Hydroboration-oxidation of methyl abietate by diborane in THF occurred preferentially at the sterically unhindered β -side of the molecule without involving the ester. The known hydroboration-oxidation product methyl 7 β -hydroxy-13 α -isopropylpodocarp-8(14)-en-15 α -oate and previously unknown methyl 7 β -hydroxy-13-isopropyl-8 β -podocarp-13(14)-en-15 α -oate, 14 β -hydroxy-13 α -isopropylpodocarp-7(8)-en-15 α -oate, and 7 β ,14-dihydroxy-13 α -isopropyl-8 β -podocarpan-15 α -oate, i.e., products from monohydroboration-oxidation at the ∆ 7,8 - and ∆ 13,14 -bonds without their respective shifts and from dihydroboration, were obtained.

AbstractThe oxidation of menthene sulfides (I) with H2O2 yields the corresponding unsaturated sulfones (II).

Prolonged treatment of menth-4-en-3-yl sulfides with H2O2 in acidic medium leads to saturated menthan-3-yl sulfones, the same products having been obtained from menth-4-en-3-yl sulfoxides in acidic medium in the absence of H2O2. The mechanism was evaluated by quantum chemical calculations.

The condensation of 7-oxooctyl 7-oxooctanoate and bis(7-oxooctyl) hexanedioate with bicyclo-[2.2.1]heptane-2- endo ,3- endo -dicarbohydrazide and its 5- endo ,6- endo - and 5- endo ,6- exo -dihydroxy derivatives obtained from dimethyl norbornene-2- endo ,3- endo -dicarboxylate gave the corresponding macrocyclic lactones containing a ketone azine fragment instead of the expected hydrazide moiety.

The behavior of seven-membered lactones from the triterpenoid betulin and S-(+)-camphor in a novel reaction with organoaluminum compounds was studied using low-temperature reduction of monoterpene sevenmembered lactones by an excess of diisobutylaluminum hydride in CH (2) Cl (2) .

Earlier, we discovered a novel reaction in the chemistry of organoaluminum compounds - the formation of O-isobutyl acetals during low-temperature (-70 °С) treatment of a number of seven-membered lactones with a twofold (or more) molar amount of diisobutylaluminium hydride in methylene chloride. In addition, it was shown that the acyclic derivatives of (-)-mentholactone - methyl 6-hydroxy-3,7-dimethyl-octanoate and its 6-oxo analogue - also enter into the low-temperature reduction reaction of diisobutylaluminum hydride in methylene chloride. Moreover, methyl 6-hydroxy-3,7-dimethyloctanoate in this reaction behaves similarly to (-)-mentholactone: when 4 equivalents of diisobutylaluminium hydride acts on it, the reaction proceeds with the predominant formation of isobutyl acetal as the only (2S,7S)-epimer. Methyl 6-oxo-3,7-dimethyl octanoate in a low-temperature reduction reaction with 4 equivalents of diisobutylaluminium hydride in methylene chloride acts as a mixture of (-)-mentholactone and isomentolactone, leading to a mixture of (2S,7S)-, (2S,7R)- and (2R,7R)-isobutyl acetals in a ratio of 3.2: 1.3: 1.0, respectively. In the present work, when low-temperature reduction was involved in the reaction with diisobutylaluminium hydride, methyl (3R)-6-hydroxy- or (3R)-6-oxo-3-isopropylheptanoates available from carvomentolactone reacted without the formation of isobutyl acetal: a mixture of (2: 1) 6-hydroxy-(3R)-isopropylheptanal and (4R)-isopropyl-7-methyloxepan-2-ol was obtained.

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.

Ozonolysis of (1 R ,3 R )- p -menth-4-en-3-ol in methylene chloride or methanol in the presence of pyridine afforded a mixture of equimolar amounts of epimeric 1-[(2 R ,4 S ,6 S )- and 1-[(2 S ,4 S ,6 S )-6-hydroxy-4-methyltetrahydro-2 H -pyran-2-yl]-2-methylpropan-1-ones. A probable reaction mechanism is discussed.

The reactions of (R)-n-menth-4-en-3-one and its derivatives with N-containing reagents were studied. New menthane-type acetamides were synthesized.

Properties of new halogenated polymeric products containing dichlorocyclopropane groups in the macromolecules and obtained by modification of syndiotactic 1,2-polybutadiene were studied. The influence of the degree of the polymer functionalization on the rheological and physicochemical properties and on the heat resistance of the dichlorocyclopropane derivatives of syndiotactic 1,2-polybutadiene was revealed. Dichlorocyclopropanated 1,2-polybutadiene can be used as a component of plasticized polyvinyl chloride formulations, improving the processability of the polymeric compound.

We discovered and studied the chemiluminescence occurring during the oxidation of 3-bromo-5-hydrazino-1-(thietan-3-yl)-1H-1,2,4-triazole with superoxide anion. The chemiluminescence wavelength interval was 400-590 nm with the maxima (at 436 and 540 nm) matching the peak fluorescence wavelengths of the reaction products. The possible reaction products were determined by NMR spectroscopy, mass spectrometry, IR and UV spectroscopy. The quantum yield of chemiluminescence was 10-9 E/mol.

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.

Treatment with hydroxylamine and semicarbazide hydrochlorides of peroxide products obtained by ozonolysis of olefins in tetrahydrofuran gives mainly carboxylic acids and their derivatives.

An optically pure macrolide containing 1,3-dioxolane, gem-dimethylcyclopropyl, and hydrazide fragments was synthesized from (+)-3-carene via [1+1]-condensation of the product from sequential ozonolysis—reduction and Tishchenko disproportionation of (3S,4S)-[(3R,4R)-4-isopropyl-3-methyl-6-oxoheptyl]-4-isopropyl-3-methyl-6-oxoheptanoate with the hydrazide of L-(+)-tartaric acid acetonide.

The synthesis of two potentially useful 23and 29-membered macrolides containing a pyridine ring and dihydrazide fragments was developed starting from tetrahydropyran. It was based on [1+1]-condensation of 7’-oxooctyl-7oxooctanoate and bis(7-oxooctyl)hexanedioate with 2,6pyridinedicarboxylic acid hydrazide. The structure of the macrocycles obtained was confirmed using by IR and NMR spectroscopy and mass spectrometry.

We have studied the interaction of 7-oxooctyl-7-oxooctanoate and bis(7-oxooctyl)hexanedioate, available from tetrahydropyran, with phthalic dihydrazide. It was found, that instead of expected macrolides containing hydrazide fragments, the corresponding macrocycles containing azine fragments are formed. Such compounds were obtained earlier via the interaction of substrates and hydrazine hydrate.

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.

Thiylation of ( R )-4-menthen-3-one and its derivatives was studied. New sulfides and sulfoxides of the menthane series were synthesized.