Identification of the sex pheromone of the lesser date moth, Batrachedra amydraula, using sequential SPME auto-sampling

The identification of the sex pheromone of the lesser date moth, Batrachedra amydraula (Meyrick) was based on GC-MS analysis of volatiles released by virgin females using sequential SPME auto-sampling of headspace and by synthesis of the key component, (4Z,7Z)-4,7-decadien-1-yl acetate. Substantial capture of males in a date palm plantation using a bait consisting of the key component and 5Z-decen-1-yl acetate in a ratio of 1:2 indicated that these are the essential components of the sex pheromone. Addition of 4Z-decen-1-yl acetate and decan-1-yl acetate, which were also identified, did not affect trap-capture. The lesser date moth is the first member of the Batrachedridae whose sex pheromone has been identified. (4Z,7Z)-4,7-Decadien-1-yl acetate is a novel compound among moth sex pheromones.     

GCxGC/TOF MS technique-A new tool in identification of insect pheromones: Analysis of the persimmon bark borer sex pheromone gland

Conventional gas chromatography with electroantennographic detection (GC-EAD) and two-dimensional (GC × GC) gas chromatography using a time-of-flight mass spectrometric detector (TOFMS), were combined to analyse the female sex pheromone gland extract of the persimmon bark borer, Euzophera batangensis. GC-EAD analysis produced two EAD responses in GC areas where no compounds were detected by FID detection. GC × GC/TOFMS analysis of this area indicated the presence of several chemicals, including (Z9,E12)-tetradeca-9,12-dien-1-ol and (Z9)-tetradec-9-en-1-ol, pheromone components of closely related Euzophera species. Spectral characteristics, retention behaviour and the ability to elicit GC-EAD responses imply that both identified unsaturated alcohols are candidates for E. batangensis sex pheromone components. GC × GC/TOFMS facilitated the analysis of complex matrices on a subnanogram level and was shown to have great potential as a powerful tool in the analysis of insect pheromones.     

Sequential alkynylation of ω-bromoalkyl triflates: facile access to unsymmetrical non-conjugated diynes including precursors to diene pheromones

Sequential treatment of ω-bromoalkyl triflates with an alkynyllithium at 0 °C followed by addition of a second alkynyllithium and NaI and heating the reaction mixture provides a simple one-pot access to unsymmetrical diynes in good yields. These diynes may be transformed stereoselectively into diene pheromones such as (Z,Z)- and (E,Z)-3,13-octadecadienyl acetate.     

(6Z,9Z,12Z)-6,9,12-Octadecatriene and (3Z,6Z,9Z,12Z)-3,6,9,12-icosatetraene, the novel sex pheromones produced by emerald moths

(6Z,9Z,12Z)-6,9,12-Octadecatriene and (3Z,6Z,9Z,12Z)-3,6,9,12-icosatetraene, hydrocarbons unsaturated more highly than usual lepidopteran Type II pheromones, were identified from geometrid females of Hemithea tritonaria and Thalassodes immissaria intaminata, respectively. The triene was synthesized by a double Wittig reaction between hexanal and an ylide derived from (Z)-1,6-diiodo-3-hexene, and the tetraene was synthesized by a coupling between (Z)-3-undecenal and an ylide derived from (3Z,6Z)-1-iodo-3,6-nonadiene. Each synthetic compound attracted males of the corresponding emerald moths in a field.     

(3S,5R)-6-(benzyloxy)-3-methylhexane-1,5-diol in the synthesis of insect pheromones with methyl-branched carbon chain and of amphidinolide L C 7 –C 14 fragment

New building block (3S,5R)-6-(benzyloxy)-3-methylhexane-1,5-diol was obtained, and based thereon new formal syntheses of (Z)-trogodermal, a component of the sex pheromone of smaller tea tortrix and of the alarm pheromone of ants of genus Crematogaster were suggested. A new synthetic protocol for (3S)-5-methyl-5-oxopentyl acetate and (3S)-5-(benzyloxy)-3-methylpentanal, convenient building blocks for insect pheromones designing was developed. A new simple and efficient asymmetric synthesis of C⁷–C¹⁴ fragment of the cytotoxic macrolactone amphidinolide L was carried out.     

A convenient method for the synthesis of (Z)-α-haloacrylates: Lewis base-catalyzed carbonyl olefination using α-halo-C,O-bis(trimethylsilyl)ketene acetals

A highly useful method for the stereoselective synthesis of (Z)-α-haloacrylates from various aldehydes that uses α-halogenated ethyl-C,O-bis(trimethylsilyl)ketene acetals in the presence of a Lewis base catalyst such as acetate salts was established. This procedure gives the corresponding α-halo-α,β-unsaturated esters in high yields with excellent stereoselectivity from E/Z mixtures of ketene silyl acetals under mild conditions.     

Preparation of stereochemically pure <Emphasis Type="Italic">E</Emphasis>- and <Emphasis Type="Italic">Z</Emphasis>-alkenoic acids and their methyl esters from bicyclo[<Emphasis Type="Italic">n</Emphasis>.1.0]alkan-1-ols. Application in the synthesis of insect pheromones

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).     

Synthesis of 7E,9Z-dodecadienyl acetate,the sex pheromone ofLobesia botrana Shiff

Two syntheses of 7E,9Z-dodecadienyl acetate from 1,3-butadiyne were carried out using either 2E,4Z-heptadienyl acetate or 1-bromo-3E,5Z-octadiene as the key intermediates. The latter underwent organocopper cross-coupling with the respective complementary Grignard reagents (prepared from the corresponding 1-tert-butoxy--chlorohydrins) as alkylating agents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 766–768, April, 1993.     

Syntheses of (4E,6E, 11Z)-4,6,11-hexadecatrienyl acetate and (4E, 6E, 11Z)-4,6,11-hexadecatrienal, female sex pheromones of eri-silkworm, Samia cynthia ricini (Lepidoptera: Saturniidae)

Syntheses of (4E,6E,11Z)-4,6,11-hexadecatrienyl acetate (1) and (4E,6E, 11Z)-4, 6,11-hexadecatrienal (2), female sex pheromones of eri-silkworm,Samia cynthia ricini have been achieved through Claisen ortho ester rearrangement of (6).     

用于昆虫外激素研究的微量顶空收集及热解吸气相色谱进样方法初探

描述了一个结合项空气流收集与无溶剂热解吸气相色谱进样的方法。用填充PorapskQ的微量注射器作为吸附管进行气流收集。将收集物不经溶剂洗脱直接进行热解吸进样。用人工合成的昆虫外激素化合物反-7-十二碳单烯乙酸酯（E-7-DA）及顺-5,反-7-十二碳二烯乙酸酯（Z-5,E-7-DDA）测定了方法的回收率,初步探索了运用于昆虫外激素分析的可行性,并讨论了提高回收率的途径。     

Dienic sex pheromones : Stereoselective syntheses of (7E,9Z)-7,9-dodecadien-1-yl acetate, (E)-9,11-dodecadien-1-yl acetate,and of (9Z), 11E)-9,11- tetradecadien-1-yl acetate by palladium-catalyzed reactions

Pure (7E,9Z-7, 9-dodecadien-1-yl acetate (1), the sex pheromone of Lobesiabotrana, has been prepared in 21.6% overall yield by a reaction scheme involving; (i) the cross-coupling of (E) - 8 - (2 - tetrahydropyranyloxy) -1 - octenyldisiamylborane with 1 - bromo - 1 - butyne, in the presence of a Pd (O) catalyst and base; (ii) the acetylation of the crude product of this reaction; (iii) the (Z)-stereoselective reduction of the obtained conjugated (E)-enyn-1-yl acetate. (E)-9,11-Dodecadien-1-yl acetate (2), a sex pheromone component of Diparopsiscastanea, has been analogously obtained (in 54.3% overall yield) by cross-coupling of (E) - 10 - (2 - tetrahydropyranyloxy) - 1 - decenyl borane with vinyl bromide, in the presence of a Pd (O) catalyst and base, followed by acetylation of the crude product. Compound 2, which was 87.7% chemically pure, was purified by column chromatography over SiO₂-AgNO₃. Chemically pure (9Z, 11E) - 9,11 - tetradecadien - 1 - yl acetate (3), a sex pheromone component of Spodopteralittoralis, has been prepared (in 30.2% overall yield) by reaction of 10 - (2 - tetrahydropyranyloxy) - 1 - decynylamagnesium bromide with (E)-1-iodo-1-butene, in the presence of a Pd (O) catalyst, followed by acetylation of the crude product and by (Z)-stereoselective reduction of the obtained (E)-enyn-1-yl acetate.The stereoisomeric purity of 1, 2 and 3 has been evaluated by glc analysis on glass capillary columns or by reverse phase hplc analysis.     

Alternative instrumentation for the analysis of total carbon dioxide (TCO2) in equine plasma

The analysis of total carbon dioxide (TCO₂) in equine plasma is conventionally done in Australia and elsewhere using Beckman Synchron EL-ISE® analysers. This instrument is no longer being manufactured and has not been supported by the supplier since December 2008. For testing for TCO₂ to continue, it is necessary to evaluate and commission alternative instrumentation. In this paper, we compare the Beckman Synchron EL-ISE®, the Beckman Synchron CX®5, the Beckman UniCel DxC®600 and the Randox Daytona? instruments. Results indicate that all four instruments perform in accordance with the manufacturer’s specifications. The Beckman CX 5, DxC 600 and Randox Daytona instruments are therefore all suitable alternatives for routine screening in a laboratory environment. Only the Randox Daytona instrument is sufficiently ‘portable’, i.e. it can be readily transported and used on-site at a racecourse (typically in a purpose-built modest-size laboratory vehicle). The three Beckman instruments are suitable for ‘confirmatory analysis’ using the quality-accredited method (Racing Science Centre), but the principle of operation of the Randox Daytona instrument may preclude its use in confirmatory analysis. Instrument costs may affect purchase decisions.     

(9Z)-9,13-Tetradecadien-11-ynal, the sex pheromone of the avocado seed moth, Stenoma catenifer

The highly unsaturated aldehyde (9Z)-9,13-tetradecadien-11-ynal and the corresponding alcohol were identified as possible sex pheromone components of the avocado seed moth, Stenoma catenifer. The aldehyde as a single component attracted more male moths than caged virgin female moths, and addition of the analogous alcohol and/or acetate decreased attraction. A stereospecific synthesis of the pheromone is described.     

General methodology for the synthesis of conjugated dienic insect sex pheromones

A general methodology for the synthesis of various types of dienic insect sex pheromones (Z-E, E-Z, Z-Z) is based on the carbocupration of acetylene by functionalised or non-functionalised lithium dialkyl cuprates, followed by the coupling of the resulting Z dialkenyl cuprates with functionalised or non-functionalised E or Z alkenyl iodides under Pd° catalysis. The following compounds were efficiently synthesized with a high degree of stereoisomeric purity: (E-Z)7, 9-dodecadien,-l-yl acetate 1 (Lobesia botrana), (E-Z)10, 12-hexadecadien,-l-ol 2 (Bombyx mori), (Z-E)9, 11-tetradecadien,-l-yl acetate 3Spodoptera littoralis), (Z-E)5, 7-dodecadien-l-ol 4 (Malascoma disstria), (Z-Z)11, 13-Hexadecadien-l-al 5 (Amyelois transitella), (Z)9,ll-dodecadien-l-yl acetate 6 (Diparopsis castanea) and (Z-Z)9,11-tridecadien-l-yl acetate 22 (a known “pseudo-pheromone”).     

Application of portable Raman instruments for fast and non-destructive detection of minerals on outcrops

Raman spectral signatures have been obtained in situ for a series of minerals using portable Raman instruments. Cerussite, anglesite, wulfenite, titanite, calcite, tremolite, andradite and quartz were detected using portable Raman spectrometer First Defender XL (Ahura). Baryte, almandine and realgar Raman spectra obtained by this instrument in the field were compared to the data measured by the other mobile Raman instrument Inspector Raman (DeltaNu). Bench Raman dispersive microspectrometer (InVia Reflex, Renishaw) was used for comparative purposes. All spectra were obtained using a 785nm diode excitation. Although displaying lower spectral resolution comparing with the laboratory confocal instrument both portable instruments permit unambiguous detection of minerals in the field. These possibilities designate portable Raman machines as excellent tools for field geological applications. Miniaturised Raman instrument combined with LIBS will be included in the payload of the EXO Mars mission and would open interesting research possibilities in other in situ field planetary studies.     

A new and efficient synthesis of (3E,8Z,11Z)-tetradeca-3,8,11-trienyl acetate,the major sex pheromone component of the tomato leafminer Tuta absoluta

An efficient synthesis of (3E,8Z,11Z)-tetradeca-3,8,11-trienyl acetate, the major sex pheromone component of the tomato leafminer moth, Tuta absoluta, was accomplished. The synthesis started with but-3-yn-1-ol and gave an overall yield of 41%.     

Synthesis of the enantiomers of (3Z,9Z)-cis-6,7-epoxy-3,9-octadecadiene,one of the major components of the sex pheromone of Ectropis oblique Prout

Both enantiomers of (3Z,9Z)-cis-6,7-epoxy-3,9-octadecadiene, one of which is the major component of the sex pheromone of Ectropis oblique Prout, were synthesized in 23% overall yield for the (?)-(6S,7R)-enantiomer and 18% yield for the (+)-(6R,7S)-isomer. This protocol uses a sequential regioselective ring-opening strategy and provides a convenient and reliable access to other structurally related insect sex pheromones. Preliminary biological studies revealed that (?)-(6S,7R)-2a was roughly as active as the natural pheromone, while racemic (±)-2 was less bioactive and (+)-2b was much less bioactive.     

Analysis of insect pheromones by quadrupole mass fragmentography and high-resolution gas chromatography.

A sensitive technique is described for the analysis of insect pheromones. Insect extracts are separated into fractions by column chromatography and are analyzed directly by quadrupole mass fragmentography on high-resolution glass capillary columns and by mass spectrometry. Applications are illustrated with two important pests. In the codling moth, trans-8, trans-10-dodecadien-1-ol was found to be present at a level of 3.5 ng per female, and in the European grapevine moth trans-7, cis-9-dodecadienyl acetate at a level of 1.6 ng. Both compounds appear to be present in high isomeric purity in the female insect and are absent in the corresponding males.     

Tellurium in organic synthesis: an approach to the synthesis of (Z,E)-dienic precursors of insect pheromones

A simple and straightforward route to (Z,E)-dienic precursors of insect pheromones was developed. The route features a cross-coupling of a (Z,E)-dienic telluride with an alkyl Lipshutz cuprate.     

Stereoselective synthesis of the pink bollworm sex pheromone, (Z,Z)-7,11-hexadecadienyl acetate and its (Z,E)-isomer

Two components of the sex pheromone of the pink bollworm moth, (Z, Z)-7,11-hexadecadienyl acetate and its (Z, E)-isomer, were synthesized employing the Grignard coupling reaction as a key step.