ISSN:
0947-3440
Keywords:
Cyano compounds, conjugated
;
Phenylacetylenes
;
Radical anions
;
Electrochemistry
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 6n·-. 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 6h2·-. By contrast, the tricyanoacrylates 8 can be reversibly reduced to their respective radical anions and dianions.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.1995199509231
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