CN110143856B

CN110143856B - Method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound

Info

Publication number: CN110143856B
Application number: CN201910504455.XA
Authority: CN
Inventors: 刘钦胜; 江忠萍; 左伯军; 李金涛; 张作山
Original assignee: SHANDONG ACADEMY OF PESTICIDE SCIENCES
Current assignee: SHANDONG ACADEMY OF PESTICIDE SCIENCES
Priority date: 2019-06-12
Filing date: 2019-06-12
Publication date: 2022-09-02
Anticipated expiration: 2039-06-12
Also published as: CN110143856A

Abstract

The invention discloses a method for synthesizing a dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound, wherein omega-bromodecanol and dihydropyran are used under the action of a catalyst to obtain corresponding acetal, acetal and trialkyl/aryl phosphite are used for generating acetal dialkyl/aryl phosphonate, the acetal dialkyl/aryl phosphonate is reacted with n-hexanal under the action of organic base, hydrolysis and deprotection are carried out to generate (Z, E) -10-hexadecene-1-ol with the E type as the main part, and the (Z, E) -10-hexadecene-1-ol with the E type as the main part is subjected to oxidation reaction with an oxidant to obtain the (Z, E) -10-hexadecene aldehyde with the E type as the main part. The method has the advantages of less side reaction in the synthesis process and high product purity.

Description

Method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound

Technical Field

The invention relates to a dichocrocis punctiferalis sex pheromone, in particular to a chemical synthesis method of a (Z, E) -10-hexadecene compound, and belongs to the technical field of biological pesticides.

Background

A omnivorous insect of the genus Diacrocis borer of the Lepidoptera family of the peach borer (dichocrococissiliformis) is mainly distributed in tens of provinces of China, from northern to Heilongjiang, from southern to Yunnan, from west to Xinjiang and Tibet, and is widely harmful to varieties of crops, besides peaches, plum, apricot, pear, apple, fig, plum, cherry, pomegranate, grape, hawthorn, persimmon, walnut, Chinese chestnut, orange, litchi, longan, loquat, mango, pineapple and other fruits, economic crops such as corn, sorghum, sunflower, soybean, cotton, hyacinth bean, castor bean and other economic crops, and forest trees such as pine, fir, juniper, ailanthus and the like.

China is the first world where peaches are produced and consumed, the total yield in 2016 is about 1350 million tons, and the yield accounts for about 66% of the total world amount, however, in some regions of China, such as the south of the Yangtze river, the loss caused by dichocrocis punctiferalis is very serious, and even the wording "ten peaches are damaged by nine worms" is provided.

In addition, when the dichocrocis punctiferalis damages corns, the egg laying amount of hundreds of plants can reach 1729; when the sunflower is damaged, the damage rate of the early-sowing hybrid oil sunflower can reach 62 percent, and the damage rate of the late-sowing hybrid oil sunflower can reach 90 percent; in east China, dichocrocis punctiferalis is also a major pest that damages chestnuts. In terms of planting area, the planting area of peaches in 2016 years in China exceeds 1000 ten thousand mu; the planting area of the corn in the same year is 5.57 hundred million mu; the planting area of the sunflowers in the same year is 1490 ten thousand mu; in 2015, the planting area of the Chinese chestnut is 2700 ten thousand mu, and the damage of dichocrocis punctiferalis on other crops due to mixed feeding can be seen, so that spots can be seen.

The motheating property of the peach borers larvae, the moth-raising period and the like are long, and chemical pesticides are applied for a long time, so that the drug resistance is increased, the control effect is obviously reduced, the number of natural enemies is reduced, and the ecological environment is damaged. The insect sex pheromone is a trace chemical substance which is secreted in vitro by an individual of a certain sex of an insect, is accepted by a receptor of an individual of the same sex, and causes the individual of the opposite sex to generate a certain reproductive behavior response (such as foraging orientation, mating and the like). The insect sex pheromone is a novel pest control technology, has the characteristics of strong specificity, no residue, environmental friendliness and the like, and is an agricultural green ecological control technology.

The sex pheromone of the dichocrocis punctiferalis is a (Z, E) -10-hexadecene compound, wherein the ratio of the isomers of the Z formula to the isomers of the E formula is 3:7 to 1:9, and the best insect-trapping effect is that the ratio of the isomers of the Z formula to the isomers of the E formula is 1: 9. The total synthesis yield reported at home and abroad is only about 36%, the product refining process is long, the cost is high, and impurities are more, so that the drug effect of the preparation product cannot be satisfactory. The study of the synthesis method of sex pheromone of dichocrocis punctiferalis began in the seventies of the last century. There are several synthetic methods as follows:

1. undecylenic acid is used as a raw material, after peracid hydroxylation and methanol esterification, sodium periodate is used for oxidizing and cracking glycol functional groups to obtain corresponding aldehyde ester, the corresponding aldehyde ester and bromotriphenylhexyl phosphine salt are subjected to wittig reaction to obtain E/Z mixture olefine acid ester with the yield of about 1:1 in 60%, alcohol is obtained by ester reduction, PCC is oxidized to obtain a final product, the GC purity is 96.3%, the total 6 steps are carried out, and the total yield is 13.25%.

Although the raw materials of undecylenic acid and bromohexane are easy to obtain in the reaction, the wittig reaction needs a reaction at a temperature of minus 40 ℃, the total yield is low, and the double bond cis-trans configuration is low.

2. Bromodecanol and hexanal are used as raw materials, bromo-n-decyltriphenylphosphine salt is prepared, then wittig reaction is carried out in the presence of DMSO sodium salt to obtain corresponding alcohol, and a final product can be obtained by PCC oxidation, wherein the stereoselectivity E/Z is 6.6:93.4, and the total yield is about 27%.

The conditions of the route are relatively mild, but when the bromo-n-decyltriphenylphosphine salt is formed, side reaction is easy to occur, and the polymer of bromodecanol is introduced, so that the bromodecanol is brought into enol obtained by the wittig reaction, and the wittig reaction can generate the polymer; however, in the wittig reaction post-treatment, the by-product of triphenylphosphine oxide and its analogues need to be removed, and even though the triphenylphosphine oxide is removed by a complexation method in zinc chloride anhydrous ethanol, an additional method is still needed to remove the triphenylphosphine oxide analogues, so that the post-treatment is complicated and the cost is high.

In addition, the trans configuration of the obtained enol is too low, an additional method is needed for isomerization, the isomerization yield is about 90%, and only products with E: Z being 76:24 can be obtained, and the best insect-attracting effect is a distance away from the E: Z being 9: 1.

3. Undecylenic acid is used as a starting material by Jiangsu chemical industry institute and insect hormone research institute, and E-10-hexadecenal and Z-10-hexadecenal are synthesized by steps of bromination, elimination, reduction, protection, condensation, cis-hydrogenation, trans-hydrogenation, deprotection, oxidation and the like. The method has long steps, no experimental data and high reaction conditions.

4. The synthesis of the sex pheromone trans-10-hexadecenal and the cis isomer thereof is reported by Liu Meng, Bozhou, Haemazara and Hades in the institute of Chinese academy animals, and relates to three routes, wherein one route is the same as the method 2; the other method is simply an isomerization method by dehalogenation of dibromide in method 2; the last is the acetylide route.

9-bromo-nonanol tetrahydropyrane ether and heptyne are used as raw materials to prepare 10-hexadecylene alcohol tetrahydropyrane ether, the 10-hexadecylene alcohol tetrahydropyrane ether is converted into 10-hexadecylene alcohol through hydrolysis, excess lithium aluminum hydride is used as a reducing agent to reduce the alkynol, and a product is obtained through a PCC oxidation method.

5. Chenjiawei of chemical system of Hubei university in 1987 adopts 1, 10-decanediol to selectively carry out unilateral dihydropyrane ether protection and oxidation to aldehyde, then carries out wittig reaction with polymer supported hexyl triphenylphosphine bromide and sodium hydride, and obtains the product through deprotection, isomerization and oxidation to aldehyde.

In the same year, Chenjiawei in organic chemistry 3, 224-226 published another polymer-supported synthesis document, entitled "research on polymer reagents II" Synthesis of sex pheromone of dichocrocis punctiferalis, trans-10-hexadecene-1-aldehyde, using polymer reagents. The 1, 10-decanediol is brominated at one side, salified with polymer supported triphenyl phosphine, subjected to wittig reaction in the presence of sodium hydride and DMSO, isomerized and oxidized to obtain a product, and the two methods have high cost, difficult regeneration of resin and great difficulty in protecting the hydroxyl group at one side of the 1, 10-decanediol. 6. Undecylenic acid is used as a raw material, is reduced into alcohol by lithium aluminum hydride, is added with bromine and is dehalogenated into undecylenic alcohol, is coupled with n-pentane bromide under the action of THP protection and butyl lithium, is deprotected, is hydrogenated in a trans-form, and is oxidized to obtain (E) -10-hexadecenal, and the total yield is about 34 percent. Propargyl alcohol and bromo-n-octane are coupled under the action of alkali metal amide, an acetylene bond is shifted to obtain terminal alkynol, and then the terminal alkynol is coupled with n-butyl bromide under the action of alkali metal amide, nickel is subjected to catalytic hydrogenation, and oxidation is carried out to obtain (Z) -10-hexadecenal, wherein the total yield is about 28%.

7. By adopting a method similar to the method 2, the Schlosser-Wittig reaction of the plum Handong replaces the Wittig reaction to obtain the enol with high trans-form selectivity, and the enol is oxidized to obtain the enal. The Schlosser-Wittig reaction yield was 60%, E/Z is 98/2, no isomerization was required. However, phenyllithium-lithium bromide is a base (4 times equivalent), reacts at-70 degrees, and is high in cost and harsh in conditions.

Disclosure of Invention

The invention aims to provide a method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compounds, which takes omega-bromodecanol as an initial raw material, improves the stability of the raw material through hydroxyl protection, avoids the polymerization side reaction of the raw material, improves wittig reaction, improves the yield and the reaction selectivity, has few side reactions in the synthesis process and has high product purity.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compounds comprises the following steps:

(1) reacting omega-bromodecanol with dihydropyran under the action of a catalyst to obtain corresponding acetal;

(2) carrying out an Abuzov reaction on acetal and trialkyl/aryl phosphite to generate acetal dialkyl/aryl phosphonate;

(3) reacting the acetal dialkyl/aryl phosphonate with n-hexanal under the action of organic base, hydrolyzing and deprotecting to generate (Z, E) -10-hexadecene-1-ol with E as a main component;

(4) and (Z, E) -10-hexadecene-1-alcohol with the E type as the main component is subjected to oxidation reaction by an oxidant to obtain the (Z, E) -10-hexadecene aldehyde with the E type as the main component.

The synthesis method comprises the steps of taking omega-bromodecanol as a raw material, reacting with dihydropyran under the action of a catalyst to obtain corresponding acetal, reacting the acetal with trialkyl/aryl phosphite to generate acetal dialkyl/aryl phosphonate, reacting the acetal dialkyl/aryl phosphonate with n-hexanal under the action of organic base, hydrolyzing and deprotecting to generate (Z, E) -10-hexadecene-1-ol with the main E type, and oxidizing the (Z, E) -10-hexadecene-1-ol with the main E type with an oxidizing agent to obtain the (Z, E) -10-hexadecene aldehyde with the main E type. The synthesis process has less side reaction and high product purity.

After the raw material of the omega-bromodecanol is protected by the dihydropyranyl ether, the omega-bromodecanol is more stable than the omega-bromodecanol and cannot generate a polymerization reaction in the subsequent process; and through Arbuzov reaction substitution and triphenyl phosphine salifying reaction, through wittig-horner substitution wittig reaction, the yield is high, the side reaction is less, and the cis-trans structure ratio of the product is favorable to be in a proper range.

Preferably, the synthesis method of the invention comprises the following steps:

(1) heating omega-bromodecanol and dihydropyran in an organic solvent for reflux reaction under the action of a catalyst, removing the catalyst after the reaction is finished, and removing the solvent to obtain THP protected omega-bromodecanol, commonly known as acetal;

(2) mixing the acetal obtained in the step (1) with trialkyl/aryl phosphite, and reacting at a certain temperature to obtain dialkyl/aryl acetal phosphonate protected by THP;

(3) reacting the THP-protected dialkyl/aryl acetal phosphonate obtained in the step (2) with n-hexanal in an anhydrous ether mixed solvent under the action of organic base to generate THP-protected hexadecenol mainly taking the E type, and hydrolyzing to obtain 10-hexadecene-1-ol mainly taking the E type;

(4) the (Z, E) -10-hexadecene-1-alcohol with the E type as the main component is oxidized in a lower halogenated solvent by an oxidant to obtain the (Z, E) -10-hexadecene aldehyde with the E type as the main component, and the molar ratio of Z to E in the product is 1:7-20, preferably 1: 9.

The method takes omega-bromodecanol as a raw material, and prepares the product through THP protection, Arbuzov reaction, wittig-horn reaction, hydrolysis reaction and oxidation reaction, the method uses triphenyl phosphorus with low yield and poor selectivity for salification reaction and wittig reaction, and simultaneously avoids complex and fussy procedures for removing triphenyl oxyphosphorus and suspected triphenyl oxyphosphorus, the yield is higher, and the process scheme is more economic and environment-friendly.

Preferably, the molar ratio of 10-bromodecanol to dihydropyran in step (1) is from 1:1 to 1:1.2, for example, 1:1.05, 1:1.1, 1:1.15, 1:1.2, and the like. The above molar ratio range of 10-bromodecanol and dihydropyran allows for both sufficient conversion of 10-bromodecanol and conversion of only one of the bromides to the salt.

Preferably, the molar concentration of 10-bromodecanol in the halogenated solvent is from 1.0mol/L to 5.0 mol/L.

Preferably, the reaction time is 1-2h, preferably 2h, with stirring at room temperature.

Preferably, the solvent in step (2) is the reactant itself, wherein, in order to ensure the completeness of the acetal reaction, the phosphite ester is added in an excessive amount, which is helpful for conversion, but in view of cost and raw material recovery, the excessive amount is preferably 50%, and the temperature rise is favorable for the smooth and stable and sufficient reaction, so that the reaction yield is high, but the energy consumption will also rise, and preferably under the protection of inert gas, the side reaction is less, and the product purity is high.

Preferably, the organic base in step (3) is sodium hydride.

Preferably, the organic base is added as a solution.

The Wittig-horner reaction adopts a mixed solvent, and the organic base adopts sodium hydride, so that the Wittig-horner reaction is more favorable for being carried out under a low-temperature homogeneous condition, and the ratio of cis-trans structures of the product is favorable for being in a proper range.

Preferably, the organic base has a molar concentration of 0.5mol/L to 5.0 mol/L.

Preferably, the solvent of the organic base solution is tetrahydrofuran and N, N-dimethylformamide.

Preferably, the mass concentration of the hydrochloric acid is 5 to 15%, preferably 10%.

Preferably, the THP protected acetal phosphonate, organic base, aldehyde are in a molar ratio of 1:1.2 to 2.5:1.0 to 1.2, e.g., 1:1.3:1.1, 1:1.5:1.2, 1:1.7:1.15, 1:2:1.05, etc.

Preferably, the THP-protected acetal phosphonate ester has a molar concentration in the mixed solvent of 0.5mol/L to 3.0 mol/L.

Preferably, the reaction time after adding the organic base is more than 0.5h, preferably 1-1.5 h. The reaction is preferably carried out with stirring.

Preferably, the reaction time after adding the aldehyde diluted by the solvent is more than 2h, preferably 3h to 20 h.

Preferably, the solvent used for the solvent-diluted aldehyde is tetrahydrofuran.

The molar concentration of the aldehyde after dilution with the solvent is not particularly limited, and may be, for example, 0.5 to 10 mol/L.

After the reaction is finished, the reaction is stopped, preferably adding lower aliphatic alcohol first and then adding diluted acid to destroy sodium hydride which cannot be reacted, so as to avoid the problem of reaction flushing; preferably, the alcohol is added dropwise; preferably, the lower aliphatic alcohol is ethanol, preferably in an amount of excess equivalents of sodium hydride after the wittig-horner reaction has theoretically taken place.

Preferably, the treatment after separation is extraction with benzene solvent, more preferably toluene, washing with saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, distilling to obtain crude product, and separating by silica gel column chromatography to obtain (Z, E) -10-hexadecene-1-ol mainly in E type.

The extraction can be carried out several times, and the organic phases after extraction can be combined for the next step.

Preferably, the molar concentration of the (Z, E) -10-hexadecen-1-ol with E type as the main component in the step (3) in the toluene is 1.0mol/L to 3.0 mol/L.

Preferably, the benzene solvent is a combination of 1 or more than 2 of benzene, toluene and xylene.

Preferably, the hydrolysis is carried out for 1h-2h at normal temperature, and the acid which is slightly excessive in the acid neutralization process is preferably utilized for neutralization; the pH value after neutralization should be less than 5.0, and the pH value is preferably controlled to be 3.0-4.0.

Preferably, the (Z, E) -10-hexadecen-1-ol formed, predominantly in E-form, is concentrated by distillation under reduced pressure.

The inert gas used in the present invention may be any one of inert gases commonly used in the art, such as 1 or a combination of several of helium, neon, argon, and nitrogen.

Preferably, the reaction solvent in step (4) is dichloromethane; the reaction temperature ranges from-10 ℃ to 40 ℃, and room temperature is preferred; preferably the oxidant is PCC; the molar concentration of PCC in the solvent may range from 0.1mol/L to 1.0mol/L, preferably 0.5 mol/L; the reaction may be carried out in air, preferably in a common inert atmosphere, such as helium, neon, argon, nitrogen, and the like, and combinations thereof, more preferably nitrogen.

Preferably, the (Z, E) -10-hexadecenal with E type as the main component is generated, and in the post-treatment purification process, the solvent dichloromethane is removed by atmospheric distillation, and then low-boiling ether such as diethyl ether, propyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether and the like is added for dissolution, preferably methyl tert-butyl ether; the preferred amount of ether added is to control the theoretical product concentration to 0.4-0.6 mol/L; the ether solution of the product is preferably subjected to adsorption and column chromatography to remove possible impurities, wherein the adsorption and column chromatography can be made of common column chromatography silica gel, diatomite, kaolin, montmorillonite, chalk, etc., the adsorption is preferably diatomite, and the column chromatography is preferably silica gel.

Preferably, the mobile phase after column chromatography is washed by water to remove possible impurities such as metal ions, and the amount of water added is preferably 0.2 times of the volume of the product solution, and the number of washing times is preferably 3.

Preferably, the washed liquid is dried over a common neutral drying agent to remove water, such as magnesium sulfate, sodium sulfate, etc., and then filtered, and concentrated under reduced pressure in a water bath with the temperature controlled below 45 ℃.

Preferably, the concentrated solution is preserved after adding commercially available antioxidant, such as 1, 4-hydroquinone, vitamin E, tert-butyl hydroquinone, tea polyphenols, etc., and the addition amount can be 0.01% -1.00%, preferably 0.1%, preferably vitamin E.

According to the technical scheme, the beneficial effects of the invention are as follows:

(1) after the raw material omega-bromodecanol is protected by THP, the self-condensation reaction can not occur in the subsequent process, thereby avoiding the purity reduction of an intermediate and the introduction of excessive impurities to the subsequent reaction;

(2) the process of forming the quaternary phosphonium salt is replaced by the Abuzov reaction, so that the yield and the purity are higher;

(3) the wittig-horner reaction is used for replacing the wittig reaction, so that the cis-trans structure proportion of the product is kept in a proper range, the process of isomerization is avoided independently, and the problem that triphenyl phosphine oxide and similar substances are difficult to remove after the reaction is finished is also avoided;

(4) in the wittig-horner reaction post-treatment, a method of neutralizing and stopping the reaction by using lower fatty alcohol and acid step by step is adopted, so that the safety is greatly improved, and the problem of reaction and material flushing is avoided.

Drawings

FIG. 1 shows a scheme for synthesizing (Z, E) -10-hexadecenal in accordance with an example of the present invention.

FIG. 2 is a liquid chromatogram of hexadecenol according to example of the present invention.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The conditions used in the examples may be further adjusted according to the manufacturer's conditions, and the unexplained conditions are generally conventional experimental conditions.

Examples

A method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compounds comprises the following operation steps:

(1) THP protected acetals

48.5g (0.20mol) of monobromosol, a yellow-brown transparent liquid, 1.0g (0.02eq.), 25.2g (0.30mol) of dihydropyridine and 300ml of dichloromethane are added into a 500ml three-neck flask, stirred at room temperature for 1h, then distilled under reduced pressure in a water bath at 40 ℃ to remove the solvent and the redundant dihydropyran, added with 250ml of 60-90 petroleum ether and 50ml of water for washing, dried by anhydrous sodium sulfate, and concentrated to obtain 62.3g of yellow-brown transparent liquid with the yield of 97%.

(2) Abuzov reaction

235g (1.50mol) of triethyl phosphite, a small amount of catalyst iodine and nitrogen protection are added into a 500ml three-neck flask, the oil bath heating temperature is 150 ℃, 160.5g (0.50mol) of acetal protected by THP is dripped, the reaction is finished for 15h, the byproduct ethyl bromide is continuously distilled during the reaction, the temperature is reduced to 50 ℃ after the reaction is finished, reduced pressure distillation is started, the oil bath temperature is gradually increased to 110 ℃, and distillation cannot be carried out at the temperature of 110 ℃ in 10Pa, 177.9g of light yellow liquid is obtained in total, and the yield is 94%.

(3) Synthesis of hexadecenol

Adding 100ml of dry and dehydrated N, N-dimethylformamide and 33g (0.825mol) of 60% sodium hydride into a 2000ml flask under the protection of nitrogen, adding 150ml of dehydrated tetrahydrofuran, stirring, dropwise adding a tetrahydrofuran solution of the product at room temperature, wherein the tetrahydrofuran solution contains 150ml of dehydrated tetrahydrofuran, cleaning a funnel by using tetrahydrofuran, releasing a large amount of hydrogen in the middle, reducing the temperature after releasing the hydrogen, cooling in an ice-water bath at the internal temperature of-5-0 ℃, dropwise adding 65g/200ml of THF (0.65mol) of hexanal, gradually heating to about 25 ℃, continuously reacting for 1h, dropwise adding 50ml of absolute ethyl alcohol, continuously releasing the hydrogen, dropwise adding a 5% hydrochloric acid solution till the pH is 5-6, stopping stirring, layering, separating liquid, wherein the upper layer is a THF phase, performing rotary evaporation concentration at the temperature of 45-60 ℃ in the water bath, extracting the water phase for 2 times by using 100ml of ethyl acetate, separating, adding the ethyl acetate phase into the tetrahydrofuran concentrated solution to obtain light yellow transparent liquid, performing vacuum distillation by a water pump at the temperature of 60 ℃ in a water bath, and continuously distilling by using an oil pump at the same temperature until no fraction is distilled at the temperature of 60 ℃ under 10Pa to obtain 87g of the product in total, wherein the GC content is 96.5%, and the yield is 70%.

The product is mainly in E configuration through liquid chromatography detection, and E: Z is 9: 1.

(4) PCC oxidation

Adding 80.0g (0.37mol) of pyridinium chlorochromate into a 1000ml three-neck flask under the protection of nitrogen, adding 600ml of dichloromethane in total, stirring and dissolving to obtain an orange red transparent liquid, wherein the solid at the bottom is insoluble; dissolving 87g of hexadecenol mainly having the E-type configuration in 300ml of dichloromethane, dropwise adding the enol at room temperature for reaction, wherein the solution becomes black along with the dropwise addition, and continuously stirring at room temperature for reaction for 1 hour after the dropwise addition is finished; then distilling off dichloromethane in water bath at 45 ℃ under normal pressure, adding 600ml of methyl tert-butyl ether and about 200ml of silica gel for column chromatography after the completion, stirring for 30min, filtering, washing a filter cake for 2 times by 150ml of methyl tert-butyl ether, combining ether phases, adding 150ml of water, washing for 2 times, separating liquid, adsorbing and removing dark substances from an organic phase liquid through column chromatography, adding a small amount of antioxidant, and carrying out rotary evaporation in water bath at 40 ℃ under the protection of nitrogen to obtain a light yellow green transparent liquid with pungent smell, wherein the total amount is 80.0g, the GC content is 98%, and the yield is 94%.

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims

1. A method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound is characterized by comprising the following operation steps:

(1) heating omega-bromodecanol and dihydropyran in an organic solvent for reflux reaction under the action of a catalyst, removing the catalyst after the reaction is finished, and removing the solvent to obtain THP protected omega-bromodecanol;

(2) mixing the omega-bromodecanol obtained in the step (1) with trialkyl phosphite or triaryl phosphite, and reacting at a certain temperature to obtain corresponding tetrahydropyranyl-protected acetal dialkyl phosphonate or acetal diaryl phosphonate;

(3) reacting the dialkyl acetal phosphonate or diaryl acetal phosphonate obtained in the step (2) with n-hexanal in a mixed solvent through the action of organic base to generate THP-protected hexadecenol mainly taking the E type, and hydrolyzing to generate (Z, E) -10-hexadecene-1-ol mainly taking the E type;

(4) oxidizing (Z, E) -10-hexadecene-1-alcohol with E type as main component in lower aliphatic halohydrocarbon or lower aliphatic ether solvent with oxidant to obtain (Z, E) -10-hexadecene aldehyde with E type as main component;

in the step (1), the molar ratio of the omega-bromodecanol to the dihydropyran is 1:1-1: 1.2;

in the step (1), the solvent is any one of tetrahydrofuran, methyl tert-butyl ether, diethyl ether, dichloromethane, dichloroethane, chloroform, acetonitrile, acetone and butanone;

the catalyst in the step (1) is pyridinium p-toluenesulfonate;

the adding amount of the catalyst in the step (1) is 0.1-5% of the total amount of the reaction system.

2. The method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound according to claim 1, wherein the reaction temperature in the step (2) is 100 ℃ to reflux temperature, and the reflux temperature is 100 ℃ to 200 ℃;

in the step (2), the molar equivalent of the trialkyl phosphite or triaryl phosphite added is 1.0-5.0 times of that of the omega-bromodecanol;

and (3) the reaction atmosphere in the step (2) is an atmospheric common environment or an inert gas protective atmosphere.

3. The method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound according to claim 2, wherein the mixed solvent in the step (3) is one or a combination of anhydrous ether, strong polar dipolar solvent and benzene solvent;

in the step (3), the molar ratio of the acetal dialkyl phosphonate or acetal diaryl phosphonate to the organic base is 1: 1-2: 1;

in the step (3), the reaction temperature of the acetal phosphonic acid dialkyl ester or acetal phosphonic acid diaryl ester and the organic base is between-10 ℃ and 45 ℃;

the reaction temperature of the step (3) is-25 ℃ to 25 ℃ when n-hexanal is dripped;

the reaction time after the organic base is added in the step (3) is more than 0.5 h; wherein, the solvent used for diluting the n-acetaldehyde is tetrahydrofuran;

quenching the reaction by adding lower aliphatic alcohol in the step (3), wherein the added lower aliphatic alcohol is one of methanol, ethanol, propanol and butanol;

after the reaction in the step (3) is finished, adding acid to adjust the pH value to 5-6, wherein the used acid is diluted acid and is one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid;

and (3) the reaction atmosphere of the hexanal and the acetal dialkyl phosphonate or acetal diaryl phosphonate is protected by inert gas.

4. The method according to claim 1, wherein in the step (3), the step (3) of separating is carried out by quenching with absolute ethanol, adding diluted acid aqueous solution for neutralization, separating, extracting the water phase with organic solvent, washing with saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, distilling to obtain crude product, and separating by silica gel column chromatography to obtain the (Z, E) -10-hexadecene-1-ol with E type as main component.

5. The method for synthesizing a dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound according to claim 1, wherein in the step (3), the molar concentration of the (Z, E) -10-hexadecene-1-ol in the mixed solvent is 0.5-3.0 mol/L; the mixed solvent is a combination of 1 or more than 2 of an ether solvent, a benzene solvent and a strong polar dipolar solvent; the molar ratio of the organic base to the (Z, E) -10-hexadecene-1-ol is 1-3: 1; the organic base is 1 or 2 of sodium hydride and potassium hydride; neutralizing and hydrolyzing for 4-20 h at 50-60 ℃.

6. The method according to claim 1, wherein in the step (4), the lower aliphatic halogenated hydrocarbon is one of dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethane and tetrachloroethane, the aliphatic ether solvent is one of diethyl ether, methyl tert-butyl ether, propyl ether and ethylene glycol dimethyl ether,

the reaction temperature in the step (4) is-15 ℃ to 65 ℃;

in the step (4), the oxidant is pyridinium chlorochromate;

and (4) protecting the oxidation reaction atmosphere in the step (4) by inert gas.

7. The method for synthesizing dichocrocis punctiferalis sex pheromone (Z, E) -10-hexadecene aldehyde compound according to claim 1, wherein the molar ratio of the (Z, E) -10-hexadecene-1-ol to the oxidant in the step (4) is 1: 1.0-1.5; the mass ratio of the halogenated solvent to the (Z, E) -10-hexadecene-1-ol is 3-15: 1; the molar concentration of the (Z, E) -10-hexadecen-1-ol in the halogenated solvent is 0.3mol/L-3.0 mol/L; the reaction is carried out at room temperature, and the reaction time is 1-10 h; after the (Z, E) -10-hexadecene-1-alcohol reacts with an oxidant, distilling out most of halogenated solvent, then adding an ether solvent and an auxiliary agent in a normal pressure distillation mode, wherein the ether solvent is methyl tert-butyl ether, the auxiliary agent is common column chromatography silica gel, kieselguhr, kaolin, montmorillonite and chalk, and the adding amount of the kieselguhr is 1-5 times of the mass of the (Z, E) -10-hexadecene-1-alcohol.