CN111253228B - Industrial synthesis method of dichocrocis punctiferalis sex pheromone - Google Patents
Industrial synthesis method of dichocrocis punctiferalis sex pheromone Download PDFInfo
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to an industrial synthesis method of dichocrocis punctiferalis sex pheromone, which comprises the steps of taking 1, 10-decanediol as a raw material, preparing 10-bromodecanol through unilateral bromination reaction, reacting with triphenylphosphine to obtain 10-hydroxydecyl triphenylphosphine salt, carrying out Wittig reaction with n-hexanal under the action of alkali to obtain 10-hexadecene-1-ol mainly in cis form, isomerizing enol mainly in cis form under the action of p-methylthiophenol to obtain 10-hexadecene-1-ol mainly in trans form, and finally oxidizing under the action of an oxidizing agent to obtain a final product of 10-hexadecene aldehyde. The method has mild reaction conditions and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to an industrial synthesis method of dichocrocis punctiferalis sex pheromone.
Background
The dichocrocis punctiferalis belongs to the family of lepidoptera borer. The alias peach moth borer, peach fruit borer, peach moth borer, leopard striped rice borer, etc. Dichocrocis punctiferalis eating impurity and wide host, and can harm various fruit trees and crops, such as peach, plum, apricot, apple, pear, chinese chestnut, pomegranate, sunflower disc and the like. The dichocrocis punctiferalis larva not only eats fruits and influences the fruit development, but also discharges excrement in the fruits, thus causing serious influence on the fruit yield, quality, commodity value and the like and causing serious economic loss to fruit growers. In recent years, with the adjustment of agricultural industrial structures, the planting area of peach trees is continuously enlarged, and the occurrence of dichocrocis punctiferalis is increasingly serious. At present, the moth borer prevention and control still mainly comprises chemical pesticides, the long-term prevention not only destroys the ecological environment of an orchard, but also causes the pesticide residue of fruits to exceed the standard and the drug resistance of pests to be enhanced, and easily causes harm and hidden danger to human health. The insect sex pheromone shows good application effect in the aspects of monitoring, preventing and controlling dichocrocis punctiferalis, and is a green, environment-friendly, efficient and sustainable development prevention and control means.
Konno et al, 1982, extracted a component from the gonad of the female moth of the fruit-eating dichocrocis punctiferalis, and the chemical structure was identified as trans-10-hexadecenal. The field test shows that the attracting effect of the trans-10-hexadecenal and the cis-10-hexadecenal is 3 times higher than that of pure trans-10-hexadecenal because the proportion of the trans-10-hexadecenal and the cis-10-hexadecenal is 9. In 1986, liu Meng et al synthesized sex pheromone of dichocrocis punctiferalis, and proved that the sex pheromone of dichocrocis punctiferalis is a mixture of cis, trans-10-hexadecenal.
The foreign research on the synthesis and application of sex pheromone of dichocrocis punctiferalis is more, and although many related researches are also made in China, some problems still exist in the aspect of synthesis. The method can be divided into an acetylide route and a Wittig reaction route according to the starting raw materials, wherein the acetylide route raw materials are difficult to obtain, the route is long, and an acetylene bond is required to be selectively reduced; the Wittig reaction route is short and the base required for the Wittig reaction is usually n-butyllithium or phenyllithium in order to obtain predominantly trans olefins. However, the metal organic compounds are very active, flammable and explosive, have strict requirements on reaction conditions, and are not suitable for large-scale production.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an industrial synthesis method of dichocrocis punctiferalis sex pheromone, which has the advantages of easily obtained raw materials, simple and convenient operation and high yield.
In order to realize the purpose, the invention provides a method for synthesizing sex pheromone of dichocrocis punctiferalis, which comprises the following steps:
(1) 1, 10-decanediol is taken as a raw material, and 10-bromo-1-decanol is prepared through unilateral bromination reaction;
1, 10-decanediol, toluene and 48% hydrobromic acid (1.2 eq) are added into a three-neck flask, the mixture is heated to 110 ℃, the 48% hydrobromic acid (0.44 eq) is added after refluxing for 24 hours, the heating and refluxing are continued for 24 hours, and a small amount of raw material residue is detected by gas chromatography. After cooling to room temperature, the mixture was diluted with 500ml of petroleum ether, the hydrobromic acid was separated by liquid separation, and the organic phase was washed successively with saturated sodium bicarbonate and saturated brine, and dried over anhydrous sodium sulfate. Spin-drying the mixture to obtain the 10-bromo-1-decanol.
(2) Reacting 10-bromo-1-decanol with triphenylphosphine to obtain 10-hydroxydecyl triphenylphosphine salt;
10-bromo-1-decanol, acetonitrile, triphenylphosphine (1.1 eq) were added to a three-neck flask and heated to 94 ℃ under reflux for 48 h. After the reaction is finished, the reaction solution is cooled to room temperature, and acetonitrile is dried by spinning. Adding toluene, heating and refluxing to homogeneous phase, stirring for 15min, cooling to room temperature, pouring out the upper layer of toluene, and repeating twice. Then washing with diethyl ether to obtain white solid 10-hydroxy decyl triphenyl phosphine salt.
(3) The 10-hydroxy decyl triphenylphosphine salt and n-hexanal are subjected to a Wittig reaction under the action of alkali to obtain 10-hexadecene-1-ol mainly in cis form;
adding 10-hydroxydecyl triphenylphosphine salt and tetrahydrofuran, N in a mechanically-stirred three-neck flask 2 Opening the kettle, adding alkali, controlling the reaction temperature below 20 ℃, and stirring for half an hour at room temperature after the addition is finished. Cooling to 0 deg.C in ice bath, adding tetrahydrofuran solution of n-hexanal, controlling internal temperature not to exceed 5 deg.C, dropwise adding, reacting at 0 deg.C for half an hour, and stirring at room temperature for 1 hr. Adding saturated ammonium chloride for quenching, separating an organic phase, extracting an aqueous phase by using ethyl acetate, washing the organic phase by using salt water, and drying by using anhydrous sodium sulfate. And (4) spin-drying, and separating and purifying the crude product by column chromatography to obtain the 10-hexadecene-1-alcohol.
Wherein the base is potassium tert-butoxide, sodium dimethyl sulfoxide or sodium amide, preferably potassium tert-butoxide; the mol ratio of the alkali to the 10-hydroxydecyl triphenylphosphine salt is (2-2.5) to 1; the molar ratio of base to 10-hydroxydecyl triphenylphosphine salt is preferably 2.2.
(4) Isomerizing cis-form main 10-hexadecene-1-alcohol under the action of p-methylthiophenol to obtain trans-form main 10-hexadecene-1-alcohol;
sequentially adding 10-hexadecene-1-alcohol and p-toluene thiophenol into a single-mouth bottle, heating to 80-120 ℃ in an oil bath, and stirring for 0.5-2 hours. After the reaction, the mixture was extracted with ethyl acetate, and the organic phase was washed with a 10% aqueous sodium hydroxide solution, water and brine, respectively. Drying with anhydrous sodium sulfate, spin-drying, and purifying the crude product by column chromatography to obtain trans-mainly 10-hexadecene-1-ol.
Among them, p-methylthiophenol is used in an amount of 0.5 to 2%, preferably 1%, based on the mass of 10-hexadecen-1-ol.
(5) The trans-predominant 10-hexadecen-1-ol is oxidized to the corresponding enal under the action of an oxidizing agent.
Wherein the oxidant is oxygen or iodobenzene acetate, and the dosage of the oxygen is 20-40eq; preferably iodobenzene acetate; the dosage of the iodobenzene acetate is 1.2-1.6eq, preferably 1.4eq.
The specific synthetic route of the method is as follows:
the invention has the beneficial effects that: the invention uses cheap and safe alkali to carry out Wittig reaction, firstly obtains the enol mainly in cis form, and then carries out isomerization on methyl thiophenol to obtain the enol mainly in trans form, the condition is obviously mild, the invention is suitable for large-scale production, and the problems of flammable and explosive potential safety hazards caused by using butyl lithium or phenyl lithium as alkali, harsh reaction condition, unsuitability for large-scale production and the like are avoided. The final oxidant is iodobenzene acetate, rather than toxic pyridinium chlorochromate (PCC).
Detailed Description
The invention will now be further described with reference to specific examples, which are intended to illustrate, but not to limit the invention further.
Example 1:
synthesis of 10-bromo-1-decanol
1, 10-decanediol (321g, 1.712mol), toluene (1000 ml) and 48% hydrobromic acid (231ml, 2.054mol, 1.2eq) are added into a 2L three-mouth bottle, the bottle is heated to 110 ℃, the 48% hydrobromic acid (84ml, 0.753mol, 0.44eq) is added after refluxing for 24 hours, the bottle is continuously heated and refluxed for 24 hours, and a small amount of raw material residue is detected by gas chromatography. After cooling to room temperature, the mixture was diluted with 500ml of petroleum ether, the hydrobromic acid was separated by liquid separation, and the organic phase was washed successively with saturated sodium hydrogencarbonate (400 ml. Times.2) and saturated brine (400 ml. Times.2) and dried over anhydrous sodium sulfate. The 10-bromo-1-decanol was obtained by spin-drying (yield 84%).
Example 2:
synthesis of 10-hydroxydecyl triphenylphosphine salt
10-bromo-1-decanol (357g, 1.424mol), acetonitrile (1000 ml), triphenylphosphine (409g, 1.566mol, 1.1eq) was added to a 2L three-necked flask and heated to 94 ℃ under reflux for 48 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and the acetonitrile was dried by spinning. Adding 500ml of toluene, heating and refluxing to homogeneous phase, stirring for 15min, cooling to room temperature, pouring out the upper layer of toluene, and repeating twice. Washing with diethyl ether gave a white solid, 10-hydroxydecyl triphenylphosphine salt, in 88% yield.
Example 3:
synthesis of 10-hexadecen-1-ol
The quaternary phosphonium salt (655g, 1.278mol) obtained in example 2, tetrahydrofuran 1000ml, and N were charged in a 3L mechanically-stirred three-necked flask 2 And (3) opening the size, adding potassium tert-butoxide (315g, 2.812mol, 2.2eq) for 3-4 times, controlling the reaction temperature below 20 ℃, and stirring for half an hour at room temperature after the addition. Cooling to 0 deg.C in ice bath, adding n-hexanal (213g, 2.136mol, 1.2eq) in tetrahydrofuran (200 ml), controlling the internal temperature not to exceed 5 deg.C, dropping, reacting at 0 deg.C for half an hour, and stirring at room temperature for 1 hr. After quenching with saturated ammonium chloride (500 ml), the organic phase was separated, the aqueous phase was extracted with ethyl acetate (500 ml. Times.2), the organic phase was washed with brine (500 ml. Times.2), and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =15: 1-10) to give 10-hexadecene-1-ol (cis-trans ratio 91.
Example 4:
synthesis of 10-hexadecen-1-ol
The quaternary phosphonium salt (655g, 1.278mol) obtained in example 2, tetrahydrofuran 1000ml, and N were charged in a 3L mechanically-stirred three-necked flask 2 Opening, adding potassium tert-butoxide (287g, 2.556mol, 2eq) in 3-4 times, controlling reaction temperature below 20 deg.C, and finishing additionStirring for half an hour. Cooling to 0 deg.C in ice bath, adding n-hexanal (213g, 2.136mol, 1.2eq) in tetrahydrofuran (200 ml), controlling the internal temperature not to exceed 5 deg.C, dropping, reacting at 0 deg.C for half an hour, and stirring at room temperature for 1 hr. After quenching with saturated ammonium chloride (500 ml), the organic phase was separated, the aqueous phase was extracted with ethyl acetate (500 ml. Times.2), the organic phase was washed with brine (500 ml. Times.2), and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =15:1 to 10) to give 10-hexadecene-1-ol (cis-trans ratio 91.
Example 5:
synthesis of 10-hexadecen-1-ol
The quaternary phosphonium salt (655g, 1.278mol) obtained in example 2, tetrahydrofuran 1000ml, and N were charged in a 3L mechanically-stirred three-necked flask 2 Opening the reactor, adding potassium tert-butoxide (359g, 3.195mol,2.5 eq) in 3-4 times, controlling the reaction temperature below 20 ℃, and stirring for half an hour at room temperature after the addition. Cooling to 0 deg.C in ice bath, adding n-hexanal (213g, 2.136mol, 1.2eq) in tetrahydrofuran (200 ml), controlling the internal temperature not to exceed 5 deg.C, dropping, reacting at 0 deg.C for half an hour, and stirring at room temperature for 1 hr. After quenching with saturated ammonium chloride (500 ml), the organic phase was separated, the aqueous phase was extracted with ethyl acetate (500 ml. Times.2), the organic phase was washed with brine (500 ml. Times.2), and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =15: 1-10) to yield 10-hexadecene-1-ol (cis-trans ratio 91.
Example 6:
synthesis of 10-hexadecen-1-ol
Into a dry 100ml round bottom flask was added 40ml of anhydrous dimethylsulfoxide, 4.8g of 60% sodium hydride
(121.8 mmol, 2.1eq), heated to 72 ℃ and stirred for 1 hour, and cooled to room temperature to obtain the sodium salt of dimethyl sulfoxide for later use. 30g (58 mmol) of 10-hydroxydecyl triphenylphosphine salt and 150ml of tetrahydrofuran were charged in a 250ml three-necked flask, and the prepared dimethyl sulfoxide sodium salt (121.8 mmol) was added dropwise thereto and stirred at room temperature for half an hour. The mixture was cooled to 0 ℃ in an ice bath, and a solution of n-hexanal (6.3 g, 63.8mmol, 1.1eq) in tetrahydrofuran (20 ml) was added dropwise thereto, followed by reaction at 0 ℃ for half an hour at room temperature for 1 hour. Quenched by addition of saturated ammonium chloride (100 ml), extracted with ethyl acetate (100 ml. Times.2), washed with brine (50 ml. Times.2) and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =15: 1-10) to give 10-hexadecen-1-ol in predominantly cis (cis to trans ratio 93: 7) in 74% yield (sodium hydride is required for the preparation of dimethyl sulfoxide sodium salt, hydrogen gas is generated, and there is a safety hazard).
Example 7:
synthesis of 10-hexadecen-1-ol
The quaternary phosphonium salt (655g, 1.278mol) obtained in example 2, tetrahydrofuran 1000ml, and N were charged in a 3L mechanically-stirred three-necked flask 2 Opening the size, adding sodium amide (110g, 2.812mol, 2.2eq) in 3 times, controlling the reaction temperature below 20 ℃, and stirring for half an hour at room temperature after the addition is finished. Cooling to 0 deg.C in ice bath, adding n-hexanal (213g, 2.136mol, 1.2eq) in tetrahydrofuran (200 ml), controlling the internal temperature not to exceed 5 deg.C, dropping, reacting at 0 deg.C for half an hour, and stirring at room temperature for 1 hr. After quenching with saturated ammonium chloride (500 ml), the organic phase was separated, the aqueous phase was extracted with ethyl acetate (500 ml. Times.2), the organic phase was washed with brine (500 ml. Times.2), and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =15: 1-10) to give 10-hexadecene-1-ol (cis-trans ratio 91.
Example 8:
isomerization of 10-hexadecen-1-ol
100g of 10-hexadecene-1-ol and 1g of p-toluenesulfonol were sequentially added to a 250ml single-neck flask, and the mixture was heated in an oil bath to 100 ℃ and stirred for 0.5 hour. After the reaction, the mixture was extracted with 500ml of ethyl acetate, and the organic phase was washed with a 10% aqueous solution of sodium hydroxide, water and brine, respectively. Dried over anhydrous sodium sulfate, spun dried, and the crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =15: 1-10) to give predominantly trans 10-hexadecene-1-ol (cis-trans ratio 25. E10-16OH map data: 1 H NMR(300MHz,CDCl 3 ):δ5.36-5.38(m,2H),3.62(t,J＝6.6Hz,2H),1.27-1.96(m,24H),0.87(t,J＝6.9Hz,3H)； 13 C NMR(75MHz,CDCl 3 ):δ130.61,130.53,63.28,33.02,32.80,31.62,29.85,29.80,29.65,29.56,29.35,25.96,22.77,14.30.
example 9:
isomerization of 10-hexadecen-1-ol
100g of 10-hexadecene-1-ol and 0.5g of p-toluenesulfonol were sequentially added to a 250ml single-neck flask, and the mixture was heated in an oil bath to 100 ℃ and stirred for 0.5 hour. After the reaction, the mixture was extracted with 500ml of ethyl acetate, and the organic phase was washed with a 10% aqueous solution of sodium hydroxide, water and brine, respectively. Dried over anhydrous sodium sulfate, spin-dried, and the crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate = 15.
Example 10:
isomerization of 10-hexadecen-1-ol
100g of 10-hexadecene-1-ol and 2g of p-toluenesulfonol were sequentially added to a 250ml single-neck flask, and the mixture was heated in an oil bath to 100 ℃ and stirred for 0.5 hour. After the reaction, the mixture was extracted with 500ml of ethyl acetate, and the organic phase was washed with a 10% aqueous solution of sodium hydroxide, water and brine, respectively. Dried over anhydrous sodium sulfate, spun-dried, and the crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =15: 1-10) to give 10-hexadecene-1-ol predominantly in trans (cis-trans ratio 23.
Example 11:
oxidation of 10-hexadecen-1-ol
A250 ml round bottom flask was charged with 113g of iodobenzene acetate, 4.3g of 4-hydroxy-2, 6-tetramethylpiperidine oxide and 300ml of methylene chloride, and then 60g of 10-hexadecene-1-ol was added dropwise thereto at a temperature of 0 ℃ and the mixture was stirred at 0 ℃ for 3 hours after completion of the addition. And after the reaction is finished, adding a saturated sodium thiosulfate solution for quenching, extracting by using dichloromethane, washing an organic phase by using water, drying by using anhydrous sodium sulfate, and performing spin drying to obtain a crude product. The crude product was added to a solution of sodium bisulfite (90 g) in water (400 ml), mechanically stirred at room temperature for four hours, added to acetonitrile (80 ml), stirred and filtered to give the aldehyde sodium bisulfite salt. The filter cake was washed with water (100 ml), acetonitrile (50 ml), dichloromethane (100 ml. Times.2), respectively. Transferring the drained filter cake into a three-neck bottle, adding 500ml of water, 100g of potassium carbonate and 200ml of petroleum ether, heating to 60 ℃, and stirringStirring for 3 hours, extracting with ethyl acetate to obtain free aldehyde, washing the organic phase with water and brine respectively, drying and spin-drying to obtain 10-hexadecenal (the cis-trans ratio is 25. E10-16Ald profile data: 1 H NMR(300MHz,CDCl 3 ):δ9.71(s,1H),5.29(m,2H),2.36(m,2H),1.25-1.97(m,22H),0.85(t,J＝6.6Hz,3H)； 13 C NMR(75MHz,CDCl 3 ):δ202.80,130.41,130.21,43.89,32.56,31.39,29.70,29.58,29.33,29.19,29.04,22.63,22.07,14.05.
example 12:
oxidation of 10-hexadecen-1-ol
In a 250ml round bottom flask were placed 20g of 10-hexadecene-1-ol, ferric nitrate nonahydrate (0.1 eq), 2, 6-tetramethylpiperidine oxide (0.1 eq), sodium chloride (0.1 eq), 120ml of dichloroethane, and pure oxygen was passed through with controlled gas flow rate (2-3 bubbles/sec) and stirred at room temperature overnight. After the reaction, the sand core funnel was filled with diatomaceous earth and filtered, and the filter cake was washed with ethyl acetate (50 ml. Times.4). The crude product was purified by column chromatography (eluent petroleum ether/ethyl acetate =20: 1) to give 10-hexadecenal (cis-trans ratio 25: 75) in 75% yield.
Comparative example 1:
isomerization of 10-hexadecen-1-ol
100g of 10-hexadecene-1-ol, 1g of iodine and 250mL of petroleum ether are sequentially added into a 500mL single-mouth bottle, and the mixture reacts for 4 hours under the illumination condition, and the cis-trans ratio is unchanged or is not reacted under the gas phase detection. The reaction time was extended to 12 hours and no reaction was observed.
Claims (3)
1. The method for synthesizing sex pheromone of dichocrocis punctiferalis is characterized by comprising the following steps:
(1) 1, 10-decanediol is taken as a raw material, and 10-bromo-1-decanol is prepared through unilateral bromination reaction;
(2) Reacting 10-bromo-1-decanol with triphenylphosphine to obtain 10-hydroxydecyl triphenylphosphine salt;
the dosage of triphenylphosphine is 1.1eq, and the reaction conditions are as follows: heating to 94 ℃ and refluxing for 48 hours;
(3) The 10-hydroxy decyl triphenylphosphine salt and n-hexanal are subjected to a Wittig reaction under the action of alkali to obtain 10-hexadecene-1-ol with cis as a main component;
the alkali used in the Wittig reaction is potassium tert-butoxide, sodium dimethyl sulfoxide or sodium amide;
the molar ratio of the alkali to the 10-hydroxydecyl triphenylphosphine salt is 2-2.5;
(4) Isomerizing the cis-form main 10-hexadecene-1-alcohol under the action of p-methylthiophenol to obtain trans-form main 10-hexadecene-1-alcohol;
the usage amount of p-methylthiophenol is 0.5-2% of the mass of 10-hexadecene-1-alcohol;
(5) The trans-predominant 10-hexadecene-1-ol is oxidized into corresponding olefine aldehyde under the action of an oxidizing agent;
the oxidant is oxygen or iodobenzene acetate.
2. The method for synthesizing dichocrocis punctiferalis sex pheromone according to claim 1, wherein in the step (1), bromination is performed by using 48% hydrobromic acid, and the using amount of the 48% hydrobromic acid is 1.64eq; the bromination reaction temperature is 110 ℃, and the reaction time is 48 hours.
3. The method for synthesizing dichocrocis punctiferalis sex pheromone according to claim 1, wherein the dosage of iodobenzene acetate in the step (5) is 1.2 to 1.6eq of 10-hexadecene-1-ol, and the dosage of oxygen is 20 to 40eq.
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