I. D. Kalikhman

Reaction of 1-acyl-2-phenylacetylenes with thiosemicarbazide

ConclusionsThe reaction of 1-acyl-2-phenylacetylenes with thiosemicarbazide in methanol at 60‡C gives 2-amino-7-hydroxy-6,7-dihydro-1,3,4-thiadiazepines which, upon heating in -vacuum fragment with the formation of 3,5-disubstituted pyrazoles.

Reaction of copper derivatives of monosubstituted acetylenes with benzoyl chloride

ConclusionsDepending on the substituents in the aroxyl group, the reaction of copper aroxypropynylides with benzoyl chloride can proceed in three directions and lead respectively to the formation of allenicγ-ketoethers,1,6-diaroxy-2,4-hexadiynes, or aryl benzoates. Copper phenoxyethynylide forms phenyl benzoate under these conditions.

Synthesis of some functional derivatives from aroxyacetylenes and aroxypropynes

Conclusions1.Some tertiary aroxyethynylcarbinols were obtained for the first time.2.The reaction of benzaldehyde with phenoxyacetylene is stereospecific and gives the phenyl ester of trans-cinnamic acid.3.Phenoxyacetylene adds GeCl4 to give the cis and trans adducts in a 1∶1 ratio. SiCl4. under the same conditions gives only traces of the adduct.

Reactions of aromatic acetylenic ethers with triethylgermane

ConclusionsThe addition of Et3GeH to the phenoxy- and phenylthioacetylenes under the influence of (Ph3P)3RhCl is both nonstereo- and nonregiospecific. The analogous reaction with 3-aroxy-1-propynes is stereospecific but nonregioselective.

Germylation and silylation of phenoxy- and phenylthiopropynes and phenoxyallene

Conclusions1.Reaction of triethylgermyllithium with 3-phenoxy- or 3-phenylthio-1-propyne occurs principally in the direction of metallization at the acetylenic hydrogen atom. The isomeric 1-phenoxy- or 1-phenylthio-1-propynes under these conditions do not form addition products at the triple bond. In reaction with phenoxyallene the Et3Ge anion mainly attacks the terminal methylene group.2.Hydrogermylation and hydrosilylation of these compounds takes place nonregiospecifically with formation of the α and β adducts. Phenoxyallene adds on to triethylgermane in the 1,2- and 2,3- positions.