Preparation method of tea leaf roller sex pheromone

Abstract

The invention relates to the technical field of chemical pesticides, in particular to a preparation method of sex pheromone of tea leaf rollers. The invention provides a preparation method of sex pheromone of tea leaf roller, which is short in synthetic route, more than 80% in most of reaction yield, simple and convenient in synthetic method, two isomer target products of the sex pheromone of tea leaf roller can be obtained in the shortest time, and (R)-10-methyl dodecyl acetate, namely (R)-1, 2, 3-trimethyl-1, 3-pentanediol, is prepared through seven-step reaction. The total yield is 53%, and the (S)-10-methyl dodecyl acetate, namely (S)-1, is prepared through a four-step reaction, and the total yield is 54%.

Description

Technical Field

[0001] The invention relates to the technical field of chemical pesticides, and in particular to a method for preparing a sex pheromone of the tea leafroller. Background Art

[0002] Tea is an important cash crop with extensive economic and cultural value worldwide. The tea leaf roller is a significant pest that harms tea trees. Its larvae primarily feed on leaves. They also attack young buds and branches, causing damage or even death. In the long term, this not only impacts the growth of tea trees but also affects tea yield and quality, leading to economic losses for tea farmers. Excessive pesticide residues caused by traditional pesticides have become a bottleneck restricting the development of my country's tea industry. Using insect pheromones for control does not affect tea quality and offers excellent control effectiveness.

[0003] In recent years, the control of the tea leaf roller has primarily involved agricultural, physical, biological, and chemical control. Agricultural control primarily involves timely tea leaf picking and the removal and destruction of tea leaf roller pods. Gardens are cleaned annually in winter to remove fallen leaves and dead branches, and to prune shaded, weak, and diseased branches. In heavily infested tea gardens, light pruning is performed in winter or early spring, and the cut branches are burned. Physical control involves using blacklights or solar-powered frequency-oscillating insecticidal lamps to lure and kill adult insects during their peak infestation period. Biological control has explored methods such as using natural enemies, sex attractants, biopesticides, and releasing trichogrammatic wasps to capture and kill tea leaf rollers. If chemical pesticides are not used in tea gardens for several years, the number of natural enemies of the tea leaf roller will increase, and the occurrence of the tea leaf roller will be suppressed by natural enemies. With the growing demand for food safety, reducing the use of chemical pesticides and using insect pheromones for control are gaining increasing attention.

[0004] The sex pheromone components of the tea leaf roller have been identified as (R)-10-methyldodecyl acetate and (S)-10-methyldodecyl acetate, among which the (R)-configuration tea leaf roller sex pheromone has stronger biological activity than the (S)-configuration tea leaf roller sex pheromone.

[0005] In 1988, Brown et al. used (R)-sec-butyl-(2,3-dimethylbutyl)methoxyborane as a chiral source and constructed a CC backbone via an acetylation coupling reaction, resulting in the preparation of the (R)-configured sex pheromone of the tea leaf roller with a 7% overall yield. In 1995, Sankaranarayanan et al. discovered a chemoenzymatic method for the synthesis of the tea leaf roller sex pheromone. The key steps involved the Wittig-Horner reaction and C. rugosa lipase-catalyzed acetylation, but the overall yield was only 1.9%. In 2002, Chow et al. reported a method for preparing (R)- and (S)-configured tea leaf roller sex pheromones by hydrolytic kinetic resolution (HKR) using terminal olefin benzyl ethers as starting materials. However, the overall yield of this method was very low, making it unsuitable for large-scale production. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to address the deficiencies of the above-mentioned prior art and provide a method for preparing the sex pheromone of the tea leaf roller. The method has a short synthesis route, and the yield of most reactions is above 80%. The synthesis method is simple and can obtain the target product in the shortest time. (R)-10-methyldodecyl acetate, namely (R)-1, is prepared through 7 reactions with a total yield of 53%. (S)-10-methyldodecyl acetate, namely (S)-1, is prepared through 4 reactions with a total yield of 54%.

[0007] The present invention provides a method for preparing a sex pheromone of a tea leaf roller, comprising the following steps:

[0008] S1. Under argon atmosphere, add dry THF to (R)-4-benzyl-2-oxazolidinone, stir thoroughly after cooling, add n-BuLi dropwise, allow to cool and react thoroughly, then add n-butyryl chloride dropwise, allow to cool and react a second time, then heat naturally and stir overnight;

[0009] Post-reaction treatment: quenching, extraction, drying, filtration, concentration and column chromatography are performed to obtain (R)-4-benzyl-3-butyryl oxazolinone;

[0010] S2. Add dry THF to the (R)-4-benzyl-3-butyryl oxazolinone obtained in S1, add NaHMDS dropwise after cooling, stir, and then add MeI dropwise. Allow to react fully, adjust the temperature, and stir overnight.

[0011] Post-reaction treatment: quenching, extraction, drying, concentration and column chromatography were performed to obtain (R)-4-benzyl-3-((R)-2-methylbutyryl)oxazolinone;

[0012] S3. Under argon atmosphere, dry Et2O and dry CH3OH were injected into the (R)-4-benzyl-3-((R)-2-methylbutyryl)oxazolinone obtained in S2. After cooling, LiBH4 was added dropwise with stirring. The mixture was transferred to an ice-water bath and stirred thoroughly for reaction.

[0013] Post-reaction treatment: quenching, extraction, drying, concentration under reduced pressure and column chromatography are performed in sequence to obtain (R)-2-methylbutanol;

[0014] S4. Under argon atmosphere, take the (R)-2-methylbutanol, Ph3P, PT-SH and dry THF obtained in S3, add DEAD dropwise in an ice-water bath, and allow to react fully after natural temperature increase;

[0015] Post-reaction treatment: vacuum distillation and column chromatography to obtain (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole;

[0016] S5. Under argon atmosphere, (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole obtained in S4, dry CH2Cl2 and m-CPBA were stirred thoroughly at room temperature for reaction;

[0017] Post-reaction treatment: sodium thiosulfate was added to remove excess m-CPBA, and then saturated NaHCO3 solution was added to remove the acid. The product was extracted, dried, filtered, concentrated, and column chromatographed to obtain (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole.

[0018] S6. Under argon atmosphere, mix 1,8-octanediol and dry CH2Cl2, add glacial acetic acid, DCC, and DMAP in an ice-water bath, and heat naturally while stirring overnight.

[0019] Post-reaction treatment: quenching, washing, extraction, drying, filtration and concentration, column chromatography and quenching are performed in sequence to obtain 8-hydroxyoctyl acetate;

[0020] S7. Under argon atmosphere, take the 8-hydroxyoctyl acetate obtained in S6, dry CH2Cl2, silica gel and PCC, and stir the reaction at room temperature;

[0021] Post-reaction treatment: Take a sand core funnel and fill it with diatomaceous earth, connect a vacuum pump and compact it with silica gel, then add petroleum ether, filter, distill under reduced pressure and concentrate to obtain 8-acetoxyoctanal;

[0022] S8. Under argon atmosphere, mix the (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole obtained in S5 with 1% dry THF, cool and stir, add NaHMDS dropwise and stir to fully react, then add the mixture of 8-acetoxyoctanal obtained in S7 and 2% dry THF dropwise, cool and fully react a second time, adjust the temperature and stir overnight;

[0023] Post-reaction treatment: quenching, extraction, washing, drying, concentration and column chromatography are performed in sequence to obtain (R)-10-methyldodec-8-en-1-yl acetate;

[0024] S9. Take the (R)-10-methyldodec-8-en-1-yl acetate obtained in S8, dry CH3OH, and 10% Pt / C, evacuate the H2 bag with a vacuum pump, refill with H2, ventilate five times, and stir at room temperature for complete reaction.

[0025] Post-reaction treatment: (R)-10-methyldodecyl acetate was obtained by vacuum distillation and column chromatography;

[0026] S10. Under argon atmosphere, take the (R)-10-methyldodecyl acetate, Ph3P, PT-SH and dry THF obtained in S9, add DEAD dropwise in an ice-water bath, and then naturally warm to room temperature to fully react;

[0027] Post-reaction treatment: vacuum distillation and column chromatography gave (S)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole;

[0028] S11. Under argon atmosphere, (S)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole obtained in S10, dry CH2Cl2 and m-CPBA were stirred at room temperature for reaction;

[0029] Post-reaction treatment: sodium thiosulfate was added to remove excess m-CPBA, and then saturated NaHCO3 solution was added to remove the acid. The product was extracted, dried, filtered, concentrated, and column chromatographed to obtain (S)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole.

[0030] S12. Under argon atmosphere, mix the (S)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole obtained in S11 with 1% dry THF, cool and stir, add NaHMDS dropwise and stir to react thoroughly, then add a mixture of 8-acetoxyoctanal and 2% dry THF dropwise, cool and stir twice to react thoroughly, adjust the temperature and stir overnight;

[0031] Post-reaction treatment: quenching, extraction, washing, drying, filtration, concentration and column chromatography are performed in sequence to obtain (S)-10-methyldodec-8-en-1-yl acetate;

[0032] S13. Take the (S)-10-methyldodec-8-en-1-yl acetate obtained in S12, CH3OH, and 10% Pt / C, evacuate the H2 bag with a vacuum pump, refill with H2, ventilate five times, and stir at room temperature for complete reaction.

[0033] Post-reaction treatment: (S)-10-methyldodecyl acetate was obtained by vacuum distillation and column chromatography.

[0034] According to the method for preparing the sex pheromone of the tea leaf roller provided by the present invention, the mass volume ratio of (R)-4-benzyl-2-oxazolidinone, dry THF, n-BuLi and n-butyryl chloride in S1 is 10.0 g:190 mL:27.1 mL:8.8 mL;

[0035] The mass volume ratio of (R)-4-benzyl-3-butyryloxazolinone, dry THF, NaHMDS and MeI in S2 is 3.5 g:70 mL:14.1 mL:4.4 mL;

[0036] The mass volume ratio of (R)-4-benzyl-3-((R)-2-methylbutanoyl)oxazolidinone, dry Et2O, dry CH3OH and LiBH4 in S3 is 2.0 g:25 mL:0.7 mL:2.7 mL;

[0037] The mass volume ratio of (R)-2-methylbutanol, Ph3P, PT-SH, dry THF and DEAD in S4 is 3.0 g:10.6 g:7.2 g:140 mL:6.3 mL;

[0038] The mass volume ratio of (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole, dry CH2Cl2 and m-CPBA described in S5 is 3.1 g:54 mL:10.7 g;

[0039] The mass volume ratio of 1,8-octanediol, dry CH2Cl2, glacial acetic acid, DCC, and DMAP described in S6 is 1.0 g:75 mL:0.8 mL:2.8 g:0.04 g;

[0040] The mass volume ratio of 8-hydroxyoctyl acetate, dry CH2Cl2, silica gel and PCC in S7 is 1.5 g:30 mL:2.6 g:2.6 g;

[0041] The mass volume ratio of (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole, dry THF 1, NaHMDS, 8-acetoxyoctanal and dry THF 2 described in S8 is 0.2 g:3 mL:0.5 mL:0.2 g:3 mL;

[0042] The mass volume ratio of (R)-10-methyldodec-8-en-1-yl acetate, dry CH3OH and 10% Pt / C in S9 is 0.2 g:10 mL:0.1 g;

[0043] The mass volume ratio of (R)-10-methyldodecyl acetate, Ph3P, PT-SH, dry THF, and DEAD in S10 is 2.0 g:7.1 g:4.9 g:140 mL:4.3 mL;

[0044] The mass volume ratio of (S)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole, dry CH2Cl2 and m-CPBA in S11 is 1.3 g:30 mL:4.6 g;

[0045] The mass volume ratio of (S)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole, dry THF1, NaHMDS, 8-acetoxyoctanal and dry THF2 described in S12 is 1.4 g:10 mL:2.8 mL:1.3 g:10 mL;

[0046] The mass volume ratio of (S)-10-methyldodec-8-en-1-yl acetate, CH3OH and 10% Pt / C described in S13 is 0.6 g:30 mL:0.4 g.

[0047] According to the method for preparing the sex pheromone of the tea leaf roller provided by the present invention, the stirring time in S1, S8, and S12 is 15 minutes, and the sufficient reaction time is 30 minutes;

[0048] The time for the secondary full reaction in S1 is 30 min;

[0049] The cooling time in S2 and S3 is 15 minutes, and the stirring time is 30 minutes;

[0050] The time for the full reaction in S2 is 2 hours;

[0051] The stirring reaction time in S3, S5, S7 and S11 is 12 hours;

[0052] The time for the full reaction in S4 and S10 is 10 hours;

[0053] The time for the secondary full reaction in S8 and S12 is 3 hours;

[0054] The time required for the stirring reaction to be complete in S9 and S13 is 24 hours.

[0055] According to the method for preparing the sex pheromone of the tea leaf roller provided by the present invention, the quenching solution in S1, S2, S8, and S12 is saturated NH4Cl, the quenching solution in S3 is NaOH with a concentration of 1 mol / L, and the quenching solution in S6 is water;

[0056] The extraction agent in S1, S2, S8, and S12 is ethyl acetate, the extraction agent in S3 is diethyl ether, and the number of extractions is 3;

[0057] The drying substance in S1, S2, S5, S6, S11, and S12 is anhydrous sodium sulfate, and the drying substance in S3 and S8 is anhydrous magnesium sulfate;

[0058] The temperature of the reduced pressure concentration in S3 is 3°C;

[0059] The extraction solvent used in S5, S6 and S11 is CH2Cl2;

[0060] The washing solution in S6 is saturated sodium bicarbonate, and the washing solutions in S8 and S12 are saturated salt water.

[0061] The filtration solution in S7 is CH2Cl2;

[0062] The concentration temperature in S8 is 30°C;

[0063] The vacuum distillation temperature in S9 and S12 is 30° C.

[0064] The eluent for the column chromatography in S12 was 50:1 PE / EA.

[0065] According to the method for preparing the sex pheromone of the tea leafroller provided by the present invention, the temperature of the ice water bath in S3, S4, S6 and S10 is 0°C.

[0066] According to the method for preparing the sex pheromone of the tea leafroller provided by the present invention, the temperature after cooling in S1, S2 and S8 to S11 is -78°C, the temperature after cooling in S3 is -30°C, and the temperature after adjustment in S2, S8 and S12 is -50°C.

[0067] Among the two isomers of the tea leaf roller sex pheromone, the structural formula of (R)-1 is:

[0068]

[0069] The structural formula of (S)-1 is:

[0070]

[0071] Compared with the prior art, the present invention has the following advantages:

[0072] The present invention provides a method for preparing a sex pheromone of a tea leaf roller. The method has a short synthesis route, and the yield of most reactions is above 80%. The synthesis method is simple and can obtain the target product in the shortest time. (R)-1 is prepared through 7 reaction steps with a total yield of 53%, and (S)-1 is prepared through 4 reaction steps with a total yield of 54%. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] In order to more clearly illustrate the technical solutions in the present invention or the prior art, a brief introduction will be given below to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0074] Figure 1 and Figure 2 These are the hydrogen and carbon spectra of (R)-1, respectively;

[0075] Figure 3 and Figure 4 These are the hydrogen and carbon spectra of (S)-1, respectively. DETAILED DESCRIPTION

[0076] Example 1

[0077] This embodiment provides a novel method for efficiently and conveniently synthesizing the sex pheromone (R)-10-methyldodecyl acetate of the tea leaf roller moth. The specific steps are as follows:

[0078] S1. Take a single-necked round-bottom flask, add (R)-4-benzyl-2-oxazolidinone, and under Ar atmosphere, add dry THF (dry tetrahydrofuran), slowly add n-BuLi (n-butyl lithium solution) dropwise with a syringe at -78°C, stir for 30 minutes, then add n-butyryl chloride dropwise, then react at -78°C for 30 minutes, stop cooling and allow to warm naturally, and stir overnight to obtain compound (R)-4-benzyl-3-butyryl oxazolidinone, i.e., (R)-4;

[0079] The molar ratio of compound (R)-4-benzyl-2-oxazolidinone, n-BuLi and n-butyryl chloride 3 is 1:1.2:1.5;

[0080] Compound (R)-4 was prepared using n-butyl chloride as the raw material through the Evans synthesis reaction with n-butyl lithium and (R)-4-benzyl-2-oxazolidinone (R)-2. Compared with the general method, the reaction yield was greatly improved, reaching 98%.

[0081] S2. Take a single-necked round-bottom flask, add (R)-4 and dry THF in sequence, and under Ar atmosphere, cool at -78°C for 15 min, then slowly add NaHMDS (sodium bis(trimethylsilyl)amide) dropwise. Then, stir at -78°C for 30 min, and then add MeI (iodomethane) dropwise. After reacting for 2.0 h, adjust the temperature to -50°C, and stir overnight to obtain compound (R)-4-benzyl-3-((R)-2-methylbutanoyl)oxazolinone, i.e., (R)-5.

[0082] The molar ratio of compound (R)-4, NaHMDS, and MeI was 1:2:5;

[0083] Compound (R)-5 was prepared from compound (R)-4 via a chiral asymmetric synthesis reaction using NaHMDS and iodomethane. Optimizing the reaction conditions resulted in fewer by-products and a significantly improved yield of 89%.

[0084] S3. Take a single-necked round-bottom flask and add compound (R)-5 in sequence. Under Ar atmosphere, inject dry Et2O and dry CH3OH with a syringe, cool at -30°C for 15 minutes, add LiBH4 (lithium aluminum hydride) dropwise, and then stir at -30°C for 30 minutes. Transfer to an ice-water bath at 0°C and stir for 12 hours to obtain compound (R)-2-methylbutanol, i.e., (R)-6;

[0085] The molar ratio of compound (R)-5 to LiBH4 is 1:0.7;

[0086] Compound (R)-5 was used as the raw material and compound (R)-6 was prepared by LiBH4 reduction. By optimizing the post-treatment conditions, the reaction yield reached 90%.

[0087] S4. Take a single-necked round-bottom flask and add compound (R)-6, Ph3P (triphenylphosphine), 5-mercapto-1-phenyl-tetrazolyl (PT-SH) and dry THF in sequence. Under Ar atmosphere, DEAD (diethyl azodicarboxylate) is added dropwise in an ice-water bath. The temperature is naturally raised to room temperature and the reaction is carried out for 10.0 h to obtain compound (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazolyl, i.e., (R)-8.

[0088] The molar ratio of compound (R)-6, Ph3P, PT-SH 7, and DEAD was 1:1.2:1.2:1.2;

[0089] S5. Take a single-necked round-bottom flask, add compound (R)-8, dry CH2Cl2, and m-CPBA (m-chloroperbenzoic acid) in sequence, and stir at room temperature under Ar atmosphere for 12.0 h to obtain compound (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole;

[0090] The molar ratio of compound (R)-8 and m-CPBA was 1:5;

[0091] Compound (R)-6 was synthesized by Mitsunobu reaction with PT-SH, Ph3P and DEAD and oxidation with m-CPBA, with a two-step yield of 96%.

[0092] S6. Take a single-necked round-bottom flask, add 1,8-octanediol and dry CH2Cl2, place it in an ice-water bath at 0°C, add glacial acetic acid, DCC (N,N'-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine), and under Ar atmosphere, naturally raise the temperature at 0°C and stir overnight to obtain the compound 8-hydroxyoctyl acetate;

[0093] The molar ratio of 1,8-octanediol, glacial acetic acid, DCC, and DMAP was 1:2:2:0.05;

[0094] Using 1,8-octanediol as the raw material, the monoesterified compound 8-hydroxyoctyl acetate was prepared by adding glacial acetic acid, DCC, and DMAP. Compared with the conventional monoesterification method, the reaction yield increased from 46% to 72%. This method breaks through conventional experimental methods, omitting the steps of adding and deprotecting groups, and simplifying the experimental route.

[0095] S7. Take a single-necked round-bottom flask, add compound 8-hydroxyoctyl acetate, dry CH2Cl2 (anhydrous dichloromethane), silica gel, and PCC in sequence, and stir at room temperature under Ar atmosphere for 12.0 h to obtain compound 8-acetoxyoctanal;

[0096] The molar ratio of compound 8-hydroxyoctyl acetate, silica gel, and PCC is 1:1.5:1.5;

[0097] S8. Take a single-necked round-bottom flask and add the (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole obtained in S5. Under Ar atmosphere, add dry THF and stir at -78°C for 15 minutes. Then, add NaHMDS dropwise. After stirring for 30 minutes, add a mixture of the compound 8-acetoxyoctanal and dry THF dropwise. After reacting at -78°C for 3.0 hours, adjust the temperature to -50°C, and stir overnight to obtain the compound (R)-10-methyldodec-8-en-1-yl acetate, i.e., (R)-13.

[0098] The molar ratio of the compound (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole, NaHMDS, and the compound 8-acetoxyoctanal is 1:1.3:1.5;

[0099] Compound (R)-13 was prepared by coupling reaction of compound (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole with 8-acetoxyoctanal. The reaction conditions were optimized and the yield was significantly improved to 86%.

[0100] S9. Take a single-necked round-bottom flask and add compound (R)-13, dry CH3OH, and 10% Pt / C in sequence. Evacuate the H2 bag with a vacuum pump, then refill it with H2, connect the round-bottom flask, and ventilate it five times with a vacuum pump to completely expel the air. Stir at room temperature for 24.0 h to obtain compound (R)-10-methyldodecyl acetate, i.e., (R)-1.

[0101] The molar ratio of compound (R)-13 and 10% Pt / C was 1:0.08;

[0102] The specific reaction formula of the preparation method provided in this embodiment is as follows:

[0103]

[0104]

[0105] Example 2

[0106] This embodiment provides a novel method for preparing the sex pheromones of the tea leaf roller (R)-10-methyldodecyl acetate and (S)-10-methyldodecyl acetate, and the specific steps are as follows:

[0107] S1. Synthesis of Compound (R)-4

[0108]

[0109] Take a 500 mL single-necked round-bottom flask, add 10.0 g of compound (R)-4-benzyl-2-oxazolidinone (R)-2 and 190 mL of dry THF, under Ar atmosphere, stir and cool at -78 ° C for 15 min, add 27.1 mL of n-BuLi dropwise, and react at -78 ° C for 30 min after the addition is complete;

[0110] Then, 8.8 mL of n-butyryl chloride was added dropwise, and the mixture was reacted at -78°C for 30 min. The refrigeration was turned off and the temperature was naturally raised. The reaction was stirred overnight to complete the reaction.

[0111] Post-reaction treatment: The reaction was quenched with saturated NH4Cl solution, extracted three times with EA, and the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography to obtain 13.5 g of compound (R)-4-benzyl-3-butyryl oxazolinone as a light yellow oily liquid (R)-4, with a yield of 98%;

[0112] The results of hydrogen-carbon spectrum detection of (R)-4 are as follows:

[0113] [α] 25 D =-48.9 (c = 0.2, CHCl3).

[0114] 1 H NMR (600MHz, CDCl3) δ7.33(t,J=7.2Hz,2H),7.27(t,J=7.4Hz,1H),7.21(t,J=7.1Hz,2H),4.69-4.66(m,1H),4.21-4.15(m,2 H),3.29(dd,J=3.2,13.4Hz,1H),2.98-2.85(m,2H),2.77(dd,J=9.6,13.4Hz,1H),1.77-1.70(m,2H),1.01(t,J=7.4Hz,3H);

[0115] 13 C NMR (150MHz, CDCl3) δ173.20,153.43,135.27,129.35,128.87,127.26,66.10,55.06,37.86,37.31,35.74,18.10,17.64,13.61,13.52;

[0116] S2. Synthesis of Compound (R)-5

[0117]

[0118] Take a 250 mL single-necked round-bottom flask, add 3.5 g of compound (R)-4 and 70 mL of dry THF, cool at -78 ° C for 15 min, slowly add 14.1 mL of NaHMDS dropwise, then stir at -78 ° C for 30 min, add 4.4 mL of MeI dropwise, react at -78 ° C for 2.0 h, adjust the temperature to -50 ° C, and stir overnight;

[0119] Post-reaction treatment: The reaction was quenched with saturated NH4Cl solution, extracted three times with EA, dried over anhydrous sodium sulfate, concentrated, and column chromatography to afford 3.7 g of compound (R)-4-benzyl-3-((R)-2-methylbutyryl)oxazolinone, i.e., a light yellow oily liquid (R)-5, in an 89% yield.

[0120] The results of hydrogen-carbon spectrum detection of (R)-5 are as follows:

[0121] [α] 25 D =-47.9 (c = 0.2, CHCl3).

[0122] 1 H NMR (600MHz, CDCl3) δ7.33(t,J=7.6Hz,2H),7.27(t,J=7.3Hz,1H),7.21(d,J=7.1Hz,2H),4.70-4.66(m,1H),4.21-4.16(m,2H),3.67-3.61(m,1H ),3.27(dd,J=3.2,13.4Hz,1H),2.77(dd,J=9.6,13.3Hz,1H),1.81-1.74(m,1H),1.51-1.44(m,1H),1.22(d,J=6.9Hz,3H),0.93(t,J=7.4Hz,3H);

[0123] 13 C NMR (150MHz, CDCl3) δ177.17,153.08,135.33,129.43,128.91,127.31,65.99,55.33,39.16,37.89,26.39,16.88,11.63;

[0124] S3. Synthesis of Compound (R)-6

[0125]

[0126] A 250 mL three-necked round-bottom flask was added with 2.0 g of compound (R)-5. Under Ar atmosphere, 25 mL of dry Et2O and 0.7 mL of dry CH3OH were injected with a syringe. The mixture was cooled at -30°C for 15 min, and 2.7 mL of LiBH4 was added dropwise. The mixture was then stirred at -30°C for 30 min and transferred to an ice-water bath at 0°C and stirred for 12.0 h.

[0127] Post-reaction treatment: The reaction was quenched with 1 mol / L NaOH solution, extracted three times with diethyl ether, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure in an ice-water bath at 3°C. Column chromatography afforded 0.6 g of compound (R)-2-methylbutanol, i.e., a light yellow oil (R)-6, with a yield of 90%.

[0128] The results of hydrogen-carbon spectrum detection of (R)-6 are as follows:

[0129] [α] 25 D =-2.4 (c = 0.5, CHCl3).

[0130] 1 H NMR (600MHz, CDCl3) δ3.82(s,1H),3.45(dd,J=6.0,10.6Hz,1H),3.35(dd,J=6.7,10.6Hz,1H),1.54-1.43(m,2H),1.14-1.09(m,1H),0.91-0.89(m,6H);

[0131] 13 C NMR (150MHz, CDCl3) δ67.36,37.07,25.59,15.87,11.05;

[0132] S4. Synthesis of Compound (R)-8

[0133]

[0134] Take a 250 mL single-necked round-bottom flask and add 3.0 g of compound (R)-6, 10.6 g of Ph3P, 7.2 g of compound PT-SH and 140 mL of dry THF in sequence. Under the protection of Ar atmosphere, 6.3 mL of DEAD was added dropwise in an ice-water bath. The temperature was naturally raised and the reaction was carried out for 10.0 h.

[0135] Post-reaction treatment: The solvent was removed by distillation under reduced pressure, and column chromatography was used to separate 8.2 g of compound (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole, i.e., compound (R)-8, as a light yellow oil, in a yield of 99%.

[0136] The results of hydrogen-carbon spectrum detection of (R)-8 are as follows:

[0137] [α] 25 D =-10.09 (c = 0.2, CHCl3).

[0138] 1 H NMR (600MHz, CDCl3) δ7.60-7.53(m,5H),3.45(dd,J=7.1,15.2Hz,1H),3.26(dd,J=8.9,15.2Hz,1H),1 .89-1.85(m,1H),1.57-1.51(m,1H),1.32-1.27(m,1H),1.03(d,J=8.0Hz,3H),0.93(t,J=8.9Hz,3H);

[0139] 13 C NMR(150MHz, CDCl3)δ154.70,130.00,129.71,123.79,40.05,34.35,28.46,18.56,11.13.HRMS(ESI)m / z calcd for C 12 H 17 N4S + (M+H) + :249.1174,found 249.1178;

[0140] S5. Synthesis of Compound (R)-9

[0141]

[0142] Take a 250 mL single-necked round-bottom flask, add 3.1 g of compound (R)-8, 54 mL of dry CH2Cl2 and 10.7 g of m-CPBA in sequence, and stir at room temperature for 12.0 h under Ar atmosphere protection;

[0143] Post-reaction treatment: A sufficient amount of saturated sodium thiosulfate solution was added to the reaction system to remove excess m-CPBA, and saturated sodium bicarbonate solution was added to remove organic acid. The mixture was extracted with CH2Cl2, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain 3.4 g of (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole, i.e., compound (R)-9, as a light yellow oil, in a yield of 97%.

[0144] The results of hydrogen-carbon spectrum detection of (R)-9 are as follows:

[0145] [α] 25 D =-5.36 (c = 0.3, CHCl3).

[0146] 1 H NMR (600MHz, CDCl3) δ8.21(d,J=9.6Hz,1H),8.01(d,J=9.7Hz,1H),7.65-7.58(m,2H),3.58-3.54(m,1H) ,3.37-3.32(m,1H),1.48-1.40(m,1H),1.14-1.01(m,2H),0.87(t,J=8.3Hz,3H),0.79(t,J=8.1Hz,3H);

[0147] 13 C NMR(150MHz, CDCl3)δ154.01,133.01,131.44,129.65,125.11,61.44,29.62,29.25,19.18,10.69.HRMS(ESI)m / z calcd for C 12 H 17 N4O2S + (M+H) + :281.1072,found281.1073;

[0148] S6. Synthesis of Compound 11

[0149]

[0150] Take a 250 mL single-necked round-bottom flask, add 1.0 g of 1,8-octanediol and 75 mL of dry CH2Cl2, place it in an ice-water bath at 0°C, add 0.8 mL of glacial acetic acid, 2.8 g of DCC and 0.04 g of DMAP, and under Ar atmosphere, naturally heat at 0°C and stir overnight;

[0151] Post-reaction treatment: the reaction was quenched with water, washed with saturated sodium bicarbonate solution, extracted with CH2Cl2 three times, dried over anhydrous sodium sulfate, filtered and concentrated, and subjected to column chromatography to obtain 0.8 g of a colorless oily compound 8-hydroxyoctyl acetate, i.e., compound 11, in a yield of 72%;

[0152] Compound 11 was tested by hydrogen and carbon spectroscopy, and the results were:

[0153] 1 H NMR (600MHz, CDCl3) δ4.04(t,J=6.8Hz,2H),3.63(t,J=6.6Hz,2H),2.04(s, 3H),1.70(s,1H),1.62-1.59(m,2H),1.57-1.53(m,2H),1.37-1.32(m,8H);

[0154] 13 C NMR(150MHz, CDCl3)δ171.27,64.59,62.96,32.70,29.24,29.16,28.54,25.80,25.62,20.99.HRMS(ESI)m / z calcd for C 10 H 21 O3 + (M+H) + :198.1491,found198.1474;

[0155] S7. Synthesis of Compound 12

[0156]

[0157] To a 100 mL single-necked round-bottom flask, 1.5 g of compound 118-hydroxyoctyl acetate, 30 mL of dry CH2Cl2, 2.6 g of silica gel, and 2.6 g of PCC were added in sequence. Under Ar atmosphere, the reaction was stirred at room temperature for 12.0 h.

[0158] Post-reaction treatment: Take a G6 glass frit funnel, fill it with diatomaceous earth, connect a vacuum pump and compact it with silica gel, use petroleum ether to precipitate chromium ions, then filter it with CH2Cl2, distill and concentrate under reduced pressure to obtain 1.3 g of light yellow liquid compound 8-acetoxyoctanal, i.e., compound 12, with a yield of 89%;

[0159] Compound 12 was tested by hydrogen and carbon spectroscopy, and the results were:

[0160] 1 H NMR (600MHz, CDCl3) δ9.74(t,J=1.8Hz,1H),4.02(t,J=7.2Hz,2H),2.40(dt,J=1.6,7.3Hz,2H),2.02(s,3H),1.62-1.60(m,4H),1.31(s,6H);

[0161] 13 C NMR (150MHz, CDCl3) δ202.67,171.15,64.41,43.76,28.93,28.89,28.44,25.63,21.87,20.92;

[0162] S8. Synthesis of Compound (R)-13

[0163]

[0164] A 100 mL single-necked round-bottom flask was added with 0.2 g of compound (R)-9. Under Ar atmosphere, 3 mL of dry THF was added and stirred at -78°C for 15 min. 0.5 mL of NaHMDS was added dropwise and stirred for 30 min. A mixture of 0.2 g of compound 8-acetoxyoctanal and 3 mL of dry THF was then added dropwise. The mixture was reacted at -78°C for 3.0 h, then the temperature was adjusted to -50°C and stirred overnight.

[0165] Post-reaction treatment: Quench the reaction by dropwise addition of saturated ammonium chloride solution at -50°C, extract three times with ethyl acetate, wash with saturated brine, and dry the organic phase over anhydrous magnesium sulfate. Because the product is very weak and volatile, it is concentrated at 30°C to yield a pale yellow oil. Column chromatography afforded 0.2 g of compound (R)-10-methyldodec-8-en-1-yl acetate, a pale yellow liquid (R)-13, in an 86% yield.

[0166] The results of hydrogen-carbon spectrum detection of (R)-13 are as follows:

[0167] (Z / E 3:1)[α] 25 D =-2.82 (c = 0.2, CHCl3).

[0168] 1 H NMR (600MHz, CDCl3) δ5.35-5.08(m,2H),4.05(t,J=8.2Hz,2H),2.35-2.29(m,1H),2.04(s,3H),2.02-1 .94(m,2H),1.62-1.58(m,2H),1.35-1.24(m,10H),0.93(dd,J=8.1,14.4Hz,3H),0.83(t,J=8.9Hz,3H);

[0169] 13 C NMR (150MHz, CDCl3) δ171.22,136.24,136.19,128.49,128.43,64.63,33.37,32.52,30.25,29. 85,29.79,29.57,29.14,29.08,28.93,28.58,27.40,25.87,21.04,20.99,20.45,11.95,11.75;

[0170] S9. Synthesis of Compound (R)-1

[0171]

[0172] Take a 250 mL single-necked round-bottom flask and add 0.2 g of compound (R)-13, 10 mL of dry CH3OH, and 0.1 g of 10% Pt / C in sequence. Evacuate the H2 bag with a vacuum pump, then refill it with H2 and connect it to the round-bottom flask. Use a vacuum pump to ventilate 5 times to expel all air. Stir at room temperature for 24.0 h until the reaction is complete.

[0173] Post-reaction treatment: The solvent methanol was distilled off under reduced pressure at 30°C, and column chromatography was performed to obtain 0.1 g of compound (R)-10-methyldodecyl acetate, i.e., a colorless liquid (R)-1, with a yield of 81%.

[0174] The results of hydrogen-carbon spectrum detection of (R)-1 are as follows:

[0175] [α] 25 D =-2.25 (c = 0.2, CHCl3).

[0176] 1 H NMR (600MHz, CDCl3) δ4.05 (t, J = 8.1Hz, 2H), 2.04 (s, 3H), 1.64-1.59 (m, 2H), 1.35-1.26 (m, 15H), 1.16-1.06 (m, 2H), 0.88-0.83 (m, 6H);

[0177] 13 C NMR (150MHz, CDCl3) δ171.24,64.66,36.62,34.39,29.97,29.60,29.52,29.48,29.25,28.60,27.08,25.90,21.01,19.21,11.39;

[0178] S10. Synthesis of compound (S)-8

[0179]

[0180] Take a 250 mL single-necked round-bottom flask and add 2.0 g (S)-2-methylbutanol, 7.1 g Ph3P, 4.9 g PT-SH and 140 mL dry THF in sequence. Under Ar atmosphere protection, 4.3 mL DEAD was added dropwise in an ice-water bath at 0 °C, and then the temperature was naturally raised to room temperature and reacted for 10.0 h.

[0181] Post-reaction treatment: The solvent was removed by distillation under reduced pressure, and column chromatography was used to separate 5.2 g of (S)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole, i.e., compound (S)-8, as a light yellow oil, in a yield of 93%.

[0182] The results of hydrogen-carbon spectrum detection of (S)-8 are as follows:

[0183] [α] 25 D = +12.35 (c = 0.2, CHCl3).

[0184] 1 H NMR (600MHz, CDCl3) δ7.59-7.51(m,5H),3.45(dd,J=5.9,12.6Hz,1H),3.26(dd,J=7.4,12.6Hz,1H),1 .89-1.82(m,1H),1.57-1.50(m,1H),1.32-1.25(m,1H),1.02(d,J=6.7Hz,3H),0.93(t,J=7.4Hz,3H);

[0185] 13 C NMR(150MHz, CDCl3)δ154.73,133.73,130.01,129.72,123.84,40.10,34.41,28.49,18.57,11.13.HRMS(ESI)m / z calcd for C 12 H 17 N4S + (M+H) + :249.1174,found249.1178;

[0186] S11. Synthesis of Compound (S)-9

[0187]

[0188] Take a 250 mL single-necked round-bottom flask, add 1.3 g of compound (S)-8, 30 mL of dry CH2Cl2 and 4.6 g of m-CPBA in sequence, and stir at room temperature for 12.0 h under Ar atmosphere protection;

[0189] Post-reaction treatment: A sufficient amount of saturated sodium thiosulfate solution was added to the reaction system to remove excess m-CPBA, and saturated sodium bicarbonate solution was added to remove organic acid. The mixture was extracted with CH2Cl2, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain 1.4 g of (S)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole, i.e., compound (S)-9, as a light yellow oil, in a yield of 96%.

[0190] The results of hydrogen-carbon spectrum detection of (S)-9 are as follows:

[0191] [α] 25 D =+9.16 (c=0.3, CHCl3);

[0192] 1 H NMR (600MHz, CDCl3) δ7.69-7.67(m,2H),7.64-7.58(m,3H),3.81(dd,J=4.9,14.5Hz,1H),3.58(dd,J=7.9,14.5 Hz,1H),2.31-2.23(m,1H),1.63-1.56(m,1H),1.47-1.39(m,1H),1.15(d,J=6.8Hz,3H),0.94(t,J=7.4Hz,3H);

[0193] 13 C NMR(150MHz, CDCl3)δ154.0,133.0,131.4,129.6,125.1,61.4,29.6,29.2,19.1,10.6.HRMS(ESI)m / z calcd for C 12 H 17 N4O2S + (M+H) + :281.1072,found 281.1075;

[0194] S12. Synthesis of Compound (S)-13

[0195]

[0196] To a 100 mL single-necked round-bottom flask, 1.4 g of compound (S)-9 was added. Under Ar atmosphere, 10 mL of dry THF was added, and the mixture was cooled at -78 °C for 15 min. 2.8 mL of a 2.0 M solution of NaHMDS in tetrahydrofuran was added dropwise, and the mixture was stirred for 30 min. Then, a mixture of 1.3 g of 8-acetoxyoctanal and 10 mL of dry THF was added dropwise. After stirring at -78 °C for 3.0 h, the temperature was adjusted to -50 °C and stirred overnight.

[0197] Post-reaction treatment: saturated NH4Cl was added to the reaction system at -50°C to quench the reaction, and the mixture was extracted three times with EA, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography to obtain 1.1 g of (S)-10-methyldodec-8-en-1-yl acetate, i.e., a light yellow oil (S)-13, with a yield of 97%;

[0198] Compound (S)-9 and (S)-12 were coupled to prepare compound (S)-13. The reaction conditions were optimized and the reaction yield was greatly improved to 97%.

[0199] The results of hydrogen-carbon spectrum detection of (S)-13 are as follows:

[0200] (Z / E:3:1mixture)[α] 25 D = +2.67 (c = 0.2, CHCl3).

[0201] 1 H NMR (600MHz, CDCl3) δ5.35-5.08(m,2H),4.04(t,J=6.8Hz,2H),2.34-2.29(m,1H),2.03(s,3H),2.02-1 .92(m,2H),1.53-1.58(m,2H),1.34-1.23(m,10H),0.92(dd,J=6.8,13.4Hz,3H),0.83(t,J=7.4Hz,3H);

[0202] 13 C NMR (150MHz, CDCl3) δ171.18,136.23,136.17,128.47,128.42,64.61,38.35,33.36,32.51,30.24,29.84, 29.78,29.13,29.11,29.06,28.92,28.57,27.39,25.86,25.85,21.02,20.96,20.43,11.92,11.73,0.98;

[0203] S13. Synthesis of target compound (S)-1

[0204]

[0205] To a single-necked 250 mL round-bottom flask, 0.6 g of compound (S)-13, 30 mL of CH3OH, and 0.4 g of 10% Pt / C were added in sequence. The H2 bag was evacuated with a vacuum pump, then refilled with H2 and connected to the round-bottom flask. The air was purged five times with a vacuum pump and the mixture was stirred at room temperature for 24.0 h until the reaction was complete.

[0206] Post-reaction treatment: The solvent methanol was distilled off under reduced pressure at 30°C, and column chromatography was performed using 50:1 PE / EA as the eluent to obtain 0.4 g of compound (S)-10-methyldodecyl acetate, i.e., a colorless oil (S)-1, in a yield of 62%.

[0207] The (S)-10-methyldodecyl acetate was subjected to hydrogen carbon spectrum detection, and the result was:

[0208] [α] 25 D = +1.78 (c = 0.5, CHCl3).

[0209] 1 H NMR (600MHz, CDCl3) δ4.04 (d, J = 6.8 Hz, 2H), 2.04 (s, 3H), 1.63-1.58 (m, 2H), 1.33-1.26 (m, 15H), 1.14-1.04 (m, 2H), 0.84 (q, J = 7.1, 13.3Hz, 6H);

[0210] 13 C NMR (150MHz, CDCl3) δ171.22,64.65,36.61,34.37,29.96,29.59,29.47,29.25,28.58,27.07,25.89,20.99,19.19,11.38.

[0211] The total synthesis equations of the two isomers of the tea leaf roller sex pheromone are as follows:

[0212]

[0213] Table 1 Total synthesis of two isomers of the sex pheromone of the tea leaf roller

[0214]

[0215] Compared with the general synthetic route, the synthetic route provided in this embodiment is short, and the yield of most steps is above 80%. The synthetic method is simple and can obtain the target product in the shortest time. (R)-1 is prepared through 7 steps with a total yield of 53%, and (S)-1 is prepared through 4 steps with a total yield of 54%.

[0216] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent variation made to the above embodiment based on the essence of the invention technology shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing a sex pheromone of the tea leaf roller, characterized in that: The following steps are involved: S1. Under argon atmosphere, add dry THF to (R)-4-benzyl-2-oxazolidinone, stir thoroughly after cooling, add n-BuLi dropwise, allow to cool and react thoroughly, then add n-butyryl chloride dropwise, allow to cool and react a second time, then heat naturally and stir overnight; Post-reaction treatment: quenching, extraction, drying, filtration, concentration and column chromatography are performed to obtain (R)-4-benzyl-3-butyryl oxazolinone; S2. Add dry THF to the (R)-4-benzyl-3-butyryl oxazolinone obtained in S1, add NaHMDS dropwise after cooling, stir, and then add MeI dropwise. Allow to react fully, adjust the temperature, and stir overnight. Post-reaction treatment: quenching, extraction, drying, concentration and column chromatography were performed to obtain (R)-4-benzyl-3-((R)-2-methylbutyryl)oxazolinone; S3. Under argon atmosphere, dry Et2O and dry CH3OH were injected into the (R)-4-benzyl-3-((R)-2-methylbutyryl)oxazolinone obtained in S2. After cooling, LiBH4 was added dropwise with stirring. The mixture was transferred to an ice-water bath and stirred thoroughly for reaction. Post-reaction treatment: quenching, extraction, drying, concentration under reduced pressure and column chromatography are performed in sequence to obtain (R)-2-methylbutanol; S4. Under argon atmosphere, take the (R)-2-methylbutanol, Ph3P, PT-SH and dry THF obtained in S3, add DEAD dropwise in an ice-water bath, and allow to react fully after natural temperature increase; Post-reaction treatment: vacuum distillation and column chromatography to obtain (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole; S5. Under argon atmosphere, (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole obtained in S4, dry CH2Cl2 and m-CPBA were stirred and reacted at room temperature; Post-reaction treatment: sodium thiosulfate was added to remove excess m-CPBA, and then saturated NaHCO3 solution was added to remove the acid. The product was extracted, dried, filtered, concentrated, and column chromatographed to obtain (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole. S6. Under argon atmosphere, mix 1,8-octanediol and dry CH2Cl2, add glacial acetic acid, DCC, and DMAP in an ice-water bath, and heat naturally while stirring overnight. Post-reaction treatment: quenching, washing, extraction, drying, filtration and concentration, column chromatography and then quenching to obtain 8-hydroxyoctyl acetate; S7. Under argon atmosphere, take the 8-hydroxyoctyl acetate obtained in S6, dry CH2Cl2, silica gel and PCC, and stir the reaction at room temperature; Post-reaction treatment: Take a sand core funnel and fill it with diatomaceous earth, connect a vacuum pump and compact it with silica gel, then add petroleum ether, filter, distill under reduced pressure and concentrate to obtain 8-acetoxyoctanal; S8. Under argon atmosphere, mix the (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole obtained in S5 with 1% dry THF, cool and stir, add NaHMDS dropwise and stir to fully react, then add the mixture of 8-acetoxyoctanal obtained in S7 and 2% dry THF dropwise, cool and fully react a second time, adjust the temperature and stir overnight; Post-reaction treatment: quenching, extraction, washing, drying, concentration and column chromatography are performed in sequence to obtain (R)-10-methyldodec-8-en-1-yl acetate; S9. Take the (R)-10-methyldodec-8-en-1-yl acetate obtained in S8, dry CH3OH, and 10% Pt / C, evacuate the H2 bag with a vacuum pump, refill with H2, ventilate five times, and stir at room temperature for complete reaction. Post-reaction treatment: (R)-10-methyldodecyl acetate was obtained by vacuum distillation and column chromatography; S10. Under argon atmosphere, take the (R)-10-methyldodecyl acetate, Ph3P, PT-SH and dryTHF obtained in S9, add DEAD dropwise in an ice-water bath, and then naturally warm to room temperature to fully react; Post-reaction treatment: vacuum distillation and column chromatography gave (S)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole; S11. Under argon atmosphere, (S)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole obtained in S10, dry CH2Cl2 and m-CPBA were stirred at room temperature for reaction; Post-reaction treatment: sodium thiosulfate was added to remove excess m-CPBA, and then saturated NaHCO3 solution was added to remove the acid. The product was extracted, dried, filtered, concentrated, and column chromatographed to obtain (S)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole. S12. Under argon atmosphere, mix the (S)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole obtained in S11 with 1% dry THF, cool and stir, add NaHMDS dropwise and stir to react thoroughly, then add a mixture of 8-acetoxyoctanal and 2% dry THF dropwise, cool and stir twice to react thoroughly, adjust the temperature and stir overnight; Post-reaction treatment: quenching, extraction, washing, drying, filtration, concentration and column chromatography are performed in sequence to obtain (S)-10-methyldodec-8-en-1-yl acetate; S13. Take the (S)-10-methyldodec-8-en-1-yl acetate obtained in S12, CH3OH, and 10% Pt / C, evacuate the H2 bag with a vacuum pump, refill with H2, ventilate five times, and stir at room temperature for complete reaction. Post-reaction treatment: (S)-10-methyldodecyl acetate was obtained by vacuum distillation and column chromatography.

2. The method for preparing the sex pheromone of the tea leaf roller according to claim 1, characterized in that: The mass volume ratio of (R)-4-benzyl-2-oxazolidinone, dry THF, n-BuLi and n-butyryl chloride in S1 is 10.0 g:190 mL:27.1 mL:8.8 mL; The mass volume ratio of (R)-4-benzyl-3-butyryloxazolinone, dry THF, NaHMDS and MeI in S2 is 3.5 g:70 mL:14.1 mL:4.4 mL; The mass volume ratio of (R)-4-benzyl-3-((R)-2-methylbutanoyl)oxazolidinone, dry Et2O, dry CH3OH and LiBH4 in S3 is 2.0 g:25 mL:0.7 mL:2.7 mL; The mass volume ratio of (R)-2-methylbutanol, Ph3P, PT-SH, dry THF and DEAD in S4 is 3.0 g:10.6 g:7.2 g:140 mL:6.3 mL; The mass volume ratio of (R)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole, dry CH2Cl2 and m-CPBA described in S5 is 3.1 g:54 mL:10.7 g; The mass volume ratio of 1,8-octanediol, dry CH2Cl2, glacial acetic acid, DCC, and DMAP described in S6 is 1.0 g:75 mL:0.8 mL:2.8 g:0.04 g; The mass volume ratio of 8-hydroxyoctyl acetate, dry CH2Cl2, silica gel and PCC in S7 is 1.5 g:30 mL:2.6 g:2.6 g; The mass volume ratio of (R)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole, dry THF 1, NaHMDS, 8-acetoxyoctanal and dry THF 2 described in S8 is 0.2 g:3 mL:0.5 mL:0.2 g:3 mL; The mass volume ratio of (R)-10-methyldodec-8-en-1-yl acetate, dry CH3OH and 10% Pt / C in S9 is 0.2 g:10 mL:0.1 g; The mass volume ratio of (R)-10-methyldodecyl acetate, Ph3P, PT-SH, dry THF, and DEAD in S10 is 2.0 g:7.1 g:4.9 g:140 mL:4.3 mL; The mass volume ratio of (S)-5-((2-methylbutyl)thio)-1-phenyl-1H-tetrazole, dry CH2Cl2 and m-CPBA in S11 is 1.3 g:30 mL:4.6 g; The mass volume ratio of (S)-5-((2-methylbutyl)sulfonyl)-1-phenyl-1H-tetrazole, dry THF 1, NaHMDS, 8-acetoxyoctanal and dry THF 2 described in S12 is 1.4 g:10 mL:2.8 mL:1.3 g:10 mL; The mass volume ratio of (S)-10-methyldodec-8-en-1-yl acetate, CH3OH and 10% Pt / C described in S13 is 0.6 g:30 mL:0.4 g.

3. The method for preparing the sex pheromone of the tea leaf roller according to claim 1, characterized in that: The stirring time in S1, S8 and S12 is 15 min, and the sufficient reaction time is 30 min; The time for the secondary full reaction in S1 is 30 min; The cooling time in S2 and S3 is 15 minutes, and the stirring time is 30 minutes; The time for the full reaction in S2 is 2 hours; The stirring reaction time in S3, S5, S7 and S11 is 12 hours; The time for the full reaction in S4 and S10 is 10 hours; The time for the secondary full reaction in S8 and S12 is 3 hours; The time required for the stirring reaction to be complete in S9 and S13 is 24 hours.

4. The method for preparing the sex pheromone of the tea leaf roller according to claim 1, characterized in that: The quenching solution in S1, S2, S8, and S12 is saturated NH4Cl, the quenching solution in S3 is 1 mol / L NaOH, and the quenching solution in S6 is water; The extraction agent used in S1, S2, S8, and S12 is ethyl acetate, the extraction agent used in S3 is diethyl ether, and the number of extractions is 3; The drying substance in S1, S2, S5, S6, S11, and S12 is anhydrous sodium sulfate, and the drying substance in S3 and S8 is anhydrous magnesium sulfate; The temperature of the reduced pressure concentration in S3 is 3°C; The extraction solvent used in S5, S6 and S11 is CH2Cl2; The washing solution in S6 is saturated sodium bicarbonate, and the washing solutions in S8 and S12 are saturated salt water. The filtration solution in S7 is CH2Cl2; The concentration temperature in S8 is 30°C; The vacuum distillation temperature in S9 and S12 is 30° C. The eluent for the column chromatography in S12 was 50:1 PE / EA.

5. The method for preparing the sex pheromone of the tea leaf roller according to claim 1, characterized in that: The temperature of the ice water bath in S3, S4, S6 and S10 is 0°C.

6. The method for preparing the sex pheromone of the tea leaf roller according to claim 1, characterized in that: The temperature after cooling in S1, S2 and S8 to S11 is -78°C, the temperature after cooling in S3 is -30°C, and the temperature after adjustment in S2, S8 and S12 is -50°C.

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