R. A. Zainullin

Synthesis of Biologically Active Substances Based on Phenoxyethanol Derivatives

By reaction of phenoxyethanol with diverse structure acyl chlorides phenoxyethanol esters were synthesized containing in the molecule fragments of undecene acid and also of some ketocarboxylic acids. The latter acids were obtained by ozonation of alkylcyclenes.

Synthons for biologically active compounds on the basis of naphthalene ozonolysis products

Ozonolysis of naphthalene in aqueous methanol, followed by the reduction of peroxy compounds thus formed with potassium iodide in the presence of acetic acid, gave 3-methoxy-2-benzofuran-1(3H)-one. In the absence of water, the product was methyl o-formylbenzoate. The latter was used as a synthon for the preparation of aromatic analogs of (2E)-2,6-dimethyloct-2-ene-1,8-diol ethers which are effective juvenoids.

Ozonolysis of (1R,cis)-4,7,7-Trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one

The structure of peroxides forming in ozonolysis of enololactone and their further transformations are determined by the structure of the initial substrate and by effect of solvent used for ozonolysis.

Synthesis of nitrogen-containing phenoxyacetic acid derivatives

Nitrogen-containing phenoxyacetic acid derivatives were synthesized by reactions of substituted phenoxyacetic acids with amines, urea, and ethyl carbamate.

Ozonolysis of Alkenes and Study of Reactions of Polyfunctional Compounds: LXIV. Synthesis of Ambreinolide and 8α,13-Epoxy-14,15,16-trisnorlabd-12-ene Proceeding from Isoabienol Ozonolysis

The ozonolysis of isoabienol in MeOH followed by hydrogenation of the peroxide ozonolysis products on Lindlar catalyst afforded ambreinolide that under treatment with diisobutylaluminum hydride furnished 8α,13-epoxy-14,15,16-trisnorlabd-12-ene.

Synthesis of dicyclopropanes from 4,7,7-Trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one

New optically active dicyclopropanes were synthesized on the basis of transformation products of 4,7,7-trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one using dichlorocarbene or sulfoxonium ylide in the key cyclopropanation stages.

Ozonolysis of 3-Caren-5-one

Cleavage by ozonolysis of a cyclic unsaturated ketone, 3-caren-5-one, was investigated under different conditions. The main reaction product is ketocaronic acid. A scheme of ketocaronic acid formation was suggested basing on kinetics of ozone reaction with 3-caren-5-one and thermal decomposition of peroxides.

Synthesis of aryl-containing terpenoids based on 1,4-dihydronaphthalene

Successive transformations including oxidation of 1,4-dihydronaphthalene into 1,2,3,4-tetrahydronaphthalen-2-one, Reformatskii reaction of the latter with methyl bromoacetate, ozonolysis of the Reformatsky reaction product, and Emmons olefination of the aldehyde group in methyl 3-oxo-5-(2-formylphenyl)pentanate thus formed gave analogs of highly active dienoate juvenoids having an aromatic ring in their molecules.

Synthesis of 4α-Hydroxy-6,6-dimethyl-3-oxabicyclo[3.1.0]hex-2-one by Ozonolysis of (1R, cis)-4,7,7-Trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one

4 -Hydroxy-6,6-dimethyl-3-oxabicyclo[3.1.0]hex-2-one ( 1) is an intermediate in the synthetic pathways to many effective pyrethroids with the gem-dimethylcyclopropane ring [1, 2]. One of the approaches to the synthesis of 1 is ozonolysis of (1R,cis)-4,7,7-trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one ( 2), which is readily obtained from (+)-3-carene [2]. A detailed investigation of the ozonolysis of enollactone 2 showed that the reaction is exceedingly sens itive to the solvent in which the ozonolysis is performed and the reductant used to decompose the peroxide ozonolysis products. These affec t the yield of the desired lactol 1. The maximum yield is attained with ozonolysis (-5 (C) in alcohols. It has been found that the reaction occurs through intermediate alkoxylactols ( 3-5), hydrolysis of which (55 ml of 1% oxalic acid per 0.03 mole of 3-5, 20(C, 3 h) completes the synthesis of 1.

Reaction of lithium acetylides with car-3-ene-2,5-dione

The reaction of car-3-ene-2,5-dione (1), an oxidation product of (+)-car-3-ene, with lithium acetylides proceeds stereospecifically, but not regioselectively, to give only mixtures of regioisomeric acetylenic alcohols with thesyn-orientation of the hydroxy group.