JPH09263567A - New naphthol ester compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new naphthol ester compound useful as additives such as a high-boiling solvent, an ultraviolet absorber, an electron adjustor, a plasticizer, etc., producible under relatively mild conditions in a high yield. SOLUTION: This naphthol ester compound is shown by formula I (R<1> is an alkyl, an aryl, an alkyloxy or an aryloxy; R<2> is an alkyl or an aryl) such as 1,1'-[(2-methylcarbonyloxy-5-methyl-m-phenylene)-dimethlylene]bis-2- methylcarbonyloxynaphthalene. The compound of formula I is obtained by reacting a naphthol derivative of formula II with an esterifying agent selected from an acid of the formula R<2> COOH, its acid anhydride, acid halide and ester compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ester compound of naphthol and a method for producing the same.

[0002]

A novel ester compound of naphthol represented by the following general formula (1) is a compound unknown in literature,
It is a compound useful as an additive such as a high boiling point solvent, an ultraviolet absorber, a charge control agent and a plasticizer.

[0003]

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[0004]

The object of the present invention is to provide a novel ester compound of naphthol represented by the general formula (1). Furthermore, the present invention provides a naphthol derivative represented by the following general formula (2) and R
² COOH (wherein R ² represents an alkyl group or an aryl group) or an acid thereof, or an esterification agent selected from an acid anhydride, an acid halide or an ester compound thereof, which is characterized in that It is an object of the present invention to provide a method for producing a novel ester compound of naphthol represented by the formula (1).

[0005]

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[0006]

The compound of the present invention is an ester compound of naphthol represented by the general formula (1). The compound of the present invention is prepared, for example, by reacting 1 equivalent of 4-substituted phenol with 2 equivalents of a formaldehyde aqueous solution under alkaline conditions to prepare 2,6-di (hydroxymethyl)-.
It is converted to a phenol derivative, and this is further combined with 2 equivalents of 2-
It is dehydrated and condensed with naphthol to be converted into the naphthol derivative represented by the general formula (2), and 3 equivalents of R ² C
It can be produced by reacting with an acid represented by OOH (wherein R ² represents an alkyl group or an aryl group), or an esterifying agent selected from an acid anhydride, an acid halide or an ester compound thereof.

Used to Prepare Compounds of the Invention 4
The substituted phenol is preferably C _{1 to} C ₄ 4
- alkylphenol, a C ₁ -C ₄ 4-alkyloxy phenol, 4-phenylphenol, 4-phenoxy phenol, and more preferably 4-methylphenol, 4-ethylphenol, 4-t-butylphenol, 4-methoxy They are phenol, 4-phenylphenol, and 4-phenoxyphenol.

As the aqueous formaldehyde solution which acts on these 4-substituted phenols, aqueous solutions having various concentrations can be used. Since the reaction of the 4-substituted phenol with the aqueous formaldehyde solution under alkaline conditions proceeds quantitatively, the formaldehyde content of the aqueous formaldehyde solution to be used may be 2 equivalents relative to the 4-substituted phenol. It may be used in a slight excess amount.

Furthermore, the reaction of dehydrating and condensing the 2,6-di (hydroxymethyl) -phenol derivative produced in this reaction and 2-naphthol proceeds almost quantitatively.
The amount of 2-naphthol used is 2 equivalents with respect to the 2,6-di (hydroxymethyl) -phenol derivative, but a slight excess may be used if necessary.

R ² C acting on the naphthol derivative represented by the general formula (2) produced by this dehydration condensation reaction
OOH (provided that R ² represents an alkyl group or an aryl group)
The acid represented by or the acid anhydride, acid halide, or ester compound thereof is preferably C _{1 to} C ₄
Carboxylic acid and benzoic acid, or their acid anhydrides, acid halides, or ester compounds thereof, more preferably acetic acid, propionic acid, acetic anhydride, propionic anhydride, benzoic anhydride, acetic acid chloride, propionic acid. These are chloride, benzoyl chloride, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and methyl benzoate. The amount of the acid or its acid anhydride, acid halide or ester compound used is preferably 3 equivalents with respect to the naphthol derivative represented by the general formula (2). In consideration of this, an excessive amount may be used.

[0011]

The present invention will be described in more detail with reference to the following examples. Example 1 Into a three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, 108.1 g of 4-methylphenol was inserted, and 70 g of 48% sodium hydroxide aqueous solution was added while maintaining the internal temperature at 40 ° C. under a nitrogen stream. Was dropped for 1 hour. After dropping,
Add 100 ml of water to increase the stirring efficiency, and add 4 more
Stirred at 0 ° C. for 20 minutes. Next, 171.6 g of 35% formaldehyde aqueous solution was added dropwise over 1 hour while maintaining the internal temperature at 40 ° C., and after completion of the addition, the mixture was stirred at 40 ° C. for 4 hours. Next, keeping the internal temperature at 40 ° C, 84 g of 36% hydrochloric acid aqueous solution
The mixture was neutralized with and the crystals were collected by filtration. The crystals collected by filtration are 100 m of water
After being washed several times with l, dried under reduced pressure at 40 ° C. for 20 hours, and
42.1 g of 2,6-di (hydroxymethyl) -4-methylphenol was obtained. Next, 84.1 g of this 2,6-di (hydroxymethyl) -4-methylphenol and 2-
144.2 g of naphthol and 120 ml of water were inserted into a three-necked flask equipped with a thermometer, a stirrer and a reflux tube, and heated under reflux for 6 hours while stirring. The crystals were collected by filtration, washed with 100 ml of water several times, and then dried under reduced pressure at 80 ° C. for 5 hours to obtain 200 g of 1,1 ′-[(2-hydroxy-5-methyl-m-phenylene). Dimethylene] di-2-
I got naphthol. Furthermore, 40 g of this 1,1 ′-[(2-hydroxy-5-methyl-m-phenylene) dimethylene] di-2-naphthol, 40 g of acetic acid and 100 g of acetic anhydride.
g was inserted into a three-necked flask equipped with a thermometer, a stirrer, and a reflux tube, and heated under reflux for 4 hours with stirring. After heating under reflux, the mixture was cooled, 50 ml of acetic acid was added, the crystals were collected by filtration, washed with 50 ml of acetic acid several times, dried under reduced pressure at 150 ° C. for 10 hours, and 47.7 g of 1,1 ′-[(2-methylcarbonyloxy White crystals of -5-methyl-m-phenylene) dimethylene] bis-2-methylcarbonyloxynaphthalene were obtained. The melting point of the obtained crystal was 214 ° C., and the elemental analysis results are shown in Table 1.

[0012]

[Table 1]

The infrared absorption spectrum analysis result (PERK
IN ELMER2000FT-IR) is as shown in Fig. 1. The nuclear magnetic resonance spectrum analysis result (JEOL-EX400) is as shown in FIG.

Example 2 108.1 g of 4-methylphenol was placed in a three-necked flask equipped with a thermometer, a stirrer and a dropping funnel, and 48% hydroxylation was carried out under a nitrogen stream while maintaining the internal temperature at 40 ° C. 70 g of an aqueous sodium solution was added dropwise over 1 hour. After dropping,
Add 100 ml of water to increase the stirring efficiency, and add 4 more
Stirred at 0 ° C. for 20 minutes. Next, 171.6 g of 35% formaldehyde aqueous solution was added dropwise over 1 hour while maintaining the internal temperature at 40 ° C., and after completion of the addition, the mixture was stirred at 40 ° C. for 4 hours. Next, keeping the internal temperature at 40 ° C, 84 g of 36% hydrochloric acid aqueous solution
The mixture was neutralized with and the crystals were collected by filtration. The crystals collected by filtration are 100 m of water
After being washed several times with l, dried under reduced pressure at 40 ° C. for 20 hours, and
42.1 g of 2,6-di (hydroxymethyl) -4-methylphenol was obtained. Next, 84.1 g of this 2,6-di (hydroxymethyl) -4-methylphenol and 2-
144.2 g of naphthol and 120 ml of water were inserted into a three-necked flask equipped with a thermometer, a stirrer and a reflux tube, and heated under reflux for 6 hours while stirring. The crystals were collected by filtration, washed with 100 ml of water several times, and then dried under reduced pressure at 80 ° C. for 5 hours to obtain 200 g of 1,1 ′-[(2-hydroxy-5-methyl-m-phenylene). Dimethylene] di-2-
I got naphthol. Further, 40 g of this 1,1 '-[(2-hydroxy-5-methyl-m-phenylene) dimethylene] di-2-naphthol, 40 g of propionic acid and 100 g of propionic anhydride were attached to a thermometer, a stirrer and a reflux pipe. The mixture was placed in a 3-necked flask and heated under reflux for 4 hours with stirring. After heating under reflux, the mixture was cooled, 50 ml of propionic acid was added, the crystals were collected by filtration, washed several times with 50 ml of propionic acid, recrystallized with acetone / isopropanol, and then 10
After drying under reduced pressure at 0 ° C. for 10 hours, 42.0 g of 1,1′-
White crystals of [(2-ethylcarbonyloxy-5-methyl-m-phenylene) dimethylene] bis-2-ethylcarbonyloxynaphthalene were obtained. The melting point of the obtained crystal was 134 ° C., and the elemental analysis results are shown in Table 2.

[0015]

[Table 2]

The infrared absorption spectrum analysis result (PERK
IN ELMER2000FT-IR) is as shown in FIG. The nuclear magnetic resonance spectrum analysis result (JEOL-EX400) is as shown in FIG.

[0017]

INDUSTRIAL APPLICABILITY According to the present invention, a novel ester compound of naphthol can be produced in good yield under relatively mild conditions. The novel naphthol ester compound of the present invention is
It is a compound useful as an additive such as a high boiling point solvent, an ultraviolet absorber, a charge control agent and a plasticizer.

[Brief description of drawings]

FIG. 1 1,1 ′-[(2-methylcarbonyloxy-
5-methyl-m-phenylene) dimethylene] bis-2-
It is a figure which shows the infrared absorption spectrum of methyl carbonyloxy naphthalene (compound 1).

FIG. 2 shows 1,1 ′-[(2-methylcarbonyloxy-
5-methyl-m-phenylene) dimethylene] bis-2-
FIG. 3 is a diagram showing a nuclear magnetic resonance spectrum of methylcarbonyloxynaphthalene (Compound 1).

FIG. 3 shows 1,1 ′-[(2-ethylcarbonyloxy-
5-methyl-m-phenylene) dimethylene] bis-2-
It is a figure which shows the infrared absorption spectrum of ethyl carbonyloxy naphthalene (compound 2).

FIG. 4: 1,1 ′-[(2-ethylcarbonyloxy-
5-methyl-m-phenylene) dimethylene] bis-2-
FIG. 3 is a diagram showing a nuclear magnetic resonance spectrum of ethylcarbonyloxynaphthalene (Compound 2).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuhiro Yamaguchi 1618 Ida, Nakahara-ku, Kawasaki-shi, Kanagawa Inside the Nippon Steel Corporation Technology Development Division (72) Takashi Matsumoto 1618 Ida, Nakahara-ku, Kawasaki-shi, Kanagawa Address: Nippon Steel Corporation, Technology Development Division

Claims (2)

[Claims] 1. A novel naphthol ester compound represented by the following general formula (1). Embedded image 2. A naphthol derivative represented by the following general formula (2) and an acid represented by R ² COOH (wherein R ² represents an alkyl group or an aryl group) or an acid anhydride, acid halide or acid thereof. A method for producing a novel ester compound of naphthol represented by the general formula (1), which comprises reacting with an esterifying agent selected from ester compounds. Embedded image