55701-09-2Relevant academic research and scientific papers
Assignment of absolute configurations of permethrin and its synthon 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid by electronic circular dichroism, optical rotation, and X-ray crystallography
Bicker, Wolfgang,Kacprzak, Karol,Kwit, Marcin,Laemmerhofer, Michael,Gawronski, Jacek,Lindner, Wolfgang
experimental part, p. 1027 - 1035 (2009/10/10)
The availability of single stereoisomers of biologically/toxicologically relevant chiral compounds such as the pyrethroid-type insecticide permethrin (PM) and the reliable determination of their absolute configurations are of central importance for the de
Molecular cloning, purification, and biochemical characterization of a novel pyrethroid-hydrolyzing esterase from Klebsiella sp. strain ZD112
Wu, Pei C.,Liu, Yu H.,Wang, Zhuo Y.,Zhang, Xiao Y.,Li, He,Liang, Wei Q.,Luo, Na,Hu, Ji M.,Lu, Jia Q.,Luan, Tian G.,Cao, Li X.
, p. 836 - 842 (2007/10/03)
The gene encoding pyrethroid-hydrolyzing esterase (EstP) from Klebsiella sp. strain ZD112 was cloned into Escherichia coli and sequenced. A sequence analysis of the DNA responsible for the esfP gene revealed an open reading frame of 1914 bp encoding for a protein of 637 amino acid residues. No similarities were found by a database homology search using the nucleotide and deduced amino acid sequences of the esterases and lipases. EstP was heterologously expressed in E. coli and purified. The molecular mass of the native enzyme was approximately 73 kDa as determined by gel filtration. The results of sodium dodecyl sulfate - polyacrylamide gel electrophoresis and the deduced amino acid sequence of EstP indicated molecular masses of 73 and 73.5 kDa, respectively, suggesting that EstP is a monomer. The purified EstP not only degraded many pyrethroid pesticides and the organophosphorus insecticide malathion, but also hydrolyzed ρ-nitrophenyl esters of various fatty acids, indicating that EstP is an esterase with broad substrates. The Km for trans- and cis-permethrin and kcat/Km values indicate that EstP hydrolyzes both these substrates with higher efficiency than the carboxylesterases from resistant insects and mammals. The catalytic activity of EstP was strongly inhibited by Hg2+, Ag+, and ρ-chloromercuribenzoate, whereas a less pronounced effect (3-8% inhibition) was observed in the presence of divalent cations, the chelating agent EDTA, and phenanthroline.
Purification and characterization of a novel pyrethroid hydrolase from Aspergillus niger ZD11
Liang, Wei Q.,Wang, Zhuo Y.,Li, He,Wu, Pei C.,Hu, Ji M.,Luo, Na,Cao, Li X.,Liu, Yu H.
, p. 7415 - 7420 (2007/10/03)
The pyrethroid pesticides residues on foods and environmental contamination are a public safety concern. Pretreatment with pyrethroid hydrolase has the potential to alleviate the conditions. For this purpose, a fungus capable of using pyrethroid pesticides as a sole carbon source was isolated from the soil and characterized as Aspergillus niger ZD11. A novel pyrethroid hydrolase from cell extract was purified 41.5-fold to apparent homogeneity with 12.6% overall recovery. It is a monomeric structure with a molecular mass of 56 kDa, a pl of 5.4, and the enzyme activity was optimal at 45°C and pH 6.5. The activities were strongly inhibited by Hg2+, Ag+, and p-chloromercuribenzoate, whereas less pronounced effects (5-10% inhibition) were observed in the presence of the remaining divalent cations, the chelating agent EDTA and phenanthroline. The purified enzyme hydrolyzed various insecticides with similar carboxylester. trans-Permethrin is the preferred substrate.
Development of pyrethroid substrates for esterases associated with pyrethroid resistance in the tobacco budworm, Heliothis virescens (F.)
Huang, Huazhang,Ottea, James A.
, p. 6539 - 6545 (2007/10/03)
Assays to detect esterases associated with resistance to organophosphorus and pyrethroid insecticides in larvae of H. virescens were developed and evaluated. Cross-resistance to a variety of insecticides was measured in strains resulting from selection with either profenofos (OP-R) or cypermethrin (PYR-R), and resistance in both strains appeared to have a metabolic component. Esters were synthesized that coupled 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate, the acid moiety of some pyrethroid insecticides, with groups (e.g., p-nitrophenyl-) that could be detected spectrophotometrically following hydrolysis of the resulting esters. Activities toward these pyrethroid esters were significantly higher in both resistant strains than those in a susceptible reference strain. In addition, all pyrethroid esters significantly increased the toxicity of cypermethrin in bioassays with larvae from both PYR-R and OP-R strains. The biological and biochemical activities of these compounds are compared with those with more conventional esterase substrates and insecticide synergists, and the utility of pyrethroid esters as components of rapid assays for detecting esterases associated with insecticide resistance is discussed.
Nitrile biotransformation for highly enantioselective synthesis of 3-substituted 2,2-dimethylcyclopropanecarboxylic acids and amides
Wang, Mei-Xiang,Feng, Guo-Qiang
, p. 621 - 624 (2007/10/03)
Biotransformations of differently configured 2,2-dimethyl-3-substitued-cyclopropanecarbonitriles were studied using a nitrile hydratase/amidase-containing Rhodococcus sp. AJ270 whole-cell catalyst under very mild conditions. Although all of the cis-3-aryl-2,2-dimethylcyclopropanecarbonitriles appeared inert toward the biocatalyst, a number of racemic trans-isomers efficiently underwent a highly enantioselective hydrolysis to produce (+)-(1R,3R)-3-aryl-2,2-dimethylcyclopropanecarboxylic acids and (-)-(1S,3S)-3-aryl-2,2-dimethylcyclopropanecarboxamides in high yields with excellent enantiomeric excesses in most cases. The overall enantioselectivity of the biotransformations of nitriles originated from the combined effects of 1R-enantioselective nitrile hydratase and amidase, with the later being a dominant factor. The influence of the substrates on both reaction efficiency and enantioselectivity was discussed in terms of steric and electronic effects. Coupled with chemical transformations, biotransformations of nitriles provided convenient syntheses of optically pure geminally dimethyl-substituted cyclopropanecarboxylic acids and amides, including chrysanthemic acids, in both enantiomeric forms.
Free radical addition of haloalkanes to polymer bound olefins and its application to the solid-phase synthesis of pyrethroids
Kumar,Chakravarthy, P.Pawan,Shesha Rao,Reddy, P.Sunder Ram,Yadav
, p. 7817 - 7819 (2007/10/03)
Polymer bound olefins undergo free radical initiated 1,2-addition when reacted with a variety of haloalkanes. The strategy could be applied successfully to the solid-phase synthesis of dihaloethenylcyclopropane carboxylic acids which are the key fragments of synthetic pyrethroids.
An efficient and selective conversion of hydrazides into esters and acids
Srinivas,Subba Reddy,Yadav,Ramalingam
, p. 376 - 377 (2007/10/03)
Hydrazides are selectively oxidised to esters/acids in high yields using Oxone in the presence of an appropriate alcohol/water as a nucleophile at ambient temperature. A variety of functional groups including alkenes, alcohols, ethers, cyclopropyl groups and nitriles are unaffected.
Enzyme catalysed kinetic resolution of racemic 2,2-dimethyl-3-(2,2- disubstituted vinyl) cyclopropane carboxylic acids anchored on polymer supports
Nanda,Bhaskar Rao,Yadav
, p. 5905 - 5908 (2007/10/03)
Kinetic resolution of trans-substituted cyclopropane carboxylic acids anchored on a solid support by lipase is described.
Biological Activity of Pyrethroid Analogs in Pyrethroid-Susceptible and -Resistant Tobacco Budworms, Heliothis virescens (F.)
Shan, Guomin,Hammer, Robert P.,Ottea, James A.
, p. 4466 - 4473 (2007/10/03)
The phenoxybenzyl moiety of conventional pyrethroids is a major site of oxidative metabolism in resistant tobacco budworms, Heliothis virescens (F.). In this study, this group was replaced with known P450 monooxygenase-inhibiting or oxidatively blocked groups. A variety of isomers (1R/1S, cis/trans) of the resulting chrysanthemates were tested as insecticides or synergists against tobacco budworms that were insecticide-susceptible (LSU) or that expressed metabolic resistance to cypermethrin (Pyr-R). A number of compounds with pentafluorophenyl, methylenedioxyphenyl, and propargyloxyphenyl groups were insecticidal, and activity was dependent on both geometric and stereochemical configuration of the acid moiety. Both trans and cis isomers of 1(R)-fenfluthrin, which contains a pentafluorophenyl group, suppressed resistance to cypermethrin in Pyr-R insects, confirming that oxidative metabolism of the phenoxybenzyl moiety is a major mechanism of resistance in this strain. Of the methylenedioxyphenyl compounds, 1R, trans, and cis isomers were toxic and partially suppressed resistance in Pyr-R larvae. Similarly, both trans and cis isomers of α(S),1(R)-propargyloxyphenyl-containing compounds were insecticidal. Finally, α(R),1(R)-cis-methylenedioxyphenyl- and -propargyloxyphenyl- containing compounds were nontoxic but significantly enhanced toxicity of cypermethrin.
Search for Routes of Synthesis of Permethrin and Chloropermethrin Starting from Halogen-containing Alkenoic Acids
Badanyan,Stepanyan,Mikaelyan,Ovivyan,Panosyan
, p. 34 - 41 (2007/10/03)
Promising procedures were developed for the synthesis of permethrin and I-chloropermethrin starting from acid chloride, nitrile, and esters of 3,3-dimethyl-2,2,4,6,6-pentachloro-5-alkenoic acid and 3,3-dimethyl-2,2,6,6-tetrachloro-5-alken-4-olide, which were prepared by adding derivatives of trichloroacetic acid to 1,1-dichloro-4-methyl-1,3-pentadiene in the presence of catalytic amounts of monovalent copper ions and amine.
