E. A. Dikusar

Preparative synthesis of menthone oxime esters

Procedures are developed for the preparation of menthone oxime esters as accessible perfumes and fragrant additives synthesized from natural raw materials.

Synthesis and structure—aroma correlation of anisaldehyde oxime esters

Preparative syntheses from anisaldehyde 1 of the anti-isomer of anisaldehyde oxime 2 and anisaldehyde oxime esters 3a-q in 84-93% yields were developed. The structure—aroma correlation of 2 and 3a-q was studied.

Synthesis of 1,3- and 1,4-bis-methoxy- and ethoxy-4-(m-carborane-C-methanoyloxy)phenylmethylene- and phenylmethyl]phenylenediamines

Abstract1,3- and 1,4-bis[3-methoxy and ethoxy-4-(m-carborane-C-methanoyloxy)phenylmethylene]phenylenediamines were synthesized from the vanillin and vanillal m-carborane-C-carboxylates by the reaction with 1,3- and 1,4-phenylenediamines in anhydrous methanol. Reduction of the title compounds with Na[BH(OAc)3] in benzene yielded 1,3- and 1,4-bis[3-methoxy- and ethoxy-4-(m-carborane-C-methanoyloxy)phenylmethyl] phenylenediamines.

Thermal Stability of Peroxyalkynes

The thermal stability of mono- and disubstituted peroxyalkynes was compared. The reaction order and the apparent activation energy for the first step of decomposition of the peroxides were determined. The strength of the O-O bond in 3-tert-alkyl(cycloalkyl, aralkyl)peroxy-3-methyl-1-butynes and 2-tert-alkylperoxy-2-methyl-2-alkynes was estimated.

Alcohols, Ethers, and Esters with Peroxy Groups Prepared from 2-tert-Butylperoxy-2-methylpentan-4-one

Abstract2-tert-Butylperoxy-2-methylpentan-4-one reacts with butyllithium providing saturated tertiary peroxyalcohol, with 1-lithioalkynes, among them lithiooxy- and peroxy-containing, gives rise to the corresponding tertiary acetylene mono- and diperoxyalcohols and diols. The thermal stability of peroxides obtained was evaluated by derivatography.

Polymerization of styrene initiated by acetylenic peroxides

The initiating activity of acetylenic peroxides in polymerization of styrene was studied. The kinetic parameters of the polymerization and its initiation were calculated. The effect exerted by the structure of radicals on the initiating activity of peroxides was evaluated.

Synthesis of 1-Acetamido-2-acetyladamantane

The triple bond of 2-ethynyl-2-adamantanol virtually did not hydrolyze under Kucherov reaction conditions in aqueous ethanol and methanol. In aqueous acetic acid arose a mixture of 2-acetyl-2-adamantanol and its acetate. In good yield the 2-acetyl-2-adamantanol was obtained by Kucherov reaction in aqueous THF. This alcohol with acetonitrile under conditions of Ritters reaction (catalysis with sulfuric acid) afforded a mixture of 1-acetamido-2-acetyl-, 1-acetamido-4-cis- and 1-acetamido-4-trans-acetyladamantanes in 8:1:1 ratio.

Terpene and steroid alkynyl peroxides

A method was developed for preparation of alkynyl peroxides from terpene and steroid aldehydes and ketones by reaction of lithium peroxyacetylides with the corresponding aldehydes and ketones followed by treating the intermediate lithium alcoholates with acyl chlorides.

Peroxide-containing Lithium Tetraalkoxyborates

Reactions of aliphatic and alicyclic ketones with lithium tert-alkylperoxyacetylides gave lithium peroxy alcoholates. Their reactions with trialkyl borates yielded peroxide-containing lithium tetraalkoxyborates.

Thermal Stability of Mono- and Polycyclic Peroxyalcohols and Their Derivatives by Thermal Analysis

A comparative study of the thermal stability of 33 mono- and polycyclic peroxyalcohols, as well as ethers and esters derived from them was performed by thermal analysis. Reaction orders and apparent rate constants of the first stage of peroxide decomposition were determined from the DTA curves. Semiempirical quantum-chemical calculations of the strength of the O-O bond in peroxycycloalkanols and peroxyalcohols of the adamantane series and their derived esters were performed.