L. P. Botsman

Transformations of peroxide products of olefins ozonolysis

The review summarizes the main laws of olefin ozonolysis and also further transformation of the peroxide products in “splitting” reactions and at the treatment with oxidants and reducers.

Synthesis of 10-hydroxy- and 9-oxo-2E-decenoic acids from oleic acid

A practical synthesis of biologically active 10-hydroxy- and 9-oxo-2E-decenoic acids, components of mandibular gland secretion of honeybee (Apis mellifera L.), is developed using ozonolysis-reduction of oleic acid and 1,9-diacetoxynon-1-ene in the key steps.

Transformations of peroxide olefin ozonolysis products under the action of hydroxylamine and semicarbazide hydrochlorides in isopropyl alcohol

Hydroxylamine and semicarbazide hydrochlorides were shown to be efficient as reducing agents toward peroxide products of ozonolysis of various olefins with different degrees of substitution. The rate of the transformations aldehyde → aldehyde oxime → nitrile → ester upon treatment of peroxides with hydroxylamine hydrochloride in isopropyl alcohol was lower than in methanol.

Transformations of peroxide products of olefin ozonolysis under the action of semicarbazide in methanol

Peroxide products generated by ozonolysis of non-1-ene, 3-carene, stereoisomeric α-pinenes, (−)-limonene, and castor oil were subjected to transformations by the action of semicarbazide and hydrazine-1,2-dicarboxamide in methanol.

Ozonolysis of Unsaturated Compounds in the Synthesis of Insect Pheromones and Juvenoids

Research from the last 20 years on the use of ozonolysis of cyclic and acyclic mono- and dienes and aromatic compounds in various steps of the total synthesis of insect pheromones and juvenoids was reviewed.

Ozonolytic transformations of (S)-(−)-limonene

Partial ozonolysis of (S)-(−)-limonene in cyclohexane-methanol yields 1-methyl-4-(prop1-en-2-yl)-7,8,9-trioxabicyclo[4.2.1]nonane as a mixture of diastereoisomers at a ratio of 2: 3. Nitrogen-containing organic compounds (semicarbazide and hydroxylamine hydrochlorides) favor cyclization of intermediate ozonolysisreduction products, whereas the reduction with dimethyl sulfide, NaBH4, and NaBH(OAc)3 follows conventional pattern.

Synthesis of a Multifunctional Pheromone of the Honeybee Apis mellifera Via Condensation of 7-Oxooctanal with Malonic Acid

Condensation of 7-oxooctanal with malonic acid in a Doebner reaction produces 9-oxo-2E-decenoic acid (42% yield) and a comparable amount of products from Tishchenko disproportionation of the starting aldehyde (7-oxooctyl-7-oxooctanoate) and re-esterification by acetic acid (7-oxooct-1-ylacetate and 7-oxooctanoic acid).

OZONOLYTIC TRANSFORMATION OF (S)-(-)-LIMONENE IN HCl-ISOPROPANOL

Partial ozonolysis of (S)-(–)-limonene (ee 50%) in cyclohexane:isopropanol at 2–4°C formed the 1,2,4-trioxolane as a mixture of diastereomers in a 3:2 ratio. A solution of HCl in i-PrOH acted as a cleaving agent during decomposition of the peroxides and a cyclizing agent during formation of the diastereomeric 1,2,4-substituted cyclohexanes.

Transformation of peroxide products of olefin ozonolysis under treatment with hydroxylamine and semicarbazide hydrochlorides in acetic acid

Hydrochlorides of hydroxylamine and semicarbazide efficiently reduce peroxide products of olefin ozonolysis in a system CH2Cl2-AcOH leading to the formation of carboxylic acids and their derivatives. The application of water as the solvent component favors the increase in the fraction of nitrogen-containing organic compounds (semicarbazones, keto- and aldoximes, nitriles) and reduction in the yield of carboxylic acids.

Ozonolytic Transformations of 10-Undecenoic Acid in Various Solvents Through the Action of Hydroxylamine and Semicarbazide Hydrochlorides

Ozonolytic transformations of 10-undecenoic acid, which is available from castor oil, were studied. Syntheses of several α, ω-bifunctional sebacic acid derivatives were developed.