Insect pheromones and their analogs. XLIX. Synthesis of tridec-4-en-1-yl acetate — The sex pheromone ofKeiferia lycopersicella

Using the Claisen rearrangement at the stage of constructing the double bond, we have synthesized tridec-4Een-1 yl acetate, the sex pheromone of the tomato pinwormKeiferia lycopersicella.Institute of Petrochemistry and Catalysis, Academy of Sciences of the Republic of Bashkortostan, Republic of Bashkortostan; b) Scientific-Research Institute of Fine Organic Synthesis, Academy of Sciences of the Republic of Bashkortostan. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 490–493, May–June, 1995. Original article submitted November 9, 1994.     

Synthesis of tridec-4-en-1-yl acetate — The sex pheromone of Keiferia lycopersicella

A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, p. 444, May–June, 1991.     

Synthesis of (E)-dodec-3-en-1-yl acetate — The main component of sex pheromones of Scrobipalpa ocellatella and Scrobipalpopsis solanivora

(E)-Dodec-3-en-l-yl acetate — the main component of the sex pheromones ofScrobipalpa ocellatella andScrobipalpopsis solanivora — has been obtained by a three-stage synthesis from decanal and malonic acid. The overall yield of pheromone was 33% calculated on the initial aldehyde.A. S. Sadykov Institute of Bioorganic Chemistry, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 682–683, September–October, 1988.     

Synthesis of dodec-5E-en-1-ol — The pheromone of Tricimba cincta — And tetradec-5E-1-yl acetate — An imitator of the pheromone of Rhynchopacha sp.

On the basis of a modified Knoevenagel reaction starting from octanol and decanal, the stereodirected synthesis has been effected of dodec-5E-en-ol (the pheromone of the grass flyTricimba cincta — and tetradec-5E-en-yl acetate) an imitator of the pheromone of the mothRhynchopacha sp. A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 129–132, January–February, 1991.     

Bisindoles. 18. Some electrophilic substitution reactions in the 1,2-di(indol-5-yl)ethane series

A quantum-chemical calculation has been made and the laws of the electron-density distribution in the molecule of 1,2-di(indol-5-yl)ethane have been determined. The electrophilic substitution reactions most characteristic for it have been studied.For communications 15–17, see [1–3].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 73–77, January, 1984.     

Synthesis of (Z)-tetradec-11-en-1-ol and (Z)-hexadec-11-en-1-ol from dodecane-1,12-diol

A method has been developed for obtaining (Z)tetradec-11-en-1-ol and (Z)-hexadec-11-en-1-ol via dodec-11-yn-1-ol.A. N. Nesmeyanov Institute of Organometallic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 776–779, November–December, 1984.     

Vinyl cation rearrangement in the solvolysis of 5α-cholest-1-en-1-yl triflate

Solvolysis of $\text{1}$ in buffered aqueous acetone gives a mixture of the rearranged alcohols $\text{2}$, $\text{3}$, $\text{4}$, and $\text{5}$ as a result of a possibly concerted ionization migration to the double bond.     

Interaction of dimethylsulfoxonium methylide with 5-allyl-2,3,5-trichloro-4,4-dimethoxycyclopent-2-en-1-one

Dimethylsulfoxonium methylide in DMSO initiates unusual oxidative skeletal transformations of trichlorocyclopentenone. Lactone, cyclic orthoester, and a number of by-products of hydrolysis, substitution, and reduction were isolated and characterized. The expected epoxide was obtained in low yield.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2958–2960, December, 1996.     

Chiral azole derivatives. Part 5: Synthesis of enantiomerically pure 1-[α-(benzofuran-2-yl)arylmethyl]-1H-1,2,4-triazoles, antifungal and antiaromatase agents

Racemic and enantiopure benzofuranmethanamines 5a–c have been reacted with N-Boc-3-(4-cyanophenyl)oxaziridine to give N-Boc-hydrazines 7a–c, which have in turn been transformed by deprotection and cyclisation into triazoles 4a–c, potent antiaromatase agents, in good overall yield and with high enantiomeric excess.     

Synthesis and reactivity of bis(3,5-dimethylpyrazol-1-yl)ethane tetracarbonylmolybdenum and tungsten X-ray crystal structureof bis(3,5-dimethylpyrazol-1-yl)ethane tetracarbonyltungsten

Bis(3,5-dimethylpyrazol-1-yl)ethane tetracarbonylmolybdenum (1a) and tungsten (1b) have been synthesized by the direct reaction of bis(3,5-dimethylpyrazolyl)ethane (bmpze) with M(CO)₆ (M = Mo or W). The molecular structure (1b), determined by x-ray crystallography, showed the seven-membered ring W–N–N–C–C–N–N to be in the boat conformation. Upon treatment with RSnCl3 (R=Ph or Cl) in CH₂Cl₂ at room temperature, complexes (1a) and (1b) gave the seven-coordinate oxidative-addition products [(bmpze)M(CO)₃(SnCl₂R)Cl] [M = Mo, R = Ph, (2a); M = W, R=Ph, (2b); M = Mo, R = Cl, (2c); M = W, R = Cl, (2d)]. When complexes (1b) and (2b) were heated under reflux with 1,2-bis(diphenylphosphino)ethane (dppe), the ligand, bmpze, in these complexes was easily removed. The novel compounds were characterized by ¹H-n.m.r., i.r. and elemental analysis.     

Synthesis of substituted cyclopentanones from 6-methylhept-5-en-2-one

Readily available tert-butyl- and phenyl sulfoxide derivatives of methylheptenone were converted by the Pummerer method to the corresponding five-membered keto sulfides which are probable precursors of iridanes and related terpent cyclopentanoids.Translated from Izvestiya Akademii Nauk SSSR, No. 7, pp. 1569–1574, July, 1991.     

Molecular structure of 1e-phenyl-1a-thioxo-2a,5e-dimethyl-3e,5a-dimorpholinomethylphosphorinan-4-one

Institute of Chemical Sciences, Kazakh SSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 5, pp. 167–171, September–October, 1990.     

Reactions of 1, 5-diketones. XX. Semicyclic 1, 5-diketones in the fischer reaction

Monophenylhydrazones involving both the phenacyl carbonyl group and the ring carbonyl group are formed as intermediates in the reaction of semicyclic 1, 5-diketones of the 2-(phenacylobenzyl) cyclohexanone type with phenylhydrazine in acid media. The former undergo subsequent conversion to the corresponding substituted indoles, whereas the latter are converted to substituted 1H-2, 3, 3a, 4-tetrahydropyrido [3, 2, l-j, k] carbazoles; in addition, the corresponding 5, 6, 7, 8-tetrahydroquinoline derivatives are also partially formed.See [1] for communication XIX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 645–650, May, 1976.     

Synthesis of S-(carboran-1-yl)thiophosphates and S-(carboran-1-yl)-thiophosphonates

Conclusions New S-(carboran-1-yl)thiophosphates and S(carboran-1-yl)thiophosphonates were obtained by the reaction of derivatives of lithiumcarboranes with bis(dialkoxythiophosphoryl)disulfides or halo derivatives of pentavalent phosphorus.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 194–197, January, 1989.     

Alkynylhalocarbenes. 2. Generation of (alkyn-1-yl)-chlorocarbenes by basic solvolysis of 1,1-dichloro-2-alkynes and their reaction with olefins: Synthesis of 1-chloro-1-alkynylcyclopropanes

1,1-Dichloro-2-alkynes R¹CCCHCl₂ (4a–g; R¹=Me, n-Pr, c-Pr, t-Bu, Ad, Nor, Ph) were synthesized with yields of 50–75% by chlorination with PCl₅ of formylacetylenes (3a–g), prepared by oxidation of propargyl alcohols (1a–d) with CrO₃·Py·HCl complex or acidolysis of propargyl acetals (2a–c) in the presence of catalytic quantities of pyridine; the corresponding alkynylchlorocarbenes, R¹CCCCl (5a–g) were generated from them with powdered KOH in a two-phase system or t-BuOK. The latter were trapped by olefins with formation of 1-chloro-1-alkynylcyclopropanes (6a–t) with yields of up to 90%.See [1] for Communication 1.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1128–1135, May, 1992.     

Highly unsaturated polymers Communication 6. Poly(1, 3, 5-triethynylbenzene)

Summary A highly unsaturated triacetylenic hydrocarbon, 1,3,5-triethynylbenzene, was synthesized, and the oxidative polycondensation of this gave a three-dimensional oligomer containing alternating diacetylenic groups and aromatic nuclei in its molecule.For Communications 1–5 see [1–5].     

1, 5-Rearrangement of enol acylates of aryl 1H.-1, 2, 4-triazol-1-ylmethyl ketones

The rearrangement of enol acylates of aryl 1H-1, 2, 4-triazol-1-ylmethyl ketones at 140–150°C in acetic anhydride is studied. The migration of the acyl group to the C(5) atom of the heterocycle is found to be intramolecular. The characteristics of the original and final products are presented. X-ray structural studies of the enol acetates of 2, 4-dichlorophenyl 1H-1, 2, 4-triazol-1-ylmethyl ketone and 2, 4-dichlorophenyl 5-acetyl-1H-1, 2, 4-triazol-1-ylmethyl ketone are carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 560–564, March, 1993.     

Synthesis of glycidyl ethers of tertiary 1-alkoxy-1-en-3-ynols

Conclusions New unsaturated glycidyl ethers have been prepared by reaction of tert-1-alkoxy-1-en-3-ynols with epichlorohydrin in alkaline solution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2792–2795, December, 1975.     

Synthesis and structure of 1-(4-chlorophenyl)-3-(5-methyl-1, 3-dioxan-5-yl)-(1,2),(3,4)-diepoxybutane

The synthesis and X-ray structural study of 1-(4-chlorophenyl)-3-(5-methyl-1,3-dioxan-5-yl)-(1,2), (3,4)-diepoxybutane are described.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 715–718, April, 1995.     

Insect pheromones and their analogs. LVIII. Synthesis of hexadeca-7Z,11E-dien-1-yl acetate — a component of the sex pheromones ofPectinophora gossypiella andSitotroga cerealella

A new synthesis of hexadeca-7Z,11E-dien-1-yl acetate — a component of the sex pheromones of the pink bollworm (Pectinophora gossypiella) and the Angoumois grain moth (Sitotroga cerealella) — is proposed that is based on a thermal Claisen rearrangement.Scientific-Research Institute of Small-Tonnage Chemical Products and Reagents, Ufa, fax 8-(3472) 43 17 31. Ufa State Petrotechnical University. Institute of Petrochemistry and Catalysis, Academy of Sciences of the Republic of Bashkortistan, Ufa, fax-8(3472) 31 27 50. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 231–234, March–April, 1998.