Dimethylcyclopropanecarboxylic acid

Bicker W, Kacprzak K, Kwit M, Lammerhofer M, Gawronski J, Lindener W (2009) 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. Tetrahedron Asymmetry 20 1027-1035... 

In a recent study, chiral separations for pyrethroic acids, which are the chiral building blocks of synthetic pyrethroids and the primary metabolites of the acid part of these potent ester insecticides, have been developed [62], For example, a polar-organic mobile phase allowed the complete baseline resolution of all four stereoisomers of chrysanthemic acid (2,2-dimethyl-3-(2-methylprop-l-enyl)-cyclopropanecarboxylic acid) on a 0-9-(tcrt-butylcarbamoyl)quinine-based CSP(acjj = 1.20, oLtrans = 1-35, critical Rs = 3.03) (Figure 1,32a). This chiral acid is the precursor of pyrethroids like allethrin, phenothrin, resmethrin, and tetramethrin but not excreted as metabolite. The primary acid metabolite of these pyrethroids is chrysanthemum dicarboxylic acid (3-[(l )-2-carboxyprop-l-enyl]-2,2-dimethylcyclopropanecarboxylic acid) the stereoisomers of which could also be resolved with a reversed-phase eluent (acetonitrile— 30-mM ammonium acetate buffer 90 10, v/v pHa = 6.0) and employing an O-9-(2,6-diisopropylphenylcarbamoyl)quinine-based CSP ads = 1-09, atrans = 1-50,... 

In lake water, permethrin degraded more rapidly than in flooded sediments to trans- and a 5-(dichlorovinyl)dimethylcyclopropanecarboxylic acid. The cis- isomer was more stable toward biological and chemical degradation than the trans isomer (Sharom and Solomon, 1981). 

In the initial phase of our work we prepared a set of benzyl esters of the 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid (DVA) which were monosubstituted in the meta position. The substituents were chosen to cover a broad spectrum of physicochemical parameter space by selecting them from Hansch s cluster sets( ). In addition, substituents with no bridging group, one atom and two atom bridges were included to probe the need for a bridging atom. 

Dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid (3-phenoxyphenyl) methyl ester, 3-(phenoxyphenyl) methyl (+)-cis, Irons 3 (2,2-dichloroethenyl) 2,2-dimethylcyclopropanecarboxylate, Ambush, Pounce. 

Wang, M.X. and Wang, G.Q. 2002. Enzymatic synthesis of optically active 2-methyl- and 2,2-dimethylcyclopropanecarboxylic acids and their derivatives. Journal of Molecular... 

Production of Carboxylic Acids Using Amidases (S)-2,2-Dimethylcyclopropanecarboxylic Acid [(S)-Ibuprofen]... 

Dimethylcyclopropanecarboxylic acid is an intermediate for the synthesis cilastatin, a dehydropeptidase I inhibitor. Lonza has developed an industrial two-step biotransformation process starting from racemic 2,2-dimethylcyclopropane nitrile (34 Scheme 18). The stereoselective amidase has been found in Comomo-nas acidovorans and cloned into a fast-growing E. coli strain which produces large amounts of biomass [92, 93]. 

Pyrethroid esters derived from [1,1 -biphenyl]-3-methanol have been of interest at FMC(5-7). It has been reported that [1,1 -biphenyl]-3-methanol esterified with both cis-3-(2-chloro-3,3,3-trifluoro-l-propenyl)-2,2-dimethylcyclopropanecarboxylic acid and cis-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid produced esters which have initial and residual activity surpassing that of permethrin against a number of insects. It occurred to us that this same enhancement of activity might be observed with alkyl... 

Useful applications of this ring contraction of a-halocyclobutanones have been reported, in particular in the field of pyrethrins and pyrethroids. For instance, the biologically interesting 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylic acids were obtained from optically active a-halocyclobutanones by stereospecific C4 to C3 ring contraction and subsequent elimination of... 

Finally, the desired (l, 3/ )-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (20) was obtained in 86% yield by one-pot ring contraction and dehydrochlorination on treatment with sodium hydroxide, followed by acidification with hydrochloric acid, as a 83 17 cis/trans mixture, from which pure cw-acid was isolated by liquid chromatography. The undesired ( —)-cw-(2/ ,45)-cyclobutanone was recycled after its racemization with tetrabutylam-monium chloride or hydrobromic acid, which render the total synthesis chirally economic. Several patents are based on the ring contraction of a-halocyclobutanones. For a review on the use of cyclobutanones and cyclobutenones as intermediates in the synthesis of naturally occurring target molecules, especially for the formation of cyclopropanes by ring contraction, see ref 64h. 

Reaction of methyl 4-bromo-2-methoxycarbonyl-4-methylpent-2-enoate (24) with 3.2 equivalents of sodium cyanide in dimethyl sulfoxide at 20 °C for 3 hours leads to the formation of dimethyl 3-cyano-2,2-dimethylcyclopropane-l,l-dicarboxylate (25) which is readily de-methoxycarbonylated to give tra 5-3-cyano-2,2-dimethylcyclopropanecarboxylic acid (26) in 67% overall yield. This compound can be conveniently transformed into chrysanthemic acid and hemicaronic aldehyde. ... 

The acetals of various cyclopropanecarbaldehydes and cyclopropyl ketones have been converted directly to acids or esters. Acetal 9 was treated with ozone followed successively by potassium hydroxide and hydrochloric acid to give (S )-2,2-dimethylcyclopropanecarboxylic acid (10) in 85% yield.Other acetals react in an identical fashion under the same condi-... 

Synonyms (Cyano (3-phenoxyphenyl) methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate 3-(2,2-Dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid cyano (3-phenoxyphenyl)-methyl ester Classification Pyrethroid Empirical C22H19CI2NO3 Properties Odorless cryst. (pure) yel.-brn. vise, semisolid (tech.) sol. in methanol, acetone, xylene, methylene dichloride insol. in water m.w. 416.3 dens. 1.25 (20 C) m.p. 60-80 C dec. slowly > 220 C flash pt. 115.6 C probably not combustible... 

CAS 52918-63-5 52820-00-5 Synonyms (S)-a-Cyano-3-phenoxybenzyl(1 R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate Decamethrin 3-(2,2-Dibromoethenyl)-2,2-dimethylcyclopropanecarboxylic acid cyano (3-phenoxyphenyl)- methyl ester Esbecythrin Classification Pyrethroid Empirical C22HigBr2N03... 

Dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid cyano (3-phenoxyphenyl)-methyl ester. See Cypermethrin... 

The recovery of the individual enantiomeric acids from the diastereomeric amides has not been carried out to any large extent, because of the inherent stability of the amide bond and the risk of racemization during hydrolysis. Jiang and Soderlund [62] reported the recovery of the individual enantiomers of 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid, a synthetic pyrethoid precursor, from its S( — )-(phenyl)ethylamide diastereomers by refluxing in 6 M hydrochloric acid at... 

Soil Permethrin biodegraded rapidly via hydrolysis yielding 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid and 3-phenoxybenzyl alcohol (Kaufman et al., 1981). The reported half-life in soil containing 1.3-51.3% organic matter and pH A.2-1.1 is <38 days (Worthing and Hance, 1991). 

Dibromoethenyl)-2,2-dimethylcyclopropanecarboxylic acid cyano(3-phenoxyphenyl)methyl ester, 9CI. Decamethrin. Decis. K-Othrine. Butox. Butoflin [52918-63-5]... 

Chloro-3,2,3- trifluro- l-propenyl)-2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrqfluorO 4-methylpheny )methyl ester, 9CI [79538-32-2]... 

CgH Of Bicyclopropyl, 32B, 116 CeHio02f trans-2,trans-3-Dimethylcyclopropanecarboxylic acid, 38B,... 

Chrysanthemum dicarhoxylic acid Chrysanthemum dicarboxylic acid, 3-[(lE)-2-carboxyprop-l-enyl]-2,2-dimethylcyclopropanecarboxylic acid CAS no. 497-95-0 (generic)... 

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