- Method for preparation of Octadecadienyl acetate as major sex pheromone of cherry tree borer, Synanthedon bicingulate
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The present invention relates to a method for producing a sex pheromone of cherry tree borer (Synanthedon bicingulata) in an attempt to control the same. More specifically, provided is a method for stereoselectively producing high purity (3E,13Z)- octadecadienyl acetate and (3Z,13Z)-octadecadienyl acetate respectively which are major sex pheromones of cherry tree borer from a cheap starting material in an efficient, simple, and economically feasible way.COPYRIGHT KIPO 2018
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- Sequential alkynylation of ω-bromoalkyl triflates: Facile access to unsymmetrical non-conjugated diynes including precursors to diene pheromones
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Sequential treatment of ω-bromoalkyl triflates with an alkynyllithium at 0°C followed by addition of a second alkynyllithium and NaI and heating the reaction mixture provides a simple one-pot access to unsymmetrical diynes in good yields. These diynes may be transformed stereoselectively into diene pheromones such as (Z,Z)- and (E,Z)-3,13-octadecadienyl acetate. Graphical Abstract
- Armstrong-Chong, Rosemary J.,Matthews, Kristopher,Chong, J. Michael
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p. 10239 - 10244
(2007/10/03)
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- Synthesis of (3Z,13Z)-3,13-octadecadienyl acetate - Sex pheromone of Synanthedon tenuis-using readily available C11-synthon
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Synthesis of (3Z,13Z)-3,13-octadecadienyl acetate has been achieved from the readily available 10-undecen-1-ol using cheaper reagents and less number of steps. In the key step alkylation of an alkyne is performed with solid sodamide giving the product in 50% yield. The method can be easily scaled-up.
- Narasimhan,Ganeshwar Prasad,Madhavan
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- Method for the preparation of an alkynyl compound
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A novel and efficient method is proposed for the synthetic preparation of a long-chain alkynyl compound in a one-pot reaction without isolating the intermediate from the reaction mixture. The inventive method comprises the steps of: (a) a Grignard coupling reaction of an ω-halogeno-1-alkynyl magnesium halide compound of the general formula X1 MgC C(CH2)n X2, in which X1 is a halogen atom, X2 is an atom of Br or I and n is 3 to 10, and a Grignard reagent of the general formula RMgX1, in which R is a group selected from the class consisting of alkyl groups, alkenyl groups, alkynyl groups, alkapolyenyl groups, aryl groups and hydrocarbon groups having protected hydroxy group to give an intermediate compound of the general formula X1 MgC C(CH2)n R; (b) subjecting the intermediate compound to a reaction with a reactant selected from the class consisting of C2 -synthons, C1 -synthons and chlorosilane compounds having reactivity with the intermediate compound at the X1 Mg-terminal; and (c) hydrolyzing the reaction product obtained in step (b).
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- 1,(ω-1)-Dienes: solvent controlled unilateral or bilateral metallation
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In hexane, i.e. under heterogeneous conditions, 1,(ω-1)-dienes readily undergo double deprotonation to give bis(allylmetal) intermediates.In tetrahydrofuran at -75 or -50 deg C, however, only monometallation occurs with dienes having chains of up to 12 carbon atoms.The practical potential of such selective monosubstitution reactions is demonstrated by two novel pheromone syntheses.
- Moret, Etienne,Desponds, Olivier,Schlosser, Manfred
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- Stereoselective synthesis of (Z,Z)-3, 13-octadecadien-1-ol, (Z,Z)-3, 13-octadecadien-1-yl acetate and their (E,Z)isomers
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(Z,Z)-3,13-Octadecadien-1-ol (VIII), (Z,Z)-3,13-octadecadien-1-yl acetate (IX) and their corresponding (E,Z) isomers (X and XI) have been synthesized via Li2CuCl4 catalysed coupling reaction of (Z)-8-tridecylmagnesium bromide with mesylate (II) as a key step.
- Trehan, I R,Kad, G L,Singh, Vasundhara,Vig, Rakesh
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p. 563 - 566
(2007/10/02)
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Coupling reactions of lithium compounds, (Z)-carbonyl olefination of phosphonium ylides and 'crossed' Wittig olefination of bisylides are the key reaction steps in the synthesis principle for nonconjugated, bisolefinic Lepidoptera pheromones and structural analogs. Double unsaturated (E,Z)- and (E,E)-1-vinyl halides are converted into the corresponding (E,Z)- and (E,E)-1-vinyl lithium compounds and coupled selectively to (E,Z)- and (E,E)-alkadienols, alkadienals and alkadienyl acetates with different carbon chain length, geometry and relative positions of double bonds. 'Crossed' Wittig reactions of 1,ω-alkylidene bisylides with two different alkanals gives rise to the formation of corresponding (Z,Z)-dienic sex attractants and derivatives. A monounsaturated (E)-1-vinyl iodide is the synthon for the preparation of an (E)-alkenyl bromide which is converted to an (E)-alkenyl phosphonium salt and (Z)-selectively olefinated to (Z,E)-isomers of moth sex pheromones.
- Bestmann,Zeibig,Vostrowsky
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p. 1039 - 1047
(2007/10/02)
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- A CONVENIENT SYNTHESIS OF 2,13- AND 3,13-OCTADECADIENYL ACETATES, SEX PHEROMONE COMPONENTS OF THE Synanthedon SPECIES
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The sex pheromone components of several Synanthedon species, 2,13- and 3,13- octadecadienyl acetates (Ic, Id, IIc, IId), have been synthesized following the acetylenic route of chain elongation.Starting from ω-alkyn-1-ols III, the final compounds were constructed in five steps in about 30percent overall yields.Transformation of triple bond containing intermediates into the corresponding (Z)- and (E)-olefins was achieved either by hydrogenation over the P2-Ni catalyst or by using a dispersion of sodium in toluene.The title pheromones were generated in more than 97percent stereoisomeric purity. 1H and 13C NMR data of all derivatives are included.
- Hoskovec, Michal,Saman, David,Koutek, Bohumir
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p. 2270 - 2281
(2007/10/02)
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- SYNTHESIS OF PHEROMONES, IV. CHEMISTRY OF THE WITTIG REACTION, I. EFFECTS OF REACTION CONDITIONS ON THE STEREOSELECTIVITY AND YIELD OF THE WITTIG REACTION
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The reactions of nonstabilized triphenylphosphorus ylides with aldehydes have been studied in detail.The stereochemistry and yields of the alkene products are highly dependent upon base used for the generation of the ylide, the solvent and reaction temperature.The synthesis of sex pheromone components by Wittig reaction are also described.
- Vinczer, Peter,Juvancz, Zoltan,Novak, Lajos,Szantay, Csaba
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p. 797 - 820
(2007/10/02)
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- SIMPLE AND STEREOCONTROLLED SYNTHESIS OF AN OPTIMAL ISOMERIC MIXTURE OF 3,13-OCTADECADIEN-1-YL ACETATES
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A simple route has been developed for the preparation of the optimal isomeric mixture of 3,13-octadecadien-1-yl acetates (ODDA) which is the active sex pheromone of many Synanthedon species.The stereocontrolled formation of double bonds have been achieved via Wittig reaction and subsequent reduction of C-C triple bond.
- Vinczer, Peter,Baan, Gabor,Juvancz, Zoltan,Novak, Lajos,Szantay, Csaba
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p. 1257 - 1270
(2007/10/02)
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- A NOVEL STEREOCONTROLLED SYNTHESIS OF (Z,Z)-3,13-OCTADECDIEN-1-YL ACETATE, THE SEX PHEROMONE OF SYNANTHEDON SPECIES
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Starting from 10-undecenoic acid, a stereocontrolled synthesis of (Z,Z)-3,13-octadecadien-1-yl acetate with high sterochemical purity was achieved by the use of Wittig-olefinations for the introductions of (Z)-double bonds.
- Vinczer, Peter,Baan, Gabor,Novak, Lajos,Szantay, Csaba
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p. 2701 - 2704
(2007/10/02)
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- Some alkali metal alkyl amides as alkyne isomerization reagents : selective isomerization of one triple bond of a diynol
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The lithium and sodium salts of 1,2-diaminoethane, 1,3-diaminopropane, n-butylamine, and the lithium salt of isobutylamine were studied as potential reagents for isomerzation of triple bonds in alkyn-1-ols.The sodium salts of the diamines afforded high yields of the ω-alkyn-1-ol.Somewhat surprisingly, the sodium salt of n-butylamine also effects isomerization to the terminal position.The lithium salt of 1,3-diaminopropane gave the highest conversion of 2- to 3-alkyn-1-ol.A novel, selective rearrangement of one triple bond of a diynol, a 2,ω- to 3,ω-diyn-1-ol isomerization, was incorporated into a synthesis of the insect sex pheromone 3,13-octadecadienol acetate.
- Abrams, Suzanne R.,Nucciarone, Donaato D.,Steck, Warren F.
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p. 1073 - 1076
(2007/10/02)
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