Transformations of peroxide ozonolysis products of natural olefins by <Emphasis Type="Italic">N</Emphasis>-containing organic compounds in methanol

Transformations of peroxide ozonolysis products of cyclic and acyclic natural olefins with different degrees of saturation by hydroxylamine and semicarbazide hydrochlorides were investigated. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 272–275, May–June, 2009.     

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.     

Mannich reaction in a number of six-membered heterocyclic γ-ketones

Aminomethylation of 2,2-dimethyl-4-oxotetrahydropyran gave a number of its aminomethyl derivatives, which were converted to tertiary γ-amino alcohols by phenylation. The individual structural and geometrical isomers were isolated, and their structures were established by mass spectrometry and PMR and IR spectroscopy.     

Mannich reaction in a number of six-membered heterocyclic γ,-ketones. X. Stereochemistry of the reduction and phenylation of 2, 2-dimethyl-5-dimethylaminomethyl-4-oxotetrahydropyran

2, 2-Dimethyl-5-dimethylaminomethyl-4-oxotetrahydropyran was subjected to reduction with lithium aluminum hydride, sodium borohydride, aluminum isopropoxide, and lithium in liquid ammonia, to catalytic hydrogenation over Raney nickel, and phenylation with phenyllithium. The quantitative ratios in the resulting mixtures of stereoisomeric 2, 2-dimethyl-5-dimethylaminomethyl-4-hydroxytetrahydropyrans and their dependence on the character of the reducing agents were established by means of gas — liquid chromatography and PMR spectroscopy. The individual geometrical isomers of the amino alcohols were isolated, and their three-dimensional structures were studied by means of their PMR and IR spectra.See [1] for communication IX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 611–616, May, 1976.     

Insect pheromones and their analogues. XVI. Practical synthesis of hexadec-9Z-enal — A component of the sex pheromone of the cotton bollwormHeliothis armigera

A synthesis of hexadec-9Z-enal — a component of the sex pheromone of the cotton boll-wormHeliothis armigera (Hübner) — based on cyclooctene (I) is proposed. Through a solution of 22 g of (I), 250 ml of cyclohexane, and 40 ml of MeOH is passed (at 5°C) 0.2 M O₃/O₂, the solution is decanted off, and the precipitated ozonide is dissolved in 200 ml of MeOH and is reduced with 19 g of NaBH₄ (40°C) with the isolation, after the usual working up, of 23.4 g of octane-1,8-diol (II). From 0.5 mole of (II) and 0.6 mole of 45% HBr 8-bromooctan-1-ol (III) is obtained and this is converted into 1-(2-THPL)oxy)-8-bromooctane (IV). The condensation of (IV) with oct-1-yne (Ar, LiNH₂, HMPTA, 10°C, 1 h, and then 55°C, 10 h) leads to 1-(2-THPL-oxy)hexadec-9-yne (V) the hydrolysis of which (MeOH, H₂O, p-TsOH, 20°C for 20 h) yields hexadec-9-yn-ol (VI). The reduction of (VI) (Et₂O, iso-BuMgBr, Cp₂TiCl₂, 0°C, 15 min, then 20°C, 1 h) yieldshexadec-9Z-en-l-ol (VII). The oxidation of (VII) (PyHCrO ₃ ⁺ Cl^–, CH₂Cl₂, 20°C, 2 h) gives hexadex-9Z-enal (VIII). Characteristics of the compounds (yield (%), n _D ^{20 (25)}: (II) – 80, mp 61–62°C; (III) – 75, 1.4807; (IV) – 99, —; (V) – 52, 1,4650; (VI) – 85, 1.4657; (VII) – 99, 1.4650; (VIII) – 98, 1.4600. Characteristics of the IR and PMR spectra of compounds (V–VII) are given.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 286–289, March–April, 1987.     

Ozonolysis of Ricinolic Acid Derivatives and Transformations of the Ozonolysis Products under Barton Reaction Conditions

The possibility of functionalizing the alkyl part of ricinolic acid using the Barton reaction was investigated. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 529–534, November–December, 2005.     

Pheromones of insects and their analogs. XXVIII. Practical synthesis of tetradeca-9Z,12E-dien-1-yl acetate — A component of the sex pheromones of insects of the order lepidoptera

Tetradeca-9Z,12E-dien-l-yl acetate, a sex pheromone of the Indian meal mothPlodia interpunctella has been synthesized from the readily available product of the hydrodimerization of butadiene — octa-1,7-diene.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 276–279, March–April, 1991.     

A new method for the direct reduction of products of ozonolysis of 1-alkylcycloalkenes to ketols

A method for the direct reduction of peroxide products of ozonolysis of 1-alkylcycloalkenes (with Δ³-carene and α-pinene as examples) to the corresponding ketols with NaBH(OAc)₃ was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 198–199, January, 1999.     

Synthesis of derivatives of (S)-2-alkanols, components of pheromones ofDrosophila mulleri andRhyzopertha dominica, from (S)-(+)-3,7-dimethylocta-1,6-diene

Effective routes for the synthesis of (S)-2-acetoxytridecane, the sex pheromone of the fruit flyDrosophila mulleri, and (S)-1-methylbutyl 2-methyl- and 2,4-dimethylpent-2E-enoates, components of the aggregation pheromone of the lesser grain borerRhyzopertha dominica, were developed on the basis of (S)-4-methylhex-5-en-1-yl tosylate accessible from (S)-(+)-dihydromyreene. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1929–1931, November, 2000.     

Synthesis from 10-undecenoic acid of octadeca-2E,13Z-dienylacetate, a component of the sex pheromones ofSynanthedon tipuliformis andZenzera pyrina

A new synthesis of octadeca-2E,13Z-dienylacetate from 10-undecenoic acid is developed by constructing the carbon framework of the pheromone in the key step and introducing the 2E double bond by Doebner condensation of hexadec-11-ynal and malonic acid.Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, 450054, Ufa, prospekt Oktyabrya, 71, fax: (3472) 35 60 66. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 164–166, March–April, 2000.