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Synthesis and electrochemical properties of 4‐phenyl‐1‐buten‐3‐yne‐1,1,2‐tricarbonitriles and tricyanoacrylates
Author(s) -
Dulog Lothar,
Körner Bernd,
Heinze Jürgen,
Yang Jianjun
Publication year - 1995
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.1995199509231
Subject(s) - tetracyanoethylene , chemistry , nitrile , acetonitrile , medicinal chemistry , halide , pyridine , electrochemistry , ion , polymer chemistry , photochemistry , organic chemistry , electrode
The reaction of phenylacetylenes 4a–h with copper(I) acetate ( 5 ) and TCNE (tetracyanoethylene) in THF/acetonitrile gave 4‐phenyl‐1‐buten‐3‐yne‐1,1,2‐tricarbonitriles 6a–h. 4i did not react to give 6i . The phenylacetylenes 4b–i were prepared by a two‐step synthesis starting from the corresponding phenyl halides 1b–i . The tricyanoacrylates 8 were synthesized from the corresponding cyanoacetates 7 , TCNE and catalytic amounts of pyridine in THF. – Cyclovoltammetric investigations showed that the butenynes 6 and the tricyanoacrylates 8 are strong electron acceptors which can be easily reduced. The radical anions 6 ˙ − are unstable in aceto‐nitrile and react irreversibly with 6 to give oligomeric anions 6 n ˙− . Only 4‐(2,4,6‐trimethoxyphenyl)‐1‐buten‐3‐yne‐1,1,2‐tricarbonitrile ( 6h ) is reduced to a radical anion 6h ˙− which associates with 6h in a reversible follow‐up process to form a dimeric anion 6h 2 ˙− . By contrast, the tricyanoacrylates 8 can be reversibly reduced to their respective radical anions and dianions.