- Stereoselective synthesis of 11(E)-tetradecen-1-yl acetate-Sex pheromone of sod webworm (Loxostege sticticalis)
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On the basic of Claisen rearrangement using orthoesters we carried out stereoselective synthesis of 11(E)-tetradecen-1-yl acetate, a sex pheromone of sod webworm (Loxostege sticticalis), which is a specially dangerous pests of crops.
- Shakhmaev,Ishbaeva,Shayakhmetova
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- SYNTHESIS OF PHEROMONES AND RELATED MATERIALS VIA OLEFIN METATHESIS
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Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.
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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 0191; 0192
(2013/09/12)
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- Production of pheromones and fragrances from substituted and unsubstituted 1-alken-3yl alkylates
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Compounds of the formula (I) wherein R2 is a branched or unbranched, saturated or ethylenically mono or di unsaturated aliphatic radical, Z is —CH2OH, —CH2OAc or —CHO, m is a whole positive integer of one or more, and Ac is an acetyl group are synthesized by a process wherein a 1-alken-3-yl alkylate, is reacted with a halo alkanol Grignard reagent.
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Page/Page column 4
(2010/05/13)
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- Synthesis of (Z/E)-11-tetradecen-1-ol, a component of Ostrinia nubilalis sex pheromone
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11-Tetradecen-1-ol acetate is a mixture of geometric isomers with the Z/E-conformations in a 94:6 ratio that is used as an attractant to trap corn pests. It has a powerful attractive action similar to that of an isomeric mixture of 11-tetradecenyl acetate with the Z/E-conformation in a 95:5 ratio that was extracted from the peritoneal cavity of male Ostrinia nubilalis Hubner in Xinjing (PRC).
- Li,Yong,Aisa
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p. 224 - 226
(2008/12/22)
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- Process for preparing functional group-containing olefinic compounds
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A process for preparing functional group-containing olefinic compounds comprises the steps of (a) reacting at least one alkylidene phosphorane with at least one carbonyl-containing compound that comprises at least one group that is a leaving group, or that is capable of subsequent conversion to a leaving group, to form an olefinic compound that comprises at least one leaving group, the carbonyl-containing compound being selected from the group consisting of ketones and aldehydes; and (b) reacting the olefinic compound with at least one functional group-containing nucleophile to form a functional group-containing olefinic compound.
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Page column 11-12
(2010/02/10)
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- Metathesis syntheses of pheromones or their components
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The present invention relates to metathesis syntheses for insect sex-attractant pheromones or their components, such as E-5-decenyl acetate, the major component of the Peach Twig Borer pheromone; (5R,6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition attractant pheromone; E9,Z11-hexadecadienal, the pecan nut casebearer moth pheromone; 9-tetradecenyl formate, an analog of the Diamondback Moth (DBM) pheromone; 11-tetradecenyl acetate, the Omnivorous Leafroller (OLR) pheromone; E-4-tridecenyl acetate, the major component of the Tomato Pinworm (TPW) pheromone; E,E-8,10-dodecadienol, the Codling Moth (CM) pheromone. The syntheses preferably employ a Class I-IV metathesis catalyst, entail few reaction steps, use generally commercially available starting materials, and have relatively short process times. These syntheses produce good yields without the need for expensive or sophisticated equipment. The invention also provides an inexpensive route for producing omega-haloalkenols by cross-metathesizing alpha-omega-diacetoxy alkenes and alpha-omega-dihalides to yield omega-haloalkenols, which are easily converted into omega-haloalkanols under traditional hydrogenation methods.
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- Metathesis syntheses of pheromones or their components
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The present invention relates to metathesis syntheses for insect sex-attractant pheromones or their components, such as E-5-decenyl acetate, the major component of the Peach Twig Borer pheromone; (5R, 6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition attractant pheromone; E9, Z11-hexadecadienal, the pecan nut casebearer moth pheromone; 9-tetradecenyl formate, an analog of the Diamondback Moth (DBM) pheromone; 11-tetradecenyl acetate, the Omnivorous Leafroller (OLR) pheromone; E-4-tridecenyl acetate, the major component of the Tomato Pinworm (TPW) pheromone; E,E-8,10-dodecadienol, the Codling Moth (CM) pheromone. The syntheses preferably employ a Class I-IV metathesis catalyst, entail few reaction steps, use generally commercially available starting materials, and have relatively short process times. These syntheses produce good yields without the need for expensive or sophisticated equipment. The invention also provides an inexpensive route for producing omega-haloalkenols by cross-metathesizing alpha-omega-diacetoxy alkenes and alpha-omega-dihalides to yield omega-haloalkenols, which are easily converted into omega-haloalkanols under traditional hydrogenation methods.
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- Synthesis of 5-decenyl acetate and other pheromone components
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The present invention relates to syntheses of 5-decenyl acetate, the major component in Peach Twig Borer pheromone, and other pheromone components. The syntheses entails few reaction steps, use commercially available starting materials, and have relatively short process times. A preferred embodiment of the syntheses involves self-metathesizing 1-hexene in the presence of Grubbs' catalyst, [(PCy3)2Cl2]Ru═CHPh. The resulting 5-decene is then reacted with an alcohol or acetate protected hexene under vacuum to yield 5-decenyl acetate. These syntheses produce good yields without the need for expensive or sophisticated equipment.
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- Stereospecific synthesis of 11E-tetradecenal, 11E-tetradecen-1-ol, and its acetate, pheromone components of insects of Lepidoptera order, from 10-undecenoic acid
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A regio-and stereospecific synthesis of 11E-tetradecen-1-ol and its derivatives, which are pheromone components of many insect species of Lepidoptera order, by means of a reaction of methylmagnesium cuprate reagent with 1,12-tridecadien-3-yl acetate by the SN2' mechanism, was carried out.
- Ishmuratov,Yakovleva,Kharisov,Muslukhov,Tolstikov
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p. 1035 - 1037
(2007/10/03)
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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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- INSECT PHEROMONES AND THEIR ANALOGUES. XXXVII. SYNTHESIS OF TETRADEC-11E-ENAL AND OF TETRADEC-11E-EN-1-OL AND ITS ACETATE FROM UNDECENOIC ACID
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A stereospecific synthesis has been achieved of tetradec-11E-enal and of tetradec-11E-en-1-ol and its acetate - components of the pheromones of many species of insects of the order Lepidoptera - from the readily available undecenoic acid, using the Knoevenagel reaction and catalytic hydroalumination.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Vakhidov, R. R.,Berg, A. A.,Muslukhov, R. R.,Tolstikov, G. A.
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p. 237 - 240
(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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- 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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- OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XXXV. SYNTHESIS OF 8Z-DODECENYL- AND 11Z-TETRADECENYL ACETATES FROM THE CYCLIC DIMER OF BUTADIENE
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The stereoselective synthesis of 8Z-dodecenyl- and 11Z-tetradecenyl acetates which are components of the sex pheromones of many species of insect of the order Lepidoptera, was realized on the basis of the partial ozonolysis of (Z,Z)-1,5-cyclooctadiene and its isomerization product (Z,Z)-1,3-cyclooctadiene.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Galeeva, R. I.,Kharisov, R. Ya.,Sokol'skaya, O. V.,at al.
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p. 646 - 651
(2007/10/02)
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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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- A "TUNABLE" STEREOSELECTIVE ALKENE SYNTHESIS BY IODODESILYLATION OF VINYLSILANES
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The stereoselectivity of iododesilylation of terminal E-vinylsilanes varies with changing amount of Lewis acid.The use of this "tunable" stereoselective reaction was demonstrated by the syntheses of two insect sex pheromones with defined E/Z isomeric rations.
- Chan, T. H.,Koumaglo, K.
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p. 883 - 886
(2007/10/02)
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- Pheromones via Organoboranes. 2. Vinylic Organoboranes. 8. Applications of the General Stereoselective Synthesis of (E)-Disubstituted Alkenes via Thexylchloroborane-Dimethyl Sulfide to the Synthesis of Pheromones Containing an (E)-Alkene Moiety
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Various (E)-pheromones of the general structure (E)-X-alken-1-yl acetates, (E)-X-alken-1-ols, and (E)-X-alken-1-als have been prepared via thexylchloroborane-dimethyl sulfide (ThxBHCl*SMe2).Hydroboration of acetate-functionalized alkenes with ThxBHCl*SMe2 gives cleanly the corresponding thexylalkylchloroboranes (ThxBRCl, B).Hydridation of B with potassium triisopropoxyhydride (KIPBH) at -78 deg C gives cleanly the corresponding thexylalkylboranes (ThxBRH, C).These are quenched immediately with 1-halo-1-alkynes to give B-(cis-1-halo-1-alkenyl)thexylalkylboranes (D).Treatment of D with sodium methoxide results in the displacement of bromine by the alkyl group on boron to produce B-(trans-1-alkyl-1-alkenyl)thexylborinates (E).Protonolysis of E with acetic acid provides (E)-X-alken-1-yl acetates in high yields and in >99percent isomeric purities.Treatment of (E)-X-alken-1-yl acetates with base affords the corresponding (E)-X-alken-1-ols.Oxidation of (E)-X-alken-1-ols with dimethyl sulfoxide activated by oxalyl chloride or the complex of dimethyl sulfide and chlorine produces (E)-X-alken-1-als quantitatively.By properly choosing the starting functionalized alkenes and 1-halo-1-alkynes, various (E)-pheromones can be prepared easily.The present procedure appears to be general.There does not appear to be any limitation on the length of the carbon chain or the position of the double bond in the target molecules.
- Brown, Herbert C.,Lee, Hsiupu D.,Kulkarni, Surendra U.
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p. 5282 - 5286
(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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- SYNTHESIS OF(E) AND (Z) ALKENES VIA PALLADIUM OR NICKEL-CATALYZED REACTION OF VINYL CHLORIDES WITH GRIGNARD REAGENTS.
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We herein described (i) a useful transformation of (E) and (Z) vinyl chlorides into E (and Z) olefins and (ii) an efficient preparation of monoenic alcohols or acetates and its application to insect pheromones.
- Ratovelomanana, Victorin,Linstrumelle, Gerard
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p. 179 - 188
(2007/10/02)
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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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- α-Haloallyllithium Species. Coupling with Alkyl Bromides
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The regiospecific α-alkylation of in situ generated α-chloroallyllithium species with primary alkyl bromides and the synthetic utility of the derived secondary allylic chloride intermediates are described.
- Macdonald, Timothy L.,Narayanan, Amirthalingam B.,O'Dell, Dale E.
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p. 1504 - 1506
(2007/10/02)
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- INSECT SEX PHEROMONES. STEREOSELECTIVE SYNTHESIS OF SEVERAL (Z)- AND (E)-ALKEN-1-OLS, THEIR ACETATES, AND OF (9Z,12E)-9,12-TETRADECADIEN-1-YL ACETATE
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Several female sex pheromone components produced by moths belonging to the order of Lepidoptera, and potential attractants of Dacus oleae (Diptera:Tripetidae) have been synthesized in high chemical and stereoisomeric purity by improved acetylenic routes involving alkylation of lithium 1-alkyn-1-ides in HMPT, followed by (Z) and (E) highly stereoselective reduction of the derived internal alkynes.Particular care has been paid to optimize the parameters of the reactions used and to evaluate the chemical and isomeric purity of the reaction products.The compounds synthesized include (Z)- and (E)-5-nonen-1-ol, (Z)- and (E)-7-dodecen-1-yl acetate, (Z)- and (E)-7-teradecen-1-yl acetate, (Z)- and (E)-7-nonen-1-ol, (Z)- and (E)-9-tetradecen-1-yl acetate, (Z)- and (E)-10-tetradecen-1-yl acetate, (Z)- and (E)-11-tetradecen-1-yl acetate.Pure (Z)-6-nonen-1-ol, which is an attractant of olive fruit fly, D. oleae, and very probably, a constituent of the sex pheromone of females of this insect, has been prepared by a rather efficient copper-catalyzed reaction between (Z)-3-hexen-1-ylmagnesium bromide and oxetane. (9Z,12E)-9,12-Tetradecadien-1-yl acetate, which is the pheromone of Anagasta kuenniella, Ephestia elutella, Cadra figulella, Spodoptera exigua, S. litura, and a component of the sex pheromones of several other Lepidoptera, has been conveniently prepared by using the copper-catalyzed coupling reaction between (E)-1-chloro-2-butene and 10-tetrahydropyranyloxy-1-decenylmagnesium bromide, followed by acetylation and Z-stereoselective reduction of the derived 1,4-enyne.All syntheses have been conducted on a scale to yield less than 50 mmol of the pure sex pheromone components, but seem adaptable for much larger quantities.
- Rossi, Renzo,Carpita, Adriano,Gaudenzi, Loretta,Quirici, Maria Grazia
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p. 237 - 246
(2007/10/02)
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