toluene, benzene, isopropyl ether, vinyl-acetic ester, methylene dichloride, chloroform, hexanaphthene, normal heptane or methyl tertiary butyl ether.
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| CN101503729B (en) * | 2008-12-08 | 2012-10-31 | 浙江大学 | Enzymatic resolution method of dl 1-phenylethanol compounds |
| CN104830943B (en) * | 2015-03-18 | 2019-03-01 | 上海皓元生物医药科技有限公司 | A kind of preparation method of Ai Er ossification alcohol intermediate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008410A (en) * | 1986-05-28 | 1991-04-16 | Sumitomo Chemical Company, Limited | Method for producing furfuryl alcohols |
| CN1656230A (en) * | 2002-03-22 | 2005-08-17 | 陶氏环球技术公司 | Enzymatic resolution of propylene glycol alkyl (or aryl) ethers and ether acetates |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008410A (en) * | 1986-05-28 | 1991-04-16 | Sumitomo Chemical Company, Limited | Method for producing furfuryl alcohols |
| CN1656230A (en) * | 2002-03-22 | 2005-08-17 | 陶氏环球技术公司 | Enzymatic resolution of propylene glycol alkyl (or aryl) ethers and ether acetates |
Non-Patent Citations (4)
| Title |
|---|
| Lipase-catalyzed domino kinetic resolution/intramolecularDiels-Alder reaction:one-pot synthesis of optically active7-oxabicyclo[2.2.1]heptenes from furfuryl alcohols andbeta-substituted acrylic acids. Shuji Akai, et al.Chem. Eur. J.,No.18. 2002 |
| Lipase-catalyzed domino kinetic resolution/intramolecularDiels-Alder reaction:one-pot synthesis of optically active7-oxabicyclo[2.2.1]heptenes from furfuryl alcohols andbeta-substituted acrylic acids. Shuji Akai, et al.Chem. Eur. J.,No.18. 2002 * |
| 酶法合成光学活性化合物. 李玉新.精细化工中间体，第34卷第1期. 2004 |
| 酶法合成光学活性化合物. 李玉新.精细化工中间体，第34卷第1期. 2004 * |
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Assignee: Changzhou Kangmei Chemical Co., Ltd. Assignor: Zhejiang University Contract fulfillment period: 2009.6.12 to 2014.6.9 Contract record no.: 2009320001108 Denomination of invention: Process for resolution preparation of allyl furfural alcohol with optical activity by enzyme method Granted publication date: 20081022 License type: Exclusive license Record date: 20090716 |
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