Chemical Synthesis And Field Application Of The Sex Attractant Of Soybean Pod Borer Leguminivora Glycinivorella

Leguminivora glycinivorella （Matsumura）, one of the most destructive soybean pestsin north China, which results in severe loss in soybean yield and quality. It is difficult formonitoring and controlling this target pest due to its special biology and damage. Insecticidespraying is currently the most effective method for controlling this insect. However,resistance, environmental pollution, especially pesticide residues and food safety havealways been troubled by insecticide.Utilizing pheromone-baited sex attractants to forecast and control of insect pests is anew strategy of integrated pest management development since the1960s, which is specific,efficient, environmentally-friendly, non-polluting, and do no harm to beneficial insects andcan basically meet the requirements of the sustainable development of agriculture.Application of this technology in the control of soybean pod borer is undoubtedly the bestchoice among biorational chemical ecological control.In order to develop efficient lures for soybean pod borer L. glycinivorella in China,（E,E）-8,10-dodecadienyl acetate （E8,E10-12:Ac）, the main component of the pheromone ofL. glycinivorella, and its structure-related compounds were synthesized by two methods.The field attractiveness to L. glycinivorella males of unitary, binary and multi-componentformulations of synthetic compounds was systematically evaluated, coupling with thepheromone applied technology such as trap type and septum colour in the field.Additionally, the influences of nine plant volatiles linalool,（E）-2-hexenal （E2-6:Ald）,benzaldehyde,（Z）-3-hexen-1-ol （Z3-6:OH）,（Z）-3-hexenyl acetate （Z3-6:Ac）,（E）-2-hexenylacetate （E2-6:Ac）,（E）-2-hexen-1-ol （E2-6:OH）, geraniol, phenylacetaldehyde （PAA） andthree antioxidants2,6-ditertbutyl-4-methylphenol （BHT）, butylated hydroxylanisole （BHA）and tertbutylhydroquinone （TBHQ） on the attractiveness to L. glycinivorella males are alsoevaluated in the field. The main conclusions are listed below.1.（E,E）-8,10-Dodecadienyl acetate （E8,E10-12:Ac）, the main component of the sexpheromone of L. glycinivorella, was synthesized via C6+C6coupling reactions startingfrom cheap sorbic acid and1,6-hexanediol in a approximate total yield of30%. The keystep was the coupling of2-（（6-bromohexyl）oxy）tetrahydro-2H-pyran Grignard reagent and （E,E）-2,4-hexadienyl acetate catalysed by Li2CuCl4. Its analogues （E）-8-dodecenol（E8-12:OH）,（E）-8-dodecenyl acetate （E8-12:Ac）,（E）-10-dodecenol （E10-12:OH）,（E）-10-dodecenyl acetate （E10-12:Ac）,（E,E）-8,10-dodecadienal （E8,E10-12:Ald）,（E）-8-dodecenal（E8-12:Ald）,（E）-10-dodecenal （E10-12:Ald）,（Z）-9-tetradecenol （Z9-14:OH）,（Z）-9-tetradecenyl acetate （Z9-14:Ac）,（Z）-11-tetradecenol （Z11-14:OH）, and （Z）-11-tetradecenylacetate （Z11-14:Ac） were synthesized in the similar procedures of C8+C4，C6+C8，C8+C6coupling reactions with1,8-octanediol,（E）-2-hexenyl acetate,（E）-2-butenyl acetate,（Z）-3-octenyl acetate and （Z）-3-hexenyl acetate, respectively. The structures of the syntheticcompounds were confirmed by^<sup>1H NMR,¹³C NMR and GC-MS. This method could be usedin synthesis of insect sex pheromone due to starting from cheap raw materials with lessby-products and wild reaction conditions.2. The main component of the sex pheromone of L. glycinivorella E8,E10-12:Ac andits isomers was synthesized in two steps with a good yield of56%approximately via thereaction of tetramethyldiamidophosphoric acid chloride with epoxide of （E）-9-dodecenylacetate （E9-12:Ac）. Four geometrical isomers of conjugated dienic can be obtained in shortroute, each of which could be applied in the control of target insect as the main or minorpheromone component. Nevertheless, this method needs to be further studied due tounsuccessful complete separation of four isomers mixture.3. E8,E10-12:Ac, E10-12:Ac, E8-12:OH,14:Ac and Z9-14:Ac alone displayeddifferent attractiveness to L. glycinivorella males. A total of8different lures which baitedwith E8,E10-12:Ac （0.1mg）, E10-12:Ac （0.1mg）, E10-12:Ac （0.5mg）, E8-12:OH （0.01mg）, E8-12:OH （0.1mg）,14:Ac （0.1mg），Z9-14:Ac （0.5mg） or Z9-14: Ac （0.1mg） wasmore attractive to L. glycinivorella males.4. E8-12:OH, E10-12:Ac, E8,E10-12:Ald, E8-12:Ald, E10-12:Ald,14:Ac, andZ9-14:Ac all showed a synergistic effect to E8,E10-12:Ac at certain dosages. The binarymixtures of E8,E10-12:Ac and E10-12:Ald, Z9-14:Ac,14:Ac, E8-12:Ald, E8,E10-12:Ald,E8-12:OH, or E10-12:Ac in proper ratios respectively give17.00,10.98,10.67,6.73,5.54,4.30and4.50fold increases in trap catch over the standard pheromone lure. Theattractiveness of ternary, quaternary, and multi-component formulations of E8,E10-12:Acand E10-12:Ac, E8-12:OH, E8,E10-12:Ald, E8-12:Ald, E10-12:Ald,14:Ac, or Z9-14:Ac incertain ratios was superior to the standard pheromone lures.5. By themselves of the nine plant volatiles, linalool （0.1mg）,（Z）-3-hexenyl acetate（0.1mg）, and geraniol （0.1mg,1.0mg）, were weakly attractive to L. glycinivorella malesbut significantly reduced mean catches when higher doses were combined with pheromones.Conversely,（E）-2-hexenal, benzaldehyde, and phenylacetaldehyde, were not attractive to L. glycinivorella males at any dose tested, but significantly increased mean catch when certaindoses were combined with the binary pheromone blend. Other plant volatiles, such as（Z）-3-hexen-1-ol,（Z）-3-hexenyl acetate, and （E）-2-hexenyl acetate, were unattractive ontheir own but significantly reduced mean catch of L. glycinivorella males when certaindoses were combined with the pheromones. Addition of the antioxidants BHT, BHA andTBHQ in the lure increased the mean catch and prolonged the duration, and BHT showedthe best result.6. The binary mixture of E8,E10-12:Ac with E10-12:Ald or Z9-14:Ac and thequaternary-component formulations of E8,E10-12:Ac, E10-12:Ac, E8-12:OH andE8,E10-12:Ald are more attractive to the standard pheromone lures, they as novelpheromone blends demonstrate potential uses in pheromone traps to monitor or control L.glycinivorella populations in China. The research on field applied technology showed thatwater-pot trap and green septum deserves promotion in the practical application ofpheromone control of soybean pod borer.The main component of the pheromone of L. glycinivorella, and its structure-relatedcompounds were synthesized with good overall yields, regiospecificities, andstereoselectivities in this thesis, which provides scientific basis and basic techniques forinsect sex pheromone laboratory synthesis and small batch production of unsaturated enoland esters. Components and formulations highly attractive to L. glycinivorella males havebeen obtained through large number of field trials, which basically determined its actualapplication value and laid a theoretical foundation for the chemical ecological control ofsoybean pod borer.