Free Radical Chain Nucleophilic Substitution Reactions of 1-Chloro-1-cyclopropyl-1-nitroethane and 2-Chloro-2-nitrohept-6-ene.

Article abstract of DOI:10.1021/jo00214a018

1-Chloro-1-cyclopropyl-1-nitroethane and 2-chloro-2-nitrohept-6-ene underwent free radical chain substitution reactions in which the chlorine was replaced by the nucleophiles Me2C=NO2^-, c-C3H5C(CH3)=NO2^-, CH2=CH(CH2)3C(CH3)=NO2^-, (EtO2C)2CMe^-, Me3C(O^-=CH2 or the enolate anion of 2-methyl-1,3-cyclopentanedione.Ring opening or closure reactions were not observed in these substitutions or in the reaction of 1-chloro-1-cyclopropyl-1-nitroethane with (n-Bu)3SnH to form 1-cyclopropyl-1-nitroethane.A 1-nitro substituent retards the rate of the cyclopropylcarbinyl radical ring opening by a factor of the at least 10⁴ at 40 deg C.