51760-35-1Relevant academic research and scientific papers
GENERAL METHODOLOGY FOR THE SYNTHESIS OF CONJUGATED DIENIC INSECT SEX PHEROMONES
Gardette, M.,Jabri, A.,Alexakis, A.,Normant, J. F.
, p. 2741 - 2750 (1984)
A general methodology for the synthesis of various type 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 Pd0 catalysis.The following compounds were efficiently synthesized with a high degree of stereoisomeric purity: (E-Z)7,9-dodecadien,-1-yl acetate 1 (Lobesia botrana), (E-Z)10,12-hexadecadien,-1-ol 2 (Bombyx mori), (Z-E)9,11-tetradecadien,-1-yl acetate 3 (Spodoptera littoralis), (Z-E)5,7 dodecadien-1-ol 4 (Malascoma disstria), (Z-Z)11, 13-Hexadecadien-1-al 5 (Amyelois transitella), (Z)9,11-dodecadien-1-yl acetate 6 (Diparopsis castanea) and (Z-Z)9,11-tridecadien-1-yl acetate 22 (a known "pseudo-pheromone").
Z9, 11 - codlemone acetate synthesis method
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Paragraph 0012; 0019; 0020; 0026; 0027; 0033; 0034; 0040, (2017/10/21)
The invention discloses a synthesis method of Z9,11-dodecadienol acetate. The synthesis method comprises the following steps: (1) by taking 1,9-nonanediol as a raw material, performing unilateral oxidation to synthesize 9-hydroxyl-1-nonanal; (2) synthesizing an intermediate Z9,11-dodecadienol; (3) synthesizing the Z9,11-dodecadienol acetate. The synthesis method has the advantages of mild synthesis conditions, short reaction time, easy operation, wide application range, high yield, low cost and easy industrialization, the process flow is shortened, and three wastes are few. In a synthesis reaction of the 9-hydroxyl-1-nonanal, silica gel is added, the dispersion of PCC (Pyridinium Chlorochromate) is facilitated, the opportunity of oxidation of two hydroxyls is reduced by adding the PCC in batches, the reaction is performed at room temperature, and energy is saved; after the reaction is completed, ethyl ether and water are added for extraction, and the yield of reactants is improved. In the synthesis process of the Z9,11-dodecadienol, a phase transfer catalyst 18-crown ether-6 and non-polar solvent benzene are adopted to react so as to obtain a cis-product; meanwhile, weak alkali potassium carbonate is adopted, so that the protection of the hydroxyls of the 9-hydroxyl-1-nonanal is avoided, and a reaction synthesis route is shortened.
"Ene"-Type Reaction of the Pummerer Rearrangement Product Derived from 4-Chlorophenyl Methyl Sulphoxide: Synthesis of Some Insect Sex Pheromones
Ishibashi, Hiroyuki,Komatsu, Hajime,Ikeda, Masazumi
, p. 2548 - 2561 (2007/10/02)
The Pummerer rearrengement product (8) derived from 4-chlorophenyl methyl sulphoxide (7) and trifluoroacetic anhydride undergoes an ene type reaction with terminal olefins to give the products (9).Oxidation of (9) followed by thermolysis of the resultant sulphoxides provides a general synthesis of the terminal conjugated dienes (10).Using this method, dodeca-9,11-dienyl acetate (16), the sex pheromone of the red bollworm moth, has been prepared.Transformations of the ene products (9) to some other insect sex pheromones such as bombykol (20) and tetradec-11-enyl acetate (24) are also described.
Mass Spectra of Dodecadienic Compounds with a Conjugated Double Bond, Lepidopterous Sex Pheromones
Ando, Tetsu,Katagiri, Yoshio,Uchiyama, Masaaki
, p. 413 - 422 (2007/10/02)
All geometrical isomers of 5,7-, 6,8-, 7,9-, 8,10- and 9,11-dodecadien-1-ols, and their acetates and aldehyde derivatives were analyzed by electron impact mass spectrometry.The abundance of molecular ion (M(1+)) was observed in every spectrum, and the relative intensity of M(1+) tended to be strong if the compound possessed an (E)-double bond(s).In addition to M(1+), (1+) (alcohols) and (1+) (acetates), every dienic compound showed typical series of CnH(2n-2)(1+)CnH(2n-5)(1+) with abundance maxima around C4, C5, C6 or C7.Each double bond positional isomer characteristically yielded different ion peaks in the series, which were useful for its distinction from other isomers.These results indicate that the chemical structure of a natural pheromone of Lepidoptera is easily deduced successfully by GC-MS analysis if it is a conjugated dienic pheromone.
INSECT PHEROMONES AND THEIR ANALOGUES. IX. STEREOSPECIFIC SYNTHESIS OF (Z)-DODECA-9,11-DIENYL ACETATE, A COMPONENT OF THE SEX PHEROMONE OF THE COTTON BOLLWORM MOTH Diparopsis cactanea
Balezina, G. G.,Ishmuratov, G. Yu.,Odinokov, V. N.,Selimov, F. A.,Dzhemilev, U. M.,Tolstikov, G. A.
, p. 354 - 357 (2007/10/02)
A method has been developed for the stereospecific synthesis of (Z)-dodeca-9,11-dienyl acetate, a component, together with the corresponding (E) isomer, of the sex pheromone of the red cotton bollworm moth, that is based on the coupling of vinylacetylene with either 8-hydroxyoctanal or 8-bromoctan-1-ol to form a C12 enynic compound in which the acetylenic bond is then reduced stereospecifically with 9-borabicyclononane.
Regiochemical Convergence in the Reaction of Heterosubstituted Allylic Carbanions via Allylic Aluminum and Boron "Ate" Complexes
Yamamoto, Yoshinori,Yatagai, Hidetaka,Saito, Yoshikazu,Maruyama, Kazuhiro
, p. 1096 - 1104 (2007/10/02)
The regiochemistry in reactions of heterosubstituted allylic carbanions (1) is highly controlled via allylic aluminum or boron "ate" complexes which direct both carbonyl compounds and reactive halides to the α-position with high regioselectivity.For example, carbonyl compounds react with the oxygen- (3), sulfur- (12), selenium- (20), and silicon- (25) substituted allylic carbanions at the α-position via the ate complexes.Although the reactions of the ate complexes (2) with aldehydes generally produce a mixture of erythro and threo isomers, the aluminum ate comlex of 3b gives the erythro isomer (5) with very high stereoselectivity.This procedure is applied to the stereoselective synthesis of exo-brevicomin (9).With allylic halides, the oxygen- (3a) and sulfur- (12) substituted allylic carbanions again react at the α-position via the ate complexes.However, the coupling mode is entirely different; the α-α' coupling product (10) is obtained from 3a, while the α-γ' coupling product (15) is produced from 12.
Stereoselective Syntheses of E- and Z-9,11-Dodecadien-1-yl Acetates: The Major Sex Pheromones of the Red Bollworm Moth
Ochiai, Masahito,Ukita, Tatsuzo,Fujita, Eiichi
, p. 1641 - 1645 (2007/10/02)
The sex pheromones 1 and 2 of the red bollworm moth were synthesized in a highly stereoselective manner.The key step of their syntheses was the olefination reaction of E- and Z-allyl phenyl sulfones 8 and 12, affording the corresponding dienes 9 and 15, respectively.Keywords - E-9,11-dodecadien-1-yl acetate; Z-9,11-dodecadien-1-yl acetate; sex pheromone; red bollworm moth; allyl sulfone; tri-n-butylstannylmethyl iodide
