2.2- Dimethylcyclopropane-1 -carboxylate

Mixtures of stereoisomeric 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane carboxylic acids (the acid moieties of permethrin insecticide), CDI, and chiral amines have been investigated by capillary gas chromatography. The diastereomeric amides could be identified by GC/MS-spectrometry [413... 

By screening 53 Rhodococcus and Pseudomonas strains, an NHase-amidase biocatalyst system was identified for the production of the 2,2-dimethylcyclopropane carboxylic acid precursor of the dehydropeptidase inhibitor Cilastatin, which is used to prolong the antibacterial effect of Imipenem. A systematic study of the most selective of these strains, Rhodococcus erythropolis ATCC25 544, revealed that maximal product formation occurs at pH 8.0 but that ee decreased above pH 7.0. In addition, significant enantioselectivity decreases were observed above 20 °C. A survey of organic solvent effects identified methanol (10% v/v) as the... 

Figure 8.6 Preparation of (S)-2,2-dimethylcyclopropane carboxylic acid, a precursor of Cilastatin...

Yeom, S.-J., Kim, H.-J. and Oh, D.-K. (2007) Enantioselective production of 2,2-dimethylcyclopropane carboxylic acid from 2,2-dimethylcyclopropane carbonitrile using the nitrile hydratase and amidase of Rhodococcus erythropolis ATCC 25544. Enzyme and Microbial Technology, 41, 842-848. 

Table I. (2-Substituted [1,1 -Biphenyl]-3-yl)methyl cis-3-(2,2-Dichloroethylenyl)-2,2-Dimethylcyclopropane Carboxylates...

Chemical Name cyano(3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclo-propanecarboxylate (RS)-a-cyano-3-phenoxybenzyl(lR5,3R5 lR5,35R)-3(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate Uses nonsystemic insecticide with contact and stomach action to control a wide range of insects in fruits, vegetables, vines, potatoes, cucurbits, capsicums, cereals, maize, soybeans, cotton, coffee, coca, rice, pecans, ornamentals and forestry, etc. also used to control flies in animal houses and mosquitoes, cockroaches, houseflies and other pests in public health. 

Practical applications include the synthesis of rran5-2-phenylcyclopropanamine (trade name tranylcypromine), an antidepressant acting as a monoamine oxidase inhibitor [20 a], of 2,2-dimethylcyclopropane carboxylate from isobutene [20 b], a key step in the commercial production of cilastatin, 3 (eq. (4)), and of esters of chrysanthemic acid 4 (using the methylene bis(diphenyloxazoline) 5) [ 17, 21 ] (eq. (5)). Cilastatin is a dehydropeptidase which acts as an in vivo stabilizer of the car-bapenem antibiotic imipenem with achiral diazoesters. 

Synonyms S-a-Cyano-3-phenoxybenzyl-( lR)-ds-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-carboxylate Butox Decis K-Otbrine Kordon Sadetbrin AEF 032640 NRDC 161 QMS 1998 RU 22974 SHA 209400... 

In this work it was reported that the biological activity and residual properties of biphenyl-3-ylmethyl (1R,S)-cis-3-(2,2-di-chlorovinyl)-2,2-dimethylcyclopropanecarboxylate were about one-half that of the corresponding 3-phenoxybenzyl ester. The preparation of a series of substituted derivatives of biphenyl-3-ylmethyl (1R,S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylates resulted in esters with significantly greater insecticidal activity and broader spectrum of biological activity than the conventional pyrethroid insecticides(7). The 2-monosubstituted derivatives were found to be the most active compounds in this series with the 2-methyl compound being the most active. This result encouraged us to combine these biphenyl-3-ylmethyl compounds with alkyl aryl methanone oximes. 

Pyrethroids were found to selectively increase the sodium conductance. The time- and voltage-dependency of this increase has been analysed quantitatively for two molecules S-bioallethrin (9) and methanotetramethrin (3,4,5,6-tetrahydrophthal.imidomethyl (1RS)-cis-3 [(RS)-2,2-dimethylcyclopropyI]-2,2 dimethylcyclopropane-carboxylate also referred to as Pyrethroid I). For small... 

Some synthetic or natural exogenous compounds have been proved to potentiate defense responses (Figure 7.5). These include 2,2-dichloro-3,3-dimethylcyclopropane carboxylic acid (DDCC), which is reported to protect... 

See Diethyl cyanomethylphosphonate a-Cyano-3-phenoxybenzyl) a-(4-chlorophenyl) isovalerate 2-a-Cyano-3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutyrate a-Cyano-3-phenoxybenzyl-2-(4-chlorophenyl)-3-methylbutyrate. See Fenvalerate (S)-a-Cyano-3-phenoxybenzyl(1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate. See Deltamethrin a-Cyano-3-phenoxybenzyl (S)-2-(4-difluoromethoxyphenyl)-3-methylbutyrate. See Flucythrinate... 

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... 

Synonyms Ammo Ardap Avicade Barricade CCN52 (+)-a-Cyano-3-phenoxy-benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane carboxylate Cyano(3-phenoxyphe-nyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-carboxylate Cymbush Cyperkill FMC 30980 FMC 45497 FMC 45806 Imperator JF 5705F Kafil super NRDC 149 NRDC 160 NRDC 166 PP 383 Ripcord Siperin Stockade WL 43467. 

Cilastatin (Sumitomo). Ethyl dimethylcyclopropane carboxylate is an intermediate for cilastatin, an inhibitor for dehydropeptidase I, which is administered in combination with the carbapenem antibiotic imipenem. It is produced by Sumitomo on a small scale via addition of a carbene to isobutene (lg,59). 

Since 1998, as a conq>onent of quarantine practices against red and ittq)orted fire ant (RIFA) infestation, all plant containers at this and other nurseries in this region have been required to be treated with bifenftirin (2-methylbiphenyl-3-yl-methyl(Z)-(lRS)-cw-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropane-carboxylate). The treatment is typically carried out by incorporating a granular bifenthrin formulation, Talstar , into potting mixes... 

Problems with subsequent reaction of a 1-halocyclopropene may be avoided by reduction of the dihalocyclopropane to a monohalocyclopropane prior to dehydrohalogenation. Thus 3,3-dimethylcyclopropene may be obtained in multi-gram quantities by treatment of l-bromo-3,3-dimethylcyclopropane with potassium t-butoxide in DMSO at —78 °C19). Dehydrohalogenation of a series of related 3,3-dialkyl substituted monochloro- or monobromo-cyclopropanes leads to moderate yields of cyclopropenes (11, R = alkyl, alkenyl, aryl, CN, Cl, Rl = H, Ph, t-Bu, R2 = H)20) Indeed, dehydrobromination of (12) leads to either mono- or di-cyclopropenes 2l>. Reaction of a dihalocyclopropane with an alkyl lithium at low temperature followed by carboxylation of the derived 1-lithio-l-halocyclopropane provides a convenient source of 1-halocyclopropane carboxylates dehydrohalogenation leads to cyclo-... 

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