在[BMIM][PF_6]离子液中外消旋DL-薄荷醇催化手性选择性酯化

摘要在疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM][PF6])和正己烷介质中分别进行了酯酶Candida rugosa催化外消旋(DL)-薄荷醇的手性选择性酯化反应。试验结果表明,[BMIM][PF6]中的酯化反应速率,酯化转化率和手性选择性都优于正己烷。当加酶量大于130 U/mL时,离子液体中的酯化反应在2~8 h范围内出现最大转化率;在正己烷中,酶用量在67~167 U/mL范围内,其酯化转化率也随时间呈逐渐上升,无极值出现。另外,在离子液体中,水含量的增加在一定程度上可以增大酯化手性选择性,但反应速率会被降低。

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	袁毅
	姜晓妍

关键词：酯酶手性选择性酯化离子液体

Abstract： Enantioselective esterification of(DL)-menthol by Candida rugosa lipase was studied in ionic liquid of 1-butyl-3-methyl-imidazolium hexafluorophosphate and hexane respectively using propionic anhydride as an acylating agent.It was found that the reaction rate was much higher in the ionic liquid than those in hexane.Moreover,the conversion and enantioselectivity in the ionic liquid were also higher than that in hexane.Maximal percentage of conversion was obtained in 2 h to 8 h in the ionic liquid when the enzyme load was higher than 130 U/mL.In hexane,the reaction percentage of conversion did not reach a maximum point when the enzyme load was as high as 167 U/mL.Moreover,higher water content in the ionic liquid was favorable for obtaining higher enantioselectivity,however it lowered the reaction rate and(DL)-menthol conversion.

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Received 2008-11-15; published 2008-11-15

引用本文:

袁毅;姜晓妍;.在[BMIM][PF_6]离子液中外消旋DL-薄荷醇催化手性选择性酯化[J]. 化学工业与工程, 2008,25(6): 493-498

YUAN Yi,JIANG Xiao-yan.Enantioselective Esterification of(DL)-Menthol by Lipase in Ionic Liquid[BMIM][PF_6][J]. Chemcial Industry and Engineering, 2008,25(6): 493-498

[1]	ROGERS R D,SEDDON K R.Ionic Liquids[C]∥Industrial Applications to Green Chemistry.ACS Symp.Series 818,American Chemical Society,Washington DC,2002.
[2]	SHELDON R A.Biocatalysis in ionic liquids[J].GreenChemistry,2002,4(2):147-151.
[3]	袁毅,白姝,姜晓妍,等.离子液体中酶催化反应的研究进展[J].化工进展,2005,24(7):701-707.
[4]	WASSERSCHEID P,KEIM W.Ionic liquids:New“solutions”for transition metal catalysis[J].Angew ChemInt Ed Engl,2000,39(21):3 772-3 789.
[5]	SHELDON R.Catalytic reactions in ionic liquids[J].Chem Comm(Camb),2001(1):2 399-2 407.
[6]	ERBELDINGER M,MESIANO A J,RUSSELL A J.Enzymatic catalysis of formation of Z-aspartame in ionicliquid:An alternative to enzymatic catalysis in organicsolvents[J].Biotechnol Prog.2000,16(6):1-
[7]	ECKSTEIN M,SESING M,KRAGL U.At low wateractivity-αchymotrypsin is more active in an ionic liquidthan in non-ionic organic solvents[J].Biotechnol Lett.2002,24(11):867-872
[8]	MATTIAS P,UWE T B.Increased stability of an esterasefrom Bacillus stearothermophilus in ionic liquids ascompared to organic solvents[J].J Mol Catalysis B:Enzymatic.2003,22(1/2):21-27
[9]	KIM M J,CHOI M Y,LEE J K.Enzymatic selectiveacylation of glycosides in ionic liquids:significantlyenhanced reactivity and regioselectivity[J].J Mol CatalysisB:Enzymatic.2003,26(3/6):115-118
[10]	ITOH T,NISHIMURA Y,OUCH N I.1-Butyl-2,3-dimethylimidazolium tetrafluoroborate:The most desirableionic liquid solvent for recycling use of enzyme in lipase-catalyzed transesterification using vinyl acetate as acyl donor[J].J Mol Catalysis B:Enzymatic.2003,26(3/6):41-45
[11]	NARA S J,HARJANI J R,SALUNKHE M M.Lipase-catalysed transesterification in ionic liquids and organicsolvents:A comparative study[J].Tetrahedron Lett,2002,43:2 979-2 982.
[12]	袁毅,白姝,姜晓妍.离子液体和有机溶剂中薄荷醇催化选择性酯化[J].化学工业与工程.2006,23(6):480-485 浏览
[13]	KRZYSZTOF O,ERYKA G J,MICHEL T.Ionic liquids asa new reaction medium for oxidase-peroxidase-catalyzedsulfoxidation[J].Tetrahedron:Asymmetry,2003,14(17):2 487-2 490.
[14]	CHO S W,RHEE J S.Immobilization of lipase for effectiveinteresterification of fats and oils in organic solvent[J].Biotechnol Bioeng.1993,41(2):204-210
[15]	HUDDLESTON J G,WILLAUER H D,SWATLOKI R P.Room temperature ionic liquids as novel media for“clean”liquid-liquid extraction[J].J Chem Soc Chem Comm,1998,16:1 765-1 766.
[16]	PARK S,KAZLAUSKAS R J.Improved preparation anduse of room temperature ionic liquids in lipase-catalyzedenantio-and regioselective acylations[J].J Org Chem,2001,66(25):8 395-8 401.
[17]	STRAATHOF A,JONGEJAN J.The enantiomeric ratio:origin,determination and prediction[J].Enzyme MicrobTechnol.1997,21(8):559-571
[18]	ATHAWALE V,MANJREKAR N,ATHAWALE M.Enzymatic synthesis of chiral menthyl methacrylate monomerby pseudomonas cepacia lipase catalysed resolution of(DL)-menthol[J].J Mol Catalysis B:Enzymatic.2001,16(3/4):169-173
[19]	WU W H,AKOH C C,PHILLIPS R S.Lipase-catalyzedstereoselective esterification ofD-Lmenthol in organicsolvents using acid anhydrides as acylating agents[J].Enzyme Microb Technol.1996,18(7):536-539
[20]	CHARLES M G.New developments in catalysis using ionicliquids[J].Applied Catalysis A:General.2001,222(1/2):101-117
[21]	BONHOTE P,DIAS A P,PAPAGEORGIOU N.Hydrophobic,highly conductive ambient temperature ionicliquids[J].Inorg Chem.1996,35(5):1-
[22]	BARROS R,WEHTJE E,ADLERCREUTZ P.Masstransfer studies on immobilized-αchymotrypsin biocatalystsprepared by deposition for use in organic medium[J].Biotechnol Bioeng.1998,59(3):364-373
[23]	DIEGO T D,LOZANO P,GMOUH S,et al.Understanding structure-stability relationships ofCandidaantartica LipaseB in ionic liquids[J].Biomacromolecules.2005,6(3):1-
[24]	ZAKS A,KLIBANOV A M.Enzyme-catalyzed processes inorganic solvents[J].Proc Natl Acad Sci USA,1985,82(10):3 192-3 196.
[25]	KAFTZIK N,WASSERSCHEID P,KRAGL U.Use of ionicliquids to increase the yield and enzyme stability in theβ-galactosidase catalysed synthesis of N-acetyllactosamine[J].Org Proc Res Dev.2002,6(4):553-557
[26]	HOWARTH J,PARAIC J.Immobilized baker’s yeastreduction of ketones in an ionic liquid,[BMIM][PF6]andwater mix[J].Tetrahedron Lett,2001,42(42):7 517-7 519.
[27]	WEHTJE E,COSTES D,ADLERCREUTZ P.Enantio-selectivity of lipases:Effects of water activity[J].J MolCatalysis B:Enzymatic.1997,3(5):221-230
[28]	HANSSON T,ANDERSSON M,WEHTJE E.Influence ofwater activity on the competition between-βglycosidase-catalysed transglycosylation and hydrolysis in aqueoushexanol[J].Enzyme Microb Technol.2001,29(8):527-534