BACKGROUND: Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D-mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)-3-formyl-2,2-dimethylcyclopropane-1-carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D-mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)-3-[(Z)-2-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropane-1-carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana.
BACKGROUND:Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D-mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)-3-formyl-2,2-dimethylcyclopropane-1-carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D-mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)-3-[(Z)-2-(4-chlorophenyl)vinyl]-2,2-dimethylcyclopropane-1-carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana.
Authors: David Chandler; Alastair S Bailey; G Mark Tatchell; Gill Davidson; Justin Greaves; Wyn P Grant Journal: Philos Trans R Soc Lond B Biol Sci Date: 2011-07-12 Impact factor: 6.237
Authors: Elson S de Alvarenga; Vânia M T Carneiro; Gabriela C Resende; Marcelo C Picanço; Elizeu de Sá Farias; Mayara Cristina Lopes Journal: Molecules Date: 2012-11-26 Impact factor: 4.411