Synthesis method of phyllocnistis appendiculata sex pheromone

Abstract

The invention relates to the technical field of chemical pesticides, in particular to a synthesis method of phyllocnistis appendiculata sex pheromone. According to the synthesis method of the phyllocnistis appendiculata sex pheromone, provided by the invention, the synthesis steps are simplified, the yield of most reactions is 90% or above, the synthesis method is simple and convenient, a target product can be obtained in the shortest time, the phyllocnistis appendiculata sex pheromone (10R, 14R)-10, 14-dimethyl octadecene is prepared through 14-step reactions, and the total yield is 38.5%; according to the method, the phyllocnistis appendiculata sex pheromones (5R, 9R)-5, 9-dimethyl octadecane and (5R, 9R)-5, 9-dimethyl heptadecane are prepared through a reaction in 12 steps, and the total yields are 52.8% and 52.3% respectively.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical pesticides, and particularly relates to a method for synthesizing the sex pheromone of Lyonetia prunifoliella. Background Art

[0002] Lyonetia prunifoliella mainly includes Lithocolletis ringoniella, Phyllonorycter ringoneella and Argyresthia conjugella, and mainly harms fruit trees such as apples and pears. This insect mainly damages the leaves of fruit trees. The larvae burrow into the lower epidermis of the leaves to feed on the mesophyll, forming sieve-like insect spots. In the case of minor damage, it affects the photosynthesis of the fruit tree leaves. In the case of severe damage, it causes early defoliation of the fruit trees, affecting the growth and yield of the fruit trees. In the arid orchard areas of Shaanxi, the long-term use of a large amount of chemical pesticides has killed most of the natural enemies of Lyonetia prunifoliella, making Lyonetia prunifoliella very rampant, becoming the main pest of apples, seriously affecting the quality of apples, and causing inestimable economic losses to fruit farmers.

[0003] Using pheromones for prevention and control will not affect the quality of apples, and it is an ideal prevention and control method. In 1997, Gries et al. identified that the sex pheromone of Lyonetia prunifoliella is a mixture composed of three components, namely (10R,14R)-10,14-dimethyloctadecene (10R,14R)-1, (5R,9R)-5,9-dimethyloctadecane (5R,9R)-2, and (5R,9R)-5,9-dimethylheptadecane (5R,9R)-3, in a ratio of (1:1:1). Field experiments have shown that only the mixture composed of the three components has an attracting effect on male moths. And research has shown that if the component (10R,14R)-1 is absent, the two components (5R,9R)-2 and 3 have no attracting effect on male moths, proving that (10R,14R)-10,14-dimethyloctadecene (10R,14R)-1 has a communication function in the process of attracting male moths.

[0004] In 1999, Mori et al. first reported that six compounds of the sex pheromone of the apple leaf miner were synthesized by constructing a carbon-carbon skeleton through two Grignard reagent coupling reactions using (R)- and (S)-citronellol as chiral sources respectively. Given the high cost of chiral raw materials, this synthetic route was difficult to realize industrial production. In 2000, Mori et al. reported that methyl (2R)-3-hydroxy-2-methylpropionate and methyl (2S)-3-hydroxy-2-methylpropionate were used as chiral sources, and the synthetic route of the sex pheromone of the apple leaf miner was improved by two alkylation reactions of methyl sulfone and two Grignard reagent coupling reactions to construct the carbon-carbon skeleton. In 2005, Summeren et al. reported that two compounds of the sex pheromone of the apple leaf miner were prepared by using 2,7-dienecyclooctanone as a raw material, obtaining chiral centers containing two methyl groups through two metal-catalyzed asymmetric 1,4-conjugate addition reactions, and constructing the carbon-carbon skeleton through two Grignard coupling reactions. However, the metal-catalyzed asymmetric conjugate addition reaction of 2,7-dienecyclooctanone has complex reaction conditions and is not suitable for large-scale production. In 2009, Yadav reported that (10R,14R)-10,14-dimethyloctadecene, (5R,9R)-5,9-dimethyloctadecane and (5R,9R)-5,9-dimethylheptadecane were prepared by using D-phenylalanine as a raw material, constructing chiral centers containing two methyl groups through the Evans asymmetric alkylation method, and constructing the carbon-carbon skeleton through the TosMIC alkylation coupling reaction. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a synthetic method of the sex pheromone of the apple leaf miner, including (10R,14R)-10,14-dimethyloctadecene, (5R,9R)-5,9-dimethyloctadecane and (5R,9R)-5,9-dimethylheptadecane, aiming at the deficiencies of the above-mentioned prior art.

[0006] The present invention provides a synthetic method of the sex pheromone of the apple leaf miner. The compound (10R,14R)-1 prepared in S21 is (10R,14R)-10,14-dimethyloctadecene, the (5R,9R)-2 prepared in S23 is (5R,9R)-5,9-dimethyloctadecane, and the (5R,9R)-3 prepared in S25 is (5R,9R)-5,9-dimethylheptadecane.

[0007] The present invention has the following advantages compared with the prior art:

[0008] The synthetic method of the sex pheromone of Lyonetia clerkella provided by the present invention simplifies the synthetic steps, and the yields of most reactions are above 90%. The synthetic method is simple and can obtain the target product in the shortest time. The sex pheromone of Lyonetia clerkella (10R,14R)-10,14-dimethyloctadecene is prepared through 14-step reactions with a total yield of 38.5%; the sex pheromones of Lyonetia clerkella (5R,9R)-5,9-dimethyloctadecane and (5R,9R)-5,9-dimethylheptadecane are prepared through 12-step reactions with total yields of 52.8% and 52.3% respectively. Description of the Drawings

[0009] Figure 1 and Figure 2 are the hydrogen spectrum and carbon spectrum of (10R,14R)-1 respectively;

[0010] Figure 3 and Figure 4 are the hydrogen spectrum and carbon spectrum of (5R,9R)-2 respectively;

[0011] Figure 5 and Figure 6 are the hydrogen spectrum and carbon spectrum of (5R,9R)-3 respectively. Detailed Embodiments

[0012] Example 1

[0013] This example provides a synthetic method of the sex pheromone of Lyonetia clerkella. The specific steps are as follows:

[0014] S1. Add hexanoic acid to a single-necked flask. Under the protection of an argon atmosphere (Ar), add anhydrous tetrahydrofuran (dry THF), cool at -78°C for 15 min, add triethylamine and pivaloyl chloride in sequence, and then react at -78°C for 20 min;

[0015] Transfer to room temperature and react for 1 h, cool at -78°C for 15 min, add (R)-4-benzyl-oxazolinone (R)-5 and lithium chloride, react at -78°C for 1.0 h, stop refrigeration and let it warm up naturally overnight, and then perform post-treatment of the reaction to obtain the compound (R)-4-benzyl-3-hexanoyl-oxazolinone;

[0016] The molar ratio of hexanoic acid, triethylamine, pivaloyl chloride, (R)-4-benzyl-oxazolinone (R)-5 and lithium chloride is 1:2:1.2:1:3;

[0017] S2. Add the (R)-4-benzyl-3-hexanoyl oxazolidinone prepared in S1 and dry THF into a single-necked flask. Under the protection of an argon atmosphere, cool it at -78 °C for 15 min, then add sodium bis(trimethylsilyl)amide (NaHMDS) dropwise. After that, stir at -78 °C for 30 min;

[0018] Add methyl iodide (MeI) dropwise. After that, react at -78 °C for 2 h. Adjust the temperature to -50 °C and let it react overnight. After the reaction workup, the compound (R)-4-benzyl-3-((R)-2-methylhexanoyl)oxazolidinone is obtained;

[0019] The molar ratio of (R)-4-benzyl-3-hexyl oxazolidinone, NaHMDS, and MeI is 1:2:5;

[0020] S3. Add lithium aluminum hydride (LiAlH4) into a two-necked round-bottom flask. Under the protection of an argon atmosphere and in an ice-water bath at 0 °C, inject dry THF. Take another single-necked round-bottom flask, add the (R)-4-benzyl-3-((R)-2-methylhexanoyl)oxazolidinone prepared in S2 into it. Under the protection of an argon atmosphere, then inject dry THF. Add the mixture into the reaction system, and then let it warm up naturally from 0 °C and stir overnight. After the reaction workup, the compound (R)-2-methyl-1-hexanol is obtained;

[0021] The molar ratio of (R)-4-benzyl-3-((R)-2-methylhexanoyl)oxazolidinone and LiAlH4 is 1:4;

[0022] S4. Add the (R)-2-methyl-1-hexanol prepared in S3, 2-mercaptobenzothiazole (BT-SH), triphenylphosphine (Ph3P), and dry THF into a single-necked round-bottom flask in sequence. Start stirring in an ice-water bath at 0 °C, add diisopropyl azodicarboxylate (DIAD) dropwise. After that, let it warm up naturally at 0 °C and stir overnight. After the reaction workup, the compound (R)-2-methylhexyl benzothiazole sulfide is obtained;

[0023] The molar ratio of (R)-2-methyl-1-hexanol, BT-SH, and Ph3P is 1:1.2:1.2;

[0024] S5. Add the (R)-2-methylhexyl benzothiazole sulfide prepared in S4, anhydrous CH2Cl2, and meta-chloroperoxybenzoic acid (m-CPBA) into a single-necked round-bottom flask in sequence. Stir and react at room temperature for 12 h. After the reaction workup, the compound (R)-2-methylhexyl benzothiazole sulfone is obtained;

[0025] The molar ratio of (R)-2-methylhexyl benzothiazole sulfide and m-CPBA is 1:5;

[0026] S6. Take a single-necked flask, add 4-benzyloxybutyric acid, under the protection of an argon atmosphere, add dry THF, cool it at -78 °C for 15 min, add triethylamine and pivaloyl chloride in sequence, and then react at -78 °C for 20 min;

[0027] Transfer it to room temperature and react for 1 h, cool it at -78 °C for 15 min, add (S)-4-benzyl-oxazolinone (S)-5 and lithium chloride, react at -78 °C for 1.0 h, turn off the refrigeration and let it warm up naturally overnight, and obtain the compound (S)-4-benzyl-3-(4-(benzyloxy)butyryl)oxazolinone after post-treatment of the reaction;

[0028] The molar ratio of 4-benzyloxybutyric acid, triethylamine, pivaloyl chloride, (S)-4-benzyl-oxazolinone (S)-5 and lithium chloride is 1:2:1.2:1:3;

[0029] Using inexpensive hexanoic acid and 4-benzyloxybutyric acid as raw materials, carrying out acylation reactions with triethylamine, pivaloyl chloride, lithium chloride and oxazolinone respectively to prepare (R)-4-benzyl-3-hexanoyl oxazolinone and (S)-4-benzyl-3-(4-(benzyloxy)butyryl)oxazolinone. Compared with the general method, the reaction yield is greatly improved, and there are no by-products generated, and the yields reach 93% and 100%;

[0030] S7. Take a single-necked flask, add the (S)-4-benzyl-3-(4-(benzyloxy)butyryl)oxazolinone prepared in S6, under the protection of an argon atmosphere, cool it at -78 °C for 15 min, dropwise add NaHMDS, and then stir at -78 °C for 30 min;

[0031] Dropwise add MeI, and then react at -78 °C for 2 h, adjust the temperature to -50 °C overnight, and obtain the compound (S)-4-benzyl-3-((S)-2-methyl-4-benzyloxybutyryl)oxazolinone after post-treatment of the reaction;

[0032] The molar ratio of (S)-4-benzyl-3-(4-(benzyloxy)butyryl)oxazolinone, NaHMDS and MeI is 1:2:5;

[0033] Using (R)-4-benzyl-3-hexyloxazolinone and (S)-4-benzyl-3-(4-benzyloxybutyryl)oxazolinone as raw materials, carrying out chiral asymmetric synthesis reactions through iodomethane and NaHMDS, optimizing the reaction conditions, with fewer reaction by-products, and the reaction yield reaching 95%;

[0034] S8. Take two round-bottomed flasks and add LiAlH4 to them. Under the protection of an argon atmosphere and in an ice-water bath at 0 °C, inject dry THF. Take another single-necked round-bottomed flask and add (S)-4-benzyl-3-((S)-2-methyl-4-benzyloxybutanoyl)oxazolidinone prepared in S7 to it. Under the protection of an argon atmosphere, inject dry THF again. Add the mixed solution to the reaction system, then let it warm up naturally from 0 °C and stir overnight. After the reaction workup, compound (S)-2-methyl-4-benzyloxy-1-butanol is obtained.

[0035] The molar ratio of (S)-4-benzyl-3-((S)-2-methyl-4-benzyloxybutanoyl)oxazolidinone to LiAlH4 is 1:4.

[0036] S9. Add (S)-2-methyl-4-benzyloxy-1-butanol prepared in S8 to a single-necked round-bottomed flask. Under the protection of an argon atmosphere, inject anhydrous CH2Cl2 with a syringe. At 0 °C, add imidazole and stir for 15 min, then add tert-butyldimethylchlorosilane (TBSCl). Then let it warm up to room temperature and react for 12 h. After the reaction workup, compound (S)-2-methyl-4-benzyloxybutoxy-tert-butyldimethylsilane is obtained.

[0037] The molar ratio of (S)-2-methyl-4-benzyloxy-1-butanol, imidazole, and TBSCl is 1:2:1.5.

[0038] S10. Add (S)-2-methyl-4-benzyloxybutoxy-tert-butyldimethylsilane, ethyl acetate, and 10% Pd / C to a single-necked round-bottomed flask in sequence. Then connect a hydrogen bag and displace hydrogen five times with a water pump. Stir at 35 °C for 24 h until the reaction is complete, and compound (S)-3-methyl-4-(tert-butyldimethylsiloxy)-1-butanol is obtained.

[0039] The molar ratio of (S)-2-methyl-4-benzyloxybutoxy-tert-butyldimethylsilane to 10% Pd / C is 1:0.08.

[0040] S11. Add (S)-3-methyl-4-(tert-butyldimethylsiloxy)-1-butanol and anhydrous CH2Cl2 to a single-necked round-bottomed flask in sequence. Then add 4A molecular sieve and pyridinium chlorochromate (PCC) in sequence. Stir at room temperature overnight and react for 12 h. After the reaction workup, compound (S)-3-methyl-4-(tert-butyldimethylsiloxy)butanal is obtained.

[0041] The molar ratio of (S)-3-methyl-4-(tert-butyldimethylsiloxy)-1-butanol, 4A molecular sieve, and PCC is 1:1.5:1.5.

[0042] S12. Add the (R)-2-methylhexyl benzothiazole sulfone prepared in S5 into a single-necked round-bottom flask. Under the protection of an argon atmosphere, add dry THF, cool it at -78 °C for 15 min, add LiHMDS dropwise, stir for 30 min, then add the mixed solution of (S)-3-methyl-4-dimethyltert-butylsilyloxybutyraldehyde prepared in S11 and dry THF dropwise. Stir at -78 °C for 3 h, then adjust the temperature to -50 °C and stir overnight. After the reaction workup, compound (2S,6R)-2,6-dimethyldec-4-en-1-dimethyltert-butyloxysilane is obtained;

[0043] (R)-2-methylhexyl thiazole sulfone, LiHMDS and (S)-3-methyl-4-dimethyltert-butylsilyloxybutyraldehyde have a molar ratio of 1:1.2:1.2;

[0044] S13. Add the (2S,6R)-2,6-dimethyldec-4-en-1-dimethyltert-butyloxysilane prepared in S12, methanol and 10% Pt / C into a single-necked round-bottom flask in sequence, then connect a hydrogen bag, displace hydrogen with a water pump five times, and stir at 35 °C for 16 h until the reaction is complete to obtain compound (2S,6R)-2,6-dimethyldecan-1-ol;

[0045] (2S,6R)-2,6-dimethyldec-4-en-1-dimethyltert-butyloxysilane and 10% Pt / C have a molar ratio of 1:0.08;

[0046] S14. Add the (2S,6R)-2,6-dimethyldecan-1-ol prepared in S13, BT-SH, Ph3P and dry THF into a single-necked round-bottom flask in sequence. Start stirring in an ice-water bath at 0 °C, then add diethyl azodicarboxylate (DEAD) dropwise, and then let it warm up naturally at 0 °C and stir overnight. After the reaction workup, compound 2-(2S,6R)-2,6-dimethyldecyl benzothiazole sulfide is obtained;

[0047] (2S,6R)-2,6-dimethyldecan-1-ol, BT-SH and Ph3P have a molar ratio of 1:3:3;

[0048] Using (R)-2-methylhexyl benzothiazole sulfone and (S)-3-methyl-4-(dimethyl tert-butyl silyloxy) butyraldehyde as raw materials, (2S,6R)-2,6-dimethyldec-4-ene-1-dimethyl tert-butyloxysilane was synthesized through the Julia-Kocienski olefination reaction with a yield of 95%. (2S,6R)-2,6-Dimethyldec-4-ene-1-dimethyl tert-butyloxysilane was converted to (2S,6R)-2,6-dimethyldecan-1-ol under the action of Pt / C, and then the key intermediate 2-(2S,6R)-2,6-dimethyldecyl thiazole sulfone was obtained through two steps of Mitsunobu reaction and m-CPBA oxidation, with an overall yield of 83% for the four steps;

[0049] S15: 2-(2S,6R)-2,6-Dimethyldecyl thiazole sulfide prepared in S14, anhydrous CH2Cl2 and m-CPBA were successively added to a single-necked round-bottom flask, and the mixture was stirred at room temperature for 12 h. After the reaction work-up, compound 2-(2S,6R)-2,6-dimethyldecyl benzothiazole sulfone was obtained;

[0050] The molar ratio of 2-(2S,6R)-2,6-dimethyldecyl thiazole sulfide to m-CPBA is 1:5;

[0051] S16: 1,7-Heptanediol was added to a single-necked round-bottom flask. Under the protection of an argon atmosphere, anhydrous CH2Cl2 was injected with a syringe. At a temperature of 0 °C, imidazole was added, and after stirring for 15 min, tert-butyldimethylchlorosilane (TBSCl) was added, and then the mixture was allowed to rise to room temperature and react for 16 h. After the reaction work-up, compound 7-((dimethyl tert-butylsilyl)oxy)-1-heptanol was obtained;

[0052] The molar ratio of 1,7-heptanediol, imidazole and TBSCl is 1:2:0.9;

[0053] S17: 7-((Dimethyl tert-butylsilyl)oxy)-1-heptanol prepared in S16 and anhydrous CH2Cl2 were successively added to a single-necked round-bottom flask, and then 4A molecular sieve and PCC were successively added. The mixture was stirred overnight at room temperature for 12 h. After the reaction work-up, compound 7-((dimethyl tert-butylsilyl)oxy)heptanal was obtained;

[0054] The molar ratio of 7-((dimethyl tert-butylsilyl)oxy)-1-heptanol, 4A molecular sieve and PCC is 1:1.5:1.5;

[0055] S18. Add the 2-(2S,6R)-2,6-dimethyldecylthiazole sulfone prepared in S15 to a single-necked round-bottom flask. Under the protection of an argon atmosphere, add dry THF, cool it at -78 °C for 15 min, add NaHMDS dropwise, stir for 30 min, then add dropwise the mixed solution of 7-((tert-butyldimethylsilyl)oxy)heptanal prepared in S17 and dry THF. After stirring at -78 °C for 3 h, adjust the temperature to -50 °C and stir overnight. After the reaction work-up, the compound (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane is obtained;

[0056] The molar ratio of 2-(2S,6R)-2,6-dimethyldecylthiazole sulfone, NaHMDS and 7-((dimethyl-tert-butylsilyl)oxy)heptanal is 1:1.2:1.2;

[0057] S19. Add the (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane prepared in S18, methanol and 10% Pt / C to a single-necked round-bottom flask, then connect a hydrogen bag. Replace the hydrogen with a water pump five times, stir at 35 °C for 16 h until the reaction is complete. After the reaction work-up, the compound (9S,13R)-9,13-dimethylheptadecan-1-ol is obtained;

[0058] The molar ratio of (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane and 10% Pt / C is 1:0.08;

[0059] S20. Add the (9S,13R)-9,13-dimethylheptadecan-1-ol prepared in S19 and anhydrous CH2Cl2 to a single-necked round-bottom flask in sequence, then add 4A molecular sieve and PCC in sequence, stir overnight at room temperature, react for 12.0 h. After the reaction work-up, the compound (9R,13R)-9,13-dimethylheptadecanal is obtained;

[0060] The molar ratio of (9S,13R)-9,13-dimethylheptadecan-1-ol, 4A molecular sieve and PCC is 1:1.5:1.5;

[0061] S21. Take a two-necked round-bottom flask and add methyltriphenylphosphonium bromide ([MePPh3]Br). Under the protection of an argon atmosphere, add dry THF, cool it at 0 °C for 15 min, add n-butyllithium (n-BuLi) dropwise, stir for 30 min, then add dropwise the mixed solution of (9R,13R)-9,13-dimethylheptadec-7-aldehyde prepared in S20 and dry THF. Stir at 0 °C for 2 h. After the reaction work-up, the compound (10R,14R)-1 is obtained;

[0062] (9R,13R)-9,13-dimethylheptadecan-7-al, [MePPh3]Br, and n-BuLi have a molar ratio of 1:2.5:2.3;

[0063] S22: Add the 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone prepared in S14 to a single-necked round-bottom flask. Under the protection of an argon atmosphere, add dry THF, cool it to -78 °C for 15 min, add NaHMDS dropwise, stir for 30 min, then add a mixture of n-octanal and dry THF dropwise. After stirring at -78 °C for 3 h, adjust the temperature to -50 °C and stir overnight. After the reaction workup, the compound (10S,14R)-10,14-dimethyloctadec-8-ene is obtained;

[0064] The molar ratio of 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone, NaHMDS, and n-octanal is 1:1.2:1.2;

[0065] S23: Add the (10S,14R)-10,14-dimethyloctadec-8-ene prepared in S22, methanol, and 10% Pt / C to a single-necked round-bottom flask in sequence, then connect a hydrogen bag, displace hydrogen with a water pump five times, and stir at 35 °C for 16 h until the reaction is complete. After the reaction workup, the compound (5R,9R)-2 is obtained;

[0066] The molar ratio of (10S,14R)-10,14-dimethyloctadec-8-ene and 10% Pt / C is 1:0.08;

[0067] S24: Add the 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone prepared in S14 to a single-necked round-bottom flask. Under the protection of an argon atmosphere, add dry THF, cool it to -78 °C for 15 min, add NaHMDS dropwise, stir for 30 min, then add a mixture of n-heptanal and dry THF dropwise. After stirring at -78 °C for 3 h, adjust the temperature to -50 °C and stir overnight. After the reaction workup, the compound (9S,13R)-9,13-dimethylheptadec-7-ene is obtained;

[0068] The molar ratio of 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone, NaHMDS, and n-heptanal is 1:1.2:1.2;

[0069] S25: Add the (9S,13R)-9,13-dimethylheptadec-7-ene prepared in S24, methanol, and 10% Pt / C to a single-necked round-bottom flask in sequence, then connect a hydrogen bag, displace hydrogen with a water pump five times, and stir at 35 °C for 16 h until the reaction is complete. After the reaction workup, the compound (5R,9R)-3 is obtained;

[0070] (9S,13R)-9,13-dimethylheptadec-7-ene and 10% Pt / C have a molar ratio of 1:0.08;

[0071] The reaction equation of the method provided in this example is as follows:

[0072]

[0073]

[0074] Using the key intermediate 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone as a raw material, and reacting with the compounds 7-((dimethyl-tert-butylsilyl)oxy)heptanal, n-octanal and n-heptanal respectively through the Julia-Kocienski olefination reaction to synthesize (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane, (10S,14R)-10,14-dimethyloctadec-8-ene and (9S,13R)-9,13-dimethylheptadec-7-ene;

[0075] (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane undergoes three steps of Pt / C-catalyzed hydrogenation, PCC oxidation and Wittig reaction to obtain the sex pheromone (10R,14R)-1 of Lyonetia clerkella, and the total yield after four steps is 70%.

[0076] (10S,14R)-10,14-dimethyloctadec-8-ene and (9S,13R)-9,13-dimethylheptadec-7-ene are respectively subjected to Pt / C-catalyzed hydrogenation to obtain the sex pheromones (5R,9R)-2 and (5R,9R)-3 of Lyonetia clerkella, and the yields are 98% and 95% respectively;

[0077] Compared with the general synthesis route, this synthesis route is shorter, and the yields of most reactions are above 90%. The synthesis method is simple and the target product can be obtained in the shortest time. The sex pheromone (10R,14R)-1 of Lyonetia clerkella is prepared through 14-step reactions with a total yield of 38.5%; the sex pheromones (5R,9R)-2 and (5R,9R)-3 of Lyonetia clerkella are prepared through 12-step reactions with total yields of 52.8% and 52.3% respectively. The reaction equations of different steps are as follows:

[0078]

[0079] The yields of different steps are shown in Table 1 below:

[0080] Table 1

[0081]

[0082] Example 2

[0083] This example provides a method for synthesizing the sex pheromone of Lyonetia clerkella, and the specific steps are as follows:

[0084] S1. Add 3.0 g of hexanoic acid to a 250 mL single-necked flask. Under the protection of an argon atmosphere (Ar), add 110 mL of anhydrous tetrahydrofuran (dry THF), cool at a temperature of -78 °C for 15 min, sequentially add 7.2 mL of triethylamine (Et3N) and 3.8 mL of pivaloyl chloride (PivCl), and then react at a temperature of -78 °C for 20 min;

[0085] Transfer to a room temperature environment and react for 1 h. Then place it in a low-temperature reaction bath, cool at a temperature of -78 °C for 15 min, add 4.6 g of (R)-4-benzyl-oxazolinone (R)-5 and 3.8 g of lithium chloride (LiCl), react at a temperature of -78 °C for 1.0 h, stop refrigeration and let it warm up naturally overnight, and then transfer to stir at room temperature for 2 h;

[0086] Post-treatment of the reaction: Quench the reaction with water, extract with ethyl acetate, dry and concentrate with anhydrous sodium sulfate, and obtain 6.6 g of a pale yellow oil by column chromatography, namely the compound (R)-4-benzyl-3-hexyloxazolinone;

[0087]

[0088] Perform 1H NMR and 13C NMR detection on (R)-4-benzyl-3-hexyloxazolinone, and the results are as follows:

[0089] 1 H NMR(600MHz,CDCl3)δ7.33(t,J=7.2Hz,2H),δ7.28(d,J=7.4Hz,1H),7.21(d,J=7.2Hz,2H),4.69-4.65(m,1H),4.21-4.15(m,2H),3.30(dd,J=3.1,10.3Hz,1H),2.30-2.87(m,2H),2.77(dd,J=9.7,13.4Hz,1H),1.74-1.65(m,2H),1.38-1.36(m,4H),0.92(t,J=7.0Hz,3H);

[0090] 13 C NMR(150MHz,CDCl3)δ173.42,153.43,135.31,129.39,128.91,127.30,66.11,55.12,37.91,35.46,31.25,23.92,22.40,13.89;

[0091] S2. Add 9.1 g of (R)-4-benzyl-3-hexyloxazolidinone prepared in S1 and 130 mL of dry THF to a 500 mL single-necked flask. Under the protection of an argon atmosphere, cool it at -78 °C for 15 min, add dropwise 33 mL of sodium bis(trimethylsilyl)amide (NaHMDS), then stir at -78 °C for 30 min, add dropwise 10.3 mL of methyl iodide (MeI), and then react at -78 °C for 2 h. Adjust the temperature to -50 °C and leave it overnight.

[0092] Work-up of the reaction: Add saturated NH4Cl solution to the reaction system at -50 °C to quench the reaction. Extract it with EA three times successively, wash it with saturated brine, dry it over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 9.1 g of a pale yellow oil, namely compound (R)-4-benzyl-3-((R)-2-methylhexanoyl)oxazolidinone, with a yield of 95%.

[0093]

[0094] Perform 1H NMR and 13C NMR tests on (R)-4-benzyl-3-((R)-2-methylhexanoyl)oxazolidinone, and the results are as follows:

[0095] [α] 25 D = -13.67 (c = 0.08, CH3OH);

[0096] 1 1H NMR (600 MHz, CDCl3) δ 7.33 (t, J = 7.2 Hz, 2H), 7.27 (t, J = 7.3 Hz, 1H), 7.21 (d, J = 7.2 Hz, 2H), 4.70 - 4.66 (m, 1H), 4.21 - 4.16 (m, 2H), 4.21 - 4.16 (m, 2H), 3.77 - 3.68 (m, 1H), 3.27 (dd, J = 3.2, 13.4 Hz, 1H), 2.77 (dd, J = 10.0, 13.4 Hz, 1H), 2.7 (dd, J = 9.5, 13.4 Hz, 1H), 1.78 - 1.72 (m, 1H), 1.45 - 1.39 (m, 1H), 1.32 - 1.27 (m, 5H), 1.22 (d, J = 6.8 Hz, 3H), 0.89 (t, J = 6.8 Hz, 3H);

[0097] 1313C NMR (150 MHz, CDCl3) δ 177.36, 153.05, 135.34, 129.43, 128.90, 127.30, 85.98, 55.33, 37.90, 37.64, 33.12, 29.40, 22.70, 17.34, 13.94;

[0098] S3. Add 3.8 g of lithium aluminum hydride (LiAlH4) to a 250 mL two-necked round-bottom flask. Under the protection of an argon atmosphere and an ice-water bath, inject 60 mL of dry THF. Take another single-necked round-bottom flask, add 7.3 g of (R)-4-benzyl-3-((R)-2-methylhexanoyl)oxazolidinone prepared in S2 to it. Under the protection of an argon atmosphere, inject another 40 mL of dry THF, add the mixed solution to the reaction system, then let it warm up naturally from 0 °C and stir overnight.

[0099] Work-up of the reaction: Under an ice-water bath, add water, 10% NaOH solution, and water in a ratio of 1:2:3 to the reaction system in sequence to quench the reaction. Then transfer it to a sintered funnel for filtration. Wash the gel-like substance with EA. Extract the filtrate with EA, dry it over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 2.9 g of a pale yellow oily substance, namely compound (R)-2-methyl-1-hexanol, with a yield of 98%.

[0100]

[0101] Perform 1H NMR and 13C NMR tests on (R)-2-methyl-1-hexanol. The results are as follows:

[0102] [α] 25 D = +23.25 (c = 0.08, CH3OH);

[0103] 1 1H NMR (600 MHz, CDCl3) δ 3.50 (dd, J = 5.8, 10.4 Hz, 1H), 3.41 (dd, J = 6.5, 10.4 Hz, 1H), 1.64 - 1.56 (m, 1H), 1.42 - 1.21 (m, 6H), 1.13 - 1.07 (m, 1H), 0.90 (q, J = 6.8, 14.1 Hz, 6H);

[0104] 13 13C NMR (150 MHz, CDCl3) δ 68.41, 35.73, 32.83, 29.18, 22.96, 16.56, 14.05;

[0105] S4. In a 100 mL single-necked round-bottom flask, successively add 0.7 g of (R)-2-methyl-1-hexanol prepared in S3, 1.3 g of 2-mercaptobenzothiazole (BT-SH), 2.0 g of triphenylphosphine (Ph3P), and 25 mL of dry THF. Start stirring in an ice-water bath, add dropwise 0.7 mL of diisopropyl azodicarboxylate (DIAD), and then let it warm up naturally at 0 °C and stir overnight.

[0106] Work-up of the reaction: Directly rotary evaporate THF, and obtain 1.1 g of a yellow oil by column chromatography, namely compound (R)-2-methylhexyl benzothiazole sulfide, with a yield of 81%.

[0107]

[0108] Perform 1H NMR and 13C NMR detection on (R)-2-methylhexyl benzothiazole sulfide, and the results are as follows:

[0109] [α] 25 D = -9.87 (c = 0.08, CH3OH).

[0110] 1 1H NMR (600 MHz, CDCl3) δ 7.84 (d, J = 8.10 Hz, 1H), 7.72 (d, J = 7.95 Hz, 1H), 7.40 - 7.37 (m, 1H), 7.28 - 7.24 (m, 1H), 3.41 - 3.38 (m, 1H), 3.20 - 3.16 (m, 1H), 1.53 - 1.49 (m, 1H), 1.36 - 1.29 (m, 5H), 1.05 (d, J = 6.7 Hz, 3H), 0.89 (t, J = 6.2 Hz, 3H);

[0111] 13 13C NMR (150 MHz, CDCl3) δ 167.68, 153.32, 135.12, 125.91, 124.01, 121.37, 120.83, 40.69, 35.76, 33.18, 29.05, 22.76, 19.32, 14.01;

[0112] S5. In a 250 mL single-necked round-bottom flask, successively add 0.99 g of (R)-2-methylhexyl benzothiazole sulfide prepared in S4, 15 mL of anhydrous CH2Cl2, and 3.8 g of m-chloroperoxybenzoic acid (m-CPBA), and stir at room temperature for 12 h.

[0113] Workup: Sodium thiosulfate was added to the reaction system to remove the excess m-CPBA, and saturated NaHCO3 solution was added to remove the acid. The mixture was extracted three times with CH2Cl2 successively, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain 1.1 g of a colorless oil, namely compound (R)-2-methylhexyl benzothiazole sulfone, with a yield of 99%;

[0114]

[0115] The 1H NMR and 13C NMR spectra of (R)-2-methylhexyl benzothiazole sulfone were measured, and the results were as follows:

[0116] [α] 25 D = -13.67 (c = 0.06, CH3OH);

[0117] 1 1H NMR (500 MHz, CDCl3) δ 8.21 (d, J = 8.0 Hz, 1H), 8.01 (d, J = 8.3 Hz, 1H), 7.65 - 7.57 (m, 2H), 3.57 - 3.53 (m, 1H), 3.37 - 3.32 (m, 1H), 2.30 - 2.26 (m, 1H), 1.51 - 1.45 (m, 1H), 1.3 - 1.24 (m, 5H), 1.13 (d, J = 6.7 Hz, 3H), 0.86 - 0.83 (m, 3H);

[0118] 13 13C NMR (125 MHz, CDCl3) δ 166.77, 152.38, 138.70, 127.93, 127.59, 125.38, 122.32, 60.75, 36.30, 28.44, 22.48, 19.84, 13.88;

[0119] HRMS (APCI) m / z calcd for C 14 H 20 NO2S2 + (M + H) + : 298.0935, found 298.0924;

[0120] S6. A 500 mL single-necked flask was charged with 6.7 g of 4-benzyloxybutyric acid. Under an argon atmosphere, 140 mL of dry THF was added, and the mixture was cooled to -78 °C for 15 min. 9.6 mL of triethylamine and 1.1 mL of pivaloyl chloride were added successively, and then the reaction was carried out at -78 °C for 20 min;

[0121] Transfer to room temperature and react for 1 h. Place it in a low-temperature reaction bath and cool it at -78 °C for 15 min. Add 6.1 g of (S)-4-benzyl oxazolinone (S)-5 and 4.4 g of lithium chloride, and react at -78 °C for 1.0 h. After turning off the refrigeration, let it warm up naturally overnight;

[0122] Work-up of the reaction: Quench the reaction with water, extract with ethyl acetate, dry over anhydrous sodium sulfate and concentrate. Column chromatography gives 12.6 g of a pale yellow oil, namely compound (S)-4-benzyl-3-(4-(benzyloxy)butyryl)oxazolinone, with a yield of 100%;

[0123]

[0124] Perform 1H NMR and 13C NMR tests on (S)-4-benzyl-3-(4-(benzyloxy)butyryl)oxazolinone, and the results are as follows:

[0125] 1 H NMR(600MHz,CDCl3)δ7.37-7.32(m,6H),7.28(d,J=6.7Hz,2H),7.19(d,J=7.3Hz,2H),4.63-4.58(m,1H),4.52(s,2H),4.12-4.07(m,2H),3.59(t,J=6.2Hz,2H),3.26(dd,J=3.2,13.4Hz,1H),3.08(t,J=7.2Hz,2H),2.71(dd,J=9.6,13.4Hz,1H),2.07-2.03(m,2H);

[0126] 13 C NMR(150MHz,CDCl3)δ172.89,153.33,138.33,135.25,129.27,128.78,128.22,127.55,127.41,127.15,72.73,69.11,65.99,54.98,37.70,32.33,24.36;

[0127] S7. Add 8.4 g of (S)-4-benzyl-3-(4-(benzyloxy)butyryl)oxazolinone prepared in S6 to a 500 mL single-necked flask. Under the protection of an argon atmosphere, add 120 mL of dry THF, cool it at -78 °C for 15 min, add dropwise 30.5 mL of NaHMDS, then stir at -78 °C for 30 min, add dropwise 9.5 mL of MeI, then react at -78 °C for 2 h, and adjust the temperature to -50 °C overnight;

[0128] Workup after reaction: The reaction was quenched by adding saturated NH4Cl solution to the reaction system at -50 °C, and then extracted with EA three times successively, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain 8.8 g of a pale yellow oil, namely compound (S)-4-benzyl-3-((S)-2-methyl-4-(benzyloxy)butanoyl)oxazolinone, with a yield of 91%;

[0129]

[0130] The 1H NMR and 13C NMR spectra of (S)-4-benzyl-3-((S)-2-methyl-4-(benzyloxy)butanoyl)oxazolinone were measured, and the results were as follows:

[0131] [α] 25 D = +15.75 (c = 0.08, CH3OH);

[0132] 1 1H NMR (600 MHz, CDCl3) δ 7.33 - 7.27 (m, 7H), 7.24 - 7.21 (m, 1H), 7.15 (d, J = 7.2 Hz, 2H), 4.42 (d, J = 2.7 Hz, 2H), 4.0 - 3.92 (m, 2H), 3.73 (t, J = 8.6 Hz, 1H), 3.59 - 3.51 (m, 2H), 3.18 (dd, J = 3.3, 13.4 Hz, 1H), 2.7 (dd, J = 9.5, 13.4 Hz, 1H), 2.21 - 2.14 (m, 1H), 1.77 - 1.71 (m, 1H), 1.26 - 1.2 (d, J = 6.9 Hz, 3H);

[0133] 13 13C NMR (150 MHz, CDCl3) δ 177.03, 153.20, 138.50, 135.40, 129.35, 128.78, 128.21, 127.58, 127.46, 127.17, 72.78, 68.43, 65.79, 55.15, 37.95, 35.11, 33.61, 18.01;

[0134] S8. Add 3.7 g of LiAlH4 to a 250 mL two-necked round-bottom flask. Under the protection of an argon atmosphere and an ice-water bath, inject 60 mL of dry THF. Take another single-necked round-bottom flask, add 8.7 g of (S)-4-benzyl-3-((S)-2-methyl-4-(benzyloxy)butanoyl)oxazolinone prepared in S7 to it. Under the protection of an argon atmosphere, inject another 38 mL of dry THF, add the mixed solution to the reaction system, and then let it warm up naturally from 0 °C and stir overnight;

[0135] Work-up after reaction: Under an ice-water bath, water, 10% NaOH solution were successively added to the reaction system in a ratio of 1:2:3 to quench the reaction with water. Then it was transferred to a sintered funnel for filtration. The gel-like substance was washed with EA. The filtrate was extracted with EA, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography to obtain 3.3 g of a colorless oily substance, namely compound (S)-2-methyl-4-benzyloxy-1-butanol, with a yield of 95%;

[0136]

[0137] The 1H NMR and 13C NMR of (S)-2-methyl-4-benzyloxy-1-butanol were measured, and the results were as follows:

[0138] [α] 25 D = +7.5 (c = 0.36, CHCl3);

[0139] 1 1H NMR (600 MHz, CDCl3) δ 7.36 - 7.32 (m, 4H), 7.30 - 7.27 (m, 1H), 4.52 (s, 2H), 3.61 - 3.57 (m, 1H), 3.54 - 3.47 (m, 2H), 3.42 (dd, J = 6.5, 10.9 Hz, 1H), 2.76 (s, 1H), 1.84 - 1.78 (m, 1H), 1.73 - 1.67 (m, 1H), 1.59 - 1.54 (m, 1H), 0.92 (d, J = 6.9 Hz, 3H);

[0140] 13 13C NMR (150 MHz, CDCl3) δ 137.99, 128.40, 127.71, 127.67, 73.10, 68.64, 68.03, 34.06, 33.97, 29.65, 17.13;

[0141] S9. 1.4 g of (S)-2-methyl-4-benzyloxy-1-butanol prepared in S8 was added to a 250 mL single-necked round-bottom flask. Under the protection of an argon atmosphere, 30 mL of anhydrous CH2Cl2 was injected with a syringe. At 0 °C, 8.9 g of imidazole was added and stirred for 15 min, then 8.9 g of tert-butyldimethylchlorosilane (TBSCl) was added, and then the temperature was naturally raised to room temperature and the reaction was carried out for 12 h;

[0142] Work-up after reaction: CH2Cl2 was removed by rotary evaporation, and column chromatography was carried out to obtain 2.2 g of a colorless oily substance, namely compound (S)-(2-methyl-4-benzyloxybutoxy)dimethyl-tert-butylsilane, with a yield of 98%;

[0143]

[0144] The (S)-(2-methyl-4-benzyloxybutoxy)dimethyl-tert-butylsilane was subjected to 1H NMR and 13C NMR tests, and the results were as follows:

[0145] [α] 25 D = +0.7 (c = 0.14, CH3OH);

[0146] 1 1H NMR (600 MHz, CDCl3) δ 7.26 (d, J = 4.4 Hz, 4H), 7.21 - 7.17 (m, 1H), 4.42 (dd, J = 12.0, 15.5 Hz, 2H), 3.48 - 3.42 (m, 1H), 3.40 - 3.31 (m, 2H), 1.71 - 1.67 (m, 2H), 1.35 - 1.31 (m, 1H), 0.82 (d, J = 6.7 Hz, 12H), 0.05 (s, 6H);

[0147] 13 13C NMR (150 MHz, CDCl3) δ 138.66, 128.29, 127.57, 127.41, 72.80, 68.67, 68.19, 33.17, 32.93, 25.92, 18.29, 16.79, -5.42;

[0148] S10. 2.5 g of (S)-(2-methyl-4-benzyloxybutoxy)dimethyl-tert-butylsilane prepared in S9, 30 mL of ethyl acetate and 0.7 g of 10% Pd / C were successively added to a 250 mL single-necked round-bottom flask. Then, a hydrogen bag was connected, and the hydrogen was displaced five times with a water pump. The mixture was stirred at 35 °C for 24 h until the reaction was complete;

[0149] Work-up after reaction: The 10% palladium-carbon was removed by filtration. The filtrate was concentrated with a rotary evaporator and directly subjected to column chromatography to obtain 1.7 g of a colorless oil, i.e., compound (S)-3-methyl-4-(dimethyl-tert-butylsiloxy)-1-butanol, with a yield of 98%;

[0150]

[0151] The (S)-3-methyl-4-(dimethyl-tert-butylsiloxy)-1-butanol was subjected to 1H NMR and 13C NMR tests, and the results were as follows:

[0152] [α] 25 D = +2.8 (c = 0.1, CH3OH);

[0153] 11H NMR (600 MHz, CDCl3) δ 3.66 - 3.64 (m, 1H), 3.58 - 3.57 (m, 1H), 3.48 (dd, J = 4.7, 10.0 Hz, 1H), 3.39 (dd, J = 7.1, 9.9 Hz, 1H), 3.12 (s, 1H), 1.76 - 1.70 (m, 1H), 1.60 - 1.50 (m, 2H), 0.86 (d, J = 6.8 Hz, 12H), 0.03 (s, 6H);

[0154] 13 13C NMR δ (150 MHz, CDCl3) 60.86, 37.71, 33.72, 25.80, 18.21, 17.17, -5.54, -5.57;

[0155] S11. To a 250 mL single-necked round-bottom flask, add 5.8 g of (S)-3-methyl-4-(dimethyl-tert-butylsilyloxy)-1-butanol prepared in S10 and 100 mL of anhydrous CH2Cl2 successively. Then add 8.2 g of 4A molecular sieve and 8.2 g of pyridinium chlorochromate (PCC) successively, and stir overnight at room temperature for 12.0 h;

[0156] Work-up of the reaction: Add petroleum ether to the reaction system to precipitate chromium, then filter through a sintered funnel lined with diatomaceous earth and silica gel, wash with ether, and concentrate to obtain 4.3 g of a colorless oil, namely compound (S)-3-methyl-4-(dimethyl-tert-butylsilyloxy)butanal, with a yield of 79%;

[0157]

[0158] The 1H NMR and 13C NMR of (S)-3-methyl-4-(dimethyl-tert-butylsilyloxy)butanal were detected, and the results were as follows:

[0159] [α] 25 D = -8.8 (c = 0.2, CHCl3);

[0160] 1 1H NMR (600 MHz, CDCl3) δ 9.73 (t, J = 2.7 Hz, 1H), 3.54 - 3.51 (m, 1H), 3.35 - 3.31 (m, 1H), 2.48 - 2.45 (m, 1H), 2.45 - 2.16 (m, 1H), 0.91 (d, J = 7.89 Hz, 3H), 0.85 (d, J = 5.94 Hz, 9H), 0.02 (d, J = 10.56 Hz, 6H);

[0161] 1313C NMR(150MHz,CDCl3)δ202.63,67.71,48.21,31.45,25.85,18.25,16.66,-5.52;

[0162] S12. Add 5.8 g of (R)-2-methylhexyl benzothiazole sulfone prepared in S5 to a 250 mL single-necked round-bottom flask. Under the protection of an argon atmosphere, add 40 mL of dry THF, cool to -78 °C for 15 min, add dropwise 12 mL of LiHMDS, stir for 30 min, then add dropwise a mixture of 5.0 g of (S)-3-methyl-4-(dimethyl-tert-butylsilyloxy)butyraldehyde prepared in S11 and 30 mL of dry THF. Stir at -78 °C for 3 h, then adjust the temperature to -50 °C and stir overnight;

[0163] Work-up of the reaction: Add saturated NH4Cl to the reaction system at -50 °C to quench the reaction. Extract with EA three times in sequence, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 5.5 g of a pale colorless oil, namely (2S,6R)-2,6-dimethyldec-4-ene-1-dimethyl-tert-butyloxysilane, with a yield of 95%;

[0164]

[0165] Perform 1H NMR and 13C NMR tests on (2S,6R)-2,6-dimethyldec-4-ene-1-dimethyl-tert-butyloxysilane. The results are as follows:

[0166] (Z / E 3:2 mixture)[α] 25 D = +1.17 (c = 0.06, CH3OH);

[0167] 1 1H NMR(600MHz,CDCl3)δ5.68 - 5.47(m,2H),3.81 - 3.76(m,1H),3.73 - 3.69(m,1H),2.46 - 2.40(m,1H),2.20 - 2.09(m,1H),2.01 - 1.93(m,1H),1.63 - 1.55(m,6H),1.31 - 1.16(m,19H),0.38(d,J = 2.94Hz,6H);

[0168] 13CNMR (150 MHz, CDCl3) δ 138.07, 137.48, 126.42, 126.33, 68.11, 67.85, 37.29, 36.92, 36.81, 36.48, 36.32, 36.14, 31.61, 31.06, 29.72, 29.63, 25.95, 22.88, 22.80, 21.24, 21.00, 18.34, 16.51, 16.43, 14.10, -5.35;

[0169] S13. To a 250 mL single-necked round-bottom flask, add 5.5 g of (2S,6R)-2,6-dimethyldec-4-en-1-yl dimethyl tert-butoxysilane prepared in S12, 70 mL of methanol, and 2.9 g of 10% Pt / C in sequence. Then connect a hydrogen bag, and displace hydrogen five times with a water pump. Stir at 35 °C for 16 h until the reaction is complete;

[0170] Work-up of the reaction: Remove CH3OH using a rotary evaporator and directly perform column chromatography to obtain 3.4 g of a colorless oil, namely compound (2S,6R)-2,6-dimethyldecan-1-ol, with a yield of 100%;

[0171]

[0172] Perform 1H NMR and 13C NMR tests on (2S,6R)-2,6-dimethyldecan-1-ol, and the results are as follows:

[0173] [α] 25 D = +1.37 (c = 0.08, CH3OH);

[0174] 1 H NMR (500 MHz, CDCl3) δ 3.52 - 3.49 (m, 1H), 3.44 - 3.40 (m, 1H), 1.63 - 1.67 (m, 1H), 1.37 - 1.34 (m, 2H), 1.32 - 1.12 (m, 9H), 1.10 - 1.06 (m, 3H), 0.92 (d, J = 8.04 Hz, 3H), 0.90 - 0.87 (m, 3H), 0.84 (d, J = 7.92 Hz, 3H);

[0175] 13 C NMR (125 MHz, CDCl3) δ 68.47, 37.28, 36.81, 35.77, 33.42, 32.69, 29.33, 24.37, 23.02, 19.64, 16.54, 25.94, 14.14;

[0176] S14. 0.5 g of (2S,6R)-2,6-dimethyldecan-1-ol prepared in S13, 1.4 g of BT-SH, 2.2 g of Ph3P and 25 mL of dry THF were successively added to a 100 mL single-necked round-bottom flask. Under an ice-water bath, stirring was started, and then 1.3 mL of diethyl azodicarboxylate (DEAD) was added dropwise. After that, the temperature was allowed to rise naturally at 0 °C and stirred overnight.

[0177] Work-up of the reaction: THF was directly removed by rotary evaporation, and column chromatography gave 0.9 g of a yellow oil, namely compound 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfide, with a yield of 92%.

[0178]

[0179] 1H NMR and 13C NMR of 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfide were measured, and the results were as follows:

[0180] [α] 25 D = -2.0 (c = 0.06, CH3OH);

[0181] 1 1H NMR (600 MHz, CDCl3) δ 7.85 (d, J = 9.7 Hz, 1H), 7.75 (d, J = 9.5 Hz, 1H), 7.74 (d, J = 9.9 Hz, 1H), 7.30 (d, J = 9.7 Hz, 1H), 3.43 - 3.37 (m, 1H), 3.22 - 3.18 (m, 1H), 1.97 - 1.90 (m, 1H), 1.52 - 1.46 (m, 1H), 1.39 - 1.21 (m, 10H), 1.14 - 1.09 (m, 2H), 1.07 (d, J = 8.0 Hz, 3H), 0.88 (t, J = 8.0 Hz, 3H), 0.85 (d, J = 7.9 Hz, 3H);

[0182] 13 13C NMR (150 MHz, CDCl3) δ 167.75, 153.34, 135.14, 125.96, 124.06, 121.41, 120.87, 40.78, 37.07, 36.79, 36.37, 33.26, 32.67, 29.32, 24.32, 23.02, 19.64, 19.34, 14.14;

[0183] S15. Add 2.5 g of 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfide prepared in S14, 37 mL of anhydrous CH2Cl2 and 6.4 g of m-CPBA into a 250 mL single-necked round-bottom flask in sequence, and stir and react at room temperature for 12 h;

[0184] Work-up of the reaction: Add sodium thiosulfate to the reaction system to remove the excess m-CPBA, add saturated NaHCO3 solution to remove the acid, extract with CH2Cl2 three times in sequence, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 2.6 g of a colorless oil, namely compound 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone, with a yield of 95%;

[0185]

[0186] Perform 1H NMR and 13C NMR detection on 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone, and the results are as follows:

[0187] [α] 25 D = +7.4 (c = 0.08, CHCl3);

[0188] 1 1H NMR (500 MHz, CDCl3) δ 8.22 (d, J = 8.15 Hz, 1H), 8.02 (d, J = 7.75 Hz, 1H), 7.64 - 7.59 (m, 2H), 3.58 - 3.54 (m, 1H), 3.37 - 3.32 (m, 1H), 2.30 - 2.26 (m, 1H), 1.47 - 1.43 (m, 1H), 1.32 - 1.19 (m, 10H), 1.14 (d, J = 6.7 Hz, 3H), 1.06 - 0.99 (m, 2H), 0.87 (d, J = 7.0 Hz, 3H), 0.80 - 0.77 (m, 3H);

[0189] 13 13C NMR (125 MHz, CDCl3) δ 166.78, 152.70, 136.74, 127.95, 127.60, 125.41, 122.33, 60.82, 36.94, 36.77, 32.58, 29.24, 28.54, 23.74, 22.97, 19.83, 19.52, 14.12. HRMS (ESI) m / z calcd for C 14 H 20 NO2S2 + (M + H) + : 368.1718, found 368.1726;

[0190] S16. Add 2.5 g of 1,7 - heptanediol to a 250 mL single - necked round - bottom flask. Under the protection of an argon atmosphere, inject 75 mL of anhydrous CH₂Cl₂ with a syringe. At a temperature of 0 °C, add 2.6 g of imidazole and stir for 15 min. Then add 2.6 g of dimethyl tert - butylchlorosilane (TBSCl), and then let it rise to room temperature naturally and react for 16 h;

[0191] Workup of the reaction: Quench the reaction with water, extract with ethyl acetate, dry over anhydrous sodium sulfate and concentrate. Column chromatography gives 3.3 g of a colorless oil, namely 7 - ((dimethyl - tert - butylsilyl)oxy)-1 - heptanol, with a yield of 73%;

[0192]

[0193] Perform ¹H NMR and ¹³C NMR detection on 7 - ((dimethyl - tert - butylsilyl)oxy)-1 - heptanol. The results are as follows:

[0194] 1 ¹H NMR (500 MHz, CDCl₃) δ 3.61 - 3.56 (m, 4H), 1.55 - 1.48 (m, 4H), 1.31 (s, 6H), 0.89 (s, 1H), 0.87 (s, 9H), 0.02 (s, 6H);

[0195] 13 ¹³C NMR (125 MHz, CDCl₃) δ 63.84, 63.60, 33.35, 29.81, 26.56, 18.95, - 4.69;

[0196] S17. Add 4.0 g of 7 - ((dimethyl - tert - butylsilyl)oxy)-1 - heptanol prepared in S16 and 65 mL of anhydrous CH₂Cl₂ to a 250 mL single - necked round - bottom flask in sequence. Then add 5.3 g of 4A molecular sieve and 5.3 g of PCC in sequence, and stir overnight at room temperature for 12 h;

[0197] Workup of the reaction: Add petroleum ether to the reaction system to precipitate chromium. Then filter through a sintered - glass funnel lined with diatomaceous earth and silica gel, wash with ether, and concentrate to obtain 3.1 g of a colorless oil, namely 7 - ((dimethyl - tert - butylsilyl)oxy)heptanal, with a yield of 78%;

[0198]

[0199] Perform ¹H NMR and ¹³C NMR detection on 7 - ((dimethyl - tert - butylsilyl)oxy)heptanal. The results are as follows:

[0200] 11H NMR (600 MHz, CDCl3) δ 9.76 - 9.75 (m, 1H), 3.40 (t, J = 7.74 Hz, 1H), 2.44 - 2.40 (m, 2H), 1.65 - 1.62 (m, 2H), 1.52 - 1.50 (m, 2H), 1.40 - 1.33 (m, 4H), 0.89 (s, 9H), 0.04 (s, 6H);

[0201] 13 13C NMR (150 MHz, CDCl3) δ 202.94, 63.08, 43.84, 32.58, 28.94, 25.96, 25.58, 22.04, 18.36, -5.25;

[0202] S18. Add 0.6 g of 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone prepared in S15 to a 100 mL single-necked round-bottom flask. Under the protection of an argon atmosphere, add 10 mL of dry THF, cool to -78 °C for 15 min, add dropwise 0.9 mL of NaHMDS, stir for 30 min, then add dropwise a mixture of 0.5 g of 7-((dimethyl-tert-butylsilyl)oxy)heptanal prepared in S17 and 2 mL of dry THF. Stir at -78 °C for 3 h, then adjust the temperature to -50 °C and stir overnight;

[0203] Work-up of the reaction: Add saturated NH4Cl to the reaction system at -50 °C to quench the reaction. Extract with EA three times in sequence, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 0.6 g of a pale yellow oil, namely compound (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane, with a yield of 98%;

[0204]

[0205] Perform 1H NMR and 13C NMR tests on (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane, and the results are as follows:

[0206] (Z / E 1:2 mixture) [α] 25 D = -1.79 (c = 0.1, CHCl3);

[0207] 11H NMR (600 MHz, CDCl3) δ 5.36 - 5.08 (m, 2H), 3.59 (t, J = 7.98 Hz, 2H), 2.02 - 1.96 (m, 2H), 1.31 - 1.15 (m, 19H), 1.06 - 1.05 (m, 2H), 0.94 - 0.87 (m, 16H), 0.84 - 0.82 (m, 3H), 0.05 (d, J = 2.10 Hz, 6H);

[0208] 13 13C NMR (150 MHz, CDCl3) δ 136.49, 128.30, 63.33, 37.85, 37.48, 37.17, 36.77, 32.18, 31.63, 29.93, 29.34, 28.93, 27.47, 25.99, 25.70, 24.94, 23.04, 21.48, 21.00, 19.71, 18.43, 14.18, -5.27;

[0209] S19. Add 2.1 g of (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane prepared in S18, 20 mL of methanol and 0.9 g of 10% Pt / C to a 250 mL single-necked round-bottom flask, then connect a hydrogen bag. Replace the hydrogen with a water pump five times and stir at 35 °C for 16 h until the reaction is complete;

[0210] Work-up of the reaction: Remove CH3OH using a rotary evaporator and directly perform column chromatography to obtain 1.6 g of a colorless oil, namely the compound (9S,13R)-9,13-dimethylheptadecane-1-ol, with a yield of 100%;

[0211]

[0212] The 1H NMR and 13C NMR spectra of (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethyl-tert-butylsilane were measured, and the results were as follows:

[0213] [α] 25 D = -1.15 (c = 0.13, CHCl3);

[0214] 1 1H NMR (600 MHz, CDCl3) δ 3.64 (t, J = 5.94 Hz, 2H), 1.59 - 1.54 (m, 2H), 1.35 - 1.20 (m, 24H), 1.10 - 1.04 (m, 4H), 0.88 (t, J = 6.96 Hz, 3H), 0.83 (dd, J = 1.5, 6.6 Hz, 6H);

[0215] 13 13C NMR (150 MHz, CDCl3) δ 63.11, 37.41, 37.36, 37.13, 37.03, 36.83, 36.73, 32.80, 32.73, 32.71, 29.93, 29.65, 29.44, 29.34, 27.06, 25.73, 24.45, 23.04, 19.75, 19.68, 14.19;

[0216] S20: 259 mg of (9S,13R)-9,13-dimethylheptadecan-1-ol prepared in S19 and 5 mL of anhydrous CH2Cl2 were successively added to a 100 mL single-necked round-bottom flask. Then, 294 mg of 4A molecular sieve and 294 mg of PCC were successively added, and the mixture was stirred overnight at room temperature for 12.0 h;

[0217] Workup of the reaction: Petroleum ether was added to the reaction system to precipitate chromium. Then, the mixture was filtered through a sintered funnel lined with diatomaceous earth and silica gel, washed with ether, and concentrated to obtain 86 mg of a pale yellow oil, namely, compound (9R,13R)-9,13-dimethylheptadecanal, with a yield of 82%;

[0218]

[0219] 1H NMR and 13C NMR of (9R,13R)-9,13-dimethylheptadecanal were measured, and the results were as follows:

[0220] [α] 25 D = -1.14 (c = 0.07, CHCl3);

[0221] 1 1H NMR (600 MHz, CDCl3) δ 9.76 (t, J = 1.8 Hz, 1H), 2.42 (td, J = 1.86, 7.38 Hz, 2H), 1.66 - 1.57 (m, 2H), 1.36 - 1.20 (m, 20H), 1.08 - 1.05 (m, 4H), 0.88 (t, J = 6.96 Hz, 3H), 0.83 (dd, J = 2.04, 6.60 Hz, 6H);

[0222] 1313C NMR (150 MHz, CDCl3) δ 203.00, 43.91, 37.40, 37.39, 37.35, 37.34, 37.08, 36.98, 36.82, 36.73, 32.73, 32.70, 29.76, 29.39, 29.33, 29.16, 26.98, 24.44, 23.03, 22.06, 19.74, 19.72, 19.67, 16.65, 14.18;

[0223] S21. Take a 100 mL two-necked round-bottom flask, add 2.3 g of methyltriphenylphosphonium bromide ([MePPh3]Br). Under the protection of an argon atmosphere, add 10 mL of dry THF, cool it at 0 °C for 15 min, dropwise add 2.3 mL of n-butyllithium (n-BuLi), stir for 30 min, then dropwise add a mixture of 0.7 g of (9R,13R)-9,13-dimethylheptadecanal prepared in S20 and 5 mL of dry THF, and stir at 0 °C for 2 h;

[0224] Work-up of the reaction: Add saturated NH4Cl to the reaction system at 0 °C to quench the reaction. Extract with EA three times in sequence, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 0.6 g of a pale colorless oil, namely compound (10R,14R)-1, with a yield of 87%;

[0225]

[0226] Perform 1H NMR and 13C NMR tests on (10R,14R)-1, and the results are as follows:

[0227] [α] 25 D = +24.00 (c = 0.04 CH3OH);

[0228] 1 1H NMR (600 MHz, CDCl3) δ 5.85 - 5.78 (m, 1H), 5.01 - 4.98 (m, 1H), 4.94 - 4.92 (m, 1H), 2.06 - 2.03 (m, 2H), 1.39 - 1.32 (m, 4H), 1.28 - 1.20 (m, 18H), 1.11 - 1.05 (m, 4H), 0.89 (t, J = 6.96 Hz, 3H), 0.84 (dd, J = 1.62, 6.60 Hz, 6H);

[0229] 1313C NMR (150 MHz, CDCl3) δ 139.06, 113.86, 37.23, 37.18, 36.94, 36.84, 33.61, 32.54, 32.52, 29.75, 29.35, 29.15, 28.96, 28.75, 26.87, 24.26, 23.05, 22.84, 19.55, 19.49, 13.96;

[0230] S22. Add 2.3 g of 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone prepared in S14 to a 100 mL single-necked round-bottom flask. Under the protection of an argon atmosphere, add 25 mL of dry THF, cool to -78 °C for 15 min, add dropwise 3.7 mL of NaHMDS, stir for 30 min, then add dropwise a mixture of 1.0 g of n-octanal and 10 mL of dry THF. Stir at -78 °C for 3 h, then adjust the temperature to -50 °C and stir overnight;

[0231] Work-up of the reaction: Add saturated NH4Cl to the reaction system at -50 °C to quench the reaction. Extract with EA three times in sequence, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 1.7 g of a colorless oil, namely compound (10S,14R)-10,14-dimethyloctadec-8-ene, with a yield of 98%;

[0232]

[0233] Perform 1H NMR and 13C NMR tests on (10S,14R)-10,14-dimethyloctadecene. The results are as follows:

[0234] (Z / E 2:3 mixture) [α] 25 D = +24.00 (c = 0.04, CH3OH);

[0235] 1 1H NMR (500 MHz, CDCl3) δ 5.35 - 5.08 (m, 2H), 2.05 - 1.94 (m, 2H), 1.34 - 1.13 (m, 22H), 1.09 - 1.03 (m, 2H), 0.95 - 0.87 (m, 9H), 0.83 (d, J = 6.5 Hz, 3H);

[0236] 13CNMR(125MHz,CDCl3)δ136.46,128.46,128.35,37.90,37.54,37.15,36.73,32.18,32.74,32.59,31.89,31.64,29.97,29.73,29.34,29.22,29.09,27.50,24.94,24.73,23.04,22.68,21.41,20.94,19.72,14.13;

[0237] S23. Add 395 mg of (10S,14R)-10,14-dimethyloctadec-8-ene prepared in S22, 6 mL of methanol and 220 mg of 10% Pt / C to a 100 mL single-necked round-bottom flask in sequence, then connect a hydrogen bag. Replace hydrogen with a water pump five times and stir at 35 °C for 16 h until the reaction is complete;

[0238] Work-up of the reaction: Remove EtOH using a rotary evaporator and directly perform column chromatography to obtain 372 mg of a colorless oil, namely compound (5R,9R)-2, with a yield of 98%;

[0239]

[0240] Perform 1H NMR and 13C NMR tests on (5R,9R)-2. The results are as follows:

[0241] [α] 25 D =+6.50(c = 0.1, CH3OH);

[0242] 1 H NMR(500MHz,CDCl3)δ1.36 - 1.31(m, 2H), 1.28 - 1.20(m, 24H), 1.10 - 1.04(m, 4H), 0.90 - 0.87(m, 6H), 0.84(dd, J = 1.05, 6.55Hz, 6H);

[0243] 13 C NMR(125MHz,CDCl3)δ68.47, 37.28, 36.81, 35.77, 33.42, 32.69, 29.33, 24.37, 23.02, 19.64, 16.54, 25.94, 14.14;

[0244] S24: Add 472 mg of 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone prepared in S14 to a 100 mL single-necked round-bottom flask. Under the protection of an argon atmosphere, add 8 mL of dry THF, cool at -78 °C for 15 min, add dropwise 1.6 mL of NaHMDS, stir for 30 min, then add dropwise a mixture of 220 mg of n-heptanal and 2 mL of dry THF. After stirring at -78 °C for 3 h, adjust the temperature to -50 °C and stir overnight.

[0245] Work-up of the reaction: Add saturated NH4Cl to the reaction system at -50 °C to quench the reaction. Extract with EA three times in sequence, wash with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate, and perform column chromatography to obtain 317 mg of a colorless oil, namely compound (9S,13R)-9,13-dimethylheptadec-7-ene, with a yield of 92%.

[0246]

[0247] Perform 1H NMR and 13C NMR tests on (9S,13R)-9,13-dimethylheptadec-7-ene. The results are as follows:

[0248] (Z / E 2:3 mixture)[α] 25 D = +24.00 (c = 0.04, CH3OH);

[0249] 1 1H NMR (500 MHz, CDCl3) δ 5.36 - 5.08 (m, 2H), 2.03 - 1.94 (m, 2H), 1.42 - 1.15 (m, 20H), 1.09 - 1.03 (m, 2H), 0.95 - 0.87 (m, 9H), 0.83 (d, J = 6.50 Hz, 3H);

[0250] 13 13C NMR (125 MHz, CDCl3) δ 136.45, 128.46, 128.36, 37.90, 37.53, 37.15, 36.75, 32.60, 31.78, 31.63, 29.94, 29.69, 29.34, 29.04, 28.80, 27.51, 24.94, 24.73, 23.05, 22.66, 21.41, 20.96, 19.72, 14.14;

[0251] S25. Add 317 mg of (9S,13R)-9,13-dimethylheptadec-7-ene prepared in S24, 5 mL of methanol, and 186 mg of 10% Pt / C to a 100 mL single-necked round-bottom flask in sequence. Then connect a hydrogen bag, and displace hydrogen with a water pump five times. Stir at 35 °C for 16 h until the reaction is complete.

[0252] Workup after reaction: Remove EtOH with a rotary evaporator and directly perform column chromatography to obtain 303 mg of a colorless oil, which is compound (5R,9R)-3, with a yield of 95%.

[0253]

[0254] Perform 1H NMR and 13C NMR tests on (5R,9R)-3. The results are as follows:

[0255] [α] 25 D = +6.50 (c = 0.1, CH3OH);

[0256] 1 1H NMR (500 MHz, CDCl3) δ 1.37 - 1.33 (m, 2H), 1.31 - 1.19 (m, 22H), 1.10 - 1.04 (m, 4H), 0.90 - 0.87 (m, 6H), 0.84 (dd, J = 1.00, 6.60 Hz, 6H);

[0257] 13 13C NMR (125 MHz, CDCl3) δ 37.40, 37.16, 36.85, 32.75, 31.04, 29.71, 29.37, 27.10, 24.47, 23.06, 22.70, 19.72, 14.15.

[0258] As described above, it is only a preferred embodiment of the present invention and does not impose any limitation on the present invention. Any simple modification, change, and equivalent change made to the above embodiments according to the technical essence of the invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A method for synthesizing the sex pheromone of Lyonetia clerkella, characterized in that, It includes the following steps: S1. Under the protection of an argon atmosphere, anhydrous tetrahydrofuran is added to hexanoic acid. After cooling, triethylamine and pivaloyl chloride are added in sequence. After sufficient reaction, (R)-4-benzyl-oxazolinone (R)-5 and lithium chloride are added, and after reaction again, it is transferred to room temperature for stirring; Post-treatment of the reaction: After quenching, extraction, drying and concentration, and column chromatography in sequence, compound (R)-4-benzyl-3-hexanoyl-oxazolinone is obtained; S2. Under the protection of an argon atmosphere, the (R)-4-benzyl-3-hexanoyl-oxazolinone prepared in S1 and dry THF are mixed. After cooling, NaHMDS is added dropwise, and after stirring, MeI is added dropwise, and sufficient reaction occurs; Post-treatment of the reaction: After quenching, extraction, washing, drying, filtration, concentration, and column chromatography in sequence, compound (R)-4-benzyl-3-((R)-2-methylhexanoyl)-oxazolinone is obtained; S3. Under the protection of an argon atmosphere and an ice-water bath, dry THF is injected into LiAlH4. At the same time, under the protection of an argon atmosphere, dry THF is injected into the (R)-4-benzyl-3-((R)-2-methylhexanoyl)-oxazolinone prepared in S2, and after mixing, sufficient reaction occurs; Post-treatment of the reaction: Under the ice-water bath, after quenching, filtration, washing, extraction, drying, filtration, concentration, and column chromatography in sequence, compound (R)-2-methyl-1-hexanol is obtained; S4. The (R)-2-methyl-1-hexanol, BT-SH, Ph3P, and dry THF prepared in S3 are mixed in sequence. Stirring is started under the ice-water bath, and DIAD is added dropwise, and sufficient reaction occurs; Post-treatment of the reaction: THF is removed by rotary evaporation and column chromatography is performed to obtain compound (R)-2-methylhexyl thiazole sulfide; S5. The (R)-2-methylhexyl thiazole sulfide, anhydrous CH2Cl2, and m-CPBA prepared in S4 are mixed in sequence and stirred at room temperature for reaction; Post-treatment of the reaction: Sodium thiosulfate is added to remove the excess m-CPBA, and then saturated NaHCO3 solution is added to remove the acid. After extraction, washing, drying, filtration, concentration, and column chromatography in sequence, compound (R)-2-methylhexyl thiazole sulfone is obtained; S6. Under the protection of an argon atmosphere, dry THF is added to 4-benzyloxybutyric acid. After cooling, triethylamine and pivaloyl chloride are added in sequence. After sufficient reaction, (S)-4-benzyl-oxazolinone (S)-5 and lithium chloride are added, and reaction occurs again; Post-treatment of the reaction: After quenching, extraction, drying and concentration, and column chromatography in sequence, compound (S)-4-benzyl-3-(4-(benzyloxy)butanoyl)-oxazolinone is obtained; S7. Under the protection of an argon atmosphere, dry THF is added to the (S)-4-benzyl-3-(4-(benzyloxy)butanoyl)-oxazolinone prepared in S6. After cooling, NaHMDS added dropwise is fully stirred, and then MeI is added dropwise, and sufficient reaction occurs; Post-treatment of the reaction: After quenching, extraction, washing, drying, filtration, concentration, and column chromatography in sequence, compound (S)-4-benzyl-3-((S)-2-methyl-4-benzyloxybutanoyl)-oxazolinone is obtained; S8, under the protection of argon atmosphere and ice water bath, inject dry THF1 into LiAlH4, and at the same time, under the protection of argon atmosphere, inject dry THF2 into the (S)-4-benzyl-3-((S)-2-methyl-4-benzyloxybutyryl)oxazolinone prepared in S7, mix and react fully; Post-reaction treatment: in an ice-water bath, sequentially quenching, filtering, washing, extracting, drying, filtering, concentrating and column chromatography are performed to obtain compound (S)-2-methyl-4-benzyloxybutanol; S9, under the protection of argon atmosphere, inject anhydrous CH2Cl2 into the (S)-2-methyl-4-benzyloxybutanol prepared in S8, add imidazole and stir, then add TBSCl and react fully; Post-reaction treatment: concentration and column chromatography to obtain compound (S)-2-methyl-4-benzyloxybutoxydimethyl-tert-butylsilane; S10, sequentially mix the (S)-2-methyl-4-benzyloxybutoxydimethyl-tert-butylsilane, ethyl acetate and 10% Pd / C prepared in S9, connect a hydrogen bag, replace the hydrogen with a water pump, and stir to react; Post-reaction treatment: filtering, concentrating and column chromatography were performed to obtain compound (S)-3-methyl-4-dimethyl-tert-butylsiloxybutanol; S11, sequentially mixing the (S)-3-methyl-4-dimethyl-tert-butylsiloxybutanol, anhydrous CH2Cl2, 4A molecular sieve and PCC prepared in S10, and stirring to react at room temperature; Post-reaction treatment: adding petroleum ether, filtering, washing and concentrating in sequence to obtain compound (S)-3-methyl-4-dimethyl-tert-butylsilyloxybutyraldehyde; S12, under the protection of argon atmosphere, add dry THF1 to the (R)-2-methylhexylthiazole sulfone prepared in S5, add LiHMDS dropwise after cooling, stir thoroughly, and then add dropwise the mixed solution of (S)-3-methyl-4-dimethyl-tert-butylsilyloxybutyraldehyde and dry THF2 prepared in S11, and react thoroughly; Post-reaction treatment: quenching, extraction, washing, drying, filtering, concentration and column chromatography are performed in sequence to obtain the compound (2S, 6R)-2,6-dimethyl-4-decenyl-1-dimethyl-tert-butyloxysilane; S13, sequentially mix the (2S,6R)-2,6-dimethyl-4-decenyl-1-dimethyl-tert-butyloxysilane, methanol and 10% Pt / C prepared in S12, connect a hydrogen bag, replace the hydrogen with a water pump, and fully react; Post-reaction treatment: concentration and column chromatography to obtain compound (2S,6R)-2,6-dimethyldecan-1-ol; S14, sequentially mix the (2S,6R)-2,6-dimethyldecan-1-ol, BT-SH, Ph3P and dry THF prepared in S13, and add DEAD dropwise while stirring in an ice-water bath to fully react; Post-reaction treatment: after removing THF, column chromatography was performed to obtain the compound 2-((2S,6R)-2,6-dimethyldecyl)thiobenzothiazole; S15. Sequentially mix 2-((2S,6R)-2,6-dimethyldecyl)benzothiazole prepared in S14, anhydrous CH₂Cl₂ and m-CPBA, and stir the reaction at room temperature; Work-up of the reaction: Add sodium thiosulfate to remove the excess m-CPBA, then add saturated NaHCO₃ solution to remove the acid, and sequentially carry out extraction, washing, drying, filtration, concentration and column chromatography to obtain the compound 2-(2S,6R)-2,6-dimethyldecylbenzo[b]thiophene 1-oxide; S16. Under the protection of an argon atmosphere, inject anhydrous CH₂Cl₂ into 1,7-heptanediol, add imidazole and stir, then add TBSCl and react fully; Work-up of the reaction: Sequentially carry out quenching, extraction, drying and concentration and column chromatography to obtain the compound 7-(tert-butyldimethylsilyloxy)-1-heptanol; S17. Sequentially mix 7-(tert-butyldimethylsilyloxy)-1-heptanol prepared in S16, anhydrous CH₂Cl₂, 4A molecular sieve PCC, and stir the reaction at room temperature; Work-up of the reaction: Add petroleum ether, and sequentially carry out filtration, washing and concentration to obtain the compound 7-(tert-butyldimethylsilyloxy)heptanal; S18. Under the protection of an argon atmosphere, add dry THF1 to the 2-(2S,6R)-2,6-dimethyldecylbenzo[b]thiophene 1-oxide prepared in S15, wait for cooling and then dropwise add NaHMDS, stir fully, and then dropwise add the mixed solution of 7-(tert-butyldimethylsilyloxy)heptanal prepared in S17 and dry THF2, and react fully; Work-up of the reaction: Sequentially carry out quenching, extraction, washing, drying, filtration, concentration and column chromatography to obtain the compound (9S,13R)-9,13-dimethylheptadec-7-en-1-yl tert-butyldimethylsilane; S19. Sequentially mix the (9S,13R)-9,13-dimethylheptadec-7-en-1-yl tert-butyldimethylsilane prepared in S18, methanol and 10% Pt / C, then connect a hydrogen bag, displace hydrogen with a water pump, and stir the reaction; Work-up of the reaction: Carry out concentration and column chromatography to obtain the compound (9S,13R)-9,13-dimethylheptadecan-1-ol; S20. Sequentially mix the (9S,13R)-9,13-dimethylheptadecan-1-ol prepared in S19, 5 mL, anhydrous CH₂Cl₂, 4A molecular sieve and PCC, and stir the reaction at room temperature; Work-up of the reaction: Add petroleum ether, and sequentially carry out filtration, washing and concentration to obtain the compound (9R,13R)-9,13-dimethylheptadecanal; S21. Under the protection of an argon atmosphere, add dry THF1 to [MePPh₃]Br, wait for cooling and then dropwise add n-BuLi, stir fully, and then dropwise add the mixed solution of (9R,13R)-9,13-dimethylheptadecanal prepared in S20 and dry THF2, and stir the reaction; Work-up of the reaction: Sequentially carry out quenching, extraction, washing, drying, filtration, concentration and column chromatography to obtain the compound (10R,14R)-1; S22. Under the protection of an argon atmosphere, add dry THF1 to 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone prepared in S14. After cooling, add NaHMDS dropwise, stir well, and then add a mixture of n-octanal and dry THF2 dropwise, and stir for reaction; Work-up of the reaction: Compound (10S,14R)-10,14-dimethyloctadecene was obtained successively by quenching, extraction, washing, drying, filtration, concentration, and column chromatography; S23. Mix (10S,14R)-10,14-dimethyloctadecene prepared in S22, methanol, and 10% Pt / C successively, then connect a hydrogen bag, displace hydrogen with a water pump, and stir for reaction; Work-up of the reaction: Compound (5R,9R)-2 was obtained by concentration and column chromatography; S24. Under the protection of an argon atmosphere, add dry THF1 to 2-(2S,6R)-2,6-dimethyldecylbenzothiazole sulfone prepared in S14. After cooling, add NaHMDS dropwise, stir well, and then add a mixture of n-heptanal and dry THF2 dropwise, and stir for reaction; Work-up of the reaction: Compound (9S,13R)-9,13-dimethylheptadec-7-ene was obtained successively by quenching, extraction, washing, drying, filtration, concentration, and column chromatography; S25. Mix (9S,13R)-9,13-dimethylheptadec-7-ene prepared in S24, methanol, and 10% Pt / C successively, then connect a hydrogen bag, displace hydrogen with a water pump, and stir for reaction; Work-up of the reaction: Compound (5R,9R)-3 was obtained by concentration and column chromatography; 2. The synthetic method of the sex pheromone of Lyonetia clerkella as claimed in claim 1, wherein The mass-volume ratio of n-hexanoic acid, anhydrous tetrahydrofuran, triethylamine, pivaloyl chloride, (R)-4-benzyl-oxazolinone (R)-5, and lithium chloride in S1 is 3.0 g: 110 mL: 7.2 mL: 3.8 mL: 4.6 g: 3.8 g; The mass-volume ratio of (R)-4-benzyl-3-hexanoyl-oxazolinone, dry THF, NaHMDS, and MeI in S2 is: 9.1 g: 130 mL: 33 mL: 10.3 mL; The mass-volume ratio of LiAlH4, dry THF1, (R)-4-benzyl-3-((R)-2-methylhexanoyl)oxazolinone, and dry THF2 in S3 is 3.8 g: 60 mL: 7.3 g: 40 mL; The mass-volume ratio of (R)-2-methyl-1-hexanol, BT-SH, Ph3P, dry THF, and DIAD in S4 is 0.7 g: 1.3 g: 2.0 g: 25 mL: 0.7 mL; The mass-volume ratio of (R)-2-methylhexylbenzothiazole sulfide, anhydrous CH2Cl2, and m-CPBA in S5 is 0.99 g: 15 mL: 3.8 g; The mass-volume ratio of 4-benzyloxybutyric acid, dry THF, triethylamine, pivaloyl chloride, (S)-4-benzyl-oxazolinone (S)-5, and lithium chloride in S6 is 6.7 g: 140 mL: 9.6 mL: 1.1 mL: 6.1 g: 4.4 g; As described in S7, the mass-volume ratio of (S)-4-benzyl-3-(4-(benzyloxy)butanoyl)oxazolidinone, dry THF, NaHMDS, and MeI is 8.4 g : 120 mL : 30.5 mL : 9.5 mL; As described in S8, the mass-volume ratio of LiAlH4, dry THF1, (S)-4-benzyl-3-((S)-2-methyl-4-benzyloxybutanoyl)oxazolidinone, and dry THF2 is 3.7 g : 60 mL : 8.7 g : 38 mL; As described in S9, the mass-volume ratio of (S)-2-methyl-4-benzyloxy-1-butanol, anhydrous CH2Cl2, imidazole, and TBSCl is 1.4 g : 30 mL : 8.9 g : 8.9 g; As described in S10, the mass-volume ratio of (S)-2-methyl-4-benzyloxybutoxy-1-dimethyl-tert-butylsilane, ethyl acetate, and 10% Pd / C is 2.5 g : 30 mL : 0.7 g; As described in S11, the mass-volume ratio of (S)-4-((tert-butyldimethylsilyloxy)-3-methyl-1-butanol, anhydrous CH2Cl2, 4A molecular sieve, and PCC is 5.8 g : 100 mL : 8.2 g : 8.2 g; As described in S12, the mass-volume ratio of (R)-2-methylhexyl thiazole sulfone, dry THF1, LiHMDS, (S)-4-((tert-butyldimethylsilyloxy)-3-methylbutanal, and dry THF2 is 5.8 g : 40 mL : 12 mL : 5.0 g : 30 mL; As described in S13, the mass-volume ratio of tert-butyl(((2S,6R)-2,6-dimethyldec-4-en-1-yl)oxy)dimethylsilane, methanol, and 10% Pt / C is 5.5 g : 70 mL : 2.9 g; As described in S14, the mass-volume ratio of (2S,6R)-2,6-dimethyldecan-1-ol, BT-SH, Ph3P, dry THF, and DEAD is 0.5 g : 1.4 g : 2.2 g : 25 mL : 1.3 mL; As described in S15, the mass-volume ratio of 2-(2S,6R)-2,6-dimethyldecyl thiazole sulfide, anhydrous CH2Cl2, and m-CPBA is 2.5 g : 37 mL : 6.4 g; As described in S16, the mass-volume ratio of 1,7-heptanediol, anhydrous CH2Cl2, imidazole, and TBSCl is 2.5 g : 75 mL : 2.6 g : 2.6 g; As described in S17, the mass-volume ratio of 7-((tert-butyldimethylsilyl)oxy)-1-heptanol, anhydrous CH2Cl2, 4A molecular sieve, and PCC is 4.0 g : 65 mL : 5.3 g : 5.3 g; As described in S18, the mass-volume ratio of 2-(2S,6R)-2,6-dimethyldecyl thiazole sulfone, dry THF1, NaHMDS, 7-((tert-butyldimethylsilyl)oxy)heptanal, and dry THF2 is 0.6 g : 10 mL : 0.9 mL : 0.5 g : 2 mL; The mass-volume ratio of (((9S,13R)-9,13-dimethylheptadec-7-en-1-yl)oxy)dimethylsilane, methanol and 10% Pt / C described in S19 is 2.1 g : 20 mL : 0.9 g; The mass-volume ratio of (9S,13R)-9,13-dimethylheptadecan-1-ol, anhydrous CH2Cl2, 4A molecular sieve and PCC described in S20 is 259 mg : 5 mL : 294 mg : 294 mg; The mass-volume ratio of [MePPh3]Br, dry THF1, n-BuLi, (9R,13R)-9,13-dimethylheptadecanal and dry THF2 described in S21 is 2.3 g : 10 mL : 2.3 mL : 0.7 g : 5 mL; The mass-volume ratio of 2-(2S,6R)-2,6-dimethyldecyl thiazole sulfone, dry THF1, NaHMDS, n-octanal and dry THF2 described in S22 is 2.3 g : 25 mL : 3.7 mL : 1.0 g : 10 mL; The mass-volume ratio of (10S,14R)-10,14-dimethyloctadecene, methanol and 10% Pt / C described in S23 is 395 mg : 6 mL : 220 mg; The mass-volume ratio of 2-(2S,6R)-2,6-dimethyldecyl thiazole sulfone, dry THF1, NaHMDS, n-heptanal and dry THF2 described in S24 is 472 mg : 8 mL : 1.6 mL : 220 mg : 2 mL; The mass-volume ratio of (9S,13R)-9,13-dimethylheptene, methanol and 10% Pt / C described in S25 is 317 mg : 5 mL : 186 mg.

3. The synthetic method of the sex pheromone of Lyonetia clerkella Linnaeus according to claim 1, characterized in that The sufficient reaction conditions described in S1 and S6 are: first react at -78 °C for 20 min, then transfer to room temperature environment and react for 1 h, and then cool at -78 °C for 15 min. The conditions for the second reaction described in S1 and S6 are: react at -78 °C for 1.0 h and naturally warm up overnight; The stirring time described in S1 is 2 h; The sufficient stirring temperature described in S2 and S7 is -78 °C, the sufficient stirring time is 30 min, and the sufficient reaction conditions are to react at -78 °C for 2 h and then adjust the temperature to -50 °C and leave overnight; The sufficient reaction conditions described in S3, S4, S8, S14 are: naturally warm up from 0 °C and stir overnight; The stirring reaction time described in S5, S11, S15, S17, S20 is 12 h; The stirring temperature described in S9 and S16 is 0 °C, the stirring time is 15 min, and the sufficient reaction conditions are to naturally rise to room temperature; The sufficient reaction time described in S9 is 12 h; The number of times of replacing hydrogen with a water pump described in S10, S13, S19, S23 and S25 is 5 times, The stirring reaction conditions described in S10 are: stir at 35 °C for 24 h; The time for sufficient stirring in S12, S18, S22 and S24 is 30 min. The conditions for sufficient reaction are as follows: Stir at a temperature of -78°C for 3 h, and then adjust the temperature to -50°C and stir overnight. The conditions for the stirring reaction in S13, S19, S23 and S25 are: Stir at a temperature of 35°C for 16 h. The time for sufficient reaction in S16 is 16 h. The time for sufficient stirring in S21 is 30 min. The conditions for the stirring reaction are: Stir at a temperature of 0°C for 2 h.

4. The synthesis method of the sex pheromone of Lyonetia clerkella as claimed in claim 1, wherein The solution used for quenching in S1, S6 and S16 is water, and the solution used for extraction is ethyl acetate. The conditions for quenching in S2, S7, S12, S18, S22 and S24 are to add saturated NH4Cl solution to the reaction system at a temperature of -50°C to quench the reaction. The solvent for extraction is EA, the number of extraction times is 3 times, and the solution for washing is saturated brine. The solution used for quenching in S3 and S8: Add water, 10% NaOH solution and water in a volume ratio of 1:2:3 in sequence. The instrument for filtration is a fritted funnel, the solution used for washing is EA, and the solvent for extraction is EA. The solvent for extraction in S5 and S15 is CH2Cl2, the number of extraction times is 3 times, and the solution for washing is saturated brine. The instrument for concentration in S9, S10, S13, S19, S23 and S25 is a rotary evaporator. The method for filtration in S11, S17 and S20 is: Pad diatomaceous earth and silica gel in a fritted funnel, and the solution used for washing is ether. The conditions for quenching in S21 are to add saturated NH4Cl solution to the reaction system at a temperature of 0°C to quench the reaction. The solvent for extraction is EA, the number of extraction times is 3 times, and the solution for washing is saturated brine.

5. The synthetic method of the sex pheromone of Lyonetia clerkella as claimed in claim 1, wherein The temperature of the ice-water bath in S3, S4, S8 and S14 is 0°C.

6. The synthetic method of the sex pheromone of Lyonetia clerkella as claimed in claim 1, wherein, The substances used for drying and concentration in S1 - S25 are all anhydrous sodium sulfate.

7. The synthesis method of the sex pheromone of Lyonetia clerkella according to claim 1, wherein The conditions for cooling in S1 - S18 and S22 - S24 are to cool at a temperature of -78°C for 15 min, and the cooling in S21 is to cool at 0°C for 15 min.

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