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Absolute rate constants for the reactions of phenylhalocarbenes with alkynes
Author(s) -
Moss Robert A.,
Jang Eun G.,
Ho GuoJie
Publication year - 1990
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610031111
Subject(s) - chemistry , alkyne , alkene , reaction rate constant , entropy of activation , activation energy , medicinal chemistry , computational chemistry , stereochemistry , organic chemistry , kinetics , catalysis , physics , quantum mechanics
Additions of phenylchlorocarbene and phenylfluorocarbene to representative alkynes are rapid (10 6 –10 7 l mol −1 s −1 ). The variation of the rate constants with alkyne structure parallels that observed with analogous alkene substrates. The addition of phenylchlorocarbene to 3‐hexyne is characterized by a very low activation energy (∼ 2 kcal mol −1 ) and a large, negative entropy of activation (∼ −20 e.u.).