title: Dichlorination of (hexadehydro-Diels-Alder generated) benzynes and a protocol for interrogating the kinetic order of bimolecular aryne trapping reactions.
abstract: The efficient dichlorination of benzynes prepared by the hexadehydro-Diels-Alder (HDDA) reaction is reported. Cycloisomerization of a triyne substrate in the presence of dilithium tetrachlorocuprate is shown to provide dichlorinated products A by capture of the benzyne intermediate. A general strategy for discerning the kinetic order of an external aryne trapping agent is presented. It merely requires measurement of the competition between bimolecular vs unimolecular trapping events (here, dichlorination vs intramolecular Diels-Alder (IMDA) reaction to give A vs B, respectively) as a function of the concentration of the trapping agent.
authors: Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors: Dawen
authors: D
authors: Niu
authors: Tao
authors: T
authors: Wang
authors: Brian P
authors: BP
authors: Woods
authors: Thomas R
authors: TR
authors: Hoye
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D006843:Hydrocarbons, Chlorinated / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure
chemical_list: D001555:Benzene Derivatives; D006843:Hydrocarbons, Chlorinated; C524146:benzyne