CN115466162A - Process for preparing (cis ) -3,6, 9-nonadecatriene - Google Patents

Process for preparing (cis ) -3,6, 9-nonadecatriene Download PDF

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CN115466162A
CN115466162A CN202211271546.1A CN202211271546A CN115466162A CN 115466162 A CN115466162 A CN 115466162A CN 202211271546 A CN202211271546 A CN 202211271546A CN 115466162 A CN115466162 A CN 115466162A
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solution
reaction
nonadecatriene
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oxy
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刘红霞
荆小院
郝玉杰
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Inner Mongolia Nongxin Technology Co ltd
Shanxi Yuanjie Technology Co ltd
Chongzhutou Suzhou Biotechnology Co ltd
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Inner Mongolia Nongxin Technology Co ltd
Shanxi Yuanjie Technology Co ltd
Chongzhutou Suzhou Biotechnology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/34—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen reacting phosphines with aldehydes or ketones, e.g. Wittig reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

Abstract

The invention provides a preparation method of (cis ) -3, 6, 9-nonadienyl. The preparation method comprises the following steps: taking 1-tetrahydropyranoxy-3-butyne as a raw material, reacting with p-toluenesulfonic acid-2-pentyne-1-alcohol ester to generate 3, 6-nonadien-1-alcohol, then hydrogenating under the catalysis of Lindlar to generate (Z, Z) -3, 6-nonadien-1-alcohol, carrying out bromination reaction on the product to generate (Z, Z) -1-bromo-3, 6-nonadien, then reacting with triphenylphosphine to generate a phosphonium salt, and finally carrying out Wittig reaction with decanal to generate (Z, Z, Z) -3, 6, 9-19: Hy. The obtained product is determined as a target product (Z, Z, Z) -3, 6, 9-19: Hy. after spectral analysis. Compared with the traditional method, the preparation method provided by the invention has the advantages that a high-purity analytical reagent is adopted as the raw material, so that the reagent is cheap and easy to obtain; the reaction conditions are mild, and the operation is simple and convenient; and the purity of the product is up to 90% or above, and the contained geometric isomer is reduced by 80% compared with the traditional method.

Description

Process for preparing (cis ) -3,6, 9-nonadecatriene
Technical Field
The invention belongs to the field of pest control, and particularly relates to a preparation method of (cis, cis-) 3,6, 9-nonadecatriene.
Background
The family of the rulers is the next to noctuidae in the order of lepidoptera, with about 12,000 species worldwide and about 43 species in china. The adult ulexidae has slender body, wide and thin wing, various tentacle shapes, main nocturnal character and high phototaxis, and only individual species are active only in the daytime. The dipteraceae larvae mainly damage fruit trees, tea trees, mulberry trees, cotton, forest trees and the like.
The current methods for preventing and controlling inchworm pests mainly comprise the following steps: natural enemies are used for preventing and treating, for example, the trichogramma dendrolimi and the Chouioia cunea can be used for preventing and treating the ectropis obliqua, the prevention and treatment effect can reach about 50 percent, and the prevention and treatment effect is obvious; the spring looper can also be trapped and killed by using an insecticidal lamp, so that the population density of the spring looper can be reduced, or an adhesive tape is wound on the tree for control, so as to prevent the female moth from laying eggs on the tree; furthermore, the biological pesticide is used for preventing and controlling, for example, the 0.6 percent matrine aqueous agent can prevent and control spring geometrid with good effect, and the effect of using 45 percent of propyl bromide phoxim emulsifiable solution to prevent and control wood geometrid 27217is good.
The sex pheromone components of the ulexidae insects which are identified at present are mainly unsaturated hydrocarbon compounds and corresponding epoxy derivatives or hydrocarbon compounds with methyl side chains, and generally contain 2-4 double bonds (the types of 3 double bonds are the most), namelyAnd chiral isomerism (S or R conformation) to form the racemate. Wherein (cis ) -3,6, 9-nonadecatriene is a main pheromone component of the insect pests in the family of the Dipteraceae and is present inAgriopis marginaria(Fabricius, 1776), betula platyphylla Smith,Ascotis selenaria ([Denis & Schiffermüller], 1775)，)，Cabera erythemaria (Guenee, 1857)，Caripeta angustiorata (Walker, 1863)，Colotois pennaria (Linnaeus, 1761)，Erannis defoliaria (Clerck, 1759)，Eufidonia convergaria (Walker, 1860)，Hypagyrtis piniata (Packard, 1870)，Ourapteryx sambucaria (Linnaeus, 1758)，Paleacrita vernata (Peck, 1795)，Peribatodes rhomboidaria ([Denis & Schiffermüller]1775), for the traditional method for synthesizing (cis ) -3,6, 9-nonadecatriene (Z3Z 6Z9-19 hy), such as the generation and prevention technology of gaultheria zizanoides, zhang showa, wanglihong, scientific research in forestry S436.65, mainly uses linolenic acid as raw material, and prepares cis, cis) -3,6, 9-nonadecatriene after coupling with methyl magnesium bromide grignard reagent after reduction and bromination. Because the raw material has low purity and contains a large amount of homologous compounds and isomer impurities with similar boiling points and chemical properties, the purity of the product is often lower than 20 percent, and the activity in bioassay is poor.
Disclosure of Invention
An object of the present invention is to provide a process for producing (cis ) -3,6, 9-nonadecatriene, and to provide at least the advantages which will be described later.
Another object of the present invention is to provide a process for preparing (cis ) -3,6, 9-nonadecatriene, which comprises reacting 1-tetrahydropyranyloxy-3-butyne as a raw material with 2-pentyn-1-ol p-toluenesulfonate to produce 3, 6-nonadien-1-ol, followed by hydrogenation under the catalysis of Lindlar to produce (Z, Z) -3, 6-nonadien-1-ol, followed by bromination to produce (Z, Z) -1-bromo-3, 6-nonadiene, (Z, Z) -1-bromo-3, 6-nonadiene reacting with triphenylphosphine to produce phosphonium salt, and finally reacting with decanal by wittig reaction to produce (Z, Z) -3,6,9-19 hy, wherein the obtained product is determined as the target product (Z, Z) -3,6,9-19 hy after spectroscopic analysis, and has high purity as a raw material, and is easy to obtain a cheap reagent; the reaction condition is mild, and the operation is simple and convenient; the purity of the product is as high as more than 90%, and the geometric isomer contained in the product is reduced by 80% compared with that in the traditional method.
The technical scheme of the invention is as follows:
a process for preparing (cis ) -3,6, 9-nonadecatriene comprising the steps of:
preparing 3, 6-nondiyne-1-alcohol by using 1-tetrahydropyrrolyl-oxy-3-butyne and p-toluenesulfonic acid-2-pentyne-1-alcohol ester;
preparing (Z, Z) -3, 6-nonadien-1-ol by using the ethanol solution of the 3, 6-nonadiyne-1-ol, lindlar catalyst and quinoline;
carrying out bromination reaction on the (Z, Z) -3, 6-nonadiene-1-alcohol to obtain (Z, Z) -1-bromo-3, 6-nonadiene;
reacting the (Z, Z) -1-bromo-3, 6-nonadiene and triphenylphosphine to obtain (Z, Z) -3, 6-nonadienyl triphenyl phosphine bromide;
(cis ) -3,6, 9-nonadecatriene was obtained using the (Z, Z) -3, 6-nonadienyl triphenyl phosphine bromide, hexamethylphosphoric triamide, and sodium bis (trimethylsilyl) amide.
Preferably, the preparation method of (cis ) -3,6, 9-nonadecatriene, wherein the preparation of 3, 6-nonadiyn-1-ol by using 1-tetrahydropyrrolyl-oxy-3-butyne and p-toluenesulfonic acid-2-pentyne-1-ol ester comprises the following steps:
24.0 g of 1-tetrahydropyrrolyl-oxo-3-butyne was weighed out and dissolved in 100mL of dry, anhydrous THF. Slowly dropping an ethylmagnesium bromide (2M, THF) solution with stirring under ice bath conditions, wherein the dropping time is 1 hour, the molar ratio of the 1-tetrahydropyrrolyl-oxy-3-butyne to the ethylmagnesium bromide is 1.2, after the dropwise addition is completed, continuously stirring the reaction mixture for about 1.5 hours, adding 0.86 g of cuprous bromide, continuously stirring for half an hour, slowly dropping a THF (50 mL) solution of p-toluenesulfonic acid-2-pentyn-1-ol ester (36 g) into the bottle, increasing the temperature to room temperature after the addition is completed, and continuously stirring for 1.5 hours, wherein the volume ratio of the THF solution of the p-toluenesulfonic acid-2-pentyn-1-ol ester to the volume of the 1-tetrahydropyrrolyl-oxy-3-butyne solution is 1:2;
after the reaction is finished, the reaction solution is mixed with a 1-tetrahydropyrrolyl-oxy-3-butynyl solution in a volume ratio of 1:1, separating out an organic layer, extracting a water layer twice with diethyl ether, and finally combining organic phases, wherein the volume ratio of the diethyl ether to the 1-tetrahydropyrrolyl-oxy-3-butynyl solution is 2:1;
the combined organic phases were washed three times with distilled water, dried overnight with anhydrous magnesium sulfate powder, and the volume ratio of distilled water to 1-tetrahydropyrrolyl-oxy-3-butynyl aqueous solution was 2:1;
filtering to remove the drying agent, and concentrating to obtain a crude product of 1-tetrahydropyranyl-oxy-3, 6-nonadiyne;
hydrolyzing the crude product with a methanol solution of p-toluenesulfonic acid with a volume concentration of 2%, and stirring the mixture to react at 23 ℃ for about 18 hours, wherein the volume ratio of the methanol solution of p-toluenesulfonic acid to the 1-tetrahydropyrrolyl-oxy-3-butyne solution is 2:1;
after the reaction is finished, adding a saturated solution of sodium bicarbonate to be neutral, filtering, and concentrating to remove methanol;
dissolving the residue with water, extracting with diethyl ether for three times, mixing to obtain organic phase, drying with anhydrous magnesium sulfate, concentrating to obtain crude alcohol, and vacuum distilling to obtain 3, 6-nonadiyne-1-ol, wherein the volume ratio of ethanol to 1-tetrahydropyrrolyl-oxy-3-butyne solution is 3:1.
preferably, the preparation of (Z, Z) -3, 6-nonadien-1-ol using the ethanolic solution of 3, 6-nonadien-1-ol, lindlar catalyst and quinoline in the preparation method of (cis ) -3,6, 9-nonadien-1-ol comprises:
stirring and mixing 100mL of 3, 6-nonadiyne-1-alcohol ethanol solution, 2.0 g of Lindlar catalyst and 0.5 mL of quinoline, introducing hydrogen, stirring at room temperature, absorbing hydrogen, and keeping the reaction process for 2 hours, wherein the concentration of the 3, 6-nonadiyne-1-alcohol ethanol solution is 1.4mol/L;
after the reaction is finished, filtering the catalyst, distilling to remove ethanol, dissolving the crude product in diethyl ether, washing with 100mL of 1N hydrochloric acid, 100mL of saturated sodium bicarbonate and 200mL of saturated sodium chloride aqueous solution respectively, and adding anhydrous magnesium sulfate to dry the organic phase; after removing the ether by rotary evaporation, distillation was carried out under reduced pressure to give 16.5 g of (Z, Z) -3, 6-nonadien-1-ol.
Preferably, in the method for preparing (cis ) -3,6, 9-nonadecatriene, the bromination reaction of the (Z, Z) -3, 6-nonadien-1-ol to obtain (Z, Z) -1-bromo-3, 6-nonadien comprises the following steps:
(Z, Z) -3, 6-nonanediol-1-ol (7.0 g) and 20g of carbon tetrabromide (20 g) were dissolved in 200mL of methylene chloride, 18g of triphenylphosphine was added in three portions and the reaction was stirred in an ice bath for 1.5 hours, then methylene chloride was distilled off, the product was extracted with n-hexane (4 x 20 mL) three times, the organic phases were combined, all the solvent was removed by concentration, and 8.2g of (Z, Z) -1-bromo-3, 6-nonanediol was obtained by distillation under reduced pressure.
Preferably, the method for preparing (cis ) -3,6, 9-nonadecatriene, wherein the (Z, Z) -1-bromo-3, 6-nonadienyl triphenyl phosphonium bromide is obtained by reacting (Z, Z) -1-bromo-3, 6-nonadiene and triphenylphosphine comprises:
and (3) mixing the following components in percentage by mass: 8, (Z, Z) -1-bromo-3, 6-nonane diline and triphenylphosphine are mixed, then argon is introduced, and the mixture is heated and stirred in an oil bath for 40 hours, and the temperature is kept at 75 ℃;
after the reaction, the crude product was dissolved in dichloromethane and transferred to a round-bottomed flask, the dichloromethane was distilled off, the residual solid portion was washed off with diethyl ether to remove excess triphenylphosphine, and 13.0g of viscous (Z, Z) -3, 6-nonadienyltriphenylphosphonium bromide was obtained by distilling off the diethyl ether.
Preferably, the method for preparing (cis ) -3,6, 9-nonadecatriene comprises the following steps of:
cooling a mixed solution consisting of 15mL of hexamethylphosphoric triamide, THF25mL and 3.2g of (Z, Z) -3, 6-nonadienyl triphenyl phosphonium bromide to-45 ℃, adding 1.06 g of bis (trimethylsilyl) sodium amide under stirring, continuing stirring for 30 minutes after the reaction solution becomes reddish brown, and dropwise adding 0.89 g of decanal;
after stirring for about three hours, slowly raising the temperature to 0 ℃, adding 30mL of distilled water into the reaction product, extracting the reaction product for three times by using n-hexane (3 x 20 mL), and finally combining the reaction product into an organic phase;
washing the organic phase with distilled water, drying with anhydrous magnesium sulfate, and concentrating to obtain crude (cis ) -3,6, 9-nonadecatriene;
the crude product was separated by column chromatography on silica gel using petroleum ether as eluent to give (Z, Z, Z) -3,6, 9-nonadecatriene 0.95g.
The invention has the beneficial effects that:
1. a series of structurally similar compounds can be synthesized according to the method of the invention. Provides a simple and effective method for preparing the compounds.
2. The compound synthesized by the invention is one of the components of sex pheromones of a plurality of insects in the family of the Plutella xylostella, and can be widely used for the identification and the biological activity evaluation of the sex pheromones of the insects in the family.
3. The product of the invention can be used for the comprehensive control of the dipteraceae pests, reduces the harm and reduces the environmental pollution caused by pesticide control.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a synthesis scheme of one example of a process for preparing (cis ) -3,6, 9-nonadecatriene provided by the present invention;
FIG. 2 is a gas chromatogram of (Z, Z, Z) -3,6,9-19 prepared by the present invention;
FIG. 3 is a mass spectrum of (Z, Z, Z) -3,6,9-19, hy, obtained by the present invention.
Detailed Description
The present invention is described in further detail below to enable those skilled in the art to practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
As shown in figure 1, the method comprises the steps of taking 1-tetrahydropyranyloxy-3-butyne as a raw material, reacting the raw material with p-toluenesulfonic acid-2-pentyne-1-alcohol ester to generate 3, 6-nonadiene-1-alcohol, then hydrogenating the reaction product under Lindlar catalysis to generate (Z, Z) -3, 6-nonadiene-1-alcohol, carrying out bromination reaction on the product to generate (Z, Z) -1-bromo-3, 6-nonadiene, reacting the product with triphenylphosphine to generate phosphonium salt, and finally carrying out Wittig reaction on the product with decanal to generate (Z, Z, Z) -3,6,9-19 Hy, wherein the obtained product is determined as a target product (Z, Z, Z) -3,6,9-19 Hy.
The medicines and instruments used in the present invention are shown in tables 1 and 2.
TABLE 1 description of the respective drugs
Medicine and its preparing process Purity of Manufacturer of the product
1-tetrahydropyranyloxy-3-butyne 99% SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
Ethyl magnesium bromide AR96% SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
Quinolines 99.99% Shanghai Swallow dance Biotech Co., ltd
Linder catalyst Analytical purity SINOCOMPOUND CATALYSTS Co.,Ltd.
Carbon tetrabromide 99.9% SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd.
Triphenylphosphine and its use Analytical purity TCI
Tetrahydropyrans 99.9% Shandong Weiming chemical Co Ltd
Cuprous bromide Analytical purity Suzhou bin chemical Co., ltd
Hexamethylphosphoric triamide 99.9% Chemical industry for good faith and credibility of Shijiazhuang
Table 2 description of the respective instruments
Instrument for measuring the position of a moving object Model number Company(s)
Gas chromatograph GC-MS Agela Technologies, toronto, USA
Electric mixer BLD0-17-1.1KW type Environmental protection equipment strength factory in Yixing city Nuode
Rotary evaporator HPG-9245 type Nantong tri Crystal Glass Instrument Co.,Ltd.
Temp. -regulating electric heating jacket ZNBC type Henan Jiangyi Kerui instruments ltd
Analytical balance ZA120R4 type Shanghai Zan Wei-Jie-Liang Co Ltd
Ultrasonic cleaner BKE-1002T type Hangzhou Boke ultrasonic Equipment Ltd
Circulating water type multipurpose vacuum pump ZILMET type Dongguan City hongkong vacuum equipment Co Ltd
Electric heating constant temperature blast air drying box DHG type Shanghai third forest electronic technology Co., ltd
Vacuum oil pump FPL type Shanxi Boshan Pump industry Co., ltd
The experimental method of the invention is as follows:
1 gas chromatography-Mass Spectrometry conditions
GC, thermo company (Trace 1300) in USA, TG-5 (30 m.times.0.25 mm.times.0.25 μm,5% Phenyl methyl polysiloxane) carrier gas mode is nitrogen.
The chromatographic temperature-raising program is as follows: maintaining at 40 deg.C for 2 min, heating to 160 deg.C at 4 deg.C.min-1, heating to 270 deg.C at 20 deg.C.min-1, and maintaining for 3 min.
MS: the ionization mode of mass spectrum of EI (Electron ionization) of Thermo company (ISQ) in America, the scanning speed of 70eV, the scanning range of 30-600 m/z, the quadrupole temperature of 150 ℃, the ion source temperature of 280 ℃ and the emission current of 150 muA. And (3) carrying out full-scan scanning on the mass spectrogram by adopting an NIST standard spectral library system, searching substances corresponding to each spectral peak in the qualitative mass spectrogram by using a computer, and giving out possible substance molecular structures and relative contents according to the similarity.
2. Synthesis procedure
2.1.3 preparation of 6-nonyldiyn-1-ol
24.0 g of 1-tetrahydropyrrolyl-oxo-3-butyne was weighed, dissolved in 100mL of dry anhydrous THF, transferred to a 250mL three-necked flask, equipped with a stirrer and a condenser, and protected with N2. Under ice-bath conditions, a solution of ethyl magnesium bromide (2M, THF) was slowly added dropwise with stirring over 1 hour. After the addition was complete, the reaction mixture was stirred for about 1.5 hours, 0.86 g of cuprous bromide was added, and a solution of 2-pentyne-1-ol p-toluenesulfonate (36 g) in THF (50 mL) was slowly added dropwise with stirring for half an hour, allowed to warm to room temperature, and stirred for 1.5 hours. After the reaction, the reaction was terminated with 100mL of a saturated ammonium bromide solvent, and the organic layer was separated, the aqueous layer was extracted twice with ether, and finally the organic phases were combined, washed three times with distilled water, and dried overnight with anhydrous magnesium sulfate powder. Filtering to remove a drying agent, and concentrating to obtain a 1-tetrahydropyranyl oxy-3, 6-nonadiyne crude product;
the crude product was hydrolyzed with 2% p-toluenesulfonic acid solution in methanol and stirred at 23 ℃ for about 18 hours. After the reaction, saturated solution of sodium bicarbonate was added to neutrality, after filtration, methanol was removed by concentration, the obtained residue was dissolved in water, extracted with diethyl ether three times, the organic phases were combined, dried over anhydrous magnesium sulfate, concentrated to obtain crude alcohol, and distilled under reduced pressure to obtain 17.5g of 3, 6-nonadiyne-1-ol.
2.2 Preparation of (Z, Z) -3, 6-nonanedi-1-ol
Into a 250mL three-necked round bottom flask equipped with an electromagnetic stirrer were added 100mL of an ethanol solution of 3, 6-nonadiyn-1-ol, 2.0 g of Lindlar catalyst and 0.5 mL of quinoline, and after stirring and mixing, hydrogen was introduced, and hydrogen absorption was carried out with stirring at room temperature, and the reaction was continued for 2 hours. After the reaction is finished, filtering the catalyst, distilling to remove ethanol, dissolving the crude product in diethyl ether, washing with 100mL of 1N hydrochloric acid, 100mL of saturated sodium bicarbonate and 200mL of saturated sodium chloride aqueous solution respectively, and adding anhydrous magnesium sulfate to dry the organic phase; after removing the ether by rotary evaporation, distillation was carried out under reduced pressure to give 16.5 g of (Z, Z) -3, 6-nonanediol-1-ol.
2.3 Preparation of (Z, Z) -1-bromo-3, 6-nonanediene
In a 500mL three-necked flask, (Z, Z) -3, 6-nonanediol (7.0 g) and 20g of carbon tetrabromide (20 g) were charged in 200mL of methylene chloride under a cold bath, and after stirring and reacting for 1.5 hours in an ice bath with 18g of triphenyl phosphine added three times, methylene chloride was distilled off, the product was extracted with n-hexane (4X 20 mL) three times, the organic phases were combined, and all the solvent was removed by concentration, and 8.2g of (Z, Z) -1-bromo-3, 6-nonanediol was obtained by distillation under reduced pressure.
2.4 Preparation of (Z, Z) -3, 6-nonadienyl triphenyl phosphonium bromide
6.27g of (Z, Z) -1-bromo-3, 6-nonanediene (30.9 mmol) and 8.5g of triphenylphosphine (32.5 mmol) are introduced into a 100mL three-necked flask, argon is introduced, and the oil bath is heated and stirred for 40 hours, the temperature being maintained at 75 ℃. After the reaction, the crude product was dissolved in methylene chloride and transferred to a round-bottomed flask, methylene chloride was distilled off, the remaining solid portion was washed off with diethyl ether to remove excess triphenylphosphine, and 13.0g of (Z, Z) -3, 6-nonadienyl triphenylphosphonium bromide was distilled off to obtain a viscous form.
2.5 Preparation of (Z, Z, Z) -3,6, 9-nonadecatriene
Adding a mixed solution consisting of 15mL of hexamethylphosphoric triamide, THF25mL and 3.2g of (Z, Z) -3, 6-nonadienyl triphenyl phosphonium bromide into a 250mL three-neck flask, cooling to-45 ℃, adding 1.06 g of bis (trimethylsilyl) sodium amide under stirring, stirring until the reaction solution becomes reddish brown, continuing to stir for 30 minutes, and then dropwise adding 0.89 g of decanal; after the addition, the reaction is stirred for about three hours, the temperature is slowly raised to 0 ℃,30 mL of distilled water is added into the reaction product, the mixture is extracted by n-hexane (3 x 20 mL) for three times, and finally the organic phase is combined; washing the organic phase with distilled water, drying with anhydrous magnesium sulfate, and concentrating to obtain a crude product; the crude product was separated by column chromatography on silica gel using petroleum ether as eluent to give 0.95g of (Z, Z, Z) -3,6, 9-nonadecatriene.
3. Analysis of results
3.1.1 (Z, Z, Z) -3,6,9-19 Hy gas chromatography analysis
The analysis of the above-mentioned product (Z, Z, Z) -3,6, 9-19H by GC-MS type gas chromatography was carried out as shown in FIG. 2, and the retention time on a TG-5 column was 27.18min.
3.1.2 Mass Spectrometry of the Hypecoridae sex pheromone component (Z, Z, Z) -3,6,9-19
As shown in FIG. 3, the peak of the base is m/Z262, the molecular formula is Cl9H34, the fragment peaks of the more abundant characteristic ions are m/Z260, m/Z206, m/Z148, m/Z133, m/Z119, m/Z105, m/Z93, m/Z91, m/Z79, m/Z55, m/Z43 and the reported Z 3 Z 6 Z 9 Mass spectral data of-19.
Discussion 4
The experimental design uses 1-tetrahydropyranyl-oxy-3-butyne as initial raw material, the p-toluenesulfonic acid-2-pentyne-1-alcohol ester reacts to obtain 3, 6-nonadiene-1-alcohol, the reaction is carried out by catalytic hydrogenation and bromination respectively, the reaction is carried out with triphenylphosphine to generate phosphonium salt, finally the phosphonium salt and decanal are subjected to Wittig reaction to obtain a final product, and the final product is correct after gas chromatography and mass spectrometry.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the details shown in the description and the examples, which are set forth, but are fully applicable to various fields of endeavor as are suited to the particular use contemplated, and further modifications will readily occur to those skilled in the art, since the invention is not limited to the details shown and described without departing from the general concept as defined by the appended claims and their equivalents.

Claims (6)

1. A method for preparing (cis ) -3,6, 9-nonadecatriene, which is characterized by comprising the following steps:
preparing 3, 6-nonadiyne-1-ol from 1-tetrahydropyranyl-oxy-3-butyne and p-toluenesulfonic acid-2-pentyne-1-ol ester;
preparing (Z, Z) -3, 6-nonadien-1-ol using the ethanolic solution of 3, 6-nonadiyn-1-ol, lindlar's catalyst, and quinoline;
carrying out bromination reaction on the (Z, Z) -3, 6-nonadiene-1-alcohol to obtain (Z, Z) -1-bromo-3, 6-nonadiene;
reacting the (Z, Z) -1-bromo-3, 6-nonadiene and triphenylphosphine to obtain (Z, Z) -3, 6-nonadienyl triphenyl phosphine bromide;
utilizing the (Z, Z) -3, 6-nonadienyl triphenyl phosphonium bromide, hexamethyl phosphoric triamide and sodium bis (trimethylsilyl) amide to obtain the (cis ) -3,6, 9-nonadecatriene.
2. The process for preparing (cis ) -3,6, 9-nonadecatriene according to claim 1, wherein the preparation of 3, 6-nonadiyn-1-ol using 1-tetrahydropyrrolyl-oxy-3-butyne and p-toluenesulfonic acid-2-pentyn-1-ol ester comprises:
weighing 24.0 g of 1-tetrahydropyrrolyl-oxy-3-butynyl, and dissolving in 100mL of dry anhydrous THF;
under the ice bath condition, slowly dripping an ethyl magnesium bromide (2M, THF) solution under stirring for 1 hour, wherein the molar ratio of 1-tetrahydropyrrolyl-oxy-3-butyne to ethyl magnesium bromide is 1.2;
after the dropwise addition, the reaction mixture was stirred for about 1.5 hours, 0.86 g of cuprous bromide was added, the flask was slowly added dropwise with stirring for half an hour, a 50ml of THF solution containing 36g of p-toluenesulfonic acid-2-pentyne-1-ol ester was added, the temperature was raised to room temperature after the addition was completed, and the stirring was continued for 1.5 hours, wherein the volume ratio of the THF solution of p-toluenesulfonic acid-2-pentyne-1-ol ester to the volume of the 1-tetrahydropyrrolyl-oxy-3-butyne solution was 1:2;
after the reaction is finished, the volume ratio of the reaction solution to the 1-tetrahydropyrrolyl-oxy-3-butyne solution is 1:1, and separating out an organic layer, extracting a water layer twice with diethyl ether, and finally combining organic phases, wherein the volume ratio of the diethyl ether to the 1-tetrahydropyrrolyl-oxy-3-butyne solution is 2:1;
the combined organic phases were washed three times with distilled water, dried overnight with anhydrous magnesium sulfate powder, and the volume ratio of distilled water to 1-tetrahydropyrrolyl-oxy-3-butynyl aqueous solution was 2:1;
filtering to remove a drying agent, and concentrating to obtain a 1-tetrahydropyranyl oxy-3, 6-nonadiyne crude product;
hydrolyzing the crude product with a methanol solution of p-toluenesulfonic acid with a volume concentration of 2%, and stirring the mixture to react at 23 ℃ for about 18 hours, wherein the volume ratio of the methanol solution of p-toluenesulfonic acid to the 1-tetrahydropyrrolyl-oxy-3-butyne solution is 2:1;
after the reaction is finished, adding a saturated solution of sodium bicarbonate to be neutral, filtering, and concentrating to remove methanol;
dissolving the residue with water, extracting with diethyl ether for three times, mixing to obtain organic phase, drying with anhydrous magnesium sulfate, concentrating to obtain crude alcohol, and vacuum distilling to obtain 3, 6-nonadiyne-1-alcohol, wherein the volume ratio of ethanol to 1-tetrahydropyrrolyl-oxy-3-butyne solution is 3:1.
3. the process for preparing (cis ) -3,6, 9-nonadecatriene according to claim 1, wherein the preparation of (Z, Z) -3, 6-nonadien-1-ol using the ethanolic solution of 3, 6-nonadiyn-1-ol, lindlar catalyst and quinoline comprises:
stirring and mixing 100mL of 3, 6-nonadiyne-1-alcohol ethanol solution, 2.0 g of Lindlar catalyst and 0.5 mL of quinoline, introducing hydrogen, stirring at room temperature, absorbing hydrogen, and keeping the reaction process for 2 hours, wherein the concentration of the 3, 6-nonadiyne-1-alcohol ethanol solution is 1.4mol/L;
after the reaction is finished, filtering the catalyst, distilling to remove ethanol, dissolving the crude product in diethyl ether, washing with 100mL of 1N hydrochloric acid, 100mL of saturated sodium bicarbonate and 200mL of saturated sodium chloride aqueous solution respectively, and adding anhydrous magnesium sulfate to dry the organic phase; after removing the ether by rotary evaporation, distillation was carried out under reduced pressure to give 16.5 g of (Z, Z) -3, 6-nonadien-1-ol.
4. The process for producing (cis ) -3,6, 9-nonadecatriene according to claim 1, wherein the bromination of (Z, Z) -3, 6-nonadien-1-ol to obtain (Z, Z) -1-bromo-3, 6-nonadien comprises:
after dissolving 7.0 g of (Z, Z) -3, 6-nonanediene-1-ol and 20g of 20-tetrabrominated carbon in 200mL of methylene chloride and adding 18g of triphenyl phosphorus three times under ice-bath conditions with stirring for 1.5 hours, the methylene chloride was evaporated, the product was extracted with n-hexane (4 x 20 mL) three times, the organic phases were combined, concentrated to remove all the solvent, and distilled under reduced pressure to give 8.2g of (Z, Z) -1-bromo-3, 6-nonanediene.
5. The process for producing (cis ) -3,6, 9-nonadecatriene according to claim 1, wherein the reaction of (Z, Z) -1-bromo-3, 6-nonadienyl, triphenylphosphine to obtain (Z, Z) -3, 6-nonadienyl triphenyl phosphonium bromide comprises:
mixing the components in a mass ratio of 6:8, (Z, Z) -1-bromo-3, 6-nonane diline and triphenylphosphine are mixed, then argon is introduced, and the mixture is heated and stirred in an oil bath for 40 hours, and the temperature is kept at 75 ℃;
after the reaction, the crude product was dissolved in methylene chloride and transferred to a round-bottomed flask, methylene chloride was distilled off, the remaining solid portion was washed off with diethyl ether to remove excess triphenylphosphine, and 13.0g of (Z, Z) -3, 6-nonadienyl triphenylphosphonium bromide was distilled off to obtain a viscous form.
6. The method for preparing (cis ) -3,6, 9-nonadecatriene according to claim 1, wherein the step of using the (Z, Z) -3, 6-nonadienyl triphenyl phosphonium bromide, hexamethyl phosphoric triamide and sodium bis (trimethylsilyl) amide to obtain the (cis ) -3,6, 9-nonadecatriene comprises:
cooling a mixed solution consisting of 15mL of hexamethylphosphoric triamide, THF25mL and 3.2g of (Z, Z) -3, 6-nonadienyl triphenyl phosphonium bromide to-45 ℃, adding 1.06 g of bis (trimethylsilyl) sodium amide under stirring, continuing stirring for 30 minutes after the reaction solution becomes reddish brown, and dropwise adding 0.89 g of decanal;
after about three hours of stirring reaction, slowly raising the temperature to 0 ℃, adding 30mL of distilled water into the reaction product, extracting the reaction product for three times by using n-hexane (3 x 20 mL), and finally combining the organic phases;
washing the organic phase with distilled water, drying with anhydrous magnesium sulfate, and concentrating to obtain crude (cis ) -3,6, 9-nonadecatriene;
the crude product was separated by column chromatography on silica gel using petroleum ether as eluent to give (Z, Z, Z) -3,6, 9-nonadecatriene 0.95g.
CN202211271546.1A 2022-10-18 2022-10-18 Process for preparing (cis ) -3,6, 9-nonadecatriene Pending CN115466162A (en)

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CN108467336A (en) * 2018-04-27 2018-08-31 常州大学 A kind of synthetic method of 18 carbon triolefins of tea geometrid sex pheromone (Z, Z, Z) -3,6,9-

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