- Method for synthesizing (9Z, 12E)-9,12-tetradecadien-1-ol acetate
-
The invention belongs to the technical field of green pesticide synthesis, and discloses a novel method for synthesizing (9Z, 12E)-9,12-tetradecadien-1-ol acetate. According to the method, malonic acid and 9-bromo-1-nonyl alcohol are used as two starting raw materials. The method comprises the following steps: carrying out a Knoevenagel condensation reaction on malonic acid and propionaldehyde inthe presence of piperidine acetate to generate (E)-3-pentenoic acid, then carrying out lithium aluminum hydride reduction to obtain (E)-3-penten-1-ol, carrying out bromination reaction, and refluxingwith triphenylphosphine in acetonitrile to obtain (E)-3-pentenyltriphenylphosphine bromide; carrying out a PCC oxidation reaction on 9-bromo-1-nonanol to obtain 9-bromononanal, and then reacting the 9-bromononanal with potassium acetate to obtain 9-acetoxynonanal; and finally, carrying out a Wittig reaction on (E)-3-pentenyltriphenylphosphine bromide and 9-acetoxynonanal so as to obtain (9Z, 12E)-9,12-tetradecadien-1-ol acetate. An E-type double bond is constructed by utilizing the Knoevenagel condensation reaction of malonic acid and propionaldehyde, and the method has the advantages of mildreaction conditions, environmental friendliness, simple synthetic route and the like.
- -
-
-
- SYNTHESIS OF PHEROMONES AND RELATED MATERIALS VIA OLEFIN METATHESIS
-
Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.
- -
-
Paragraph 0110
(2018/09/12)
-
- Double-Bond Isomerization: Highly Reactive Nickel Catalyst Applied in the Synthesis of the Pheromone (9 Z,12 Z)-Tetradeca-9,12-dienyl Acetate
-
A highly reactive nickel catalyst comprising NiCl2(dppp) or NiCl2(dppe) with zinc powder, ZnI2 and Ph2PH, was applied in the isomerization of terminal alkenes to Z-2-alkenes. The double-bond geometry of the 2-alkene can be controlled via the reaction temperature to yield the 2-Z-alkenes in excellent yields and high Z-selectivities. The formation of other constitutional isomers, such as 3-alkenes, is suppressed on the basis of the proposed mechanism via a 1,2-hydride shift from the metal to the Ph2P ligand. The nickel-catalyzed isomerization reaction was then applied in the synthesis of (9Z,12Z)-tetradeca-9,12-dienyl acetate, a pheromone with a 2Z,5Z-diene subunit.
- Weber, Felicia,Schmidt, Anastasia,R?se, Philipp,Fischer, Michel,Burghaus, Olaf,Hilt, Gerhard
-
supporting information
p. 2952 - 2955
(2015/06/30)
-
- SYNTHESIS OF Z-OLEFIN-CONTAINING LEPIDOPTERAN INSECT PHEROMONES
-
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.
- -
-
Paragraph 0200; 0201
(2013/09/12)
-
- Concise syntheses of insect pheromones using Z-Selective cross metathesis
-
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.
-
p. 310 - 314
(2013/02/23)
-
- Facile synthesis of mill moth's sex pheromone components
-
An improved method for the preparation of mill moth's sex pheromone components in high diastereomeric purity is described. Copyright Taylor & Francis Group, LLC.
- Hornyanszky, Gabor,Rohaly, Janos,Novak, Lajos
-
p. 1533 - 1540
(2008/09/20)
-
- 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)
-
- 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.
-
p. 238 - 240
(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)
-
- MILD PROTECTION AND DEPROTECTION OF ALCOHOLS AS TER-BUTYL ETHERS IN THE FIELD OF PHEROMONE SYNTHESIS
-
α,ο-Halohydrins and ο-acetylenic alcohols are protected as t-butyl ethers by reaction with isobutene and an acid catalyst : Amberlyst H-15. t-Butyl ethers are, in turn, cleaved to acetates by Ac2O and 10 percent FeCl3 in Et2O solvent.Under these mild conditions conjugated dieneic systems are neither destroyed nor isomerized.
- Alexakis, A.,Gardette, M.,Colin, S.
-
p. 2951 - 2954
(2007/10/02)
-
- SYNTHESES WITH SULFONES XLVII : STEREOSELECTIVE ACCESS TO 1,3- AND 1,4-DIENES THROUGH HYDROGENOLYSIS OF BENZENESULFONYLDIENES. APPLICATION TO PHEROMONE SYNTHESIS.
-
The stereospecific reduction of EE 2-benzenesulfonyl-1,3-dienes to ZE 1,3-dienes with Grignard reagents under transition metal catalysis is described.Hydrogenolysis of the sulfonyl moiety of 2-benzenesulfonyl-1,4-dienes to ZE 1,4-dienes with sodium dithionite is reported.These techniques have been applied to the stereoselective synthesis of (7E, 9Z) dodecadienyl acetate 3d, (9Z, 11E) tetradecadienyl acetate 3e and (9Z, 12E) tetradecadienyl acetate, 6b.
- Cuvigny, T.,Penhoat, C. Herve Du,Julia, M.
-
p. 859 - 872
(2007/10/02)
-
- Synthesis of (9Z, 12E)-9,12-Tetradecadien-1-yl-Acetate
-
Synthesis of 1,4-dienyl acetate (1), a sex pheromone of many lepidopterous insects, has been accomplished.The approach involves carbon-carbon coupling via acetylene route, catalytic partial hydrogenation, reduction of propargylic alcohol to trans allylic alcohol and reductive elimination of mesylate (8).
- Chattopadhyay, A.,Mamdapur, V. R.
-
p. 868 - 869
(2007/10/02)
-
- Pheromones, XXXV. - Stereoselective Syntheses of 1,4-Alkadienes
-
The stereoselective synthesis of 1,4-alkadienes via Julia synthesis, Wittig reaction, Crombie synthesis and methylene interruption of conjugated alkadienylphosphonates is described.
- Bestmann, Hans Juergen,Koschatzky, Karl-Heinrich,Plenchette, Alain,Suess, Joachim,Vostrowsky, Otto
-
p. 536 - 544
(2007/10/02)
-
- Preparation of unsaturated aliphatic insect pheromones using cyclic phosphonium ylids
-
This process relates to the synthesis of unsaturated aliphatic esters useful as insect sex attractants, including gossyplure, the insect sex pheromone of the pink bollworm moth, Pectinophora gossypiella, and intermediates therefor. The process utilizes a cyclic phosphonium (Wittig) reagent.
- -
-
-
- 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)
-
- Process for preparing cis-olefins
-
A process for preparing cis-olefins of the formula STR1 where R is alkyl or alkenyl and R1 is alkyl and alkenyl, both optionally substituted by hydroxy, carbalkoxy or acyloxy, which comprises an ylide solution of the compound R--CH2 --P+ (C6 H5)3 Br- in hexaalkyl phosphoric acid triamide and adding an aldehyde of the formula R1 --CHO.
- -
-
-