Kinetics of reaction extraction separation of 2-phenylbutyric acid enantiomers

doi:10.11949/j.issn.0438-1157.20161190

Abstract

Abstract:

Kinetics research on the reactive extraction of 2-phenylbutyric acid enantiomers using hydroxyethyl-β-cyclodextrin(HE-β-CD) as extractant was performed in a Lewis cell.A homogeneous reaction model and a two-film theory were employed to describe the mass transfer mechanism of the reactive extraction process.The process parameters affecting the initial extraction rate, including agitation speed, interfacial area, pH value of aqueous phase, initial concentration of 2-phenylbutyric acid(2-PBA) enantiomers and initial concentration of extractant, were separately studied.The results showed that the reaction between hydroxyethyl-β-cyclodextrin and 2-phenylbutyric acid was a fast reaction.It was found that the reaction was first order in 2-phenylbutyric acid and second order in hydroxyethyl-β-cyclodextrin.The forward rate constants for the extraction of(+)-2-phenylbutyric acid and(-)-2-phenylbutyric acid were 2.829×10^-4 and 1.803×10^-4m⁶·mol^-2·s^-1, respectively.The results were useful for the design and operation of reactive extraction process in large-scale production, and provide scientific basis for equipment design and process intensification.

Key words: kinetics, extraction, chemical reactive, 2-phenylbutyric acid

摘要：

通过恒界面池法进行了羟乙基-β-环糊精反应萃取2-苯基丁酸对映体的动力学研究。采用双膜理论和均相反应模型描述了萃取过程的相际传质机理，并考察了搅拌速率、界面面积、对映体初始浓度和萃取剂初始浓度等因素对2-苯基丁酸对映体的萃取动力学的影响。实验结果表明羟乙基-β-环糊精与2-苯基丁酸对映体之间的包合反应属于“快反应”；2-苯基丁酸对映体反应分级数为1，羟乙基-β-环糊精反应分级数为2；（+）-2-苯基丁酸和（-）-2-苯基丁酸在278 K下的反应速率常数分别为2.829×10^-4、1.803×10^-4 m⁶·mol^-2·s^-1。该萃取动力学研究为大规模生产中的反应萃取过程的设计和操作以及设备的设计和过程强化提供了科学的依据。

关键词: 动力学, 萃取, 化学反应, 2-苯基丁酸

CLC Number:

O643.12

JIANG Pan, ZHANG Panliang, ZENG Lelin, XU Weifeng, TANG Kewen. Kinetics of reaction extraction separation of 2-phenylbutyric acid enantiomers[J]. CIESC Journal, 2017, 68(1): 163-169.

蒋盼, 张盼良, 曾乐林, 许卫凤, 唐课文. 反应萃取分离2-苯基丁酸对映体的动力学[J]. 化工学报, 2017, 68(1): 163-169.

References 37

[1]	HEFNAWY M M, ABOUL-ENEIN H Y. A validated LC method for the determination of vesamicol enantiomers in human plasma using vancomycin chiral stationary phase and solid phase extraction[J]. J. Pharm. Biomed. Anal., 2004, 35(3):535-543.
[2]	GUXMÁN A, YUSTE F, TOSCANO R A, et al. Absolute configuration of (-)-5-benzoyl-1,2-dihydro-3H-pyrrolo[1,2-alpha]-pyrrole-l-carboxylic acid, the active enantiomer of ketorolac[J]. J. Med. Chem., 1986, 29(4):589-591.
[3]	MITSCHER L A., SHARMA P N, CHU D T W, et al. Chiral DNA gyrase inhibitors (Ⅱ):Asymmetric synthesis and biological activity of the enantiomers of 9-fluoro-3-methyl-10-(4-methyl-1-piperazinyl)-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid (ofloxacin)[J]. J. Med. Chem., 1987, 30(12):2283-2286.
[4]	PLENGE P, MELLERUP E T, HONORÉ T, et al. The activity of 25 paroxetine/femoxetine structure variants in various reactions, assumed to be important for the effect of antidepressants[J]. J. Pharm. Pharmacol., 1987, 39(11):877-882.
[5]	SHUM W P, CHEN J, CANNARSA M J. Synthesis and enantiomeric purity determination of chiral 3-benzylglycidol, a key synthon for HIV protease inhibitors[J]. Chirality, 1994, 6(8):681-684.
[6]	HALABI A, FERRAYOLI C, PALACIO M, et al. Validation of a chiral HPLC assay for (R)-salbutamol sulfate[J]. J. Pharm. Biomed. Anal., 2004, 34(1):45-51.
[7]	CERLETTI C, MANARINI S, COLOMA M, et al. The (+)-enantiomer is responsible for the antiplatelet and anti-inflammatory activity of (±)-indobufen[J]. J. Pharm. Pharmaco., 1990, 42(12):885-887.
[8]	VIEGAS R M C, AFONSO C A M, CRESPO J G, et al. Racemic resolution of propranolol in membrane contactors:modelling and process optimization[J]. J. Membr. Sci., 2007, 305(1/2):203-214.
[9]	GOURLAY M D, KENDRICK J, LEUSEN F J J. Predicting the spontaneous chiral resolution by crystallization of a pair of flexible nitroxide radicals[J]. Cryst. Growth. Des., 2008, 8(8):2899-2905.
[10]	HUERTA F F, BÄCKVALL J E. Enantioselective synthesis of β-hydroxy acid derivatives via a one-pot aldol reaction-dynamic kinetic resolution[J]. Org. Lett., 2001, 3(8):1209-1212.
[11]	GINESTA X, PERICAS M A, RIERA A. Straightforward entry to the pipecolic acid nucleus. enantioselective synthesis of baikiain[J]. Tetrahedron. Lett., 2002, 43(5):779-782.
[12]	MAKINO K, GOTO T, HIROKI Y, et al. Stereoselective synthesis of anti-β-hydroxy-α-amino acids through dynamic kinetic resolution[J]. Angew. Chem. Int. Ed., 2004, 43(7):882-884.
[13]	SCHURIG V. Separation of enantiomers by gas chromatography[J]. J. Chromatogr. A., 2001, 906(1/2):275-299.
[14]	GUO Z, WANG H Y, ZHANG Y. Chiral separation of ketoprofen on an achiral C8 column by HPLC using norvancomycin as chiral mobile phase additives[J]. J. Pharm. Biomed. Anal., 2006, 41(1):310-314.
[15]	WANG Z, CAI C Q, LIN Y T, et al. Enantioselective separation of ketoconazole enantiomers by membrane extraction[J]. Sep. Purif. Technol., 2011, 79(1):63-71.
[16]	KEURENTJES J T F, NABUURS L, VEGTER E A. Liquid membrane technology for the separation of racemic mixtures[J]. J. Membr. Sci., 1996, 113(2):351-360.
[17]	LOMSADZE K, MARTÍNEZ-GIRÓN A B, CASTRO-PUYANA M, et al. About the role of enantioselective selector-select and interactions and the mobilities of diastereomeric associates in enantiomer separations using CE[J]. Electrophoresis, 2009, 30(16) 2803-2811.
[18]	YU T, DU Y X, CHEN B. Evaluation of clarithromycin lactobionate as a novel chiral selector for enantiomeric separation of basic drugs in capillary electrophoresis[J]. Electrophoresis, 2011, 32(14):1898-1905.
[19]	HOLBACH A, GODDE J, MAHENDRARAJAH R, et al. Enantioseparation of chiral aromatic acids in process intensified liquid-liquid extraction columns[J]. AIChE J., 2015, 61(1):266-276.
[20]	STEENSMA M, KUIPERS N J M, DE HAAN A B, et al. Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols[J]. Chem. Eng. Sci., 2007, 62(5):1395-1407.
[21]	SCHUUR B, WINKELMAN J G M, HEERES H J. Equilibrium studies on enantioselective liquid-liquid amino acid extraction using a cinchona alkaloid extractant[J]. Ind. Eng. Chem. Res., 2008, 47(24):10027-10033.
[22]	TANG K W, FENG X F, ZHANG P L, et al. Experimental and model study on multistage enantioselective liquid-liquid extraction of ketoconazole enantiomers in centrifugal contactor separators[J]. Ind. Eng. Chem. Res., 2015, 54(35):8762-8771.
[23]	ZHANG X B, GUO C C, LI Z Z, et al. An optical fiber chemical sensor for mercury ions based on a porphyrin dimer[J]. Anal. Chem., 2002, 74(4):821-825.
[24]	PRELOG V, KOVA?EVI? M, EGLI M. Lipophilic tartaric acid esters as enantioselective ionophores[J]. Angew. Chem. Int. Ed., 1989, 28(9):1147-1152.
[25]	LYNAM C, JENNINGS K, NOLAN K, et al. Tuning and enhancing enantioselective quenching of calixarene hosts by chiral guest amines[J]. Anal. Chem., 2002, 74(1):59-66.
[26]	WEBB T H, WILCOX C S. Enantioselective and diastereoselective molecular recognition of neutral molecules[J]. Chem. Soc. Rev., 1993, 22(6):383-395.
[27]	SALEH M I, BARI M F, JAB M S, et al. Kinetics of lanthanum(Ⅲ) extraction from nitrate-acetato medium by Cyanex 272 in toluene using the single drop technique[J]. Hydrometallurgy, 2002, 67(1/2/3):45-52.
[28]	EI-HEFNY N E, EI-DESSOUKY S. Equilibrium and kinetic studies on the extraction of gadolinium(Ⅲ) from nitrate medium by di-2-ethylhexylphosphoric acid in kerosene using a single drop technique[J]. J. Chem. Technol. Biotechnol., 2006, 81(3):394-400.
[29]	YULIZAR Y, OHASHI A, NAGATANI H, et al. Kinetic study of Ni(Ⅱ) and Zn(Ⅱ) complexation with a pyridylazo extractant by a centrifugal liquid membrane method[J]. Anal. Chim. Acta., 2000, 419(1):107-114.
[30]	NAGATANI H, WATARAI H. Direct spectrophotometric measurement of demetalation kinetics of 5,10,15,20-tetraphenylporphyrinatozinc(Ⅱ) at the liquid-liquid interface by a centrifugal liquid membrane method[J]. Anal. Chem., 1998, 70(14):2860-2865.
[31]	PLUCINSKI P, NITSCH W. The calculation of permeation rates through supported liquid membranes based on the kinetics of liquid-liquid extraction[J]. J. Membr. Sci., 1988, 39(1):43-59.
[32]	JÖNSSON J Å, LÖKVIST P, AUDUNSSON G, et al. Mass transfer kinetics for analytical enrichment and sample preparation using supported liquid membranes in a flow system with stagnant acceptor liquid[J]. Anal. Chim. Acta., 1993, 277(1):9-24.
[33]	CICERI D, MASON L R, HARVIE D J E, et al. Extraction kinetics of Fe(Ⅲ) by di-(2-ethylhexyl) phosphoric acid using a Y-Y shaped microfluidic device[J]. Chem. Eng. Res. Des., 2014, 92(3):571-580.
[34]	EI-HEFNY N E. Kinetics and mechanism of extraction and stripping of neodymium using a Lewis cell[J]. Chem. Eng. Process., 2007, 46(7):623-629.
[35]	WASEWAR K L, HEESINK A B M, VERSTEEG G F, et al. Reactive extraction of lactic acid using alamine 336 in MIBK:equilibria and kinetics[J]. J. Biotechnol., 2002, 97(1):59-68.
[36]	BORA M M, BORTHAKUR S, RAO P G, et al. Study on the reactive extraction and stripping kinetics of certain β-lactam antibiotics[J]. Chem. Eng. Process., 2008, 47(1):1-8.
[37]	DORAISWAMY L K. Heterogeneous Reactions:Analysis, Examples and Reactor Design:Vol. 2[M]//SHARMA M M. New York:John Wiley & Sons Inc., 1984:17-45.