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High‐energy kinetic study of chemically activated 1,1‐dichlorocyclopropane
Author(s) -
Eichler K.,
Heydtmann H.
Publication year - 1981
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550131102
Subject(s) - chemistry , ketene , isomerization , reaction rate constant , kinetic energy , activated complex , inert gas , photochemistry , photodissociation , activation energy , inert , kinetics , computational chemistry , medicinal chemistry , organic chemistry , catalysis , physics , quantum mechanics
1,1‐Dichlorocyclopropane has been produced by addition of CH 2 ( 1 A 1 ) to 1,1‐dichloroethylene. CH 2 ( 1 A 1 ) was generated by the photolysis of ketene at 277–334 nm. The 1,1‐dichlorocyclopropane was formed in a chemically activated state, had an energy content between 386 and 400 kJ/mol, and reacted in two parallel channels to 2,3‐dichloropropene and 1,1‐dichloropropene. 1,1‐Dichloropropene was also formed directly by insertion of CH 2 ( 1 A 1 ) into the CH bond of 1,1‐dichloroethylene. As secondary reactions elimination of HCl from chemically activated 2,3‐dichloropropene occurred with 3‐chloropropyne and chloroallene as products. In some of the experiments perfluoropropane was added as an inert gas. The apparent rate constants for the isomerization and elimination reactions are reported. The results of RRKM calculations including distribution functions for the activated 1,1‐dichlorocyclopropane and a step‐ladder model for the deactivation verify the proposed reaction scheme.