- Simple synthesis method for sex pheromones of oriental fruit moths
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The invention belongs to the field of chemical synthesis, and particularly relates to a simple synthesis method for sex pheromones of oriental fruit moths. The method includes subjecting 1,8-octandiolas a raw material to unilateral bromination reaction to obtain 8-bromooctanol, reacting the 8-bromooctanol with triphenylphosphine to obtain 8-hydroxyoctyl triphenylphosphonium salt, subjecting the 8-hydroxyoctyl triphenylphosphonium salt and n-butanal to Wittig reaction under the action of an alkali to obtain (Z/E)-8-dodecene-1-alcohol, and performing acetylation under the action of pyridine andacetic anhydride to obtain a target product. The cis-trans ratio of enol obtained after the Wittig reaction ranges from 91.8:8.2 to 92.9:7.1; within the optimal attraction range, and by strictly controlling the amount of the acetic anhydride, the properly proportioned sex pheromones of the oriental fruit moths can be obtained according to a 'one-pot' method.
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Paragraph 0029-0043
(2019/06/27)
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- SYNTHESIS OF Z-OLEFIN-CONTAINING LEPIDOPTERAN INSECT PHEROMONES
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The present invention is directed to methods of synthesizing insect pheromones, particularly lepidopteran insect pheromones, their precursors and derivatives from inexpensive, readily available starting materials using olefin metathesis catalysis.
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Paragraph 0193; 0194
(2013/09/12)
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- Concise syntheses of insect pheromones using Z-Selective cross metathesis
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Very short synthetic routes to nine cisolefin-containing pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported (see scheme). These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z olefins.
- Herbert, Myles B.,Marx, Vanessa M.,Pederson, Richard L.,Grubbs, Robert H.
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supporting information
p. 310 - 314
(2013/02/23)
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- Copper-catalyzed cross-coupling of (Z)-allyl phenyl ethers with Grignard compounds in the synthesis of insect pheromones
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(8Z)-Dodec-8-en-1-yl acetate (pheromone of oriental fruit moth Grapholita molesta) and (9Z)-dodec-9-en-1-yl acetate (pheromone of grape berry moth Paralobesia viteana) containing impurities of isomeric structures were synthesized via copper-catalyzed cross-coupling of (Z)-1-phenoxyhex-2-ene and (Z)-1-phenoxypent-2-ene, respectively, with Grignard compounds in the key stage.
- Petrushkina,Kalinin
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experimental part
p. 1897 - 1899
(2009/02/08)
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- Use of enyne compounds in the synthesis of insect pheromones
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A new approach has been developed to the synthesis of monogenic insect pheromones with acetogenin and macrolide structures, using the low reactivity of ozone and of 9-borabicyclo[3.3.1]nonane towards an acetylenic function as compared with a vinyl function.
- Ishmuratov,Ishmuratova,Odinokov,Tolstikov
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- PHEROMONES OF INSECTS AND THEIR ANALOGS. XXI. SYNTHESIS OF ALK-8Z-EN-1-OLS AND THEIR ACETATES FROM A FUNCTIONALLY DIFFERENTIATED PRODUCT OF OZONOLYSIS OF CYCLOOCTENE
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Dodec-8Z-en-1-ol (VIII) and tetradec-8Z-en-1-ol (IX) and the corresponding acetates (X and IX) - components of the sex pheromones of many species of Lepidoptera - have been synthesized from cyclooctene (I) in three stages.The ozonolysis of (I) ( -70 deg C, CH2Cl2-MeOH), NaHCO3; -20 deg C, Ac2O/Et3N) led to methyl 8-oxooctanoate (II).The DNPH of (II), (III), mp 59-61 deg C.The coupling of (II) with n-C3H17CH=PPh3 (IV) or with n-C5H11CH=PPh3 (V) (-70 deg C , 2h; 25 deg C, 15h, Ar) gave the methyl esters of dodec-8Z-enoic (VI) and tetradec-8Z-enoic (VII) acids, respectively.The reduction of (VI) and (VII) gave the corresponding alcohols (VIII) and (IX) by the acetylation (Ac2O-Py, 25 deg C, 24h) of which, (X) and (XI) , were obtained.The yields (percent): (II) 80, (VI) 45, (VII) 60, (VIII) 95, (IX) 90, (X) 75, (XI) 74.The IR and PMR spectra of compounds (II) and (VI-XI) are given.
- Odinokov, V. N.,Akhmetova, V. R.,Khasanov, Kh. D.,Abduvakhabov, A. A.,Tolstikov, G. A.,Panasenko, A. A.
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p. 240 - 243
(2007/10/02)
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- SYNTHESES A L'AIDE DE SULFONES (XXXVII). SYNTHESE DE TROIS PHEROMONES A UNE DOUBLE LIAISON Z : Z, 8-DDA; Z, 9-DDA; Z, 9-TDA.
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The title compounds Z,8-dodecen-1yl acetate, Z,9-dodecen-1yl acetate and Z,9-tetradecen-1yl-acetate have been synthesized in three efficient steps: the reaction mixture from metalated ω-hydroxy sulfones and appropriate aldehydes was quenched with acetic anhydride yielding a diastereoisomeric mixture of β-acetoxy sulfones.Convergent elimination with powdered sodium hydroxide led to the E vinylic sulfone.Stereospecific hydrogenolysis of the sulfonyl group was carried out with sodium dithionite leading to the unsaturated alcohol (> 99percent Z).
- Julia, Marc,Stacino, Jean-Pierre
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p. 2469 - 2474
(2007/10/02)
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- The Synthesis of (Z)-8-Dodecen-1-ol and its Acetate, Pheromone Components of the Oriental Fruit Moth (Grapholita molesta)
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The two main sex pheromone components of the Oriental fruit moth (Grapholita molesta), viz. (Z)-8-dodecen-1-ol and its acetate, have been synthesized from (Z,E,E)-1,5,9-cyclododecatriene in approximately 15 percent overall yield.
- Aukrust, Audun,Rongved, Pal,Skatteboel, Lars
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p. 267 - 272
(2007/10/02)
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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 OF Grapholitha funebrana AND Grapholitha molesta
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A new route is proposed for the synthesis of dodec-8E-enyl and dodec-8Z-enyl acetates which is based on the reaction of the Grignard reagent from the readily accessible 1-bromo-5-(1-ethoxyethoxy)pentane with 1-bromohept-3-yne - the bromide obtained from product of the β-hydroxyethylation of pent-1-yne with 2-chloroethylvinyl ether, hept-3-yn-1-ol, by a double decomposition reaction of its tosylate with lithium bromide.The key synthon - dodec-8-yn-1-ol - was converted with the aid of sodium in liquid ammonia into the stereochemical individual dodec-8E-enol, while its reduction with the aid of 9-borabicyclononane (BBN) gave the stereoisomeric alcohol exclusively with the Z configuration, as followed from the results of capillary GLC and the IR spectra of the corresponding acetates.The PMR spectra of the compounds synthesized are also given.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Balezina, G. G.,Tolstikov, G. A.
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p. 372 - 374
(2007/10/02)
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- ω-HYDROXYALKYL-PHOSPHONIUM SALTS AS "INSTANT-YLID" COMPONENTS: EXTREMELY CONVENIENT AND HIGHLY CIS-SELECTIVE SYNTHESIS OF ALKENOL-TYPE PHEROMONES
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In less than 2 hours, (Z)-alkenols of 97-98percent stereoisomeric purity may be prepared and isolated (!) if a new type of "instant-ylids" is used.
- Schaub, Bruno,Blaser, Gottfried,Schlosser, M.
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p. 307 - 310
(2007/10/02)
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