JP2009292764A - Method for producing hydroxyanilide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method by which a hydroxyanilide useful as a production raw material or a production intermediate in various applications such as an electronic material, a resist material and a material for printing can efficiently be produced from an industrially available raw material. <P>SOLUTION: The method for producing the hydroxyanilide includes reacting a carboxylic anhydride with an aminophenol in a nitrile-based solvent. The aminophenol is dissolved or dispersed in the nitrile-based solvent, and the carboxylic anhydride diluted by the nitrile-based solvent is continuously or sequentially added thereto. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing hydroxyanilide which is useful as a production raw material or production intermediate in various applications such as electronic materials, resist materials, and printing materials.

  As a method for producing hydroxyanilide, it is produced by reacting an aminophenol, an acylating agent and a base in an organic solvent-water mixed solvent (for example, Patent Document 1). However, this method is difficult to purify the resulting hydroxyanilide and is not an efficient production method.

  Further, as a method for solving this problem, a method for producing aminophenols and an acylating agent by reacting them in an alcohol solvent has been proposed (for example, Patent Document 2). This method is easy to purify and can be produced efficiently. However, depending on the reaction conditions, there is a problem that an ester compound in which the solvent used and the acylating agent react as impurities may be produced. It was.

In particular, in the field of electronic materials and resist materials, which are developing rapidly in recent years, polymerizable impurities are considered to be one of the causes of material performance deterioration, and raw materials and intermediates that do not contain polymerizable impurities are required. It was. Therefore, the creation of an efficient production method that does not contain polymerizable impurities has been desired.
JP 2003-300094 A JP 2006-176455 A

  An object of the present invention is to provide a method capable of efficiently producing hydroxyanilide from a commercially available raw material.

  As a result of intensive studies to solve the problems of the conventional method, the present inventors have found that the above problems can be solved by reacting an acrylic anhydride and aminophenol in a nitrile solvent. The invention has been reached.

  That is, the present invention is a method for producing hydroxyanilide, which comprises reacting a carboxylic acid anhydride and aminophenol in a nitrile solvent.

  In the present invention, the carboxylic acid anhydride is represented by the general formula (1).

(In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group.)
It is a manufacturing method of the hydroxyanilide of Claim 1.

  In the present invention, the aminophenol is represented by the general formula (2).

(In the formula, R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, alkyl group, alkoxy group, alkyl carboxyl group, alkyl sulfo group. The alkyl group, alkoxy group, alkyl carboxyl group, and alkyl sulfo group are linear, branched, or cyclic substituents having 1 to 30 carbon atoms, some of which are halogen atoms. Or an oxygen atom, a nitrogen atom, or a sulfur atom. At least one of R _{2 to} R ₆ is a hydroxyl group).

  Furthermore, the present invention relates to any one of the above, wherein the aminophenol is dissolved or dispersed in the nitrile solvent, and then the carboxylic anhydride diluted with the nitrile solvent is added continuously or sequentially. This is a method for producing hydroxyanilide.

  The production method of the present invention is advantageous in that it does not contain impurities and can produce hydroxyanilide efficiently.

  Hereinafter, the present invention will be described in detail. In the present invention, a carboxylic acid anhydride and an aminophenol are reacted in a nitrile solvent.

  Examples of the carboxylic anhydride used in the present invention include alkyl carboxylic anhydrides such as acetic anhydride, propionic anhydride, and isobutyric anhydride, and carboxylic anhydrides having a polymerizable moiety.

  The carboxylic acid anhydride having a polymerization site is represented by the general formula (1)

(In formula (1), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group.).

  The amount of carboxylic acid anhydride is 0.6 to 2.0 equivalents, preferably 0.8 to 1.3 equivalents, more preferably 0.8 to 1.3 equivalents of aminophenol used from the viewpoints of simplicity in the purification step and economy. It is desirable that it is 9-1.1 equivalent.

  On the other hand, the aminophenol used in the present invention is a compound represented by the general formula (2)

(In the formula, R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, alkyl group, alkoxy group, alkyl carboxyl group, alkyl sulfo group. The alkyl group, alkoxy group, alkyl carboxyl group, and alkyl sulfo group are linear, branched, or cyclic substituents having 1 to 30 carbon atoms, some of which are halogen atoms. , An oxygen atom, a nitrogen atom, or a sulfur atom. At least one of R _{2 to} R ₆ is a hydroxyl group).

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example.

  Examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a cyclopropyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a cycloheptyl group, a bicyclo [2.2.1] heptyl group, and an n-octyl group. Group, a cyclooctyl group or a bicyclo [2.2.2] octyl group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, a phenoxy group, a methoxymethoxy group, and a 2-methoxyethoxy group.

  Examples of the carboxy group include an acetyl group, a pivaloyl group, a benzoyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a t-butoxycarbonyl group.

  Examples of the nitrile compound used as the solvent include lower nitrile compounds having 1 to 10 carbon atoms such as acetonitrile, propionitrile, n-butyronitrile, isobutyronitrile, and benzonitrile. These solvents may be used alone or in combination.

  The amount of the nitrile solvent used is 1 to 20 times, preferably 2 to 10 times the amount of aminophenol used. If it is less than 1 time, there is no effect to add, and if it exceeds 20 times, it is not economically preferable.

  In the production method of the present invention, when the carboxylic acid anhydride has a polymerizable moiety, a polymerization inhibitor may be used to prevent the polymerizable moiety from being polymerized. Examples thereof include hydroquinone, methoquinone, 6-t-butyl-2,4-xylenol, but are not particularly limited thereto. A plurality of polymerization inhibitors may be used.

  The amount of the polymerization inhibitor is 0.01% to 10%, preferably 0.1% to 1%, based on the weight of the carboxylic anhydride used. If it is less than 0.01%, the effect of inhibiting polymerization is not sufficient, and if it exceeds 10%, it is economically undesirable.

  The reaction atmosphere is not particularly limited. In addition to an inert gas such as nitrogen, helium or argon, air may be used. Further, oxygen may be used for the purpose of suppressing the polymerization reaction during the reaction.

  In the reaction method, aminophenol is dissolved or dispersed in a nitrile solvent, and then a carboxylic acid anhydride is added continuously or sequentially. For the purpose of controlling the reaction temperature or facilitating the addition of the solid carboxylic acid anhydride, the carboxylic acid anhydride may be diluted with a nitrile solvent. In the present invention, since the carboxylic acid anhydride does not react with the nitrile solvent, the operability is improved by the addition of the solvent. At this time, the amount of the nitrile solvent used for dilution is not particularly limited, but is preferably 10 to 50% of the total amount of the reaction solvent. The temperature of the acrylic anhydride (or solution) to be added is desirably −10 to 100 ° C., preferably 0 to 60 ° C., in view of the stability of the acrylic anhydride.

  The reaction temperature is −10 to 100 ° C., preferably 0 to 60 ° C. from the viewpoint of the stability of the added carboxylic acid anhydride, the stability of the generated polymerizable compound, and the solubility of the generated polymerizable compound. It is desirable to be. When the reaction temperature is lower than −10 ° C., the reaction does not proceed, and when it exceeds 100 ° C., a side reaction may proceed, which is not preferable.

The completion of the reaction can be confirmed using, for example, thin layer chromatography (TLC), high performance liquid chromatography (HPLC), nuclear magnetic resonance spectrum ( ¹ H-NMR), etc. The reaction time usually varies depending on the reaction substrate used. Within 2 hours after addition of carboxylic acid anhydride.

  After completion of the reaction, the resulting carboxylic acid hydroxyanilide is purified by adding the obtained reaction mixture to a poor solvent or by adding a poor solvent to the reaction mixture to precipitate the target carboxylic acid hydroxyanilide crystals. Can do.

  The poor solvent is not particularly limited as long as it is a solvent that is miscible with the nitrile solvent and has low solubility of the produced carboxylic acid hydroxyanilide. For example, pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene And hydrocarbon solvents having 5 to 10 carbon atoms such as ether solvents such as diethyl ether, diisopropyl ether and di-t-butyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and water. It is done.

  The amount of the poor solvent is not particularly limited as long as the produced carboxylic acid hydroxyanilide can be sufficiently precipitated, and is preferably 10 to 10000%, preferably 50 to 5000% based on the weight of the obtained reaction mixture. If it is less than 10%, the precipitation of the reaction mixture is not sufficient, and exceeds 5000%.

The target carboxylic acid hydroxyanilide precipitated can be recovered by using a filter. Moreover, what is necessary is just to wash | clean with a poor solvent etc. as needed. After the recovery, the remaining solvent can be removed with a vacuum dryer or the like.
"Example"
Next, the present invention will be described in detail based on examples. In addition, this invention is not limited to this Example.

  Synthesis of 4-hydroxymethacryloyloxyanilide (3)

4-Aminophenol (100.20 g) and acetonitrile (400.80 g) were added to a 2 L four-necked flask equipped with a stirring blade, a condenser, and a thermometer. Next, nitrogen gas was flowed into the flask and the stirring blade was rotated. After controlling the temperature of the mixture in the flask to 30 to 32 ° C. using a water bath, methacrylic anhydride (142.86 g) dissolved in acetonitrile (100.20 g) using a dropping funnel was taken over 1 hour. It was dripped. After dropwise addition of the entire amount of the methacrylic anhydride solution, the temperature of the water bath was raised so that the temperature of the reaction mixture was 50 to 53 ° C., and the reaction mixture was then controlled to be 50 to 53 ° C. and stirred for 30 minutes. . Thereafter, a small amount was sampled, and disappearance of the raw material was confirmed by ¹ H-NMR. At this time, no by-product derived from the solvent was confirmed.

The reaction mixture obtained by adding diisopropyl ether (3.0 kg) to a 5 L 4-neck separable flask equipped with a stirring blade was added dropwise. After stirring for 1 hour after the temperature of the mixture inside the flask reached 25 ° C., the precipitated crystals were filtered by Nutsche, and the crystals were washed with a small amount of diisopropyl ether. The crystals were collected and dried with a vacuum dryer to obtain 4-hydroxymethacryloyloxyanilide (95.99 g, purity 99.9 LC%, yield 59%). The recovered filtrate was concentrated under reduced pressure to obtain crude crystals (64.51 g), which were recrystallized from a mixed solution of acetonitrile-diisopropyl ether to give 4-hydroxymethacryloyloxyanilide (39.01 g, purity 99). .3%, yield 24%). The crystals thus obtained were analyzed by ¹ H-NMR, and it was confirmed that no solvent-derived impurities were contained.

  The carboxylic acid hydroxyanilide compound obtained by the production method of the present invention can be suitably used as an electronic material, a resist material, a raw material for a printing material, or an intermediate.

Claims (4)

  A process for producing hydroxyanilide, comprising reacting a carboxylic acid anhydride and aminophenol in a nitrile solvent. Carboxylic anhydride is represented by the general formula (1)

(In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group.)
The method for producing hydroxyanilide according to claim 1. Aminophenol is represented by the general formula (2)

(In the formula, R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, alkyl group, alkoxy group, alkyl carboxyl group, alkyl sulfo group. The alkyl group, alkoxy group, alkyl carboxyl group, and alkyl sulfo group are linear, branched, or cyclic substituents having 1 to 30 carbon atoms, some of which are halogen atoms. And optionally substituted with an oxygen atom, a nitrogen atom, or a sulfur atom. At least one of R _{2 to} R ₆ is a hydroxyl group). The aminophenol is dissolved or dispersed in a nitrile solvent, and then the carboxylic anhydride diluted with the nitrile solvent is added continuously or sequentially. A process for producing the hydroxyanilide described.