63142-56-3

Basic information

• Product Name: ethyl cis-()-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate
• Synonyms: Cyclopropanecarboxylic acid, 3-(2,2-dichloroethenyl)-2,2-dimethyl-, ethyl ester, (1R,3R)-rel-; cis-(+-)-3-(2,2-Dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid, ethyl ester; Ethyl cis-(1)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate; Ethyl cis-2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate
• CAS NO: 63142-56-3
• Molecular Formula: C₁₀H₁₄Cl₂O₂
• Molecular Weight: 237.125
• EINECS: 262-531-6;263-922-4
• Mol File: 63142-56-3.mol

Chemical Properties

• CAS DataBase Reference: ethyl cis-()-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate(CAS DataBase Reference)
• NIST Chemistry Reference: ethyl cis-()-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate(63142-56-3)
• EPA Substance Registry System: ethyl cis-()-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate(63142-56-3)

Safety Data

• Hazardous Substances Data: 63142-56-3(Hazardous Substances Data)

Upstream product

• 623-73-4 diazoacetic acid ethyl ester 
• 55667-43-1 1,1-dichloro-4-methyl-penta-1,3-diene 
• 67401-42-7 (+/-)-cis-2,2-dimethyl-3-(2',2'-dichlorovinyl)cyclopropanecarboxamide 
• 64788-83-6 ethyl cis-3-(1-hydroxy-2,2,2-trichloroethyl)-2,2-dimethylcyclopropanecarboxylate 
• 38692-37-4 ethyl (±)-(1S,3R)-3-formyl-2,2-dimethylcyclopropanecarboxylate 
• 60856-71-5 (+/-)-cis-cyanoaldehyde 
• 111455-25-5 Acetic acid (E)-5-cyano-1,1,4,4-tetramethyl-5-(2,4,6-trimethyl-benzenesulfonyl)-pent-2-enyl ester 
• 111455-27-7 (+/-)-cis-3-(2'methyl-1'-propenyl)-2,2-dimethyl-1-cyano-1-(2'-4'-6'-trimethyl-phenylsulfonyl)cyclopropane 
• 61820-11-9 (+/-)-cis-2,2-dimethyl-3-(2',2'-dichlorovinyl)cyclopropanecarbonitrile 
• 2198-88-1 (+/-)-cis-2,2-dimethyl-3-(2',2'-dimethylvinyl)cyclopropanecarbonitrile 
• 60066-54-8 ethyl 4-bromo-6,6,6-trichloro-3,3-dimethylhexanoate 
• 7796-72-7 ethyl 3,3-dimethylpent-4-enoate 
• 63435-29-0 ethyl 6,6,6-trichloro-3,3-dimethyl-4-hexenoate 
• 60066-84-4 ethyl 2,2-dimethyl-3-(2,2,2-trichloroethyl)-cyclopropanecarboxylate 

Downstream Products

• 569679-06-7 3-(tert-butyl) 2-methyl (1R,2S,5S)-6,6-dimethyl-3-azabicyclo[3.1.0]hexane-2,3-dicarboxylate 
• 55667-40-8 1(R)-cis-permethrinic acid 
• 78548-58-0 (1S,3S)-3-(2,2-Dichloro-vinyl)-2,2-dimethyl-cyclopropanecarboxylic acid ethyl ester 
• 55701-08-1 (-)-cis-(1S,3S)-2,2-dimethyl-3-(2',2'-dichlorovinyl)cyclopropanecarboxylic acid 
• 60940-88-7 (1R,3R)-3-(2,2-Dichloro-vinyl)-2,2-dimethyl-cyclopropanecarboxylic acid ethyl ester 
• 133575-09-4 ethyl cis-3-<(Z)-2-chloro-2-phenylethenyl>-2,2-dimethylcyclopropanecarboxylate 

Relevant articles and documents

Reductive Addition of Polyhalomethanes and Their Related Compounds to Aldehydes and 1,2-Elimination of the Coupling Products in a Pb/Al Bimetal Redox System

A Pb/Al bimetal system was used to carry out reductive addition of tetrachloromethane, tetrabromomethane, bromotrichloromethane, trichloroacetamide, and trichloroacetonitrile to aldehydes.Subsequent 1,2-elimination of the halogen atom and hydroxyl group from the coupling products was also performed with the Pb/Al bimetal system.The technology was successfully applied to stereocontrolled syntheses of ethyl trans- and cis-3-(2,2-dihaloethenyl)-2,2-dimethylcyclopropanecarboxylates.

Synthesis of ethyl (+/-)-cis-3-(2,2-dihalogenovinyl)-2,2-dimethylcyclopropanecarboxylate

The two (+/-) cis pyrethroid ethyl esters 2a,b have been synthesized.These esters are obtained via stereoselective ScN' cyclization of 3b to 5b.Desulfonylation of 5b with retention of configuration at low temperature (Na/Hg, -30 deg C) affords (+/-)-cis-chrysanthemonitrile 6.This nitrile is converted into cis aldehyde 7 which by Wittig reaction provides pyrethroid nitriles 8a and 8b, respectively.Finally hydrolysis of the nitrile group gives the esters 2a and 2b in 30percent overall yield from 3b.

A Convenient Synthesis of Ethyl 3-(2,2-Dihaloethenyl)-2,2-dimethylcyclopropanecarboxylates and Its Modifications for cis-Isomer Enrichment

A synthesis of the title compounds 5 involves the reaction between 3-methyl-2-buten-1-ol and triethyl orthoacetate to produce ethyl 3,3-dimethyl-4-pentenoate, which is followed by the addition of various carbon tetrahalides to the double bond.The reaction of resulting adducts with a base affords 5 in high yields.Stereoselective preparation of the cis-isomer was achieved by the following two methods: First one involves selective transformation of ethyl 4-bromo-6,6,6-trichloro-3,3-dimethylhexanoate to ethyl 6,6,6-trichloro-2,3-dimethyl-4-hexanoate (8a) with piperidine followed by the selective conversion of 8a to cis-2,2-dichloroethenyl compound (cis-5a).Second one is based on the stereoselective cyclization of ethyl 4,6,6,6-tetrachloro-3,3-dimethyl-hexanoate (t-BuONa/solvent/HMPA) to ethyl cis-2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate which is transformed into cis-5a without cis-trans isomerisation.

TRANSITION-METAL-CATALYSED REACTIONS OF DIAZOESTERS : SYNTHESIS OF CHRYSANTHEMIC AND PERMETHRIC ACID ESTERS BY CYCLOPROPANATION OF CONJUGATED DIENES

Pyrethroid precursors (permethric and chrysanthemic acid esters) are efficiently synthesized by rhodium(II)-catalysed cyclopropanation of the properly substituted conjugated diene.Reaction selectivities depend on both the catalyst counter-ion and the diazoester alkoxy-group (carbene precursor) and are attributed to non-bonded interactions.