CN117142916B - Preparation method of allyl sulfone compound - Google Patents

Abstract

The invention discloses a preparation method of allyl sulfone compounds, which comprises the following steps: adding sulfinic acid and allyl alcohol into a reaction solvent in an inert gas atmosphere, and stirring and reacting for 8-36 h at the temperature of 20-60 ℃; wherein, the sulfinic acid is selected from any one of normal aryl sulfinic acid, heteroaryl sulfinic acid, condensed ring sulfinic acid, straight-chain aliphatic sulfinic acid and cyclic aliphatic sulfinic acid; the allyl alcohol is selected from any one of n-aryl allyl alcohol, heteroaryl allyl alcohol, condensed ring allyl alcohol, linear alkane allyl alcohol and cyclic alkane allyl alcohol; after the TLC monitoring reaction is completed, the reaction liquid obtained in the step (1) is subjected to solvent removal and purification to obtain the allyl sulfone compound. The method has the advantages of wide substrate application range, simple steps, convenient operation, high product yield, environmental protection, no need of using any catalyst or ligand, and potential application value for fine chemistry and industrial production.

Description

A kind of preparation method of allyl sulfone compound

Technical Field

The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a method for preparing an allyl sulfone compound.

Background Art

Allyl sulfone compounds are widely present in natural products and are commonly found in drug molecules and functional materials, such as anti-abnormal cell proliferation drugs, cysteine protease inhibitors, thyroid-stimulating receptor antagonists and antibacterial agents. Because they contain allyl and sulfone groups, they can also be used as multi-purpose building blocks in chemical synthesis.

Considering the wide application value of allyl sulfone, people have developed various methods to effectively construct the functional group skeleton. The most traditional method is generally to prepare it by cross-coupling reaction of functionalized allyl compounds and active sulfonyl precursors under transition metal catalysis, but these reactions will produce harmful byproducts of different stoichiometric amounts and have low atom economy. With the development of research, people have found that alcohol is a relatively abundant resource, widely present in nature, cheap, easy to obtain, and environmentally friendly. The most ideal way to construct the allyl skeleton is to directly use allyl alcohol and sulfonyl precursors for dehydration cross-coupling reaction. However, it is well known that the C-OH bond has a high activation barrier and is not easy to break. In order to overcome this difficulty, researchers have proposed different solutions, such as adding triethylamine, boron hydroxide, trimethylsilyl chloride and other additives to achieve this goal. However, when acidic additives are added, only aromatic sulfonyl groups are compatible with this reaction, which greatly limits the scope of the substrate and the reaction is highly dependent on the choice of additives. At the same time, it also requires a higher transition metal catalytic equivalent, a higher reaction temperature and an effective ligand, and the cost is high.

With the continuous development of research, a water-promoted synthesis strategy for allyl sulfone (Nature Communications., 2018, 9, 1321.) has achieved the efficient preparation of allyl sulfone compounds using active allyl alcohol as raw material in water phase at room temperature, but this strategy is only applicable to highly active allyl alcohols (Morita-Baylis-Hillman alcohols and 1,3-diaryl allyl alcohols). In order to solve the serious limitation of substrates faced by direct sulfonation of allyl alcohol to prepare allyl sulfone olefins, a palladium and calcium co-catalytic system was subsequently developed (CN110627693 A). The mutual activation strategy can efficiently complete the construction of the allyl sulfone skeleton using inactive allyl alcohol as raw material at room temperature. However, the involvement of heavy metals leads to a sudden increase in costs.

Summary of the invention

The object of the present invention is to provide a method for preparing allyl sulfone compounds.

The present invention is achieved by a method for preparing an allyl sulfone compound, the method comprising the following steps:

(1) Under an inert gas atmosphere, sulfinic acid and allyl alcohol are added to a reaction solvent, and the mixture is stirred at 20 to 60° C. for 8 to 36 hours; wherein:

The sulfinic acid is selected from any one of normal aryl sulfinic acid, heteroaryl sulfinic acid, condensed ring sulfinic acid, straight chain aliphatic sulfinic acid and cyclic aliphatic sulfinic acid;

The allyl alcohol is selected from any one of normal aryl allyl alcohol, heteroaryl allyl alcohol, condensed ring allyl alcohol, linear alkane allyl alcohol, and cyclic alkane allyl alcohol;

The reaction solvent is selected from any one of tetrahydrofuran, ethylene glycol dimethyl ether, toluene, dimethyl sulfoxide, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dichloromethane, dichloroethane, dimethyl carbonate and diethyl carbonate;

(2) After the reaction is complete as monitored by TLC, the reaction solution obtained in step (1) is freed of solvent and purified to obtain an allyl sulfone compound.

Preferably, in step (1), the molar volume ratio of the sulfinic acid, allyl alcohol and reaction solvent is 0.9-18 mmol: 0.3-9 mmol: 2-4 mL.

Preferably, in step (1), the sulfinic acid is selected from any one of 4-methylbenzenesulfinic acid, 4-methoxybenzenesulfinic acid, 2-nitrobenzenesulfinic acid, trifluoromethylsulfinic acid, 4-fluorobenzenesulfinic acid, 4-(trifluoromethyl)benzenesulfinic acid, benzylsulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 4-chlorobenzenesulfinic acid, 4-(tert-butyl)benzenesulfinic acid, 2-naphthylsulfinic acid, 9-anthrylsulfinic acid, 3-methylbenzenesulfinic acid, thiophene-2-sulfinic acid, furan-2-sulfinic acid, pyridine-2-sulfinic acid, indole-3-sulfinic acid, ethylsulfinic acid, butylsulfinic acid, methylsulfinic acid, cyclopropanesulfinic acid and dextrorotatory camphorsulfinic acid.

Preferably, in step (1), the allyl alcohol is selected from (E)-3-phenylprop-2-en-1-ol, (E)-3-(4-fluorophenyl)prop-2-en-1-ol, (E)-3-(3-fluorophenyl)propyl-2-en-1-ol, (E)-3-(4-(trifluoromethyl)phenyl)propyl-2-en-1-ol, (E)-3-(4-bromophenyl)propyl-2-en-1-ol, (E)-3-(4-methoxyphenyl)propyl-2-en-1-ol, (E)-3-(4-(trifluoromethyl)phenyl)propyl-2-en-1-ol (E)-3-(2-nitrophenyl)prop-2-en-1-ol, (E)-3-(2-nitrophenyl)prop-2-en-1-ol, (E)-3-(thiophen-2-yl)prop-2-en-1-ol, (E)-3-(pyridin-3-yl)propyl-2-en-1-ol, (E)-3-(furan-2-yl)prop-2-en-1-ol, (E)-3-(indol-2-yl)prop-2-en-1-ol, (E)-3-(4-(tert-butyl)phenyl)propyl-2-en-1-ol, (E)-3-(3 ,5-dimethylphenyl)propyl-2-en-1-ol, 1-(naphthalene-2-yl)propyl-2-en-1-ol, 1-(anthracen-2-yl)propyl-2-en-1-ol (E)-3-(4-((trimethylsilyl)ethynyl)phenyl)propyl-2-en-1-ol, (E)-5,9-dimethyldeca-2,8-dien-1-ol, (E)-3-(3-phenoxyphenyl)propyl-2-en-1-ol, (E)-2-bromopropane-3-phenylpropyl-2-en-1-ol, (E)- 3-phenylbutyl-2-en-1-ol, (E)-2-methyl-3-phenylprop-2-en-1-ol, (E)-3-cyclohexylprop-2-en-1-ol, (E)-5,9-dimethyldeca-1,8-dien-3-ol, (2E, 4E)-5-phenyl-2,4-pentadien-1-ol, (E)-4-phenyl-3-buten-2-ol, (E)-3-(2-methoxyphenyl)propyl-2-en-1-ol, (E)-3-methylprop-2-en-1-ol.

Preferably, in step (1), the reaction is stirred at 40° C. for 10 h.

Preferably, in step (2), the solvent removal is to remove the reaction solvent by a vacuum rotary evaporator, the purification is to purify by thin layer chromatography/column chromatography, and the developing solvent system is petroleum ether/ethyl acetate = 5/1.

The present invention overcomes the deficiencies of the prior art and provides a method for preparing an allyl sulfone compound, comprising the following steps:

(1) In an inert gas atmosphere, sulfinic acid and allyl alcohol are added to a reaction solvent and stirred at 20 to 60° C. for 8 to 36 hours. The chemical equation of the reaction is:

In the reaction formula, compound 1 is allyl alcohol, wherein R ¹ is selected from any one of alkyl (C1-C15 chain alkyl or cycloalkyl), n-aryl (methyl, methoxy, cyano, nitro, tert-butyl, fluoro, trifluoromethyl, chloro, bromo, ferrocenyl, ethynyl, trimethylsilaneethynyl on the benzene ring), condensed ring aryl (naphthalene, anthracene), and heteroaryl (furan, indole, pyridine, thiophene) groups;

Compound 2 is sulfinic acid, R ² is selected from any one of alkyl (C1-C15 chain alkyl or cycloalkyl), n-aryl (methyl, methoxy, cyano, nitro, tert-butyl, fluoro, trifluoromethyl, chloro, bromo, ferrocenyl, ethynyl, trimethylsilaneethynyl on the benzene ring), condensed ring aryl (naphthalene, anthracene), heteroaryl (furan, indole, pyridine, thiophene) groups;

(2) removing the reaction solvent from the reaction solution obtained in step (1), and purifying the solution by thin layer chromatography/column chromatography to obtain an allyl sulfone compound.

In the preparation method of the present invention, allyl sulfone is synthesized by direct dehydration cross coupling of allyl alcohol and sulfinic acid under the condition of no metal catalysis, so that the reaction occurs in an environmentally friendly manner under mild conditions.

Compared with the shortcomings and deficiencies of the prior art, the present invention has the following beneficial effects: the allyl alcohol used in the preparation method of the present invention is an allyl alcohol with simple synthesis and good conversion rate, and has a wide range of applicable substrates, such as various substituted phenyl groups and alkyl groups on the allyl alcohol, and has the characteristics of low preparation cost; in addition, the preparation method of the present invention has simple steps, convenient operation, high product yield, and only water as the by-product, and has the characteristics of high atom economy and green environmental protection; and the preparation method of the present invention does not need to use any catalyst and ligand, and has potential application value in fine chemistry and industrial production; the obtained allyl sulfone compound can be used as an organic synthesis building block to carry out various derivatizations by utilizing its allyl and sulfone moieties, and is also an important skeleton widely present in natural products, biological and drug molecules, and has potential biological activity and drug activity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a hydrogen nuclear magnetic resonance spectrum of compound 3 in Example 1 of the present invention;

FIG2 is a carbon NMR spectrum of compound 3 in Example 1 of the present invention;

FIG3 is a hydrogen nuclear magnetic resonance spectrum of compound 5 in Example 2 of the present invention;

FIG4 is a carbon NMR spectrum of compound 5 in Example 2 of the present invention;

FIG5 is a hydrogen nuclear magnetic resonance spectrum of compound 9 in Example 4 of the present invention;

FIG6 is a carbon NMR spectrum of compound 9 in Example 4 of the present invention;

FIG7 is a hydrogen nuclear magnetic resonance spectrum of compound 11 in Example 5 of the present invention;

FIG8 is a carbon NMR spectrum of compound 11 in Example 5 of the present invention.

DETAILED DESCRIPTION

In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

Example 1

(1) In a 10 mL Shrek tube, under nitrogen atmosphere, 0.3 mmol (E)-3-phenylprop-2-en-1-ol and 0.9 mmol benzenesulfinic acid were added to 3 mL of dichloromethane and stirred at 40° C. for 10 h. The reaction equation is:

(2) After the reaction was completed as monitored by TLC, the solvent was removed by vacuum rotary evaporator and the product was separated by thin layer chromatography. The developing solvent was petroleum ether/ethyl acetate system (5/1). The product was a light yellow solid compound 3 with a yield of 82%.

Compound 3 was characterized, and its NMR spectra are shown in Figures 1 and 2, specifically:

¹ H NMR (400MHz, Chloroform-d) δ7.83-7.78(m,2H),7.59-7.53(m,1H),7.48-7.43(m,1H),7.26-7.16(m,5H),6.29( dt,J＝15.8,1.3Hz,1H),6.07-5.97(m,1H),3.88(dd,J＝7.6,1.2Hz,2H). ¹³ C NMR(100MHz,Chloroform-d)δ139.33,138.43,135.83,133.91,129.22,128.78,128.63,126.72,115.18,60.58,29.80.IR(KBr):3056,2919,1647,1317,1135, 749cm ^-1 .HRMS (ESI/[M+H] ⁺ )Calcd.for:C ₁₅ H ₁₅ O ₂ S259.0793, found 259.0790.

The characterization results showed that compound 3 was (cinnamylsulfonyl)benzene.

Example 2

(1) In a 10 mL Shrek tube, under nitrogen atmosphere, 0.3 mmol (E)-3-phenylprop-2-en-1-ol and 0.9 mmol 4-methylbenzenesulfinic acid were added to 3 mL of dichloromethane and stirred at 40° C. for 15 h. The reaction equation is:

(2) After the reaction was completed as monitored by TLC, the solvent was removed by vacuum rotary evaporator and the product was separated by thin layer chromatography. The developing solvent was petroleum ether/ethyl acetate system (5/1). The product was a light yellow solid compound 5 with a yield of 75%.

Compound 5 was characterized, and its NMR spectra are shown in Figures 3 and 4, specifically:

¹ H NMR (400MHz, Chloroform-d) δ7.78-7.73 (m, 2H), 7.34-7.26 (m, 7H), 6.38 (dt, J = 15.9, 4.0Hz, 1H), 6.14-6.05 (m, 1H),3.93(dd,J=7.6,1.2Hz,2H),2.42(s,3H). ¹³ C NMR(100MHz,Chloroform-d)δ144.85,139.09,135.92,135.62,129.82,128.74,128.59,128.55,126.71,115.43,60.63,21.73.IR(KBr):3023,2921,1649,131 4,1149,814cm ^-1 .HRMS(ESI/[M+H] ⁺ )Calcd.for:C ₁₆ H ₁₇ O ₂ S273.0949,found 273.0943.

The characterization results showed that compound 5 was 1-(cinnamylsulfonyl)-4-methylbenzene.

Example 3

(1) In a 10 mL Shrek tube, under nitrogen atmosphere, 0.3 mmol (E)-3-phenylprop-2-en-1-ol and 0.9 mmol 4-methoxybenzenesulfinic acid were added to 3 mL of dichloromethane and stirred at 40° C. for 10 h. The reaction equation is:

(2) After the reaction was completed as monitored by TLC, the solvent was removed by vacuum rotary evaporator and the product was separated by thin layer chromatography. The developing solvent was petroleum ether/ethyl acetate system (5/1). The product was a light yellow solid compound 7 with a yield of 69%.

Compound 7 was characterized as follows:

¹ H NMR (400MHz, Chloroform-d) δ7.82-7.77(m,2H),7.34-7.26(m,5H),7.01-6.95(m,2H),6.38(d,J＝15.9Hz,1H) ,6.16-6.06(m,1H),3.93(dd,J＝7.5,1.3Hz,2H),3.86(s,3H). ¹³ C NMR(100MHz,Chloroform-d)δ163.82,139.01,135.87,130.74,129.96,128.73,128.54,126.68,115.56,114.33,60.77,55.75.IR(KBr):3013,2921,1648,131 7,1087,759cm ^-1 .HRMS(ESI/[M+H] ⁺ )Calcd.for:C ₁₆ H ₁₇ O ₃ S289.0898, found 289.0892.

The characterization results showed that compound 7 was 1-(cinnamylsulfonyl)-4-methoxybenzene.

Example 4

(1) In a 10 mL Shrek tube, under nitrogen atmosphere, 0.3 mmol (E)-3-cyclohexylprop-2-en-1-ol and 0.9 mmol benzenesulfinic acid were added to 3 mL of dichloromethane and stirred at 40° C. for 18 h. The reaction equation is:

(2) After the reaction was completed as monitored by TLC, the solvent was removed by vacuum rotary evaporator and the product was separated by thin layer chromatography. The developing solvent was petroleum ether/ethyl acetate system (5/1). The product was a light yellow liquid compound 9 with a yield of 48%.

Compound 9 was characterized, and its magnetic spectra are shown in Figures 5 and 6, specifically:

¹ H NMR (400MHz, Chloroform-d) δ7.84 (m, 2H), 7.64 (td, J = 7.1, 3.3Hz, 1H), 7.54 (t, J = 7.7Hz, 2H), 5.41-5.30 (m ¹³ C NMR(100MHz,Chloroform-d)δ147.41,138.14,133.68,128.98,128.74,113.77,60.32,40.75,32.29,26.02,25.80.IR(KBr):3064,2924,1661,1446,1318,748cm ^-1.HRMS (ESI/[M+H] ⁺ )Calcd.for:C ₁₅ H ₂₁ O ₂ S265.1262, found 265.1256.

Nuclear characterization results showed that compound 9 was (E)-((3-cyclohexylallyl)sulfonyl)benzene.

Example 5

(1) In a 10 mL Shrek tube, under nitrogen atmosphere, 0.3 mmol 5,9-dimethyldeca-1,8-dien-3-ol and 1.2 mmol benzenesulfinic acid were added to 3 mL dichloromethane and stirred at 40°C for 24 h. The reaction equation is:

(2) After the reaction was completed as monitored by TLC, the solvent was removed by a vacuum rotary evaporator and the product was separated by thin layer chromatography using a petroleum ether/ethyl acetate system (10/1) as the developing solvent. The product was a light yellow liquid compound 11 with a yield of 43%.

Compound 11 was characterized, and its NMR spectra are shown in Figures 7 and 8, specifically:

¹ H NMR (400MHz, Chloroform-d) δ7.86 (dq, J＝8.4, 1.5Hz, 2H), 7.67-7.61 (m, 1H), 7.59-7.50 (m, 2H), 5.56-5.45 (m, 1H),5.43-5.30(m,1H),5.10-5.00(m,1H),3.77(d,J＝7.1Hz,2H),2.09-1.77(m,4H),1.68(s,3H),1.60 (d,J＝12.7Hz,3H),1.49-1.32(m,1H),1.28-1.16(m,1H),1.12-0.97(m,1H),0.75(d,J＝6.6Hz,3H). ^13C NMR(100MHz,Chloroform-d)δ140.59,138.42,133.72,131.45,129.14,128.59,124.66,117.10,60.30,40.04,36.58,32.39,25.87,25.56,19.34,17.79.IR( KBr):3063,2961,2920 ,2854,1664,1319,764cm ^{- 1} .HRMS(ESI/[M+H] ⁺ )Calcd.for:C ₁₈ H ₂₇ O ₂ S 307.1732, found 307.1723.

The characterization results showed that compound 11 was (E)-(5,9-dimethyldeca-2,8-dien-1-yl)sulfonyl)benzene.

Example 6

This Example 6 is basically the same as Example 1, except for step (1): in a 250 mL Shrek tube, under a nitrogen environment, 7.5 mmol (E)-3-phenylprop-2-en-1-ol and 22.5 mmol benzenesulfinic acid were added to 75 mL dichloromethane, and the reaction was stirred at 40° C. for 12 h. The yield of the obtained product was 81%.

Embodiments 7 to 14

Examples 7 to 14 are substantially the same as Example 1, except that the differences are shown in Table 1 below:

Table 1 Comparison of differences

serial number Reaction solvent temperature H ₂ O(equiv.) HCOOH(equiv.) Yield Example 7 1,2-Dichloroethane 60℃ - - 72% Example 8 1,2-Dichloroethane 100℃ - - 63% Example 9 Toluene 60℃ - - 66% Example 10 Trifluorotoluene 80℃ - - 65% Embodiment 11 Dichloromethane 50℃ - - 75% Example 12 Trifluorotoluene 120℃ - - 55% Example 13 Dichloromethane 40℃ 1.0 - 74% Embodiment 14 Dichloromethane 40℃ - 2.0 74%

Examples 15 to 20

Examples 15 to 20 are substantially the same as Example 1, except that the differences are shown in Table 2 below:

Table 2 Comparison of differences

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. A method for preparing an allyl sulfone compound, characterized in that the method comprises the following steps: (1) Under an inert gas atmosphere, add sulfinic acid and allyl alcohol to a reaction solvent and stir the reaction at 20-60°C for 8-36 h; wherein: The sulfinic acid is selected from any one of normal aryl sulfinic acid, heteroaryl sulfinic acid, condensed ring sulfinic acid, straight chain aliphatic sulfinic acid and cyclic aliphatic sulfinic acid; The allyl alcohol is selected from any one of n-aryl allyl alcohol, heteroaryl allyl alcohol, condensed ring allyl alcohol, linear alkane allyl alcohol, and cyclic alkane allyl alcohol; The reaction solvent is selected from any one of dichloroethane, dichloromethane, trifluorotoluene and toluene; In step (1), the molar volume ratio of the sulfinic acid, allyl alcohol, and reaction solvent is 0.9 mmol: 0.3 mmol: 2-4 mL; (2) After the reaction is complete as monitored by TLC, the reaction solution obtained in step (1) is freed from the solvent and purified to obtain an allyl sulfone compound. 2. The method according to claim 1, characterized in that in step (1), the sulfinic acid is selected from any one of 4-methylbenzenesulfinic acid, 4-methoxybenzenesulfinic acid, 2-nitrobenzenesulfinic acid, trifluoromethylsulfinic acid, 4-fluorobenzenesulfinic acid, 4-(trifluoromethyl)benzenesulfinic acid, benzylsulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 4-chlorobenzenesulfinic acid, 4-(tert-butyl)benzenesulfinic acid, 2-naphthylsulfinic acid, 9-anthrylsulfinic acid, 3-methylbenzenesulfinic acid, thiophene-2-sulfinic acid, furan-2-sulfinic acid, pyridine-2-sulfinic acid, indole-3-sulfinic acid, ethylsulfinic acid, butylsulfinic acid, methylsulfinic acid, cyclopropanesulfinic acid, and dextrorotatory camphorsulfinic acid. 3. The method according to claim 1, characterized in that in step (1), the allyl alcohol is selected from ( E )-3-phenylprop-2-en-1-ol, ( E )-3-(4-fluorophenyl)prop-2-en-1-ol, ( E )-3-(3-fluorophenyl)propyl-2-en-1-ol, ( E )-3-(4-(trifluoromethyl)phenyl)propyl-2-en-1-ol, ( E )-3-(4-bromophenyl)propyl-2-en-1-ol, ( E )-3-(4-methoxyphenyl)propyl-2-en-1-ol, ( E)-3-(4-nitrophenyl)prop-2-en-1-ol, (E ) -3-(2-nitrophenyl)prop-2-en-1-ol, (E)-3-(thiophen-2-yl)prop-2-en-1-ol, ( E )-3-(4-(trifluoromethyl)phenyl ) propyl-2-en-1-ol, )-3-(pyridin-3-yl)propyl-2-en-1-ol, ( E )-3-(furan-2-yl)propyl-2-en-1-ol, ( E )-3-(indol-2-yl)propyl-2-en-1-ol, ( E )-3-(4-(tert-butyl)phenyl)propyl-2-en-1-ol, ( E )-3-(3,5-dimethylphenyl)propyl-2-en-1-ol, 1-(naphthalen-2-yl)propyl-2-en-1-ol, 1-(anthracen-2-yl)propyl-2-en-1-ol ( E )-3-(4-((trimethylsilyl)ethynyl)phenyl)propyl-2-en-1-ol, ( E )-5,9-dimethyldecan-2,8-dien-1-ol, ( E any one of ( E )-3-(3-phenoxyphenyl)propyl-2-en-1-ol, ( E )-2-bromopropane-3-phenylpropyl-2-en-1-ol, ( E )-3-phenylbutyl-2-en-1-ol, ( E )-2-methyl-3-phenylprop-2-en-1-ol, (E)-3-cyclohexylprop-2-en-1-ol, ( E )-5,9-dimethyldeca-1,8-dien-3-ol, (2E , 4E )-5-phenyl-2,4-pentadien-1-ol, ( E )-4-phenyl-3-buten-2-ol, ( E )-3-(2-methoxyphenyl)propyl-2-en-1-ol and ( E )-3-methylprop-2-en-1-ol. 4. The method according to claim 1, characterized in that, in step (1), the reaction is stirred at 40°C for 10 h. 5. The method according to claim 1, characterized in that, in step (2), the solvent removal is to remove the reaction solvent by a vacuum rotary evaporator, and the purification is to purify by thin layer chromatography/column chromatography, and the developing solvent system is petroleum ether/ethyl acetate = 5/1.