- Synthesis of cis-12-Nonadecen-9-one, cis-13-Icosen-10-one, the Pheromone of Peach Fruit Moth, and cis-15-Henicosen-11-one, the Pheromone of Douglas Fir Tussock Moth
-
A convenient synthesis of cis-12-nonadecen-9-one (4a), cis-13-icosen-10-one (4b), the feromone of peach fruit moth, and cis-15-henicosen-11-one (4c), the pheromone of Douglas fit tussock moth, is described. 4a was synthesized from methyl 3-oxoundecanoate and 1-bromo-2-nonyne (2a) via 12-nonadecyn-9-one.The higher homolog 4b could be obtained from methyl-3-oxododecanoate and 2a.Similarly, 4c was prepared from methyl 3-oxotridecanoate and 1-bromo-3-nonyne (2b).
- Ito, Shota,Saito, Norio,Hatakeda, Kiyotaka,Goto, Tomio
-
-
Read Online
- Concise syntheses of insect pheromones using Z-Selective cross metathesis
-
Very short synthetic routes to nine cisolefin-containing pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported (see scheme). These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z olefins.
- Herbert, Myles B.,Marx, Vanessa M.,Pederson, Richard L.,Grubbs, Robert H.
-
supporting information
p. 310 - 314
(2013/02/23)
-
- SYNTHESIS OF Z-OLEFIN-CONTAINING LEPIDOPTERAN INSECT PHEROMONES
-
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.
- -
-
Paragraph 0206; 0207
(2013/09/12)
-
- Grignard-triggered fragmentation of vinylogous acyl triflates: Synthesis of (Z)-6-heneicosen-11-one, the Douglas fir tussock moth sex pheromone
-
Grignard reagents react with vinylogous acyl triflates in toluene via an addition-fragmentation sequence to afford alkynyl ketones. A streamlined synthesis of (Z)-6-heneicosen-11-one, the sex pheromone of the Douglas fir tussock moth, illustrates the utility of this method. Georg Thieme Verlag Stuttgart.
- Jones, David M.,Kamijo, Shin,Dudley, Gregory B.
-
p. 936 - 938
(2007/10/03)
-
- Sex pheromone and related compounds in the Ishigaki and Okinawa strains of the tussock moth Orgyia postica (Walker) (Lepidoptera: Lymantriidae)
-
Two distinct electroantennographycally active (EAG-active) components, A and B, and a weakly active component C were found in a solvent extract from virgin females of the Ishigaki strain of the tussock moth, Orgyia postica (Walker). Components A, B, and C were found in the extract of the females at 4.0, 0.5, and 4.0 ng/female respectively. Components A, B, and C were identified as (6Z,9Z,11S,12S)-11,12-epoxyhenicosa-6,9-diene [(11S,12S)-1: posticlure], (6Z)-henicos-6-en-11-one (2), and (6Z,9Z)-henicosa-6,9-diene (3), respectively. Component B was absent in the extract from the Okinawa strain, in which components A and C were present at 2.0 and 1.5 ng/female respectively. (11S,12S)-1 and the racemic mixture showed attractiveness for both the Okinawa and Ishigaki strains, whereas (11R,12R)-1 did not. The addition of 2 significantly reduced the trap catches with (11S,12S)-1 on the Okinawa strain which lacked 2, while there was no significant inhibitory effect on the Ishigaki strain. The addition of 3 to (11S,12S)-1 did not significantly affect trap catches at Ishigaki or Okinawa. This confirmed that the attractant pheromone of O. postica of the Ishigaki strain is also (11S,12S)-1.
- Wakamura, Sadao,Arakaki, Norio,Yamamoto, Masanobu,Hiradate, Syuntaro,Yasui, Hiroe,Kinjo, Kunio,Yasuda, Tetsuya,Yamazawa, Hiroyuki,Ando, Tetsu
-
p. 957 - 965
(2008/02/03)
-
- Synthesis of the four components of the female sex pheromone of the painted apple moth, Teia anartoides.
-
Four pheromone components of the female painted apple moth (Teia anartoides), an Australian insect pest, were synthesized. These were (Z)-6-henicosen-11-one (1), (6Z, 8E)-6,8-henicosadien-11-one (2), (Z)-cis-9,10-epoxy-6-henicosene (3), and (Z)-cis-9,10-epoxy-6-icosene (4). 2-Dodecanone was converted to 1 and 2, and both the enantiomers of 3 and 4 were synthesized from the enantiomers of 4-tert-butyldimethylsilyloxy-cis-2,3-epoxy-1-butanol.
- Muto, Shin-etsu,Mori, Kenji
-
p. 1559 - 1567
(2007/10/03)
-
- Multicomponent reactions involving 2-methyleneaziridines: Rapid synthesis of 1,3-disubstituted propanones
-
Ring opening of 1-alkyl-2-methyleneaziridines 1 or 2 is accomplished with organocopper reagents (R2CuLi or RMgX/CuI) in the presence of boron trifluoride diethyl etherate giving 1-substituted propan-2-ones 3-9 in 42-88% yield. Ring opening with RMgC1/CuI in the absence of the Lewis acid allows further alkylation of the metalloenamine (metalated imine) intermediate in a regiocontrolled manner. The sequential formation of two new intermolecular carbon-carbon bonds in this reaction provides a rapid entry into a variety of 1,3-disubstituted propan-2-ones, including 11 and 14-23. The scope and mechanism of this multicomponent reaction (MCR) has been assessed. It is established that this MCR tolerates alkyl, aryl, and benzyiic Grignard reagents and a wide range of electrophiles, including alkyl iodides, bromides, and tosylates, as well as epoxides and aldehydes. In addition, gem-dimethyl substitution on the exocyclic double bond of the 2-methyleneaziridine is tolerated. This MCR has been applied to the one-pot synthesis of (Z)-6-heneicosen11-one, 25, an important sex attractant of the Tussock moth. Using 3-deuterio-1-(1-phenylethyl)2-methyleneaziridine, 26, we determined that this MCR occurs predominantly by direct ring opening at the sp3-hybridized aziridine carbon atom (C-3).
- Hayes, Jerome F.,Shipman, Michael,Twin, Heather
-
p. 935 - 942
(2007/10/03)
-
- Synthesis of (Z)-6-heneicosen-11-one, (+/-)(Z)-14-methyl-8-hexadecen-1-ol and (+/-)-5,6-dehydrosenedigitalene
-
Three naturally occurring compounds (Z)-6-heneicosen-11-one (1), (+/-)-(Z)-14-methyl-8-hexadecen-1-ol (2) and (+/-)-5,6-dehydrosenedigitalene (3) have been synthesised using lithium tetrachlorocuperate catalysed coupling reaction.
- Sharma, M. L.,Verma, Sadhana,Chand, Tek
-
p. 1030 - 1034
(2007/10/03)
-
- Pheromones via organoboranes: Part III - A short and convenient synthesis of (Z)-6-heneicosen-11-one
-
Synthesis of (Z)-6-heneicosen-11-one (5) has been achieved starting from undecanal using Grignard reaction, hydroboration with dibromoborane-dimethyl sulphide followed by hydridation (LAH), hydroboration of 1-heptyne and iodine induced rearrangement.
- Dhillon, Ranjit S.,Singh, Swaranjit,Singh, Jasvinder
-
p. 365 - 367
(2007/10/02)
-
- Synthesis via ultrasound: A very short and convenient synthesis of (Z) and (E)-heneicos-6-en-11-ones
-
(Z)-Heneicos-6-en-11-one (1) and its E-isomer (2), the sex pheromones of Douglas fir tussock moth, have been synthesised utilising ultrasonic waves.
- Trehan, I. R.,Singh, Jasvinder,Arora, Ajay K.,Kaur, Jasamrit,Kad, G. L.
-
p. 468 - 469
(2007/10/02)
-
- SYNTHESIS OF (Z)-HENICOSEN-11-ONE - A COMPONENT OF THE SEX PHEROMONES OF INSECTS OF THE Orgya FAMILY (ORGYIDAE)
-
The synthesis of (Z)-6-henicosen-11-one - a component of the sex pheromones of insects of the orgya family (Orgyidae) -from furfural is described.
- Kovalev, V. G.,Nasser, Fadel Ahmed,Sorochinskaya, A. M.
-
p. 1750 - 1753
(2007/10/03)
-
- Use of organoboranes in the synthesis of pheromones: A convenient synthesis of (Z)-6-heneicosen-11-one and (Z)-5-undecen-2-one, pheromones from the Douglas Fir Tussock Moth and the Bontebok, respectively
-
Treatment of thexylborane with a halomagnesiumdialkylcuprate afforded the corresponding (R-alkyl)thexylborane in favourable yields. A second reaction with a halomagnesiumdialkenylcuprate produced the totally mixed (R-alkyl)(E-alkenyl)thexylborane. Subsequent treatment with sodium cyanide and benzoyl chloride followed by alkaline peroxide yielded an unsaturated ketone. In this way, (Z)-6-heneicosen-11-one, a sex pheromone of the Douglas Fir Tussock Moth, and (Z)-5-undecen-2-one, a pheromone from the pedal gland of the Bontebok, were prepared.
- White,Whiteley
-
p. 1141 - 1144
(2007/10/02)
-
- New and Convenient Synthesis of (Z)-Heneicos-6-en-11-one, the Douglas Fir Tussock Moth (Orgyia pseudotsugata) Sex Pheromone, and (Z)-Non-6-en-2-one, the Immediate Precursor for the Synthesis of Brevicomin, the Sex Attractant of the Western Pine Beetle Dentroctonus brevicomis
-
Convenient syntheses of (Z)-heneicos-6-en-11-one and (Z)-non-6-en-2-one were achieved from (Z)-1-nitrodec-4-ene and (Z)-1-nitrohept-4-ene.Solvent-free nitroaldol reaction of (Z)-1-nitro-alkenes 1 with the aldehydes 2 on Amberlyst A-21, followed by in situ oxidation, gave the α-nitro ketones 3.Denitration via p-tolylsulphonylhydrazones and removal of the protecting group gave the title compounds 6a and 6b in 60 and 53 percent overall yield.
- Ballini, Roberto
-
p. 1419 - 1421
(2007/10/02)
-
- A stereospecific route to functionalized alkenes from tetrahydrofurfurylic acetates, synthesis of pheromones
-
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
-
p. 3059 - 3062
(2007/10/02)
-
- Selective Cleavage of Dimethylhydrazones to the Carbonyl Compounds Using Silica Gel and its Application in the Synthesis of (Z)-9-Tetradecenyl Acetate
-
A new method for the selective hydrolytic cleavage of dimethylhydrazones consists of treatment of the hydrazones with silica gel (pH 6.80) in wet tetrahydrofuran.Utilizing this method as one of the key steps, (Z)-9-tetradecenyl acetate, the pheromone of Spodoptera frugiperda, was synthesized.
- Mitra, R. B.,Reddy, G. Bhaskar
-
p. 694 - 698
(2007/10/02)
-
- SYNTHETIC INVESTIGATIONS IN THE REGION OF INSECT ATTRACTANTS (SEX ATTRACTANTS). XII. A NEW SYNTHESIS OF ETHYL 9-OXO-TRANS-2-DECENOATE AND CIS-6-HENEICOSEN-11-ONE
-
Ethyl 9-oxo-trans-2-decenoate (the sex pheromone of the queen honeybee Apis mellifera) was obtained from the monoacetals of glutaconaldehyde and glutaraldehyde by reaction with acetylmethylenetriphenylphosphorane and diethylphosphonoacetone followed by hydrogenation, hydrolysis, and reaction with ethoxycarbonylmethylene triphenylphosphorane. cis-6-Heneicosen-11-one, which is the principal component of the sex pheromones of insects of the Orgyia (Lepidoptera) family, was obtained by the condensation of the monoacetal of glutaraldehyde with pentylmethylenetriphenylphosphorane followed by hydrolysis of the acetal to cis-5-undecenal, reaction of the latter with decylmagnesium bromide, and oxidation of the secondary alcohol.
- Kovalev, B. G.,Dzhumakulov, T.,Abduvakhabov, A. A.
-
p. 1909 - 1912
(2007/10/02)
-
- Two-step Syntheses of (Z)-6-Heneicosen-11-one and (Z)-1,6-Heneicosadien-11-one, Sex Pheromones of Douglas-Fir Tussock Moth
-
Syntheses of (Z)-6-heneicosen-11-one (1) and (Z)-1,6-heneicosadien-11-one (2) have been achieved in two steps using acetone dimethylhydrazone (3) as key starting material.
- Mitra, R. B.,Reddy, G. Bhasker
-
p. 691 - 692
(2007/10/02)
-
- A NEW SYNTHESIS OF (Z)-6-HENEICOSEN-11-ONE AND 2-METHYLHEPTADECANE
-
The synthesis of the title pheromones involves solvomercuration of an olefin and reductive carbon-carbon bond formation with α,β-unsaturated carbonyl compounds to give the key intermediates 3(a and b), which by simple conventional methods offered (1) and (2).
- Dasaradhi, L.,Bhalerao, U. T.
-
p. 1845 - 1850
(2007/10/02)
-
- Reaction of α-Silyl Esters with Grignard Reagents: A Synthesis of β-Keto Silanes and Ketones. Preparation of the Douglas Fir Tussock Moth Pheromone
-
A variety of α-diphenylmethylsilyl esters have been prepared and reacted with Grignard reagents.The reaction is relatively slow in refluxing THF and can be controlled to allow the addition of 1 equiv of the Grignard reagent, providing the corresponding β-keto silane.Protiodesilylation of the β-keto silane results in the overall conversion of an ester to a ketone.This ester to ketone methodology has been applied to a two-step synthesis of the pheromone of the Douglas fir tussock moth.The β-keto silanes are viable precursors to regioselectively generated enol silyl ethers.The reaction of ethyl 2-methyl-2-(diphenylmethylsilyl)propionate with vinylmagnesium bromide or 2-methyl 1-propenylmagnesium bromide results in the addition of 2 equiv of the Grignard reagent, the second in a Michael fashion.
- Larson, Gerald L.,Hernandez, David,Lopez-Cepero, Ingrid Montes de,Torres, Luz E.
-
p. 5260 - 5267
(2007/10/02)
-
- New Functions of (Arene)tricarbonylchromium(0) Complexes as Hydrogenation Catalysts: Stereospecific Semihydrogenation of Alkynes and Highly Chemoselective Hydrogenation of α,β-Unsaturated Carbonyl Compounds
-
An impressive stereo- and chemoselective catalytic hydrogenation procedure for alkynes (to (Z)-alkenes) and α,β-unsturated carbonyl compounds (to the saturated analogues) using (arene)Cr(CO)3 catalysts is described.
- Sodeoka, Mikiko,Shibasaki, Masakatsu
-
p. 1147 - 1149
(2007/10/02)
-
- PHEROMONE 511): SYNTHESE VON UNGESATTINGEN PHEROMONKETONEN AUS ORGYIA PSEUDOTSUGATA (DOUGLAS FIR TUSSOCK MOTH) UND CARPOSINA NIPONENSIS (PEACH FRUIT MOTH) (LEPIDOPTERA)
-
The principal (9, 27) and minor (17, 28) sex pheromone components of both, the Douglas fir tussock moth (orgyia pseudotsugata) and the peach fruit moth (Carposina niponensis), have been synthesized in four steps each, using the chain-lengtheningdifunctionalisation of Grignard reagents by reaction with ketenylidenetriphenylphosphorane as the key step.
- Bestmann, Hans Jurgen,Schmidt, Martin
-
p. 6171 - 6174
(2007/10/02)
-
- Enamine synthesis using the Horner-Wittig reaction. Part 2. New acyl anion equivalents derived from (aminomethyl)diphenylphosphine oxides
-
Using the Horner-Wittig reagents (1-morpholino-alkyl)diphenylphosphine oxides (1), aromatic as well as aliphatic α,β-unsaturated aldehydes can be converted into the morpholino enamines of their respective homologous phenyl, ethyl and styryl ketones.These enamines can be easily converted into the corresponding ketones by mild, acid-catalyzed hydrolysis.The usefulness of these phosphine oxides as acyl anion equivalents is further demonstrated by the synthesis of dihydrojasmone and of (Z)-6-henicosen-11-one.
- Broekhof, N. L. J. M.,Elburg, P. van,Hoff, D. J.,Gen, A. van der
-
p. 317 - 321
(2007/10/02)
-
- NEW STEREOCONTROLLED APPROACH TO SOME INSECT PHEROMONES VIA SILICON-DIRECTED BECKMANN FRAGMENTATION
-
The major components of sex pheromones of potato tuberworm moth and Douglas fir tussock moth have been synthesized via the regio- and stereo-controlled Beckmann fragmentation assisted by trimethylsilyl group.
- Nishiyama, Hisao,Sakuta, Koji,Itoh, Kenji
-
p. 223 - 226
(2007/10/02)
-
- Preparation of (Z)-Alkenes, Ketones, and Alkynes via Trialkyltin Chloride Induced Intramolecular Transfer Reaction of Lithium 1-Alkynyltrialkylborates. Stereoselective Synthesis of the Sex Pheromones of the Douglas Fir Tussock Moth, the Gipsy Moth, and the Wild Silkmoth Antheraea poly...
-
Trialkyltin chloride was used to induce selective migration of a primary alkyl group from the boron atom to the adjacent acetylenic carbon atom of lithium 1-alkynyltrialkylborate complexes derived from B-alkyl-9-borabicyclononanes and 1-lithio-1-alkynes.Protonolysis of the resultant olefinic intermediate substituted with boron and tin functionalities on the adjacent vinyl carbon atoms provided the corresponding (Z)-alkene.Oxidation or iodination afforded the corresponding ketone or alkyne, respectively.The high selectivity of 9-borabicyclononane as ahydroborating agent toward the terminal double bond allowed easy incorporation of internal double bond and triple bond into the alkyl group of the starting B-alkyl-9-borabicyclononane.Various types of diene, enyne, enone, ynone and diyne were synthesized.These reactions were also successfully adopted for the stereoselective synthesis of sex pheromones of the Douglas fir tussock moth, the gypsy moth, and the wild silkmoth Antheraea polyphemus.
- Wang, Kung K.,Chu, Kai-Hsuan
-
p. 5175 - 5178
(2007/10/02)
-
- REDUCTIVE CLEAVAGE OF 2-ACYL TETRAHYDROFURANES. SYNTHESIS OF (Z)-6-HENEICOSEN-11-ONE, PHEROMONE OF THE DOUGLAS FOR TUSSOCK MOTH
-
(Z)-6-heneicosen-11-one was prepared using the reductive cleavage of 2-tetrahydrofuryldecylketone 6 to 5-oxo-pentadecan-1-ol 7 as the key step of the synthesis.
- Fernandez, S.,Quintanilla, R.,Hernandez, J. E.
-
p. 621 - 628
(2007/10/02)
-
- Strategic Synthesis based on Cyclohexadienes: Preparation of 2-, 2,3- and 2,4-Substituted Cyclohexenones; Synthesis of (Z)-Heneicosa-6-en-11-one
-
The mesomeric anions, generated from 1-methoxycyclohexa-1,4-diene, 1-methoxy-5-methylcyclohexa-1,4-diene, and 1-methoxy-4-methylcyclohexa-1,4-diene with potassium amide in liquid ammonia, have been readily alkylated and the resulting dienes were hydrolysed to yield 2-alkyl-, 2,3-dialkyl- and 2,4-dialkyl-cyclohex-2-enones in good yield.Arylation of the above mesomeric anions followed by hydrolysis afforded 2-arylcyclohex-2-enones in addition to substituted biphenyls.A new and efficient synthesis of the male sex attractant of the Douglas Fir Tussock Moth, (Z)-heneicosa-6-en-11-one is described using the above methodology.
- Pramod, Kakumanu,Ramanathan, Halasya,Rao, G. S. R. Subba
-
-
- A CHEMOSELECTIVE DESULFURIZATION METHOD VIA HOMOGENEOUS NICKEL CATALYSIS
-
Isopropylmagnesium bromide in the presence of bis-(triphenylphosphino)-nickel(II) chloride reduces vinyl sulfides stereospecifically to the corresponding olefins without overreduction - a process which serves as a key step in the synthesis of the sex pheromone of the Douglas fir tussock moth.
- Trost, Barry M.,Ornstein, Paul L.
-
p. 3463 - 3466
(2007/10/02)
-
- A SIMPLE SYNTHESIS OF HENEICOS-6Z-EN-1-ONE - THE SEX PHEROMONE OF Orgyia pseudotsugata
-
A method is proposed for synthesizing the insect sex pheromone heneicos-6Z-en-11-one and its homolog eicos-6Z-en-11-one.
- Sokolovskaya, S. V.
-
-
- A New Synthesis of (Z)-Heneicos-6-en-11-one, Sex Pheromone of Douglas Fir Lepidoptera Orgyia pseudotsugata
-
2-Octyn-1-ol (II) on hydrogenation over Lindlar's catalyst provides (Z)-2-octen-1-ol (III).Conversion of III into the corresponding bromide (IV) with PBr3 and subsequent alkylation of ethyl monosodiomalonate with IV in benzene/DMF mixture gives the diester (V) in high yield.Removal of one carbethoxy group of (V) on heating with NaCl/H2O in DMSO affords ethyl 4(Z)-decenoate (VI) which on LAH reduction yields the carbinol (VII).Treatment of VII with PBr3 in dry ether furnishes the bromide (VIII) which easily forms Grignard reagent (IX) with dry Mg turnings in anhyd.THF.The reagent (IX) on reaction with undecanal furnishes (Z)-heneicos-6-en-11-ol (X).Oxidation of X with Corey's reagent provides (Z)-heneicos-6-en-11-one (I).
- Vig, O. P.,Sharma, M. L.,Verma, N. K.,Malik, Neera
-
p. 950 - 951
(2007/10/02)
-