Preparation method and application of tetrahydrofuran cyclostyrene compound

Abstract

The invention relates to the field of organic synthesis, in particular to a preparation method and application of a tetrahydrofuran cyclostyrene compound. The method comprises the following steps: under the condition of a first solvent, carrying out contact reaction on an alpha-aryl-2-methyl butenol compound and an optional cyclization reagent; the tetrahydrofuran cyclostyrene compound has a structure as shown in a formula (1). In the # imgabs0 # formula (1), R1 is selected from hydrogen, saturated alkane, saturated alkoxy, cyclic hydrocarbon and aromatic hydrocarbon; r2 is selected from hydrogen, saturated alkane, saturated alkoxy, cyclic hydrocarbon and aromatic hydrocarbon. The tetrahydrofuran cyclostyrene compound prepared by the method has the advantages of simple process and high synthesis efficiency.

Description

Technical Field

[0001] The invention relates to the field of organic synthesis, and in particular to a preparation method and application of a tetrahydrofuran cyclostyrene compound. Background Art

[0002] In recent years, with the rapid development of large-scale and ultra-large-scale integrated circuits, photoresist, as one of the key materials for fine pattern processing in microelectronics technology, has also ushered in a period of rapid development. Photoresist, also known as photoresist and photoresist material, is the most critical material in the photolithography process. Through photochemical reactions, the required fine patterns are transferred from the mask to the substrate to be processed through photolithography processes such as exposure and development. Photolithography technology is widely used in the modern electronic information industry. Photolithography technology is the smallest and most precise processing technology that humans can achieve so far. Photoresist is the key material of photolithography technology. Photolithography is the longest and most difficult process in the entire integrated circuit manufacturing process, accounting for about 50% of IC manufacturing time and about 1 / 3 of IC production cost. Photoresist is the most important consumable in the photolithography process, and the quality of photoresist has an important impact on the photolithography process.

[0003] Photoresist is mainly composed of film-forming resin, photosensitizer (photoinitiator, photosensitizer or photoacid generator, etc.), organic solvent, additives and other additives. After being exposed to light sources of different wavelengths, the photoresist can undergo polymerization, cross-linking or photolysis in the exposed area, causing significant changes in the physical properties of the material, especially solubility and affinity; after being treated with appropriate solvents to dissolve the soluble part, the pattern designed on the mask can be transferred to the substrate.

[0004] According to the different exposure wavelengths, integrated circuit photoresists have experienced a development process since the 1980s, from ultraviolet photoresists (UV, G line 436nm and I line 365nm) to deep ultraviolet photoresists (DUV, KrF 248nm and ArF 193nm) and then to the next generation of extreme ultraviolet photoresists (EUV, 13.5nm). The development of photoresists directly affects the development of integrated circuit processes.

[0005] Film-forming resin plays a decisive role in the various properties of photoresist. Film-forming resin is generally formed by free radical copolymerization of multiple monomers. 248nm photoresist generally has the following requirements for the main resin: 1) high light transparency at 248nm wavelength; 2) high resolution and 3) high resistance to dry corrosion. Among the common synthetic monomers, p-hydroxystyrene contains a benzene ring structure that can be used to improve the etching resistance of photoresist. The hydroxyl group in the structure is soluble in alkaline solution and plays a solubilizing role. The chemically amplified photoresist formed by partially protecting the hydroxyl groups on p-hydroxystyrene and its derivatives can not only improve the shortcomings brought by full protection of the hydroxyl groups, but also improve the sensitivity of the photoresist, becoming the most widely used film-forming resin in the field of 248nm photoresist.

[0006] Tetrahydrofuran cyclostyrene compounds can be prepared by a carbon-carbon bond coupling method for the preparation of photoresists. However, due to the presence of substituents on the benzene ring, the regioselectivity of the coupling reaction is low, resulting in many preparation steps and low yield in the entire process. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of complicated 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, wherein the preparation method has the advantages of simple process and high synthesis efficiency.

[0008] In order to achieve the above object, the present invention provides a method for preparing a tetrahydrofuran cyclostyrene compound, the method comprising: contacting and reacting an α-aryl-2-methylbutenol compound with a cyclization reagent under a first solvent condition; 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; and R2 is selected from hydrogen, saturated alkanes, saturated alkoxy groups, cyclic hydrocarbons, and aromatic hydrocarbons.

[0011] The second aspect of the present invention provides an application of a tetrahydrofuran cyclostyrene compound prepared by the preparation method described in the first aspect in the preparation of a photoresist.

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

[0013] The method for preparing tetrahydrofuran cyclostyrene compounds has the advantages of simple process and high synthesis efficiency. DETAILED DESCRIPTION

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

[0015] The present invention provides a method for preparing a tetrahydrofuran cyclostyrene compound, the method comprising: contacting and reacting an α-aryl-2-methylbutenol compound with an optional cyclization reagent;

[0016] The tetrahydrofuran cyclostyrene compound has a structure as shown in formula (1);

[0017]

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

[0019] The reaction formula is:

[0020]

[0021] The method 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 the formula (1), R1 is selected from hydrogen, C1-C6 straight-chain saturated alkanes, C1-C6 branched saturated alkanes, C1-C6 straight-chain saturated alkoxyl groups, C1-C6 branched saturated alkoxyl groups, C3-C6 cyclic hydrocarbons, and C6-C9 aromatic hydrocarbons; R2 is selected from hydrogen, C1-C6 straight-chain saturated alkanes, C1-C6 branched saturated alkanes, C1-C6 straight-chain saturated alkoxyl groups, C1-C6 branched saturated alkoxyl groups, C3-C6 cyclic hydrocarbons, and C6-C9 aromatic hydrocarbons.

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

[0024] According to a preferred embodiment of the present invention, the non-chlorine halogenated hydrocarbon or hydrocarbon ether is at least one of n-butyl bromide, 2-butyl bromide, 2-ethyl ether, 2-isobutyl ether, cyclopentane bromide, and benzyl bromide; the alkyl benzene sulfonate is butyl benzene sulfonate, the alkyl p-toluene sulfonate is butyl p-toluene sulfonate, the alkyl methane sulfonate is butyl methane sulfonate, and the alkyl trifluoromethane sulfonate is butyl trifluoromethane sulfonate. By adopting the above-mentioned 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, chloroform, 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 comprises: mixing the cyclization reagent, the α-aryl-2-methylbutenol compound and the first solvent, cooling the mixture, and then adding a catalyst for reaction. By adopting the above-mentioned 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 comprises: 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 washing detergent 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 desiccant is selected from at least one of anhydrous sodium sulfate, anhydrous magnesium sulfate, anhydrous potassium carbonate and molecular sieves.

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

[0033] According to a preferred embodiment of the present invention, the solvent removal method is at least one of reduced pressure distillation, atmospheric pressure 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 of 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 contact reaction conditions include: time is 0.1-20h, preferably 1-8h.

[0037] According to a preferred embodiment of the present invention, the conditions of the contact reaction include: the mass ratio of the cyclization 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 the present invention, as long as the purpose of the present invention can be achieved, according to a preferred embodiment of the present invention, the catalyst is methanesulfonic acid. By adopting the above preferred scheme, 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 comprises: in an inert gas atmosphere, subjecting a Group VIII metal source, a second solvent, and an aromatic boronic acid to a first treatment, and then adding a sulfonic acid, a compound represented by formula (2), and butadiene to 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 comprises: diluting with a solvent, solid-liquid separation, removing the solvent and purifying after the second treatment.

[0045] According to a preferred embodiment of the present invention, the sulfonic acid is an aryl sulfonic acid, and preferably the sulfonic acid is at least one selected from 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 aromatic boronic acid is selected from one of 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, 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 of the first treatment include: the mass ratio of the solvent, the Group VIII metal compound and the aromatic boronic 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 of 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 of the first treatment include: a time of 0.1-5h, preferably 0.2-1h.

[0052] According to a preferred embodiment of the present invention, the conditions of 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 of the second treatment include: a time of 0.01-55h, preferably 10-30h.

[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 by the first treatment; the mass ratio of sulfonic acid, butadiene and the compound represented by formula (2) is 1-15:100-800:40-300, preferably 2-10:130-450:40-200.

[0055] The invention provides an application of a tetrahydrofuran cyclostyrene compound prepared by the preparation method in the preparation of a photoresist. The application method comprises: using the tetrahydrofuran cyclostyrene compound as a polymerizable monomer and reacting it with other polymerizable monomers to obtain a corresponding resin as an important raw material in the production of the photoresist.

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

[0057] In the following examples, unless otherwise specified, the raw materials are all commercially available.

[0058] Example 1

[0059] S1: In a 100mL autoclave, add 99.2mg of RuI3, 15g of tetrahydrofuran, and 61mg of phenylboric acid. After nitrogen replacement, stir at room temperature for 20 minutes. Then add 158mg of benzenesulfonic acid, 4.1g of p-vinylbenzyl alcohol, and 10g 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, add 15g of tetrahydrofuran to dilute, filter the insoluble matter with diatomaceous earth, and remove the solvent from the filtrate under reduced pressure. The residue is purified by column chromatography to obtain pure compound 1-1, 5.1g, with a yield of 90%.

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

[0061] Example 2

[0062] S1: In a 100mL autoclave, add 65.4mg of CoAc2, 15g of 2-methyltetrahydrofuran, and 61mg of phenylboric acid. After nitrogen replacement, stir at room temperature for 20 minutes. Then add 175mg of benzenesulfonic acid, 4.4g of 3-methyl-4-vinylbenzyl alcohol, and 10g 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, add 15g of 2-methyltetrahydrofuran to dilute, filter the insoluble matter with diatomaceous earth, and remove the solvent from the filtrate under reduced pressure. The residue is purified by column chromatography to obtain pure compound 2-1, 5.5g, with a yield of 91%.

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

[0064] Example 3

[0065] S1: In a 100mL autoclave, add 110mg of Ir(acac)3, 15g of xylene, and 70mg of phenylboric acid. After nitrogen replacement, stir at room temperature for 20 minutes. Then add 145mg of benzenesulfonic acid, 4.4g of 2-methyl-4-vinylbenzyl alcohol, and 10g 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, add 15g of xylene to dilute, filter the insoluble matter with diatomaceous earth, and remove the solvent from the filtrate under reduced pressure. The residue is purified by column chromatography to obtain pure compound 3-1, 5.5g, with a yield of 91%.

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

[0067] Example 4

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

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

[0070] Example 5

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

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

[0073] Example 6

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

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

[0076] Comparative Example 1

[0077] In a fully dried 250mL three-necked flask with a reflux condenser, add 4.2g of 2-bromo-4-butyl-3-methyltetrahydrofuran, 100g of anhydrous tetrahydrofuran, and 0.912g of magnesium powder. After nitrogen replacement, heat and reflux for 4 hours and cool naturally to room temperature. Cool the system to -10°C in an ice-salt bath, add 50g of anhydrous tetrahydrofuran solution containing 5.4g of triisopropyl borate, react at 60°C for 6 hours after the addition is completed, and cool naturally to room temperature. Slowly add 20g of 2mol / L hydrochloric acid solution and stir at room temperature for 2 hours. Filter the insoluble matter with diatomaceous earth, and remove the solvent from the filtrate under reduced pressure. The residue is purified by column chromatography to obtain 1.65g of pure compound with a yield of 46.7%. In a fully dried 250mL three-necked flask, add 1.65g of the above compound, 1.95g of p-bromostyrene, 99.4mg of palladium acetate, 142mg of di-tert-butyl methylphosphine, 2.98g of potassium tert-butoxide, and 100g of anhydrous tetrahydrofuran. After nitrogen substitution, react at room temperature for 24 hours. Filter the insoluble matter with diatomaceous earth, and evaporate the filtrate to remove the solvent under reduced pressure. The residue is purified by column chromatography to obtain 1.17g of pure compound with a yield of 54.3%.

[0078] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a tetrahydrofuran cyclostyrene compound, characterized in that: The method comprises: under a first solvent condition, an α-aryl-2-methylbutenol compound is contacted with an optional cyclization reagent for reaction; The tetrahydrofuran cyclostyrene compound has a structure as shown in formula (1); In formula (1), R1 is selected from hydrogen, saturated alkanes, saturated alkoxy groups, cyclic hydrocarbons, and aromatic hydrocarbons; and R2 is selected from hydrogen, saturated alkanes, saturated alkoxy groups, cyclic hydrocarbons, and aromatic hydrocarbons.

2. The preparation method according to claim 1, wherein In the formula (1), R1 is selected from hydrogen, C1-C6 straight-chain saturated alkanes, C1-C6 branched saturated alkanes, C1-C6 straight-chain saturated alkoxyl groups, C1-C6 branched saturated alkoxyl groups, C3-C6 cyclic hydrocarbons, and C6-C9 aromatic hydrocarbons; R2 is selected from hydrogen, C1-C6 straight-chain saturated alkanes, C1-C6 branched saturated alkanes, C1-C6 straight-chain saturated alkoxyl groups, C1-C6 branched saturated alkoxyl groups, C3-C6 cyclic hydrocarbons, and C6-C9 aromatic hydrocarbons.

3. The preparation method according to claim 1 or 2, wherein The cyclization agent is selected from at least one of alkyl non-chlorine halides, alkyl benzene sulfonates, alkyl p-toluene sulfonates, alkyl methane sulfonates and alkyl trifluoromethanesulfonates, preferably at least one of n-butyl bromide, 2-butyl bromide, 2-bromoethyl ether, 2-isobutyl ether, cyclopentane bromide, benzyl bromide, butyl benzenesulfonate, butyl p-toluenesulfonate, butyl methanesulfonate and butyl trifluoromethanesulfonate; and / or The first solvent is selected from at least one of dichloromethane, chloroform, 1,2-dichloroethane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,2-dimethyltetrahydrofuran and toluene.

4. The preparation method according to any one of claims 1 to 3, wherein The contact reaction step comprises: mixing a cyclization reagent, an α-aryl-2-methylbutenol compound and a first solvent, cooling the mixture, and then adding a catalyst for reaction; and / or The preparation method further comprises: 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 any one of claims 1 to 4, wherein: The conditions of the contact reaction include: The temperature is 5-60°C, preferably 20-35°C; and / or The time is 0.1-20h, preferably 1-8h; and / or The mass ratio of the cyclization reagent, the α-aryl-2-methylbutenol compound, the first solvent and the catalyst is 1-45:1-45:40-1000:1; preferably, the catalyst is methanesulfonic acid.

6. The preparation method according to any one of claims 1 to 5, wherein: The preparation of the α-aryl-2-methylbutenol compound comprises: in an inert gas atmosphere, subjecting a Group VIII metal source, a second solvent, and an aromatic boronic acid to a first treatment, and then adding a sulfonic acid, a compound represented by formula (2), and butadiene to a second treatment; 7. The preparation method according to claim 6, wherein: The sulfonic acid is an aryl sulfonic acid, preferably at least one selected from benzenesulfonic acid, p-toluenesulfonic acid, p-trifluoromethylbenzenesulfonic acid and 2,4,6-trimethylbenzenesulfonic acid; and / or The aryl boronic acid is selected from one of phenylboronic acid, 3-acyl-4-methylphenylboronic acid, 3-fluorophenylboronic acid and / or 2,4-difluorophenylboronic acid, preferably 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, ether and acetonitrile.

8. The preparation method according to claim 6 or 7, wherein: The Group VIII metal is at least one selected from Ru, Ir, Co and Rh, preferably Ru.

9. The preparation method according to any one of claims 6 to 8, wherein: The conditions of 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; and / or The temperature is 5-60°C, preferably 20-35°C; and / or The time is 0.1-5h, preferably 0.2-1h; and / or The conditions of the second treatment include: The temperature is 35-145°C, preferably 60-110°C; and / or The time is 0.01-55h, preferably 10-30h; and / or The mass of butadiene added is 20-200% of the total mass of the material obtained by the first treatment; the mass ratio of sulfonic acid, butadiene and the compound represented by formula (2) is 1-15:100-800:40-300, preferably 2-10:130-450:40-200.

10. Use of the tetrahydrofuran cyclostyrene compound prepared by the preparation method according to any one of claims 1 to 9 in the preparation of photoresist.

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