Mechanism Studies of Solvolysis of Benzoyl Chlorides along the Substituents

?????? ?????? ??? ????????? ?????? ?????? ????????? 2-(chloromethyl)benzoyl chloride (?????? 1), 3-(chloromethyl)benzoyl chloride (?????? 2), 4-(chloromethyl)benzoyl chloride (?????? 3), 2,6-difluoro-4-methyoxybenzoyl chloride (?????? 4)??? ????????? ???????????? ??????????????? ?????? ????????? ???????????????. ????????? ????????? ?????? ??????????????? 25.0 ????????? ??????????????? ???????????? ???????????????, extended-Grunwald-Winstein???(G-W???)??? ???????????? ??????????????? ??? ????????? ?????? ?????? ??????????????? ?????? ?????????(l)??? ?????? ??????????????? ?????? ?????????(m)??? ?????????. ??????, ?????? ???????????? ??????(kinetic solvent isotope effect)??? ??? ?????? ?????? ???????????? ???????????? ?????? ????????? ??????????????? ?????? ????????? ?????? ??????????????? ???????????? ????????? ??????????????? ???????????? ?????? ??????????????? ???????????????. ?????? 1??? extended G-W?????? ????????? ??????, ???????????? ?????? ??? ????????? ??????????????? ??????????????? ???????????? ?????? ???????????? dissociative SN2 ????????? ??????????????? ??????????????? ???????????????. ????????? ortho ????????? chloromethyl ???????????? ????????? ?????? ????????? ?????? ?????? ????????? ????????? ??? ????????????. ?????? 2??? 3??? ????????? ????????? ?????? ?????? ??????????????? ????????? ????????? ???????????????, G-W?????? ????????? ??????????????? ???????????? ?????? ???????????? ????????????. ?????? 2??? ???????????? ?????? ??????????????? addition-elimination ??????????????? ?????????????????????, ???????????? ??????????????? dissociative SN2 ??????????????? ???????????? ????????? ????????????. ?????? chloromethyl?????? ?????? ???????????? ???????????? ?????? ??????1?????? ???????????? ?????? ????????? ???????????? ???????????? ????????????. ?????? 3??? ?????? ????????? ?????? ?????????????????? associative SN2 ???????????????, ??????????????? ?????? ??????????????? dissociative SN2 ??????????????? ??????????????? ????????????. ?????? ??????, ?????? 2?????? ?????? 3??? ????????? ??????????????? ???????????? ?????? ????????? ????????? ?????? ?????? ??? ??? ?????????. ?????? ???????????? ???????????? ??? ?????? ????????? ?????? ?????? 3??? ???????????? ????????? ??? ????????? ?????? meta ????????? ????????? ????????? ????????????, para ????????? ????????? ???????????? ????????? chloromethyl?????? ?????? ????????? ????????? ???????????? inductive effect??? ???????????? ???????????? ????????????. ?????? 2??? 3??? ?????? 1??? ?????? ???????????? ????????? ????????? ???????????? ????????? ?????? ????????? ????????? ????????? ????????? ????????? ?????? ?????? ????????????(inductive effect)?????? ????????? ???????????? ??? ??? ??????. ??????????????? ?????? 4??? ??? ????????? ???????????? ????????? ????????? para ????????? methoxy ???????????? resonance effect??? ????????? ?????? ???????????? ???????????? ????????? ????????? ??????????????? ionization ??????????????? ???????????? ????????? ?????? ?????????. ????????? ????????? 4-methoxybenzoyl chloride??? ????????? ???????????? ??? ?????? ??????????????? ?????? ????????? ????????????, ?????? ortho ????????? ?????? ??? ?????? F ????????? ?????? ?????? ????????? ?????? ?????? ????????? ??????????????? ???????????? ?????? ?????? ????????????. ??? ????????? ?????? 1, 2, 3??? ????????? chloromethyl?????? ????????? ?????? ?????????????????? ????????? ??? ??? ?????????. ??????, ?????? 4??? ????????? ????????? F ????????? methoxy??? ??? ?????? ???????????? ???????????? ??? ?????? ???????????? ??? ??? ??? ?????????. Benzoyl chloride?????? ????????? ?????? ?????? ??????????????? ???????????? ??? ?????? ?????? ?????? ????????? ?????? ????????? ????????? ?????? ?????? ??????. ??? ????????? Benzoyl chloride?????? ?????? ????????? ?????? ??????????????????, ?????? ???????????? ????????? ?????? ?????? ?????????????????? ????????? ?????? ??? ????????? ????????????.Maste