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0039203297
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Note
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23
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0039203296
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Note
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We had observed that a reaction of 4 (23.4 mg, 0.0206 mmol) with tetracyanethylene (TCNE) (11.8 mg, 0.092 mmol) in THF solution (2 ml) resulted in the formation of ethyl (E)-2-cyano-3-phenylpropenoate (0.011 mmol, 52%), benzalomalononitrile (0.0012 mmol, 12%) and ethyl 2,3,3-tricyano-propenoate (0.0021 mmol, 10%). Although formation of 1,1-dicyano-2-phenylethylene and ethyl 2,3,3-tricyanopropenoate can be regarded as a formal olefin metathesis of TCNE with ethyl (E)-2-cyano-3-phenylpropenoate [17], this reaction actually proceeded in the absence of Re complexes. It is known that hydrolysis of TCNE gives malononitrile and dicyanoketone. Michael reaction of the generated malononitrile with ethyl (E)-2-cyano-3-phenylpropenoate followed by the elimination of ethyl cyanoacetate gives 1,1-dicyano-2-phenylethylene. The resulting ethyl cyanoacetate successively reacts with TCNE to yield ethyl 2,3,3-tricyanopropenoate and malononitrile [18]. All these reactions were independently determined.
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24
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0040982124
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0003855565
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Quartz optical cell having 3-way stopcock was used for UV-Vis analyses. cf. (a) Wiley Interscience, New York
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Quartz optical cell having 3-way stopcock was used for UV-Vis analyses. cf. (a) A. Yamamoto, Organotransition Metal Chemistry, Wiley Interscience, New York, 1986, pp. 169.
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Yamamoto, A.1
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(b) G.M. Sheldrick, SHELXL93, University of Göttingen, Germany, 1993.
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