Process for the preparation of tetrahydrofuran-styrenes and their use

Abstract

The application relates to the field of organic synthesis, in particular to a preparation method and application of a tetrahydrofuran ring styrene compound. The method comprises the following steps: under the condition of a first solvent, an alpha-aryl-2-methyl butene alcohol compound is contacted with an optional cyclization reagent to react; the tetrahydrofuran ring styrene compound has a structure as shown in formula (1); in formula (1), R1 is selected from hydrogen, a saturated alkane, a saturated alkoxy, a cyclic hydrocarbon and an aromatic hydrocarbon; and R2 is selected from hydrogen, a saturated alkane, a saturated alkoxy, a cyclic hydrocarbon and an aromatic hydrocarbon. The tetrahydrofuran ring styrene compound prepared by the method has the advantages of simple flow and high synthesis efficiency.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, specifically to a method for preparing and applying tetrahydrofuran-based styrene compounds. Background Technology

[0002] In recent years, with the rapid development of large-scale and very large-scale integrated circuits, photoresist, as one of the key materials for micro-patterning in microelectronics technology, has also ushered in a period of rapid development. Photoresist, also known as photoresist or photoresist material, is the most critical material in the photolithography process. Through photochemical reactions, and after photolithography processes such as exposure and development, the required micro-patterns are transferred from a photomask to the substrate to be processed. Modern electronic information industries extensively utilize photolithography technology. Photolithography is the smallest and most precise processing technology achievable by mankind to date, and photoresist is the key material in photolithography. Photolithography is the most time-consuming and difficult process in the entire integrated circuit manufacturing process, accounting for about 50% of IC manufacturing time and about one-third of the cost. Photoresist is the most important consumable in the photolithography process, and its quality has a significant impact on the photolithography process.

[0003] Photoresist is mainly composed of film-forming resin, photosensitizers (photoinitiators, photosensitizers, or photoacid-generating agents, etc.), organic solvents, additives, and other components. After exposure to light sources of different wavelengths, the photoresist can polymerize, cross-link, or photodegrade in the exposed areas, causing significant changes in the material's physical properties, especially its solubility and affinity. After treating with appropriate solvents to dissolve the soluble portions, the pattern designed on the photomask can be transferred to the substrate.

[0004] Depending on the exposure wavelength, integrated circuit photoresists have evolved since the 1980s, progressing from ultraviolet (UV, G-line 436nm and I-line 365nm) to deep ultraviolet (DUV, KrF 248nm and ArF 193nm) photoresists, and then to the next generation of extreme ultraviolet (EUV, 13.5nm) photoresists. The development of photoresists directly impacts the development of integrated circuit manufacturing processes.

[0005] Film-forming resins play a decisive role in the various properties of photoresists. Film-forming resins are generally formed by free radical copolymerization of multiple monomers. 248nm photoresists typically require the following from their base resin: 1) high optical transparency at 248nm wavelength; 2) high resolution; and 3) high resistance to dry etching. Among common synthetic monomers, p-hydroxystyrene contains a benzene ring structure, which can be used to improve the etching resistance of photoresists. The hydroxyl groups in the structure are soluble in alkaline solutions, thus acting as a solubilizer. Chemically amplified photoresists, formed by partially protecting the hydroxyl groups on p-hydroxystyrene and its derivatives, not only overcome the shortcomings of full hydroxyl protection but also improve the sensitivity of the photoresist, making it the most widely used film-forming resin in the field of 248nm photoresists.

[0006] Tetrahydrofuran-based styrene compounds can be used to prepare photoresists via carbon-carbon coupling. However, due to the presence of substituents on the benzene ring, the regioselectivity of the coupling reaction is low, resulting in a complex preparation process with many steps and low yield. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of complex preparation process and low synthesis efficiency of tetrahydrofuran cyclostyrene compounds in the prior art, and to provide a new preparation method and application of tetrahydrofuran cyclostyrene compounds. This preparation method has the advantages of simple process and high synthesis efficiency.

[0008] To achieve the above objectives, the present invention provides a method for preparing a tetrahydrofuran cyclostyrene compound, the method comprising: reacting an α-aryl-2-methylbutenol compound with a cyclizing agent under a first solvent condition; wherein the tetrahydrofuran cyclostyrene compound has a structure as shown in formula (1);

[0009]

[0010] In formula (1), R1 is selected from hydrogen, saturated alkanes, saturated alkoxy groups, cyclic hydrocarbons, and aromatic hydrocarbons; R2 is selected from hydrogen, saturated alkanes, saturated alkoxy groups, cyclic hydrocarbons, and aromatic hydrocarbons.

[0011] The second aspect of this invention provides the application of a tetrahydrofuran-cyclostyrene compound prepared by the preparation method described in the first aspect in the preparation of photoresists.

[0012] Through the above technical solution, the present invention has the following advantages:

[0013] The method of this invention for preparing tetrahydrofuran-cyclostyrene compounds has the advantages of simple process and high synthesis efficiency. Detailed Implementation

[0014] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0015] This invention provides a method for preparing tetrahydrofuran-cyclic styrene compounds, the method comprising: reacting an α-aryl-2-methylbutenol compound with an optionally cyclizing agent;

[0016] The tetrahydrofuran ring styrene compound has the structure shown in formula (1);

[0017]

[0018] In formula (1), R1 is selected from hydrogen, saturated alkanes, saturated alkoxy groups, cyclic hydrocarbons, and aromatic hydrocarbons; R2 is selected from hydrogen, saturated alkanes, saturated alkoxy groups, cyclic hydrocarbons, and aromatic hydrocarbons.

[0019] The reaction formula is:

[0020]

[0021] The method of this invention for preparing tetrahydrofuran-cyclostyrene compounds has the advantages of simple process and high synthesis efficiency.

[0022] According to a preferred embodiment of the present invention, in formula (1), R1 is selected from hydrogen, C1-C6 straight-chain saturated alkanes, branched C1-C6 saturated alkanes, C1-C6 straight-chain saturated alkoxy groups, branched C1-C6 saturated alkoxy groups, C3-C6 cyclic hydrocarbons, and C6-C9 aromatic hydrocarbons; R2 is selected from hydrogen, C1-C6 straight-chain saturated alkanes, branched C1-C6 saturated alkanes, C1-C6 straight-chain saturated alkoxy groups, branched C1-C6 saturated alkoxy groups, C3-C6 cyclic hydrocarbons, and C6-C9 aromatic hydrocarbons.

[0023] According to a preferred embodiment of the present invention, the cyclizing agent is selected from at least one of non-chlorohalogenated hydrocarbon or hydrocarbon ethers, alkylbenzene sulfonates, alkyl p-toluene sulfonates, alkyl methane sulfonates and alkyl trifluoromethane sulfonates, preferably non-chlorohalogenated hydrocarbon or hydrocarbon ethers.

[0024] According to a preferred embodiment of the present invention, the non-chlorohalogenated hydrocarbon or hydrocarbon ether is at least one selected from n-bromobutane, 2-bromobutane, 2-bromoethyl ethyl ether, 2-isobutyl ethyl ether, bromocyclopentane, and benzyl bromide; the alkylbenzene sulfonate is butyl benzenesulfonate, the alkyl p-toluenesulfonate is butyl p-toluenesulfonate, the alkyl methanesulfonate is butyl methanesulfonate, and the alkyl trifluoromethanesulfonate is butyl trifluoromethanesulfonate. By adopting the aforementioned preferred embodiment, the product synthesis efficiency can be further improved.

[0025] According to a preferred embodiment of the present invention, the first solvent is selected from at least one of dichloromethane, trichloromethane, 1,2-dichloroethane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,2-dimethyltetrahydrofuran, and toluene.

[0026] According to a preferred embodiment of the present invention, the contact reaction step includes: mixing the cyclizing agent, the α-aryl-2-methylbutenol compound, and the first solvent, cooling the mixture, and then adding the catalyst for reaction. By adopting the aforementioned preferred embodiment, the product synthesis efficiency can be further improved.

[0027] According to a preferred embodiment of the present invention, the cooling method is ice-water bath cooling.

[0028] According to a preferred embodiment of the present invention, the preparation method further includes: after the contact reaction, quenching, washing, separation of the organic phase, drying, solid-liquid separation, solvent removal and purification.

[0029] According to a preferred embodiment of the present invention, the quenching method is quenching with ice water.

[0030] According to a preferred embodiment of the present invention, the detergent for washing is selected from at least one of sodium bicarbonate solution, sodium carbonate solution, potassium bicarbonate solution, and potassium carbonate solution.

[0031] According to a preferred embodiment of the present invention, the drying agent is selected from at least one of anhydrous sodium sulfate, anhydrous magnesium sulfate, anhydrous potassium carbonate, and molecular sieve.

[0032] According to a preferred embodiment of the present invention, the solid-liquid separation method is at least one of filtration, vacuum filtration, etc.

[0033] According to a preferred embodiment of the present invention, the solvent removal method is at least one of vacuum distillation, atmospheric distillation, and freeze drying.

[0034] According to a preferred embodiment of the present invention, the purification method is at least one of chromatography, recrystallization, and distillation.

[0035] According to a preferred embodiment of the present invention, the conditions for the contact reaction include a temperature of 5-60°C, preferably 20-35°C.

[0036] According to a preferred embodiment of the present invention, the conditions for the contact reaction include a time of 0.1-20 hours, preferably 1-8 hours.

[0037] According to a preferred embodiment of the present invention, the conditions for the contact reaction include: the mass ratio of the cyclizing reagent, the α-aryl-2-methylbutenol compound, the first solvent, and the catalyst is 1-45∶1-45∶40-1000∶1.

[0038] By adopting the aforementioned preferred contact conditions, the product synthesis efficiency can be further improved.

[0039] In this invention, any method that achieves the objective of the invention is acceptable. According to a preferred embodiment of the invention, the catalyst is methanesulfonic acid. By employing the aforementioned preferred method, the product synthesis efficiency can be improved.

[0040] According to a preferred embodiment of the present invention, the preparation of the α-aryl-2-methylbutenol compound includes: performing a first treatment on a group VIII metal source, a second solvent, and arylboronic acid under an inert gas atmosphere, and then adding sulfonic acid, the compound shown in formula (2), and butadiene for a second treatment;

[0041]

[0042] The reaction formula is:

[0043]

[0044] According to a preferred embodiment of the present invention, the preparation of the α-aryl-2-methylbutenol compound further includes: dilution with solvent, solid-liquid separation, solvent removal and purification after the second treatment.

[0045] According to a preferred embodiment of the present invention, the sulfonic acid is an aryl sulfonic acid, preferably selected from at least one of benzenesulfonic acid, p-toluenesulfonic acid, p-trifluoromethylbenzenesulfonic acid and 2,4,6-trimethylbenzenesulfonic acid.

[0046] According to a preferred embodiment of the present invention, the arylboronic acid is selected from phenylboronic acid, 3-acyl-4-methylphenylboronic acid, 3-fluorophenylboronic acid and / or 2,4-difluorophenylboronic acid, preferably phenylboronic acid.

[0047] According to a preferred embodiment of the present invention, the second solvent is selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,2-dimethyltetrahydrofuran, toluene, p-xylene, o-xylene, m-xylene, dichloromethane, chloroform, diethyl ether, and acetonitrile.

[0048] According to a preferred embodiment of the present invention, the Group VIII metal is selected from at least one of Ru, Ir, Co and Rh, preferably Ru.

[0049] According to a preferred embodiment of the present invention, the conditions for the first treatment include: the mass ratio of the solvent, the group VIII metal compound and the arylboronic acid is 70-350:0.01-15:1, preferably 90-250:0.5-8:1.

[0050] According to a preferred embodiment of the present invention, the conditions for the first treatment include: a temperature of 5-60°C, preferably 20-35°C.

[0051] According to a preferred embodiment of the present invention, the conditions for the first processing include: a time of 0.1-5 hours, preferably 0.2-1 hours.

[0052] According to a preferred embodiment of the present invention, the conditions for the second treatment include: a temperature of 35-145°C, preferably 60-110°C.

[0053] According to a preferred embodiment of the present invention, the conditions for the second processing include: a time of 0.01-55 h, preferably 10-30 h.

[0054] According to a preferred embodiment of the present invention, the conditions of the second treatment include: the mass of butadiene added is 20-200% of the total mass of the material obtained from the first treatment; the mass ratio of sulfonic acid, butadiene and the compound shown in formula (2) is 1-15:100-800:40-300, preferably 2-10:130-450:40-200.

[0055] This invention provides an application of the tetrahydrofuran cyclostyrene compound prepared by the above preparation method in the preparation of photoresist. The application method includes: using the tetrahydrofuran cyclostyrene compound as a polymerizing monomer and other polymerizing monomers to obtain the corresponding resin through polymerization reaction, which is an important raw material in the production of photoresist.

[0056] The present invention will be described in detail below through embodiments.

[0057] Unless otherwise specified, the raw materials used in the following examples are all commercially available products.

[0058] Example 1

[0059] S1: In a 100 mL autoclave, add 99.2 mg of RuI3, 15 g of tetrahydrofuran, and 61 mg of phenylboronic acid. After purging with nitrogen, stir at room temperature for 20 minutes. Then add 158 mg of benzyl sulfonic acid, 4.1 g of p-vinylbenzyl alcohol, and 10 g of cooled butadiene, and react at 85 °C for 20 hours. After natural cooling, carefully release the gas in a fume hood. Collect the residue in the autoclave, dilute with 15 g of tetrahydrofuran, filter through diatomaceous earth to remove insoluble matter, and remove the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 1-1, 5.1 g, yield 90%.

[0060] S2: In a 250 mL three-necked flask, add 130 g of dichloromethane, 5.1 g of compound 1-1, and 4.4 g of n-butane bromide. Cool in an ice-water bath for 10 min, then add 0.3 g of catalyst dropwise. After the addition is complete, stir the mixture at room temperature for 5 h. After the reaction is complete, quench the reaction with ice water, wash with saturated sodium bicarbonate solution, separate the organic phase, dry with anhydrous sodium sulfate, filter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give 4.8 g of pure compound 1-2, yield 72%.

[0061] Example 2

[0062] S1: In a 100 mL autoclave, add 65.4 mg of CoAc2, 15 g of 2-methyltetrahydrofuran, and 61 mg of phenylboronic acid. After purging with nitrogen, stir at room temperature for 20 minutes. Then add 175 mg of benzenesulfonic acid, 4.4 g of 3-methyl-4-vinylbenzyl alcohol, and 10 g of cooled butadiene. React at 85 °C for 20 hours. After natural cooling, carefully release the gas in a fume hood. Collect the residue in the autoclave, dilute with 15 g of 2-methyltetrahydrofuran, filter through diatomaceous earth to remove insoluble matter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give 5.5 g of pure compound 2-1, yield 91%.

[0063] S2: In a 250 mL three-necked flask, add 130 g of dichloromethane, 5.5 g of compound 2-1, and 4.6 g of n-butane bromide. Cool in an ice-water bath for 10 min, then add 0.4 g of catalyst dropwise. After the addition is complete, stir the mixture at room temperature for 5 h. After the reaction is complete, quench the reaction with ice water, wash with saturated sodium bicarbonate solution, separate the organic phase, dry with anhydrous sodium sulfate, filter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 2-2, 5.4 g, yield 71%.

[0064] Example 3

[0065] S1: In a 100 mL autoclave, add 110 mg of Ir(acac)3, 15 g of xylene, and 70 mg of phenylboronic acid. After purging with nitrogen, stir at room temperature for 20 minutes. Then add 145 mg of benzenesulfonic acid, 4.4 g of 2-methyl-4-vinylbenzyl alcohol, and 10 g of cooled butadiene. React at 85 °C for 20 hours. After natural cooling, carefully release the gas in a fume hood. Collect the residue in the autoclave, dilute with 15 g of xylene, filter through diatomaceous earth to remove insoluble matter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 3-1, 5.5 g, yield 91%.

[0066] S2: In a 250 mL three-necked flask, add 130 g of dichloromethane, 5.5 g of compound 3-1, and 5.0 g of n-butane bromide. Cool in an ice-water bath for 10 min, then add 0.5 g of catalyst dropwise. After the addition is complete, stir the mixture at room temperature for 5 h. After the reaction is complete, quench the reaction with ice water, wash with saturated sodium bicarbonate solution, separate the organic phase, dry with anhydrous sodium sulfate, filter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 3-2, 5.5 g, in 72% yield.

[0067] Example 4

[0068] S1: In a 100 mL autoclave, add 70.5 mg of CoAc2, 15 g of tetrahydrofuran, and 61 mg of phenylboronic acid. After purging with nitrogen, stir at room temperature for 20 minutes. Then add 158 mg of benzyl sulfonic acid, 4.1 g of p-vinylbenzyl alcohol, and 10 g of cooled butadiene. React at 85 °C for 20 hours. After natural cooling, carefully release the gas in a fume hood. Collect the residue in the autoclave, dilute with 15 g of tetrahydrofuran, filter through diatomaceous earth to remove insoluble matter, and remove the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 4-1, 5.0 g, yield 87%.

[0069] S2: In a 250 mL three-necked flask, add 130 g of dichloromethane, 5.0 g of compound 1-1, and 4.4 g of n-butane bromide. Cool in an ice-water bath for 10 min, then add 0.3 g of catalyst dropwise. After the addition is complete, stir the mixture at room temperature for 5 h. After the reaction is complete, quench the reaction with ice water, wash with saturated sodium bicarbonate solution, separate the organic phase, dry with anhydrous sodium sulfate, filter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 4-2, 4.4 g, yield 71%.

[0070] Example 5

[0071] S1: In a 100 mL autoclave, add 99.2 mg of RuI3, 15 g of tetrahydrofuran, and 61 mg of phenylboronic acid. After purging with nitrogen, stir at room temperature for 20 minutes. Then add 158 mg of benzyl sulfonic acid, 4.1 g of p-vinylbenzyl alcohol, and 10 g of cooled butadiene, and react at 85 °C for 20 hours. After natural cooling, carefully release the gas in a fume hood. Collect the residue in the autoclave, dilute with 15 g of tetrahydrofuran, filter through diatomaceous earth to remove insoluble matter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 5-1, 5.1 g, yield 90%.

[0072] S2: In a 250 mL three-necked flask, add 130 g of dichloromethane, 5.1 g of compound 5-1, and 5.5 g of butyl benzenesulfonate. Cool in an ice-water bath for 10 min, then add 0.3 g of catalyst dropwise. After the addition is complete, stir the mixture at room temperature for 5 h. After the reaction is complete, quench the reaction with ice water, wash with saturated sodium bicarbonate solution, separate the organic phase, dry with anhydrous sodium sulfate, filter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 5-2, 5.3 g, in 67% yield.

[0073] Example 6

[0074] S1: In a 100 mL autoclave, add 99.2 mg of RuI3, 15 g of tetrahydrofuran, and 61 mg of phenylboronic acid. After purging with nitrogen, stir at room temperature for 20 minutes. Then add 158 mg of benzyl sulfonic acid, 4.1 g of p-vinylbenzyl alcohol, and 10 g of cooled butadiene, and react at 85 °C for 20 hours. After natural cooling, carefully release the gas in a fume hood. Collect the residue in the autoclave, dilute with 15 g of tetrahydrofuran, filter through diatomaceous earth to remove insoluble matter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give pure compound 6-1, 5.1 g, in 90% yield.

[0075] S2: In a 250 mL three-necked flask, add 130 g of dichloromethane, 5.1 g of compound 6-1, and 6.9 g of butyl benzenesulfonate. Cool in an ice-water bath for 10 min, then add 0.3 g of catalyst dropwise. After the addition is complete, stir the mixture at room temperature for 5 h. After the reaction is complete, quench the reaction with ice water, wash with saturated sodium bicarbonate solution, separate the organic phase, dry with anhydrous sodium sulfate, filter, and evaporate the solvent from the filtrate under reduced pressure. Purify the residue by column chromatography to give 4.5 g of pure compound 6-2, yield 68%.

[0076] Comparative Example 1

[0077] In a thoroughly dried 250 mL three-necked flask equipped with a reflux condenser, 4.2 g of 2-bromo-4-butyl-3-methyltetrahydrofuran, 100 g of anhydrous tetrahydrofuran, and 0.912 g of magnesium powder were added. After purging with nitrogen, the mixture was heated under reflux for 4 hours and then allowed to cool naturally to room temperature. The system was cooled to -10 °C using an ice-salt bath. 50 g of anhydrous tetrahydrofuran solution containing 5.4 g of triisopropyl borate was added dropwise. After the addition was complete, the reaction was carried out at 60 °C for 6 hours and then allowed to cool naturally to room temperature. 20 g of 2 mol / L hydrochloric acid solution was slowly added, and the mixture was stirred at room temperature for 2 hours. The insoluble matter was filtered through diatomaceous earth, and the solvent was removed from the filtrate by vacuum distillation. The residue was purified by column chromatography to give 1.65 g of pure compound, with a yield of 46.7%. In a thoroughly dried 250 mL three-necked flask, 1.65 g of the above compound, 1.95 g of p-bromostyrene, 99.4 mg of palladium acetate, 142 mg of di-tert-butylmethylphosphine, 2.98 g of potassium tert-butoxide, and 100 g of anhydrous tetrahydrofuran were added. After purging with nitrogen, the mixture was reacted at room temperature for 24 hours. The insoluble matter was filtered through diatomaceous earth, and the solvent was removed from the filtrate by vacuum distillation. The residue was purified by column chromatography to give 1.17 g of pure compound, in 54.3% yield.

[0078] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a tetrahydrofuran-cyclic styrene compound, characterized in that, The method includes: reacting an α-aryl-2-methylbutenol compound with a cyclizing agent under first solvent conditions; The tetrahydrofuran ring styrene compound has the structure shown in formula (1); ； In formula (1), R1 is selected from hydrogen, C1-C6 straight-chain saturated alkanes, branched C1-C6 saturated alkanes, C1-C6 straight-chain saturated alkoxy groups, branched C1-C6 saturated alkoxy groups, C3-C6 cyclic hydrocarbons, and C6-C9 aromatic hydrocarbons; R2 is selected from C1-C6 straight-chain saturated alkanes and branched C1-C6 saturated alkanes. The preparation of the α-aryl-2-methylbutenol compound includes: a first treatment of a group VIII metal source, a second solvent, and arylboronic acid under an inert gas atmosphere, followed by the addition of sulfonic acid, the compound shown in formula (2), and butadiene for a second treatment; ； The α-aryl-2-methylbutenol compounds have the structure shown in formula (3); The Group VIII metal is selected from at least one of Ru, Ir, Co, and Rh; The sulfonic acid is selected from at least one of benzenesulfonic acid, p-toluenesulfonic acid, p-trifluoromethylbenzenesulfonic acid, and 2,4,6-trimethylbenzenesulfonic acid; The cyclizing agent is selected from at least one of alkyl non-chloro halides, alkyl benzene sulfonates, alkyl p-toluene sulfonates, alkyl methane sulfonates, and alkyl trifluoromethane sulfonates.

2. The preparation method according to claim 1, wherein, The first solvent is selected from at least one of dichloromethane, trichloromethane, 1,2-dichloroethane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,2-dimethyltetrahydrofuran, and toluene.

3. The preparation method according to claim 2, wherein, The cyclizing agent is selected from at least one of n-bromobutane, 2-bromobutane, butyl benzenesulfonate, butyl p-toluenesulfonate, butyl methanesulfonate, and butyl trifluoromethanesulfonate.

4. The preparation method according to claim 1, wherein, The contact reaction steps include: mixing the cyclizing agent, α-aryl-2-methylbutenol compound, and a first solvent, cooling the mixture, and then adding a catalyst to react; and / or The preparation method further includes: after the contact reaction, quenching, washing, separation of the organic phase, drying, solid-liquid separation, solvent removal and purification.

5. The preparation method according to claim 1, wherein, The conditions for the contact reaction include: Temperature is 5-60℃; and / or The time is 0.1-20 hours; and / or The mass ratio of the cyclizing agent, α-aryl-2-methylbutenol compound, first solvent, and catalyst is 1-45∶1-45∶40-1000∶1.

6. The preparation method according to claim 5, wherein, The conditions for the contact reaction include: The temperature is 20-35℃; and / or The time is 1-8 hours; and / or The catalyst is methanesulfonic acid.

7. The preparation method according to claim 1, wherein, The arylboronic acid is selected from phenylboronic acid; and / or The second solvent is selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,2-dimethyltetrahydrofuran, toluene, p-xylene, o-xylene, m-xylene, dichloromethane, chloroform, diethyl ether, and acetonitrile.

8. The preparation method according to claim 1, wherein... The group VIII metal is Ru.

9. The preparation method according to claim 1, wherein, The conditions for the first processing include: The mass ratio of the solvent, the Group VIII metal compound, and the arylboronic acid is 70-350:0.01-15:1; and / or Temperature is 5-60℃; and / or The time is 0.1-5 hours; and / or The conditions for the second processing include: Temperatures range from 35 to 145°C; and / or The time is 0.01-55h; and / or The mass of butadiene added is 20-200% of the total mass of the material obtained from the first treatment; the mass ratio of sulfonic acid, butadiene and the compound shown in formula (2) is 1-15:100-800:40-300.

10. The preparation method according to claim 9, wherein, The conditions for the first processing include: The mass ratio of the solvent, the Group VIII metal compound, and the arylboronic acid is 90-250:0.5-8:1; and / or The temperature is 20-35℃; and / or The time is 0.2-1 hour; and / or The conditions for the second processing include: Temperature is 60-110℃; and / or The time is 10-30 hours; and / or The mass of butadiene added is 20-200% of the total mass of the material obtained from the first treatment; the mass ratio of sulfonic acid, butadiene and the compound shown in formula (2) is 2-10:130-450:40-200.

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