CN112645904A - Novel method for synthesizing sex pheromone component of fall webworm - Google Patents
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Abstract
The invention belongs to the technical field of chemical production, and particularly relates to a method for synthesizing a novel sex pheromone component of fall webworms, wherein the sex pheromone component of the fall webworms is I [ (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosa diene ] and II [ (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-henesa triene ]. The method has the advantages that the carbon tetrabromide and the triphenylphosphine are used, so that the bromination reaction of the key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol (compound 1) can be carried out mildly, the method is simple and convenient, and the yield is high; according to the invention, 1, 4-heptadiyne and 1-heptene-3, 6-diyne are used for introducing related structural fragments, so that reaction steps are reduced, and the reaction yield is improved; the invention uses nickel acetate and sodium borohydride in situ generated P-2 type nickel as the catalyst by abolishing the use of the Linderler palladium catalyst, thereby reducing the production cost, preventing the over hydrogenation of carbon-carbon triple bond, having mild and controllable reaction and good yield.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a novel method for synthesizing sex pheromone components of fall webworms.
Background
The fall webworms, also called fall webworms, fall webworms and fall webworms, belong to lepidoptera and fall webworms, are world-wide quarantine pests which draw attention, mainly harm fruit trees, street trees and ornamental trees, particularly bear the weight of broad-leaved trees, cause serious harm to garden trees, economic forests, farmland protection forests and the like, and are listed as the first foreign invasive species in China at present.
The fall webworm is a leaf eating pest which seriously harms various plants and has the characteristics of harm: firstly, the edible impurities can harm various plants including forest trees, fruit trees, crops and flowers; secondly, the reproductive capacity is strong, three generations of the adult fall webworms are bred in one year, and 0.77 hundred million larvae can be bred after the three generations of the adult fall webworms in early spring 1; thirdly, the transmission path is wide, and long-distance transmission can be carried out along with goods, transport tools and the like all the year round; fourthly, the harm is serious, and all the leaves of green plants can be eaten in a very short time during outbreak, so that the ecological safety is seriously threatened. The fall webworm is not only a forestry pest but also an agricultural pest, and is listed as a worldwide quarantine object. Although the conventional chemical control method adopted for controlling the fall webworms has quick effect, the sprayed chemical not only pollutes the environment, but also kills other beneficial natural enemies of various pests; over the last two or three years, the drug resistance of the fall webworms is enhanced, the fall of soil is heavy, and serious disasters can be caused to various plants and the ecological environment.
The fall webworm has wide host range and can harm more than 300 plants in China. The favorite tree species include poplar, mulberry, phoenix tree, maple, etc., and also harm the broad-leaved tree species such as willow, locust tree, camptotheca acuminata, ailanthus altissima, etc. Besides trees and fruit trees, the fertilizer can also harm crops and vegetables. The larva of the fall webworm has large food intake, reaches the peak after four ages, and can eat the leaves of the whole plant overnight during a major outbreak, so that the plant grows and develops badly, and in severe cases, the tree dies, crops do not harvest, and serious economic loss is caused.
The invasion and propagation ways of the fall webworms are quite various, the enhancement of the monitoring of the insect situation is the basic work for preventing and controlling the fall webworms, and the method has important practical significance for preventing the spread of the epidemic situation by taking prevention and control measures. The method is a mature monitoring technology, and has the characteristics of high accuracy and remarkable effect.
The sex attractant for the fall webworms mainly comprises three effective components of (9Z, 12Z, 15Z) -octadecenedial, (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene and (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosatriene, and the latter two optically active epoxy compounds are important components, and the synthesis steps are long, the difficulty is high, and the scale-up production is difficult to meet the market demands. At present, sex attractants of the fall webworms in China mostly depend on imports, are expensive and high in cost, so that monitoring and control by utilizing the fall webworm sex pheromone bring heavier economic burden to production units, and the application in a large range is blocked.
For (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene and (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosatriene, the following two more practical synthetic methods are reported:
1. the invention patent CN 201010127021.1-simple stereoselective synthetic method of sex pheromone of fall webworm, its reported production route of two optically active epoxy compounds is as follows:
after (2S, 3R) -2, 3-epoxy-1-tetradecanol is prepared, the obtained product reacts with trifluoromethyl sulfonic anhydride to generate sulfonic ester, and then (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene and (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosadiene are respectively obtained through coupling, hydrogenation, bromination, reduction or elimination reaction.
2. The invention patent CN201610499450.9, a synthetic method of sex pheromone of fall webworm, reports a synthetic route of sex pheromone (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosapiene.
In this patent, (2S, 3R) -2, 3-epoxy-1-tetradecanol is produced, then reacted with trifluoromethanesulfonic anhydride to produce sulfonate, instead coupled with 1, 4-heptadiyne, and then hydrogenated to obtain a sex pheromone (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene.
In the production methods of the two patents, the key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol is subjected to a sulfoesterification reaction by adopting trifluoromethyl sulfonic anhydride, and subsequent reactions are carried out after high-activity trifluoromethyl sulfonate is generated. Through synthetic research, the trifluoromethyl sulfonic anhydride is found to have high reactivity and oxidability, and the trifluoromethyl sulfonic ester generated by the reaction has very high reactivity and is easy to generate side reactions such as elimination, substitution and the like; therefore, even if the sulfoesterification is carried out at about-80 ℃, the reaction is still difficult to control, the yield is only 20 percent, and even a sulfoesterified product cannot be obtained.
In view of the good application prospect of the sex pheromone of the fall webworm, a novel synthetic method is found to obtain the sex pheromone component of the fall webworm with high optical purity, so that a good production process needs to be developed, and the industrial production of the sex pheromone component-based attractant can be realized.
Disclosure of Invention
Objects of the invention
In view of the above problems in the prior art, the technical problem to be solved by the present invention is to provide a new synthesis method of sex pheromone components (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosyl diene and (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-henesyl triene) of fall webworm.
(II) technical scheme
In order to solve the technical problems, the invention provides a method for synthesizing a novel sex pheromone component of fall webworm, wherein the sex pheromone component of the fall webworm is I [ (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosyl diene ] and II [ (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosyl triene ], and the route of the synthetic method is as follows:
the specific synthetic product is represented by Arabic numerals according to the number in the structural formula, and R or S represents the absolute configuration of the compound.
Preferably, the method comprises the following steps:
1) reacting the compound 1 with carbon tetrabromide and triphenylphosphine in an organic solvent at-15-30 ℃, and filtering, concentrating and purifying to obtain a compound 2;
2) performing coupling reaction on the compound 3 and the compound 2 in tetrahydrofuran and hexamethylphosphoramide under the action of n-butyllithium at the temperature of-60-25 ℃, and extracting, drying, concentrating and purifying to obtain a compound 5;
3) performing coupling reaction on the compound 4 and the compound 2 in tetrahydrofuran and hexamethylphosphoramide under the action of n-butyllithium at the temperature of-60-25 ℃, and extracting, drying, concentrating and purifying to obtain a compound 6;
4) at room temperature, the compound 5 is subjected to coupling reaction with ethylenediamine in ethanol under the action of a catalyst, hydrogenation reaction with hydrogen is carried out, and the compound I is obtained through filtration, concentration and purification;
5) and (2) performing coupling reaction on the compound 6 and ethylenediamine in ethanol under the action of a catalyst at room temperature, performing hydrogenation reaction on the compound and hydrogen, and filtering, concentrating and purifying to obtain a compound II.
Preferably, the organic solvent in step 1) is one of dichloromethane, chloroform, ethyl acetate, chlorobenzene, dichlorobenzene, pyridine, phenol and dichloroethane.
Preferably, the organic solvent in step 1) is dichlorobenzene, 2-bromomethane or ethyl acetate.
Preferably, the molar ratio of the compound 1 to carbon tetrabromide to triphenylphosphine in the step 1) is 1: 1.4.
Preferably, the tetrahydrofuran in step 2), 3): the volume ratio of hexamethylphosphoramide is 5: 1.
Preferably, the molar ratio of the compound 3 to the n-butyllithium to the compound 2 in the step 2) is 2: 1; the molar ratio of the compound 4 to the n-butyllithium to the compound 2 in the step 3) is 2: 1.
Preferably, the catalyst in the step 4) and the step 5) is P-2 type nickel generated in situ by nickel acetate and sodium borohydride.
Preferably, the amount of the P-2 type nickel used in the step 4) is 15% of the molar amount of the compound 5; the amount of the P-2 type nickel used in the step 5) is 15% by mole based on the amount of the compound 6.
The technical scheme of the invention has the following beneficial technical effects:
1. the invention can carry out bromination reaction on the key intermediate (2S, 3R) -2, 3-epoxy-1-tetradecanol (compound 1) mildly by using carbon tetrabromide and triphenylphosphine, and has the advantages of simplicity, convenience and high yield.
2. According to the invention, the 1, 4-heptadiyne and the 1-heptene-3, 6-diyne are used for introducing related structural fragments, so that the reaction steps are reduced, and the reaction yield is improved.
3. The invention uses nickel acetate and sodium borohydride in situ generated P-2 type nickel as the catalyst by abolishing the use of the Linderler palladium catalyst, thereby reducing the production cost, preventing the over hydrogenation of carbon-carbon triple bond, having mild and controllable reaction and good yield.
4. The synthesis method provided by the invention has the advantages of low cost, simple reaction conditions and few reaction steps, and is suitable for large-scale production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1:
the synthesis method of the sex pheromone components of the fall webworm (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene (I) and the sex pheromone components of the fall webworm (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosadriene (II) comprises the following steps:
the method comprises the following specific steps:
step 1 Synthesis of Compound 2
Dissolving 2.5 g of compound 1 in 100 ml of ethyl acetate, stirring for dissolving, adding 3.5 g of triphenylphosphine, stirring for dissolving, cooling ice salt to-5 ℃, and adding 4.8 g of carbon tetrabromide in batches within 40 minutes; naturally heating to room temperature for reaction, detecting by TLC, adding 450 ml of normal hexane, stirring for 40 minutes, filtering, concentrating the filtrate by a thin film chromatography, and purifying the residue by column chromatography (V (ethyl acetate): (normal hexane) ═ 1: 35) to obtain 3 g of compound 2.
Step 2 Synthesis of Compound 5
Dissolving 1.6 g of 1, 4-heptadiyne (compound 3) in 100 ml of tetrahydrofuran and hexamethylphosphoramide (V (tetrahydrofuran): (hexamethylphosphoramide) ═ 5: 1), cooling to-83 ℃, dropwise adding 10 ml of 1.6M n-butyllithium/n-hexane solution within 20 minutes, and stirring to react for 35 minutes after dropwise adding; then 3 g of compound 2/20 ml of tetrahydrofuran solution is added dropwise, the mixture is naturally heated to room temperature and stirred overnight, 250 ml of water is added dropwise for extraction and reaction, dichloromethane is used for extraction, organic phases are combined, the mixture is washed for 3 times by saturated saline solution, dried by anhydrous sodium sulfate, concentrated and purified by column chromatography (V (ethyl acetate): (normal hexane) ═ 1: 70) to obtain 2.9 g of compound 5.
Step 3 Synthesis of Compound 6
Dissolving 1.5 g of 1-heptene-3, 6-diyne (compound 4) in 100 ml of tetrahydrofuran, cooling to-83 ℃, dropwise adding 10 ml of 1.6M n-butyllithium/n-hexane solution within 20 minutes, and stirring to react for 35 minutes after dropwise adding; then 3.5 g of compound 2/20 ml of hexamethylphosphoramide solution is dropped into the mixture, the mixture is naturally heated to room temperature and stirred overnight, 260 ml of water is dropped into the mixture to perform extraction and quenching reaction, dichloromethane is used for extraction, organic phases are combined, the mixture is washed by saturated saline solution for 3 times, and the mixture is dried by anhydrous sodium sulfate, concentrated and purified by column chromatography (V (ethyl acetate): (petroleum ether) ═ 1: 70) to obtain 2.8 g of compound 6.
Step 4 Synthesis of (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosane (I)
Adding 0.2 g of nickel acetate and 100 ml of ethanol into a reaction bottle, stirring and dissolving, replacing 3 times by nitrogen, adding 400 mg of sodium borohydride, stirring for 35 minutes, and injecting 6 ml of ethylenediamine; replacing the reaction system with hydrogen for 2 times, injecting 3.5 g of compound 5/20 ml of ethanol solution, and continuously stirring at room temperature for reaction; after the reaction is finished, the reaction is filtered, concentrated and purified by column chromatography (V (ethyl acetate): (petroleum ether): 1: 55) to obtain 3 g of (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosene, 1HNMR (400MHz, CDCl 3): δ 0.88(t, 3H), 0.98(t, 3H), 1.26-1.58(m, 20H), 2.09(q, 2H), 2.24(dt, 1H), 2.40(dt, 1H), 2.80(t, 3H), 2.91-2.97(m, 2H), 5.29-5.53(m, 4H); calculated HRMSm/z (M + Na +): 328.1622, found: 328.2628.
step 5 Synthesis of (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosa triene (II)
Adding 0.2 g of nickel acetate and 100 ml of ethanol into a reaction bottle, stirring and dissolving, replacing 3 times by nitrogen, adding 400 mg of sodium borohydride, stirring for 35 minutes, and injecting 6 ml of ethylenediamine; replacing the reaction system with hydrogen for 2 times, injecting 3.5 g of compound 6/20 ml of ethanol solution, and continuously stirring at room temperature for reaction; after the reaction is finished, the reaction is filtered, concentrated and purified by column chromatography (V (ethyl acetate): (petroleum ether) ═ 1: 50) to obtain (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosyltriene 2.9 g and 1HNMR (400MHz, CDCl 3): δ 0.88(t, 3H), 1.21-1.58(m, 20H), 2.23(dt, 1H), 2.41(dt, 1H), 2.89-2.99(m, 4H), 5.12(d, 1H), 5.24(dt, 1H), 5.40(dt, 1H), 5.44-5.56(m, 2H), 6.04(dd, 1H), 6.64(ddd, 1H); calculated HRMSm/z (M + Na +): 327.2663, found: 327.2674.
example 2:
the sex pheromone component of fall webworm (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene, (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosatriene, (9Z, 12Z, 15Z) -octadecatrienal (the synthesis method refers to JeifengHu, Xi aoweiHan, YuYuYuan, Zhuangzhishi, Angew.Chem.Ed.2017, 56: 13342 and 13346.) synthesized in example 1 is dissolved in 120 μ L of heavy distilled dichloromethane according to the set mass ratio (25: 4: 1-12: 1.2: 1) to prepare the sex pheromone solution of fall webworm with a certain concentration, and the solution is placed in a refrigerator and stored at-30 ℃ for later use.
Selecting a cuff type rubber plug as a sex pheromone carrier, and naturally drying the rubber plug after the rubber plug is cleaned by absolute ethyl alcohol. Then dripping the sex attractant solution into a concave cup of a special reverse rubber plug according to different required proportions and dosages, and sealing with a sealing film for later use after the solvent is volatilized. The field test is carried out in mulberry forest of wild store in Shushan district of Hefei city, Anhui province, the time is from 7 months and 25 days to 8 months and 20 days in 2020, the trap is a net type trap, each formula of the sex pheromone solution of the fall webworm is repeated for 4 times, and the repeated times are carried out by taking an imported lure as reference. The trappers are hung at the position 2.0-3.0 meters away from the ground outdoors, the distance between every two trappers is about 30 meters, the trapper trapping amount is counted once every 2 days and cleaned, and meanwhile, the trapping core position is changed, so that the influence of the position on the trapping effect is reduced. The test results are shown in Table 1.
TABLE 1 amount of Male Bombycis mori of Sporidia elata Blume trapped by self-combustion with attractant in different ratios
| Numbering | The ratio of the components | Total amount of trapped drug | Average trapping number (head) | Daily trapping quantity (head) |
| 1 | 20∶3∶1 | 65 | 32.5±1.5 | 4.4±0.8 |
| 2 | 20∶2∶1 | 109 | 36.5±2.1 | 5.9±0.6 |
| 3 | 20∶1∶1 | 109 | 37.1±3.0 | 6.2±1.3 |
| 4 | 10∶3∶1 | 90 | 30.1±1.9 | 5.0±1.2 |
| 5 | 10∶2∶1 | 153 | 46.7±2.9 | 7.8±1.6 |
| 6 | 10∶1∶1 | 205 | 68.7±2.1 | 11.2±1.6 |
| Inlet lure core | - | 148 | 41.9±2.2 | 6.7±1.2 |
The test results in table 1 show that different composition ratios of the components in the sex pheromone lure core have different luring effects on the male moths of the fall webworms. In a moth-luring activity test in the field, the moth-luring activity of the compound (9Z, 12Z, 15Z) -octadecenedial to (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosane to (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosane is the highest when the ratio is 10: 1, 68.7 male moths are lured on average every 3 days, and the moth-luring activity is obviously more than that of other ratios and imported luring cores. The mixture ratio of 10: 2: 1, 20: 1 and 20: 2: 1 also has good attraction activity, and the male hyphantria cunea moths can be attracted to 46.7 heads, 37.1 heads and 36.5 heads of the hyphantria cunea moths respectively every 3 days on average.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (9)
1. A novel method for synthesizing sex pheromone components of fall webworms is characterized in that the sex pheromone components of the fall webworms are I [ (3Z, 6Z, 9S, 10R) -9, 10-epoxy-3, 6-heneicosadiene ] and II [ (3Z, 6Z, 9S, 10R) -9, 10-epoxy-1, 3, 6-heneicosadriene ], and the route of the synthetic method is as follows:
the specific synthetic product is represented by Arabic numerals according to the number in the structural formula, and R or S represents the absolute configuration of the compound.
2. The method of synthesizing a sex pheromone component of fall webworm according to claim 1, comprising the steps of:
1) reacting the compound 1 with carbon tetrabromide and triphenylphosphine in an organic solvent at-15-30 ℃, and filtering, concentrating and purifying to obtain a compound 2;
2) performing coupling reaction on the compound 3 and the compound 2 in tetrahydrofuran and hexamethylphosphoramide under the action of n-butyllithium at the temperature of-60-25 ℃, and extracting, drying, concentrating and purifying to obtain a compound 5;
3) performing coupling reaction on the compound 4 and the compound 2 in tetrahydrofuran and hexamethylphosphoramide under the action of n-butyllithium at the temperature of-60-25 ℃, and extracting, drying, concentrating and purifying to obtain a compound 6;
4) at room temperature, the compound 5 is subjected to coupling reaction with ethylenediamine in ethanol under the action of a catalyst, hydrogenation reaction with hydrogen is carried out, and the compound I is obtained through filtration, concentration and purification;
5) and (2) performing coupling reaction on the compound 6 and ethylenediamine in ethanol under the action of a catalyst at room temperature, performing hydrogenation reaction on the compound and hydrogen, and filtering, concentrating and purifying to obtain a compound II.
3. The method for synthesizing a novel sex pheromone component of fall webworm as claimed in claim 2, wherein the organic solvent in step 1) is one of dichloromethane, chloroform, ethyl acetate, chlorobenzene, dichlorobenzene, pyridine, phenol and dichloroethane.
4. The method for synthesizing a novel sex pheromone component of fall webworm as claimed in claim 3, wherein the organic solvent in step 1) is dichlorobenzene, 2-bromomethane or ethyl acetate.
5. The method for synthesizing a novel sex pheromone component of fall webworm as claimed in claim 2, wherein the molar ratio of the compound 1 to carbon tetrabromide to triphenylphosphine in step 1) is 1: 1.4.
6. The method for synthesizing a sex pheromone component of a novel fall webworm as claimed in claim 2, wherein the tetrahydrofuran in the steps 2) and 3): the volume ratio of hexamethylphosphoramide is 5: 1.
7. The method for synthesizing a sex pheromone component of a novel fall webworm as claimed in claim 2, wherein the molar ratio of the compound 3 to n-butyllithium to the compound 2 in the step 2) is 2: 1; the molar ratio of the compound 4 to the n-butyllithium to the compound 2 in the step 3) is 2: 1.
8. The method for synthesizing a novel sex pheromone component of fall webworm as claimed in claim 1, wherein the catalyst in the steps 4) and 5) is P-2 type nickel generated in situ by nickel acetate and sodium borohydride.
9. The method for synthesizing a sex pheromone component of a novel fall webworm as claimed in claim 1, wherein the amount of the P-2 type nickel used in the step 4) is 15% of the compound 5 by mole; the amount of the P-2 type nickel used in the step 5) is 15% by mole based on the amount of the compound 6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116649342A (en) * | 2023-05-30 | 2023-08-29 | 中捷四方生物科技股份有限公司 | Fall webworm attractant |
| CN117243221A (en) * | 2023-09-14 | 2023-12-19 | 中捷四方生物科技股份有限公司 | Fall-back fall webworm disorientation dispersing agent |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116649342A (en) * | 2023-05-30 | 2023-08-29 | 中捷四方生物科技股份有限公司 | Fall webworm attractant |
| CN117243221A (en) * | 2023-09-14 | 2023-12-19 | 中捷四方生物科技股份有限公司 | Fall-back fall webworm disorientation dispersing agent |
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Application publication date: 20210413 |