화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.31, 335-342, November, 2015
DOI10.1016/j.jiec.2015.07.007  Export Citation
Kinetics and mechanism of regioselective monoacetylation of 3-aryloxy-1,2-propandiols using immobilized Candida antarctica lipase
Sandip V. Pawar, and Ganapati D. Yadav†
  • Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai 400 019, India
E-mail:
Optically pure 3-aryloxy-1,2-propanediols are important intermediates in the synthesis of various pharmaceutical compounds. This study reports the kinetics and mechanism of lipase catalyzed regioselective monoacetylation of 3-aryloxy-1,2-propandiols. Regioselective monoacetylation of 3-(2-methylphenoxy) propane-1,2-diol was chosen as a model reaction and various commercially available lipases were screened as catalysts. Candida antarctica lipase B (Novozyme 435) was found to be the best catalyst among all considering the yield and excess of monoacetylated product. Important reaction parameters were optimized systematically to improve the rate of reaction and conversion, viz., speed of agitation, reaction solvent, catalyst loading, reaction temperature and mole ratio. The study of initial rate and progress curve demonstrated that the reaction obeys the ternary complex mechanism and 3-(2-methylphenoxy) propane-1,2-diol inhibits the reaction at higher concentrations. Theoretical predictions and experimental rates match very well based on non-linear regression analysis. Under optimized reaction conditions the study was further extended to regioselective monoacetylation of a variety of 3-(aryloxy)-1,2-propanediols.
Keywords:Immobilized lipase;3-Aryloxy-1,2-propanediol;Kinetic study;Enzyme catalysis;Regioselective monoacetylation;Ternary complex mechanism
  1. Park HG, Do JH, Chang HN, Biotechnol. Bioeng., 8, 1 (2003)
  2. Pawar SV, Yadav GD, Ind. Eng. Chem. Res., 53(19), 7986 (2014)
  3. Kumar S, Mohan U, Kamble AL, Pawar S, Banerjee UC, Bioresour. Technol., 101(17), 6856 (2010)
  4. Pawar SV, Meena VS, Kaushik S, Kamble A, Kumar S, Chisti Y, Banerjee UC, Biotechniques, 2, 319 (2012)
  5. Yadav GD, Sajgure AD, Dhoot SB, in: Bhattacharya SK (Ed.), Enzyme Mixtures and Complex Biosynthesis, Landes Biosciences, Austin, TX, 2007.
  6. Pawar SV, Yadav GD, J. Mol. Catal. B-Enzym., 101, 115 (2014)
  7. Sandoval M, Hoyos P, Cortes A, Bavaro T, Terrenic M, Hernaiz MJ, RSC Adv., 4, 55495 (2014)
  8. Yadav GD, Pawar SV, Appl. Microbiol. Biotechnol., 96(1), 69 (2012)
  9. Yadav GD, Devi KM, J. Am. Oil Chem. Soc., 78, 347 (2001)
  10. Xiao MT, Huang YY, Shi XA, Guo YH, Enzyme Microb. Technol., 37(6), 589 (2005)
  11. Ye N, Xu JH, J. Mol. Catal. B-Enzym., 9, 233 (2002)
  12. Zhang YY, Liu JH, Biochem. Eng. J., 54, 40 (2011)
  13. Theil F, Lemke K, Ballschuh S, Kunath A, Schick H, Tetrahedron: Asymmetry, 6, 1323 (1995)
  14. Yadav GD, Lathi PS, J. Mol. Catal. B-Enzym., 32, 107 (2005)
  15. Lee D, Williamson CL, Chan LN, Taylor MS, J. Am. Chem. Soc., 134(19), 8260 (2012)
  16. Yasmin T, Jiang T, Han BX, Catal. Lett., 116(1-2), 46 (2007)
  17. Ren B, Rahm M, Zhang X, Zhou Y, Dong H, J. Org. Chem., 79, 8134 (2014)
  18. Jing K, Duan R, Sun J, Wang S, Lu Y, Adv. Mater. Res., 690-693, 1218 (2013)
  19. Theil F, Weidner J, Ballschuh S, Kunath A, Schick H, J. Org. Chem., 59, 388 (1994)
  20. Oger C, Marton Z, Brinkmann Y, Bultel-Ponce V, Durand T, Graber M, Galano JM, J. Org. Chem., 75, 1892 (2010)
  21. Framis V, Camps F, Clapes P, Tetrahedron Lett., 45, 5031 (2004)
  22. Meena VS, Banerjee UC, Monatsh. Chem., 143, 951 (2012)
  23. Bevilaqua JV, Pinto JC, Lima LM, Barreiro EJ, Alves TLM, Freire DMG, Biochem. Eng. J., 21, 103 (2004)
  24. Pires-Cabrala P, da Fonseca MMR, Ferreira-Diasc S, Biochem. Eng. J., 48, 246 (2010)
  25. Su GD, Huang DF, Han SY, Zheng SP, Lin Y, Appl. Microbiol. Biotechnol., 86(5), 1493 (2010)
  26. Yadav GD, Borkar IV, J. Chem. Technol. Biotechnol., 48, 7915 (2009)
  27. Yadav GD, Dhoot SB, J. Mol. Catal. B-Enzym., 57, 34 (2009)
  28. Yadav GD, Devi KM, Chem. Eng. Sci., 59(2), 373 (2004)
  29. Sontakke JB, Yadav GD, J. Chem. Technol. Biotechnol., 86(5), 739 (2011)
  30. Yadav GD, Lathi PS, J. Mol. Catal. A-Chem., 223(1-2), 51 (2004)
  31. Acosta A, Filice M, Fernandez-Lorente G, Palomo JM, Guisan JM, Bioresour. Technol., 102(2), 507 (2011)
  32. Yadav GD, Pawar SV, J. Mol. Catal. B-Enzym., 109, 62 (2014)
  33. Shin SK, Sim JE, Kishimura H, Chun BS, J. Ind. Eng. Chem., 18(1), 546 (2012)
  34. Yang G, Wu JP, Xu G, Yang LR, Bioresour. Technol., 100(19), 4311 (2009)
  35. Masoumi HRF, Basri M, Kassim A, Abdullah DK, Abdollahi Y, Gani SSA, Rezaee M, J. Ind. Eng. Chem., 20(4), 1973 (2014)
  36. Yadav GD, Sajgure AD, Dhoot SB, J. Chem. Technol. Biotechnol., 83(8), 1145 (2008)
  37. Lee H, Haque ASMT, Kim SB, Lee YB, Chun BS, J. Ind. Eng. Chem., 20(3), 1097 (2014)
  38. Yadav GD, Borkar IV, Ind. Eng. Chem. Res., 47(10), 3358 (2008)
  39. Yadav GD, Jadhav SR, Microporous Mesoporous Mater., 86, 215 (2005)
  40. Prlainovic NZ, Bezbradica DI, Knezˇevic´-Jugovic ZD, Stevanovic SI, Ivic´ MLA, Uskokovic´ PS, Mijin DZ, J. Ind. Eng. Chem., 19(1), 279 (2013)
  41. Yadav GD, Pawar SV, Bioresour. Technol., 109, 1 (2012)
  42. Theil F, Ballschuh S, Kunath A, Schick H, Tetrahedron: Asymmetry, 2, 1031 (1991)
  43. Moussou P, Archelas A, Baratti J, Furstoss R, Tetrahedron: Asymmetry, 9, 1539 (1998)
  44. Turgut Y, Aral T, Hosgoren H, Tetrahedron: Asymmetry, 20, 2293 (2009)
  45. Gao J, Cui Y, Yu J, Lin W, Wang Z, Qian G, Dyes Pigment., 87, 204 (2010)
  46. Egri G, Kolbert A, Balint J, Fogassy E, Novak L, Poppe L, Tetrahedron: Asymmetry, 9, 271 (1998)
  47. Tanino T, Aoki T, Chung WY, Watanabe Y, Ogino C, Fukuda H, Kondo A, Appl. Microbiol. Biotechnol., 82(1), 59 (2009)
  48. Raza S, Fransson L, Hult K, Protein Sci., 10, 329 (2001)
  49. Jing Q, Kazlauskas RJ, Chirality, 20, 724 (2008)
  50. Kirk O, Christensen MW, Org. Proc. Res. Dev., 6, 446 (2002)
  51. Ollis DL, Cheah E, Cygler M, Dijkstra B, Frolow F, Franken SM, Harel M, Remington SJ, Silman I, Schrag J, Sussman JL, Verschueren KHG, Goldman A, Protein Eng., 5, 197 (1992)
  52. Uppenberg J, Oehrner N, Norin M, Hult K, Kleywegt GJ, Patkar S, Waagen V, Anthonsen T, Jones TA, Biochemistry, 34, 16838 (1995)
  53. Orrenius C, Hæffner F, Rotticci D, Ohrner N, Norin T, Hult K, Biocatal. Biotransform., 16, 1 (1998)