JP7407651B2 - Method for producing 3-acetoxystyrene - Google Patents

Description

The present invention relates to a method for producing 3-acetoxystyrene, a compound useful as an intermediate material for hydroxystyrene polymers, which are known to be useful as photoresist materials.

Hydroxystyrene derivatives, such as p-hydroxystyrene, are aromatic compounds that have potential utility in a wide variety of industrial applications.
In particular, with the recent miniaturization and high integration of semiconductor devices, there is a demand for photoresist materials with high resolution and high sensitivity. Hydroxystyrenes are known to be useful, and hydroxystyrene derivatives, which are raw materials for polyhydroxystyrenes, can be obtained by, for example, protecting the hydroxyl group in the molecule with an acetoxy group, an ethoxyethoxy group, a tetrahydropyranyl group, etc. These compounds are very useful as raw materials for resist materials.
Various methods for producing acetoxystyrene, in which the hydroxyl group of a hydroxystyrene derivative is protected with an acetoxy group, are conventionally known.

For example, for 3-acetoxystyrene, hydroxybenzaldehyde is acetylated to form acetoxybenzaldehyde, and then zinc metal is reacted with dibromomethane in an organic solvent using an active chloride such as trimethylchlorosilane or acetyl chloride as a catalyst to produce acetoxystyrene. A method for obtaining this is disclosed (see, for example, Patent Document 1).
Another method is to react 1-(3-acetoxyphenyl)ethylcarboxylate with an acidic catalyst such as a mineral acid, an acidic ion exchange resin, an organic acid, or an inorganic compound, and distill out the product acetoxystyrene by continuous distillation. Disclosed (for example, see Patent Document 2)
Furthermore, a method is disclosed in which meta-tertiary butoxystyrene is used as a starting material and reacted with an acetylating agent such as acetic anhydride in the presence of an aliphatic carboxylic acid catalyst such as formic acid, acetic acid, propionic acid, or oxalic acid. (For example, see Patent Document 3).
A method for obtaining 3-acetoxystyrene by a high-pressure reaction in an ethylene atmosphere using 3-acetoxybromobenzene as a starting material in the coexistence of a palladium catalyst and a base such as an amine has been disclosed (for example, see Patent Document 4).
However, in order to obtain the desired product using each of the above methods, highly toxic alkyl halides and highly flammable gases are used, equipment for special reactions, and processes for collecting and detoxifying by-product gases are required. I may need it. For this reason, these methods are not satisfactory as simple production methods with excellent safety and economy, and a further improved method has been desired.

Japanese Patent Application Publication No. 8-157410 Japanese Patent Application Publication No. 2004-331515 Japanese Patent Application Publication No. 10-316618 JP 2019-210274 Publication

The purpose of the present invention is to solve the drawbacks of the above-mentioned conventional techniques, to use industrially easily available raw materials, and to avoid using harmful reaction reagents or requiring special equipment. The object of the present invention is to provide a new method for producing 3-acetoxystyrene.

In order to solve the above problems, the present inventors conducted a detailed study on a method for producing 3-acetoxystyrene.
As a result, we found conditions for producing highly pure 3-acetoxystyrene using industrially easily available raw materials, without using harmful reaction reagents, or without requiring special equipment. The present invention has now been completed.

（一般式（１）中、Ｒ^１は、１－エトキシエチル基、１－シクロヘキシルオキシエチル基または２－テトラヒドロピラニル基を示し、Ｘは塩素原子、臭素原子またはヨウ素原子を示す。）で表される芳香族ハロゲン化合物とマグネシウムとを反応させる工程
ｉｉ） ｉ）で得られた反応生成物と臭化ビニルまたは塩化ビニルとを、ニッケル触媒の存在下で反応させて、一般式（２）

（一般式（２）中、Ｒ^１は１－エトキシエチル基、１－シクロヘキシルオキシエチル基または２－テトラヒドロピラニル基を示す。）で表されるオキシスチレン誘導体を得る工程
ｉｉｉ） ｉｉ）で得られたオキシスチレン誘導体を、スルホン酸化合物の存在下で、無水酢酸と反応させる工程 That is, the method for producing 3-acetoxystyrene of the present invention has the following configuration.
[1] A method for producing 3-acetoxystyrene, including the following steps i) to iii).
i) General formula (1) below

(In the general formula (1), R ¹ represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group, and X represents a chlorine atom, a bromine atom, or an iodine atom.) ii) The reaction product obtained in i) is reacted with vinyl bromide or vinyl chloride in the presence of a nickel catalyst to form a compound of general formula (2).

(In the general formula (2), R ¹ represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group.) Step iii) Obtaining an oxystyrene derivative represented by ii) A step of reacting the obtained oxystyrene derivative with acetic anhydride in the presence of a sulfonic acid compound.

[2] A method for producing 3-acetoxystyrene, wherein the sulfonic acid compound according to [1] is a compound selected from the group consisting of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

As described above, according to the present invention, highly pure 3- A method for producing acetoxystyrene can be provided.

（一般式（１）中、Ｒ^１は、１－エトキシエチル基、１－シクロヘキシルオキシエチル基、２－テトラヒドロピラニル基を示し、Ｘは塩素原子または臭素原子またはヨウ素原子を示す。）で表される芳香族ハロゲン化合物とマグネシウムを反応させ、
次いで得られた反応生成物と臭化ビニルまたは塩化ビニルとをニッケル触媒の存在下で反応させることで得られる、一般式（２）

（一般式（２）中のＲ^１は１－エトキシエチル基、１－シクロヘキシルオキシエチル基または２－テトラヒドロピラニル基を示す。）で表されるオキシスチレン誘導体を、スルホン酸化合物の存在下で、無水酢酸と反応させることを特徴とする３－アセトキシスチレンの製造方法に係る。さらに上記のスルホン酸化合物が、硫酸、メタンスルホン酸、ｐ－トルエンスルホン酸およびトリフルオロメタンスルホン酸からなる群から選ばれるものである方法に係る。 The present invention will be explained in detail below.
The method for producing 3-acetoxystyrene of the present invention is as follows.
General formula (1) below

(In the general formula (1), R ¹ represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group, and X represents a chlorine atom, a bromine atom, or an iodine atom.) Reacting the aromatic halogen compound and magnesium,
General formula (2) obtained by then reacting the obtained reaction product with vinyl bromide or vinyl chloride in the presence of a nickel catalyst.

(R ¹ in general formula (2) represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group.) In the presence of a sulfonic acid compound, an oxystyrene derivative represented by , relates to a method for producing 3-acetoxystyrene, which is characterized by reacting it with acetic anhydride. The method further relates to a method in which the above-mentioned sulfonic acid compound is selected from the group consisting of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.

Here, in this specification, the step i) of reacting the aromatic halogen compound represented by the general formula (1) with magnesium to obtain a reaction product is referred to as a Grignardization step or Grignardization reaction. Alternatively, the product obtained by the Grignardization step or the Grignardization reaction and vinyl bromide or vinyl chloride are reacted in the presence of a nickel catalyst to obtain an oxystyrene derivative represented by the above general formula (2).ii ) is called a cross-coupling process or cross-coupling reaction. Furthermore, the oxystyrene derivative represented by the above general formula (2) is reacted with acetic anhydride in the presence of a sulfonic acid compound to obtain 3-acetoxystyrene. That's what it means.

As described above, according to the present invention, a method for producing 3-acetoxystyrene is provided, and in particular, highly pure 3-acetoxystyrene can be produced by a simple process using a Grignard reaction, a cross-coupling reaction, and a functional group conversion reaction. We can provide a manufacturing method. Each step will be explained in detail below.

（一般式（１）中、Ｒ^１は、１－エトキシエチル基、１－シクロヘキシルオキシエチル基または２－テトラヒドロピラニル基を示し、Ｘは塩素原子、臭素原子またはヨウ素原子を示す。）で表される芳香族ハロゲン化合物とマグネシウムとを反応させる工程である。 <Grignard process (i) process)>
The Grignard process uses the following general formula (1)

(In the general formula (1), R ¹ represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group, and X represents a chlorine atom, a bromine atom, or an iodine atom.) This is a step of reacting an aromatic halogen compound and magnesium.

The amount of magnesium used in the Grignard process may be in the range of 0.8 to 2.0 times the mole, preferably 1.0 to 1.0 times the mole of the aromatic halogen compound used as the raw material. The range is 5 times the molar amount. If the amount is less than 0.8 times the molar amount, the aromatic halogen compound as a raw material may remain, and impurities resulting from the coupling reaction of unreacted aromatic halogen compounds with the Grignard reagent may increase, resulting in a decrease in yield. There is. Moreover, if it is more than 2.0 times the mole, post-treatment becomes complicated and a large amount of acidic aqueous solution used as a magnesium deactivator may be required, so it is preferable to avoid it from an economical point of view.

（一般式（２）中、Ｒ^１は１－エトキシエチル基、１－シクロヘキシルオキシエチル基または２－テトラヒドロピラニル基を示す。）で表されるオキシスチレン誘導体を得る工程である。 <Process of cross-coupling step (ii))>
In the cross-coupling step, the reaction product obtained in i) is reacted with vinyl bromide or vinyl chloride in the presence of a nickel catalyst to form a compound of general formula (2).

(In general formula (2), R ¹ represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group.) This is a process for obtaining an oxystyrene derivative represented by the following formula.

The amount of vinyl bromide or vinyl chloride used in the cross-coupling reaction may be at least 1.0 times the mole of the aromatic halogen compound represented by the general formula (1), and should be used in accordance with economic efficiency and post-treatment process. Considering the complexity involved, it is preferable that the amount is 1.4 times the mole or less.

The nickel catalyst used in the method of the present invention is not particularly limited as long as it is a nickel compound, and specific examples include Ni(acac) ₂ and NiCl ₂ .
In addition, various types of ligands may be used in combination, and methods for adding the ligand include methods in which the nickel compound and the ligand are reacted in advance outside the system, and then added; A method is adopted in which particles are added and prepared in-system. Any ligand may be used as long as it coordinates with the nickel compound, and phosphorus compounds, nitrogen compounds, olefin compounds, etc. are selected. In particular, phosphorus compounds are preferred as the ligand.
Specific examples of the ligand include 1,2-bis(diphenylphosphino)ethane [dppe], 1,3-bis(diphenylphosphino)propane [dppp], and 1,4-bis(diphenylphosphino)ethane [dppp]. ) Butane [dppb], triphenylphosphine, 1,1'-bis(diphenylphosphino)ferrocene [dppf], 2,2'-bis(diphenylphosphino)-1,1-binaphthyl [BINAP], bis(2 -diphenylphosphinophenyl) ether [DPEphos], 9,9-dimethyl-4,5-bis(diphenylphosphino)zanthene [XANTphos], tri-tert-butylphosphine, 1,5-cyclooctadiene [COD], Examples include 2,2'-bipyridyl.
The amount of the nickel catalyst to be used may be in the range of 0.01 mol% to 10 mol% based on the aromatic halogen compound represented by the general formula (1), and it is economical and complicated in the post-treatment process. In consideration of the cost, it is preferably 0.1 mol% to 2.0 mol%. Further, the amount of the ligand to be used is not particularly limited, but is selected from a range of 0.5 times to 10 times the molar amount of the metal of the nickel compound.

The solvent for the Grignard reaction and subsequent cross-coupling reaction used in the method of the present invention is not particularly limited, but ether solvents and aromatic hydrocarbon solvents are preferably used, and specifically, tetrahydrofuran , cyclopentyl methyl ether, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, benzene, toluene, xylene and the like. Furthermore, the solvents may be used singly or in combination.

The temperature of the Grignardization reaction in the method of the present invention ranges from 0° C. to the reflux temperature of the solvent. Preferably it is in the range of 10°C to 40°C. Further, the temperature of the cross-coupling reaction is in the range of -10°C to the reflux temperature of the solvent, preferably in the range of 0°C to 30°C.

As an embodiment of the cross-coupling reaction in the method of the present invention, it may be carried out by adding vinyl bromide or vinyl chloride to a solution of the prepared Grignard reagent, or by adding vinyl bromide or vinyl chloride to a solution of the prepared Grignard reagent. The reaction may be carried out by adding a Grignard reagent.
After the reaction is completed, the reaction solution is treated with an acidic aqueous solution according to a conventional method, and then the organic layer is separated. Subsequently, the organic layer is washed with water, the solvent is distilled off, and then the desired oxystyrene derivative can be obtained by ordinary purification operations such as distillation and recrystallization.
Note that the oxystyrene derivative can be used in the next functional group conversion step by simply distilling off the solvent without performing any purification operations such as distillation or recrystallization. Although not particularly limited, in the water washing treatment of the organic layer, it is more preferable to wash the aqueous layer separated from the organic layer to a pH of 8 or less in order to prevent deactivation of the sulfonic acid compound in the next step.

<Step of functional group conversion step (iii))>
The functional group conversion step is a step of reacting the oxystyrene derivative obtained in ii) with acetic anhydride in the presence of a sulfonic acid compound.

The sulfonic acid compound is not particularly limited as long as it is a known sulfonic acid compound, but examples include sulfuric acid and organic sulfonic acids.More specifically, methanesulfonic acid, ethanesulfonic acid, and trifluoromethane. Aliphatic sulfonic acids such as sulfonic acid and camphorsulfonic acid, aromatic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, biphenylsulfonic acid, naphthalenesulfonic acid, and p-toluidine sulfonic acid, polystyrene sulfone Acids, polymeric sulfonic acids such as polynaphthalenesulfonic acid, polyvinylsulfonic acid, etc. can be mentioned. Among these sulfonic acid compounds, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid are preferred, and one type can be used alone or two or more types can be used in any combination.
Although not particularly limited, it is usually used in an amount of 0.1 mol % to 50 mol % based on the oxystyrene derivative represented by the general formula (2).

The amount of acetic anhydride to be used is preferably 0.8 to 5.0 equivalents relative to the oxystyrene derivative represented by the general formula (2) to be charged, in order to reduce reactivity and complexity of post-treatment. Considering this, the amount is more preferably 1.0 to 2.5 equivalents.

In the present invention, the reaction in the functional group conversion step can be sufficiently carried out without a solvent, but it can also be carried out using a solvent. The solvent that can be used is not particularly limited as long as it is inert under the reaction conditions, for example, inert to the sulfonic acid compound used, and can maintain good stirring. For example, ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, organic halogen solvents, etc. may be used singly or in mixtures thereof, and among these, aromatic hydrocarbon solvents are preferred. Further, as the aromatic hydrocarbon solvent, specifically, toluene and xylene are preferable in consideration of reactivity, solvent removability (boiling point), and economical efficiency. Furthermore, the solvents may be used singly or in combination.

The reaction time of the reaction of the present invention is not particularly limited, but from the viewpoint of suppressing by-products, it is preferably 1 hour to 20 hours. Further, the reaction temperature of the reaction in the method of the present invention can be exemplified in the range of -10°C to 100°C, but preferably in the range of 0°C to 50°C.

After the reaction is completed, the reaction solution is treated with an alkaline aqueous solution according to a conventional method, and then the organic layer is separated. Subsequently, after distilling off the solvent, the desired 3-acetoxystyrene derivative is obtained by ordinary purification operations such as vacuum distillation and column chromatography.
In addition, when purifying by vacuum distillation, a known polymerization inhibitor can be added.

Examples of the present invention are shown below, but the present invention is not construed as being limited to these Examples.
Regarding the results of the acetoxylation reaction, gas chromatography analysis was conducted under the following conditions, and the conversion rate of the raw material and the selectivity of the target product were calculated from the peak area ratio.
・Device: GC-2014 manufactured by Shimadzu Corporation (manufactured by Shimadzu Corporation)
・Column: Capillary column NB-5 (manufactured by GL Sciences, Inc.)
Acetoxylation reaction raw material conversion rate (%) = Target GC area % / (Unreacted raw material GC area % + Target GC area %) × 100
Acetoxylation reaction selectivity (%) = (target GC area %/(raw material GC area % - unreacted raw material GC area %)) x 100

Synthesis example 1
502.65 g (2.91 mol) of 3-bromophenol, 14.90 g (0.13 mol) of trifluoroacetic acid, and 750 g of toluene were added to a 2L four-neck flask equipped with a thermometer at room temperature under a nitrogen atmosphere, and ethyl 241.32 g (3.35 mol) of vinyl ether was added dropwise at 20° C. over 3 hours. It was aged for 14 hours at the same temperature.

After the reaction was completed, the resulting reaction solution was cooled to 10° C., 280 g of a 20% aqueous sodium hydroxide solution was added, and the mixture was stirred for 30 minutes. After separation, the solvent was distilled off under reduced pressure to obtain 746.88 g of 3-(1-ethoxyethoxy)bromobenzene as a reddish brown liquid.

Example 1 Synthesis of 3-(1-ethoxyethoxy)styrene In a 2L four-necked flask equipped with a thermometer, 24.80 g (1.02 mmol) of magnesium powder and 234.15 g of tetrahydrofuran were added at room temperature and under a nitrogen atmosphere. The mixture was heated to 20° C. with stirring, and 5.29 g (48.6 mmol) of ethyl bromide was added dropwise over 10 minutes, followed by stirring at the same temperature for 30 minutes.
Furthermore, 215.82 g (pure content: 200.00 g, 0.82 mmol) of 3-(1-ethoxyethoxy)bromobenzene obtained in Synthesis Example 1 was added over 3 hours, and the mixture was further aged for 3 hours.
The conversion rate of 3-(1-ethoxyethoxy)bromobenzene was 100% and the selectivity was 98%.

After adding 2.05 g (3.91 mmol) of [1,3-bis(diphenylphosphino)propane]nickel(II) dichloride and 330.5 g of toluene to the Grignard reagent obtained by the above operation, the reaction temperature was lowered. While maintaining the temperature at 20 to 30°C, 61.5 g (0.98 mol) of vinyl chloride gas was blown into the reactor over 5 hours.
The conversion rate of the Grignard reagent was 97% and the selectivity was 97%.

After the reaction was completed, a 20% aqueous ammonium chloride solution was added to the reaction solution to dissolve the generated salt, and the organic layer was separated. After washing the obtained organic layer with a 20% aqueous sodium hydroxide solution, the solvent was distilled off under reduced pressure. 172.13 g of 3-(1-ethoxyethoxy)styrene was obtained as a reddish brown liquid.
The above operation was repeated multiple times, and the obtained 3-(1-ethoxyethoxy)styrene was used in the following examples.

Example 2 Synthesis of 3-(1-ethoxyethoxy)styrene In Example 1, after the reaction was completed, 20% ammonium chloride was added to dissolve the resulting salt, and the organic layer was separated. The same procedure as in Example 1 was performed until washing with a 20% aqueous sodium hydroxide solution.
Furthermore, the organic layer was washed with saturated brine until the pH of the aqueous layer became 8 or less, and then the solvent was distilled off under reduced pressure. 171.05 g of 3-(1-ethoxyethoxy)styrene was obtained as a reddish brown liquid.
By washing the organic layer with saturated saline, the amount of remaining alkaline components can be reduced, and the action of the sulfonic acid compound used in the next step can be made more efficient.

Example 3 Synthesis of 3-acetoxystyrene (sulfuric acid catalyst)
260.33 g (2.55 mol) of acetic anhydride, 3.33 g (34.0 mmol) of sulfuric acid, and 780 g of toluene were added to a 2L four-neck flask equipped with a thermometer at room temperature under a nitrogen atmosphere, and the mixture was heated at 20°C with stirring. Then, 443.16 g (purity: 334.58 g, 1.70 mol) of 3-(1-ethoxyethoxy)styrene obtained in Example 1 was added dropwise at the same temperature over 3 hours.
After the dropwise addition, 2.51 g (25.6 mmol) of sulfuric acid was added over 10 minutes, and the mixture was aged at 20° C. for 15 hours. The conversion rate of the acetoxylation reaction was 100%, and the selectivity was 93%.

After the reaction was completed, the reaction solution was cooled to 10° C., a 10% aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 30 minutes. Pure water was further added and the mixture was stirred for 30 minutes.
After separating the organic layer, 14.04 g of 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) as a polymerization inhibitor was dissolved in the organic layer, the solvent was distilled off under reduced pressure, and then the solvent was distilled off under reduced pressure. 142.25 g of a colorless transparent liquid was obtained.

As a result of analysis by nuclear magnetic resonance analysis and mass spectrometry, it was confirmed that the colorless solution was 3-acetoxystyrene. Further, as a result of analysis by gas chromatography, the purity of 3-acetoxystyrene was 99.3%.
When the oligomer concentration was measured by GPC, it was found that the oligomer concentration was 0.04%, indicating that the contamination of polymers was also suppressed.

Example 4 Synthesis of 3-acetoxystyrene (sulfuric acid catalyst, no addition)
260.33 g (2.55 mol) of acetic anhydride, 3.33 g (34.0 mmol) of sulfuric acid, and 780 g of toluene were added to a 2L four-neck flask equipped with a thermometer at room temperature under a nitrogen atmosphere, and the mixture was heated at 20°C with stirring. Then, 442.55 g (purity: 334.58 g, 1.70 mol) of 3-(1-ethoxyethoxy)styrene obtained in Example 2 was added dropwise at the same temperature over 3 hours.
It was further aged at 20°C for 3 hours. The conversion rate of the acetoxylation reaction was 100%, and the selectivity was 94%.
After the reaction solution was cooled to 10° C., a 2% aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 30 minutes.
After separating the organic layer, 14.04 g of 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) as a polymerization inhibitor was dissolved in the organic layer, the solvent was distilled off under reduced pressure, and then the solvent was distilled off under reduced pressure. 143.02 g of a colorless transparent liquid was obtained.

As a result of analysis by nuclear magnetic resonance analysis and mass spectrometry, it was confirmed that the colorless solution was 3-acetoxystyrene. Further, as a result of analysis by gas chromatography, the purity of 3-acetoxystyrene was 99.4%.
When the oligomer concentration was measured by GPC, it was found that the oligomer concentration was 0.06%, indicating that the contamination of polymers was also suppressed.

Example 5 Synthesis of 3-acetoxystyrene (trifluoromethanesulfonic acid catalyst)
Example 4 was carried out in the same manner as in Example 4, except that trifluoromethanesulfonic acid was used instead of sulfuric acid, and 145.41 g of a colorless and transparent solution was obtained (conversion rate was 100%). Further, as a result of analysis by gas chromatography, the purity of 3-acetoxystyrene was 99.0%.
Note that the oligomer concentration was 0.06%.

Example 6 Synthesis of 3-acetoxystyrene (toluenesulfonic acid catalyst)
Example 4 was carried out in the same manner as in Example 4, except that toluenesulfonic acid monohydrate was used instead of sulfuric acid, and 130.85 g of a colorless and transparent solution was obtained (conversion rate was 100%). Further, as a result of analysis by gas chromatography, the purity of 3-acetoxystyrene was 99.1%.
Note that the oligomer concentration was 0.03%.

Comparative Example 1 Synthesis of 3-acetoxystyrene (trifluoroacetic acid catalyst)
Example 4 was carried out in the same manner as in Example 4, except that trifluoroacetic acid was used instead of sulfuric acid. However, the conversion rate of the acetoxylation reaction was low at 5.9% compared to 100% in Examples 1 to 4.

The method for producing 3-acetoxystyrene of the present invention does not require special equipment to repair by-product gas or require high-temperature reaction, so it is a simple and safe process that produces high-purity 3-acetoxystyrene. It is possible to produce acetoxystyrene. Therefore, the present invention is industrially very effective.

Claims (2)

Method for producing 3-acetoxystyrene including the following steps i) to iii) i) The following general formula (1)

(In the general formula (1), R ¹ represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group, and X represents a chlorine atom, a bromine atom, or an iodine atom.) ii) The reaction product obtained in i) is reacted with vinyl bromide or vinyl chloride in the presence of a nickel catalyst to form a compound of general formula (2).

(In the general formula (2), R ¹ represents a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, or a 2-tetrahydropyranyl group.) Step iii) Obtaining an oxystyrene derivative represented by ii) A step of reacting the obtained oxystyrene derivative with acetic anhydride in the presence of a sulfonic acid compound. The manufacturing method according to claim 1, wherein the sulfonic acid compound is a compound selected from the group consisting of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.