JP2000063308A - New tri-nucleus polyphenol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound containing phenolic structure bonded to a cyclohexane ring, having high oleophilic property and useful as a photosensitive material such as a photoresist for semiconductor. SOLUTION: The objective compound is expressed by formula I [Ar is an aryl of formula II (R1 is a 1-4C alkyl; R2 is a 5-6C cycloalkyl; R3 is phenyl; (m) is 0-3; (n) and (k) are each 0-2; m+n+k <=3) e.g. 1,4,4-tris(4-hydroxyphenyl) cyclohexane. The objective compound can be produced by reacting 4-(4- hydroxyphenyl) cyclohexanone with a phenolic compound of formula III in a reaction solvent such as methanol in the presence of an acid catalyst such as dried hydrogen chloride gas at 20-80 deg.C for about 2-48 hr under stirring.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel lipophilic compound having a phenol structure bonded to a cyclohexane ring.
It relates to a core (aromatic nucleus) polyphenol compound. Such polynuclear polyphenol compounds are used as base materials for photosensitive materials such as photoresists for semiconductors, raw materials for liquid crystal dielectric compounds for electro-optical display elements, raw materials for epoxy resins used for sealing materials for integrated circuits, and the like. It is also useful as a curing agent, a color developer and a color fading preventive used for recording heat-sensitive recording materials, and also as an additive such as a bactericide, a fungicide and a fungicide. BACKGROUND OF THE INVENTION [0002] The present inventors have considered that polynuclear polyphenols having high lipophilicity due to having a cyclohexane ring in the molecule and having a higher lipophilicity due to the asymmetric molecular structure. As a result of intensive studies to obtain a compound, a novel trinuclear (aromatic nucleus) polyphenol compound in which three phenol structures are asymmetrically bonded to a cyclohexane ring has been obtained, and the present invention has been achieved. Accordingly, an object of the present invention is to provide a novel trinuclear (aromatic nucleus) polyphenol compound having a highly lipophilic cyclohexane skeleton. According to the present invention, there is provided a compound represented by the general formula (I): (Wherein Ar is a general formula (II)) (Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms, R ₂ represents a cycloalkyl group having 5 or 6 carbon atoms, R ₃ represents a phenyl group, and m represents 0 to ₃ carbon atoms. N and k each represent an integer of 0 to 2;
n + k ≦ 3. ) Represents an aryl group. The present invention provides a trinuclear polyphenol compound represented by the formula: BEST MODE FOR CARRYING OUT THE INVENTION The trinuclear polyphenol compound according to the present invention is represented by the above general formula (I), and in the aryl group represented by the above general formula (II), R ₁ has ₁ carbon atom. And 4 to 4 alkyl groups, specifically, a methyl group, an ethyl group, a propyl group or a butyl group, and the propyl group or the butyl group may be linear or branched. R ₂ is a cycloalkyl group having 5 or 6 carbon atoms, specifically, a cyclopentyl group or a cyclohexyl group, preferably a cyclohexyl group. R ₃ represents a phenyl group. m represents an integer of 0 to 3, n and k each represent an integer of 0 to 2, and m + n + k ≦ 3. Further, the aryl group represented by the general formula (II) is preferably an alkyl-substituted-4-hydroxyphenyl group. Accordingly, specific examples of preferred tetranuclear polyphenol compounds according to the present invention include, for example, (1) 1,4,
4-tris (4-hydroxyphenyl) cyclohexane, (2) 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane, (3) 1- (4-hydroxyphenyl) ) -4,4-
Examples thereof include bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, but are not limited thereto. The trinuclear polyphenol compound according to the present invention can be converted into 4- (4-hydroxyphenyl) cyclohexanone in a reaction solvent, if necessary, in the presence of an acid catalyst by the general formula (III). Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms, R ₂ represents a cycloalkyl group having 5 or 6 carbon atoms, R ₃ represents a phenyl group, and m represents 0 to ₃ carbon atoms. N and k each represent an integer of 0 to 2;
n + k ≦ 3. )) Can be obtained by reacting the phenol. In the phenols, R ₁ , R ₂ and R ₃ are as described above, and the p-position of the hydroxyl group is preferably unsubstituted. Accordingly, in the production of the trinuclear polyphenol compound according to the present invention, specific examples of the phenol represented by the general formula (III) include, for example, phenol,
o-, m- or p-cresol, 2,3-, 2,4-, 2,5
-, 2,6- or 3,5-xylenol, 2,3,5-trimethylphenol, 3-methyl-6-t-butylphenol, 2-isopropylphenol, 2-cyclohexylphenol, 3-methyl-6-cyclohexylphenol , 2-phenylphenol, 2-t-butyl-6-phenylphenol and the like. Among these, in particular, phenol, o-cresol or 2,6-
Xylenol is preferably used. In the reaction between the phenols and 4- (4-hydroxyphenyl) cyclohexanone, the phenols are usually added in an amount of 4 to 20 mol parts per mol part of 4- (4-hydroxyphenyl) cyclohexanone. Used in In the reaction between the above phenols and 4- (4-hydroxyphenyl) cyclohexanone, a reaction solvent may or may not be used. When a reaction solvent is used, for example, an aliphatic alcohol, an aromatic hydrocarbon, or a mixed solvent thereof is used. As the alcohol, the reaction raw materials to be used, the solubility of the obtained product, the reaction conditions, the economics of the reaction, etc. are taken into consideration, and methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, isobutyl alcohol,
Examples thereof include n-butyl alcohol. Also,
Examples of the aromatic hydrocarbon solvent include toluene, xylene, cumene and the like. Such a solvent is usually used in 4- (4
(Hydroxyphenyl) cyclohexanone It is used in an amount of 100 to 500 parts by weight based on 100 parts by weight, but is not limited thereto. In the present invention, as the acid catalyst, dry hydrogen chloride gas is preferably used, but it is not limited thereto. For example, hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methane Sulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid and the like are also used. In the case of dry hydrogen chloride gas, for example, such an acid catalyst is preferably used in an amount that saturates the inside of the reaction system. Further, according to the present invention, in order to promote the reaction, a mercaptan or the like (for example, octyl mercaptan)
Can be used. The reaction is usually carried out at a temperature of from 20 ° C. to 80 ° C., preferably from 20 ° C. to 50 ° C., while blowing dry hydrogen chloride gas into the reaction mixture, while stirring, for about 2 to 48 hours. It may be performed for about 6 to 24 hours. After completion of the reaction, usually, an alkali is added to the obtained reaction mixture to neutralize the acid catalyst, and then an appropriate crystallization solvent is added to the aqueous layer, or the aqueous layer is separated and removed. Accordingly, after distilling the obtained organic layer under normal pressure or reduced pressure,
An appropriate crystallization solvent is added thereto to precipitate a crude crystal, and then the crude crystal is collected by filtration and further crystallized from an appropriate crystallization solvent to obtain the desired trinuclear substance. A high-purity polyphenol compound can be easily obtained. The above-mentioned crystallization solvent is appropriately selected in consideration of crystallization conditions, refining effects, economy and the like. As the aromatic hydrocarbon, for example, toluene, xylene, cumene And the like; and aliphatic alcohols such as methanol and ethanol; aliphatic ketones such as acetone, isopropyl ketone, methyl ethyl ketone, methyl isobutyl ketone and diisopropyl ketone; and cyclic ethers such as tetrahydrofuran and Dioxane and the like can be mentioned. The novel trinuclear polyphenol compound according to the present invention has a high lipophilicity due to having a cyclohexane ring in the molecule, and has a higher lipophilicity due to the asymmetric molecular structure. Has lipophilicity. Furthermore, the trinuclear polyphenol compound according to the present invention can be used as a raw material in various reactions, for example, a substitution reaction or a hydrogenation reaction for a phenolic aromatic ring.
Various derivatives can be obtained by performing a reaction on the phenolic hydroxyl group and the like. First, as a specific example of obtaining a derivative by a substitution reaction on a phenolic aromatic ring, for example, an olefin such as isobutene, an alcohol, a carbonyl compound, an alkyl halide or the like is added to a trinuclear polyphenol compound according to the present invention. Alternatively, various alkyl-substituted derivatives can be obtained by performing an alkylation reaction in the presence of a base catalyst. For example, by reacting an acid halide such as acetyl chloride or an acid anhydride in the presence of a Lewis acid, an acyl-substituted trinuclear polyphenol compound can be obtained. According to the Kolbe-Schmidt reaction in which carbon dioxide is reacted under pressure and heat, a carboxyl-substituted trinuclear polyphenol compound can be obtained. By reacting a nitrating agent such as nitric acid-acetic acid, a nitro-substituted trinuclear polyphenol compound can be obtained. When a methylolation reaction is performed with formaldehyde, a trinuclear polyphenol compound having a methylol group can be obtained. If acetylated with acetic anhydride in an alkaline aqueous solution,
An aldehyde-substituted trinuclear polyphenol compound can be obtained by formylating the acetyl-substituted trinuclear polyphenol compound with chloroform in an alkaline aqueous solution. By halogenating with a halogenating agent, a halogen-substituted trinuclear polyphenol compound can be obtained, and by reacting a diazonium salt, an azo-substituted trinuclear polyphenol compound can be obtained. By reacting formaldehyde with a secondary amine, an aminomethyl-substituted trinuclear polyphenol compound can be obtained. According to the reaction with nitrous acid, a nitroso-substituted trinuclear polyphenol compound can be obtained. By reacting with another phenol in the presence of an acid or alkali catalyst, a novolak resin can be obtained. Next, specific examples of obtaining a derivative by reacting with a phenolic hydroxyl group include, for example, alkyl halide, allyl halide,
By reacting epichlorohydrin or the like, corresponding trinuclear polyphenol ether compounds can be obtained. In particular, in order to convert the phenolic hydroxyl group to t-butoxycarbonyl methyl ether, the phenolic hydroxyl group must be prepared according to the present invention.
After dissolving the core polyphenol compound in a suitable solvent, the solution can be obtained by adding t-butyl chloroacetate and potassium carbonate to the resulting solution and heating with stirring. Glycidyl ether obtained by dissolving the trinuclear polyphenol compound according to the present invention in an appropriate solvent and reacting with epichlorohydrin can be used as an epoxy resin. If such glycidyl ether is further reacted with acrylic acid or methacrylic acid, an epoxy (meth) acrylate can be obtained. A trinuclear polyphenol ester can be obtained by reacting an acid anhydride, an acid chloride or the like with the phenolic hydroxyl group. In particular, for example, 1,2-
By reacting naphthoquinonediazide-4-sulfonyl chloride, a naphthoquinonediazidesulfonic acid ester of a trinuclear polyphenol compound can be obtained. In addition to the above, various polycyclic aromatic ring hydrogens can be obtained by subjecting the trinuclear polyphenol compound of the present invention to full or partial hydrogenation of the aromatic ring by, for example, gas phase reaction under pressure. Compound can be obtained. The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 (Synthesis of 1,4,4-tris (4-hydroxyphenyl) cyclohexane) 47.0 g of phenol and 7.8 g of 35% hydrochloric acid
Into a 500 mL four-necked flask, and adjust the liquid temperature to 5 mL.
After the temperature was raised to 5 ° C., a mixed solution of 19.0 g of 4- (4-hydroxyphenyl) cyclohexanone and 47.0 g of phenol was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred at 55 ° C. for 4 hours. After completion of the reaction, while stirring the reaction mixture at 55 ° C., 19.1 g of a 16% aqueous sodium hydroxide solution was added to neutralize the pH to 5 to 6, and 94 g of toluene was added thereto. , The precipitated crystals were filtered off at room temperature,
After drying, 1,4,4-tris (4-hydroxyphenyl)
Cyclohexane (88.8% purity) was obtained. Melting point: 228.3 ° C. Infrared absorption spectrum (cm ⁻¹ ): Hydroxyl group: 3265.3 Benzene ring: 1601.8 to 1510.2 Cyclohexane ring: 1448.4 Mass spectrum: M ⁺ = 360 Proton NMR spectrum : [0033] [Table 1] Example 2 (1- (4-hydroxyphenyl) -4,4-bis (3-
Synthesis of methyl-4-hydroxyphenyl) cyclohexane 54.0 g of o-cresol was charged into a 500 mL four-neck flask, and the temperature of the solution was raised to 40 ° C. A mixed solution of 19.0 g of-(4-hydroxyphenyl) cyclohexanone and 54.0 g of o-cresol was added dropwise over 3 hours. After completion of the addition, the mixture was stirred at 40 ° C for 4 hours. After completion of the reaction, 10 g of water was added thereto at 70 ° C. while stirring the reaction mixture.
25.0 g of a 5% aqueous sodium hydroxide solution to adjust the pH to 5
After neutralization to 6, the aqueous layer was separated to obtain an organic layer. 30 g of water and 100 g of toluene are added to the organic layer, and the organic layer is washed with water.
The aqueous layer was separated and removed. The crystals precipitated from the organic layer are separated by filtration at room temperature, dried and dried to give 1- (4-hydroxyphenyl)
-4,4-bis (3-methyl-4-hydroxyphenyl)
Cyclohexane (purity 89.7%) was obtained. Melting point: 188.6 ° C. Infrared absorption spectrum (cm ^-1 ): Hydroxyl group: 3258.5 Benzene ring: 1607.6 to 1506.3 Cyclohexane ring: 1449.4 Mass spectrum: M ⁺ = 388 Proton NMR spectrum Embedded image [Table 2] Example 3 (1- (4-hydroxyphenyl) -4,4-bis (3,5
Synthesis of -dimethyl-4-hydroxyphenyl) cyclohexane) 48.8 g of 2,6-xylenol was charged into a 500 mL four-neck flask, and the liquid temperature was raised to 55 ° C.
While blowing dry hydrogen chloride gas into the flask,
19.0 g of (4-hydroxyphenyl) cyclohexanone
And a mixed solution of 2,6-xylenol (61.0 g) was added dropwise over 2 hours. After completion of the addition, the mixture was stirred at 55 ° C. for 21 hours. After completion of the reaction, 20 g of water was added thereto at 70 ° C. while stirring the reaction mixture.
19.3 g of a 10% aqueous sodium hydroxide solution to adjust the pH to 5
After neutralization to 6, the aqueous layer was separated to obtain an organic layer. 30 g of water and 100 g of toluene are added to the organic layer, and the organic layer is washed with water.
The aqueous layer was separated and removed. The crystals precipitated from the organic layer are separated by filtration at room temperature, dried and dried to give 1- (4-hydroxyphenyl)
-4,4-Bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane (purity 97.2%) was obtained. Melting point: 205.7 ° C. Infrared absorption spectrum (cm ⁻¹ ): hydroxyl group: 3319.3 benzene ring: 161.4 to 1489.9 cyclohexane ring: 1451.3 mass spectrum: M ⁺ = 416 proton NMR spectrum Embedded image [Table 3]

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Takeshi Egawa             2-115, Kozaiga, Wakayama-shi Honshu             Gaku Kogyo Co., Ltd. F-term (reference) 4H006 AA01 AB03 AB49 AB76 AB92                       FC22 FC52 FE13

Claims (1)

[Claim 1] A compound represented by the general formula (I): (Wherein, Ar is a group represented by the general formula (II): (In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms, R ₂
Represents a cycloalkyl group having 5 or 6 carbon atoms, R ₃
Represents a phenyl group, m represents an integer of 0 to 3, n and k each represent an integer of 0 to 2, and m + n + k ≦ 3. ) Represents an aryl group. A) a trinuclear polyphenol compound represented by the formula: