Download PDF
Synthesis 2002(1): 0053-0058
DOI: 10.1055/s-2002-19296
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Insecticidally Active Halofenozide-[(Acyloxy)alkoxy]carbonyl and (Acyloxy)alkyl Derivatives

Mark J. Mulvihill*, Steven H. Shaber, Brian S. MacDougall, Chris Ajello, Blanca Martinez-Teipel, Rhoda Joseph, Duyan V. Nguyen, Damian G. Weaver, KiHo Chung, Arkady Gusev, Joel M. Wierenga, William D. Mathis
Rohm and Haas Company, 727 Norristown Road, Spring House, Pennsylvania, 19477, USA
Fax: +1(215)6191617; e-Mail: mark.mulvihill@osip.com;
Further Information

Publication History

Received 9 June 2001
Publication Date:
04 August 2004 (online)

    Permissions and Reprints All articles of this category

Abstract

The synthesis of a diverse series of novel insecticidally active carboxylic acid N’-benzoyl-N’-tert-butyl-N-(4-chlorobenzo-yl)hydrazinocarbonyloxy methyl and ethyl esters as well as carboxylic acid N’-benzoyl-N’-tert-butyl-N-(4-chlorobenzoyl)hydrazino methyl esters are reported.

Key words

carboxylic acids - drugs - esters - diacyl hydrazines - parallel synthesis

    References

  • 1 Thomson WT. Agricultural Chemicals, Book 1   14th ed.:  Thomson Publications; Fresno: 1998.  Insecticides. p.142-144  
    Google Scholar
  • 2 James WN, and Aller HE. inventors; U.S. Patent  5358966.  ; Chem. Abstr. 1994, 122, 3593
  • 4 Tomlin CDS. The Pesticide Manual   British Crop Protection Council; Farnham, Surrey, GU9 7PH, UK: 1997.  11th ed.. p.388-389  
    Google Scholar
  • 5a Silverman RB. The Organic Chemistry of Drug Design and Drug Action   Academic Press; San Diego, CA: 1992.  p.361-375  
    Article in Thieme ConnectGoogle Scholar
  • 5b Omar FA. Farag HH. Bodor N. Journal of Drug Targeting  1994,  2:  309 
    Article in Thieme ConnectGoogle Scholar
  • 5c Gogate US. Repta AJ. Alexander J. Int. J. Pharm.  1987,  40:  235 
    Article in Thieme ConnectGoogle Scholar
  • 5d Gogate US. Repta AJ. Int. J. Pharm.  1987,  40:  249 
    Article in Thieme ConnectGoogle Scholar
  • 5e Folkmann M. Lund FJ. Synthesis  1990,  1159 
    Article in Thieme ConnectGoogle Scholar
  • 6a It should be noted that chloroalkyl chloroformates such as chloromethyl and 1-chloroethyl chloroformates, 2 and 3, respectively, have been reported as carbonyl equivalents in the synthesis of carbamates: Barcelo G. Senet JP. Sennyey G. Synthesis  1986,  627 
    Article in Thieme ConnectGoogle Scholar
  • 6b

    We recently reported the novel cyclization reaction in which treatment of the potassium salt of N’-benzoyl-N’-tert-butyl-N-(4-chloro-benzoyl)hydrazide 1b with a carbonyl equivalent such as phosgene at -78 °C afforded 3-(4-chlorobenzoyl)-5-phenyl-3H-[1,3,4]oxadiazol-2-one: Mulvihill, M. J.; Nguyen, D. V.; MacDougall, B. S.; Weaver, D. G.; Mathis, W. D. Synthesis 2001, 1965.
    Article in Thieme Connect
  • 6c

    In light of these results, it was to our pleasant surprise that treatment of the potassium salt of halofenozide (1b) with known carbonyl equivalents such as chloroformates 2 and 3 did not afford cyclized oxadiazol-2-one products but afforded stable isolable compounds 4, 5 and 6 which were further reacted to afford stable isolable esters 7 and 8.
    Article in Thieme Connect
  • 7a Roberts WJ. Sloan KB. J. Pharm. Sci.  2000,  89:  1415 
    CrossrefGoogle Scholar
  • 7b Madec-Lougerstay R. Florent JC. Monneret C. J. Chem. Soc., Perkin Trans. 1  1999,  10:  1369 
    CrossrefGoogle Scholar
  • 7c Redden PR. Melanson RL. Jo-Anne E. Dick AJ. Int. J. Pharm.  1999,  180:  151 
    CrossrefGoogle Scholar
  • 7d Falch E. Perregaard J. Frolund B. Sokilde B. Buur A. Hansen LM. Frydenvang K. Brehm L. Bolvig T. Larsson OM. Sanchez C. White HS. Schousboe A. Krogsgaard-Larsen P. J. Med. Chem.  1999,  42:  5402 
    CrossrefGoogle Scholar
  • 7e Davidsen SK. Summers JB. Albert DH. Holms JH. Heyman RH. Magoc TJ. Conway RG. Rhein DA. Carter GW. J. Med. Chem.  1994,  37:  4423 
    CrossrefGoogle Scholar
  • 7f Alexander J. Renyer ML. Rork GS. J. Pharm. Sci.  1994,  83:  893 
    CrossrefGoogle Scholar
  • 7g Waranis RP. Sloan KB. J. Pharm. Sci.  1988,  77:  210 
    CrossrefGoogle Scholar
  • 7h Bundgaard H. Buur A. Int. J. Pharm.  1987,  37:  185 
    CrossrefGoogle Scholar
  • 7i Buur A. Bundgaard H. Falch E. Int. J. Pharm.  1985,  24:  43 
    CrossrefGoogle Scholar
  • 7j Bodor N. Woods R. Raper C. Kearney P. Kaminski JJ. J. Med. Chem.  1980,  23:  474 
    CrossrefGoogle Scholar
  • 8a Ozawa N, and Yazawa N. inventors;  WO 9308152 A1.  ; Chem. Abstr. 1993, 119, 138756
  • 8b Benneche T. Strande P. Wiggen U. Acta Chem. Scand.  1989,  43:  74 
    Google Scholar
  • 8c Grynkiewicz G. Tsien RY. Pol. J. Chem.  1987,  61:  443 
    Google Scholar
  • 8d Gruszecki W, Gdulewicz-Gruszecka M, Dunajska B, Kolodziejczyk P, and Borowski E. inventors; PL  78-206892.  ; Chem. Abstr. 1984, 102, 45492
  • 9a Finkelstein H. Ber.  1910,  43:  1528 
    Google Scholar
  • 9b Ingold CK. Structure and Mechanism in Organic Chemistry   Cornell Univ. Press; London: 1969.  2nd ed.. p.435 
    Google Scholar
3

The Presidential Green Chemistry Award for Rohm and Haas diacyl hydrazines can be found on the following web pages: http://www.turfnet.com/news/rohm_haas.asp and http://www.epa.gov/greenchemistry/past.htm.

10

Treatment of thiocarbonates with sulfuryl chloride typically affords the respective chloroformates (ref. [5e] ). However, in this case, treatment of thiocarbonate 10 with sulfuryl chloride afforded chloromethyl derivative 11 with no trace of the respective chloroformate. Chloromethyl derivative 11 was not stable to silica gel column chromatography. However, chloromethyl derivative 11 could be recrystallized from hot hexanes to afford the pure product, which was stored at -20 °C.