28079-04-1Relevant articles and documents
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
Odinokov, V. N.,Akhmetova, V. R.,Khasanov, Kh. D.,Abduvakhabov, A. A.,Tolstikov, G. A.,Panasenko, A. A.
, p. 240 - 243 (1989)
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.
SYNTHESIS OF PHEROMONE DERIVATIVES VIA Z-SELECTIVE OLEFIN METATHESIS
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Paragraph 0261; 0267, (2021/12/28)
Disclosed herein are methods for synthesizing fatty olefin metathesis products of high Z-isomeric purity from olefin feedstocks of low Z-isomeric purity. The methods include contacting a contacting an olefin metathesis reaction partner, such as acylated alkenol or an alkenal acetal, with an internal olefin in the presence of a Z-selective metathesis catalyst to form the fatty olefin metathesis product. In various embodiments, the fatty olefin metathesis products are insect pheromones. Pheromone compositions and methods of using them are also described.
SYNTHESIS OF STRAIGHT-CHAIN LEPIDOPTERAN PHEROMONES THROUGH ONE- OR TWO- CARBON HOMOLOGATION OF FATTY ALKENES
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Paragraph 0156, (2020/02/14)
Methods for the preparation of alkenes including insect pheromones are described. The methods include homologation reactions employing reagents such as 1,3-diesters, epoxides, cyanoacetates, and cyanide salts for elongation of starting materials and intermediates by one or two carbon atoms. The alkenes include insect pheromones useful in a number of agricultural applications.
Synthesis method of (Z/E)-8-dodecen-1-alcohol acetate compound
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Paragraph 0060; 0067; 0068; 0070; 0076; 0077, (2019/05/21)
The invention provides a synthesis method of a (Z/E)-8-dodecane-1-alcohol acetate compound. Specifically, the method includes the following steps: preparing 8-bromooctanol from 1,8-octanediol, then performing esterification reaction to obtain 8-Bromooctanol acetate, and then preparing omega-acetoxyoctanyl triphenyl phosphine bromide salt, and finally performing reaction through Scholoer-wittig toobtain (Z/E)-8-dodecene-1-alcohol acetate. The synthesis method has the advantages of high availability of raw materials, high yield and good selectivity, and is suitable for industrial production.
SYNTHESIS OF PHEROMONES AND RELATED MATERIALS VIA OLEFIN METATHESIS
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, (2018/09/12)
Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.
A (Z/E) - 8 - dodecene -1 - ethoxylate ester synthesis method
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, (2018/07/06)
The invention discloses a (Z/E)-8-dodecylene-1-olacetate synthesis method. The method is characterized in that 1-halogenated pentine and magnesium 1-(2-oxotetrahydropyranyl)heptylhalide as initial raw materials undergo a coupling reaction to produce 8-(2-oxotetrahydropyranyl)dodecyne, the 8-(2-oxotetrahydropyranyl)dodecyne is subjected to hydrogenation, one-pot deprotection and esterification so that (Z)-8-dodecylene-1-olacetate and (E)-8-dodecylene-1-olacetate are obtained, wherein a mole ratio of (Z)-8-dodecylene-1-olacetate to (E)-8-dodecylene-1-olacetate is (90%-99.5%): (10%-0.5%). The method utilizes 1-halogenated pentine and magnesium 1-(2-oxotetrahydropyranyl)heptylhalide as initial raw materials, provides a novel reaction route, has a short route, produces less by-product, has simple and routine processes, is free of complex post-reaction treatment processes and improves production efficiency. The method satisfies different insect pheromone trap or lure requirements on an isomer ratio in practical application and is suitable for large-scale industrial production.
A pheromone food heart insectthe pear is small (Z/E)-8-dodecene acetum acid ester synthetic method
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Paragraph 0046; 0047, (2017/02/28)
The invention provides a synthesis method of grapholitha molesta sex pheromone (Z/E)-8-dodecene acetate. The synthesis method comprises the following steps: (1) by taking methylbenzene or benzene as a solvent and 1,8-octanediol and hydrobromic acid as starting raw materials, performing unilateral bromination reaction to obtain 8-bromooctanol; (2) by taking ethanol as a solvent, adding 8-bromooctanol and triphenylphosphine into a reaction kettle, after the reaction, cooling and separating out 8-hydroxyl octyl triphenylphosphine crystals by taking methylbenzene as an eluent; (3) performing Witting reaction on the 8-hydroxyl octyl triphenylphosphine and n-butyraldehyde under the presence of a catalyst 18-crown ether-6 to obtain (Z/E)-8-dodeceneanol, wherein potassium carbonate is adopted as alkali; and (4) by taking pyridine as a solvent, reacting the (Z/E)-8-dodeceneanol with acetic anhydride or acetyl chloride to obtain (Z/E)-8-dodecene acetate. The method mild in conditions, fewer in steps, high in yield, and suitable for industrial production, and raw materials are easily available.
PALLADIUM-CATALYZED DECARBONYLATION OF FATTY ACID ANHYDRIDES FOR THE PRODUCTION OF LINEAR ALPHA OLEFINS
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Page/Page column, (2014/06/23)
The present invention is directed to methods of forming olefins, especially linear alpha olefins from fatty acids or anhydrides, each method comprising: contacting an amount of precursor carboxylic acid anhydride with a palladium catalyst comprising a bidentate bis-phosphine ligand in a reaction mixture so as to form an olefin in a product with the concomittant formation and removal of CO and water from the reaction mixture, either directly or indirectly, wherein the reaction mixture is maintained with a sub-stoichiometric excess of a sacrificial carboxylic acid anhydride, an organic acid, or both, said sub-stoichiometric excess being relative to the amount of the precursor carboxylic acid anhydride. The precursor carboxylic acid anhydride may be added to the reaction mixture directly or formed in situ by the reaction between at least one precursor carboxylic acid with a stoichiometric amount of the sacrificial acid anhydride.
Palladium-catalyzed decarbonylative dehydration of fatty acids for the production of linear alpha olefins
Liu, Yiyang,Kim, Kelly E.,Herbert, Myles B.,Fedorov, Alexey,Grubbs, Robert H.,Stoltz, Brian M.
, p. 130 - 136 (2014/03/21)
A highly efficient palladium-catalyzed decarbonylative dehydration reaction of carboxylic acids is reported. This method transforms abundant and renewable even-numbered natural fatty acids into valuable and expensive odd-numbered alpha olefins. Additionally, the chemistry displays a high functional group tolerance. The process employs a low loading of palladium catalyst and proceeds under solvent-free and relatively mild conditions.
Concise syntheses of insect pheromones using Z-Selective cross metathesis
Herbert, Myles B.,Marx, Vanessa M.,Pederson, Richard L.,Grubbs, Robert H.
supporting information, p. 310 - 314 (2013/02/23)
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.