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Research on Chemical Intermediates

, Volume 41, Issue 8, pp 5797–5808 | Cite as

A new and efficient synthetic method for the herbicide carfentrazone-ethyl based on the Heck reaction

  • Jianjian Fan
  • Juan Yu
  • Xinghua Fu
  • Rui Liu
  • Guangke He
  • Hongjun Zhu
Article

Abstract

The herbicide carfentrazone-ethyl (1) was prepared by a new and improved synthetic method. The common and inexpensive reagent ethyl acrylate was employed to replace commercially unavailable ethyl 3-hydroxy-2-methylenebutanoate, which was used in the synthetic route reported previously. Starting from iodination of 1-(4-chloro-2-fluorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole (2), an intermediate 1-(4-chloro-2-fluoro-5-iodophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole (3) was afforded in an excellent yield. Then, an intermediate ethyl 3-[2-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-4-fluorophenyl]-2-propenoate (4) was synthesized by Heck coupling of 3 with ethyl acrylate. Next, oxidative addition–elimination of 4 with OXONE ® /HCl-Et3N in one pot produced ethyl 2-chloro-3-[2-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-4-fluorophenyl]-2-propenoate (5). Finally, the target product 1 was obtained via reduction of 5 by H2. This new synthetic method exhibits the advantages of mild conditions, atom economy, low-cost, and efficiency.

Keywords

Carfentrazone-ethyl Herbicide Triazolinone Heck reaction OXONE® Hydrogenation 

Notes

Acknowledgments

We greatly acknowledge the National key technology R&D program of the Ministry of Science and Technology (2011BAE06A07-04), the Technology R&D Program of Jiangsu province (BE2012363), the Postgraduate innovation fund of Jiangsu province (2012, CXZZ12_0445) and the Graduate innovation fund of Jiangsu province (2013, CXLX13_399), P.R. China.

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Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • Jianjian Fan
    • 1
  • Juan Yu
    • 1
  • Xinghua Fu
    • 1
  • Rui Liu
    • 1
  • Guangke He
    • 1
  • Hongjun Zhu
    • 1
  1. 1.Department of Applied Chemistry, College of ScienceNanjing Tech UniversityNanjingChina

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