✍ Scribed by Christopher J. Woltermann; Harold Shechter
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Lithium phenylacetylide (1a) and N 2 O 4 (2) at À 788 yield diphenylbutadiyne (6a) by oxidative coupling, phenylacetylene (7a) by oxidation and then solvent H-abstraction, and benzoyl cyanide (8) by dimerizativerearrangement of nitroso(phenyl)acetylene (23). Nitro(phenyl)acetylene (3, R Ph) is not obtained. Benzonitrile (9), a further product, possibly results from hydrolytic decomposition of nitroso(phenyl)ketene ( 27) generated from phenylacetylenyl nitrite (26). Phenylacetylene (7a) and 2 give, along with (E)-and (Z)-1,2dinitrostyrenes (34 and 35, resp.), 3-benzoyl-5-phenylisoxazole (10), presumably as formed by cycloaddition of benzoyl nitrile oxide (40) to 7a. Further, 2 reacts with other lithium acetylides (1b ± 1e), and with sodium, magnesium, zinc, copper, and copper lithium phenylacetylides, 1f ± 1l, to yield diacetylenes 6a ± 6c and monoacetylenes 7a ± 7c. Conversions of metallo acetylide aggregates to diacetylenes are proposed to involve generation and addition reactions of metallo acetylide radical cationic intermediates in cage, further oxidation, and total loss of metal ion. Loss of metal ions from metallo acetylide radical cations and H-abstraction by noncaged acetylenyl radicals will give terminal acetylenes. The principal reactions (75 ± 100%) of heavy metal acetylides phenyl(trimethylstannyl)acetylene (44) and bis(phenylacetylenyl)mercury ( 47) with 2 are directed nitrosative additions (NO ) and loss of metal ions to give nitroso(phenyl)ketene ( 27), which converts to benzoyl cyanide (8).
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