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547.596.2+ L. P. Botsman, G. V. Nasibullina, R. R. Muslukhov, and G. A. Tolstikov 547.426.231Ozonolysis and reduction of olefinic derivatives of ricinolic acid and L-menthol were studied using hydroxylamine hydrochloride and sodium trisacetoxyborohydride to reduce the peroxide products.Key words: ozonolysis and reduction, olefinic derivatives of L-menthol and ricinolic acid, hydroxylamine hydrochloride, sodium trisacetoxyborohydride.L-Menthol and ricinolic acid are promising substrates for chiral polyfunctional compounds owing to their high optical activities and availability from mint and castor oils. The polyfunctional compounds can then be used as convenient building blocks to synthesize organic compounds with more complicated structures.Herein we report experimental results on expanding the synthetic potential of the title compounds using ozonolytic transformations of their olefinic derivatives such as castor oil (1a) and its acetate (1b), a secondary homoallylic alcohol (6) obtained from 1a [1], and the regiospecific dehydration product of L-(-)-menthol (10) [2], (R)-menth-3-ene (11) and its 3-substituted analogs (16, 18, 20, 21). The last compounds were prepared by acid dehydration (TsOH, PhH, ∆, 24 h) of previously reported [3] tertiary alcohols (13-15). 3-Methylmenthol (13) formed a single cycloolefin (16), like when oxalic acid is used (100°, 24 h) [4]. Dehydration of 3-ethylmenthol (14) produced in 87% a mixture (94:3:3) of all possible isomers at the double bond with the thermodynamically most stable 3-ethyl-p-menth-3-ene (18) dominating. The same situation was observed upon dehydration of phenyl-substituted menthol (15). The ratio of the thermodynamic (20) and kinetic (21) products was 7:3.We used hydroxylamine hydrochloride as one of the reductants of the peroxide products. It has been used only in a few instances for these purposes and always in methanol solution. Depending on the nature of the substrates, aldehydes [5], aldoximes [6,7], and methyl esters were formed [8].It seemed logical to assume that hydroxylamine hydrochloride would react with the ozonolysis products in methanol to form at first aldehydes that would then convert to aldoximes and undergo Beckmann rearrangement to the corresponding nitriles, the nitrile groups of which would convert to carboxymethyls to form the methyl esters. We confirmed this hypothesis using the conversion of the ozonolysis peroxide products into a whole series of disubstituted (1a, 1b), trisubstituted (11), and tetrasubstituted (16) olefins using hydroxylamine hydrochloride.Oxidation of castor oil (1a, 85% ricinolic acid) and its acetate (1b) by ozone (3 mol) in methanol followed by work up with hydroxylamine hydrochloride produced mixtures (1.6:4.9:1 and 1:4.6:2.4) of hydroxyester 2, C-9 diester 3, and its mononitrile derivative 4, respectively. Oxidation of homoallylic alcohol 7, which is available from castor oil (1a) [1], with an equimolar amount of ozone and work up with hydroxylamine hydrochloride produced a mixture (1:1:1.6) of the same hydroxyester 2, ...

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Phermones that are emitted during breeding and control the activity of bees near the hive play an important role in chemical communication within the bee colony [1-6].1,2-Dioleoyl-3-palmitoylglycerine was isolated and identified in 1984 as a component of the honeybee (Apis mellifera L.) breeding pheromone that can cause them to mass on artificial maternal cells of honeycombs [7].Syntheses of this compound that include mutual transesterification of trioleoyl-and tripalmitoylglycerines are known [8]. We propose a synthesis of the title compound that is based on chemoselective transformations of DL-1,2-isopropylideneglycerine, which is readily accessible from glycerine [9]. The synthetic scheme consists of transesterification in the presence of sodium ethoxide of the methyl ester of palmitic acid by diprotected triol 2, acid hydrolysis of intermediate 3 to α-monoglyceride 4, and exhaustive acylation of it by oleoylchloride. The overall yield of 1 calculated per starting 2 was 20%. EXPERIMENTALIR spectra were recorded on a UR-20 instrument as thin layers. NMR spectra were recorded on a Bruker AM-300 spectrometer (working frequency 300.13 MHz for 1 H and 75.47 MHz for 13 C) in CDCl 3 using as an internal standard the