Insect pheromones and their analogs. XIII. Synthesis of dodec-8E-enyl and dodec-8Z-enyl acetates ? Components of the sex pheromones ofGrapholitha funebrana andGrapholitha molesta

Odinokov, V. N.; Ishmuratov, G. Yu.; Balezina, G. G.; Толстиков, Г. А.

doi:10.1007/bf00574216

Cited by 4 publications

(3 citation statements)

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“…Hept-3-yn-1-yl 4-methylbenzenesulfonate was synthesized using a literature procedure in 58% yield. 1 H NMR (CDCl 3 , 600 MHz): δ 7.80 (d, J = 7.8 Hz, 2H), 7.34 (d, J = 7.7 Hz, 2H), 4.06 (q, J = 7.3 Hz, 2H), 2.51 (d, J = 7.1 Hz, 2H), 2.45 (s, 3H), 2.5 (d, J = 7.9 Hz, 2H), 1.44 (quin, J = 7.2 Hz, 2H), 0.92 (t, J = 7.4 Hz, 3H).…”

Section: Experimental Sectionsupporting

confidence: 93%

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Mechanistic Studies of Formal Thioboration Reactions of Alkynes

et al. 2017

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Several formal heteroborylative cyclization reactions have been recently reported, but little physical-organic and mechanistic data is known. We now investigate the catalyst-free formal thioboration reaction of alkynes to gain mechanistic insight into B-chlorocatecholborane (ClBcat) in its new role as an alkynophilic Lewis acid in electrophilic cyclization/dealkylation reactions. In kinetic studies, the reaction is second order globally; first order with respect to both the 2-alkynylthioanisole substrate and the ClBcat electrophile, with activation parameters of ΔG‡ = 27.1 ± 0.1 kcal mol−1 at 90 °C, ΔH‡ = 13.8 ± 1.0 kcal mol−1 and ΔS‡ = −37 ± 3 cal mol−1 K−1, measured over the range of 70–90°C. Carbon kinetic isotope effects supported a rate-determining AdE3 mechanism wherein alkyne activation by neutral ClBcat is concerted with cyclative attack by nucleophilic sulfur. A Hammett study found a ρ+ of −1.7, suggesting cationic charge buildup during the cyclization and supporting rate-determining concerted cyclization. Studies of the reaction with tris(pentafluorophenyl)borane (B(C6F5)3), an activating agent capable of cyclization but not dealkylation, resulted in the isolation of a post-cyclization zwitterionic intermediate. Kinetic studies via UV-vis spectroscopy with this boron reagent found second order kinetics, supporting the likely relevancy of intermediates in this system to the ClBcat system. Computational studies comparing ClBcat with BCl3 as an activating agent showed why BCl3, in contrast to ClBcat, failed to mediate the complete the cyclization/demethylation reaction sequence by itself. Overall, the results support a mechanism in which the ClBcat reagent serves a bifunctional role by sequentially activating the alkyne, despite being less electrophilic than other known alkyne-activating reagents, then providing chloride for post-rate-determining demethylation/neutralization of the resulting zwitterionic intermediate.

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Section: Experimental Sectionsupporting

confidence: 93%

“…1 H NMR (CDCl 3 , 600 MHz): δ 7.80 (d, J = 7.8 Hz, 2H), 7.34 (d, J = 7.7 Hz, 2H), 4.06 (q, J = 7.3 Hz, 2H), 2.51 (d, J = 7.1 Hz, 2H), 2.45 (s, 3H), 2.5 (d, J = 7.9 Hz, 2H), 1.44 (quin, J = 7.2 Hz, 2H), 0.92 (t, J = 7.4 Hz, 3H). This spectrum is in agreement with previously reported spectral data …”

Section: Experimental Sectionmentioning

confidence: 99%

Mechanistic Studies of Formal Thioboration Reactions of Alkynes

et al. 2017

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“…The experimental context was a London suburban garden containing plum and apple trees with a history of Tortrix moth damage to fruit and occasional use of Agralan moth pheromone traps for monitoring pest occurrence. The present study used Plum moth and Codling moth traps marketed for small horticultural application, using pheromone lures, based on classical scientific discovery [3] and development of synthetic forms [4]. For the present context they provided 8-dodecenyl acetates for G. funebrana and 8,10-dodecadienols for C. pomonella, possibly formulated with some proprietary fruit esters.…”

Section: Methodsmentioning

confidence: 99%

Horticultural capture patterns of two fruit moth species in traps variously baited with both pheromones

Mantle

2019

Biology

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Specificity of synthetic pheromone lures to trap plum and apple moth males is standard agricultural practice to predict timely application of insecticides to fruit trees. Compatibility of both lures in the same trap has long been accepted for capture of both in several two-moth combinations, but any specificity for their relative positioning in a trap has remained untested.Experimentally-distanced lures in a trap during a month of fruit moth activity in an English horticultural context in 2000 resulted in apparently random capture but with some pattern distortion. However, in subsequent years, when lures were deliberately distanced diagonally across the trap surface, a distorted capture pattern involving avoidance of males from their corresponding female's pheromone suggested some disturbance in olfactory sensory perception and flying response within the trap. Further application of identifying individual captured moth carcases as of plum or apple moth by dissection of abdominal genitalia apparently revealed measurable disinclination to land near their corresponding female's pheromone. Another experiment confirmed that two adjacent lures did not disturb normal moth flying within the trap, but distanced positions caused statistically-disturbed flight patterns. The report encourages further experimental testing of male moth targeting towards,

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Novel convenient synthesis of (Z/E)-8-dodecenyl acetates, components of the Grapholitha molesta sex pheromone

Huang

Lü

et al. 2006

Chem Nat Compd

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Insect pheromones and their analogs. XIII. Synthesis of dodec-8E-enyl and dodec-8Z-enyl acetates ? Components of the sex pheromones ofGrapholitha funebrana andGrapholitha molesta

Cited by 4 publications

References 4 publications

Mechanistic Studies of Formal Thioboration Reactions of Alkynes

Mechanistic Studies of Formal Thioboration Reactions of Alkynes

Horticultural capture patterns of two fruit moth species in traps variously baited with both pheromones

Novel convenient synthesis of (Z/E)-8-dodecenyl acetates, components of the Grapholitha molesta sex pheromone

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