Systematic Syntheses and Characterization of Dodecadien-1-olswith Conjugated Double Bond, Lepidopterous Sex Pheromones

Ando, Tetsu; Kurotsu, Yuichi; Kaiya, Mieko; Uchiyama, Masaaki

doi:10.1080/00021369.1985.10866671

Cited by 7 publications

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References 6 publications

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“…A similar method was applied to the polyenyl Type I components with a conjugated system to estimate 13 C chemical shift parameters. Using 1,3-butadien for the base values (C 1 117.6 and C 2 137.8 ppm), the chemical shift values of the outer carbon and the inner carbon of 1,4-dialkyl conjugated dienes with the E,E configuration were separately calculated using different substituent parameters and the correction factors for other geometrical isomers with Z,E, E,Z, and Z,Z configurations [182]. Based on the data of (E)-1,3,5-hexatriene (C 1 117.7, C 2 136.9, and C 3 133.7 ppm), the substituent parameters of three carbons in 1,6-dialkyl conjugated trienes were estimated [183].…”

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“…Some carbons of geometrical and positional isomers, which are located in a slightly different environment, afford sufficient separation of their signals. The 13 C signal assignments of dienyl and trienyl Type I pheromones [182,183] and typical Type II compounds [170,171] were completed by 2D-NMR techniques. Accumulated 13 C NMR data support the proposal that the chemical shift for an olefinic carbon of monoenyl compounds can be calculated with ethylene as a reference [184].…”

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Lepidopteran Sex Pheromones

Ando

Inomata

Yamamoto

2004

Topics in Current Chemistry

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As a consequence of the diversity of Lepidoptera, including 150,000 described species, interesting species-specific sex pheromone systems are exhibited in this insect group. The quite varied pheromones, which have been identified from female moths of nearly 530 species from around the world, are classified into groups of Type I (75%), Type II (15%), and miscellaneous (10%), according to their chemical structures. Additionally, many pheromones produced by male moths and butterflies have been known. While new sex pheromones from about 70 lepidopteran species have been reported in the last five years utilizing GC-EAD, GC-MS, LC, and NMR, our information about the pheromones is still rudimentary, and these kinds of semiochemicals remain an exciting research target for natural product chemistry. In addition to the overview of their chemical structures, this chapter deals with current methods for their identification. Furthermore, an actual application of the synthetic pheromones for pest control is briefly introduced.

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Lepidopteran Sex Pheromones

Ando

Inomata

Yamamoto

2004

Topics in Current Chemistry

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335

289

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“…22 The presence of a J coupling of 10.7 Hz for the olefinic protons in the 1 H NMR of the major isomer of 4 confirmed the Z-stereochemical assignment, in agreement with previous reports. 17,23 For the reduction of the conjugated triple bond, the traditional Lindlar hydrogenation protocol 24,25 was not stereoselective, resulting in a mixture of geometrical isomers. Using instead activated Zn as the reducing agent 26 afforded the Z7,Z9-12:Ac isomer with complete stereoselectivity and 66% yield.…”

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“…[28][29][30][31][32] Traps loaded with hexane (control) and the proportion 0:1 (OH:Ac) did not catch any males and were therefore not included in the statistical analysis. All the remaining treatments captured males, showing a population peak toward the end of the experiment (Figure 2A) blocks F 7,140 = 6.63, and treatments F 2,140 = 30.86; p < 0.0001.…”

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confidence: 99%

Synthesis and field evaluation of synthetic blends of the sex pheromone of Crocidosema aporema (Lepidoptera: Tortricidae) in soybean

González

Altesor

Alves

et al. 2012

J. Braz. Chem. Soc.

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Crocidosema (= Epinotia) aporema (Walsingham) (Lepidoptera: Tortricidae) é uma broca das axilas que se alimenta de soja e leguminosas forrageiras. Sua importância econômica é restrita à América do Sul onde pode alternar, ao longo do ano, entre leguminosas forrageiras e grãos. O feromônio sexual das fêmeas de C. aporema é composto de uma mistura 15:1 de (7Z,9Z)-dodeca-7,9-dieno-1-ol e acetato de (7Z,9Z)-dodeca-7,9-dienila. Com o intuito de desenvolver uma ferramenta para monitoramento deste inseto praga, os dois componentes do feromônio foram sintetizados e avaliou-se, em um experimento de campo no Uruguai, a captura de machos em armadilhas iscadas com diferentes misturas do feromônio sintético. Os dienos conjugados foram obtidos a partir de 2-pentin-1-ol e 1,7-heptanodiol, através da oxidação do primeiro, seguido pelo acoplamento de Wittig e redução da ligação tripla catalisada com Zn. A mistura 1:1 testada no campo foi a mais eficiente na captura dos machos. As armadilhas de feromônio foram atrativas por mais de 40 dias, mesmo com pequenas quantidades dos compostos (0,1 mg) impregnadas nos septos, e com baixas densidades populacionais dos insetos no campo.Crocidosema (= Epinotia) aporema (Walsingham) (Lepidoptera: Tortricidae) is a bud borer that feeds on soybean and forage legumes. Its economic importance is restricted to South America, where it can alternate throughout the year between forage and grain legumes. The sex pheromone of C. aporema females is composed of a 15:1 mixture of (7Z,9Z)-dodeca-7,9-dien-1-ol and (7Z,9Z)-dodeca-7,9-dienyl acetate. Aiming at the development of a monitoring tool, it was synthesized both components of the pheromone and evaluated male captures in pheromone traps baited with different blends of synthetic pheromone, in an experimental soybean field in Uruguay. The conjugated dienes were obtained from 2-pentyn-1-ol and 1,7-heptanediol, by oxidation of the former, Wittig coupling and Zn-catalyzed reduction of the triple bond. The 1:1 mixture was the most efficient in capturing males. The pheromone traps were attractive for up to 40 days, even with small septum loads (0.1 mg) and low population levels.Keywords: sex pheromone synthesis, Crocidosema (= Epinotia) aporema, pest monitoring, pheromone traps IntroductionSoybean production in Uruguay has increased dramatically in the past decade, 1 resulting in an expansion of legume-specialized insects such as Crocidosema (= Epinotia) aporema (Walsingham) (Lepidoptera: Tortricidae). This trend correlates with a significant increase in the use of insecticides, which has risen up to three-fold between 2001 and 2011. 2 C. aporema is a stem and bud borer that has become a major pest of legumes in Uruguay, Argentina, Chile and Southern Brazil.3-6 Originally from Costa Rica, this speciesSynthesis and Field Evaluation of Synthetic Blends of the Sex Pheromone of Crocidosema aporema J. Braz. Chem. Soc. 1998 is now widely distributed across South America. The insect is active throughout the year, going through 5-6 generations per year conce...

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“…(Z)-9,11-Dodecadien-1-ol (Z9,11-12:OH), its (E)-isomer (E9,11-12:OH), and their functional derivatives had been synthesized in our previous studies. 11) With reference to their synthesis, Z7,9-10:OH and E7,9-10:OH were synthesized as shown in Scheme 1A and B, respectively. One hydroxyl group of 1,7-heptanediol (1) was protected as a tetrahydropyranyl (THP) ether, and another hydroxyl group was reacted on Swern oxidation to produce aldehyde (2), which was coupled with a ylide derived from allyltriphenylphosphonium bromide using butyllithium as base to yield a Z and E mixture of THP ether of 7,9-decadien-1-ol (3).…”

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confidence: 99%

Instrumental Analysis of Terminal-Conjugated Dienes for Reexamination of the Sex Pheromone Secreted by a Nettle Moth,Parasa lepida lepida

Islam

Yamakawa

Đức

et al. 2009

Bioscience, Biotechnology, and Biochemistry

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Conjugated dienyl compounds make one of the main groups of lepidopteran sex pheromones, and GC has been frequently used to determine the configurations of the double bonds. However, the separation of two geometric isomers of a terminal-conjugated diene, such as 7,9-decadien-1-ol secreted by a nettle moth Parasa lepida lepida (Limacodidae), is assumed to be difficult. In order to clarify the chromatographic separation of the terminal dienes, 7,9-decadienyl and 9,11-dodecadienyl compounds (alcohols, acetates, and aldehydes) were analyzed by GC and HPLC. On a capillary GC column, the (E)-isomers flowed out slightly faster than the corresponding (Z)-isomers, but their peaks almost overlapped. On the other hand, HPLC equipped with an ODS column completely separated the two geometric isomers examined and the (Z)-isomers eluted from the column faster than the (E)-isomers without dependence on a functional group. In addition to undergoing direct HPLC analysis without derivatization, the dienyl alcohols were converted into 3,5-dinitrobenzoates and analyzed by LC-ESI-MS operated under the same reversed-phase condition. The two separated geometric isomers were sensitively monitored by negative ions at m=z 211, M, M+1, M+17, and M+31, which were characteristically derived from the benzoates. Based on these results, a pheromone extract of P. l. lepida was examined, and it was confirmed that the female moths exclusively produced the (Z)-isomer of the 7,9-diene. Furthermore, a GC-EAD analysis and a field evaluation with both geometrical isomers indicated that the mating communication of P. l. lepida is predominantly mediated with the (Z)-isomer.

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Systematic Syntheses and Characterization of Dodecadien-1-olswith Conjugated Double Bond, Lepidopterous Sex Pheromones

Cited by 7 publications

References 6 publications

Lepidopteran Sex Pheromones

Lepidopteran Sex Pheromones

Synthesis and field evaluation of synthetic blends of the sex pheromone of Crocidosema aporema (Lepidoptera: Tortricidae) in soybean

Instrumental Analysis of Terminal-Conjugated Dienes for Reexamination of the Sex Pheromone Secreted by a Nettle Moth,Parasa lepida lepida

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