Facile synthesis of optical pure fenoxaprop-p-ethyl[ethyl (R)-2-{4-(chloro-1,3-benzoxazol-2-yloxy)phenoxy}propionate]

광학활성 제초제 fenoxaprop-p-ethyl [ethyl (R)-2-{4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy}propionate]의 새로운 합성법

  • 류성곤 (한국화학연구원 생물화학연구부) ;
  • 고영관 (한국화학연구원 생물화학연구부) ;
  • 장해성 (한국화학연구원 생물화학연구부) ;
  • 류재욱 (한국화학연구원 생물화학연구부) ;
  • 우재춘 (한국화학연구원 생물화학연구부) ;
  • 구동완 (한국화학연구원 생물화학연구부) ;
  • 김대황 (한국화학연구원 생물화학연구부) ;
  • 정근회 (한국화학연구원 생물화학연구부)
  • Published : 2004.03.30

Abstract

Fenoxaprop-p-ethyl[Ethyl (R)-2-{4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy}propionate] is well known as a herbicide for its specific activity against the weed grasses. This compound was synthesized by the reaction of 4-(6-chloro-1,3-benzoxazol-2-yloxy)phenol and ethyl (S)-O-(p-toluenesulfonyl)lactate in good yields with high optical pure(optical purity: 99.9% up). In this process Walden inversion occurs, whereby the S-configuration of the propionic acid derivative is converted to the R-configuration of the final product. 4-(6-Chloro-l,3-benzoxazol-2-yloxy)phenol was obtained by 5 step reactions in over-all 70% yields using inexpensive raw materials.

References

  1. Arndt, Otto; Thdeodor Papenfuhs, (1987), Process for Preparation of 2,6-Dichlorobenzoxazole, USP 4,658, 034(=EP 0153656)
  2. Becherer, Johannes; Klaus Kuhlein; Ulrich Kussmaul, (1985), Process for Preparing 2-Chlorobenzoxazoles, USP 4,517,370(=EP (087701)
  3. Handte, Reinhard; Bauer Klaus; Bieringer Hermann (1983), Benzthiazole or Benzoxazole Ethers, Herbicidal Compositions and Use, USP 4,383,850(=EU 62,905)
  4. Handte, Reinhard; Jurgen Sander; Tomas Tammer (1984) Process for the preparation of 2-mercaptobenzoxazoles, USP 4,442,294
  5. Handte, Reinhard; Jurgen Sander; Tomas Tammer (1984) Process for the preparation of 2-mercaptobenzoxazoles, USP 4,442,294
  6. Helmut, Obraniak (1994) Prepn of 6-chloro-2-mercaptobenzoxazide-by reaction of 5-chloro-2aminophenol with carbon disulfide in aq soln, DE 4229235
  7. Kussmaul, Ulrich; Johannes Becherer; Reinhard Handte; Rolf Muller (1986) Process for the Preparation of Heterocyclic Phenyl Ethers, USP 4,564,682
  8. Kussmaul, Ulrich; Manfred Langer; Kuno Reh; Johannes Becherer; Herbert Wille; Rolf Muller (1987) Process for the preparation of 2-mercaptobenzoxazoles, USP 4,677,209
  9. Maleski, Robert J.; C. Edward Osborne; Sharon M. Cline (1991) A Simple Synthesis of 2(3H)-Benzoxazolones using Phenyl Chloroformate, J. Heterocyclic Chem., 28:1937-1939
  10. Marsh, David F. USP2,895,877 (1959) Composition and Method for Relieving Spasticity, USP2,895,877
  11. Ressel, Hans-Joachim; Mohanuned Aslam; Jean Pierre Demoute; Gunter Schlegel; Wolfgang Welter (2001) Method for Producing Chlorobenzoxazolene, USP 6,274,739 B1(=WO 9931037)
  12. Yamada, Megumi; Yasuo Sato; Kazuko Kobayashi; Fukio Konno; Tomoko Soneda; Takashi Watanabe, (1996) A New 5-HT3 Receptor Ligand. II. Structure-Activity Analysis of 5-HTI Receptor Agonist Action in the Gut, Chem. Pharm. Bull. 46(3):445-451
  13. Kass, Volker (1996) Process for Preparing 2-Chlorobenzo thiazoles and 2-Chlorobenzoxazoles, USP 5,502,201 (=DE 4313748)
  14. Zeiss, Hans-Joachim; Hilmar Mildenberger; Reinhardt Handte (1984) Benzoxazolyl- and benzothiazolyloxyphenoxypropionic acid derivatives, DE 3,236,730
  15. Eto, Morifusa(1985) a-(p-Aryloxyphenoxy)propionic Acid Herbicides. pp.501-518, In Bioorganic Chemistry of Pesticide(ed, Morifusa Eto), Soft Science, Inc., Yokyo, Japan
  16. Worthing, Charles R. (1991) Fenoxaprop & Fenoxprop-p. pp.373-374, In The Pesticide Manual(Ninth Edition, ed. Charles R. Worthing), Soft Science, Inc., Yokyo, Japan
  17. Chan, James H. H.; Francis Walker; Chien K. Tseng; Don R. Baker; Duane R. Arneklev, (1975), Synthesis and Herbicidal Activity of N,N-Diethyl-2-(1-naphthyloxy) propionamide and Its Optical Isomers, J. Agric. Food Chem., 23(5):1008-1010
  18. Kuhlein, Klaus; Johannes Becherer; Ulrch Kussmaul (1985) Process for the Production of Benzimidazolyl. Benzoxazolyl and Benzthiazolyloxypropionic acid Derivatives, EU 157,225(=DE 3,409,201)
  19. Handte, Reinhard (1981) 2-Benzazolyl, 2-Benzothiazolyl and 2-Imidazolyl, USP 4,263,440
  20. Moussavi, Ziaeddine; Daniel Lesieur; Charles Lespagnol; Jacques Sauzieres; Philippe Olivier (1989) 7-Acyl-2,3dihydro-1,4-benzoxazin-3-ones and normolipemic properties, Eur. J. Med. Chem, 24:55 -60
  21. Dingler, Christoph; Wolfgang Ladner; Georg A. Krei; Bryan Cooper; Bernhard Hauer(1996) Preparation of (R)-2-(4-Hydroxyphenoxy) propionic acid by biotransformation, Pesticide Science, 46(1):33- 35
  22. Nestler, Hans J.; Horlein Gerhard; Handte Reinhard; Bieringer Hermann; Schwerdtle FriedheIm; Langeluddeke Peter (1985) Herbicidal Esters of D-1-(Phenoxy4-Phenoxy)Propionic Acid, USP 4,531,969
  23. Cobbs, Carrington S.; Michael J. Barton; Lin Peng; Animesh Goswami; Adrien P. Malick; Gary J. Calton(1990) Lipase isozymes for stereoselective hydrolysis of esters or transesterification, WO 9015146
  24. Close, W. J.; Burris D. Tiffany; M. A. Spielman(1949) The Analgestic Activity of Some Benzoxazolone Derivatives, J. Am. Chem. Soc. 71:1265-1268
  25. Egon, K.; L. Gunter(1992), Process for the Production of 2-Mercaptobenzimidazoles, -oxazoles, -thiazoles, DE 4230923
  26. Johnson, Gary M.; Robert Schaeper (1997) Chromogenic Lactate Leukocyte Esterase Substrates, Bioconjugate Chem., 8:76-80
  27. Handte, Reinhard; Horlein Gerhard; Kocher Helmut; Langeluddeke Peter (1978) Heterocyclic Phenyl Ethers and Herbicides Containing Same, USP 4,130,413(=DE 2,640,730)
  28. Nestler, Hans J.; Horlein Gerhard; Handte Reinhard; Bieringer Hermann; Schwerdtle FriedheIm; Langeluddeke Peter; Frisch Peter (1993) Optical Active Herbicidal Ethyl-2-(4-(6-Chlorobenzoxazol-2-yloxy)phenoxy) propionate, USP 5,254,527(=GB 2042503)
  29. Lok, Roger; Ronald E. Lenone; Antony J. Williams (1996) Facile Rearrangements of Alkynylamino Heterocycles with Noble Metal Cations, J. Organ. Chem. 61:3289-3297
  30. Klein, J. Peter; Alistair J. Leigh; Michnick John; Anil M. Kumar; Gail E. Underiner (1997) Asymmetric Synthesis of Chiral Secondary Alcohols, USP 5,629,423
  31. Marsh, David F., V. B. Kalcheva; T. G. Deligeorgiev; D. A. Zaneva (1991) An Improved Method for the Halogenation of 2(3H)-Benzoxazolones, Dyes Pigm, 15(4):275 - 278
  32. Shridhar, D. R; M. Jogibhukta; P. S. Rao; V. K. Handa (1983) An Improved Method for the Synthesis of 2-Thioxo-2,3-dihydro-1,3-benzoxazoles [2(3H)-Benzo xazolethiones], Synthesis, pp.936-937
  33. Willms, Lothar; Reinhard Handte; Hilmar Mildenberger (1981) Process for the Production of Heterocyclic Substituted Oxyphenoxyalkanoic acid Derivatives, EU 44,497
  34. Knorr, Harald; Reinhard Handte; Lothar Willms; Thomas Tammer (1984) Process for the Manufacture of 2,6-Dichlorobenzoxazole and 2,6-Dichlorobenzthiazole, USP 4,433,153(=EP 0043573)
  35. Aichaoui, Hocine; Jacques H. Poupaert; Daniel Lesieur; Jean-Pierre Henichart, (1991), Regioselectivity in the C-acylation of 2(3H)-Benzoxazolones, Tetrahedron, 47(33):6649-6654
  36. Fu, Yue; Toshihide Baba; Yoshio Ono, (2001) Carbonylationof-o-Phenylenediamine and o-Aminophenol with Dimethyl Carbonate Using Lead Compounds as Catalysts, Journal of Catalysis, 197:91-97
  37. Kim, Dae-Whang;Hae Sung, Chang; Young Kwan, Ko; Jae Wook, Ryu; Jae Chun, Woo; Dong Wan, Koo and Jin Seog, Kim (2000) Herbicidal Phenoxypropionic Acid N-Alkyl-N-2-fluorophenyl Amide Compounds, WO 00/05956
  38. Forster, Heinz; Ludwig Eue; Hans-Joachim Santel; Robert R.. Schimidt, (1986) Silicon-containing Phenoxypropionic.. Acid Derivatives and Herbicidal Use, USP 4,596,594)
  39. Matsmoto, Hiroo; Yoshio Obara; Kazutaka Ari; Shuji Tsuchiya (1986) (+)-2-(4-Hydroxyphenoxy)propionic acid by enzymic hydrolysis of its racemic esters, JP 61135600
  40. Bonte, Jean-Paul; Daniel Lesieur; Charles Lespagnol; Jean-Claude Cazin; Micheline Cazin(1974), 6-Acylbenzo xazolinones, Eur. J. Med. Chem., 9(5):497-500