Chemical Reaction of Electron Donor–Acceptor System: A New Mechanism for the Tricyanovinylation Reaction of Some Aromatic Amines with Tetracyanoethylene

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概要

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• The tricyanovinylation reactions of several aromatic amines with tetracyanoethylene (TCNE) were investigated kinetically by observing the change of the absorbance of the charge-transfer (CT) band in 1,2-dichloroethane. The pseudo first order rate coefficient of the decay of the CT-complex (<I>k</I><SUB>obsd</SUB>) was found to obey the relation, <I>k</I><SUB>obsd</SUB>=<I>kKD<SUP>n</SUP></I>⁄(1+<I>KD</I>) (<I>K</I>: association constant of CT-complex; <I>D</I>: initial concentration of donor molecule), where <I>n</I>=1 in <I>N</I>,<I>N</I>-diethylaniline (DEA)–TCNE and <I>N</I>,<I>N</I>-di-<I>n</I>-butylaniline (DBA)–TCNE systems and <I>n</I>=2 in <I>N</I>-methyl-<I>N</I>-ethylaniline (MEA)–TCNE system. Since the currently accepted mechanism for the tricyanovinylation reaction cannot explain the case of <I>n</I>=1, we have proposed a new reaction mechanism which can explain all the kinetic data reported hitherto. Two characteristic points are involved in the new mechanism, <I>i.e.</I>, one is the unimolecular reaction of the CT-complex or the bimolecular reaction between reactants to form the σ-complex, and the other the decomposition of the σ-complex back to the component molecules. The reactions of MEA, DEA, and DBA with TCNE were discussed based on the new mechanism.

• 公益社団法人 日本化学会の論文

著者

• Shirota Yasuhiko

  Department Of Applied Chemistry Faculty Of Engineering Osaka University

• Mikawa Hiroshi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Nogami Takashi

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

• Hasegawa Yoshiki

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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