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

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

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• 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.

• 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.

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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.