Preparation method of tomato leaf miner sex pheromone, intermediate and preparation method of intermediate

Abstract

The invention discloses a preparation method of a tomato leaf miner sex pheromone, an intermediate and a preparation method of the intermediate. According to the route, commercially available 5-hexene-1-ol is innovatively used as an initiator; a new intermediate (E)-8-hydroxy-3-octene acetate capable of being used for preparing the tomato leaf miner sex pheromone and an intermediate (E)-8-aldehyde-3-octene acetate obtained through further oxidation are synthesized, then the intermediate (E)-8-aldehyde-3-octene acetate is used as an intermediate raw material to construct 8Z-double bonds through a Wittig reaction, the whole route has fewer steps, when a hydroxyl protecting group is acetyl, the number of the hydroxyl protecting group is small, and when the hydroxyl protecting group is acetyl, the number of the hydroxyl protecting group is small. The total step for preparing the two components of the tomato leaf miner sex pheromone is only four, when a hydroxyl protecting group selects other protecting groups, a deprotecting group and acetylation process with mild reaction conditions is added, the total step is also only eight, and particularly, raw materials in each step of a synthetic route are simple and easy to obtain, the reaction conditions are mild, the product selectivity is relatively high, and the method is suitable for industrial production. And large-scale production is facilitated.

Description

Technical Field

[0001] The invention relates to the field of organic synthesis, in particular to a carboxylic acid ester compound containing a carbon-carbon double bond in an acyclic compound, and specifically to a preparation method of a sex pheromone of a tomato leafminer, an intermediate and a preparation method thereof. Background Art

[0002] The tomato leafminer (Tuta absoluta) belongs to the family Lycopodiidae in the order Lepidoptera. It is one of the most destructive and aggressive pests in tomatoes and other Solanaceae (such as potatoes and tobacco). At present, the control of tomato leafminers is mainly based on chemical control, but the effect is not ideal. Since the larvae of the pest mainly develop inside plants or soil, general pesticides cannot contact them, so the lethality of pesticides is limited. In addition, the large-scale use of pesticides has also caused problems such as pesticide residues, pesticide resistance, and the killing of its natural enemies. At present, the use of integrated control strategies including the introduction of natural enemies, biological control of insect pathogens, and enhancement of crop resistance is increasingly being adopted, and its effect is relatively better than that of traditional pesticides and insecticides. Among them, the control strategy of using the sex pheromones released by female tomato leafminers to attract males of the same species is considered to be a very promising killing solution.

[0003] In 1995, AB Attygalle et al. separated and identified the main component of the sex pheromone of the tomato leafminer, (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (Tetrahedron Lett., 1995, 36: 5471-5474), and synthesized it for the first time; in 1996, FC Griepink et al. separated and identified the minor component of the sex pheromone of the tomato leafminer, (3E,8Z)-3,8-tetradecadiene acetate (Tetrahedron Lett., 1996, 37: 411-414). It is reported that the two components can be used in a 91:9 ratio to attract and kill male adults on a large scale, which can significantly reduce the number of tomato leafminers, and the combined use with insecticides has a better control effect.

[0004] At present, different strategies have been developed for the two pheromones according to the different bonding positions during synthesis. Based on the C5+C5+C4 synthesis route (route 1), THP (tetrahydropyranyl) protected 4-pentyn-1-ol is coupled with two different C5 bromosynthetons, then reduced and brominated, and then coupled with the nucleophilic C4 acetyl lithium synthon, and then reduced and acetylated with lithium aluminum hydride to obtain two pheromones. However, the total number of steps in this strategy is as long as 14, and there are some dangerous processes: such as hydrogenation reduction, lithium aluminum hydride reduction at high temperature, etc.

[0005]

[0006] Based on the synthetic route of C4+C1+C9 (Route 2), 3-butyn-1-ol protected by MOM (methoxymethyl) first reacts with C1 synthon-triethyl orthoformate to generate C5 intermediate, which is then reduced, acidified, and acetylated, and then coupled with C9 synthon-Grizzone to obtain an intermediate with a pheromone C14 skeleton, which is then deprotected and acetylated to obtain two pheromones. However, the total steps of this strategy are as long as 14 steps, and the preparation conditions of Grignard reagents are harsh, the steps are cumbersome, and there is a lot of acidic wastewater. The construction and removal of the protecting group also increase the time cost and material cost.

[0007]

[0008] It can be seen that the existing synthetic routes basically have more than 14 steps, and have problems such as harsh reaction conditions, difficult operation, long time consumption, and high material and labor costs.

[0009] It should be noted that the information disclosed in the above background technology section is only used to understand the background of the present application, so the background technology section of the present invention may contain background information about the problem or environment of the present invention, but not necessarily describe the prior art. Therefore, the content contained in the background technology section is not an admission of the applicant to the prior art. Summary of the invention

[0010] The object of the present invention is to overcome one or more deficiencies in the prior art and to provide a new method for preparing sex pheromones of tomato leafminer with fewer steps and under relatively mild conditions.

[0011] The present invention also provides an intermediate for preparing the tomato leafminer sex pheromone and a preparation method thereof.

[0012] In order to achieve the above object, a technical solution adopted by the present invention is: A method for preparing a sex pheromone of a tomato leafminer, wherein the sex pheromone of the tomato leafminer comprises (3E,8Z,11Z)-3,8,11-tetradecatriene acetate having a structure shown in formula (SP-1), and the preparation method comprises: Reaction (1): allowing the compound represented by formula (I) to undergo olefin cross-metathesis reaction with the compound represented by formula (II) and / or the compound represented by formula (III) in the presence of a metal catalyst to generate a compound represented by formula (IV);

[0013] Reaction (2): using the compound represented by formula (IV) as a substrate, oxidizing it in the presence of an oxidant to generate a compound represented by formula (V);

[0014] Reaction (3): allowing the compound represented by formula (V) to undergo a ylide reaction (Wittig reaction) with the compound represented by formula (VII) to generate a compound represented by formula (IX);

[0015] Reaction (4): using the compound represented by formula (IX) as a substrate, reacting under alkaline conditions to generate a compound represented by formula (XI);

[0016] Reaction (5): subjecting the compound represented by formula (XI) to an acetylation reaction to generate (3E,8Z,11Z)-3,8,11-tetradecatriene acetate represented by formula (SP-1);

[0017] Among them, in formula (II), formula (III), formula (IV), formula (V), and formula (IX), R is a hydroxyl protecting group; In formula (VII), R1 is halogen.

[0018] In some embodiments of the present invention, in the reaction (1), the metal catalyst comprises a combination of one or more selected from the group consisting of a tungsten catalyst, a titanium catalyst, a molybdenum catalyst, a ruthenium catalyst, and a cuprous catalyst.

[0019] Furthermore, in the reaction (1), the metal catalyst comprises a catalytic combination of a ruthenium catalyst and a cuprous catalyst, and in the catalytic combination, the molar ratio of the cuprous catalyst to the ruthenium catalyst is 1:1-15, for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:14, etc.

[0020] According to some preferred and specific aspects of the present invention, the cuprous catalyst is a combination of one or more selected from CuI, CuCl, and CuBr.

[0021] According to some preferred and specific aspects of the present invention, the ruthenium catalyst is a combination of one or more selected from bis(tricyclohexylphosphine)benzylidene ruthenium dichloride, phenylmethylenyl-[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinyl]-dichloro-(tricyclohexylphosphine)ruthenium, dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium, and (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl)dichloro(o-isopropoxybenzylidene)ruthenium.

[0022] According to some preferred and specific aspects of the present invention, the molar ratio of the compound represented by formula (II) and / or the compound represented by formula (III) to the cuprous catalyst is 1:0.01-0.2, for example, it can be 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, 1:0.15, 1:0.18, etc.

[0023] In some embodiments of the present invention, in the reaction (1), the olefin cross-metathesis reaction is controlled to be carried out in a protective atmosphere and a first solvent, the protective atmosphere is formed by introducing nitrogen and / or an inert gas, and the first solvent is a combination of one or more selected from dichloromethane, ethyl acetate, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, cyclohexane, and n-hexane.

[0024] In some embodiments of the present invention, in the reaction (1), the molar ratio of the compound represented by formula (II) and / or the compound represented by formula (III) to the compound represented by formula (I) is 1:0.1-20, and further, it can be 1:0.1-10, 1:0.1-5, etc.; according to some specific aspects of the present invention, the molar ratio of the compound represented by formula (II) and / or the compound represented by formula (III) to the compound represented by formula (I) can be 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:2, 1:5, 1:10, 1:15, etc.

[0025] In some embodiments of the present invention, in the reaction (1), the reaction temperature of the olefin cross-metathesis reaction is controlled to be 0-120°C, further, it can be 5-80°C, 5-40°C, etc.; according to some specific aspects of the present invention, the reaction temperature of the olefin cross-metathesis reaction is controlled to be 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, etc.

[0026] In some embodiments of the present invention, in the reaction (1), the reaction time of the olefin cross-metathesis reaction is controlled to be 1-40 h, for example, 2-35 h, 5-35 h, 5-30 h, 8-25 h, 10-20 h, etc.

[0027] According to some specific aspects of the present invention, the implementation method of the reaction (1) includes: mixing the compound represented by formula (I), the compound represented by formula (II) and / or the compound represented by formula (III), a metal catalyst and a first solvent at room temperature under a protective atmosphere, heating to a preset reaction temperature (for example, 5-80° C.), and stirring the reaction.

[0028] Furthermore, after the reaction (1) is completed, the solvent is first distilled off under reduced pressure, concentrated, and then purified by silica gel column chromatography to obtain a light yellow transparent liquid, which is the compound represented by formula (IV); wherein the eluent for purification by silica gel column chromatography is preferably a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably 2.5-3.5:1.

[0029] In some embodiments of the present invention, in the reaction (2), the oxidant is a combination of one or more selected from ruthenium tetroxide (RuO4), manganese dioxide (MnO2), potassium monopersulfate (Oxone), sodium hypochlorite (NaOCl), lead tetraacetate (Pb(OAc)4), sodium periodate (NaIO4), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), Dess-Martin periodinane (DMP), peroxybenzoic acid (PBA) and pyridinium dichromate (PDC).

[0030] According to a specific aspect of the present invention, in the reaction (2), the oxidant is Dess-Martin periodinane (DMP).

[0031] In some embodiments of the present invention, the reaction (2) is controlled to be carried out at -5 to 10° C. According to a specific aspect of the present invention, the reaction (2) is controlled to be carried out under ice bath conditions.

[0032] In some embodiments of the present invention, the reaction (2) is controlled to be carried out in a second solvent, and the second solvent is a combination of one or more selected from dichloromethane, ethyl acetate, tetrahydrofuran, diethyl ether, toluene, N,N-dimethylformamide, cyclohexane, and n-hexane.

[0033] In some embodiments of the present invention, in the reaction (2), the molar ratio of the compound represented by formula (IV) to the oxidant is 1:1.0-3.0, for example, 1:1.05, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.55, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, etc.

[0034] In some embodiments of the present invention, after the reaction (2) is completed, preferably, an excess of a saturated sodium thiosulfate solution and a mixed solution of saturated sodium bicarbonate are added to the reaction system, and then the mixture is fully stirred, preferably for 2 to 3 hours, and the obtained mixture is extracted with ethyl acetate to obtain an organic layer, and then the organic layer is dried with anhydrous sodium sulfate and concentrated to obtain a crude product; then, the crude product is purified by silica gel column chromatography to obtain a light yellow transparent liquid, which is the compound represented by formula (V); wherein the eluent for the silica gel column chromatography purification is preferably a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably 8-12:1.

[0035] In some embodiments of the present invention, in the reaction (3), the ylide reaction is controlled to be carried out in the presence of a first alkaline substance, and the first alkaline substance includes a combination of one or more selected from sodium hydroxide (NaOH), sodium carbonate (K2CO3), sodium hydride (NaH), n-butyl lithium (n-BuLi), lithium diisopropylamide (LDA), lithium bis(trimethylsilyl)amide (LiHMDS), sodium bis(trimethylsilyl)amide (NaHMDS), potassium bis(trimethylsilyl)amide (NaHMDS), potassium tert-butoxide ((CH3)3COK), sodium methoxide (CH3ONa) and sodium ethoxide (CH3CH2ONa).

[0036] Furthermore, the molar ratio of the compound represented by formula (V) to the first alkaline substance is controlled to be 1:1.5-3, for example, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, etc.

[0037] In some embodiments of the present invention, in the reaction (3), the molar ratio of the compound represented by formula (V) to the compound represented by formula (VII) is 1:1-3, for example, 1:1.1, 1:1.3, 1:1.4, 1:1.5, 1:1.8, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:2.95, etc.

[0038] In some embodiments of the present invention, in the reaction (3), the reaction temperature of the ylide reaction is controlled to be -78~25°C.

[0039] In some embodiments of the present invention, in the reaction (3), the reaction time of the ylide reaction is controlled to be 1-40 h, for example, 2-30 h, 2-20 h, 2-10 h, etc.

[0040] In some embodiments of the present invention, in the reaction (3), the ylide reaction is controlled to be carried out in a protective atmosphere and in a third solvent, wherein the protective atmosphere is formed by introducing nitrogen and / or an inert gas, and the third solvent includes tetrahydrofuran.

[0041] According to some specific aspects of the present invention, the implementation method of the reaction (3) includes: in a protective atmosphere and at a temperature of -10 to 10°C, adding a first alkaline substance solution to the compound represented by the formula (VII) to obtain a mixed solution, stirring the mixed solution at -10 to 10°C, then adding a solution of the compound represented by the formula (V) to the mixed solution at -78 to -65°C, and then stirring the mixture at -60 to -35°C and 10 to 25°C, respectively; wherein the dispersion solvents used in the first alkaline substance solution and the solution of the compound represented by the formula (V) are both a third solvent, and the third solvent includes tetrahydrofuran.

[0042] In some embodiments of the present invention, after the reaction (3) is completed, an excess of saturated ammonium chloride solution is added at room temperature to quench the reaction. During quenching, the saturated ammonium chloride solution is preferably added under nitrogen and stirred sufficiently. The stirring time is preferably 1 to 1.5 h. The obtained mixture is extracted with ethyl acetate to obtain an organic layer. The organic layer is then dried with anhydrous sodium sulfate and concentrated to obtain a crude product. The crude product is then purified by silica gel column chromatography to obtain a light yellow transparent liquid to obtain the compound represented by formula (IX). The eluent for the silica gel column chromatography purification is preferably a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably 18-22:1.

[0043] In some embodiments of the present invention, in the reaction (4), the alkaline condition is formed by adding a second alkaline substance or an aqueous solution thereof, and the second alkaline substance is a combination of one or more selected from sodium hydroxide, potassium hydroxide, calcium hydroxide and tetrabutylammonium fluoride (TBAF).

[0044] In some embodiments of the present invention, the reaction (4) is controlled to be carried out in a fourth solvent, and the fourth solvent is a combination of one or more selected from methanol, ethanol, isopropanol, tetrahydrofuran, and water.

[0045] In some embodiments of the present invention, the reaction temperature of the reaction (4) is controlled to be 0-60°C, for example, 5-50°C, 10-40°C, 15-35°C, etc. According to a specific aspect of the present invention, the reaction temperature of the reaction (4) is controlled to be room temperature.

[0046] In some embodiments of the present invention, the reaction time of reaction (4) is controlled to be 1-40 h, for example, 1-30 h, 1-20 h, 1-10 h, 1-5 h, etc.

[0047] According to some specific aspects of the present invention, the embodiment of the reaction (4) comprises: mixing the compound represented by the formula (IX) and the fourth solvent, then adding a second alkaline substance aqueous solution, and stirring the reaction. In some embodiments of the present invention, the second alkaline substance aqueous solution can be a sodium hydroxide aqueous solution with a concentration of 1%-15%.

[0048] In some embodiments of the present invention, after the reaction (4) is completed, the solvent is first dried by spin drying, and then water and dichloromethane are added for extraction to obtain an organic layer, which is then dried over anhydrous sodium sulfate and concentrated to obtain a crude product; thereafter, the crude product is purified by silica gel column chromatography to obtain a light yellow transparent liquid to obtain a compound represented by formula (XI); wherein the eluent for the silica gel column chromatography purification is preferably a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably 4-6:1.

[0049] In some embodiments of the present invention, in the reaction (5), the acetylation reaction is controlled to be carried out in the presence of an organic base, and the organic base comprises a combination of one or more selected from triethylamine, 4-dimethylaminopyridine, and pyridine.

[0050] According to some specific aspects of the present invention, the organic base is composed of triethylamine and 4-dimethylaminopyridine. Further, the molar ratio of the triethylamine to the 4-dimethylaminopyridine is 1:50-200, for example, 1:50-150, 1:50-120, 1:60-120, etc.

[0051] In some embodiments of the present invention, in the reaction (5), the acetylation reaction is controlled to be carried out in a fifth solvent, and the fifth solvent is a combination of one or more selected from dichloromethane, ethyl acetate, tetrahydrofuran, and pyridine.

[0052] In some embodiments of the present invention, in the reaction (5), the reaction temperature of the acetylation reaction is controlled to be 0-100°C, for example, 0-80°C, 5-70°C, 10-60°C, 15-50°C, 15-40°C, 15-35°C, etc. According to some specific aspects of the present invention, the reaction temperature of the acetylation reaction is room temperature.

[0053] In some embodiments of the present invention, in the reaction (5), the reaction time of the acetylation reaction is controlled to be 1-24 h, for example, 1-20 h, 1-15 h, 1-8 h, etc.

[0054] In some embodiments of the present invention, in the reaction (5), the acetylation reaction uses acetic anhydride to react with the compound represented by formula (XI) to prepare (3E,8Z,11Z)-3,8,11-tetradecatriene acetate represented by formula (SP-1).

[0055] According to some specific aspects of the present invention, the implementation method of the reaction (5) includes: mixing the compound represented by the formula (XI), an organic base, acetic anhydride and a fifth solvent, and reacting them.

[0056] In some embodiments of the present invention, after the reaction (5) is completed, the organic phase is washed once with hydrochloric acid, and once with a saturated sodium bicarbonate solution, the organic phases are combined, dried over anhydrous sodium sulfate, and spin-dried to obtain a light yellow transparent liquid, which is concentrated to obtain a crude product; then, the product is purified by silica gel column chromatography to obtain a light yellow transparent liquid, thereby obtaining (3E, 8Z, 11Z)-3,8,11-tetradecatriene acetate having a structure shown in formula (SP-1); wherein the eluent for the silica gel column chromatography purification is preferably a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably 18-22:1.

[0057] In some embodiments of the present invention, the hydroxyl protecting group is an acyl hydroxyl protecting group, an alkane hydroxyl protecting group, a silicon hydroxyl protecting group or an acetal hydroxyl protecting group.

[0058] Furthermore, the hydroxyl protecting group is an acetyl group, and when the hydroxyl protecting group is an acetyl group, the reaction (4) and the reaction (5) in the preparation method do not exist, and the compound represented by formula (IX) is (3E,8Z,11Z)-3,8,11-tetradecatriene acetate having a structure represented by formula (SP-1).

[0059] In some embodiments of the present invention, in formula (VII), R1 is bromine or iodine.

[0060] Another technical solution provided by the present invention is a method for preparing a sex pheromone of a tomato leafminer, wherein the sex pheromone of the tomato leafminer comprises (3E,8Z)-3,8-tetradecadienyl acetate having a structure shown in formula (SP-2), and the preparation method comprises: Reaction (a): allowing the compound represented by formula (I) to undergo olefin cross-metathesis reaction with the compound represented by formula (II) and / or the compound represented by formula (III) in the presence of a metal catalyst to generate a compound represented by formula (IV);

[0061] Reaction (b): using the compound represented by formula (IV) as a substrate, oxidizing it in the presence of an oxidant to generate a compound represented by formula (V);

[0062] Reaction (c): allowing the compound represented by formula (V) to undergo a ylide reaction with the compound represented by formula (VI) to generate a compound represented by formula (VIII);

[0063] Reaction (d): using the compound represented by the formula (VIII) as a substrate, reacting under alkaline conditions to generate the compound represented by the formula (X);

[0064] Reaction (e): subjecting the compound represented by formula (X) to an acetylation reaction to generate (3E,8Z)-3,8-tetradecadienyl acetate represented by formula (SP-2);

[0065] Among them, in formula (II), formula (III), formula (IV), formula (V), and formula (VIII), R is a hydroxyl protecting group; In formula (VI), R2 is halogen.

[0066] In some embodiments of the present invention, the reaction processes of reaction (a), reaction (b), reaction (c), reaction (d), and reaction (e) are respectively the same as the aforementioned reactions (1) to (5).

[0067] In some embodiments of the present invention, R2 is bromine or iodine.

[0068] When the hydroxyl protecting group is an acetyl group, the reaction (d) and the reaction (e) in the preparation method do not exist, and the compound represented by formula (VIII) is (3E,8Z)-3,8-tetradecadienyl acetate having a structure represented by formula (SP-2).

[0069] Another technical solution provided by the present invention is: an intermediate for preparing the sex pheromone of tomato leafminer, wherein the intermediate is selected from the compound represented by formula (IV) and / or the compound represented by formula (V);

[0070] In formula (IV) and formula (V), R is a hydroxyl protecting group.

[0071] Another technical solution provided by the present invention is a method for preparing a tomato leafminer sex pheromone intermediate, wherein the tomato leafminer sex pheromone intermediate has a structure shown in formula (V); The preparation method comprises: using the compound represented by the formula (IV) as a substrate, oxidizing in the presence of an oxidant to generate a compound represented by the formula (V);

[0072] In formula (IV) and formula (V), R is a hydroxyl protecting group.

[0073] Furthermore, the method for preparing the tomato leafminer sex pheromone intermediate further comprises: The compound represented by formula (I) is subjected to an olefin cross-metathesis reaction with the compound represented by formula (II) and / or the compound represented by formula (III) in the presence of a metal catalyst to generate a compound represented by formula (IV); .

[0074] Another technical solution provided by the present invention is a method for preparing a tomato leafminer sex pheromone intermediate, wherein the tomato leafminer sex pheromone intermediate has a structure shown in formula (IX); The preparation method comprises: allowing the compound represented by formula (V) to undergo a ylide reaction with the compound represented by formula (VII) to generate a compound represented by formula (IX);

[0075] In formula (V) and formula (IX), R is a hydroxyl protecting group other than acetyl; in formula (VII), R1 is a halogen.

[0076] Another technical solution provided by the present invention is a method for preparing a tomato leafminer sex pheromone intermediate, wherein the tomato leafminer sex pheromone intermediate has a structure shown in formula (VIII); The preparation method comprises: allowing the compound represented by formula (V) to undergo a ylide reaction with the compound represented by formula (VI) to generate a compound represented by formula (VIII);

[0077] In formula (V) and formula (VIII), R is a hydroxyl protecting group other than acetyl; in formula (VI), R2 is a halogen.

[0078] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art: The invention provides a new route for preparing sex pheromone of tomato leafminer. The route innovatively uses commercially available 5-hexen-1-ol as a starting material, synthesizes a new intermediate (E)-8-hydroxy-3-octenyl acetate which can be used as the preparation of sex pheromone of tomato leafminer and an intermediate (E)-8-aldehyde-3-octenyl acetate obtained by further oxidation, and then uses the intermediate raw material to construct 8Z-double bond through Wittig reaction. The overall route has fewer steps. When the hydroxyl protecting group selects acetyl group, the total steps for preparing two components of sex pheromone of tomato leafminer are only 4 steps. When the hydroxyl protecting group selects other protecting groups, a deprotection group and an acetylation process with mild reaction conditions are added, and the total steps are also only 8 steps. In particular, the raw materials of each step of the synthetic route of the invention are simple and easy to obtain, the reaction conditions are mild, the product selectivity is relatively high, and it is conducive to large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0079] Figure 1 (E)-8-hydroxy-3-octenyl acetate (compound represented by formula (IV)) 1 H NMR spectrum; Figure 2 (E)-8-aldehyde-3-octenyl acetate (compound represented by formula (V)) 1 H NMR spectrum; Figure 3 (3E,8Z)-3,8-tetradecadien-1-ol (compound represented by formula (X)) 1 H NMR spectrum; Figure 4 (3E,8Z,11Z)-3,8,11-tetradecatriene-1-ol (compound represented by formula (XI)) 1 H NMR spectrum; Figure 5 (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (SP-1) 1 H NMR spectrum; Figure 6 (3E,8Z)-3,8-tetradecadienyl acetate (SP-2) 1 H NMR spectrum. DETAILED DESCRIPTION

[0080] The above scheme is further described below in conjunction with specific embodiments; it should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the scope of the following embodiments; the implementation conditions adopted in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are usually the conditions in conventional experiments.

[0081] Unless otherwise specified in the following examples, all raw materials are commercially available or prepared by conventional methods in the art.

[0082] Example 1: This example provides a method for preparing (3E,8Z,11Z)-3,8,11-tetradecatriene acetate having a structure represented by formula (SP-1) and (3E,8Z)-3,8-tetradecadiene acetate having a structure represented by formula (SP-2).

[0083] Example 1-1: Preparation of (E)-8-hydroxy-3-octenyl acetate (compound represented by formula (IV)) In a 25 mL round-bottom flask, under N2 atmosphere, 5-hexen-1-ol (200 mg, 2 mmol), 3-butenyl acetate (570 mg, 5 mmol), cuprous iodide (19 mg, 0.1 mmol), Grubbs II catalyst (phenylmethylenyl-[1,3-di(2,4,6-trimethylphenyl)-2-imidazolinyl]-dichloro-(tricyclohexylphosphino)ruthenium, 336 mg, 0.4 mmol) and 5 mL of ether were added in sequence at room temperature, the reaction temperature was raised to 30 °C, stirred for 14 h, and the reaction was monitored by thin layer chromatography; after the reaction, the solvent was concentrated and purified by silica gel column chromatography (petroleum ether / ethyl acetate = 3 / 1, volume ratio) to obtain the product (E)-8-hydroxy-3-octenyl acetate, a light yellow transparent liquid, 171 mg, with a yield of 46% and a purity of 98%; the prepared product (E)-8-hydroxy-3-octenyl acetate 1 H NMR spectra are shown in Figure 1 As shown, 1 H NMR (400 MHz, Chloroform- d ) δ 5.51 (d, J = 9.1Hz, 1H), 5.42 (s, 1H), 4.06 (s, 2H), 3.65 (s, 2H), 2.33 (d, J = 8.0 Hz, 2H),2.05 (s, 5H), 1.54 (d, J = 15.2 Hz, 3H), 1.43 (s, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 171.26, 133.06, 125.55, 64.12, 62.74, 32.24, 32.10, 31.93, 25.42, 20.98.

[0084] Example 1-2: Preparation of (E)-8-aldehyde-3-octenyl acetate (compound represented by formula (V)) In a 25 mL round-bottom flask, 10 mL of dichloromethane, (E)-8-hydroxy-3-octenyl acetate (171 mg, 0.92 mmol), and Dess-Martin periodinane (424 mg, 1 mmol) were added in turn under an ice bath, and the ice bath was maintained for 2 to 4 h. The reaction was monitored by thin layer chromatography. After the reaction was completed, a mixed solution of 5 mL of saturated sodium thiosulfate solution and 5 mL of saturated sodium bicarbonate was added to the reaction, and then fully stirred for 3 h. The resulting mixture was extracted with ethyl acetate to obtain an organic layer, and then the organic layer was dried over anhydrous sodium sulfate and concentrated to obtain a crude product. The product was then purified by silica gel column chromatography (petroleum ether / ethyl acetate = 5 / 1, volume ratio) to obtain the product (E)-8-aldehyde-3-octenyl acetate, a light yellow transparent liquid, 100 mg, a yield of 59%, and a purity of 98%; the prepared product (E)-8-aldehyde-3-octenyl acetate 1 H NMR spectra are shown in Figure 2 As shown, 1 H NMR (400 MHz, Chloroform- d ) δ 9.77 (s, 1H), 5.60 – 5.38 (m, 2H), 4.08 (t, J = 6.8 Hz, 2H), 2.44 (s, 2H), 2.31 (s, 2H), 2.06 (d, J = 13.8 Hz, 5H), 1.69 (d, J = 7.3 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 202.49, 171.09, 131.98, 126.64, 63.94, 31.90, 21.65, 20.96.

[0085] Example 1-3: Preparation of (3E,8Z)-3,8-tetradecadiene acetate (compound represented by formula (VIII)) In a 50 mL three-necked flask, hexyltriphenylphosphonium bromide (307 mg, 0.72 mmol) was added under nitrogen atmosphere, and then potassium bis(trimethylsilyl)amide (0.72 mL, 0.72 mmol, 1 M tetrahydrofuran solution) was added under ice bath, and stirred for 2 h under ice bath. Then, 2 mL tetrahydrofuran solution of (E)-8-aldehyde-3-octenyl acetate (67 mg, 0.35 mmol) was added at -78 °C, and then the reaction temperature was raised to -50 °C and stirred for 2 h, and then raised to room temperature and stirred for 2 h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 4 mL of saturated ammonium chloride solution, the resulting mixture was extracted with ethyl acetate to obtain an organic layer, which was then dried over anhydrous sodium sulfate and concentrated to obtain a crude product; it was then purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20 / 1, volume ratio) to obtain the product (3E,8Z)-3,8-tetradecadiene acetate (the hydroxyl protecting group is acetyl, so the compound is SP-2), a light yellow transparent liquid, 53 mg, a yield of 60%, and a purity of 99%.

[0086] Example 1-4: Preparation of (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (compound represented by formula (IX)) In a 50 mL three-necked flask, (Z)-3-hexenyltriphenylphosphonium iodide (253 mg, 0.53 mmol) was added under nitrogen atmosphere, and then potassium bis(trimethylsilyl)amide (0.54 mL, 0.54 mmol, 1 M tetrahydrofuran solution) was added under ice bath, and stirred for 2 h under ice bath. Then, (E)-8-aldehyde-3-octenyl acetate (50 mg, 0.19 mmol) in 2 mL tetrahydrofuran solution was added at -78 °C, and then the reaction temperature was raised to -50 °C and stirred for 2 h, and then raised to room temperature and stirred for 2 h. The reaction was monitored by thin layer chromatography. After the reaction was completed, 4 mL of saturated ammonium chloride solution, the resulting mixture was extracted with ethyl acetate to obtain an organic layer, which was then dried over anhydrous sodium sulfate and concentrated to obtain a crude product; it was then purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20 / 1, volume ratio) to obtain (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (the hydroxyl protecting group is acetyl, so the compound is SP-1), a light yellow transparent liquid, 47 mg, a yield of 70%, and a purity of 99%.

[0087] In this example, 3-butenyl acetate is used as the compound represented by formula (II), that is, the hydroxyl protecting group is acetyl. Therefore, the compound represented by formula (VIII) prepared in this example is (3E,8Z)-3,8-tetradecadienyl acetate (SP-2), and the compound represented by formula (IX) is (3E,8Z,11Z)-3,8,11-tetradecadienyl acetate (SP-1). That is, the two components of the sex pheromone of the tomato leafminer can be prepared in a total of 4 steps; Among them, calculated based on 5-hexen-1-ol, the total yield of (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (SP-1) was 46%×59%×70%=18.998%, and the total yield of (3E,8Z)-3,8-tetradecadiene acetate (SP-2) was 46%×59%×60%=16.284%.

[0088] The deprotection process and acetylation process of the present invention are further described below in conjunction with the above process.

[0089] Example 1-5: Preparation of (3E,8Z)-3,8-tetradecadien-1-ol (compound represented by formula (X)) In a 50 mL three-necked flask, (3E,8Z)-3,8-tetradecadienyl acetate (47 mg, 0.18 mmol) and 10 mL of methanol were added, and then 1.3 mL of 5% sodium hydroxide aqueous solution was added at room temperature, and the mixture was stirred for 2 h at room temperature. The reaction was monitored by thin layer chromatography. After the reaction was completed, the methanol was first dried by spin drying, and then 20 mL of H2O and 20 mL of DCM (dichloromethane) were added to extract and separate the liquid to obtain an organic layer. The organic layer was then dried over anhydrous sodium sulfate and concentrated to obtain a crude product. The crude product was then purified by silica gel column chromatography (petroleum ether / ethyl acetate = 5 / 1, volume ratio) to obtain (3E,8Z)-3,8-tetradecadien-1-ol (compound shown in formula (X)), a light yellow transparent liquid, 35 mg, a yield of 90%, and a purity of 99%. Prepared (3E,8Z)-3,8-tetradecadien-1-ol 1 H NMR spectra are shown in Figure 3 shown.

[0090] Example 1-6: Preparation of (3E,8Z,11Z)-3,8,11-tetradecatriene-1-ol (compound represented by formula (XI)) In a 50 mL three-necked flask, (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (47 mg, 0.18 mmol) and 10 mL of methanol were added, and then 1.3 mL of 5% sodium hydroxide aqueous solution was added at room temperature, and stirred for 2 h at room temperature. The reaction was monitored by thin layer chromatography; after the reaction, the methanol was first spin-dried, and then 20 mL of H2O and 20 mL of DCM were added to extract and separate the liquid to obtain an organic layer, which was then dried over anhydrous sodium sulfate and concentrated to obtain a crude product; then, silica gel column chromatography was performed for purification (petroleum ether / ethyl acetate = 5 / 1, volume ratio) to obtain (3E,8Z,11Z)-3,8,11-tetradecatriene-1-ol, a light yellow transparent liquid, 35 mg, a yield of 90%, and a purity of 99%. Preparation of (3E,8Z,11Z)-3,8,11-tetradecatriene-1-ol 1 H NMR spectra are shown in Figure 4 shown.

[0091] Example 1-7: Preparation of (3E,8Z)-3,8-tetradecadienyl acetate (SP-2) In a 50 mL round-bottom flask, (3E,8Z)-3,8-tetradecadien-1-ol (61 mg, 0.29 mmol), 4-dimethylaminopyridine (1 mg, 0.008 mmol), triethylamine (88 mg, 0.87 mmol), acetic anhydride (59 mg, 0.58 mmol) and 5 mL of dichloromethane were added in sequence at room temperature and reacted for 2 h. The reaction was followed by gas chromatography. After the reaction was completed, 10 mL of 1 M hydrochloric acid was added at room temperature to wash the organic phase once, and saturated sodium bicarbonate solution was added to wash the organic phase once. The organic phases were combined, dried over anhydrous sodium sulfate, and spin-dried to obtain a light yellow transparent liquid to obtain the product (3E,8Z)-3,8-tetradecadienyl acetate (SP-2), 71 mg, with a yield of 97% and a purity of 99%; the prepared (3E,8Z)-3,8-tetradecadienyl acetate (SP-2) 1 H NMR spectra are shown in Figure 6 As shown, 1 H NMR (400 MHz, Chloroform-d) δ 5.53-5.39 (m, 1H), 5.36-5.17 (m, 3H), 3.99 (t, J = 6.9 Hz, 2H), 2.34-2.16 (m, 2H), 1.95 (d, J = 4.5 Hz, 9H), 1.35-1.11 (m, 8H), 0.82 (t, J = 6.8 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 170.84,133.17, 131.51, 130.73, 130.19, 129.78, 129.29, 128.58, 125.29, 77.42, 77.09,76.78, 64.46, 64.00, 62.52, 32.52, 32.09, 31.93, 31.47, 29.92, 29.38, 29.21,28.49, 27.14, 26.97, 26.55, 25.51, 22.52, 22.49, 20.81, 13.98.

[0092] Example 1-8: Preparation of (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (SP-1) In a 50 mL round-bottom flask, (3E,8Z,11Z)-3,8,11-tetradecatrien-1-ol (50 mg, 0.24 mmol), 4-dimethylaminopyridine (1 mg, 0.008 mmol), triethylamine (58 mg, 0.57 mmol), acetic anhydride (39 mg, 0.38 mmol) and 5 mL of dichloromethane were added in sequence at room temperature. The reaction was reacted for 2 h and the reaction was monitored by gas chromatography. After the reaction was completed, 10 mL of 1 M hydrochloric acid was added at room temperature to wash the organic phase once, and the organic phase was washed once with a saturated sodium bicarbonate solution. The organic phases were combined, dried over anhydrous sodium sulfate, and spin-dried to obtain a light yellow transparent liquid to obtain the product (3E, 8Z, 11Z)-3,8,11-tetradecatriene acetate (SP-1), 58 mg, with a yield of 97% and a purity of 99%; the prepared (3E, 8Z, 11Z)-3,8,11-tetradecatriene acetate (SP-1) 1 H NMR spectra are shown in Figure 5 As shown, 1 H NMR (400 MHz, Chloroform-d) δ 5.47 (dtt, J= 14.5, 6.5, 1.3 Hz, 1H), 5.43-5.08 (m, 5H), 4.02 (t, J = 6.9 Hz, 2H), 2.72(t, J = 6.1 Hz, 2H), 2.27 (qd, J = 6.9, 1.2 Hz, 2H), 2.09-1.87 (m, 9H), 1.38 (p, J = 7.5 Hz, 2H), 0.93 (t, J = 7.6 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ171.04, 133.15, 131.77, 130.26, 129.66, 128.74, 128.34, 127.31, 127.06,125.72, 125.39, 77.39, 77.07, 76.76, 64.52, 64.07, 32.12, 31.94, 30.30, 29.28, 28.50, 27.02, 26.97, 26.59, 25.51, 20.92, 20.51, 14.24.

[0093] It can be seen from the above process that even if the present invention selects other hydroxyl protecting groups except acetyl group, the total steps for preparing the two components of the tomato leafminer sex pheromone of the present invention only need 8 steps.

[0094] Example 2: This example is basically the same as Example 1, except that the preparation process of the compound represented by formula (IV) is different. Specifically, the preparation process of (E)-8-hydroxy-3-octenyl acetate (compound represented by formula (IV)) is as follows: In a 25 mL round-bottom flask, under N2 atmosphere, 5-hexen-1-ol (100 mg, 1 mmol), 3-butenyl acetate (570 mg, 5 mmol), cuprous iodide (19 mg, 0.1 mmol), Hoveyda-Grubbs II catalyst (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxybenzylidene)ruthenium, 62 mg, 0.1 mmol) and 5 mL of ether were added in sequence at room temperature, the reaction temperature was raised to 30 ℃, stirred for 14 h, and the reaction was monitored by thin layer chromatography. After the reaction, the solvent was concentrated and purified by silica gel column chromatography (petroleum ether / ethyl acetate = 3 / 1, volume ratio) to obtain the product (E)-8-hydroxy-3-octenyl acetate as a light yellow transparent liquid, 65 mg, with a yield of 35% and a purity of 98%.

[0095] Example 3: This example is basically the same as Example 1, except that the preparation process of the compound represented by formula (V) is different. Specifically, the preparation process of (E)-8-aldehyde-3-octenyl acetate (compound represented by formula (V)) is as follows: In a 25 mL round-bottom flask, 10 mL of dichloromethane, (E)-8-hydroxy-3-octenyl acetate (145 mg, 0.78 mmol), and Dess-Martin periodinane (662 mg, 1.56 mmol) were added in turn under ice bath, and the ice bath was maintained for 2 to 4 h. The reaction was monitored by thin layer chromatography. After the reaction was completed, a mixed solution of 5 mL of saturated sodium thiosulfate solution and 5 mL of saturated sodium bicarbonate was added to the reaction, and then stirred for 3 h. The obtained mixture was extracted with ethyl acetate to obtain an organic layer, and then the organic layer was dried with anhydrous sodium sulfate and concentrated to obtain a crude product. The product was then purified by silica gel column chromatography (petroleum ether / ethyl acetate = 5 / 1, volume ratio) to obtain the product (E)-8-aldehyde-3-octenyl acetate, a light yellow transparent liquid, 123 mg, with a yield of 86% and a purity of 98%. In this example, based on 5-hexen-1-ol, the total yield of (3E,8Z,11Z)-3,8,11-tetradecatriene acetate (SP-1) is 46%×86%×70%=27.692%, and the total yield of (3E,8Z)-3,8-tetradecadiene acetate (SP-2) is 46%×86%×60%=23.736%.

[0096] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

[0097] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A method for preparing a sex pheromone of a tomato leafminer, wherein the sex pheromone of the tomato leafminer comprises (3E,8Z,11Z)-3,8,11-tetradecatriene acetate having a structure shown in formula (SP-1), characterized in that: The preparation method comprises: Reaction (1): allowing the compound represented by formula (I) to undergo olefin cross-metathesis reaction with the compound represented by formula (II) and / or the compound represented by formula (III) in the presence of a metal catalyst to generate a compound represented by formula (IV); ； Reaction (2): using the compound represented by formula (IV) as a substrate, oxidizing it in the presence of an oxidant to generate a compound represented by formula (V); ； Reaction (3): allowing the compound represented by formula (V) to undergo a ylide reaction with the compound represented by formula (VII) to generate a compound represented by formula (IX); ； Reaction (4): using the compound represented by formula (IX) as a substrate, reacting under alkaline conditions to generate a compound represented by formula (XI); ； Reaction (5): subjecting the compound represented by formula (XI) to an acetylation reaction to generate (3E,8Z,11Z)-3,8,11-tetradecatriene acetate represented by formula (SP-1); ； Among them, in formula (II), formula (III), formula (IV), formula (V), and formula (IX), R is a hydroxyl protecting group; In the formula (VII), R1 is halogen.

2. The method for preparing the sex pheromone of tomato leafminer according to claim 1, characterized in that: In the reaction (1), the metal catalyst comprises a combination of one or more selected from the group consisting of a tungsten catalyst, a titanium catalyst, a molybdenum catalyst, a ruthenium catalyst and a cuprous catalyst; and / or, in the reaction (1), the olefin cross-metathesis reaction is controlled to be carried out in a protective atmosphere and a first solvent, the protective atmosphere is formed by introducing nitrogen and / or an inert gas, and the first solvent is a combination of one or more selected from the group consisting of dichloromethane, ethyl acetate, tetrahydrofuran, ether, toluene, N,N-dimethylformamide, cyclohexane and n-hexane; and / or, in the reaction (1), the molar ratio of the compound represented by formula (II) and / or the compound represented by formula (III) to the compound represented by formula (I) is 1:0.1-20; and / or, in the reaction (1), the reaction temperature of the olefin cross-metathesis reaction is controlled to be 0-120°C.

3. The method for preparing the sex pheromone of tomato leafminer according to claim 1, characterized in that: In the reaction (1), the metal catalyst comprises a catalytic combination of a ruthenium catalyst and a cuprous catalyst. In the catalytic combination, the molar ratio of the cuprous catalyst to the ruthenium catalyst is 1:1-15.

4. The method for preparing the sex pheromone of tomato leafminer according to claim 3, characterized in that: The cuprous catalyst is a combination of one or more selected from CuI, CuCl, and CuBr; and / or, the ruthenium catalyst is a combination of one or more selected from di(tricyclohexylphosphine)benzylidene ruthenium dichloride, phenylmethyl-[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinyl]-dichloro-(tricyclohexylphosphino)ruthenium, dichloro(o-isopropoxyphenylmethylene)(tricyclohexylphosphine)ruthenium, and (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl)dichloro(o-isopropoxybenzylidene)ruthenium; and / or, the molar ratio of the compound represented by formula (II) and / or the compound represented by formula (III) to the cuprous catalyst is 1:0.01-0.

2.

5. The method for preparing the sex pheromone of tomato leafminer according to claim 1, characterized in that: In the reaction (2), the oxidant is a combination of one or more selected from ruthenium tetroxide, manganese dioxide, potassium monopersulfate, sodium hypochlorite, lead tetraacetate, sodium periodate, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, Dess-Martin oxidant, perbenzoic acid and pyridinium dichromate; and / or, the reaction (2) is controlled to be carried out at -5 to 10 °C; and / or, the reaction (2) is controlled to be carried out in a second solvent, and the second solvent is a combination of one or more selected from dichloromethane, ethyl acetate, tetrahydrofuran, ether, toluene, N,N-dimethylformamide, cyclohexane and n-hexane; and / or, the molar ratio of the compound represented by formula (IV) to the oxidant is 1:1.0-3.

0.

6. The method for preparing the sex pheromone of tomato leafminer according to claim 1, characterized in that: In the reaction (3), the ylide reaction is controlled to be carried out in the presence of a first alkaline substance, the first alkaline substance comprises a combination of one or more selected from the group consisting of sodium hydroxide, sodium carbonate, sodium hydride, n-butyl lithium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, potassium tert-butoxide, sodium methoxide and sodium ethoxide, and the molar ratio of the compound represented by formula (V) to the first alkaline substance is controlled to be 1:1.5-3; and / or, in the reaction (3), the molar ratio of the compound represented by formula (V) to the compound represented by formula (VII) is controlled to be 1:1-3; and / or, in the reaction (3), the reaction temperature of the ylide reaction is controlled to be -78~25°C; and / or, in the reaction (3), the ylide reaction is controlled to be carried out in a protective atmosphere and in a third solvent, the protective atmosphere is formed by introducing nitrogen and / or an inert gas, and the third solvent comprises tetrahydrofuran.

7. The method for preparing the sex pheromone of tomato leafminer according to claim 1, characterized in that: The implementation method of the reaction (3) comprises: adding a first alkaline substance solution to the compound represented by the formula (VII) under a protective atmosphere at -10 to 10°C to obtain a mixed solution, stirring the mixed solution at -10 to 10°C, then adding a solution of the compound represented by the formula (V) to the mixed solution at -78 to -65°C, and then stirring and reacting at -60 to -35°C and 10 to 25°C in sequence; wherein the dispersion solvents used in the first alkaline substance solution and the solution of the compound represented by the formula (V) are both a third solvent, and the third solvent comprises tetrahydrofuran.

8. The method for preparing the sex pheromone of tomato leafminer according to claim 1, characterized in that: In the reaction (4), the alkaline condition is formed by adding a second alkaline substance or an aqueous solution thereof, wherein the second alkaline substance is a combination of one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and tetrabutylammonium fluoride; and / or, the reaction (4) is controlled to be carried out in a fourth solvent, wherein the fourth solvent is a combination of one or more selected from the group consisting of methanol, ethanol, isopropanol, tetrahydrofuran and water; and / or, the reaction temperature of the reaction (4) is controlled to be 0-60° C.; and / or, the hydroxyl protecting group is an acyl hydroxyl protecting group, an alkane hydroxyl protecting group, a silicon hydroxyl protecting group or an acetal hydroxyl protecting group.

9. The method for preparing the sex pheromone of tomato leafminer according to claim 1, characterized in that: In the reaction (5), the acetylation reaction is controlled to be carried out in the presence of an organic base, and the organic base includes a combination of one or more selected from triethylamine, 4-dimethylaminopyridine, and pyridine; and / or, in the reaction (5), the acetylation reaction is controlled to be carried out in a fifth solvent, and the fifth solvent is a combination of one or more selected from dichloromethane, ethyl acetate, tetrahydrofuran, and pyridine; and / or, in the reaction (5), the reaction temperature of the acetylation reaction is controlled to be 0-100°C; and / or, the hydroxyl protecting group is an acetyl group, and when the hydroxyl protecting group is an acetyl group, the reaction (4) and the reaction (5) in the preparation method do not exist, and the compound represented by formula (IX) is (3E,8Z,11Z)-3,8,11-tetradecatriene acetate having a structure represented by formula (SP-1); and / or, in formula (VII), R1 is bromine or iodine.

10. A method for preparing a sex pheromone of a tomato leafminer, wherein the sex pheromone of the tomato leafminer comprises (3E,8Z)-3,8-tetradecadienyl acetate having a structure shown in formula (SP-2), characterized in that: The preparation method comprises: Reaction (a): allowing the compound represented by formula (I) to undergo olefin cross-metathesis reaction with the compound represented by formula (II) and / or the compound represented by formula (III) in the presence of a metal catalyst to generate a compound represented by formula (IV); ； Reaction (b): using the compound represented by formula (IV) as a substrate, oxidizing it in the presence of an oxidant to generate a compound represented by formula (V); ； Reaction (c): allowing the compound represented by formula (V) to undergo a ylide reaction with the compound represented by formula (VI) to generate a compound represented by formula (VIII); ； Reaction (d): using the compound represented by the formula (VIII) as a substrate, reacting under alkaline conditions to generate the compound represented by the formula (X); ； Reaction (e): subjecting the compound represented by formula (X) to an acetylation reaction to generate (3E,8Z)-3,8-tetradecadienyl acetate represented by formula (SP-2); ； Among them, in formula (II), formula (III), formula (IV), formula (V), and formula (VIII), R is a hydroxyl protecting group; In formula (VI), R2 is halogen.

11. An intermediate for preparing a sex pheromone of tomato leafminer, characterized in that: The intermediate is selected from the compound represented by formula (IV) and / or the compound represented by formula (V); ； In formula (IV) and formula (V), R is a hydroxyl protecting group.

12. A method for preparing a sex pheromone intermediate of tomato leafminer, characterized in that: The tomato leafminer sex pheromone intermediate has a structure shown in formula (V); The preparation method comprises: using the compound represented by the formula (IV) as a substrate, oxidizing in the presence of an oxidant to generate a compound represented by the formula (V); ； In formula (IV) and formula (V), R is a hydroxyl protecting group.

13. The method for preparing the tomato leafminer sex pheromone intermediate according to claim 12, characterized in that: The method for preparing the tomato leafminer sex pheromone intermediate also includes: The compound represented by formula (I) is subjected to an olefin cross-metathesis reaction with the compound represented by formula (II) and / or the compound represented by formula (III) in the presence of a metal catalyst to generate a compound represented by formula (IV); 。 14. A method for preparing a sex pheromone intermediate of tomato leafminer, characterized in that: The tomato leafminer sex pheromone intermediate has a structure shown in formula (IX); The preparation method comprises: allowing the compound represented by formula (V) to undergo a ylide reaction with the compound represented by formula (VII) to generate a compound represented by formula (IX); ； In formula (V) and formula (IX), R is a hydroxyl protecting group other than acetyl; in formula (VII), R1 is a halogen.

15. A method for preparing a sex pheromone intermediate of tomato leafminer, characterized in that: The tomato leafminer sex pheromone intermediate has a structure shown in formula (VIII); The preparation method comprises: allowing the compound represented by formula (V) to undergo a ylide reaction with the compound represented by formula (VI) to generate a compound represented by formula (VIII); ； In formula (V) and formula (VIII), R is a hydroxyl protecting group other than acetyl; in formula (VI), R2 is a halogen.

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