CN112661725B - Synthetic method of sex pheromone of fall webworm - Google Patents
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Abstract
The invention relates to the technical field of fall webworm control, in particular to a synthetic method of fall webworm sex pheromone. In the method for synthesizing (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosapiene by using propiolic alcohol as a starting material, trifluoromethyl sulfonic anhydride is used for carrying out sulfoesterification reaction on key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol, and various side reactions are easy to occur. Aiming at the problems, the propiolic alcohol is used as a starting material, sharpless asymmetric dihydroxylation is used as a key step, the (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene is smoothly synthesized, the step of carrying out the sulfoesterification reaction on the key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol by using trifluoromethyl sulfonic anhydride does not exist in the preparation process, the whole reaction is mild and controllable, side reactions are few, and the enantioselectivity is high.
Description
Technical Field
The invention relates to the technical field of fall webworm control, in particular to a synthetic method of fall webworm sex pheromone.
Background
The fall webworm is moth of Hyphantriaceae and Hyphantria. It has advantages of food impurity, large breeding amount, strong adaptability and wide propagation path, is a serious harm to worldwide quarantine pests, and can harm more than 200 kinds of forest, fruit trees, crops and wild plants. The fall webworm is distributed in the united states, canada, eastern european countries, japan, korean, etc. In 1979, the plant is found for the first time in Liaoning province of China and spread to Beijing, tianjin, hebei, liaoning, shandong, shaanxi, henan and other places, and causes dramatic loss to silkworm industry, forest and fruit industry and urban greening in China.
The chemical control is the most basic method for controlling the fall webworms and has the characteristics of rapidness, easy operation and economy. But the chemical control process is difficult to achieve without polluting the natural environment, and the natural enemies of the hyphantria cunea can be killed together in the process of killing the hyphantria cunea, so that the pests generate drug resistance. The method for trapping and killing the insects by adopting the sex pheromone of the fall webworms has stronger selectivity, cannot pollute the ecological environment, cannot cause the fall webworms to generate drug resistance, and is a green, environment-friendly, efficient and sustainable development prevention and control means.
Research shows that the (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-eicosadiene separated from the sex pheromone of the fall webworm has better attraction activity. In the 80 s of the 20 th century, (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene was synthesized by K.Mori of Tokyo university in Japan, the yield of the polydiacetylene is only up to 7% at most, and a polyacetylene intermediate in the method is unstable and is easy to isomerize or oxidize. In the 90 s of the 20 th century, shanghai organic chemistry research institute of Chinese academy of sciences, linzhong, and the like, the (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene is synthesized by taking the divinyl methanol as a raw material through 10 steps of reaction, although the optical purity and the total yield of the product are improved, the divinyl methanol as the raw material is not easy to obtain, and therefore the application of the method is limited. The Chinese invention patent CN 101798293A successfully synthesizes (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene by using glycerol as a starting material, wherein the key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol is subjected to a sulfoesterification reaction by using trifluoromethyl sulfonic anhydride to generate high-activity trifluoromethyl sulfonate, and then the subsequent reaction is carried out. In the reaction process, the trifluoromethyl sulfonic anhydride has high reactivity and strong oxidizability, and the generated trifluoromethyl sulfonic ester has very high reactivity, and both of the trifluoromethyl sulfonic anhydride and the trifluoromethyl sulfonic ester are easy to generate side reactions such as elimination, substitution and the like, so that the sulfoesterification reaction is difficult to control, and even a sulfoesterified product cannot be obtained.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: in the method for synthesizing (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene by using propiolic alcohol as a starting material, if trifluoromethyl sulfonic anhydride is used for carrying out a sulfoesterification reaction on a key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol to generate high-activity trifluoromethyl sulfonate, then subsequent reactions are carried out, various side reactions are easy to occur, so that the sulfoesterification reaction is difficult to control, and even a sulfoesterified product cannot be obtained.
The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides a method for synthesizing sex pheromone of fall webworms, which takes propiolic alcohol as an initial raw material and Sharpless asymmetric dihydroxylation reaction as a key step to obtain (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosene through reaction, wherein the reaction process is as follows:
the method specifically comprises the following steps:
(1) Under the action of ice bath and catalyst, propiolic alcohol reacts with 3, 4-dihydropyran in dichloromethane for 24 hours to obtain a compound 2;
(2) Under the protection of argon at low temperature, 1-bromoundecane and the compound 2 are coupled under the action of alkali to obtain a compound 3;
(3) Under the action of a catalyst, reacting the compound 3 in an organic solvent to obtain a compound 4;
(4) Reacting the compound 4 with a reducing agent at low temperature under the protection of argon to obtain a compound 5;
(5) Under the conditions of low temperature and catalyst existence, carrying out Sharpless asymmetric dihydroxylation reaction on the compound 5 to obtain a compound 6;
(6) Under the action of alkali, reacting the compound 6 with benzenesulfonylimidazole to obtain a compound 7;
(7) Under the action of low temperature, argon protection, alkali and boron trifluoride diethyl etherate, reacting the compound 7 with trimethylsilyl acetylene to obtain a compound 8;
(8) Under alkaline conditions, reacting the compound 8 in an organic solvent to obtain a compound 9;
(9) Under the action of alkali and an iodination reagent, reacting the compound 9 with 2-pentyne-1-ol mesylate to obtain a compound 10;
(10) Under the action of catalyst, compound 10 is catalytically hydrogenated to obtain (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene.
Specifically, the catalyst in step (1) is p-toluenesulfonic acid (PTSA) or pyridinium p-toluenesulfonate (PPTS).
Specifically, the low temperature in the step (2) is-78 ℃ to 0 ℃, the base is n-butyllithium, and the molar ratio of the 1-bromoundecane to the compound 2 is 1.
Specifically, the catalyst in the step (3) is p-toluenesulfonic acid (PTSA), and the organic solvent is methanol.
Specifically, the reducing agent in the step (4) is lithium aluminum hydride, and the organic solvent is diethyl ether or tetrahydrofuran.
Specifically, the low temperature in the step (5) is 0 ℃, and the catalyst is AD-mix-alpha.
Specifically, the base in the step (6) is sodium hydride, and the benzenesulfonyl imidazole is p-toluenesulfonyl imidazole or triisopropylbenzenesulfonyl imidazole.
Specifically, in the step (7), the base is n-butyllithium, the organic solvent is tetrahydrofuran, and the molar ratio of the compound 7 to trimethylsilylacetylene is 1-3.
Specifically, the base in the step (8) is potassium carbonate or cesium carbonate, the organic solvent is methanol, and the molar ratio of the compound 8 to the base is 1.
Specifically, the base in the step (9) is potassium carbonate, the iodinating reagents are cuprous iodide and sodium iodide, the organic solvent is N, N-dimethylformamide, and the molar ratio of the compound 9 to the 2-pentyn-1-ol mesylate is 1-5.
Specifically, the catalyst in the step (10) is a P-2 nickel catalyst or a Lindlar catalyst.
The beneficial effects of the invention are:
(1) The method for preparing (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene does not have the step of carrying out the subsequent reaction after the trifluoromethyl sulfonic acid ester with high activity is generated by carrying out the sulfoesterification reaction on the key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol by using the trifluoromethyl sulfonic anhydride, side reactions such as elimination, substitution and the like are not easy to occur, the whole reaction is simple, mild and controllable, and the enantiomer selectivity is high;
(2) The total reaction yield of the (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene obtained by the invention is high and is about 10 percent.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Step (1), synthesis of compound 2:
example 1
Adding 0.3568mol of propiolic alcohol, 150mL of dichloromethane and 0.03568mol of p-toluenesulfonamide into a 250mL single-neck bottle, cooling in an ice bath, slowly dropping 42.02g of dihydropyran, stirring at room temperature for 24 hours after dropping, adding saturated aqueous sodium bicarbonate solution to quench the reaction after the reaction is finished, extracting an organic phase by dichloromethane, washing by water, washing by brine, drying by anhydrous sodium sulfate, and purifying by column chromatography to obtain the compound 2 with the yield of 90%.
Example 2
The PTSA in example 1 was replaced with pyridinium p-toluenesulfonate, and the yield of compound 2 was 89% without changing other conditions.
Step (2), synthesis of compound 3:
example 3
Under the protection of argon, 0.19173mol of compound 2 and 250mL of dry tetrahydrofuran are added into a 1000mL three-necked bottle, the mixture is cooled to-78 ℃, 71mL of n-BuLi solution with the concentration of 2.7mol/L is dropwise added, stirring is carried out for half an hour after the dropwise addition is finished, 0.1743mol of 1-bromoundecane, 40g1, 3-dimethylpropylene urea are sequentially dropwise added at-78 ℃, after the dropwise addition is finished, the temperature is slowly increased to room temperature and stirring is carried out for 24 hours, a gas chromatograph monitors the reaction until the reaction is finished, after the reaction is finished, a saturated ammonium chloride water solution is added to quench the reaction, an organic phase is extracted by ethyl acetate, and after washing, brine washing and drying by anhydrous sodium sulfate, the compound 3 is obtained after column chromatography purification, and the yield is 80%.
Example 4
The molar ratio of 1-bromoundecane to the compound 2 in example 3 was changed to 1.8, and the other conditions were not changed to obtain a compound 3 with a yield of 82%.
Example 5
The molar ratio of 1-bromoundecane to the compound 2 in example 3 was changed to 1.
Example 6
The molar ratio of 1-bromoundecane to the compound 2 in example 3 was changed to 1.
Step (3), synthesis of compound 4:
example 7
Adding 101.87mmol of compound 3, 300mL of methanol and 10.187mmol of p-toluenesulfonic acid into a 500mL single-neck bottle, stirring at room temperature for 24h, adding solid sodium bicarbonate after the reaction is finished, quenching the reaction, spin-drying the methanol, extracting an organic phase with ethyl acetate, washing with water, washing with saline, drying with anhydrous sodium sulfate, and purifying by column chromatography to obtain compound 4 with yield of 90%.
Step (4), synthesis of compound 5:
example 8
Under the protection of argon, 139.72mmol of lithium aluminum hydride and 300mL of tetrahydrofuran are added into a 500mL single-mouth bottle, ice bath cooling is carried out, 99.8mmol of compound 4 is dropwise added, after the dropwise addition is finished, stirring is carried out for 24 hours at room temperature, a gas chromatograph monitors until the reaction is finished, after ice bath cooling, 5.30mL of water, 5.30mL of sodium hydroxide aqueous solution with the mass concentration of 10% and 10.60mL of water are sequentially dropwise added, after the dropwise addition is finished, the compound 5 is obtained after diatomite suction filtration of insoluble substances, spin drying of filtrate and column chromatography purification, and the yield is 90%.
Example 9
The solvent in example 6 was changed to diethyl ether under otherwise unchanged conditions, yielding compound 5 in 84% yield.
Step (5), synthesis of compound 6:
example 10
(5) Adding 500mL of tert-butyl alcohol, 500mL of water, 94.17mmol of compound 5, 132g of AD-mix-alpha and 94.17mmol of methylsulfonamide into a 2L mechanically-stirred three-necked bottle, stirring at 0 ℃ for 24 hours, adding a sodium thiosulfate aqueous solution to quench the reaction after the reaction is finished, extracting an organic phase with ethyl acetate, washing with water, washing with brine, drying, and purifying by column chromatography to obtain a crude product, dissolving the crude product in dichloromethane, and recrystallizing at-10 ℃ to obtain the compound 6 with the yield of 70%.
Step (6), synthesis of compound 7:
example 11
Under the protection of argon, 40.59mmol of compound 6 and 350mL of tetrahydrofuran are added into a 500mL three-necked bottle, ice bath cooling is carried out, 121.77mmol of sodium hydride powder is slowly added in batches, stirring is carried out for 0.5 hour at room temperature, 97.416mmol of p-toluenesulfonylimidazole is added, stirring is carried out for 4 hours at room temperature, after the reaction is finished, water is added for quenching the reaction, ethyl acetate is used for extracting an organic phase, and after water washing, salt water washing, anhydrous sodium sulfate drying and column chromatography purification, compound 7 is obtained, and the yield is 60%. Process for preparation of Compound 7 1 H NMR(400MHz,CDCl 3 ):δ0.88(t,3H),1.20-1.60(m,20H),2.45(s,3H),2.61-2.65(m,2H),2.83(m,1H),4.32(dd,1H),7.34(d,2H),7.82(d,2H)。
Example 12
The p-toluenesulfonylimidazole in example 9 was changed to triisopropylbenzenesulfonylimidazole, and the other conditions were not changed to obtain compound 7 in a yield of 32%.
Step (7), synthesis of compound 8:
example 13
Under the protection of argon, 19.55mmol of trimethylsilyl acetylene and 150mL of dry tetrahydrofuran are added into a 250mL three-necked flask, the mixture is cooled to-78 ℃, 23mmol of n-butyl lithium n-hexane solution with the concentration of 2.7mol/L is dropwise added, after the dropwise addition, the reaction is stirred for 10min, then 8.5mL of boron trifluoride diethyl ether is dropwise added at-78 ℃, after the dropwise addition, the stirring is continued for 15min, 20mL of tetrahydrofuran solution containing 11.5mmol of compound 7 is dropwise added, and after the dropwise addition, the stirring is carried out for 24h at-78 ℃. And (3) monitoring by a gas chromatograph until the reaction is finished, adding saturated ammonium chloride aqueous solution to quench the reaction after the reaction is finished, extracting an organic phase by using ethyl acetate, and obtaining a compound 8 after water washing, salt water washing, anhydrous sodium sulfate drying and column chromatography purification, wherein the yield is 70%.
Example 14
The molar ratio of compound 7 to trimethylsilylacetylene in example 11 was changed to 1, and the other conditions were not changed to obtain compound 8 in a yield of 56%.
Example 15
The yield of compound 8 was 63% under the same conditions as in example 11 except that n-butyllithium was changed to bis (trimethylsilyl) aminolithium.
Example 16
The molar ratio of compound 7 to trimethylsilylacetylene in example 11 was changed to 1, and the other conditions were not changed to obtain compound 8 in a yield of 72%.
Step (8), synthesis of compound 9:
example 17
(8) Adding 9.98mmol of compound 8 and 80mL of anhydrous methanol into a 250mL single-mouth bottle, cooling in an ice bath, adding 49.9mmol of potassium carbonate, reacting for 5 hours, pouring the reaction solution into 500mL of water to quench the reaction after the reaction is finished, extracting an organic phase by using ethyl acetate, washing by water, washing by saline, drying by anhydrous sodium sulfate, and purifying by column chromatography to obtain the compound 9 with the yield of 70%.
Example 18
The yield of compound 9 was 55% obtained by changing the potassium carbonate in example 14 to sodium hydroxide under otherwise unchanged conditions.
Example 19
The molar ratio of compound 8 to the base in example 14 was changed to 1.
Example 20
The molar ratio of compound 8 to the base in example 14 was changed to 1.
Example 21
The molar ratio of compound 8 to the base in example 14 was changed to 1, and the other conditions were not changed to obtain compound 9 in a yield of 43%.
Example 22
The yield of compound 9 was 65% obtained by changing the potassium carbonate in example 14 to cesium carbonate under otherwise unchanged conditions.
Step (9), synthesis of compound 10:
example 23
Adding 7.56mmol of potassium carbonate, 7.56mmol of sodium iodide and 7.56mmol of cuprous iodide into a 100mL single-mouth bottle, replacing three times with argon, sequentially adding 40mL of N, N-dimethylformamide, 3.60mmol of compound 9 and 10.8mmol of 2-pentyne-1-ol mesylate under the protection of argon, stirring at room temperature for 24h for reaction, monitoring by a gas chromatograph until the reaction is finished, adding 100mL of ethyl acetate and 50mL of water after the reaction is finished, stirring uniformly, filling diatomite for filtering insoluble substances, extracting an organic phase from the filtrate by using ethyl acetate, washing by water, washing by salt water, drying by anhydrous sodium sulfate, and purifying by column chromatography to obtain the compound 10 with the yield of 90%.
Example 24
The molar ratio of compound 9 to 2-pentyn-1-ol methanesulfonate in example 17 was changed to 1, and the other conditions were not changed, whereby the yield of compound 10 was 72%.
Example 25
The molar ratio of compound 9 to 2-pentyn-1-ol methanesulfonate in example 17 was changed to 1.
Step (10), (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene synthesis:
example 26
Adding 1.95mmol of nickel acetate tetrahydrate and 40mL of ethanol into a 100mL single-neck flask, cooling by ice bath, slowly adding 1.95mmol of sodium borohydride, stirring for 20min, then adding 3.9mmol of ethylenediamine and 3.9mmol of compound 10, reacting for 5h at room temperature under hydrogen atmosphere, monitoring by a gas chromatograph until the reaction is finished, adding 50mL of ethyl acetate after the reaction is finished, filtering insoluble substances by diatomite, spin-drying filtrate, and purifying by column chromatography to obtain (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene with the optical purity of 95% e.e. and the yield of 90%. 1 H NMR(400MHz,CDCl 3 ):δ0.88(t,J＝6.8Hz,3H),0.98(t,J＝7.4Hz,3H),1.20-1.60(m,20H),2.08(quint,J＝7.4Hz,2H),2.22(dt,J＝15.1,6.4Hz,1H),2.40(dt,J＝15.1,6.4Hz,1H),2.81(t,J＝7.0Hz,2H),2.90-2.97(m,2H),5.26-5.56(m,4H)。
Example 27
Dissolving 3.9mmol of compound 10 in 40mL of methanol, adding 0.118g of Lindlar catalyst under ice-bath conditions, reacting for 1h at room temperature under hydrogen atmosphere, monitoring by a gas chromatograph until the reaction is finished, after the reaction is finished, leaching insoluble matters by diatomite, spin-drying filtrate, and purifying by column chromatography to obtain (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosene, wherein the optical purity of the compound is 95 percent, e.e., and the yield is 85 percent.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (11)
1. A method for synthesizing sex pheromone of fall webworm is characterized in that propiolic alcohol is used as an initial raw material, sharpless asymmetric dihydroxylation reaction is used as a key step, and (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene is obtained through reaction;
the synthetic method of the sex pheromone of the fall webworm is carried out according to the following steps:
(1) Under the action of ice bath and catalyst, propiolic alcohol reacts with 3, 4-dihydropyran to obtain a compound 2;
(2) Under the protection of argon, 1-bromoundecane and a compound 2 are subjected to coupling reaction under the action of alkali to obtain a compound 3, wherein the reaction temperature is-78 ℃ to 0 ℃;
(3) Under the action of a catalyst, reacting the compound 3 in an organic solvent to obtain a compound 4;
(4) Reacting the compound 4 with a reducing agent at low temperature under the protection of argon to obtain a compound 5;
(5) In the presence of a catalyst, carrying out Sharpless asymmetric double hydroxylation reaction on the compound 5 to obtain a compound 6, wherein the reaction temperature is 0 ℃;
(6) Under the action of alkali, reacting the compound 6 with benzenesulfonyl imidazole to obtain a compound 7;
(7) Under the action of low temperature, argon protection, alkali and boron trifluoride diethyl etherate, reacting the compound 7 with trimethylsilyl acetylene to obtain a compound 8;
(8) Under alkaline conditions, reacting the compound 8 in an organic solvent to obtain a compound 9;
(9) Under the action of alkali and an iodination reagent, reacting the compound 9 with 2-pentyne-1-ol mesylate to obtain a compound 10;
(10) Under the action of a catalyst, the compound 10 is subjected to catalytic hydrogenation reaction to obtain (3Z, 6Z,9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene;
the synthetic route of the sex pheromone of the fall webworm is as follows:
2. the method of synthesizing sex pheromones of fall webworm according to claim 1, wherein: the catalyst in the step (1) is p-toluenesulfonic acid or pyridinium p-toluenesulfonic acid.
3. The method of synthesizing sex pheromones of fall webworm according to claim 1, wherein: the base in the step (2) is n-butyllithium, and the molar ratio of the 1-bromoundecane to the compound 2 is 1-4.
4. The method of synthesizing sex pheromones of fall webworm according to claim 1, wherein: the catalyst in the step (3) is PTSA, and the organic solvent is methanol.
5. The method of synthesizing sex pheromones of fall webworm according to claim 1, wherein: the reducing agent in the step (4) is lithium aluminum hydride, and the organic solvent is diethyl ether or tetrahydrofuran.
6. The method for synthesizing sex pheromone of fall webworm as claimed in claim 1, wherein the method comprises the following steps: the catalyst in the step (5) is AD-mix-alpha.
7. The method for synthesizing sex pheromone of fall webworm as claimed in claim 1, wherein the method comprises the following steps: the alkali in the step (6) is sodium hydride, and the benzenesulfonyl imidazole is p-toluenesulfonyl imidazole or triisopropylbenzenesulfonyl imidazole.
8. The method of synthesizing sex pheromones of fall webworm according to claim 1, wherein: the alkali in the step (7) is n-butyllithium, the organic solvent is tetrahydrofuran, and the molar ratio of the compound 7 to the trimethylsilylacetylene is 1-3.
9. The method of synthesizing sex pheromones of fall webworm according to claim 1, wherein: the alkali in the step (8) is potassium carbonate or cesium carbonate, the organic solvent is methanol, and the molar ratio of the compound 8 to the alkali is 1-7.
10. The method of synthesizing sex pheromones of fall webworm according to claim 1, wherein: the alkali in the step (9) is potassium carbonate, the iodinating reagent is cuprous iodide and sodium iodide, the organic solvent is N, N-dimethylformamide, and the molar ratio of the compound 9 to the 2-pentyne-1-ol mesylate is 1-5.
11. The method for synthesizing sex pheromone of fall webworm as claimed in claim 1, wherein the method comprises the following steps: the catalyst in the step (10) is a P-2 nickel catalyst or a Lindlar catalyst.
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