- Method for synthesizing cis-7-tetradecenol acetate which is main component of sex pheromone of holcocerus vicarius walker
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The invention discloses a method for synthesizing cis-7- tetradecenol acetate which is a main component of sex pheromone of holcocerus vicarius walker. The method includes (1), preparing (7-bromo-heptyl-1-)-2-tetrahydropyran ether; (2), preparing (7-bromo
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Paragraph 0014
(2016/12/16)
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- Simple syntheses of (Z)-7-dodecen-1-ol, (Z)-7-tetradecen-1-yl acetate, (Z)-9-tetradecenal and (Z)-9-hexadecen-1-yl acetate from aleuritic acid
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Insect sex pheromones are used for monitoring and management of crop pests. Four compounds (Z)-7-dodecen-1-ol, (Z)-7-tetradecen-1-yl acetate, (Z)-9-tetradecenal and (Z)-9-hexadecen-1-yl acetate reported as components of some important agricultural insect pests have been synthesized from theo-aleuritic acid (9,10,16-trihydroxyhexadecanoic acid) involving simplified Wittig reactions with improved yield.
- Majee
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p. 1435 - 1438
(2013/02/23)
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- The Reactivity of the Highly Functionalized Copper, Zinc Reagents RCu(CN)ZnI Toward 1-Haloalkynes and Acetylenic Esters
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The highly functionalized organometallics RCu(CN)ZnI 1 react efficiently with 1-haloalkynes providing polyfunctionalized alkynes in high yields.This method has been used to prepare a pheromone of the Amathes c-nigrum in 3 steps and 64percent overall yield.The reagents 1 also add in the presence of an excess of Me3SiCl to acetylenic esters to afford polyfunctionalized C-silylated ethylenic esters.In the case of ethyl propiolate, the reaction is highly stereoselective and affords 97percent pure (E)-2-trimethylsilyl ethylenic esters.
- Yeh, Ming Chang P.,Knochel, Paul
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p. 4799 - 4802
(2007/10/02)
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- SYNTHESIS OF (Z)-7-TETRADECENYL ACETATE AND SEC.BUTYL (Z)-7-TETRADECENOATE FROM ALEURITIC ACID.
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Aleuritic acid (3), after acetylation, was oxidatively decarboxylated and then phase transfer oxidation of the terminal olefin gave 7,8,14-trihydroxytetradecanoic acid.Simple conventional methods led to the synthesis of titled pheromones.
- Subramanian, G. B. V.,Sharma, Rajiv
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p. 1197 - 1202
(2007/10/02)
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- Pheromones via Organoboranes. 3. Vinylic Organoboranes. 10. Stereospecific Synthesis of (Z)- and (E)-6- and -7-Alken-1-ols via Boracyclanes
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Treatment of B-(E)-1-alkenylborinanes, obtained via monohydroboration of 1-alkynes with borinane, with iodine in the presence of a base results in the migration of one end of the cycloalkyl chain from boron to the adjacent carbon, producing intermediates containing the seven-membered borepane moiety, which undergo rapid deiodoboronation to afford the (Z)-6-alkenyl-1-boronate esters.These boronate esters, upon oxidation, provide (Z)-6-alken-1-ols.The procedure is successfully extended to B-(E)-7-alkenylborepane derivatives to produce (Z)-7-alken-1-ols.The preparationof (E)-6- and -7-alken-1-ols has been carried out via borinane and borepane derivatives.Borinane, as prepared previously, hydroborates cleanly 1-bromo-1-alkynes to provide the B-((Z)-1-bromo-1-alkenyl)borinanes.Treatment of these boron intermediates with sodium methoxide results in the displacement of bromine by one end of the boracycloalkyl moiety, producing the corresponding vinylboranes containing the seven-membered borepane moiety.The intermediates, upon controlled protonolysis, followed by oxidation, afford the (E)-6-alken-1-ols.The methodology was extended to borepane derivatives to provide (E)-7-alken-1-ols.The above procedures constitute a simple, very convenient, stereospecific, and general one-pot synthesis of (Z)- and (E)-6- and -7-alken-1-ols.The methodology has been applied to the synthesis of representative pheromones containing a (Z)- or an (E)-alkene moiety in good yields.
- Brown, Herbert C.,Basavaiah, Deevi,Singh, Shankar M.,Bhat, Narayan G.
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p. 246 - 250
(2007/10/02)
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- Vinylic Organoboranes. 3. Pheromones via Organoboranes. 1. Stereospecific Synthesis of Straight-Chain Z-Monoolefinic Insect Pheromones via Lithium (1-Alkynyl)trialkylborates
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Various insect pheromones with straight-chain Z-monoolefinic structures have been prepared from lithium (1-alkynyl)trialkylborates.Treatment of lithium (1-alkynyl)trialkylborates, readily prepared from lithium acetylides and trialkylboranes, with iodine under mild conditions produces the corresponding alkynes in essentially quantitative yield.Monohydroboration of the resultant alkyne with 9-borabicyclononane yields the corresponding (Z)-olefin after protonolysis.The combination of these two reaction sequences provides a general route for the synthesis of (Z)-olefins.The position of the double bond and the carbon-chain length are easily controlled by properly choosing the initial reactants.The incorporation of functional groups is also easily achieved because of the mild reaction conditions and the tolerance of hydroboration to many functional groups.High yield and purity of the products are obtained.
- Brown, Herbert C.,Wang, Kung K.
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p. 4514 - 4517
(2007/10/02)
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- Syntheses of (Z)-9-Hexadecen-1-yl Acetate and (Z)-7-Tetradecen-1-yl Acetate
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Non-2-yn-1-ol (III) on treatment with PBr3/pyridine furnishes the bromide (IV) which reacts with ethylmonosodiomalonate to yield the diester (V).Decarbethoxylation of V followed by LAH reduction of the resultant ester (VI) gives the alcohol (VII) which on hydrogenation over Lindlar's catalyst furnishes undec-4(Z)-en-1-ol (VIII).The alcohol (III) when hydrogenated catalytically provides non-2(Z)-en-1-ol (IX).Reactions of VIII and IX with PBr3/pyridine yield the corresponding bromides (X) and (XI) which on coupling with the Grignard reagent (XII), prepared from 5-bromo-1-tetrahydropyranyloxypentane, in the presence of Li2CuCl4, followed byhydrolysis, furnish the alcohols (XIII) and (XIV), respectively.Acetylation of XIII and XIV provides the title acetates (I) and (II), respectively.
- Vig, O. P.,Sharma, M. L.,Sabharwal, Arun,Vohra, Neelam
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p. 1042 - 1044
(2007/10/02)
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- Pheromone Synthesis via Organoboranes: A Stereospecific Synthesis of (Z)-7-Alken-1-ols
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Traetment of trans-1-alkenylborepanes, obtained via monohydroboration of 1-alkynes with borepane, with iodine in the presence of a base results in the migration of one end of the cycloalkyl chain from boron to the adjacent carbon, producing intermediates containing the eight-membered borocane moiety, which undergoes a rapid deiodoboronation to afford the (Z)-7-alkenyl-1-boronate esters.These boronate esters on oxidation produce (Z)-7-alken-1-ols, providing a general, one-pot, and stereospecific synthesis of (Z)-7-alken-1-ols.
- Basavaiah, D.,Brown, Herbert C.
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p. 1792 - 1793
(2007/10/02)
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- INSECT SEX PHEROMONES. STEREOSELECTIVE SYNTHESIS OF SEVERAL (Z)- AND (E)-ALKEN-1-OLS, THEIR ACETATES, AND OF (9Z,12E)-9,12-TETRADECADIEN-1-YL ACETATE
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Several female sex pheromone components produced by moths belonging to the order of Lepidoptera, and potential attractants of Dacus oleae (Diptera:Tripetidae) have been synthesized in high chemical and stereoisomeric purity by improved acetylenic routes involving alkylation of lithium 1-alkyn-1-ides in HMPT, followed by (Z) and (E) highly stereoselective reduction of the derived internal alkynes.Particular care has been paid to optimize the parameters of the reactions used and to evaluate the chemical and isomeric purity of the reaction products.The compounds synthesized include (Z)- and (E)-5-nonen-1-ol, (Z)- and (E)-7-dodecen-1-yl acetate, (Z)- and (E)-7-teradecen-1-yl acetate, (Z)- and (E)-7-nonen-1-ol, (Z)- and (E)-9-tetradecen-1-yl acetate, (Z)- and (E)-10-tetradecen-1-yl acetate, (Z)- and (E)-11-tetradecen-1-yl acetate.Pure (Z)-6-nonen-1-ol, which is an attractant of olive fruit fly, D. oleae, and very probably, a constituent of the sex pheromone of females of this insect, has been prepared by a rather efficient copper-catalyzed reaction between (Z)-3-hexen-1-ylmagnesium bromide and oxetane. (9Z,12E)-9,12-Tetradecadien-1-yl acetate, which is the pheromone of Anagasta kuenniella, Ephestia elutella, Cadra figulella, Spodoptera exigua, S. litura, and a component of the sex pheromones of several other Lepidoptera, has been conveniently prepared by using the copper-catalyzed coupling reaction between (E)-1-chloro-2-butene and 10-tetrahydropyranyloxy-1-decenylmagnesium bromide, followed by acetylation and Z-stereoselective reduction of the derived 1,4-enyne.All syntheses have been conducted on a scale to yield less than 50 mmol of the pure sex pheromone components, but seem adaptable for much larger quantities.
- Rossi, Renzo,Carpita, Adriano,Gaudenzi, Loretta,Quirici, Maria Grazia
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p. 237 - 246
(2007/10/02)
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