JP2002161061A - New bis(1-hydroxy-2-ethylphenyl) compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new bis(4-hydroxy-3-ethylphenyl) compound which is useful as a raw material for thermoplastic synthetic resins such as a new polycarbonate resin, a raw material for thermosetting resins such as epoxy resins, a raw material for antioxidants, a raw material for heat-sensitive recording media, a raw material for photosensitive resists, and the like. SOLUTION: This new bis(1-hydroxy-2-ethylphenyl) compound of the general formula 1 [X is 9,9-fluorenyl group or 1,1-cyclohexyl group of the general formula 2 (R is methyl, ethyl, n-propyl, isopropyl, phenyl or hydroxyphenyl) is produced by reacting 2-ethylphenol with an aliphatic ketone compound and a dialkoxybenzene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel bis (1-
With respect to hydroxy-2-ethylphenyls), specifically, thermoplastic synthetic resin raw materials such as polycarbonate resins,
Thermosetting resin materials such as epoxy resin, antioxidant materials,
The 1-hydroxy-2-ethylphenyl group, which is useful as a heat-sensitive recording material material or a photosensitive resist material, has 4,4
Novel bisphenols linked at the '-position.

[0002]

2. Description of the Related Art Conventionally, bisphenols have been used in applications such as thermoplastic synthetic resin materials such as polycarbonate resins, thermosetting resin materials such as epoxy resins, antioxidant materials, heat-sensitive recording material materials, and photosensitive resist materials. Has been
Also, various bisphenols are known. In recent years, the performance required of these bisphenols has been further enhanced, and among them, when used as a polymer component, bisphenols having good heat resistance and fluidity, and having a low melting point as a compound Is being sought. Therefore, the present inventors have focused on bisphenols having a phenyl nucleus with a side chain in order to meet these requirements.

Some compounds are already known as bisphenols having a side chain attached to the phenyl nucleus. For example, Eur.Polym.J., 6 (6), 841-52, (1970), Colle.Czech
o.Chem.Comm.Vol34. , 2843-8, (1968), disclose 4,4'-isopropylidene-bis (2-ethylphenol). JP-A-61-11289 discloses 1,1,3-tris (3-ethyl-4-hydroxyphenyl) butane. However, when a polymer component or the like having a low melting point is used, bis (1-hydroxy-2-ethylphenyl) s which can be expected to have improved heat resistance, water resistance, and compatibility include 1,1-cyclohexyl groups and 9-fluorenyl. Bisphenols in which a hydroxy-2-ethylphenyl group is bonded at the 4,4′-position are not known.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention provides
In order to provide novel bisphenols having a 4-hydroxy-2-ethylphenyl group bonded at the 4,4′-position, more specifically, a novel bis (1-hydroxy-2-yl) having a low melting point. (Ethyl phenyl) compounds.

[0005]

The novel bis (1-hydroxy-2-ethylphenyl) s of the present invention are represented by the general formula (1).

[0006]

Embedded image General formula (1) (wherein, X represents a 1,1-cyclohexyl group or a 9-fluorenyl group represented by the following general formula (2))

[0007]

Embedded image General formula (2) (R represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, and a hydroxyphenyl group.)

In the present invention, in the general formula (1), when X is a 1,1-cyclohexyl group represented by the general formula (2), R is specifically a methyl group, an ethyl group, an n- A propyl group, an isopropyl group, a phenyl group and a hydroxyphenyl group.

Accordingly, as the bis (1-hydroxy-2-ethylphenyl) represented by the general formula (1) of the present invention, specifically, 1,1-bis (1-pyroxy-2-ethylphenyl) Cyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -3-methylcyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -4-methylcyclohexane, 1,1-bis ( 1-hydroxy-2-ethylphenyl) -3-ethylcyclohexane, 1,1-bis (1-hydroxy-2-
Ethylphenyl) -4-ethylcyclohexane, 1,1
-Bis (1-hydroxy-2-ethylphenyl) -3-
Isopropylcyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -4-isopropylcyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -4-n-propylcyclohexane, 1,
1-bis (1-hydroxy-2-ethylphenyl)) 4
-Phenylcyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -3-phenylcyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -4- (4′-hydroxyphenyl) Cyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl))-4- (3′-hydroxyphenyl) cyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl))-4- ( 2'-hydroxyphenyl) cyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -3- (4'-hydroxyphenyl) cyclohexane, 1,1-bis (1-hydroxy-2-ethylphenyl) -3- (3'-hydroxyphenyl) cyclohexane, 9,9-bis (1-hydroxy-2-ethylphenyl) fluorene, etc. And the like.

According to the present invention, the bis (1-hydroxy-2-ethylphenyl) represented by the general formula (I) is composed of 2-ethylphenol and a cyclohexanone represented by the following general formula (4) Or 9- represented by the following formula (5):
It can be obtained by reacting ketofluorene with an acid catalyst.

[0011]

Embedded image General formula (4) (R represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, and a hydroxyphenyl group.)

[0012]

Embedded image Equation (5)

The cyclohexanone represented by the general formula (4) is specifically cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 3-ethylcyclohexanone, 4-ethylcyclohexanone,
3-isopropylcyclohexanone, 4-isopropylcyclohexanone, 4-n-propylcyclohexanone, 3-phenylcyclohexanone, 4-phenylcyclohexanone, 3- (4'hydroxyphenyl) cyclohexanone, 4- (4'-hydroxyphenyl) cyclohexanone, 3- (3′-hydroxyphenyl) cyclohexanone, 4- (3′-hydroxyphenyl) cyclohexanone, 3- (2′-hydroxyphenyl) cyclohexanone, 4- (2′-hydroxyphenyl) cyclohexanone, and the like.

In the process for producing the novel compound of the above general formula (1) according to the present invention, the 2-ethylphenol and the cyclohexanone represented by the above general formula (4) or the 9-cyclohexanone represented by the above general formula (5) are prepared. In the reaction with ketofluorene, the above cyclohexanone or 9-ketofluorene is
It is usually used in a molar amount of 2.5 times or more, preferably 3 to 15 times the molar amount of ethylphenol, particularly preferably 3 to 10 times the molar amount.

In the above reaction, if necessary, water may be used together with 2-ethylphenol. The amount of water added
0.5 to 100 parts by weight of 2-ethylphenol
A range of 3.0 parts by weight is preferred. Water is preferred because it promotes the absorption of hydrogen chloride gas by the catalyst. Further, a reaction solvent may be used if necessary. Examples of the reaction solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic alcohols such as methanol, and mixtures thereof. Of these, aliphatic alcohols are preferably used. Preferred aliphatic alcohols include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol and n-butyl alcohol in consideration of the reaction raw materials to be used, the solubility of the obtained product, reaction conditions, and the economics of the reaction. And lower aliphatic alcohols, but methanol is particularly preferably used.

The reaction solvent is usually used in an amount of 20 to 50 parts by weight, preferably 30 to 40 parts by weight, based on 100 parts by weight of the 2-ethylphenol used. In the production method of the present invention, the acid catalyst used is, for example, hydrogen chloride gas, hydrochloric acid, sulfuric acid, sulfuric anhydride, p
-Toluenesulfonic acid, metasulfonic acid, trifluorometasulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid or trifluoroacetic acid. Such an acid catalyst is usually used, for example, in the case of hydrogen chloride gas at a saturated concentration in the reaction solution, and in the case of 35% hydrochloric acid, 2%.
-Used in an amount of 5 to 30 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of ethylphenol. The reaction temperature is usually in the range of 20 to 60C, preferably 30 to 50C. The reaction pressure is usually
The reaction is carried out under normal pressure, but depending on the boiling point of the organic solvent that may be used, the reaction may be carried out under increased or reduced pressure so that the reaction temperature falls within the above range. If the reaction is carried out under such conditions, the reaction is usually completed in about 5 to 25 hours.

In the production method of the present invention, when 2-ethylphenol is reacted with cyclohexanone or 9-ketofluorene in the presence of an acid catalyst, the embodiment is not particularly limited. Ethyl phenol, water and an acid catalyst were charged into a reaction vessel, and the temperature was increased to about 30 to 50 ° C. while stirring under a nitrogen stream, and cyclohexanone or 9-ketofluorene was added dropwise thereto. The reaction is performed at a temperature for about 2 to 20 hours. The end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis.

After completion of the reaction, an alkali solution such as aqueous ammonia or sodium hydroxide solution is added to the obtained reaction mixture to neutralize the acid catalyst, and then the desired bis (1-hydroxy- A crude crystal of (2-ethylphenyl) can be obtained. The reaction yield with respect to 2-ethylphenol is usually about 80 to 90 mol%. The bis (1-hydroxy-2-ethylphenyl) s thus obtained may be used as a product as it is, or may be purified as necessary to obtain a high-purity product. Purification method, for example, to the crude crystals, a crystallization solvent, for example, a mixture of aromatic hydrocarbons such as toluene and water is added, liquid separation is performed, and the target product is recrystallized from the remaining oil layer. Is separated by filtration and dried to obtain high-purity bis (1-hydroxy-
2-ethylphenyl) can usually be obtained as colorless crystals.

[0019]

The present invention will be described more specifically with reference to the following examples.

Example 1 [Synthesis of 1,1-bis (1-hydroxy-2-ethylphenyl) cyclohexane]

A thermometer, a dropping funnel, a backflow condenser,
2 in a 500 ml four-necked flask equipped with a stirrer
-152.7 g (1.25 mol) of ethylphenol, 2.5 g of dodecylmercaptan, 0.2 g of 75% phosphoric acid,
1.5 g of distilled water was charged, and hydrogen chloride gas was blown into this to saturate it. Thereafter, 24.6 g (0.25 mol) of cyclohexanone was added to the solution while maintaining the internal temperature at 40 ° C.
And a mixed solution of 30.5 g (0.25 mol) of 2-ethylphenol was added dropwise over 3 hours. After the completion of the dropwise addition, the reaction was continued at the same temperature for 5 hours. After completion of the reaction, 20.0 g of toluene was added to the obtained reaction mixture, and then a 16% aqueous solution of sodium hydroxide was added to neutralize the reaction mixture. Thereafter, the aqueous layer was separated and removed from the reaction mixture. Thus, a reaction completed liquid (oil layer mixture) was obtained. When the reaction-terminated liquid was analyzed by high performance liquid chromatography (HPLC), the reaction yield with respect to cyclohexanone was 86.4 mol%. Then, 100 g of distilled water was added to the reaction-terminated liquid to wash it, and the aqueous layer was separated and removed. After this washing was performed twice, the oil layer after removing the aqueous layer was distilled under reduced pressure to remove toluene and toluene.
After distilling off -ethylphenol, the mixture was crystallized and filtered twice with a mixed solution of cyclohexane and toluene, and dried to obtain 43.4 gr of 1,1-bis (1-hydroxy-2-ethylphenyl) cyclohexane as a target substance. Obtained as white crystals. (Purity 98.2%, yield 66.2 mol% based on cyclohexanone).

[0021]

Embedded image

(1) Melting point 110.5 ° C. (Mettler light transmission method) (2) Molecular weight 323.1 (LC-MS method) (3) ¹ H-NMR (400 MHZ, DMSO solvent) ────────────────────── Assignment δ (ppm) signal Proton number ──────────────────── {A 1.08 t6b, c, d 1.30-1.50m6e, f 2.10-2.20m4g 2.48q4h, i, j 6.65-6.96m6k8.95s2} ────────────────────────────

[0023]

Example 2 [Synthesis of 1,1-bis (1-hydroxy-2-ethylphenyl) -4- (4′-hydroxyphenyl) cyclohexanone]

Thermometer, dropping funnel, backflow condenser,
2 in a 300 ml four-necked flask equipped with a stirrer
-61.0 g (0.5 mol) of ethylphenol, 0.2 g of octyl mercaptan, and 9.2 g of 35% aqueous hydrochloric acid are charged, and 9.5 g (0.05 mol) of 4- (4'-hydroxyphenyl) cyclohexanone is heated at a temperature of It was added dropwise at 30 ° C. over 2 hours. After completion of the lowering, the reaction was continued at the same temperature for 4 hours. After completion of the reaction, 16% was added to the obtained reaction mixture.
An aqueous sodium hydroxide solution was added to neutralize the reaction mixture, and thereafter, the aqueous layer was separated and removed from the reaction mixture to obtain a reaction-completed liquid (oil layer mixture). After recovering 2-ethylphenol from the oil layer by distillation under reduced pressure, toluene 84.5 was used.
g was added, and the mixture was crystallized and filtered to obtain crude crystals. Next, a mixture of toluene and water was added to the crude crystals for washing, and the aqueous layer was separated and removed. After this washing was performed twice, crystallization, filtration and drying were performed to obtain 20.6 gr of 1,1-bis (1-hydroxy-2-ethylphenyl) -4- (4′-hydroxyphenyl) cyclohexanone, which was the target substance. Was obtained as white crystals. (Purity 98.6%, yield 80.0 mol% based on 4- (4'-hydroxyphenyl) cyclohexanone)

[0025]

Embedded image

(1) Melting point: 158.5 ° C. (Mettler light transmission method) (2) Molecular weight: 415.7 (LC-MS method) (3) ¹ H-NMR (400 MHZ, DMSO solvent) ────────────────────────── Assignment δ (ppm) signal Proton number ──────────────── ───────────────── a1, a2 1.06, 1.10 t 6 b, c, d, e, f, g 1.42 to 2.71 m 13 h, i, j, k, i , m, n 6.59 to 7.08 m10 o1, o2, o3 8.92, 9.01, 9.07 s3───────────────────────────── ────

[0027]

Example 3 [Synthesis of 9,9-bis (1-hydroxy-2-ethylphenyl) fluorene]

A thermometer, a dropping funnel, a backflow condenser,
2 in a 300 ml four-necked flask equipped with a stirrer
-73.2 g (0.6 mol) of ethylphenol, 2.7 g of dodecyl mercaptan, 31.5 g of toluene, and 1.4 g of methanol were charged, and hydrogen chloride gas was blown into the mixture to saturate the mixture. 27.0 g of fluorenone was added to this solution.
(0.15 mol) and 18.8 g of 2-ethylphenol
(0.15 mol) and a mixed solution of 8.2 g of methanol in 5
It was dropped over time. After completion of the lowering, the reaction was continued at the same temperature for 3 hours. After the completion of the reaction, 16
% Aqueous sodium hydroxide was added to neutralize the reaction mixture, and then the aqueous layer was separated and removed from the reaction mixture to obtain a reaction-completed liquid (oil layer mixture). When the reaction-terminated liquid was analyzed by high performance liquid chromatography (HPLC), the reaction yield with respect to fluorenone was 89.6 mol%. Next, toluene and methanol were distilled off from the reaction-terminated liquid by distillation under reduced pressure, followed by filtration to obtain crude crystals.
Next, a mixture of toluene and water was added to the crude crystals to wash them,
The aqueous layer was separated and removed. After performing this washing twice, crystallization,
After filtration and drying, 38.7 gr of 9,9-bis (1-hydroxy-2-ethylphenyl) fluorene was obtained as white crystals. (Purity: 99.6%, yield based on fluorenone: 63.3 mol%)

[0029]

Embedded image

(1) Melting point: 189.5 ° C. (Mettler light transmission method) (2) Molecular weight: 405.7 (LC-MS method) (3) ¹ H-NMR (400 MHZ, DMSO solvent) ───────────────────────── Assignment δ (ppm) signal Proton number ───────────────── ───────────────a1.00t6b2.42q4c, d, e6.62-6.89m6f, g, h, i, j, k, l, m 7.27- 7.87 m8n 9.16 s2────────────────────────────────

[0031]

The bis (4-hydroxy-3) according to the present invention
-Ethylphenyl) is a bisphenol having a low melting point because it has a structure having a 2-ethylpheno nucleus linked by a specific 1,1-cyclohexyl group or 9-fluorenyl group. When a polymer component is used, the heat resistance, water resistance, and compatibility are expected to be improved. It is expected to be used as a raw material of a resin component, a raw material of a photosensitizer, a raw material of a dissolution inhibitor and an additive, or a polymer monomer having a non-linear structure or a crosslinked structure. Further, according to the present invention, such bis (4-hydroxy-3-ethylphenyl) s can be obtained by reacting 2-ethylphenol with the cyclohexanone or 9-ketofluorene in the presence of an acid catalyst. Can be obtained in high yield.

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Claims (1)

[Claims] 1. A novel bis (1-hydroxy-2-ethylphenyl) represented by the following general formula (1): ## STR1 ## Formula (1) (wherein, X represents a 1,1-cyclohexyl group or a 9,9-fluorenyl group represented by Formula (2). General formula (2) (R represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, and a hydroxyphenyl group.)