- ORGANO-CUIVREUX VINYLIQUES 17. CARBOCUPRATION D'ALCYNES PAR DES ORGANO-CUPRATES ET -CUIVREUX FONCTIONNELS
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Some organocopper and cuprate derivatives, distally bearing a free or protected hydroxyl group, add to alkynes, to give α,ο-bifunctional olefins.
- Gardette, M.,Alexakis, A.,Normant, J. F.
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- Method for synthesizing grassland spodoptera litura sex pheromone active ingredients
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The invention belongs to the technical field of green pesticide synthesis, and discloses a novel method for synthesizing grassland spodoptera litura sex pheromone active ingredients (Z)-9-dodecene-1-alcohol acetate, (Z)-9-tetradecene-1-alcohol acetate and (Z)-11-hexadecene-1-alcohol acetate. The method comprises the steps: using bromo-alcohol as a starting raw material; and firstly generating hydroxyl phosphonium salt with triphenylphosphine, then respectively carrying out Wittig coupling reaction with propionaldehyde and valeraldehyde to generate Z-type enol, and finally carrying out acetylation reaction with acetic anhydride to prepare (Z)-9-dodecene-1-alcohol acetate, (Z)-9-tetradecene-1-alcohol acetate and (Z)-11-hexadecene-1-alcohol acetate. According to the method, hydroxyl phosphonium salt is used for Wittig reaction, two steps of hydroxyl protection and deprotection are omitted, the synthetic route is simplified, and the method has the advantages of being environmentally friendly and the like.
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Paragraph 0038-0040
(2020/07/02)
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- PRODUCTION OF FATTY OLEFIN DERIVATIVES VIA OLEFIN METATHESIS
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In one aspect, the invention provides a method for synthesizing a fatty olefin derivative. The method includes: a) contacting an olefin according to Formula I with a metathesis reaction partner according to Formula IIb in the presence of a metathesis catalyst under conditions sufficient to form a metathesis product according to Formula IIIb: and b) converting the metathesis product to the fatty olefin derivative. Each R1 is independently selected from H, C1-18 alkyl, and C2-18 alkenyl; R2b is C1-8 alkyl; subscript y is an integer ranging from 0 to 17; and subscript z is an integer ranging from 0 to 17. In certain embodiments, the metathesis catalyst is a tungsten catalyst or a molybdenum catalyst. In various embodiments, the fatty olefin derivative is a pheromone. Pheromone compositions and methods of using them are also described.
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Paragraph 0392
(2017/06/12)
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- SYNTHESIS OF Z-OLEFIN-CONTAINING LEPIDOPTERAN INSECT PHEROMONES
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The present invention is directed to methods of synthesizing insect pheromones, particularly lepidopteran insect pheromones, their precursors and derivatives from inexpensive, readily available starting materials using olefin metathesis catalysis.
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Paragraph 0177; 0178
(2013/09/12)
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- Concise syntheses of insect pheromones using Z-Selective cross metathesis
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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.
- Herbert, Myles B.,Marx, Vanessa M.,Pederson, Richard L.,Grubbs, Robert H.
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supporting information
p. 310 - 314
(2013/02/23)
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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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- Mono- and dicationic short PEG and methylene dioxyalkylglycerols for use in synthetic gene delivery systems
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A range of monocationic and dicationic dioxyalkylglycerol cytofectins have been synthesised possessing methylene and short n-ethylene glycol spacers. The monocationic compounds were found to be effective in transfections when formulated as lipopolyplexes with peptide and DNA components, in particular with shorter PEG head groups which may have less effect on peptide targeting in the ternary complex. The Royal Society of Chemistry 2008.
- Hurley, Christopher A.,Wong, John B.,Ho, Jimmy,Writer, Michele,Irvine, Scott A.,Lawrence, M. Jayne,Hart, Stephen L.,Tabor, Alethea B.,Hailes, Helen C.
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supporting information; experimental part
p. 2554 - 2559
(2009/02/02)
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- Asymmetric synthesis of long chain α-methyl-β-thiotrifluoromethyl ketones employing the SAMP-/RAMP-hydrazone alkylation methodology
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The enantioselective synthesis of both enantiomers of (Z)-1,1,1-trifluoro-3-methyl-4-thia-13-octadecen-2-one and (Z)-1,1,1-trifluoro-3-methyl-4-thia-13-hexadecen-2-one (ee ≥90%), potential inhibitors of the pheromone action of two major maize pests Sesamia nonagrioides and Ostrinia nubilalis, is described. The key step is based upon a stereoselective alkylation with methyl iodide using the SAMP-/RAMP-chiral auxiliary methodology, followed by deprotection under non-racemization conditions.
- Munoz, Lourdes,Bosch, Ma Pilar,Guerrero, Angel
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p. 651 - 658
(2007/10/03)
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- Use of enyne compounds in the synthesis of insect pheromones
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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
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- OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XLII. SYNTHESIS OF (9Z)-TETRADECENYL ACETATE AND (9Z)-HEXADECENAL FROM (Z,Z)-1,5-CYCLOOCTADIENE
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A stereocontrolled synthesis of (9Z)-tetradecenyl acetate and (9Z)-hexadecenal, which are components of the sex pheromones of the pine (Panolis flammea) and cotton (Heliothis armigera) moths respectively, was realized on the basis of the partial ozonolysis of (Z,Z)-1,5-cyclooctadiene.
- Odinokov, V. N.,Galeeva, R. I.,Ishmuratov, G. Yu.,Kargapol'tseva, T. A.,Sokol'skaya, O. V.,et al.
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p. 1986 - 1989
(2007/10/02)
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- A CONVENIENT SYNTHESIS OF 2,13- AND 3,13-OCTADECADIENYL ACETATES, SEX PHEROMONE COMPONENTS OF THE Synanthedon SPECIES
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The sex pheromone components of several Synanthedon species, 2,13- and 3,13- octadecadienyl acetates (Ic, Id, IIc, IId), have been synthesized following the acetylenic route of chain elongation.Starting from ω-alkyn-1-ols III, the final compounds were constructed in five steps in about 30percent overall yields.Transformation of triple bond containing intermediates into the corresponding (Z)- and (E)-olefins was achieved either by hydrogenation over the P2-Ni catalyst or by using a dispersion of sodium in toluene.The title pheromones were generated in more than 97percent stereoisomeric purity. 1H and 13C NMR data of all derivatives are included.
- Hoskovec, Michal,Saman, David,Koutek, Bohumir
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p. 2270 - 2281
(2007/10/02)
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- Synthesis of (Z)-9-tetradecenyl acetate, the pheromone of the fall armyworm moth from aleuritic acid
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Starting from threo- and erythro-aleuritic acids the derived terminal dicarboxylic acid half-esters have been subjected to a photochemical decarboxylation-iodination reaction to give some useful iodo esters with chain lengths of 15 carbon atoms.A synthesis of (Z)-9-tetradecenyl acetate (13), the pheromone of the fall armyworm moth is reported using the photoreaction for two successive stages from erythro half-ester.
- Subramanian, G. B. V.,Malathi, N.
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p. 806 - 809
(2007/10/02)
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- Selective Cleavage of Dimethylhydrazones to the Carbonyl Compounds Using Silica Gel and its Application in the Synthesis of (Z)-9-Tetradecenyl Acetate
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A new method for the selective hydrolytic cleavage of dimethylhydrazones consists of treatment of the hydrazones with silica gel (pH 6.80) in wet tetrahydrofuran.Utilizing this method as one of the key steps, (Z)-9-tetradecenyl acetate, the pheromone of Spodoptera frugiperda, was synthesized.
- Mitra, R. B.,Reddy, G. Bhaskar
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p. 694 - 698
(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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- SYNTHESES OF ANACARDIC ACIDS AND GINKGOIC ACID
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Syntheses of two anacardic acids , inhibitors of prostaglandin synthetase and of the growth of certain insects, and ginkgoic acid via directive metallation is reported.
- Yamagiwa, Yoshiro,Ohashi, Kinji,Sakamoto, Yoshitaka,Hirakawa, Shinji,Kamikawa, Tadao,Kubo, Isao
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p. 3387 - 3394
(2007/10/02)
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- SYNTHESES A L'AIDE DE SULFONES (XXXVII). SYNTHESE DE TROIS PHEROMONES A UNE DOUBLE LIAISON Z : Z, 8-DDA; Z, 9-DDA; Z, 9-TDA.
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The title compounds Z,8-dodecen-1yl acetate, Z,9-dodecen-1yl acetate and Z,9-tetradecen-1yl-acetate have been synthesized in three efficient steps: the reaction mixture from metalated ω-hydroxy sulfones and appropriate aldehydes was quenched with acetic anhydride yielding a diastereoisomeric mixture of β-acetoxy sulfones.Convergent elimination with powdered sodium hydroxide led to the E vinylic sulfone.Stereospecific hydrogenolysis of the sulfonyl group was carried out with sodium dithionite leading to the unsaturated alcohol (> 99percent Z).
- Julia, Marc,Stacino, Jean-Pierre
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p. 2469 - 2474
(2007/10/02)
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- ALKENYL COPPER REAGENTS-26 CARBOCUPRATION OF ALKYNES BY ORGANOCOPPER REAGENTS BEARING A PROTECTED HYDROXY OR THIOL FUNCTION
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Halohydrins, protected as ethers, acetals or chloro-magnesium alcoholates are sequentially transformed into the Li or Mg reagents and then into copper or cuprate derivatives.Addition to acetylene or propyne is discussed according to various parameters.The alkenyl copper or cuprate species, thus obtained, may react further with various electrophiles, leading to difunctionalized alkenes.
- Gardette, M.,Alexakis, A.,Normant, J. F.
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p. 5887 - 5900
(2007/10/02)
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- Metamorphosis of Castor Oil to Insect Sex-pheromones and Useful Synthons
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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.
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p. 1197 - 1207
(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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- (Z)-9-Tetradecen-1-ol formate and its use as a communication disruptant for Heliothis
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(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.
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