Synthesis of α-tocopherol analogs with unsaturated side chain and their transformation into the corresponding chromans with ω-functionalized side chain

-Tocopherol analogs with double bond-containing side chains were synthesized by condensation of trimethylhydroquinone with optically active (3R/S,4S)-3,4,8-trimethylnona-1,7-dien-3-ol and linalool in the presence of the zeolite-containing Tseokar-10 aluminosilicate. Ozonolysis of these compounds gave the corresponding chromans with -formyl or (after hydride reduction) -hydroxyl groups in the side chain.     

Insect pheromones and their analogs

(Z)-hexadec-11-enal and (Z)-hexadec-11-1-yl acetate — components of the sex pheromone of insects of the generaHeliothis andManestra, respectively — have been synthesized by the condensation of undec-10-enal with hex-1-yne, deoxygenation of the heptadec-1-en-12-yn-11-ol formed via the corresponding tosylate to heptadec-1-en-12-yne, and the selective oxonolysis of the latter.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 440–444, May–June, 1987.     

Insect pheromones and their analogs

A four-stage asymmetric synthesis of (+)-disparlure [(7R,8S)-(+)-cis-methyl-7,8-epoxyoctadecane (V)] has been effected from 8-methylnon-2Z-en-l-ol (I), obtained by the carboalumination of acetylene with tris(5-methylhexyl)aluminum using the Sharpless reaction. The asymmetric epoxidation of (I), (Ar, mol. sieve A, (+)-DET, (iOPr)₄Ti, t-BuOOH, –15°C, 20 h; H₂O, 1 h, NaOH, –7°C, 30 min) gave 8-methyl-2S,3R-epoxynonan-l-ol (II), which was oxidized (kieselguhr-CrO₃-Py, 0°C, 2 h; 25°C, 2 h) to 8-methyl-2S,3R-epoxynonan-l-al (III). The coupling of (III) with n-C₈H₁₇CH=PPh₃ (–78°C, 1 h; 25°C, 15 h) gave 2-methyl-7R,8S-epoxyoctadec-9Z-ene (IV), the hydrogenation (H₂/5% Pd-C, 25°C, 5 days) of which led to (V) in admixture with an isomerization product. Compound (V) was isolated by HPLC. Substance, yield, [] _D ²⁵ : (II), 73, –2.75°; (III), 80, [80.8°; (IV), 50, +37.25°; (V), 50, +0.8°. The IR and PMR spectra of (II–IV), the¹³C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 715–718, September–October, 1989.     

Insect pheromones and their analogs. XIV. Synthesis of muscalure — The sex pheromone ofMusca domestica

A new route to the synthesis of tricos-9Z-one — the sex pheromone of the house fly — has been developed.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 401–403, May–June, 1985.     

Synthesis of α-neryl and α-geranyl propionates — Components of the sex pheromone of San Jose scale

Summary An effective synthesis of -neryl and -geranyl propionates has been performed by the two-stage E/Z-C₅ homologization of 3-methylbut-3-en-1-yl iodide.N. D. Zelinskii Institute of Organic Chemistry, Moscow. All-Union Scientific-Research Institute of Biological Methods of Plant Protection, Kishinev. Institute of Chemistry, Bashkir Scientific Center, Urals Division, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 422–424, May–June, 1989.     

Production of (+)-norsolanadione

Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 735–736, September–October, 1991.     

Synthesis and Antioxidant Properties of Novel Polycycles with Tetrahydroquinoline and Chromane Fragments

Russian Journal of Organic Chemistry - The three-component acid-catalyzed cyclocondensation of arylamines with cyclopentadiene and 6-benzyloxy/hydroxy-(2,5,7,8-tetramethylchroman-2-yl)acetaldehyde...     

Molecular simulation of solvent-induced stokes shift in absorption/emission spectra of organic chromophores

The values of steady-state solvatochromic Stokes shifts (SS) in absorption/emission electronic spectra of organic chromophores are studied theoretically in the framework of the Hush-Marcus model. Charge distributions for chromophore solutes in their S0 and S1 states are found by means of conventional quantum-chemical methods combined with the continuum PCM approach for treating solvation effects. The solvent reorganization energies, which are expected to correlate with the solvent-induced part of 1/2 SS, are found in a molecular dynamics (MD) simulation which invokes a novel method for separation of the inertial piece of the electrostatic response (Vener, et al. J. Phys. Chem. B 2006, 110, 14950). Computations, performed in two solvents (acetonitrile and benzene), consider three organic dyes: coumarin 153 as a benchmark system and two other chromophores, for which experimental spectra are also reported. The results are found to be in reasonable agreement with the experiment. A consistent treatment of nonlinear effect in the solvent response, promoted by the polarizability of solutes and contributing to the solvent reorganization energies (Ingrosso, et al. J. Phys. Chem. B 2005, 109, 3553), improves the results of computations.