G. S. Lyashenko

Synthesis and spectroscopic investigation of aryloxy- and arylthioalkenes, alkynes, and allenes

Conclusion1.A series of aryloxy and arylthio derivatives of ethylene, methylacetylene, and allene have been synthesized. Allenyl ethers of p-cresol, p-chloro, p-bromo, p-nitro, and 2,4,6-trichlorophenol have been prepared for the first time by acetylene-allene isomerization of the corresponding propargyl ethers.2.It has been shown that the S atom in the compounds studied behaves as an effective bridge for the π, p, π-conjugated system. On account of the lower ionization potential for the unshared electron pair on S compared with O, the polarizability of the conjugated system in the sulfides is increased significantly. The s-trans conformation is apparently preferred for the phenylvinyl and phenylallenyl ethers.

Reaction of para-nitrophenoxypropynylcopper with benzoyl chloride

ConclusionsThe reaction of copper p-nitrophenoxypropynylide with benzoyl chloride proceeds with the formation of 1-p-nitrophenoxy-3-benzoylpropadiene, p-nitrophenyl benzoate, and 1,6-bis(p-nitrophenoxy)-2,4-hexadiyne. p-Nitrophenyl benzoate may be obtained as a result of the thermal fragmentation of 1-p-nitro-3-benzoylpropadiene.

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.

Determination of the Ch acidity of certain ethyne ethers by polarographic reduction of their mercury derivatives

ConclusionsNew mercury derivatives of the ethyne ethers and sulfides have been prepared and their CH acidities determined by the polarographic reduction method.

Phosphorylation of phenoxyacetylene by phosphorus pentachloride

Conclusions1.The reaction of phenoxyacetylene with PC15 gives a stable mixture of the E and Z isomers of β-phenoxy-β-chlorovinyltrichlorophosphonium hexachlorophosphate. A scheme was proposed for the phosphorylation of phenoxyacetylene.2.The dichlorides of β-phenoxy-β-chlorovinyl- and β-alkoxyvinylphosphonic acids add HCl to the double bond, while the alkoxyvinyltrichlorophosphonium hexachlorophosphates do not react with HCl.

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.

Spectroscopic investigation of propargyl aryl ethers

The UV, Raman, and IR spectra of propargyl ethers are evidence of the absence of interaction between the C≡C group and the oxygen atom through the methylene bridge.

Some transformations of aroxyacetylenes

1. It was shown that aromatic acetylenic ethers exhibit a high tendency to add to halogens, organic acids and ethanolamine. On the example of the reaction with acids it was shown that the nitro group in the p-nitrophenoxyacetylene molecule exerts a passivating effect on the triple bond. 2. We were the first to run the telomerization reaction of acetylenic ethers on the example of phenoxy-acetylene.