- 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 0018
(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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- Synthesis of highly enantioenriched hydroxy- and dihydroxy-fatty esters: Substrate precursors for cytochrome P450BioI
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A series of highly enantioenriched hydroxy- and dihydroxy-fatty esters were required as part of our ongoing investigation into cytochrome P450 BioI. This mediates the biosynthesis of pimelic acid via C-C bond cleavage of long chain fatty acids within Bacillus subtilis. Herein we report the synthesis of various stereoisomers of methyl 7-hydroxytetradecanoate, methyl 8-hydroxytetradecanoate, and methyl 7,8-dihydroxytetradecanoate in highly enantioenriched form, using a combination of asymmetric synthesis and a preparative enantioselective HPLC is reported.
- Singh, Arti A.,Zulkifli, Siti N.A.,Meyns, Michaela,Hayes, Patricia Y.,De Voss, James J.
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experimental part
p. 1709 - 1719
(2012/02/06)
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- Synthesis of carboxymethyl GLA-60 ether derivatives containing an olefin in their chains and their LPS-antagonistic activities
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Anomeric carboxymethyl GLA-60 olefine derivatives having ether chains instead of ester chains in their side chains were synthesized and their biological activities toward both human U937 cells and mouse PEC-macrophage cells were measured. The species-specific behavior of these compounds in humans (LPS-antagonistic) and mice (very weak LPS-antagonistic, but almost inactive) found this time was different from that in humans (LPS-antagonistic) and mice (endotoxic) found in the biosynthetic precursor of lipid A, such as lipid IVa. However, this fact also shows, interestingly enough, that a difference exists in the molecular recognition between human and mouse LPS receptors.
- Nakamura, Tsuyoshi,Watanabe, Yukiko,Shiozaki, Masao,Kanai, Saori,Kurakata, Shin-ichi
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p. 1011 - 1022
(2007/10/03)
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- B-5354a, b and c, new sphingosine kinase inhibitors, produced by a marine bacterium; taxonomy, fermentation, isolation, physico-chemical properties and structure determination
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In the course of our screening for inhibitors of sphingosine kinase, we found a series of active compounds in a culture broth of a novel marine bacterium, SANK 71896. The structures of the compounds, named B-5354a, b and c, were elucidated by a combination of spectroscopic analyses to be new esters of 4-amino-3-hydroxybenzoic acid with long-chain unsaturated alcohols. B-5354a, b and c inhibit sphingosine kinase activity with IC50 values of 21, 58 and 38 υM, respectively.
- Kono,Tanaka,Mizuno,Kodama,Ogita,Kohama
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p. 753 - 758
(2007/10/03)
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- Sex pheromone of female vine bud moth, Theresimima ampellophaga comprises (2s)-butyl (7z)-tetradecenoate
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The sex pheromone of the vine bud moth, Theresimima ampellophaga, released at the 3rd-5th abdominal tergites, was identified by coupled GC-EAG, GC-MS, and synthesis as (2S)-butyl (7Z)-tetradecenoate. For the first time, full stereochemistry is unambiguously defined for the sex pheromone of a member of the Zygaenidae. The synthetic compound caught significant numbers of males in field-trapping experiments.
- Subchev,Harizanov,Francke,Franke,Plass,Reckziegel,Schroeder,Pickett,Wadhams,Woodcock
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p. 1141 - 1151
(2007/10/03)
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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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- 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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- Vinylic Organoboranes. 4. A General, One-Pot Synthesis of 6- and 7-Alkyn-1-ols via Boracyclanes. Influence of Steric Effects in the Iodination of Lithium Alkynyl "Ate" Complexes of Dialkylborinates
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The iodination of the "ate" complexes derived from various B-alkoxyborinane derivatives and 1-alkynyllithium has been investigated.The results indicate the ate complex from B-methoxyborinane is converted into desired 6-alkyn-1-ol in a yield of only 22percent, with much larger amounts, 65percent, of the undesired 1-iodo-1-alkyne.Increases in the steric bulk of the alkoxy group on boron increase the yield of the required 6-alkyn-1-ol with the best results realized with B-(triphenylmethoxy)borinane.Treatment of B-(triphenylmethoxy)borinane with 1-alkynyllithium affords the corresponding "ate" complex.Subsequent iodination induces the migration of one end of the cycloalkyl chain from boron to the adjacent carbon, resulting in the formation of the one-carbon homologated borepane moiety.This then undergoes a rapid deiodoboronation to afford the corresponding (6-alkyn-1-yl)boronate ester.Oxidation of these esters produces the desired 6-alkyn-1-ols in excellent yields (85percent).An attempt to extend this reaction to di-n-alkylborinates to prepare the corresponding unsymmetrical alkynes did not achieve satisfactory results.Alternatively, the iodination of the "ate" complex from B-methylborinane and 1-alkynyllithium, followed by oxidation, provides the required 6-alkyn-1-ols in high yields.This procedure has been successfully extended to the seven-membered borepane moiety to provide the corresponding 7-alkyn-1-ols.Extension of this reaction to the di-n-alkylmethylboranes provides the corresponding unsymmetrical alkynes in good yields.Thus, these procedures constitute a simple, general and one-pot synthesis of the desired alkyn-1-ols, valuable synthons in organic synthesis.Insect pheromones, (Z)-7-tetradecenaland (Z)-7-hexadecenal, were readily prepared in excellent yields by utilizing this convenient procedure.
- Brown, Herbert C.,Basavaiah, D.,Bhat, N. G.
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p. 4518 - 4521
(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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