Synthesis and insecticidal activity of an oxabicyclolactone and novel pyrethroids

• Published in: Molecules (Basel, Switzerland) Vol. 17; no. 12; pp. 13989 - 14001
• Main Authors: de Alvarenga, Elson S, Carneiro, Vânia M T, Resende, Gabriela C, Picanço, Marcelo C, Farias, Elizeu de Sá, Lopes, Mayara Cristina
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 26.11.2012; MDPI
• Subjects: Acids; Alcohol; Animals; Furaldehyde - chemistry; furfural; Insecta - drug effects; insecticide; Insecticides; Insecticides - chemical synthesis; Insecticides - chemistry; Insecticides - pharmacology; Insects; Lactones - chemical synthesis; Lactones - chemistry; Lactones - pharmacology; Mannitol - chemistry; Molecular Structure; Nitriles - chemical synthesis; Nitriles - chemistry; oxabicyclo; Pesticides; Photochemistry; Potassium; Pyrethrins - chemical synthesis; Pyrethrins - chemistry; pyrethroid; Toxicity; Brazil
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules171213989

Deltamethrin, a member of the pyrethroids, one of the safest classes of pesticides, is among some of the most popular and widely used insecticides in the World. Our objective was to synthesize an oxabicyclolactone 6 and five novel pyrethroids 8-12 from readily available furfural and D-mannitol, respectively, and evaluate their biological activity against four insect species of economic importance namely A. obtectus, S. zeamais, A. monuste orseis, and P. americana. A concise and novel synthesis of 6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one (6) from furfural is described. Photochemical addition of isopropyl alcohol to furan-2(5H)-one afforded 4-(1'-hydroxy-1'-methylethyl)tetrahydro-furan-2-one (3). The alcohol 3 was directly converted into 4-(1'-bromo-1'-methylethyl)-tetrahydrofuran-2-one (5) in 50% yield by reaction with PBr(3) and SiO(2). The final step was performed by cyclization of 5 with potassium tert-butoxide in 40% yield. The novel pyrethroids 8-12 were prepared from methyl (1S,3S)-3-formyl-2,2-dimethylcyclopropane-1-carboxylate (7a) by reaction with five different aromatic phosphorous ylides. Compounds 6-12 presented high insecticidal activity, with 6 and 11 being the most active. Compound 6 killed 90% of S. zeamais and 100% of all the other insects evaluated. Compound 11 killed 100% of all insects tested.