- Synthesis of Z-alkenes from alkenylcatecholboranes through reaction with RMgX and I2 induced rearrangement
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Addition of RMgX and BrMg(CH2)nMgBr reagents to alkenylcatecholborane followed by iodine induced rearrangement and oxidation provided Z-olefins and Z-olefinic alcohols in moderate to good yields. This procedure is advantageous over the previous methods of synthesis of Z-olefins from alkenylboranes since the alkyl groups which are not available through hydroborations can also be utilized.
- Periasamy, Mariappan,Bhanu Prasad,Suseela, Yantrapragada
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- Synthesis of (Z)-7-dodecylene-1-alcohol and acetic ester thereof
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The invention belongs to the technical field of insect pheromone synthesis, and discloses a novel method for synthesizing (Z)-7-dodecylene-1-alcohol and acetic ester thereof. The method comprises thefollowing steps: taking n-valeraldehyde as a starting material and reacting with a Wittig reagent to obtain (Z)-7-dodecenoic acid ethyl ester; then performing reduction with lithium aluminum hydroxideto obtain (Z)-dodeca-carbon-7-alkene-1-alcohol; finally taking (Z)-dodeca-carbon-7-alkene-1-alcohol to react with acetyl chloride to obtain (Z)-7-dodecylene-1-farnesyl acetate. By adopting the method, Z-shaped double bonds are directly constructed through a coupling reaction of the Wittig reagent carrying an ester group at the tail end with aldehyde. The method is simple in synthesis route, and is environmentally friendly.
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- A Facile Synthesis of the Sex Pheromone of the Cabbage Looper Trichoplusia ni
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The sex pheromone of the cabbage looper Trichoplusia ni Hubner, (Z)-7-dodecen-1-yl acetate, was synthesized via a bimolecular nucleophilic substitution reaction between the Grignard reagent of the protected bromohydrin with (Z)-2-hepten-1-yl acetate in the presence of CuI catalyst as a key step. An efficient synthetic method of preparation of the pheromone was achieved from (Z)-2-butene-1,4-diol in four steps with an overall yield of 22.1%.
- Nguyen, Thanh-Danh,Nguyen, Cong-Hao,Im, Chan,Dang, Chi-Hien
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p. 877 - 879
(2017/03/15)
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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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- Structure-activity relationships in platelet-activating factor (PAF). 11-From PAF-antagonism to phospholipase A2 inhibition: Syntheses and structure-activity relationships in 1-arylsulfamido-2-alkylpiperazines
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1-Benzoyl-2-alkyl piperazines are strong inhibitors of Group I and II secreted PLA2s. An improvement of their activity was obtained by replacing the amide function by a sulfamide and by introduction of electrodonor substituents on the para position of the benzenesulfonyl moiety. Neither the position on one of the carbon of the piperazine ring nor the absolute configuration of this carbon have an effect on the affinity for one or the other group of PLA2, but the lipophilicity remains for these series an essential parameter. In addition structure-activity relationships allow new hypothesis on interaction of these piperazine derivatives with the catalytic site of PLA2s.
- Binisti, Carine,Assogba, Leon,Touboul, Estera,Mounier, Carine,Huet, Jack,Ombetta, Jean-Edouard,Dong, Chang Zhi,Redeuilh, Catherine,Heymans, Francoise,Godfroid, Jean-Jacques
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p. 809 - 828
(2007/10/03)
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- New synthesis of (Z)-5- and (Z)-7-monoene components of insect sex pheromones of the Lepidoptera order
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A new procedure was developed for the synthesis of (Z)-5- and (Z)-7-monoene components of sex pheromones of Lepidoptera insects based on cometathesis of readily accessible cycloocta-1,5-diene and ethylene.
- Bykov,Butenko,Egupova,Finkelshtein
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p. 1301 - 1304
(2007/10/03)
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- Synthesis of sub-units of marine polycyclic ethers by ring-closing metathesis and hydroboration of enol ethers
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A novel syntheses of Z-5-dezenol, Z-5-decenyl acetate, Z-7-dodecenol, Z- 7-dodecenyl acetate, Z-9-tricosene, Z-7,8-epoxy-methyloctadecane which are sex pheromone components of Lepidoptera and Diptera orders, have been realized via stereoselective cometathesis of 1,5-cyclooctadiene with ethylene in the presence of MoCls/SiO2-SnMe4 as a key reaction. The male cometathesis product, 1,Z-5,9-decatriene, has been converted into pheromone components monocloned above by regioselective partial hydroboration or hydrozirconation with help of 9-BBN and Cp2ZrHCl, correspondingly. The protonolysis of the obtained zirconosene derivative gave 1,Z-5-decadiene. Hydroboration-oxidation or hydroboration-C2-homologation of the latter but to Z-5- or Z-7 monoene pheromone components. Hydroboration-iodination of terminal double bond in 1,Z-5,9-decatriene, and further cross-coupling of the obtained iodine derivative with convenient lithium cuprates resulted in Z-9- tricosene, the main sex pheromone component of House Fly (Musca Domestica), or in 2-methyl-Z-7-octadecene, the presence of Gypsy Moth (Lymantria Dispar) sex attractant.
- Bykov, Victor I.,Butenko, Tamara A.,Petrova, Elena B.,Finkelshtein, Eugene Sh.
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p. 8249 - 8252
(2007/10/03)
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- Synthesis of ardisinol II
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The first and also a concise synthesis of ardisinol II by two routes in excellent yields are described.
- Sun, Wei Yan,Zong, Qin,Gu, Rue Lin,Pan, Bai Chuan
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p. 1619 - 1622
(2007/10/03)
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- Pheromone Evaluation of Four Geometric Isomers of 4,11-Hexadecadienal toward Male Eri-Silk Moths
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Four geometric isomers of 4,11-hexadecadienal were prepared and their pheromone activities to male eri-silk moths were evaluated by using the fluttering test and electro-antennography.None of these compounds showed any activity in spite of their similar structure to other pheromone mimics and to the natural pheromone.These results suggest that the presence of 6,11-double bonds is essential for pheromone activity.
- Tomida, Ichiro,Mayesawa, Tsuneaki
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p. 1962 - 1965
(2007/10/02)
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- Dispersion of Rh/Cu in a Sol-Gel Matrix. Highly Chemo- and Stereoselective Catalyst for the Reduction of Alkynes to Z-Alkenes
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Treatment of hydrated RhCl3 and Cu(NO3)2 in THF and H2O with triethoxysilane affords a highly chemo- and stereoselective catalyst system for the reduction of alkynes to Z-alkenes while alkyl-NO2, aryl-NO2, N-carbobenzyloxy, hydroxy, ester, enoate, benzyloxy, alkyl bromide, aryl bromide, and enone moieties remain unaffected.
- Tour, James M.,Pendalwar, Shekhar L.,Kafka, Cynthia M.,Cooper, Joel P.
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p. 4786 - 4787
(2007/10/02)
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- Cyclic ethers as educts for the synthesis of lepidoptra pheromones
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ω-Iodo(trialkylsiloxy)alkanes 2 prepared by ring opening of cyclic ethers with iodotrimethylsilane, are useful starting materials for the synthesis of pheromone components. Reaction with triphenylphosphine to give the corresponding Wittig reagent and subsequent coupling with lithium (Z)-dihex-1-enylcuprate gives (Z)-alken-1-ols 5 and 7, after deprotection, in good yields. The direct coupling of 2 with alkynes failed because of competition reactions, however, the more stable ω-iodo-1-(tert-butyldimethylsiloxy)alkanes were able to undergo C,C-coupling with alkynes. The thus formed 1-(tert-butyldimethylsiloxy)-5-decyne (13c) was hydrogenated and deprotected to give (E)-5-decen-1-ol (15c).
- Poleschner,Heydenreich,Martin
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p. 1231 - 1235
(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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- SYNTHESIS OF PHEROMONES, IV. CHEMISTRY OF THE WITTIG REACTION, I. EFFECTS OF REACTION CONDITIONS ON THE STEREOSELECTIVITY AND YIELD OF THE WITTIG REACTION
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The reactions of nonstabilized triphenylphosphorus ylides with aldehydes have been studied in detail.The stereochemistry and yields of the alkene products are highly dependent upon base used for the generation of the ylide, the solvent and reaction temperature.The synthesis of sex pheromone components by Wittig reaction are also described.
- Vinczer, Peter,Juvancz, Zoltan,Novak, Lajos,Szantay, Csaba
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p. 797 - 820
(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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- Synthesis of Queen Bee and Cabbage Looper Pheromones from Aleuritic Acid
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The common intermediate in the syntheses of the two title compounds (VI and VIII) is 7-hydroxyaldehyde (II), obtained by the cleavage of α-diol of aleuritic acid (I) with NaIO4.II on Grignard reaction with MeMgI followed by pyridinium chlorochromate oxidation of the resulting diol (IV) gives the ketoaldehyde (V).The latter on malonic acid condensation affords the pheromone (VI).II on stereoselective olefination gives the olefinic alcohol (VII), which on acetylation yields the pheromone (VIII).
- Chattopadhyay, A.,Mamdapur, V. R.,Chadha, M. S.
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p. 158 - 159
(2007/10/02)
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- Composite insect attractant for male white-line dart moths and a process for preparing the active ingredients thereof
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The invention relates to a composite insect attractant for male white-line dart moths [Scotia segetum] containing 7[Z]-dodecen-l-ol acetate of the formula [I] STR1 and 9[Z]-tetradecen-l-ol acetate of the formula [II] STR2 as active agents in a weight ratio of I to II of [50-99]:[50-1], optionally along with a liquid or solid adjuvant. Another object of the invention is an insect trap containing said composition and a process for attracting and trapping male white-line dart moths as well as a process for disrupting their mating by air permeation technique. The invention relates further to a novel process for the preparation of the active ingredients of the composition.
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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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- PHEROMONES OF INSECTS AND THEIR ANALOGS. V. A NEW APPROACH TO THE SYNTHESIS OF THE SEX PHEROMONES OF INSECTS OF THE ORDER Lepidoptera WHICH IS BASED ON THE SELECTIVE OZONOLYSIS OF 1-METHYLCYCLOOCTA-1Z,5Z-DIENE
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A new synthesis of 1-acetoxyalk-Z-enes (sex pheromones of insects of the order Lepidoptera) has been developed which is based on the selective ozonolysis of 1-methylcycloocta-1Z-5Z-diene - a cooligomer of isoprene and butadiene.
- Tolstikov, G. A.,Odinokov, V. N.,Galeeva, R. I.,Bakeeva, R. S.,Akhunova, V. R.
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p. 219 - 224
(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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