Acetylenes from cyclopropenones

One of the reasons for confusion in this area is the fact that cyclobutenediones absorb at much shorter wavelengths than their saturated counterparts, prompting the use of short wavelength light in photolyses this can result in formation of secondary photoproducts. It seems likely that formation of cyclopropenones and of acetylenes is the result of photochemical reaction of bisketenes, the primary products of irradiation. Acetylenes could also be formed from cyclopropenones. 

Independently Volpin17 synthesized diphenyl cyclopropenone from diphenyl-acetylene and dibromo carbene (CHBr3/K-tert.-butoxide). This reaction principle of (2 + 1) cycloaddition of dihalocarbenes or appropriate carbene sources ( caibenoids ) to acetylenic triple bonds followed by hydrolysis was developed to a general synthesis... 

Trichloromethyl lithium (generated from BrCCl3 and CH3Li at —100 °C) adds to dialkyl acetylenes and to monoalkyl acetylenes23, thus monoalkyl cyclopropenones became accessible which could not be obtained from terminal acetylenes by reaction with the above carbene sources. The 3,3-dihaIogeno-A1,2-cycIopropenes formed as primary products in the dihalocarbene reactions are usually not isolated, but are hydrolyzed directly to cyclopropenones. 

Finally, the addition of difluorocarbene (generated from FjClCCOjNa) to steroidal acetylenes has been achieved24-26 giving rise to exotic cyclopropenones bearing steroid systems as substituents, e.g. 19/20. 

From the electronic populations on the vinylic hydrogens, the acidity of vinylic C—H was estimated to be higher in cyclopropenone than in cyclopropene (0.684 e/ 0.776 e). This agrees with kinetic measurements of the H-D-exchange at n-propyl cyclopropenone23 which showed an acidity of the vinylic C—H even higher than that of the acetylenic C—H in the reference compound propargyl alcohol. 

The compound 251 decarbonylates on photolysis to bis(4-hydroxyaryl) acetylene 253, which is easily oxidized to the quinonoid cumulene 254. This is also obtained by thermal decarbonylation of the product of oxidation of cyclopropenone 251, the diquinocyclopropanone 252. Likewise, the blue derivative of 3-radialene 256 (a phenylogue of triketo cyclopropane) is formed from tris-(4-hydroxyaryl) cyclopropenium cation 255 by oxidation34. ... 

Thus asymmetric diaryl cyclopropenones were converted to the isomeric acrylic acids 318/319 by aqueous Ni(C0)4 in a similar proportion to that obtained from the corresponding acetylenes by carbonylation with the same catalyst279, whilst in non-aqueous media carbonyls like Ni(C0)4, Co2(CO)8, or Fe3(CO)12 effected de-carbonylation278, 280) probably via metal-complexed intermediates, e.g. 

The most general methods for preparing seven- or eight-membered rings from enamines are by ring expansion of the cyclobutene, cyclobutanone or chlorocyclopro-pane adducts formed by cycloaddition of acetylene carboxylates, ketenes or chlor-ocarbenes, respectively, to enamines of cyclopentanone or cyclohexanone. These are two-carbon or one-carbon ring expansions. Three-carbon ring expansions can also be carried out by cycloaddition of activated cyclopropenes or cyclopropenones. 

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