SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2021, Vol. 32 ›› Issue (4): 315-323.DOI: 10.1016/j.cjche.2020.06.013

• Biotechnology and Bioengineering • Previous Articles     Next Articles

An efficient route towards R-2-phenoxypropionic acid synthesis for biotransformative production of R-2-(4-hydroxyphenoxy)propionic acid

Haiyan Zhou, Yizuo Li, Rui Jiang, Xianlin Wang, Yuanshan Wang, Yaping Xue, Yuguo Zheng   

  1. Key Laboratory of Bioorganic Synthesis of Zhejiang Province, College of Biotechnology and Bioengineering, Zhejiang University of Technology, Hangzhou 310014, China;Engineering Research Center of Bioconversion and Biopurification of Ministry of Education, Zhejiang University of Technology, Hangzhou 310014, China;The National and Local Joint Engineering Research Center for Biomanufacturing of Chiral Chemicals, Zhejiang University of Technology, Hangzhou 310014, China
  • Received:2020-02-17 Revised:2020-05-14 Online:2021-06-19 Published:2021-04-28
  • Contact: Yaping Xue

An efficient route towards R-2-phenoxypropionic acid synthesis for biotransformative production of R-2-(4-hydroxyphenoxy)propionic acid

Haiyan Zhou, Yizuo Li, Rui Jiang, Xianlin Wang, Yuanshan Wang, Yaping Xue, Yuguo Zheng   

  1. Key Laboratory of Bioorganic Synthesis of Zhejiang Province, College of Biotechnology and Bioengineering, Zhejiang University of Technology, Hangzhou 310014, China;Engineering Research Center of Bioconversion and Biopurification of Ministry of Education, Zhejiang University of Technology, Hangzhou 310014, China;The National and Local Joint Engineering Research Center for Biomanufacturing of Chiral Chemicals, Zhejiang University of Technology, Hangzhou 310014, China
  • 通讯作者: Yaping Xue

Abstract: R-2-(4-hydroxyphenoxy)propionic acid (R-HPPA) is a key intermediate for the synthesis of classic herbicides with high selectivity against grassy weed. The main route for R-HPPA biosynthesis is to hydroxylate the substrate R-2-phenoxypropionic acid (R-PPA) at C-4 position with microbes. In order to provide sufficient R-PPA for the industrial production of R-HPPA, an effective R-PPA synthesis method was established and optimized in this work. The synthesis process mainly consisted of two steps:(1) synthesis of S-2-chloropropionic acid from L-alanine via diazotization and chlorination reactions; and (2) synthesis of R-PPA from S-2-chloropropionic acid and phenol via etherification reaction. The optimal reaction conditions were as follows:HCl:NaNO2:KI:L-Ala=2.0:1.2:0.7:1.0 (in molar), 125℃ reflux for 1.5 h, with KI as catalyst, and KI:S-2-chloropropionic acid:phenol=0.075:1.2:1.0 (in molar). Under these conditions, an improved molar conversion rate (74.9%, calculated in phenol) was achieved. After extraction using anionic exchange resin Amberlite IRA-400 (CI), R-PPA product with a purity of 95.08% was obtained. The purified R-PPA was identified and evaluated in the application of the biotransformative production of R-HPPA. The results indicated that the synthesized R-PPA supported the R-HPPA biosynthesis with a comparable yield as that of the standard R-PPA. The R-PPA synthesis method provided herein exhibited the advantages of low price and easy availability of raw materials, less toxicity of reagents, simple manipulations, and low equipment/instrument requirements.

Key words: R-2-phenoxypropionic acid, R-2-(4-hydroxyphenoxy)propionic acid, Biosynthesis, S-2-chloropropionic acid

摘要: R-2-(4-hydroxyphenoxy)propionic acid (R-HPPA) is a key intermediate for the synthesis of classic herbicides with high selectivity against grassy weed. The main route for R-HPPA biosynthesis is to hydroxylate the substrate R-2-phenoxypropionic acid (R-PPA) at C-4 position with microbes. In order to provide sufficient R-PPA for the industrial production of R-HPPA, an effective R-PPA synthesis method was established and optimized in this work. The synthesis process mainly consisted of two steps:(1) synthesis of S-2-chloropropionic acid from L-alanine via diazotization and chlorination reactions; and (2) synthesis of R-PPA from S-2-chloropropionic acid and phenol via etherification reaction. The optimal reaction conditions were as follows:HCl:NaNO2:KI:L-Ala=2.0:1.2:0.7:1.0 (in molar), 125℃ reflux for 1.5 h, with KI as catalyst, and KI:S-2-chloropropionic acid:phenol=0.075:1.2:1.0 (in molar). Under these conditions, an improved molar conversion rate (74.9%, calculated in phenol) was achieved. After extraction using anionic exchange resin Amberlite IRA-400 (CI), R-PPA product with a purity of 95.08% was obtained. The purified R-PPA was identified and evaluated in the application of the biotransformative production of R-HPPA. The results indicated that the synthesized R-PPA supported the R-HPPA biosynthesis with a comparable yield as that of the standard R-PPA. The R-PPA synthesis method provided herein exhibited the advantages of low price and easy availability of raw materials, less toxicity of reagents, simple manipulations, and low equipment/instrument requirements.

关键词: R-2-phenoxypropionic acid, R-2-(4-hydroxyphenoxy)propionic acid, Biosynthesis, S-2-chloropropionic acid