- The synthesis of long chain dialkylalkynes, dialkyldiynes and their hydrogenation to monoenes and dienes
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Long methylenic chain dialkylalkynes have been synthesised in high yield by an improved procedure. The methodology has been extended to nonconjugated diynes. Catalytic hydrogenation with a poisoned palladium catalyst affords cis-monoenes and cis, cis-dienes respectively. An improved synthesis of cis- 9-tricosene is described.
- Fisher,Tyman
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- INSECT PHEROMONES AND THEIR ANALOGS. XIV. SYNTHESIS OF MUSCALURE - THE SEX PHEROMONE OF Musca domestica
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A new route to the synthesis of tricos-9Z-one - the sex pheromone of the house fly - has been developed.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Balezina, G. G.,Bakhitov, R. Sh.,Tolstikov, G. A.
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- A stereospecific route to functionalized alkenes from tetrahydrofurfurylic acetates, synthesis of pheromones
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Pure Z or E γ-iodoalkenes were prepared by a ring opening-elimination tandem reaction of erythro or threo secondary tetrahydrofurfurylic acetates with Me3SiCl/NaI. Applications to the synthesis of pheromones of Musca domestica and of Orgyia pseudotsugata are reported.
- Amouroux, Roger,Ejjiyar, Soumeya
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- REGIOSELECTION IN THE ALKYLATION OF TRIMETHYLSILYLALLYL ANION- STEREOSELECTIVE SYNTHESIS OF DISUBSTITUTED ALKENES.
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The regioselection in the alkylation of trimethylsilylallyl anion can be controlled by the use of Schlosser's base to give predominately γ-product with trans geometry at the double bond.Application of this approach to the synthesis of Z-9-tricosene and the Gypsy month sex pheromone is demonstrated.
- Koumaglo, K.,Chan, T. H.
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- A NEW STEREOSELECTIVE SYNTHESIS OF (Z)-9-TRICOSENE, THE SEX ATTRACTANT OF THE COMMON HOUSEFLY
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"Muscalure" (9-tricosene) was prepared very readily by an instant-ylid reaction in a highly cis-selective manner although it was found difficult to assess the (Z/E)-ratio with accuracy.
- Moiseenkov, Alexander M.,Schaub, Bruno,Margot, Christian,Schlosser, Manfred
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- Cobalt-Catalyzed Decarboxylative Methylation and Ethylation of Aliphatic N-(Acyloxy)phthalimides with Organoaluminum Reagents
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A cobalt-catalyzed decarboxylative methylation of aliphatic redox-active esters [ N-(acyloxy)phthalimides; RAEs] with trimethylaluminum under mild conditions was developed, providing a method for transforming a carboxylate group into a methyl group without redox fluctuation. Primary and secondary RAEs were both amenable substrates, whereas a tertiary RAE delivered an elimination product. Triethylaluminum was also used to deliver a decarboxylative ethylation product.
- Wang, Ze-Zhong,Wang, Guang-Zu,Zhao, Bin,Shang, Rui,Fu, Yao
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supporting information
p. 1221 - 1225
(2020/08/17)
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- Stereoselective Alkyne Hydrogenation by using a Simple Iron Catalyst
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The stereoselective hydrogenation of alkynes constitutes one of the key approaches for the construction of stereodefined alkenes. The majority of conventional methods utilize noble and toxic metal catalysts. This study concerns a simple catalyst comprised of the commercial chemicals iron(II) acetylacetonate and diisobutylaluminum hydride, which enables the Z-selective semihydrogenation of alkynes under near ambient conditions (1–3 bar H2, 30 °C, 5 mol % [Fe]). Neither an elaborate catalyst preparation nor addition of ligands is required. Mechanistic studies (kinetic poisoning, X-ray absorption spectroscopy, TEM) strongly indicate the operation of small iron clusters and particle catalysts.
- Gregori, Bernhard J.,Schwarzhuber, Felix,P?llath, Simon,Zweck, Josef,Fritsch, Lorena,Schoch, Roland,Bauer, Matthias,Jacobi von Wangelin, Axel
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p. 3864 - 3870
(2019/07/31)
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- Practical and scalable synthesis of (Z)-9-Tricosene, the housefly sex pheromone
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A practical and scalable synthesis of (Z)-9-tricosene, the sex pheromone of the housefly, has been achieved by the addition of one-carbon unit from the readily available (Z)-erucic acid. The synthesis is composed of three consecutive steps, lithium aluminium hydride reduction of erucic acid, tosylation of the resulting alcohol, and copper-catalyzed Kumada- type cross-coupling of the tosylate with methylmagnesium bromide as the key step. This approach is quite straightforward and capable of scale-up synthesis.
- Kim, Miri,Pitchaiah, Arigala,Park, No-Joong,Hwang, In Taek,Lee, Kee-In
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p. 628 - 631
(2013/02/23)
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- Close-range attraction in Lygocoris pabulinus (L.)
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Males of the green capsid bug, Lygocoris pabulinus, exhibit a specific courtship behavior, i.e., a vibration of the abdomen. When both live and dead females were offered to males, this vibration behavior was elicited in most of the males tested. When females were dissected into separate body parts, heads, wings, and legs elicited equal responses, while thorax plus abdomen elicited a much lower response. When separate body parts were extracted, the leg extracts elicited significantly stronger responses than any other extract. This suggests that female L. pabulinus legs are either the source of a close-range sex pheromone or that pheromone is accumulated on the legs due to grooming behavior. The leg extracts contained several hydrocarbons such as n-alkenes, n-alkanes, and some methylalkanes. Female extracts contained more (Z)-9-pentacosene and male extracts contained more (Z)-9-heptacosene. Substrates on which females had walked elicited similar responses as female legs, indicating that the pheromone is deposited on the substrate. This enlarges the functional range of low-volatility compounds, which are thought to function only when sexes are in close vicinity or in contact.
- Drijfhout, Falko P.,Groot, Astrid T.
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p. 1133 - 1149
(2007/10/03)
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- Synthesis of sub-units of marine polycyclic ethers by ring-closing metathesis and hydroboration of enol ethers
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A novel syntheses of Z-5-dezenol, Z-5-decenyl acetate, Z-7-dodecenol, Z- 7-dodecenyl acetate, Z-9-tricosene, Z-7,8-epoxy-methyloctadecane which are sex pheromone components of Lepidoptera and Diptera orders, have been realized via stereoselective cometathesis of 1,5-cyclooctadiene with ethylene in the presence of MoCls/SiO2-SnMe4 as a key reaction. The male cometathesis product, 1,Z-5,9-decatriene, has been converted into pheromone components monocloned above by regioselective partial hydroboration or hydrozirconation with help of 9-BBN and Cp2ZrHCl, correspondingly. The protonolysis of the obtained zirconosene derivative gave 1,Z-5-decadiene. Hydroboration-oxidation or hydroboration-C2-homologation of the latter but to Z-5- or Z-7 monoene pheromone components. Hydroboration-iodination of terminal double bond in 1,Z-5,9-decatriene, and further cross-coupling of the obtained iodine derivative with convenient lithium cuprates resulted in Z-9- tricosene, the main sex pheromone component of House Fly (Musca Domestica), or in 2-methyl-Z-7-octadecene, the presence of Gypsy Moth (Lymantria Dispar) sex attractant.
- Bykov, Victor I.,Butenko, Tamara A.,Petrova, Elena B.,Finkelshtein, Eugene Sh.
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p. 8249 - 8252
(2007/10/03)
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- Opposite stereochemical effects exerted by CeCl3 and TiCl4 on the Lewis acid mediated reduction of α-alkyl-β-ketophosphine oxides with metallic hydrides: A highly stereoselective protocol for the synthesis of syn and anti α-alkyl-β-hydroxyphosphine oxides
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A general, highly efficient methodology for obtaining both syn and anti α-hydroxyphosphine oxides by reduction of the corresponding α-ketophosphine oxides is described. The nature of the Lewis acid was found to be pivotal in determining the outcome of these reactions. Strongly chelating TiCl4 led to the anti isomer in high diastereoisomeric excess in noncoordinating solvents (CH2Cl2) at -78°C with BH3/py as reducing agent, while nonchelating CeCl3 gave a high excess of the syn isomer in coordinating solvents (THF) at the same temperature with LiBH4 as reducing agent. In the latter case, CeCl3 is essential in achieving high yields and stereoselectivity, since it allows the reaction to be performed at low temperatures. Otherwise, higher temperatures (0 °C) are required, which lower both yields and selectivities. Moreover, each step of the protocol for the synthesis of stereodefined disubstituted olefins from alkylphosphine oxides (Warren's modification of the Homer procedure) has been optimized, and the optimized procedure has been applied to the synthesis of muscalure, the pheromone of the domestic fly.
- Bartoli, Giuseppe,Bosco, Marcella,Dalpozzo, Renato,Marcantoni, Enrico,Sambri, Letizia
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p. 1941 - 1950
(2007/10/03)
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- Pheromones via organoboranes: Part IV - Synthesis of (Z)-9-tricosene (Muscalure)
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Synthesis of (Z)-9-tricosene (muscalure) (9) is reported starting from oleyl alcohol by two carbon homologation via dianion of phenoxyacetic acid followed by reduction (LAH), oxidation (PCC) and Grignard reaction.
- Dhillon, Ranjit S.,Singh, Rupinder P.,Singh, Jasvinder
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p. 718 - 721
(2007/10/03)
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- Diastereoselective desulfurization of 5,6-dihydro-1,4-dithiins. Synthesis of muscalure from Musca domestica L.
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A procedure is reported for the chemo- and stereo-selective sulfur removal from 5,6-dihydro-1,4-dithiins which completes the pathway to synthesize cis configurated olefins from carbonyl compounds. A four step synthesis of (Z)- 9-tricosene (muscalure) with the dithiin moiety serving as the penultimate olefin precursor is also reported as an example of the proposed synthetic strategy.
- Caputo, Romualdo,Palumbo, Giovanni,Pedatella, Silvana
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p. 7265 - 7268
(2007/10/02)
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- Wittig reaction on some aldehydes from aleuritic acid derivatives and a synthesis of (Z)-9-tricosene
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Starting from the commercially available threo-aleuritic acid (1a) and its erythro-isomer (5), Wittig reactions have been carried out using several procedures on the aldehydes available by CrO3-Py oxidation of the terminal hydroxyl function.From the 16-iodo derivative (6) of erythro-aleuritic acid, through Wittig reaction followed by reductions and olefination of the 1,2-glycol function, (Z)-9-tricosene (4) has been synthesised.
- Bhushan, Kumar Hari,Rastogi, Archana,Subramanin, G.B.V.
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p. 966 - 970
(2007/10/02)
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- Erucic acid, a cheap source of synthetic pheromones
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Easily accessible starting materials, viz. aleuritic acid, tetrahydrofurfuryl alcohol, propargyl alcohol and undecenoic acid have earlier been used by us for the synthesis of a large number of insect pheromones.We now report that erucic acid (1), a major component of mustard oil, is yet another cheap starting material for the synthesis of pheromones (Ia and Ib) of sugarcane internode moth, Chilo sacchariphagus and mascalure (II), the pheromone of housefly, Musca domestica.
- Subbaraman, A S,Mithran, S,Mamdapur, V R
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p. 865 - 866
(2007/10/02)
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- OLEFINATION OF ALDEHYDES WITH TETRAALKYL-GEM-DIALUMOALKANES
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A new method of cis-olefination, based on the reaction of aldehydes with geminal alumolithium reagents, is proposed.
- Kuchin, A. V.,Markova, S. A.,Gorobets, E. V.,Tolstikov, G. A.
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p. 1034 - 1037
(2007/10/02)
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- IDENTIFICATION OF THE BY-PRODUCTS OF ANODIC COUPLING BETWEEN ERUCIC AND PROPIONIC ACIDS AND BETWEEN OLEIC AND HEPTANOIC ACIDS, USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY AND INFRARED SPECTROSCOPY
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A method is described as the simplest way for the synthesis of (Z)-9-tricosene, the sex pheromone of the housefly.The mixture of prodicts obtained on repeating the title syntheses appeared to be much more complex than described previously.The following by-products were identified using the GC/MS method: hydrocarbons with a straight chain - saturated C8 to C23, unsaturated C13 to C24; the dienes C20 and C21; and the methyl esters of fatty acids C7 to C22 (depending on the reaction path).In the products of the anodic coupling of erucic and propionic acids considerable amounts of high-molecular compounds were formed.The non-reported new compounds with molecular weights of 584 and 614 were formed in addition to the excepted 9,33-dotetracontadiene (m.w. 586).Their structures were elucidated by mass and ir spectroscopy as 9,20,33-dotetracontatriene (m.w. 584) and 9,34-tritetracontadien-21-one (m.w. 614).Mechanism of the formation of the by-products are proposed.
- Konopski, Leszek,Polec, Iwona
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p. 409 - 422
(2007/10/02)
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- Vinylic Organoboranes. 9. A General Stereospecific Synthesis of (Z)- and (E)-Disubstituted Alkenes via Organoboranes
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A general and stereospecific synthesis of (Z)-disubstituted alkenes using mono- and dihaloboranes is presented.The hydridation of dialkylhaloboranes in the presence of 1-alkynes provides the corresponding dialkylvinylboranes (1), representing the first general synthesis of such derivatives.Treatment with iodine in the presence of sodium methoxide induces the migration of one of the alkyl groups from boron to the adjacent carbon, followed by a rapid deiodoboronation to afford (Z)-disubstituted alkenes (2) in high yields.Similarly, the hydroboration of 1-alkynes with alkyl bromoboranes (R1BHBr*SMe2, 4) followed by iodination in the presence of sodium methoxide in methanol affords (Z)-disubstituted alkenes (2) in good yields.Both procedures constitute a general one-pot synthesis of (Z)- disubstituted alkenes from an alkene and 1-alkyne.A simple synthesis of Muscalure (7), the sex pheromone of the housefly (Musca domestica), is achieved in good yields.An alternative general stereospecific synthesis of (Z)- and (E)-disubstituted alkenes based on alkenylboronic esters is also described.
- Brown, Herbert C.,Basavaiah, Deevi,Kulkarni, Surendra U.,Bhat, Narayan G.,Prasad, J. V. N. Vara
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p. 239 - 246
(2007/10/02)
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- A CONVENIENT REDUCTION OF ALKYLATED TOSYLMETHYL ISOCYANIDES: APPLICATIONS FOR THE SYNTHESIS OF NATURAL PRODUCTS
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A convenient and simple method for the reduction of mono- and dialkylated tosylmethyl isocyanides with lithium in liquid ammonia to corresponding hydrocarbons is described.The utility of this methodology adopted in the synthesis of tricos-9Z-ene (7g), a sex pheromone of common house fly, (-)-1S,5R,7S-exo-brevicomin (17), an antipode of sex pheromone of Western pine beetle and (4S,5S)-5-hydroxy-4-decanolide (L-factor, 19), a proposed autoregulator for leukaemomycin biosynthesis.
- Yadav, J. S.,Reddy, P. Satyanarayana,Joshi, Bhalchandra V.
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p. 7243 - 7254
(2007/10/02)
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- ENAMINE CONDENSATION ON DERIVATIVES OF ALEURITIC ACID AND SYNTHESIS OF (Z)-9-TRICOSENE (MUSCALURE), ITS (E)-ISOMER, AND (E)-13-HEPTACOSENE
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Enamine condensation on (9RS,10RS)-9,10,16-triacetoxy hexadecanoyl chloride as well as (7RS,8RS)-7,8-diacetoxypentadeca-1,15-dioyl chloride using 1-morpholino-1-cyclohexene led to chain elongated products with 22 and 27 carbon atoms and its (E)-isomer while the latter led to a synthesis of (E)-13-heptacosene.
- Subramanian, G. B. V.,Mehrotra, Alka,Mehrota, Kalpana
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p. 3967 - 3972
(2007/10/02)
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- Vinylic Organoboranes. 3. Pheromones via Organoboranes. 1. Stereospecific Synthesis of Straight-Chain Z-Monoolefinic Insect Pheromones via Lithium (1-Alkynyl)trialkylborates
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Various insect pheromones with straight-chain Z-monoolefinic structures have been prepared from lithium (1-alkynyl)trialkylborates.Treatment of lithium (1-alkynyl)trialkylborates, readily prepared from lithium acetylides and trialkylboranes, with iodine under mild conditions produces the corresponding alkynes in essentially quantitative yield.Monohydroboration of the resultant alkyne with 9-borabicyclononane yields the corresponding (Z)-olefin after protonolysis.The combination of these two reaction sequences provides a general route for the synthesis of (Z)-olefins.The position of the double bond and the carbon-chain length are easily controlled by properly choosing the initial reactants.The incorporation of functional groups is also easily achieved because of the mild reaction conditions and the tolerance of hydroboration to many functional groups.High yield and purity of the products are obtained.
- Brown, Herbert C.,Wang, Kung K.
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p. 4514 - 4517
(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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- OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XXVI. SYNTHESIS OF MUSCALURE - THE SEX PHEROMONE OF THE HOUSE FLY Musca Domestica
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A new method is proposed for the stereospecific synthesis of 9Z-tricosene - the sex pheromone of the house fly Musca domestica - on the basis of the selective ozonolysis of -1,5-cyclooctadiene.The directed transformations of the functional groups in methyl 8,8-dimethoxy-4Z-octenoate and successive two-step coupling with amyl- and decylmagnesium bromides led to the pheromone with an overall yield of 30percent.
- Odinokov, V. N.,Galeeva, R. I.,Kargapol'tseva, T. A.,Tolstikov, G. A.
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p. 666 - 668
(2007/10/02)
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- SYNTHESIS OF MUSCALURE - THE PHEROMONE OF Musca domestica
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A method for obtaining cis-tricos-9-ene (muscalure) - the pheromone of the housefly - from the readily available ethyl oleate has been developed.
- Verba, G. G.,Abdukakharov, V. S.,Abduvakhabov, A. A.
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p. 655 - 657
(2007/10/02)
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- SILICON IN ORGANIC SYNTHESIS. STREREOSELECTIVE SYNTHESIS OF SOME INSECT SEX PHEROMONES
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Trialkylsilallyl anion is alkylated by alkyl halides to give regio- and strereo-selectively the γ-product with trans-strereochemistry at double bond.The trans-vinylsilanes are transformed strereoselectively to Z-vinyl iodides.Coupling of the vinyl idiodes with organometallic reagents gives Z-alkenes.This approach has been applied to the synthesis of several insect sex pheromones.
- Chan, T. H.,Koumaglo, K.
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p. 109 - 120
(2007/10/02)
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- A CONVENIENT REDUCTION OF DIALKYLATED TOSYLMETHYL ISOCYANIDE
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Dialkylated tosylmethyl isocyanides have been conveniently reduced to the corresponding hydrocarbons with lithium in liquid ammonia.This process has been succesfully utilised in the synthesis of (Z)-9-tricosene - a sex pheromone of common house fly.
- Yadav, J. S.,Reddy, P. Satyanarayana
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p. 4025 - 4028
(2007/10/02)
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- A General and Stereospecific Synthesis of Cis Alkenes via Stepwise Hydroboration: A Simple Synthesis of Muscalure, the Sex Pheromone of the Housefly (Musca domestica)
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Base-induced iodination of the vinylborane intermediates, conveniently obtained via hydroboration of 1-alkynes with alkylbromoboranes (RBHBr*SMe2) provides cis-disubstituted alkenes in good yields.Muscalure, the insect pheromone of the housefly (Musca domestica), has been prepared in 59percent yield.
- Brown, Herbert C.,Basavaiah, D.
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p. 3806 - 3808
(2007/10/02)
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- A NOVEL STEREOSPECIFIC SYNTHESIS OF MUSCALURE, THE SEX PHEROMONE OF HOUSE FLY (MUSCA DOMESTICA)
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Partial ozonolysis of 1Z,5Z-cyclooctadiene followed by selective transformations of ester and acetal groups in methyl ester of 8,8-dimethoxy-4Z-octen-1-oic acid, and by a two step elongation of carbon chain of the latter by means of tosyloxy groups replacement under action of decyl- and pentyl magnesium bromides leads to muscalure - the sex pheromone of house fly.
- Odinokov, V.N.,Tolstikov, G.A.,Galeyeva, R.I.,Kargapol'tseva, T.A.
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p. 1371 - 1372
(2007/10/02)
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- Process for the preparation of higher alkenes
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A process for the preparation of a straight-chain or branched alkene which has 20 to 24 carbon atoms and in which the ethylenic bond is located after a carbon atom numbered between 8 and 11, which process comprises reacting, in an anhydrous solvent, preferably in an oxahydrocarbon an organometallic copper compound with an alkyl or alkenylsulfonate.
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