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

doi:10.1016/j.cjche.2020.06.013

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

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

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

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

Haiyan Zhou, Yizuo Li, Rui Jiang, Xianlin Wang, Yuanshan Wang, Yaping Xue, Yuguo Zheng. An efficient route towards R-2-phenoxypropionic acid synthesis for biotransformative production of R-2-(4-hydroxyphenoxy)propionic acid[J]. Chinese Journal of Chemical Engineering, 2021, 32(4): 315-323.

References

[1] Q.-X. Liu, A.-P. Liu, A.-X. Hu, M.-Z. Huang, X.-M. Ou, H.-F. Zhou, Progress on 2-(4-aryloxyphenoxy) propionic acid derivatives, Agrochemicals 54(8) (2015) 551-558.
[2] E.S. Cleugh, Production process of optically pure 2-(4-hydroxyphenoxy) propanoic acid compounds, European Patent, IL20060173524, 2010-11-30.
[3] Y. Zhou, B. Zhu, K. Jin, Synthesis of (R)-(+)-2-(4-hydroxyphenoxy)propionic acid and purification process, Chinese Patent, CN102391104 A, 2012-03-28.
[4] Y.C. Shen, Y.X. Li, P. Wang, Technical improvement for synthesizing R-(+)-2-(4-hydroxyphenoxy)propionic acid, Chin. J. Syn. Chem. 14(4) (2006) 398-401.
[5] M.P.M. Fleer, B.J.V. Verkuijl, Optimization of the use of a chiral bio-based building block for the manufacture of DHPPA, a key intermediate for propionate herbicides, Green Chem. 16(8) (2014) 3993-3998.
[6] C.L. Wu, K.L. Liu, D.L. Ma, Technical improvement for synthesizing R-(+)-2-(4-hydroxyphenoxy)-propionic acid, Guangzhou Chem. Ind. 43(8) (2015) 92-94.
[7] J.-Q. Weng, Z.-J. Gao, B. Xu, C.-R. Ding, C.-X. Tan, Asymmetrical synthesis of R-(+)-2-(4-hydroxyphenoxy)propionic acid, J. Zhejiang Uni. Technol. 37(4) (2009) 362-365.
[8] A.L. Demain, J.L. Adrio, Contributions of microorganisms to industrial biology, Mol. Biotechnol. 38(1) (2008) 41-55.
[9] S. Thapa, H. Li, J. Ohair, S. Bhatti, F.-C. Chen, K. Al Nasr, T. Johnson, S. Zhou, Biochemical characteristics of microbial enzymes and their significance from industrial perspectives, Mol. Biotechnol. 61(8) (2019) 579-601.
[10] M. Kinne, R. Ullrich, K.E. Hammel, K. Scheibner, M. Hofrichter, Regioselective preparation of (R)-2-(4-hydroxyphenoxy)propionic acid with a fungal peroxygenase, Tetrahedron Lett. 49(41) (2008) 5950-5953.
[11] C. Dingler, W. Ladner, G.A. Krei, B. Cooper, B. Haueri, Preparation of (R)-2-(4-hydroxyphenoxy)propionic acid by biotransformation, Pestic. Sci. 46(1996) 33-35.
[12] H.-F. Hu, H.-Y. Zhou, M.-X. Wang, Y.-S. Wang, Y.-P. Xue, Y.-G. Zheng, A rapid throughput assay for screening (R)-2-(4-hydroxyphenoxy)propionic acid producing microbes, J. Microbiol. Meth. 158(2019) 44-51.
[13] H.-Y. Zhou, Y.-Z. Li, R. Jiang, H.-F. Hu, Y.-S. Wang, Z.-Q. Liu, Y.-P. Xue, Y.-G. Zheng, A high-throughput screening method for improved R-2-(4-hydroxyphenoxy)propionic acid biosynthesis, Bioprocess Biosyst. Eng. 42(10) (2019) 1573-1582.
[14] J. Metivier, M. Sauli, Process for the prepartion of dextrorotatory 2-phenoxypropionic acid derivatives, United States Patent, US4371709, 1979-11-06.
[15] W. Eveleens, J. Spaans, H.G. Wissink, Process for the preparation of optically active 2-phenoxy propioncacids and herbicdal preparations containing such acids, United States Patent, US4310689, 1982-01-12.
[16] W. Wei, X. Ouyang, S. Sun, J. Xu, M. Zeng, Preparation of R-2-(4-hydroxyphenoxy) propionic acid, Chinese Patent, 201911080109.X, 2019-11-07
[17] A. Messina, M. Flieger, F. Bachechi, M. Sinibaldi, Enantioseparation of 2-aryloxypropionic acids on chiral porous monolithic columns by capillary electrochromatography:Evaluation of column performance and enantioselectivity, J. Chromatogr. A 1120(1-2) (2006) 69-74.
[18] L.-L. Li, Y. He, C.-P. Ye, H. Liu, Estimation of solubility parameter and selection of extraction agent for (S)-2-chloropropinoic acid, Fine Chem. Intermed. 38(5) (2008) 22-24.
[19] Y. Gao, T. Kodadek, Synthesis and screening of stereochemically diverse combinatorial libraries of peptide tertiary amides, Chem. Biol. 20(3) (2013) 360-369.
[20] Y. Gao, T. Kodadek, Split- and-pool synthesis and characterization of peptide tertiary amide library, J. Vis. Exp. 88(2014) e51299.
[21] S. Paul, M. Gupta, Zinc-catalyzed Williamson ether synthesis in the absence of base, Tetrahedron Lett. 45(48) (2004) 8825-8829.
[22] G.-R. Xu, H.-M. Zhang, Y.-N. Cui, Preliminary study on diazotization reaction in saccharin production, J. Henan Sci. Technol. 13(2014) 71-72.
[23] Z.-M. Deng, J. Wang, Synthetic process of sodiumphenoxyacetate, Hubei Chem. 1(2003) 31-32.
[24] H.-P. Gong, G.-R. Fu, X.-B. Wang, Synthesis of aromatic ethers under the action of potassium iodide, Gansu Sci. Technol. 28(17) (2012) 23-25.

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

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

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 4

Recommended Articles

Metrics

Comments

[1]	Ziheng Cui, Shiding Zhang, Shengyu Zhang, Biqiang Chen, Yushan Zhu, Tianwei Tan. Green biomanufacturing promoted by automatic retrobiosynthesis planning and computational enzyme design [J]. Chinese Journal of Chemical Engineering, 2022, 41(1): 6-21.
[2]	Samra Basharat, Ziyang Huang, Mengyue Gong, Xueqin Lv, Aqsa Ahmed, Iftikhar Hussain, Jianghua Li, Guocheng Du, Long Liu. A review on current conventional and biotechnical approaches to enhance biosynthesis of steviol glycosides in Stevia rebaudiana [J]. Chinese Journal of Chemical Engineering, 2021, 29(2): 92-104.
[3]	Mohammad Hossein Sheikh-Mohseni, Sajjad Sedaghat, Pirouz Derakhshi, Aliakbar Safekordi. Green bio-synthesis of Ni/montmorillonite nanocomposite using extract of Allium jesdianum as the nano-catalyst for electrocatalytic oxidation of methanol [J]. Chinese Journal of Chemical Engineering, 2020, 28(10): 2555-2565.
[4]	LÜ Fenfen, GAO Yixian, HUANG Jiale, SUN Daohua, LI Qingbiao . Roles of Biomolecules in the Biosynthesis of Silver Nanoparticles：Case of Gardenia jasminoides Extract [J]. Chin.J.Chem.Eng., 2014, 22(6): 706-712.