- Pheromones of insects and their analogs. LIV. Synthesis of dodec-9e-en-1-ol and its acetate - Components of the sex pheromone of Sparganothis pilleriana
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Using the Claisen rearrangement in the construction of a double bond with the E configuration, we have synthesized dodec-9E-en-1-ol and its acetate, which are components of the sex pheromone of Sparganothis pilleriana.
- Odinokov,Vakhidov,Shakhmaev,Zorin
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- Synthesis of E-9-dodecen-1-yl acetate using organomanganese reagents
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The Grignard reagent obtained from 2-(6-bromohexyloxy)-tetrahydropyrane, by treatment with anhydrous manganese(II) chloride was transformed to the corresponding organomanganese reagent, which was coupled with E-1-bromo-3-hexene by treatment with anhydrous manganese chloride. Further deprotection and acetylation furnished E-9-dodecen-1-yl acetate. A second procedure involved the coupling of E-3-hexenylmanganese bromide and 6-bromohexyl acetate. Coupling reactions were carried out at 0 °C, using tetrahydrofurane and N-methylpyrrolidone as co-solvent.
- Belmar, Julio,Tellez,Baeza,Freer
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- A chemoselective reduction of alkynes to (E)-alkenes
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The trans reduction of all types of alkynes to give (E)-olefins is achieved through a two-stage trans hydrosilylation and protodesilylation. Reaction of an alkyne and a silane with the ruthenium catalyst [Cp*Ru(MeCN)3]PF6 results in
- Trost, Barry M.,Ball, Zachary T.,Joege, Thomas
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- Preparation of stereochemically pure E- and Z-alkenoic acids and their methyl esters from bicyclo[n.1.0]alkan-1-ols. Application in the synthesis of insect pheromones
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Oxidative cleavage of exo- and endo-alkyl- and hydroxyalkyl-substituted bicyclo[n.1.0]alkan-1-ols with (diacetoxy-λ3-iodanyl)benzene gave the corresponding methyl alkenoates exclusively with E or Z configuration of the double bond. This reaction was used as the key stage in the syntheses of stereoisomerically pure components of pest insect pheromones: (E)-dodec-9-en-1-yl acetate (European pine shoot moth Rhyacionia buoliana), (Z)-tetradec-11-en-1-yl acetate (European oak leafroller Tortrix viridana), and (3E,8Z,11Z)-tetradeca-3,8,11-trien-1-yl acetate (tomato leafminer Tuta absoluta).
- Zubrytski,Kananovich,Matiushenkov
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p. 813 - 823
(2017/08/02)
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- SYNTHESIS OF Z-OLEFIN-CONTAINING LEPIDOPTERAN INSECT PHEROMONES
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The present invention is directed to methods of synthesizing insect pheromones, particularly lepidopteran insect pheromones, their precursors and derivatives from inexpensive, readily available starting materials using olefin metathesis catalysis.
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Paragraph 0185; 0186
(2013/09/12)
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- Pheromones of insects and their analogs. LII. Sythesis of dodec-9-en-1-yl and tetradec-11-en-1-yl acetates from the products of the partial ozonolysis of cycloocta-1z,5z-diene and cyclodeca-1e,5z-diene
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A new approach to the synthesis of octane-1,8-and decane-1,10-diols based on the partial ozonolysis of cyclic oligomers has been developed.
- Odinokov,Botsman,Gladysheva
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p. 381 - 383
(2007/10/03)
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- An electrochemical approach to some insect pheromones with (E)-alkene moiety
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An easy access to some Lepidopteran pheromones containing (E)-alkene moiety via anodic oxidation of a partially neutralized mixture of trans-3-alkenoic acids and methyl hydrogen carboxylates has been described.
- Singh, Krishna Nand,Singh, Manorama,Misra, Ram Achal
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p. 431 - 434
(2007/10/02)
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- SIMPLE SYNTHESIS OF ACETOGENIN TRANSOID INSECT PHEROMONES STARTING FROM ACETYLCYCLOPROPANE
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A highly effective synthesis of a series of alkyl and 1-alkenyl cyclopropyl ketones, which are key components in the complete synthesis of a large number of transoid lepidoptera pheromones, has been developed, based on the alkylation of N-cyclohexyl-1-cyclopropylethylideneimine or its condensation with aldehydes.
- Cheskis, B. A.,Ivanova, N. M.,Moiseenkov, A. M.,Nefedov, O. M.
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p. 1372 - 1380
(2007/10/02)
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- Acetylcyclopropane as a Five-Carbon Building Block in the Synthesis of some Acetogenin Insect Pheromones
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Interaction of deprotonated acetylcyclopropane cyclohexylimine with several aliphatic alkyl halides, epoxides, and aldehydes efficiently gave the corresponding cyclopropyl ketones.Some of the respectible alcohols were rearranged in a highly stereoselective manner under the action of trimethylsilyl bromide in the presence of zinc bromide into the corresponding linear (E)-homoallyl bromides.The latter were used, in turn, as key intermediates in concise syntheses of thirteen terminally functionalized straight-chain oligoolefins which are known to constitute acetogenin pheromonal components for more than 65 species of lepidopteran insects.
- Moiseenkov, Alexander M.,Czeskis, Boris A.,Ivanova, Natalya M.,Nefedov, Oleg M.
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p. 2639 - 2649
(2007/10/02)
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- Preparation of 9-alkenyl ester compounds
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Process for the production of 9-alkenyl acetates is provided. The process comprises first disproportionating cyclooctene with an α-olefin to give a 1,9-alkadiene. The alkadiene is metallated to form a 1-metallo-9-alkene, which is then contacted with oxygen to produce a 9-alkenyl-1-oxymetallo compound, which is optionally hydrolyzed to the corresponding alcohol, with the alcohol being esterified to the desired 9-alkenyl ester or the 9-alkenyl-1-oxymetallo compound can be directly esterified, to produce the desired 9-alkenyl esters.
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- Exo- and Endohormones. XI. Synthesis of Monounsaturated Sex Pheromones of Lepitoptera via α-Dicetones
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α-Dicetones (5), prepared starting either with cyanohydrines (1) or with N,N-diethyl oxamate (6), were converted via the dihydrazones 11 ito acetylenes (12).Replacement of the protecting group by the acatate group and partial stereoselective reduction of the triple bond led finally to the title conpounds.
- Oprean, I.,Ciupe, Hilke,Gansca, Lucia,Hodosan, F.
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p. 283 - 289
(2007/10/02)
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- PEPARATION OF (Z) and (E)-9-DODECENYL ACETATES
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The sexual pheromones (Z)-9-dodecenyl acetate (IXa) and (E)-9-dodecenyl acetate (IXb) were synthesized using facile preparation of the acetylenic precursor 9-decyn-1-ol (IV), from tetrahydrofurfuryl chloride (I).Hydroxyl groups of intermediates in the subseqent steps were protected by the ethoxyethyl group.
- Koerblova, Eva,Romanuk, Miroslav
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p. 2284 - 2288
(2007/10/02)
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- A General Approach to the Synthesis of Mono-olefinic Insect Sex Pheromones of Z- or E-Configuration
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A series of insect sex pheromones and structually related olefins have been synthesized with high stereoisomeric purity by two sequential cross-coupling reactions.Starting with (Z)- or (E)-1-bromo-2-phenylthioethene, (1) and (2), and Grignard reagents in the presence of nickel or palladium catalysts, two types of compounds have been prepared: (i) 1,2-dialkylethenes and (ii) alkenyl acetates.In the synthesis of Z-isomers, the first step involves a cross-coupling reaction of compound (1) with the appropriate Grignard reagent in the presence of a catalytic amount of .The second cross-coupling reaction is performed on the intermediate (Z)-phenylthioalkenes using a different Grignard reagent in the presence of (dppe=Ph2PCH2CH2PPh2) as a catalyst.In the synthesis of E-isomers both steps are cross-coupling reactions of Grignard reagents in the presence of as a catalyst, the first step involving compound (2) and the second step involving the intermediate (E)-phenylthioalkenes obtained.The Grignard reagents used in the synthesis of the alkenyl acetates derive from protected ω-halohydrins.
- Fiandanese, Vito,Marchese, Giuseppe,Naso, Francesco,Ronzini, Ludovico
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p. 1115 - 1120
(2007/10/02)
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- Syntheses of the Sex Pheromone of the European Pine Shoot Moth (Rhyacionia buoliana). The Grignard Route
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Grignard-Kopplungen zwischen zwei entsprechenden Synthonen fuehren zum (E)-9-Dodecen-1-ylacetat (1), dem Sexuallockstoff des Kiefernknospentriebwicklers (Rhyacionioa buoliana).Als solche Synthon-Paare wurden 1-Brom-(E)-2-penten (2) und 7-Bromheptyltetrahydropyranylether (3) bzw. (E)-3-Hexen-1-yltosylat (4) und 6-Bromhexyltrimethylsilylether (5) eingesetzt.Das Endprodukt (1) und die wichtigsten Zwischenprodukte wurden durch ihre 1H- und 13C-NMR-Spektren charakterisiert.Durch die zweite Synthese wurden 100percent Regio- und 99percent Stereoselektivitaet erreicht.
- Popovici, N.,Botar, A. A.,Barabas, A.,Oprean, I.,Hodosan, F.
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- STEREOSPECIFIC SYNTHESIS OF PHEROMONES OF THE E-ALKENE SERIES FROM THE TELOMER OF BUTADIENE WITH PHENOL
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The stereospecific synthesis of 7E- and 9E-dodecenyl acetates, 7E- and 11E-tetradecenyl acetates, 11E-tetradecen-1-ol, and 11E-hexadecenyl acetate, i.e., E-olefinic sex pheromones, was realized from 1-phenoxy-2E,7-octadiene (the telomer of butadiene with phenol).
- Zakharkin, L. I.,Petrushkina, E. A.
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p. 1419 - 1422
(2007/10/02)
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- Synthesis of 9(E)-Dodecenyl Acetate & 9(E),11-Dodecadienyl Acetate, Female Sex Pheromones of red Bollworm Moth, Diparopsis castanea Hmps.
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Undec-10-en-1-ol (III) on the reaction with dihydropyran in the presence of catalytic amount of conc.HCl at 0 deg C provides the ether (IV) which on epoxidation with m-chloroperbenzoic acid yields the epoxide (V) in very high yields.Cleavage of V with lithium diisopropylamide under N2 atmosphere gives the 11-tetrahydropyranyloxyundec-2(E)-en-1-ol (VI) which on oxidation with pyridinium chlorochromate in dry CH2Cl2 furnishes 11-tetrahydropyranyloxyundec-2(E)-en-1-al (VII).Aldehyde (VII) on Wittig reaction using methylenetriphenylphosphorane in DMSO under N2 atmosphere affords conjugated diene (VIII) which on treatment with methanolic solution of PTS gives 9(E),11-dodecadien-1-ol (IX).Action of isopropenyl acetate on IX in the presence of PTS yields 9(E),11-dodecadienyl acetate (I).Conversion of the intermediate alcohol (VI) into the corresponding mesylate (X) with mesyl chloride/ triethylamine in dry CH2Cl2 at 0 deg and subsequent treatment of X with lithium dimethyl cuprate under N2 atmosphere results in the formation of 12-tetrahydropyranyloxyundec-3(E)-ene (XI).Removal of the protective pyranyl group in XI with PTS in methanol gives 9(E)-dodecenol (XII) which on treatment with acetic anhydride/ dry pyridine provides 9(E)-dodecenyl acetate.
- Vig, O. P.,Sharma, M. L.,Verma, N. K.,Malik, Neera
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p. 692 - 694
(2007/10/02)
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