- PHEROMONES OF INSECTS AND THEIR ANALOGS. XXVIII. PRACTICAL SYNTHESIS OF TETRADECA-9Z,12E-DIEN-1-YL ACETATE - A COMPONENT OF THE SEX PHEROMONES OF INSECTS OF THE ORDER LEPIDOPTERA
-
Tetradeca-9Z,12E-dien-1-yl acetate, a sex pheromone of the Indian meal moth Plodia interpunctella has been synthesized from the readily available product of the hydrodimerization of butadiene - octa-1,7-diene.
- Odinokov, V. N.,Dzhemilev, U. M.,Ishumuratov, G. Yu.,Botsman, L. P.,Ibragimov, A. G.,et al.
-
-
Read Online
- Effect of perfluoroalkyl chain length on monolayer behavior of partially fluorinated oleic acid molecules at the air-water interface
-
A series of oleic acid (OA) analogs containing terminal perfluoroalkyl groups (CF3, C2F5, n-C3F 7, n-C4F9 or n-C8F17) was synthesized to clarify how the fluorinated chain length affects the stability and molecular packing of liquid-expanded OA monolayers at the air-water interface. Although the substitution of terminal CF3 group for CH3 in OA had no effect on monolayer stability, further fluorination led to a gradual increase in monolayer stability at 25 ?C. Surface pressure-area isotherm revealed that partially fluorinated OA analogs form more expanded monolayers than OA at low surface pressures, and that the monolayer behavior of OA analogs with the even-carbon numbered fluorinated chain is almost the same as that of OA upon monolayer compression, whereas the behavior of OA analogs with the odd-carbon numbered fluorinated chain significantly differs from that of OA. These results indicate: (i) the terminal short part (at least C2 residue) in OA predominantly determines the liquid-expanded monolayer stability; (ii) the molecular packing state of OA may be perturbed by the substitution of a short odd-carbon numbered fluorinated chain; (iii) hence, OA analogs with even-carbon numbered chain are considered to be preferable as hydrophobic building blocks for the synthesis of fluorinated phospholipids.
- Baba, Teruhiko,Takai, Katsuki,Takagi, Toshiyuki,Kanamori, Toshiyuki
-
-
Read Online
- Synthesis and characterization of partially fluorinated stearolic acid analogs: Effect of their fluorine content on the monolayer at the air-water interface
-
Novel stearolic acid analogs (i.e., 9-octadecynoic acid analogs: 1a-d) containing the shorter perfluoroalkyl groups, CF3, C2F5, n-C3F7 or n-C4F9 group were synthesized. Equilibrium spreading pressures (πes) of their monolayers at the air-water interface were measured in order to demonstrate how the fluorine content has an effect on the stability of the fatty acid monolayers. As the fluorine content in stearolic acid molecule increased, its melting points was lowered indicating the solid bulk phase of stearolic acid became thermally unstable, while its monolayer stability evaluated by πe at 25 °C, dramatically increased and subsequently leveled off above a certain fluorine content. Under this condition, the replacement of at least five hydrogen atoms at the terminal hydrophobic segment in stearolic acid molecule by fluorine atoms (CF3CF2 group) was required to alter the bulk property of stearolic acid and exhibit the stabilization of monolayers, whereas further fluorination of stearolic acid had a minor effect on the monolayer stability. This behavior suggests the terminal fluorinated hydrophobic segment exclusively controls the interfacial stability of fatty acid monolayers.
- Takai, Katsuki,Takagi, Toshiyuki,Baba, Teruhiko,Kanamori, Toshiyuki
-
-
Read Online
- THERAPY FOR DRY EYE (DE) AND MEIBOMIAN GLAND DYSFUNCTION (MGD) BASED ON THE REPLACEMENT OF O-ACYL-Ω-HYDROXY FATTY ACIDS (OAHFA)
-
The present invention relates to a process for preparing a fatty acid, a fatty acid obtainable by said process, a composition comprising said fatty acid, an eye drop comprising said fatty acid and a method for treating dry eye disease or Meibomian gland d
- -
-
Page/Page column 26; 30; 32
(2020/09/19)
-
- Synthesis of site-specifically13C labeled linoleic acids
-
Soybean lipoxygenase-1 (SLO-1) catalyzes the C–H abstraction from the reactive carbon (C-11) in linoleic acid as the first and rate-determining step in the formation of alkylhydroperoxides. While previous labeling strategies have focused on deuterium labeling to ascertain the primary and secondary kinetic isotope effects for this reaction, there is an emerging interest and need for selectively enriched13C isotopologues. In this Letter, we present synthetic strategies for site-specific13C labeled linoleic acid substrates. We take advantage of a Corey–Fuchs formyl to terminal13C-labeled alkyne conversion, using13CBr4as the labeling source, to reduce the number of steps from a previous fatty acid13C synthetic labeling approach. The labeled linoleic acid substrates are useful as nuclear tunneling markers and for extracting active site geometries of the enzyme–substrate complex in lipoxygenase.
- Offenbacher, Adam R.,Zhu, Hui,Klinman, Judith P.
-
supporting information
p. 4537 - 4540
(2016/09/23)
-
- The (5Z)-5-Pentacosenoic and 5-Pentacosynoic Acids Inhibit the HIV-1 Reverse Transcriptase
-
The natural fatty acids (5Z)-5-pentacosenoic and (9Z)-9-pentacosenoic acids were synthesized for the first time in eight steps starting from either 4-bromo-1-butanol or 8-bromo-1-butanol and in 20-58 % overall yields, while the novel fatty acids 5-pentacosynoic and 9-pentacosynoic acids were also synthesized in six steps and in 34-43 % overall yields. The ?5 acids displayed the best IC50's (24-38 μM) against the HIV-1 reverse transcriptase (RT) enzyme, comparable to nervonic acid (IC50 = 12 μM). The ?9 acids were not as effective towards HIV-RT with the (9Z)-9-pentacosenoic acid displaying an IC50 = 54 μM and the 9-pentacosynoic acid not inhibiting the enzyme at all. Fatty acid chain length and position of the unsaturation was important for the observed inhibition. None of the synthesized fatty acids were toxic (IC50 > 500 μM) towards peripheral blood mononuclear cells. Molecular modeling studies indicated the structural determinants underlying the biological activity of the most potent compounds. These results provide new insights into the structural requirements that must be present in fatty acids so as to enhance their inhibitory potential towards HIV-RT.
- Moreira, Lizabeth Giménez,Orellano, Elsie A.,Rosado, Karolyna,Guido, Rafael V. C.,Andricopulo, Adriano D.,Soto, Gabriela Ortiz,Rodríguez, José W.,Sanabria-Ríos, David J.,Carballeira, Néstor M.
-
p. 1043 - 1050
(2015/10/05)
-
- Long-chain triazolyl acids as inhibitors of osteoclastogenesis
-
Saturated fatty acids (e.g., palmitic acid) are known to moderately inhibit the development of osteoclasts in vitro. In pursuit of more effective inhibitors of osteoclastogenesis we explored two new classes of palmitic acid analogues containing either an ether or triazolyl group at various positions along the chain. The compounds were evaluated for their ability to inhibit the formation of osteoclasts in primary mouse bone marrow cultures. The oxyacids were generally prepared by condensation of the appropriate alkyl halides and diols, followed by Jones oxidation. The triazolyl acids were prepared by copper-catalysed click chemistry between alkyl azides and acetylenic acids, or with the appropriately-protected azides and alkynes, followed by deprotection and oxidation. The oxyacids were little more effective than palmitic acid, but the triazolyl analogues were much more effective osteoclastogenesis inhibitors, especially when the triazole was distant from the acid unit.
- Marshall, Andrew J.,Lin, Jian-Ming,Grey, Andrew,Reid, Ian R.,Cornish, Jillian,Denny, William A.
-
p. 4112 - 4119
(2013/07/27)
-
- SELF-ASSEMBLED MONOLAYERS AND METHODS FOR USING THE SAME IN BIOSENSING APPLICATIONS
-
Cross-linked amphiphile constructs that form self-assembled monolayers (SAMs) on metal surfaces such as gold surfaces are disclosed. These new SAMs generate well packed and highly oriented monolayer films on gold surfaces. A method for using the SAMs in t
- -
-
Page/Page column 9; 16-17
(2013/02/27)
-
- Improved synthesis of (9Z)-9,13-tetradecadien-11-ynal, the sex pheromone of the avocado seed moth, Stenoma catenifer
-
The terminal dienyne of (9Z)-9,13-tetradecadien-11-ynal, the sex pheromone of the avocado seed moth, Stenoma catenifer, was constructed by coupling a vinyl iodide precursor with commercially available 1-buten-3-yne with Pd catalysis, resulting in a short and efficient synthesis of the pheromone.
- Zou, Yunfan,Millar, Jocelyn G.
-
body text
p. 1336 - 1337
(2010/04/29)
-
- Synthesis of photoactivatable analogues of lysophosphatidic acid and covalent labeling of plasma proteins
-
Lysophosphatidic acids hearing a benzophenone group in either the sn-1 or sn-2 chain of an oleoyl-type ester or oleyl-type ether chain and 32P in the phosphate group were synthesized. The benzophenone moiety was introduced by selective hydrobor
- Li, Zaiguo,Baker, Daniel L.,Tigyi, Gabor,Bittman, Robert
-
p. 629 - 635
(2007/10/03)
-
- Ethynylation of the ether derivatives of ω-haloalkanols with lithium acetylide-ethylenediamide complex
-
A new operationally simple and highly efficient procedure for the ethynylation of ether derivatives of ω-haloalkanols with lithium acetylide-ethylenediamine complex in N,N-dimethylacetamide is described.
- Karpinska,Lewandowska,Grodner
-
p. 937 - 942
(2007/10/03)
-
- Identification, syntheses, and characterization of the geometric isomers of 9,11-hexadecadienal from female pheromone glands of the sugar cane borer Diatraea saccharalis
-
Chemical analysis of the pheromone glands of the sugar cane borer Diatraea saccharalis has shown the presence of the four geometric isomers of 9,11-hexadecadienal (1-4), in addition to hexadecanal and (Z)-hexadec-11-enal. We here report the syntheses and characterization of compounds 1-4, One starting material, 9-decen-1-ol, has been used to obtain all of them via divergent synthetic routes.
- Santangelo, Ellen M.,Coracini, Myrian,Witzgall, Peter,Correa, Arlene G.,Unelius, C. Rikard
-
p. 909 - 915
(2007/10/03)
-
- Stereodirectional synthesis of the main component of pheromone (9Z,12E)-tetradeca-9,12-dienyl acetate by cross-coupling
-
By cross-coupling of alkynyl cuprate with crotyl halides was synthesized (9Z,12E)-tetradeca-9-12-dienyl acetate, the main component of pheromones of several insect species Lepidoptera. The assignment of the chemical shifts of diene system was performed by 1H and 13NMR spectroscopy.
- Matveeva,Erin,Leshcheva,Kurts
-
p. 765 - 770
(2007/10/03)
-
- Biosynthesis of epilachnene, a macrocyclic defensive alkaloid of the Mexican bean beetle
-
The carbon skeleton of the azamacrolide epilachnene, the principal defensive alkaloid of Epilachna varivestis pupae, can be derived from oleic acid and serine. Analytical evidence from three experiments in which insects were fed (2H35)octadecanoic acid, (Z)-9- [11,11,12,12,13,13,14,14,15,15,16,16,17,17,18,18,18-2H17]octadecenoic acid and (Z)-9-[11,11,12,12,13,13,14,14,16,16,17,17,18,18,18-2H15]octadecenoic acid, indicates that only the C-15 methylene group of oleic acid is involved in the mechanism leading to carbon-nitrogen bond formation in epilachnene. Support for this scheme is provided by the observation of an unusual ion at m/z 170 in the electron-ionization mass spectrum of epilachnene, rationalized as CH2=CH-COO-CH2-CH2-NH+=CH-CH2-CH2-CH3.
- Attygalle, Athula B.,Svatos, Ales,Veith, Martin,Farmer, Jay J.,Meinwald, Jerrold,Smedley, Scott,Gonzalez, Andres,Eisner, Thomas
-
p. 955 - 966
(2007/10/03)
-
- A versatile approach to the synthesis of 9(Z)-unsaturated acyclic insect pheromones from undec-10-enoic acid
-
A general approach to the synthesis of 9(Z)-unsaturated acyclic insect pheromones from undec-10-enoic acid was developed. The method comprises the conversion of the acid into undec-10-enyl acetate, shortening of its carbon chain to afford dec-9-enyl acetate (via 11-acetoxyundecanoic acid), and a two-step transformation of the latter into the key intermediate, dec-9-yn-1-ol, by sequential bromination - dehydrobromination. The elimination of two HBr molecules from the dibromide is effectively performed using Bu1OK in the presence of dibenzo-18-crown-6 as the catalyst.
- Ishmuratov,Kharisov,Yakovleva,Botsman,Galeeva,Ishmuratova,Tolstikov
-
p. 1595 - 1597
(2007/10/03)
-
- Titanium(II)-based Z-reduction of alkynes. Syntheses of deuterium labelled linolenic and oleic acids and (3E,8Z,11Z)-tetradeca-3,8,11-trienyl acetate, the sex pheromone of a tomato pest, Scrobipalpuloides absoluta
-
An operationally simple TiII-mediated, stereo- and regio-specific reduction of isolated, conjugated and methylene 'skipped' polyynes to the corresponding Z-polyenes in a one-pot procedure is described and applied inter alia to the syntheses of deuterium labelled linolenic and oleic acids. Final quenching with D2O (instead of H2O) results in regio- and stereo-specific Z-dideuteration of the alkyne. The synthesis of (3E,8Z,11Z)-tetradeca-3,8,11-trienyl acetate, the major sex pheromone of Scrobipalpuloides absoluta, a destructive pest of tomatoes, and the (3Z,8Z,11Z)-isomer, utilises this methodology in key reduction steps, and under- or over-reduction are negligible.
- Hungerford, Natasha L.,Kitching, William
-
p. 1839 - 1858
(2007/10/03)
-
- Use of enyne compounds in the synthesis of insect pheromones
-
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
-
-
- A chemoenzymatic approach to hydroperoxyeicosatetraenoic acids. Total synthesis of 5(S)-HPETE
-
A new synthetic approach to enantiomerically pure hydroperoxyeicosatetraenoic acids (HPETEs) is described in which the tetraene skeleton is assembled through chemoselective olefination of a protected hydroperoxy aldehyde. Soybean lipoxygenase-mediated dioxygenation of both natural and unnatural fats produces hydroperoxy dienes in high enantiomeric excess; the observed regioselectivity supports a revised hypothesis for substrate specificity. Protection of the diene hydroperoxides as peroxy ketals is followed by regioselective ozonolysis to afford enantiomerically pure 4-peroxy 2,3-enals which undergo olefination to produce peroxytetraenoates. Removal of the monoperoxy ketal and the methyl ester affords enantiomerically pure HPETEs. The generality of the strategy is illustrated with the first chemical synthesis of 5(S)-HPETE.
- Dussault,Lee
-
p. 218 - 226
(2007/10/02)
-
- Useful Direct Conversion of Tetrahydropyranyl Ethers of Fatty Alcohols into Fatty Acids
-
Tetrahydro-2-pyranyl ethers from fatty primary alcohols can be converted in a one-step procedure into the corresponding carboxylic acids in high yields.This process avoids the synthesis of symmetrical esters, particularly for long-chain compounds.This reaction proved to be useful, for instance, to produce polyunsaturated fatty acids immediately before their biological testing. - Key words: Oxidation; polyunsaturated fatty acids; tetrahydropyranyl ethers
- Gruiec, Regine,Noiret, Nicolas,Patin, Henri
-
p. 1083 - 1085
(2007/10/03)
-
- Synthesis of Deuterium Labeled Polyunsaturated Fatty Acids
-
Compounds containing carbon-carbon double bonds bearing cis deuterium atoms can be prepared conveniently by treating disubstituted acetylenes with bis(2-deuteriocyclohexyl)borane-B-D1 followed by reaction with CH3CO2D.As an example, the preparation of labeled linolenic acid is reported.
- Svatos, Ales,Attygalle, Athula B.,Meinwald, Jerrold
-
p. 9497 - 9500
(2007/10/02)
-
- Studies related to fatty acids desaturation. II. Preparation of iso-linoleic and iso-vernolic acids
-
New iso-vernolic and iso-linoleic acids have been prepared in order to study their potential inhibition action during in vivo desaturation of oleic acid in vegetal sources. - Keywords: Δ12-desaturase / modified fatty acids / Z,ω-octenyl bromides / iso-linoleic acids / iso-vernolic acids
- Gruiec, Regine,Noiret, Nicolas,Patin, Henri
-
p. 699 - 705
(2007/10/02)
-
- Synthesis of (S,E)-1-Methyl-9-dodecenyl Acetate, the Sex Pheromone of the Hessian Fly, Mayetiola destructor, by Lipase-catalyzed Enantioselective Hydrolysis
-
(S,E)-1-Methyl-9-dodecenyl acetate , the sex pheromone of the hessian fly, Mayetiola destructor, was synthesized in a highly enantiomerically pure form by Pseudomonas cepacia lipase-catalyzed hydrolysis.
- Kamezawa, Makoto,Tachibana, Hojun,Ohtani, Takehiko,Naoshima, Yoshinobu
-
p. 1962 - 1963
(2007/10/02)
-
- Additions of CuCN-Derived Stannylcuprates to Terminal Alkynes: A Comparative Spectroscopic and Chemical Study
-
The stannylcupration of terminal alkynes 4a,b with cuprates 1-3 proceeds rapidly and reversibly above -35 deg C to afford stannylcuprate intermediates 5a,b and 6a,b.These intermediates have been characterized by 2H and 13C NMR labelling experiments.Corroborating evidence for this reversible addition comes from further chemical tests and cross-over experiments that show the thermodynamic favorability of the adducts.Further comparative study of reaction products and byproducts shows 2 to be the stannylcuprate of choice for the preparation of vinylstannates from terminal alkynes.
- Singer, Robert, D.,Hutzinger, Michael W.,Oehlschlager, Allan C.
-
p. 4933 - 4938
(2007/10/02)
-
- Design, synthesis, and activity of membrane-disrupting bolaphiles
-
Four new classes of bolaphiles ("double-headed" single-chain surfactants) have been prepared, via condensation of an homologous series of linear saturated, olefinic, and acetylenic α,ω-dicarboxylic acids with hexaethylene glycol, and evaluated for their ability to induce the release of 5(6)-carboxyfluorescein (CF) entrapped within large unilamellar vesicles derived from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). Operationally, the membrane-disrupting activity of the bolaphiles has been found to vary by a factor of ca. 100, when the total number of carbon atoms which separate the carboxylate moieties range from 12 to 24; the most active bolaphile is approximately three times more active than Triton X-100. When the affinity of the bolaphiles toward POPC membranes is considered, the intrinsic membrane-disrupting activity varies by a factor of ca. 230. A "loop" model is proposed to account for the general trends in bolaphile activity that are observed, where the depth of loop penetration and loop width are presumed to be the key factors involved in determining membrane-disrupting activity. The potential utility of these surfactants as antimicrobial agents, and as anti-HIV agents in particular, is briefly discussed.
- Jayasuriya, Nimal,Bosak, Stanislav,Regen, Steven L.
-
p. 5844 - 5850
(2007/10/02)
-
- SYNTHESIS OF THE SEX PHEROMONE OF THE GRAIN MOTH Ephestia Elutella
-
A most convenient synthesis of tetradeca-9Z,12E-dien-1-ol and its acetate - components of the sex pheromone of the grain moth - has been carried out on the basis of a scheme for obtaining a cis-1,trans-4-dienic system.
- Kasymzhanova, M.,Abdukakharov, V. S.,Kamaev, F. G.,Abduvakhabov, A. A.
-
p. 708 - 713
(2007/10/02)
-
- A facile synthesis of cotton bollworm (Heliothis armigera) pheromone components: (Z)-11-Hexadecenal and (Z)-9-hexadecenal
-
(Z)-Hexadecenal (1) and (Z)-9-hexadecenal (2) have been synthesised starting from easily accessible propargyl alcohol.Alkylation of propargyl alcohol yields 3 and 4, which on acetylene-zipper reaction give terminal acetylenes (5 and 6, R'=H).Alkylation of 5 and 6 followed by depyranylation afford 7 and 8.Partial cis-hydrogenation of these with P2Ni followed by PCC oxidation give compounds 1 and 2.
- Mithran, S.,Mamdapur, V. R.
-
p. 755 - 756
(2007/10/02)
-
- Synthesis of all-trans-Parinaric Acid-d8 Specifically Deuterated at All Vinyl Positions
-
Parinaric acid is a widely used fluorescent probe of biological systems.The all-trans isomer (9(E),11(E),13(E),15(E)-octadecatetraenoic acid) specifically deuteriated at all vinyl positions was prepared by using the Wittig reaction to couple a diene phosphorane with an α,β-unsaturated aldehyde-ester.The preparation of each component included the stereoselective reduction of a substituted propynoic ester with lithium aluminum deuteride (LAD), introducing the trans double bond as well as most of the deuterium in one step, in high isotopic purity without unwanted hydrogen-deuterium exchange.By inclusion of deuterium, the probe can be used with other techniques, such as deuterium NMR and neutron diffraction, further increasing its utility.The synthesis can be used to prepare other tetraenes by correct choice of starting propynoic esters.
- Goerger, Michael M.,Hudson, Bruce S.
-
p. 3148 - 3153
(2007/10/02)
-
- SYNTHESIS AND PHISIOLOGICAL ACTIVITIES OF BOTH ENANTIOMERS OF CORIOLIC ACID AND THEIR GEOMETRIC ISOMERS
-
Both enantiomers of coriolic acid and their geometric isomers are synthesized highly selectively.These acids are found to exhibit similar inhibition activity toward spore germination of rice blast fungus.
- Kobayashi, Yuichi,Okamoto, Sentaro,Shimazaki, Toshiyuki,Ochiai, Yoshinori,Sato, Fumie
-
p. 3959 - 3962
(2007/10/02)
-
- SYNTHESIS AND BIOMETHYLENATION OF TWO HOMOALLYLICALLY FLUORINATED OLEIC ACIDS
-
Methyl 7-fluorooleate and methyl 12-fluorooleate have been synthesized in racemic form.Both of these compounds are incorporated into L. plantarum but are methylenated to a different extent.
- Buist, Peter H.,Findlay, Judy M.,Leger, Gabriel,Pon, Robert A.
-
p. 3891 - 3894
(2007/10/02)
-
- SYNTHESIS OF THE RACEMIC FORM OF (Z)-1,17-DIAMINOOCTADEC-9-ENE, AN ALIPHATIC DIAMINE FROM COCCINELLIDAE. DETERMINATION OF THE ABSOLUTE CONFIGURATION OF THE (+)-NATURALLY-OCCURRING ANTIPODE
-
The total synthesis of the title compound (1) has been achieved.Also reported is the use of lanthanide induced shifts in 1H NMR spectroscopy to assign the absolute configuration of the α-carbon atom in chiral primary α-methylalkylamines.Application of this empirical method to natural (+)-1 shows that it has the R-configuration at C-17.
- Braconnier, M.F.,Braekman, J.C.,Daloze, D.
-
p. 605 - 614
(2007/10/02)
-
- Metamorphosis of Castor Oil to Insect Sex-pheromones and Useful Synthons
-
The primary fragmentation products of Castor oil (1), namely, methyl undec-10-enoate (2) and sebacic acid (3) have been converted, using novel reactions and strategies into synthons of the type H-CC-(CH2)n-3-CH2OTHP (n=6=4; n=7=14; n=8=22; n=9=29).A surprisingly clean decarboxylative elimination of sebacic acid monoester gives methyl non-8-enoate (7), a synthon related to recefeiolide and a precursor to 4, the utility of which, has been illustrated with the synthesis of insect-pheromones of the species Grapholita molesta.Methyl dec-9-enoate (15) has been prepared by a novel and practical terminal ? to lower terminal ? degradation of 2.Compound 7 has been transformed via synthon 14 to the insect sex-pheromones of the species, Spodoptera frugiperda, Heliothis virescens and Paralobesia viteana in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxyundec-10-yne (22) readily prepared from 2, has been used to illustrate a new strategy in pheromone synthesis, namely, the use of coupling elements, leading to the preparation of bombykol in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxydodec-11-yne (29), already reported, has been transformed to vaccenic acid (30), the transposed ?-isomer of oleic acid, in good yields, thus demonstrating the use of acetylide synthons for the preparation of rare fatty acids also.
- Ranganathan, S.,Maniktala, Vibha,Kumar, Raaj,Singh, G. P.
-
p. 1197 - 1207
(2007/10/02)
-
- 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
-
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
-
p. 237 - 246
(2007/10/02)
-
- (Z)-9-Tetradecen-1-ol formate and its use as a communication disruptant for Heliothis
-
(Z)-9-Tetradecen-1-ol formate [(Z)-9-TDF], a chemical of nonbiological origin, was prepared and found to have excellent potential as an insect control agent for the corn earworm, Heliothis zea (Boddie) and tobacco budworm, H. virescens (F.). Mating of H. zea and H. Virescens moths exposed in the field to an atmosphere permeated with (Z)-9-TDF was greatly reduced. The chemical can be used alone to inhibit mating of H. zea or H. virescens or it can be dispensed together with other mating inhibitors to suppress mating in several pest species simultaneously.
- -
-
-