- Insect pheromones and their analogs I. Synthesis of the sex attractant of the codling moth
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The synthesis of the sex attractant of the codling moth Laspeyresia pomonella has been performed using as the initial compounds linear dimers of butadiene with methyl acrylate.
- Tolstikov,Dzhemilev,Khusnutdinov
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- A GENERAL AND STEREOSELECTIVE SYNTHESIS OF (E,E)-CONJUGATED DIENES.
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Cis-2,5-disubstituted-2,5-dihydrothiophene-1,1-dioxides, generated by a retro Diels-Alder reaction, lead with high stereoselectivity to (E,E)-1,4-disubstituted-1,3-dienes.The efficiency of this method is illustrated by the synthesis of two dienic insect sex pheromones.
- Bloch, R.,Abecassis, J.
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- Synthesis of dodeca-8E,10E-dien-1-ol - The sex pheromone of Laspeyresia pomonella via the acetolysis of 4-propenyl-1,3-dioxane
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A new scheme has been developed for the synthesis of dodeca-8E,10E-dien-1-ol (the sex pheromone of the codling moth) from sorbyl acetate, available from 4-propenyl-1,3-dioxane through the intermediate diacetate of 3-propenyl-2-oxapentane-1,5-diol.
- Shakova,Zorin,Musavirov,Safarov,Muslukhov,Kharisov,Ishmuratov,Rakhmankulov
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- Stereoselective Cross-Coupling of Grignard Reagents and Conjugated Dienylbromides using Iron Salts with Magnesium Alkoxides
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A convenient procedure allowing iron-catalyzed cross-coupling of alkyl or aryl Grignard reagents and conjugated dienyl bromides is reported, relying on the use of cheap and non-toxic magnesium alkoxides as sole additives. An excellent stereoselectivity is observed in the alkyl-dienyl series. This sequence has been applied to the synthesis of the sex pheromone of codling moth, illustrating its applicability for obtaining targets of industrial interest. Preliminary mechanistic studies carried out on the aryl-dienyl cross-coupling suggest that in situ generated ate homoleptic organoiron(II) species act as catalytically relevant intermediates. A modified preparative method for the realization of THF solutions of dienyl bromides as “ready-to-use” coupling partners is also discussed, circumventing the thermal instability of those derivatives.
- Chourreu, Pablo,Gayon, Eric,Guerret, Olivier,Guillonneau, Lo?c,Lefèvre, Guillaume
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supporting information
p. 4701 - 4706
(2021/09/10)
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- Synthesis method of laspeyresia pomonella sex pheromone
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The invention relates to a synthesis method of laspeyresi pomonella sex pheromone. The method comprises the steps as follows: (1) methanol is added to methyl sorbate as a raw material, and an intermediate A sorbic alcohol is obtained through 5% palladium-carbon catalytic hydrogenation reduction; (2) the intermediate A sorbitol obtained in (1) and acetic anhydride are subjected to a reaction in ethyl acetate, triethylamine and water to obtain an intermediate B sorbic acetate; (3) 6-chlorohexanol is subjected to a reaction with trimethylchlorosilane in toluene in the presence of ethyl acetate and triethylamine, after the reaction, water is added, stirring and layering are performed, and an intermediate C6-chlorohexanol trimethylsilyl ester is obtained; (4) the intermediate B sorbic acetate and the intermediate C6-chlorohexanol trimethylsilyl ester are subjected to a reaction with sodium sand in a toluene solution, then, water and sulfuric acid are dropwise added, layering and rectification are performed, and a target product E8,E10-dodecadiene-1-ol is obtained. The synthesis method has the advantages as follows: the laspeyresi pomonella sex pheromone is synthesized from available rawmaterials, the reaction route is short, and the selectivity and product yield can be increased.
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Paragraph 0030; 0037; 0038; 0039; 0046; 0047
(2019/09/17)
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- SYNTHESIS OF PHEROMONES AND RELATED MATERIALS VIA OLEFIN METATHESIS
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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.
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- (8E, 10E) - 8,10-dodecadienol-1-ol for the preparation of
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The invention discloses a preparation method of (8E, 10E)-8, 10-dodecadienol-1-alcohol. The method comprises the steps of: reacting 6-chlorohexanol with trimethylchlorosilane in the presence of methyl tertiary butyl ether and triethylamine at 0 to 5 DEG C to obtain chloride trimethylethoxysilane; then performing the Grignard reaction on the chloride trimethylethoxysilane to obtain a Grignard agent; and reacting (2E, 4E)-2, 4-hexadiene-1-dryocrassyl acetate with the Grignard agent to obtain (8E, 10E)-8, 10-dodecadienol-1-triethoxysilane; and finally hydrolyzing the (8E, 10E)-8, 10-dodecadienol-1-triethoxysilane to obtain (8E, 10E)-8, 10-dodecadienol-1-alcohol. According to the preparation method, both the purity and the yield of hydroxy-protecting reaction product are relatively high; and the initiating success rate of the Grignard reaction is relatively high, the purity of the coupling reaction product is high.
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Paragraph 0024; 0025
(2017/08/04)
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- SYNTHESIS OF OLEFINIC ALCOHOLS VIA ENZYMATIC TERMINAL HYDROXYLATION
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In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.
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Paragraph 0315; 0320
(2016/01/30)
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- Production of pheromones and fragrances from substituted and unsubstituted 1-alken-3yl alkylates
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Compounds of the formula (I) wherein R2 is a branched or unbranched, saturated or ethylenically mono or di unsaturated aliphatic radical, Z is —CH2OH, —CH2OAc or —CHO, m is a whole positive integer of one or more, and Ac is an acetyl group are synthesized by a process wherein a 1-alken-3-yl alkylate, is reacted with a halo alkanol Grignard reagent.
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Page/Page column 6
(2010/05/13)
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- Metathesis syntheses of pheromones or their components
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The present invention relates to metathesis syntheses for insect sex-attractant pheromones or their components, such as E-5-decenyl acetate, the major component of the Peach Twig Borer pheromone; (5R,6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition attractant pheromone; E9,Z11-hexadecadienal, the pecan nut casebearer moth pheromone; 9-tetradecenyl formate, an analog of the Diamondback Moth (DBM) pheromone; 11-tetradecenyl acetate, the Omnivorous Leafroller (OLR) pheromone; E-4-tridecenyl acetate, the major component of the Tomato Pinworm (TPW) pheromone; E,E-8,10-dodecadienol, the Codling Moth (CM) pheromone. The syntheses preferably employ a Class I-IV metathesis catalyst, entail few reaction steps, use generally commercially available starting materials, and have relatively short process times. These syntheses produce good yields without the need for expensive or sophisticated equipment. The invention also provides an inexpensive route for producing omega-haloalkenols by cross-metathesizing alpha-omega-diacetoxy alkenes and alpha-omega-dihalides to yield omega-haloalkenols, which are easily converted into omega-haloalkanols under traditional hydrogenation methods.
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- Syntheses of the sex pheromone of the codling moth
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Grignard coupling between appropriated synthons afforded (E, E)-8, 10-dodecadien-1-ol (1) the sex attractant pheromone of the Codling moth (Laspeyresia pomonella) a notorious pest of the apple orchards. The synthons used in this paper were (E,E)-2,4-hexadien-1-yl bromide (4, sorbyl bromide), (E,E)-2,4-hexadien-1-yl acetate (5, sorbyl acetate) and 6-bromohexan-1-ol protected as tetrahydropyranyl ether (8) or trimethylsilyl ether (9). The product 1 and the intermediate synthons were characterised by their IR, 1H and 13C-NMR and MS spectra.
- Popovici, Nicolae
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p. 221 - 224
(2007/10/03)
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- A NEW SYNTHESIS OF THE PHEROMONE OF THE CODLING MOTH - DODECA-8E,10E-DIEN-1-OL - VIA AN ENYNIC INTERMEDIATE
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A new method has been developed for the synthesis of the main component of the pheromone of the codling moth - dodeca-8E,10E-dien-1-ol - using in the key stages Wittig reactions and the trans-hydride reduction of the triple bond of an intermediate enynol.
- Khrimyan, A. P.,Makaryan, G. M.,Ovanisyan, A. L.,Wimmer, Z.,Romanyuk, M.,et al.
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p. 103 - 108
(2007/10/02)
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- Preparation of dien-1-ols, 9-hydroxydodec-10-enyl 1-tert-butyl ether and use thereof as an intermediate for synthesizing 8,10-dodecadienol
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Dien-1-ols of the general formula I STR1 where the radicals R1 to R7 are identical to or different from one another and each is hydrogen or straight-chain or branched alkyl or 1-12 carbon atoms and n is 1-14, are prepared by dehydrating a hydroxylalkenyl tert-butyl ether of the formula II STR2 in the presence of an acidic catalyst at elevated tempertures and essentially at the same time splitting off the tert-butyl protective group, as is 9-hydroxydodec-10-enyl 1-tert-butyl ether which is useful as an intermediate for synthesizing 8,10-dodecadienol.
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- Stereoselective Synthesis of (2E,4E)- and (2Z,4E)-2,4-Alkadienoates by the Ester Enolate Claisen Rearrangement of (E)-1-Alkyl-3-trimethylsilyl-2-propenyl Glycolates Followed by the Peterson Reaction
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The ester enolate Claisen rearrangement of (E)-1-alkyl-3-trimethylsilyl-2-propenyl glycolates gave (E)-erythro-2-hydroxy-3-trimethylsilyl-4-alkenoates with high diastereoselectivity, which were stereoselectively converted into (2E,4E)- and (2Z,4E)-2,4-alkadienoates by the Peterson reaction.
- Sato, Toshio,Tsunekawa, Hiroshi,Kohama, Hiromasa,Fujisawa, Tamotsu
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p. 1553 - 1556
(2007/10/02)
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- SYNTHESIS WITH SULFONES XLIV. STEREOSELECTIVE PREPARATION OF EE 1,3-DIENES BY ELIMINATION OF BENZENESULFINIC ACID FROM E HOMOALLYLIC SULFONES.
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The preparation of pure E and Z homoallylic 1,1-disulfones followed by the stereoselective reduction of one sulfonyl moiety afforded pure E and Z homoallylic sulfones respectively.Basic elimination with tBuOK in THF gave the corresponding 1,3-dienes in good yield.This reaction, highly stereoselective in the case of E homoallylic sulfones, has been used in the synthesis of (8E,10E) 8,10-dodecadienol, 10 and (9E)9,11-dodecadienol, 15, insect pheromone components.
- Penhoat, C. Herve Du,Julia, M.
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p. 4807 - 4816
(2007/10/02)
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- Stereoselective Synthesis of (E)-, (E,Z)-, and (E,E)-Conjugated Dienes via Alkylation of 3-Sulfolenes as the Key Step
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A new stereoselective method is presented for synthesizing (E)-, (E,Z)-, and (E,E)-conjugated dienes via alkylation of 3-sulfolenes as the key step.Direct alkylation of 3-sulfolene at the 2-position proceeds with good yields when labile sulfolene α-carbanion is generated in the presence of alkyl iodides in THF-HMPA solution at -78 deg C.Alkylation of 2-alkyl-3-sulfolenes gives trans-2,5-dialkyl-3-sulfolenes with 100percent regioselectivity and more than 90percent stereoselectivity.Desulfonylation of trans-3,5-disubstituted 3-sulfolenes is examined in detail, and the conditions to give stereoselectively the corresponding (E,Z)-and (E,E)-conjugated dienes are found.Applying the method, three insect pheromones, (E)-9,11-dodecadien-1-yl acetate, a sex pheromone of the red bollworm moth, (E,E)-8,10-dodecadien-1-ol, a sex pheromone of the codling moth, and (E,E)-11,13-hexadecadienal, a sex pheromone of the cabbage webworm, are easily synthesized by starting with 3-sulfolene with nearly 100percent stereoselectivity.Synthesis of cis-3,4,5-trisubstituted cyclohexenes using 2-substituted 3-sulfolenes as the diene synthons is also described.
- Yamada, Sachiko,Ohsawa, Hideto,Suzuki, Takayoshi,Takayama, Hiroaki
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p. 4934 - 4940
(2007/10/02)
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- Systematic Syntheses and Charactarization of Dodecadien-1-ols with Conjugated Double Bond, Lepidopterous Sex Pheromones
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Four geometrical isomers of 5,7-, 6,8-, 7,9- and 8,10-dodecadein-1-ols were systematically synthesized by two routes.One involved the Wittig reaction between (E)-2-alkenal and a phosphorane with an appropriate carbon chain, and yielded a mixture of (E,Z)- and (E,E)-isomers in a ratio of ca. 3:2.The other route comprised of the Wittig reaction of a 2-alkynal and the stereoselective reduction of the triple bond to a (Z)-double bond via hydroboration with dicyclohexylborane to give a mixture of (Z,Z)- and (Z,E)-isomers in a ratio of 6:1 10:1.Both the mixtures were separately chromatographed on a silica gel column impregnated with silver nitrate to give four geometrically pure isomers.With 9,11-diene they were analysed by GC on a capillary column, HPLC, silver nitrate impregnated TLC, and 13C NMR.
- Ando, Tetsu,Kurotsu, Yuichi,Kaiva, Mieko,Uchiyama, Masaaki
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p. 141 - 148
(2007/10/02)
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- THE BETAIN-YLID ROUTE TO TRANS-ALKENOLS
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The trans-selective variant of the Wittig reaction can be successfully applied to the synthesis of alkenol-type pheromones.
- Schlosser, Manfred,Tuong, Huynh Ba,Schaub, Bruno
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p. 311 - 314
(2007/10/02)
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- INSECT PHEROMONES AND THEIR ANALOGUES. X. THE STEREODIRECTED SYNTHESIS OF (E,E)-DODECA-8,10-DIENOL
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A passage from deca-1,4,9-triene (I) to (E,E)-dodeca-8,10-dienol (II) in five stages with an overall yield of 23percent has been found by the selective transformations of deca-1,4,9-trien-1-yltrimethylsilane.Thus, under mild conditions, by the hydrogenation of (I) with the aid of 9-borabicyclononane (9-BBN) followed by oxidation with H2O2 (E,E)-deca-6,8-dienol was obtained with a yield of 60percent, and this was converted quantitatively into the corresponding tosylate.The ethynylation of the latter with lithium acetylide gave (E,E)-dodecadien-1-yne (III) on a Lindlar catalyst followed by the reaction of the resulting triene with 9-BBN, as described above for (I) led to the desired codlemone (II).The IR, PMR, 13C NMR, UV, and mass spectra of the compound obtained are discussed.
- Odinokov, V. N.,Balezina, G. G.,Ishmuratov, G. Yu.,Salimgareeva, I. M.,Bogatova, N. G.,et al.
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p. 486 - 489
(2007/10/02)
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- Synthesis of Dienic Pheromones of Codling Moth and Grape Vine Moth
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The synthesis of pheromones 8E,10E-dodecadien-1-ol (I) and 7E,9Z-dodecadien-1-yl acetate (II) via sulphone intermediates has been accomplished.The α-anions of the sulphones (2) and (10) on reaction with the aldehydes (5) and (11) followed by acetylation of the resulting products in situ afford the β-acetoxysulphones (6) and (12) respectively.Reductive elimination of 6 and 12 with Na/Hg provide the dienic compounds, which on depyranylation and acetolysis yield I and II respectively.
- Kulkarni, S. M.,Mamdapur, V. R.,Chadha, M. S.
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p. 1208 - 1210
(2007/10/02)
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- STEREOSELECTIVE SYNTHESIS OF (E)-, (E,Z)- AND (E,E)-CONJUGATED DIENES VIA ALKYLATION OF 3-SULFOLENES AS KEY STEP
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Stereoselective method for synthesizing (E)-, (E,Z)- and (E,E)-conjugated dienes via alkylation of 3-sulfolenes as key step is developed.Sex pheromones with (E)- and (E,E)-conjugated diene structures are synthesized with exclusively high stereoselectivity by applying the method.
- Yamada, Sachiko,Ohsawa, Hideto,Suzuki, Takayoshi,Takayama, Hiroaki
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p. 1003 - 1006
(2007/10/02)
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- SYNTHESIS OF 8E,10E-DODECADIEN-1-OL FROM METHYL 2,5-HEPTADIENOATES
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A method is proposed for the synthesis of 8E,10E-dodecadien-1-ol (the pheromone of the codling moth) from methyl 2Z,5E-heptadienoate and from a mixture of 2E,5Z- and 2Z,5Z-heptadienoic esters.Prototropic isomerization of the methyl esters of the 2Z,5E- and of the mixture of 2E,5Z- and 2Z,5Z-heptadienoic acids takes place quantitatively with the formation of methyl 3E,5E-heptadienoate and methyl 3E,5Z-heptadienoate respectively.
- Zakharkin, L. I.,Babich, S. A.
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p. 1995 - 2000
(2007/10/02)
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- Simple, Stereospecific Syntheses of Some Insect Pheromones using the -Fe(CO)3 Protecting Group
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(Diene)Fe(CO)3 complexes have been used for totally stereospecific syntheses of insect pheromones having (E)- and (E,E)-1,3-diene skeletons.
- Knox, Graham R.,Thom, Ian G.
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p. 373 - 374
(2007/10/02)
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- Synthesis of codling moth attractant
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Sterospecific synthesis of an attractant for the codling moth by reacting sorbic aldehyde with an organo-metallic reagent to yield a 1-ether of trans-8-trans-10-dodecadiene-1,7-diol which is reduced via a 7-sulfonic acid ester to yield an ether of trans-8-trans-10-dodecadiene-1-ol and hydrolyzed to trans-8-trans-10-dodecadien-1-ol. SPC1
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