K. L. Moiseichuk

Synthesis and Reactions of Ethynyl Derivatives of Adamantanone, Verbanone, and Verbenone

Lithium acetylide was reacted with adamantanone, verbanone, and verbenone to obtain their hydroxyethynyl derivatives whose reaction with aqueous ammonia solution of silver nitrate gave the corresponding polycycloaliphatic silver acetylides. The latter react with iodine, yielding hydroxyethynyl iodides. Acetates of the adamantane-containing ethynyl alcohols were prepared.

Esters of Vanillin and Vanillal Oximes

Vanillin and vanillal oximes 2a and 2b were used to prepare the corresponding esters 3a-k, 4a-k, and 5a-c by reaction with acyl chlorides in the presence of pyridine.

Synthesis and structure—aroma correlation of citral oxime esters

Citral (3,7-dimethyl-2,6-octadienal, 1) occurs in lemongrass, cubeb, citrus, and other essential oils as a mixture of the Eand Z-isomers in a 7:3 ratio. This aldehyde ( 1) has a strong lemon odor [1] and is used widely in many perfume compositions. The goal of our work was to develop preparative synthetic methods of citral oxime esters through the reaction of citral oxime (2) with alkylcarboxylic acid anhydrides or alkyland arylcarboxylic acid chlorides in the presence of pyridine. The synthesis was performed at 20-23°C for 24-36 h by simply mixing the appropriate reagents and pro ceeded without using cooling and prolonged stirring. Citral oxime esters 3-22 were prepared in 74-88% yield.

Preparative synthesis of veratraldehyde and citral oxime esters

Procedures were developed for preparing veratraldehyde, oximes of veratraldehyde and citral, and esters of these oximes, which are readily accessible fragrance compounds that can be synthesized from commercially available raw materials.

Synthesis of Functionally Substituted Diacetylenic Alcohols and Carboxylic Acids

Diacetylenic alcohols were synthesized by the Glazer reaction of 1-alkynes with 1-alkyn-ω-ols. p- and m-Alkadiyne bezoic acid derivatives were prepared by the Cadiot-Hodkiewicz reaction of p- and m-ethynylbenzoic acid with 1-bromoalkynes.

Peroxy-containing acetylenic alcohols and ethers derived from 4-methoxybenzophenone and 1- and 2-acetonaphthones

A procedure was suggested for the synthesis of 2,5-dimethyl-2-tert-alkylperoxy-5-lithiooxy-5-methyl(phenyl)-5-naphthyl(aryl)alk-3-ynes by the reactions of the corresponding monosubstituted peroxyalkynes with butyllithium, followed by the reactions of the resulting lithium peroxy acetylenides with 4-methoxybenzophenone and 1- and 2-acetonaphthones. Lithium peroxy alcoholates are hydrolyzed with water to form peroxy-containing alcohols and react with methyl iodide in the presence of dimethyl sulfoxide to form the corresponding 2,5-dimethyl-2-tert-alkylperoxy-5-methoxy-5-methyl(phenyl)-5-naphthyl(aryl)alk-3-ynes. The thermal stability of the peroxides prepared was evaluated by thermal analysis.

Tertiary Acetylene Alcohols Prepared from 1-Octadecyne

Synthesis of tertiary acetylene alcohols was developed based on 1-octadecyne treatment with butyllithium followed by reaction of 1-octadecynyllithium with aliphatic, aromatic, alicyclic, and terpene ketones.

(-)-(R)- and (+)-(S)-Carvone in the Synthesis of Optically Active Acetylenic Alcohols, Ethers, and Dichlorosilyl Derivatives

Reaction of butyllithium with acetylene and 1-hexyne gave the corresponding lithium acetylides which reacted with (-)-(R)- and (+)-(S-carvone in a stereospecific fashion to give lithium (1-ethynyl- or 1-hexynyl)-5-isopropenyl-2-methyl-2-cyclohexenolates. Hydrolysis of the latter gave individual optically active tertiary terpene alcohols having both acetylenic and p-menthene fragment. Their treatment with methyl iodide in the presence of hexamethylphosphoric triamide afforded the corresponding methyl ethers. The reaction of 3-ethynyl-5-isopropenyl-3-methoxy-2-methylcyclohexene with butyllithium and trichloro(vinyl)silane yielded optically active dichlorosilyl-containing acetylenic compounds.

Camphor and Isocamphanone in the Synthesis of Disubstituted Acetylene Alcohols, Ethers, and Esters

By treating 1-octyne and phenylacetylene with butyllithium the corresponding lithium acetylides were obtained that with camphor and isocamphanone provided along streospecific process 2-exo-(1-octynyl or 2-phenyl-1-ethynyl)-2-endo-lithiumoxy-5,5,6-trimethylbicyclo[2.2.1]heptane and 2-endo-(1-octynyl or 2-phenyl-1-ethynyl)-2-exo-lithiumoxy-1,7,7-trimethylbicyclo[2.2.1]heptane. The hydrolysis of these lithium alcoholates occurred selectively and resulted in individual tertiary terpene alcohols containing exo-acetylene substituent in the case of camphor, endo-acetylene fragment in the case of isocamphanone. The alcohols reacted with methyl, ethyl, or butyl iodides in the presence of hexamethylphosphoramide to afford ethers, and with benzoyl chloride to furnish disubstituted esters of benzoic acid.

Synthesis of Peroxy Bond Containing Acetylene Alcohols, Ethers, and Esters, Derivatives of 2-Octanone

A synthesis was developed of 2,5-dimethyl-2-tert-alkylperoxy-5-lithiumoxy-3-undecynes by treating the corresponding peroxyalkynes with butyllithium followed by reaction of the arising lithium peroxyacetylides with 2-octanone. The lithium peroxyalcoholates undergo hydrolysis with water to furnish peroxy bond containing alcohols. They also react with methyl and ethyl iodides, alkyl and benzyl bromides in the presence of hexamethylphosphoramide to afford the corresponding 2,5-dimethyl-2-tert-alkylperoxy-5-alkyl(benzyl)oxy-3-undecynes, with benzoyl chloride they yield peroxy bond containing benzoates. The thermal stability of the peroxides obtained was estimated by derivatography.