Equilibrium of chiral extraction of 4-nitro-d,l-phenylalanine with BINAP metal complexes

• Published in: Chemical papers 2014, Vol.68 (1), p.80-89
• Main Authors: Liu, Jia-Jia, Wu, Guo-Hui, Tang, Ke-Wen, Liu, Xiong, Zhang, Pan-Liang
• Format: Article
• Language: English
• Subjects: 4-nitro-phenylalanine; BINAP; Biochemistry; Biotechnology; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; enantioselective extraction; equilibrium formation; Industrial Chemistry/Chemical Engineering; Materials Science; Medicinal Chemistry; modelling; Original Paper
• ISSN: 0366-6352; 1336-9075; 1336-9075
• DOI: 10.2478/s11696-013-0419-4

The enantioselective extraction of 4-nitro-phenylalanine (Nphy) was studied with metal-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) complexes as the chiral selector. The complex with palladium (BINAP-Pd) exhibits the highest selectivity out of the selectors studied, which is solubilised in the organic phase and preferentially extracts d -Nphy from the aqueous phase. Efficiency of extraction depends, often substantially, on a number of process variables, including types of organic solvents and metal precursors, concentration of ligand, pH, and temperature. A reactive extraction model was established to interpret the experimental data. The equilibrium formation constants and other important parameters required by the model were determined experimentally. The equilibrium formation constants were 6.73 and 1.93 for d -Nphy and l -Nphy. By way of modelling and experiment, an optimal extraction condition with pH of 7 and BINAP-Pd concentration of 1 mmol L −1 was obtained with enantioselectivity ( α ) of 3.37, which was close to the maximum of 3.48, and a performance factor (pf) of 0.195. The model was verified experimentally with excellent results.