JP2000178227A - Production of acetoxystyrenes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a photoresist material, etc., by one-stage process from an industrially readily obtainable inexpensive starting substance in a high yield by reacting a t-butoxystyrene in the presence of a catalyst. SOLUTION: (A) t-Butoxystyrene of formula I is reacted with (C) an acetylating agent in the presence of (B) a catalyst to give a compound of formula II such as o-acetoxystyrene. The component A is reacted by using acetic anhydride as the component C in the presence of at least one kind of polymerization inhibitor such as an acid amide of formula III (R1 is H or a 1-5C alkyl; R2 and R3 are each H, a 1-4C alkyl or phenyl). After the reaction is over, a neutralizing agent composed of an alkali is added to the obtained reaction mixture to neutralize the acid catalyst. Acetic acid and acetic anhydride are recovered by distillation. Preferably the obtained distillation residue is washed with water and distilled in the presence of a substituted phenol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing acetoxystyrenes.

[0002]

2. Description of the Related Art In recent years, with the background of miniaturization and high integration of semiconductor devices, photoresist materials having high resolution and high sensitivity have been demanded.
Chemically amplified resist materials for short-wavelength light such as KrF and ArF excimer lasers have been developed, and among them, polyhydroxystyrenes in which hydroxyl groups are protected by a protective group which is easily released by light irradiation are particularly useful. It is known. As such a raw material monomer for polyhydroxystyrenes, substituted oxystyrenes in which a hydroxyl group is protected by a protecting group, particularly acetoxystyrenes, have been widely used.

[0003] Various methods for producing such acetoxystyrenes are conventionally known. For example, Japanese Patent Application Laid-Open No. 8-157410 discloses that p-hydroxybenzaldehyde is acetylated to form p-acetoxybenzaldehyde, and in an organic solvent, zinc metal and an active chloride such as trimethylchlorosilane or acetyl chloride are used as a catalyst. A method for reacting methylene bromide is described. Polymer, 24, p. 995 (1983) describes a method based on the Wittg reaction in which p-acetoxybenzaldehyde is reacted with methyltriphenylphosphine bromide. J. Am. Chem. Soc., 80, p. 3645 (1985) states that p.
-A method for reacting a Grignard reagent with acetoxybenzaldehyde is described. European Patent Publication No. 355983 describes a method for dehydrating 1- (4-acetoxyphenyl) ethanol at high temperatures. Further, JP-A-6-192172 discloses that 1-
A method is described in which (4-acetoxyphenyl) ethanol is acetylated with acetyl chloride or acetic anhydride to form 1- (4-acetoxyphenyl) ethyl carboxylate, which is subjected to a high-temperature gas phase reaction.

In addition to the above, JP-A-2-47114 discloses that after brominating p-hydroxyacetophenone,
After acetylation with acetic anhydride to give 3,5-dibromo-4-acetoxybenzophenone, which was reduced with sodium borohydride to give 1- (3,5-dibromo-4-acetoxyphenyl) ethanol, Is dehydrated with potassium hydrogen sulfate to obtain 3,5-dibromo-4-acetoxystyrene.

[0005]

As described above, various methods for producing acetoxystyrenes have heretofore been known, but in many cases, hydroxybenzaldehydes or acetoxybenzaldehydes are used as starting materials, and special and expensive secondary methods are used. Since raw materials are used, it is difficult to adopt a method for producing acetoxystyrenes on an industrial scale.On the other hand, those requiring multiple reaction steps including a gas phase reaction at a high temperature not only increase the cost but also increase the production efficiency. Is bad, and wastewater,
A large amount of waste oil is emitted.

The present invention has been made to solve such problems in the production of acetoxystyrenes, and is intended to reduce the acetoxy styrene in one step from inexpensive starting materials which can be easily obtained industrially. An object of the present invention is to provide a method for producing styrenes at a high yield.

[0007]

According to the present invention, the compound represented by the general formula (I)

[0008]

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The tert-butoxystyrenes represented by the formula (II) are reacted with an acetylating agent in the presence of a catalyst.

[0010]

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There is provided a method for producing acetoxystyrenes represented by the formula:

[0012]

DETAILED DESCRIPTION OF THE INVENTION In the process according to the invention, the starting materials are of the general formula (I)

[0013]

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Tert-butoxystyrenes represented by the following formulas. Specific examples thereof include ot-butoxystyrene, pt-butoxystyrene and mt-butoxystyrene. pt-
Butoxystyrene. According to the present invention, corresponding to the above starting material, a compound represented by the general formula (II)

[0015]

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Acetoxystyrenes represented by the following formulas, ie, o-acetoxystyrene, p-acetoxystyrene or m-acetoxystyrene can be obtained. In particular, according to the present invention, p-acetoxystyrene can be preferably obtained from pt-butoxystyrene.

According to the present invention, the above-mentioned tert-butoxystyrene is reacted with an acetylating agent in the presence of a catalyst to obtain a target acetoxystyrene. Acetic anhydride or acetyl chloride is used, and among them, acetic anhydride is preferably used.
Such an acetylating agent is used in an amount of at least 1 part by mol, preferably 1.5 to 5 parts by mol, per 1 part by mol of the charged t-butoxystyrene.

Further, an acid catalyst is preferably used as the catalyst. Specific examples of the acid catalyst include mineral acids such as sulfuric acid and phosphoric acid, organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, and cation exchange resins such as polystyrenesulfonic acid.
Among these, organic sulfonic acids are preferred, and in particular,
p-Toluenesulfonic acid is preferably used. These acid catalysts are not particularly limited, but are usually used in the range of 5 to 50% by weight based on the charged t-butoxystyrenes.

According to the present invention, in order to prevent polymerization of t-butoxystyrene as a starting material and acetoxystyrene as a reaction product, it is necessary to prepare (a) a compound represented by the general formula (III):

[0020]

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(Wherein R ₁ is a hydrogen atom or a carbon number of 1 to 5)
R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. And amides represented by the formula (IV):

[0022]

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(Wherein X represents a hydrogen atom, a methyl group, an ethyl group or a hydroxyl group, Y represents a t-butyl group, a t-amyl group or a methoxy group, and m and n each represent an integer of 1-3. However, it is possible to react an acetylating agent with t-butoxystyrene in the presence of at least one polymerization inhibitor selected from the group consisting of substituted phenols represented by the formula: 2 ≦ m + n ≦ 5. preferable. Acid amides are not generally considered to be effective in preventing the polymerization of styrenes, but in the present invention are referred to as polymerization inhibitors together with the above substituted phenols.

The above acid amides include formamide,
Acetamide, N-methylformamide, propionamide, N, N-dimethylformamide, N-ethylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N, N-diethylformamide,
N, N-dimethylpropionamide, Nt-butylformamide, pivalamide (trimethylacetamide),
N, N-diethylacetamide, hexanoamide, N,
N-2-trimethylpropionamide, N, N-diethylpropionamide, N, N-diisopropylformamide, N, N-diisopropylacetamide, N, N-
Examples thereof include diisobutylformamide, formanilide, and acetanilide. Among these,
N, N-dimethylformamide is particularly preferably used. Such an acid amide is not particularly limited, but is usually in the range of 0.01 to 1.5 mole parts, preferably 1 mole part of charged t-butoxystyrene.
It is used in the range of 0.05 to 1 mol part.

Examples of the substituted phenols include t-butylhydroquinone, 4-t-butylcatechol, 2,5-di-t-butylhydroquinone, and 2,5-
Di-t-amylhydroquinone, 3-methyl-6-t-
Butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-4-ethylphenol, 2,5-
Di-t-butylphenol, 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol,
2,6-di-t-butyl-4-methylphenol, 2,4,6
-Tri-t-butylphenol, 4-methoxyphenol and the like. Although such a substituted phenol is not particularly limited, it is usually 50 to 5000 pP with respect to the charged t-butoxystyrene.
pm, preferably in the range of 100 to 1000 ppm.

In particular, in the present invention, the substituted phenols represented by the general formula (V)

[0027]

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(In the formula, Z represents a methyl group or an ethyl group, x represents 0 or 1, y represents 1 to 3, and z represents an integer of 0 to 2, provided that 1 ≦ x + y + z ≦ 5.) The t-butyl phenols represented by the following are preferably used.

Examples of such t-butylphenols include t-butylhydroquinone, 4-t-butylcatechol, 2,5-di-t-butylhydroquinone,
2,5-di-t-amylhydroquinone, 3-methyl-6
-T-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-4-ethylphenol,
2,5-di-t-butylphenol, 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol,
2,4,6-tri-t-butylphenol and the like can be mentioned.

In the present invention, the reaction between the t-butoxystyrenes and the acetylating agent may be carried out in the presence of any of the above-mentioned acid amides or substituted phenols. By performing the reaction between the t-butoxystyrenes and the acetylating agent in the presence of both phenols, the production of polymer components due to the polymerization of t-butoxystyrenes and acetoxystyrenes as reaction products can be suppressed. And the desired acetoxystyrenes can be obtained in high yield.

According to the present invention, the method of the reaction is not particularly limited, but the stirring is carried out while stirring the mixed solution comprising the acetylating agent, the acid catalyst, and the polymerization inhibitor. It is preferred to carry out the reaction by dropping butoxystyrenes. If necessary, an appropriate organic solvent can be used. The reaction temperature is usually in the range of 0 to 95 ° C, preferably in the range of 15 to 90 ° C.
When the reaction temperature is too low, the reaction rate is slow, the time required for the reaction is long, and the production of undesirable low polymers such as dimers and higher polymers is increased, while the reaction temperature is low. When it is too high, the production of undesired low polymers and high polymers similarly increases, and the yield of the target acetoxystyrenes decreases.

When t-butoxystyrenes are dropped into a mixed solution comprising an acetylating agent, an acid catalyst and the polymerization inhibitor, isobutylene gas is generated, and acetic acid is generated in the reaction mixture.

The end point of the reaction can be determined by gel permeation chromatography (GPC analysis) at the time when the unreacted t-butoxystyrene in the reaction mixture is almost consumed. After completion of the reaction, when the reaction is carried out under heating, it is preferable to cool the obtained reaction mixture to room temperature or lower, for example, 30 ° C. or lower as quickly as possible.

After completion of the reaction, a neutralizing agent is preferably added to the reaction mixture to neutralize the acid catalyst, and then a mixture of acetic acid and acetic anhydride is recovered by distillation. Thereafter, the target acetoxystyrenes can be recovered and separated by distillation.

Examples of the neutralizing agent include alkali metal salts of acetic acid such as sodium acetate and potassium acetate.
Sodium carbonate, potassium carbonate, sodium bicarbonate,
An alkali metal carbonate (hydrogen) such as potassium hydrogen carbonate can be mentioned. Further, amines, especially tertiary amines, can also be used as a neutralizing agent for the catalyst. Examples of such tertiary amines include, for example, trimethylamine, triethylamine, N, N-diethylmethylamine, N, N-dimethylisopropylamine, N, N-diisopropylamine, N, N-dimethylhexylamine, N, N-dimethylhexylamine, N-dibutylmethylamine, N, N-dimethyloctylamine, tributylamine, triisobutylamine, N, N-dimethylundecylamine, tridecylamine, N, N-dimethyldodecylamine, dimethylaniline, diethylaniline, and the like. be able to.

The neutralizing agent is not particularly limited, but is usually used in an amount of at least equimolar to 1 mole of the charged acid catalyst. However, when it is used too much, the amount of acetate in the reaction mixture increases, the operability of the subsequent distillation may be deteriorated, and the separation yield of the target product may also be reduced. Is used in the range of 1.0 to 1.5 mol part with respect to the charged acid catalyst.

According to the present invention, after completion of the reaction, a neutralizing agent is added to the reaction mixture to neutralize the acid catalyst.
Acetic acid and acetic anhydride are recovered by distillation, and subsequently, distillation is continued to recover the desired acetoxystyrenes. However, preferably, after recovering acetic acid and acetic anhydride, the inorganic salts in the distillation residue generated by the reaction between the acid catalyst and the neutralizing agent are removed by washing with water, and then the distillation residue thus treated is removed. After the addition of the above substituted phenols, the distillation residue is preferably distilled at a temperature as low as possible to recover and separate the desired acetoxystyrene. As described above, when the acetoxystyrenes are recovered from the distillation residue by distillation, the substituted phenols are not particularly limited, but are usually used when reacting the t-butoxystyrenes with the acetylating agent. They are used in substantially the same amount, that is, in the range of 50 to 5000 ppm, preferably 100 to 1000 ppm, based on t-butoxystyrenes.

[0038]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In the following Examples and Comparative Examples, the reaction was followed and the yield was determined by quantifying the amount of p-acetoxystyrene produced in the reaction mixture and the remaining amount of unreacted t-butoxystyrene by GPC. Was.

Example 1 1000 m equipped with a stirrer, thermometer and reflux condenser
306 g (3.00 mol) of acetic anhydride and 15 g (0.08 mol) of p-toluenesulfonic acid monohydrate were placed in an L-capacity four-necked flask.
Mol), 15 g (0.205 mol) of dimethylformamide
And 30 mg of t-butylhydroquinone and 70 mg
Warmed to ° C.

While maintaining the internal temperature at 70 ° C., 176 g (1.00 mol) of pt-butoxystyrene was added dropwise over 2 hours.
Thereafter, the reaction was further stirred at 70 ° C. for 30 minutes to carry out the reaction. After the reaction was completed, the resulting reaction mixture was analyzed by GPC. As a result, no unreacted pt-butoxystyrene was present (reaction rate: 100%), and the yield of the target p-acetoxystyrene was 67. 9 mol%.

7.8 g (0.0%) of sodium acetate was added to the reaction mixture.
95 mol) as a neutralizing agent, and a mixture of acetic acid and acetic anhydride was distilled off under reduced pressure. Toluene and water were added to the distillation residue, the oil layer was washed three times with water, 30 mg of t-butylhydroquinone was added to the oil layer, and toluene and low-boiling components were distilled off from the oil layer by vacuum distillation.
96.0 g of main fraction at 86 ° C / 1 mmHg (GPC purity 99.9)
5%) (yield 59 mol%).

This main fraction is subjected to gas chromatography (G
C) From mass spectrometry, infrared absorption spectrum analysis and nuclear magnetic resonance spectrum analysis, it was confirmed that it was the target p-acetoxystyrene.

GC mass spectrometry (m / z): 160
(M ⁺ ), 120 (M ⁺ -COCH ₃ ), 105 (M ⁺ -
57) Infrared absorption spectrum (KBR, cm ^-1 ): 1755
1500, 1365, 1190, 1180 Nuclear magnetic resonance spectrum (δ ppm): 2.30 (s), 5.
25 (d), 5.71 (d), 6.71 (d), 7.05-7.
44 (m)

Example 2 200 mL equipped with a stirrer, thermometer and reflux condenser
In a four-neck flask, 61.2 g (0.60 mol) of acetic anhydride and 3 g (0.016 mol) of p-toluenesulfonic acid monohydrate were added.
Mol), 3 g (0.041 mol) of dimethylformamide and 6 mg of t-butylhydroquinone, and heated to 90 ° C.

While maintaining the internal temperature at 90 ° C., 26.4 g (0.15 mol) of pt-butoxystyrene was added dropwise over 1 hour.
Thereafter, the mixture was further stirred at 90 ° C. for 5 minutes to carry out a reaction. After completion of the reaction, the obtained reaction mixture was analyzed by GPC. As a result, no unreacted pt-butoxystyrene was present (reaction rate: 100%), and the yield of the desired p-acetoxystyrene was 78. It was 2 mol%.

Example 3 200 mL equipped with a stirrer, thermometer and reflux condenser
In a four-neck flask, 61.2 g (0.60 mol) of acetic anhydride and 3 g (0.016 mol) of p-toluenesulfonic acid monohydrate were added.
Mol), 3 g (0.041 mol) of dimethylformamide and 6 mg of t-butylhydroquinone, and heated to 80 ° C.

While maintaining the internal temperature at 80 ° C., 26.4 g (0.15 mol) of pt-butoxystyrene was added dropwise over 1 hour.
Thereafter, the mixture was further stirred for 1 hour at 80 ° C. to carry out a reaction. After the reaction was completed, the resulting reaction mixture was analyzed by GPC. As a result, no unreacted pt-butoxystyrene was present (reaction rate: 100%), and the yield of the target p-acetoxystyrene was 68. 3 mol%.

To the reaction mixture was added 2.1 g of sodium carbonate (0.0 g).
2 mol) as a neutralizing agent, and a mixture of acetic acid and acetic anhydride was distilled off under reduced pressure. Toluene and water were added to the distillation residue, the oil layer was washed three times with water, 6 mg of t-butylhydroquinone was added to the obtained oil layer, and toluene and low-boiling components were distilled off from the oil layer by vacuum distillation.
14.6 g (GPC purity: 99.0%) of the main fraction was obtained at 0 to 93 ° C / 1 mmHg (yield: 59.9 mol%).

Example 4 200 mL equipped with a stirrer, thermometer and reflux condenser
In a four-neck flask, 61.2 g (0.60 mol) of acetic anhydride and 3 g (0.016 mol) of p-toluenesulfonic acid monohydrate were added.
Mol), 3 g (0.041 mol) of dimethylformamide and 6 mg of t-butylhydroquinone, and heated to 70 ° C.

While maintaining the internal temperature at 70 ° C., 26.4 g (0.15 mol) of pt-butoxystyrene was added dropwise over 1 hour.
Thereafter, the mixture was further stirred at 70 ° C. for 1 hour to carry out a reaction. After completion of the reaction, the obtained reaction mixture was analyzed by GPC. As a result, no unreacted pt-butoxystyrene was present (reaction rate: 100%), and the yield of the target p-acetoxystyrene was 64. It was 7 mol%.

2.9 g of diethylaniline was added to the reaction mixture.
(0.02 mol) as a neutralizing agent, and acetic acid, acetic anhydride and low boiling components were distilled off by distillation under reduced pressure. Subsequently, 13.7 g of a main fraction was distilled at a distillation temperature of 80 to 93 ° C./1 mmHg ( GP
C purity: 97.4%) was obtained (yield: 56.2 mol%).

Examples 5 to 8 The reaction was carried out in the same manner as in Example 4 except that 3 g of each of the acid catalysts shown in Table 1 was used instead of p-toluenesulfonic acid monohydrate. Was. Table 1 shows the results. In Table 1, the dropping time is the dropping time of pt-butoxystyrene as in Example 1, and the post-reaction time is the time after the end of dropping of pt-butoxystyrene to further react. The reaction rate was determined by quantifying the amount of pt-butoxystyrene consumed by GPC after the reaction was completed, and 100% when there was no unreacted pt-butoxystyrene, The yield is the yield (molar ratio) of p-acetoxystyrene based on pt-butoxystyrene determined by GPC.

[0053]

[Table 1]

Example 9 A reaction was carried out in the same manner as in Example 4 except that t-butylhydroquinone was not used in the reaction between pt-butoxystyrene and acetic anhydride. Although the total amount of t-butoxystyrene was consumed (reaction rate: 100%), the polymer component was produced as a by-product at a yield of 30.6 mol%, and the yield of the target p-acetoxystyrene was 60%. 0.0 mol%.

Example 10 A reaction was carried out in the same manner as in Example 4 except that 3 g (0.034 mol) of dimethylacetamide was used instead of dimethylformamide.
All butoxystyrene was consumed (reaction rate 10
0%), the polymer component is by-produced at a yield of 38.2 mol%, and the desired yield of p-acetoxystyrene is 5%.
6.0 mol%.

Example 11 Example 4 was repeated except that dimethylformamide and t-butylbutylhydroquinone were not used.
As a result, pt-butoxystyrene was completely consumed (reaction rate: 100%), but the polymer component was by-produced at a yield of 35.6 mol%. The yield of p-acetoxystyrene was 48.4 l%.

Comparative Example 1 A reaction was carried out in the same manner as in Example 4 except that p-toluenesulfonic acid monohydrate was not used.
All of the pt-butoxystyrene remained unreacted (reaction rate: 0%), and the desired p-acetoxystyrene could not be obtained.

[0058]

As described above, according to the present invention, the desired acetoxystyrenes are obtained in a single step using t-butoxystyrenes and a general acetylating agent, especially acetic anhydride as raw materials. Can be produced in high yield.
In particular, by carrying out the reaction according to the present invention in the presence of said acid amides and / or substituted phenols, t
-The reaction can be carried out while effectively preventing the polymerization of butoxystyrenes and acetoxystyrenes, to produce the desired acetoxystyrenes in high yield. Furthermore, according to the method of the present invention, since both t-butoxystyrenes and acetic anhydride are industrially produced chemicals, acetoxystyrenes can be stably produced at low cost.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Noriaki Dei 2-115, Kozaiga, Wakayama-shi F-term in Honshu Kagaku Kogyo Co., Ltd. F-term (reference) 4H006 AA02 AC48 BA35 BA36 BA50 BA51 BA52 BA66 BA72 BA94 BJ50 KA14 KA18 4H039 CA66 CD20 CD40 CD90

Claims (4)

[Claims] 1. A compound of the general formula (I) Wherein t-butoxystyrenes represented by the formula (I) are reacted with an acetylating agent in the presence of a catalyst.
I) A method for producing acetoxystyrenes represented by the formula: 2. The process for producing acetoxystyrenes according to claim 1, wherein acetic anhydride is reacted as an acetylating agent with t-butoxystyrenes in the presence of an acid catalyst. 3. The method according to claim 1, wherein (a) a compound represented by the general formula (III): (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) Acid amides and (b) the general formula (IV) (In the formula, X represents a hydrogen atom, a methyl group, an ethyl group or a hydroxyl group, Y represents a t-butyl group, a t-amyl group or a methoxy group, and m and n each represent an integer of 1-3. And 2 ≦ m + n ≦ 5.) A process for producing acetoxystyrenes, which comprises reacting t-butoxystyrenes in the presence of at least one polymerization inhibitor selected from the group consisting of: 4. The method according to claim 3, wherein after completion of the reaction, a neutralizing agent comprising an alkali is added to the obtained reaction mixture to neutralize the acid catalyst, and acetic acid and acetic anhydride are recovered by distillation. A method for producing acetoxystyrenes, wherein the obtained distillation residue is washed with water and then distilled in the presence of the substituted phenols.