JP2009035495A - Bis(4-oxocyclohexyl) compound and tetrakisphenol compound derived from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new bis(4-oxocyclohexyl) compound which can be used for photosensitive resist compositions, photosensitive polyimide resins, epoxy resins, and the like, has a low melting point, and has improved solubility in solvents and the like, and to provide a new tetrakisphenol compound derived from the same. <P>SOLUTION: Provided is a compound represented by the Figure, which can easily be produced, for example, by a two step reaction method comprising hydrogenating the nuclei of a bisphenol compound, to produce the biscyclohexanol, and then oxidizing the biscyclohexanol, to produce the bis(oxocyclohexyl) compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a novel bis (4-oxocyclohexyl) compound and a novel tetrakisphenol compound derived therefrom.
More specifically, the present invention relates to bis (4-oxocyclohexyl) having a 1,3-phenylenebisalkylene group in the central skeleton and two phenyl groups in each oxo group at both ends of the bis (4-oxocyclohexyl). The present invention relates to a tetrakisphenol compound having a bonded structure.
The bis (4-oxocyclohexyl) compound obtained by the present invention is useful as a raw material for pharmaceuticals, industrial raw materials, resin raw materials such as epoxy resins, imide resins and phenol resins, or an intermediate raw material such as antioxidants. Tetrakisphenol compounds derived from the above bis (4-oxocyclohexyl) compounds are used as photosensitive resist materials, photosensitive polyimide materials, photosensitive transparent resin insulating film materials, phenol resins, epoxy resin raw materials and curing agents, etc. Useful.

Conventionally, as the bis (4-oxocyclohexyl) compound, for example, 4,4′-bicyclohexanone, bis (4-oxocyclohexyl) methane, 2,2-bis (4-oxocyclohexyl) propane, 2,2-bis Several compounds such as (3-methyl-4-oxocyclohexyl) propane are known (Japanese Patent Laid-Open No. 49-250, Japanese Patent Laid-Open No. 8-134209, Japanese Patent Laid-Open No. 11-158108).
Examples of tetrakisphenol derived from these bis (4-oxocyclohexyl) compounds include 4,4,4 ′, 4′-tetra (4-hydroxyphenyl) bicyclohexyl 2,2-bis [4,4- Bis (4-hydroxyphenyl) cyclohexyl] propane, 2,2-bis [4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexyl] propane, 2,2-bis [4,4-bis (2- [t-Butyl-4-hydroxyphenyl) cyclohexyl] propane and the like are known (JP 2000-34248, JP 49-250). However, all of these have an alkylidene bis (cyclohexyl) skeleton or a bicyclohexane skeleton.
On the other hand, in tetrakisphenol, all of the compounds having such a central skeleton have a high melting point and poor solubility in a solvent or the like. Therefore, for example, in photosensitive resist composition applications, heat resistance and water resistance are improved. There is a desire to improve solubility in solvents while maintaining.

Japanese Patent Laid-Open No. 49-000250 Japanese Patent Application Laid-Open No. 08-134209 Japanese Patent Laid-Open No. 11-158108 JP 2000-34248 A

  Therefore, the present invention was made to improve the conventional problems as described above, and can be used for a photosensitive resist composition, a photosensitive polyimide resin, an epoxy resin, etc., heat resistance, water resistance, An object of the present invention is to provide a novel tetrakisphenol which is excellent in flexibility and has a low melting point and improved solubility in a solvent, and the present invention is a novel compound which can be a raw material compound of such tetrakisphenol. The object is to provide a novel bis (4-oxocyclohexyl) compound.

As a result of intensive studies to solve the above problems, the present inventors have found that a novel tetrakisphenol compound having a 1,3-phenylenebisalkyl group in the central skeleton can solve the above problems, and completed the present invention. .
Further, a novel bis (4-oxocyclohexyl) compound having a corresponding 1,3-phenylenebisalkyl group in the central skeleton, which can be a raw material compound of such a tetrakisphenol compound, was found and the present invention was completed.

According to the invention, the general formula (1)
General formula (1)
(In the formula, X represents a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, R ₁ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 0 to 4. The bis (4-oxocyclohexyl) compound represented by this is provided.

Moreover, according to the present invention, the general formula (2)
General formula (2)
(In the formula, R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₁ , X and n are the same as those in the general formula (1).) The tetrakisphenol compound represented by these is provided.

Since the novel tetrakisphenol compound as the target compound of the present invention is a tetrakisphenol having a central skeleton in which two cyclohexane rings are bonded via an alkyl group bonded to the 1,3-position of the phenylene group, it is highly resistant to solvents. It is economically advantageous because it is soluble, industrially efficient, and can produce high-purity products. Further, when used as a component of a composition such as a photosensitive resist, the melting point is low, the composition is easily dissolved, and the effect of suppressing crystal precipitation from the composition can be expected. Furthermore, when used as a raw material compound for various resins, improvements in heat resistance, water resistance and flexibility can be expected.
The compound obtained in the present invention is obtained by using a raw material bis (relative to mild conditions) by using palladium carbon which is cheaper than a conventional expensive rhodium carbon catalyst (JP-A-62-281832 or the like). Since 4-oxocyclohexyl) can be easily produced, it is advantageous for industrial implementation.
Moreover, the solubility in a solvent could be improved by bonding a cyclohexylalkyl group to an asymmetric 1,3-position (not 1,4-position).
Furthermore, the novel bis (4-oxocyclohexyl) compound of the raw material compound of the present invention is also a cyclohexane ring via an alkyl group bonded to the 1,3-position of the phenylene group, similarly to the novel tetrakisphenol compound of the present invention. Is a dioxo compound having a skeleton with two bonds, so when used as an intermediate compound of various chemicals, it has a low melting point, high solubility in solvents, and heat resistance, water resistance, flexibility Therefore, it is useful as a raw material for the tetrakisphenol compound of the present invention. Therefore, the novel tetrakisphenol compound of the present invention and the novel bis (4-oxocyclohexyl) compound of the present invention are photosensitive resist materials, Photosensitive polyimide material, photosensitive transparent resin insulation film material, phenol resin, epoxy resin raw material and curing agent, thermal recording It can be suitably used as a developer or anti-fading agent used in the material, or as these raw materials or raw material intermediates.

The bis (4-oxocyclohexyl) compound as a starting compound in the present invention is represented by the above general formula (1).
In the general formula (1), X represents a divalent saturated monovalent hydrogen group having 1 to 8 carbon atoms, and specifically includes a methylene group, an ethylidene group, a propane-2-ylidene group, and propane-1-ylidene. A linear or branched alkylidene group such as a group, pentane-3-ylidene group, 2-methylpropane-1-ylidene group, 2-methylbutane-1-ylidene group, n-pentane-1-ylidene group, It is a linear or branched alkylene group such as an ethylene group or a 1,2-propylene group, and X is preferably an alkylidene group of the following general formula (3).

General formula (3)
In the formula, R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that the sum of the number of carbon atoms of R ₄ and R ₅ represents an integer of 0 to 7.
Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a linear or branched propyl group, and a butyl group. Secondary alkyl groups are preferred.

In the general formula (1), R ₁ represents an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a straight chain having 3 to 8 carbon atoms, Examples include branched alkyl groups such as propyl, butyl, pentyl and octyl, and cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl. Of these, an alkyl group having 1 to 3 carbon atoms is preferable. Moreover, n shows the integer of 0-4, Preferably it is 0 or 1-2, and 0 or 1 is especially preferable. As the substitution position of the alkyl group, when n is 1, 2-position or 3-position, when n is 2, 2,5-position or 3,5-position, when n is 3, 2 , 3,5-positions, and the 2-position when n is 1 and the 2,5-position when n is 2 are preferred.

Therefore, as the bis (4-oxocyclohexyl) compound represented by the general formula (1), specifically, for example,
1,3-bis [1-methyl-1- (4-oxocyclohexyl) ethyl] benzene

1,3-bis [1-methyl-1- (2-methyl-4-oxocyclohexyl) ethyl] benzene

1,3-bis [1-methyl-1- (3,5-dimethyl-4-oxocyclohexyl) ethyl] benzene

further,
1,3-bis [1-methyl-1- (3-methyl-4-oxocyclohexyl) ethyl] benzene,
1,3-bis [1-methyl-1- (2,3,5-trimethyl-4-oxocyclohexyl) ethyl] benzene,
1,3-bis [(4-oxocyclohexyl) methyl] benzene,
1,3-bis [(3-methyl-4-oxocyclohexyl) methyl] benzene,
1,3-bis [1- (2-methyl-4-oxocyclohexyl) ethyl] benzene,
1,3-bis [1-methyl-1- (2,5-dimethyl-4-oxocyclohexyl) ethyl] benzene,
1,3-bis [2-methyl-2- (2-methyl-4-oxocyclohexyl) ethyl] benzene,
1,3-bis [1-ethyl-1- (2-methyl-4-oxocyclohexyl) ethyl] benzene,
1,3-bis [1-ethyl-1- (2-methyl-4-oxocyclohexyl) propyl] benzene,
1,3-bis [1-isopropyl-1- (2-methyl-4-oxocyclohexyl) butyl] benzene and the like.

  The method for producing the bis (4-oxocyclohexyl) compound represented by the general formula (1) in the present invention is not particularly limited. For example, bisphenols are used as a starting material, and this is subjected to nuclear hydrogenation. Thus, a two-stage reaction method can be presented in which biscyclohexanol is converted to bis (oxocyclohexyl) by oxidation.

  This includes, for example, a supported Rh catalyst, a supported Ru catalyst, a Raney nickel catalyst and the like having a bisphenol having a phenyl group in the central skeleton such as 4,4′-bis [1,3-phenylenebis (1-methylethylidene)] phenol. Hydrogenation of the phenyl nuclei at both ends under the specific conditions in the presence of ## STR4 ## yields the corresponding biscyclohexanol such as 4,4′-bis [1,3-phenylenebis (1-methylethylidene)] cyclohexanol ( This is oxidized with hypohalous acid or a salt thereof (Japanese Patent Laid-Open No. 4-59742) or oxidized in the presence of a copper-based oxidation catalyst (Japanese Patent Laid-Open No. 2002-179609). ) To obtain bisoxocyclohexyl, and its reaction formula (reaction formula 1) is shown below.

Reaction formula 1

  As other methods, bisphenols are similarly used as starting materials, in the presence of a palladium-based catalyst and an alkali metal compound (Japanese Patent Laid-Open No. 8-134209), or in the presence of an alkali metal-containing palladium catalyst (Japanese Patent Laid-Open No. 11-158108), and a one-step reaction method for obtaining bisoxocyclohexyl by direct hydrogenation. The reaction formula (reaction formula 2) of the one-step reaction is shown below.

Reaction formula 2

The one-stage reaction method can usually be carried out at a relatively low pressure of about 1 to 10 kg / cm ² , but oxocyclohexylcyclohexanol and biscyclohexanol are produced in addition to the target bisoxocyclohexyl. However, if the unsaturated bond of the raw material phenyl group is hydrogenated, by oxidizing this mixture with hypohalous acid or a salt thereof, the by-produced alcohol form becomes a ketone, which is highly bisoxo. Cyclohexyl can be produced. Therefore, as a method for producing bis (4-oxocyclohexyl) of the present invention, a bisphenol represented by the following general formula (3) is used as a raw material, and this is used in the presence of a palladium catalyst and an alkali metal compound, or an alkali. A method for producing bis (4-oxocyclohexyl), in which crude bis (4-oxocyclohexyl) obtained by hydrogenation in the presence of a metal-containing palladium catalyst and then removing the catalyst, etc. is oxidized, is preferred. It can be easily carried out and can be obtained with high yield and high purity.

General formula (3)
(In the formula, X, R ₁ and n are the same as those in the general formula (1).)

As such a bisphenol represented by the general formula (3), specifically, for example,
1,3-bis [1-methyl-1- (4-hydroxyphenyl) ethyl] benzene, 1,3-bis [1-methyl-1- (2-methyl-5-cyclohexyl-4-hydroxyphenyl) ethyl] Benzene, 1,3-bis [1-methyl-1- (3-methyl-4-hydroxyphenyl) ethyl] benzene, 1,3-bis [1-methyl-1- (2,3,5-trimethyl-4 -Hydroxyphenyl) ethyl] benzene, 1,3-bis [(4-hydroxyphenyl) methyl] benzene, 1,3-bis [(2,3,5-trimethyl-4-hydroxyphenyl) methyl] benzene, etc. be able to.
Further, such bisphenols represented by the above general formula (3) and X being an alkylidene group can be obtained, for example, by the method described in JP-A-9-143115, JP-A-2001-58968, etc. 1,3-di (1-hydroxyalkyl) benzene such as 1,3-di (2-hydroxy-2-propyl) benzene is reacted with excess phenols in the presence of an acid catalyst such as hydrogen chloride gas. Can be easily obtained.
When the bisphenol represented by the general formula (3) is 1,3-bis [1-methyl-1- (4-hydroxyphenyl) ethyl] benzene, the corresponding bis (4-oxo The production method for obtaining (cyclohexyl) is shown in the following reaction formula (reaction formula 3).

Reaction formula 3
In the hydrogenation reaction, the hydrogenation catalyst used for hydrogenation is not particularly limited as long as it reacts with high yield, and examples thereof include Raney catalysts, noble metal catalysts, noble metal supported catalysts, noble metal complex catalysts, and the like. . As the noble metal used in these noble metal catalysts, palladium (Pd), rhodium (Rh), ruthenium (Ru), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), silver (Ag) Among them, rhodium is preferable. Examples of the support used for the noble metal supported catalyst include carbon, alumina, silica and the like.
In addition, as the alkali metal-containing palladium catalyst used in the one-step reaction of the above reaction formula 2, both a palladium as a catalytic metal active component and an alkali metal as a promoter component are supported on a carrier. Carbon and alumina are preferred. Specific examples of the alkali metal component include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and the like. Sodium and sodium carbonate are preferred.

In the hydrogenation reaction, the amount of catalyst used varies depending on the type of catalyst, the amount of noble metal supported, bisphenols, concentration, etc., but is usually in the range of 0.1 to 100 wt%, preferably 0, relative to the raw material bisphenol. It is the range of 5-10 wt%.
The hydrogenation reaction is preferably performed in the presence of a solvent. The solvent to be used is not particularly limited as long as it dissolves the raw materials and does not inhibit the reaction, but aliphatic alcohols such as ethanol, 2-butanol and 2-propanol are preferable. The amount of the solvent is usually in the range of 50 to 1000 parts by weight, preferably in the range of 100 to 300 parts by weight with respect to 100 parts by weight of the raw material bisphenol. As reaction temperature, it is the range of 20-200 degreeC normally, Preferably it is the range of 100-150 degreeC. The reaction pressure (hydrogen pressure) is usually in the range of normal pressure to about 10 MPa, preferably 0.1 to 5 MPa. Under such reaction conditions, the hydrogenation reaction is usually completed in about 2 to 40 hours.

After completion of the above reaction, the catalyst is separated from the reaction product mixture by filtration, and then the filtrate containing the intermediate raw material bis (4-hydroxycycloxan) or the distillation residue obtained by distilling off the solvent from the filtrate is added to the distillation residue. An oxidizing agent such as a halogenated acid or an oxidation catalyst and, if necessary, a solvent are added to carry out the oxidation reaction.
The oxidizing agent or oxidation catalyst used in the oxidation reaction is not particularly limited as long as it reacts with a high yield. For example, copper-based oxides such as copper oxide, copper-chromium oxide, and copper-zinc oxide Examples include oxidation catalysts, hypohalous acids such as hypochlorous acid and hypobromite, or salts thereof. Preferably, it is hypohalous acid or a salt thereof, and the amount of the oxidizing agent used is usually in the range of 2 to 4 mol times relative to 1 mol part of bis (4-hydroxycycloxanane) as an intermediate raw material. is there.
It is more preferable to use an organic carboxylic acid such as acetic acid together with a hypohalous acid or a salt thereof for the reason that the reaction can be completed in a short time. The amount of the organic carboxylic acid used is a hypohalous acid or a salt thereof. It is 1-2 mol times with respect to 1 mol.

The oxidation reaction is usually performed in the presence of a solvent. The solvent to be used is not particularly limited as long as it dissolves the raw materials and does not inhibit the reaction. Examples of preferred solvents include aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and acetic acid. The amount of the solvent is usually in the range of 50 to 1000 parts by weight, preferably in the range of 100 to 300 parts by weight, with respect to 100 parts by weight of the raw material bis (4-hydroxycyclooxane).
Moreover, reaction temperature is the range of 0-100 degreeC normally, Preferably it is the range of 20-50 degreeC.
Under such reaction conditions, the oxidation reaction is usually completed in about 0.1 to 5 hours.

In order to purify the target product from the obtained reaction completion mixture after completion of the above reaction, a known method can be used as appropriate. For example, the reaction-terminated mixture is neutralized by adding alkaline water such as an aqueous sodium hydroxide solution. After neutralization, if necessary, a solvent that can be separated from water such as toluene, xylene, methyl isobutyl ketone or ether is added to separate and remove the aqueous layer, and then the aqueous layer is separated and the obtained oil layer is washed with water. Then, after distilling off the solvent as necessary, an appropriate crystallization solvent is added thereto, and the solution is crystallized or precipitated, filtered, and if necessary, obtained by filtration. The target crystal can be obtained after the solvent used for crystallization is poured into the crystal and washed.
If further purification is required as necessary, such recrystallization may be repeated a plurality of times.

Next, the tetrakisphenol compound which is another novel compound according to the present invention is represented by the above general formula 2).
In the formula, R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, or a straight chain having 3 to 8 carbon atoms. And branched alkyl groups such as propyl, butyl, pentyl and octyl, and cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl. Of these, an alkyl group having 1 to 4 carbon atoms is preferred. When both R ₂ and R ₃ are alkyl groups, at least one is preferably a primary or secondary alkyl group.
When n is 1, the substitution position of R ₁ is preferably the 2-position, and when n is 2, the substitution positions of R ₁ are preferably the 2-position and the 6-position.

Therefore, as a tetrakisphenol compound represented by the general formula (2), specifically, for example,
1,3-bis {1-methyl-1- [4,4-bis (4-hydroxyphenyl) cyclohexyl] ethyl} benzene

1,3-bis {1-methyl-1- [4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexyl] ethyl} benzene

1,3-bis {1-methyl-1- [4,4-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexyl] ethyl} benzene

further,
1,3-bis {1-methyl-1- [4,4-bis (3-ethyl-4-hydroxyphenyl) cyclohexyl] ethyl} benzene,
1,3-bis {1-methyl-1- [4,4-bis (3-isopropyl-4-hydroxyphenyl) cyclohexyl] ethyl} benzene,
1,3-bis {1-methyl-1- [4,4-bis (3-sec-butyl-4-hydroxyphenyl) cyclohexyl] ethyl} benzene,
1,3-bis {1-methyl-1- [4,4-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexyl] ethyl} benzene,
1,3-bis {1-methyl-1- [4,4-bis (4-hydroxyphenyl) -2-methylcyclohexyl] ethyl} benzene,
1,3-bis {1-methyl-1- [4,4-bis (4-hydroxyphenyl) -2,5-dimethylcyclohexyl] ethyl} benzene,
1,3-bis {1-methyl-1- [4,4-bis (3-methyl-4-hydroxyphenyl) -2-methylcyclohexyl] ethyl} benzene,
1,3-bis {[4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexyl] methyl} benzene,
1,3-bis {[4,4-bis (3-methyl-4-hydroxyphenyl) -2-methylcyclohexyl] methyl} benzene,
1,3-bis {1-methyl-1- [4,4-bis (3-methyl-4-hydroxyphenyl) -2,3,5-trimethylcyclohexyl] ethyl} benzene,
1,3-bis {2-methyl-2- [4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexyl] ethyl} benzene,
1,3-bis {1-ethyl-1- [4,4-bis (3-methyl-4-hydroxyphenyl) -2-methylcyclohexyl] ethyl} benzene,
1,3-bis {1-ethyl-1- [4,4-bis (3-methyl-4-hydroxyphenyl) -2-methylcyclohexyl] propyl} benzene,
1,3-bis {1-isopropyl-1- [4,4-bis (3-methyl-4-hydroxyphenyl) -2-methylcyclohexyl] butyl} benzene,
Etc.

The production method of the novel tetrakisphenol compound in the present invention is not particularly limited, but the novel bis (4- An oxocyclohexyl) compound is preferably used as a raw material, which is preferably produced by a condensation reaction with a phenol in a solvent in the presence of an acid catalyst.
Therefore, in the method for producing a tetrakisphenol compound according to the present invention, the raw material phenols used together with the raw material bis (4-oxocyclohexyl) compound include the following general formula (4):

General formula (4)
(In the formula, R ₂ and R ₃ are the same as those in the general formula (2).)
Specifically, for example, phenol, o-cresol, 2,6-xylenol, 2-isobutylphenol, 2-cyclopentylphenol, 2-cyclohexylphenol, 2-sec-butylphenol, 2- Examples thereof include t-butylphenol, 2-isopropylphenol, 2-ethylphenol, 2-cyclohexyl-6-methylphenol.

In the reaction of such phenols with bis (4-oxocyclohexyl), the phenol is usually in the range of 4 to 20 mol parts, preferably 8 to 1 mol parts with respect to 1 mol parts of bis (4-oxocyclohexyl). It is used in the range of 12 mole parts.
In the reaction of phenols with bis (4-oxocyclohexyl), a reaction solvent may or may not be used. However, it is preferable to use a solvent when the raw materials and the acid catalyst cannot be dissolved uniformly, or when stirring is not sufficient due to the high viscosity of the reaction solution. As a reaction solvent, lower aliphatic alcohols such as methanol, n-butanol, t-butanol and cyclohexanol, aromatic hydrocarbons such as toluene, xylene and benzene, saturation such as n-hexane, cyclohexane and n-pentane. Examples thereof include hydrocarbons, and among these, lower aliphatic alcohols having 1 to 4 carbon atoms such as methanol are preferred.
Such a solvent is usually used in a range of 0.1 to 10 times by weight, preferably 0.5 to 2 times by weight, based on 1 part by weight of phenols to be used, but is not limited thereto. .

The acid catalyst used in the present invention is not particularly limited as long as it is an acid that dissolves in the reaction mixture, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid, hydrogen chloride gas, phosphoric acid, formic acid, oxalic acid, and p-toluene. Examples of the organic acid include sulfonic acid, methanesulfonic acid, trichloroacetic acid, and trifluoroacetic acid, and hydrochloric acid and hydrogen chloride gas are preferable.
Such an acid catalyst is usually used in the range of 5 wt% to 100 wt% with respect to bis (4-oxocyclohexyl). In the case of dry hydrogen chloride gas, it is preferable to saturate the reaction system. Used in

In the case of the above reaction, when the reaction rate is slow or the yield is low, a promoter can be used as necessary to promote the reaction. Examples of such promoters include alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, n-dodecanethiol, and n-octanethiol. Such a cocatalyst is usually used in the range of 1 to 10 wt% with respect to bis (4-oxocyclohexyl).
The reaction temperature is usually in the range of 0 to 60 ° C, preferably in the range of 10 to 40 ° C. Under such reaction conditions, the reaction is usually completed in about 1 to 20 hours, preferably about 1 to 10 hours.

In the above reaction, the method for adding the raw materials and the like is not particularly limited, but a method in which a mixed solution of bis (4-oxocyclohexyl) s and phenols is dropped into an acid catalyst solution in which phenols may be present is preferable. . At that time, a solvent may be appropriately used in order to keep the reaction mixture in a liquid state.
In order to purify the target product from the obtained reaction completion mixture after completion of the reaction, a known method can be appropriately used. For example, the reaction-terminated mixture is neutralized by adding alkaline water such as an aqueous sodium hydroxide solution. After neutralization, if necessary, a solvent that can be separated from water such as toluene, xylene, methyl isobutyl ketone or ether is added to separate and remove the aqueous layer, and then the aqueous layer is separated and the obtained oil layer is washed with water. Then, if necessary, after distilling off the solvent and raw material phenols, an appropriate crystallization solvent is added thereto, and crystallization or precipitation is performed. The target product can be obtained as an amorphous body. Depending on the tetrakisphenol compound, it can also be obtained as an adduct crystal with phenols or a solvent used for crystallization.

  Specifically, the crystallization solvent is appropriately selected in consideration of crystallization conditions, purification effects, economy, etc., for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, methanol, Aliphatic alcohols such as butanol and ethanol, aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, linear and cyclic aliphatic esters such as methyl acetate, ethyl acetate and γ-butyrolactone, n-heptane, n-hexane, Examples thereof include aliphatic hydrocarbons such as cyclohexane, and aliphatic carboxylic acids such as acetic acid and butanoic acid.

In the present invention, if the purity of the obtained target product is low, further purification may be performed according to the properties of the obtained target product, if necessary. As such a purification method, when the target product is a crystal, it may be purified by recrystallization or reprecipitation one to several times, or used for crystallization or recrystallization. The solvent may be purified by pouring into the obtained crystalline or non-crystalline material and washing again.
In addition, when the obtained target product is an adduct crystal (adduct crystal) with a low boiling point compound (solvent), the adduct crystal is decomposed by heat at about 100 to 200 ° C. under reduced pressure, and the added compound (Solvent) may be removed for purification.
Furthermore, when the obtained target product is not obtained as a crystal or solid (non-crystal), the reaction mixture obtained above is subjected to distillation etc. to remove raw phenols, A crude product can be obtained, or a high-purity product can be obtained by a column separation method or the like.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(Synthesis of 1,3-bis (1-methyl-1- (4-oxocyclohexyl) ethyl) benzene);
In a 1 L capacity SUS autoclave, 26,0 g (0.768 mol) of 1,3-bis [1-methyl-1- (4-hydroxyphenyl) ethyl] benzene (hereinafter abbreviated as BisP-M), Kawaken Fine 5% After charging 2.5 g of Pd / C (AD type) and 400 g of 2-butanol and replacing the inside of the autoclave with hydrogen, the temperature was raised to 135 ° C. with stirring. Thereafter, the reaction was carried out for 13 hours while maintaining a reaction temperature of 135 ° C. and a hydrogen pressure of 0.25 MPa.
As a result of gas chromatography analysis of the reaction solution, the composition value (Area%) was 71.8% for the bis (4-oxocyclohexyl) compound, 1- (1-methyl-1- (4-hydroxycyclohexyl) ethyl) 26.3% of -3- (1-methyl-1- (4-oxocyclohexyl) ethyl) benzene, 1.5 of 1,3-bis (1-methyl-1- (4-hydroxycyclohexyl) ethyl) benzene %Met.
After completion of the reaction, the catalyst was filtered off, the filtrate was distilled and the solvent was distilled off. After 400 g of methyl isobutyl ketone and 20.5 g of acetic acid were added to and dissolved in 267 g of the obtained distillation residue, 233.0 g of a 10% hypochlorous acid aqueous solution was added dropwise over 1.5 hours at room temperature. The oxidation reaction was carried out at room temperature for 1 hour.
After completion of the reaction, the reaction mixture was neutralized by adding a 16% aqueous sodium hydroxide solution, and the aqueous layer was separated and removed. Water was added to the obtained oil layer and stirred, and then the aqueous layer was separated and removed. The same water washing operation was performed twice on the obtained oil layer. Then, after removing the solvent by distillation, 266 g of heptane was added to the residue and dissolved by heating, followed by crystallization to precipitate crystals.
The precipitated crystals were separated by filtration and dried to obtain 232.0 g of pale yellow crystals having a purity of 99% (gas chromatography analysis method) and a melting point of 100 to 100 ° C. (DSC method) (yield of 84 mol% based on BisP-M as a raw material). Got.
It was confirmed to be the target product by proton NMR analysis and liquid chromatography mass spectrometry.

Molecular weight 377 (M + Na) ⁺ (liquid chromatography mass spectrometry / atmospheric pressure chemical ionization method)
Proton NMR analysis results (400MHz, solvent: DMSO-d6, reference material: tetramethylsilane)

(Synthesis of 1,3-bis (1-methyl-1- (4,4-bis (4-hydroxyphenyl) cyclohexyl) ethyl) benzene);
A 1 L glass four-necked flask was charged with 33.0 g of methanol and 4.2 g of dodecyl mercaptan, and the inside of the flask was replaced with hydrochloric acid gas. Thereafter, 70.9 g (0.200 mol) of 1,3-bis (1-methyl-1- (4-oxocyclohexyl) ethyl) benzene (hereinafter abbreviated as 4H-BPM) obtained in Example 1 was added to 225.8 g of phenol. (2.40 mol) and 113 g of methanol dissolved therein were added dropwise to the solution over 1.5 hours with stirring while continuing to blow hydrochloric acid gas. During the dropping, the reaction solution was kept at 25-30 ° C. After completion of the dropwise addition, the reaction was continued for 1 hour at 25 to 30 ° C. while continuing to blow hydrochloric acid gas. Crystals were precipitated, and the reaction solution was solidified, so 316 g of toluene and 45 g of methanol were added. Thereafter, the reaction was continued for 4 hours while continuing to blow hydrochloric acid gas.
After completion of the reaction, the reaction solution was neutralized by adding a 16% aqueous sodium hydroxide solution, heated to 70 ° C., and the aqueous layer was separated. Water was added to the obtained oil layer, stirred and washed with water, and then the aqueous layer was separated. After the solvent was distilled off from the obtained oil layer, phenol was recovered by distillation under reduced pressure, and a mixed solution of 278 g of ethyl acetate and 139 g of cyclohexane was added to the remaining distillation residue, and the mixture was heated to dissolve and crystallized. The precipitated crystals were separated by filtration to obtain about 200 g of crude crystals.
The obtained crude crystals were recrystallized with a mixed solution of 2-propanol and methanol, cooled, filtered, dried at 180 ° C. under reduced pressure, and a transparent solid having a purity of 99.1% (HPLC analysis method) (Amorphous) 71.0 g (yield 54% based on 4H-BPM of the raw material) was obtained. It was confirmed to be the target product by liquid chromatography mass spectrometry and proton NMR analysis.

Molecular weight 693 (M−H) ⁻ (liquid chromatography mass spectrometry / atmospheric pressure chemical ionization method)
Glass transition temperature 137.3 ° C. (by differential scanning calorimeter) No melting point was observed.
Proton NMR analysis results (400MHz, solvent: DMSO-d6, reference material: tetramethylsilane)

(Synthesis of 1,3-bis (1-methyl-1- (4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexyl) ethyl) benzene);
A 1 L glass four-necked flask was charged with 108.0 g of o-cresol, 26.6 g of methanol, and 4.4 g of dodecyl mercaptan, and the inside of the flask was replaced with hydrochloric acid gas. Thereafter, the mixed solution prepared by adding 216.0 g (2.00 mol) of o-cresol and 17.7 g of methanol to 88.6 g (0.250 mol) of 4H-BPM obtained in Example 1 was supplied with hydrochloric acid gas while stirring. It was dripped over 1.0 hour, continuing. During the dropping, the reaction solution was kept at 25-30 ° C. When the reaction was continued at 25-30 ° C. for 1.5 hours while the supply of hydrochloric acid gas was continued after completion of dropping, 44.3 g of methanol was added since the reaction solution was solidified. Thereafter, the reaction was continued for 4 hours while further blowing hydrochloric acid gas.
After completion of the reaction, the reaction solution was neutralized with a 16% aqueous sodium hydroxide solution, heated to 78 ° C., and the aqueous layer was separated. To the resulting oil layer, 376 g of toluene and water were added, stirred and washed with water, and then the aqueous layer was separated. After the solvent was distilled off from the obtained oil layer, o-cresol was recovered by distillation under reduced pressure, and 469 g of toluene was added to the remaining distillation residue, which was dissolved by heating and crystallized. The precipitated crystals were separated by filtration to obtain 318 g of crude crystals.
This crude crystal was dissolved in a mixed solution of 2-propanol and methanol, recrystallized, cooled, filtered, dried at 4 KPa, 180 ° C., and dried at 48.0 Pa (HPLC), a transparent solid (non-crystalline) 67 0.0 g was obtained. It was confirmed to be the target product by liquid chromatography mass spectrometry and proton NMR analysis.

Yield 35.4% (vs. 4H-BPM)
Molecular weight 749 (M−H) ⁻ (liquid chromatography mass spectrometry / atmospheric pressure chemical ionization method)
Glass transition temperature 110.6 ° C. (by differential scanning calorimeter) Melting point was not observed.
Proton NMR analysis results (400MHz, solvent: DMSO-d6, reference material: tetramethylsilane)

[Comparative example]
(Hydrogenation of 1,4-bis [1-methyl-1- (4-hydroxyphenyl) ethyl] benzene);
1 L of SUS autoclave, 20 g (0.058 mol) of 1,4-bis [1-methyl-1- (4-hydroxyphenyl) ethyl] benzene, 2.0 g of Kawaken Fine 5% Pd / C (AD type) Then, 400 g of 2-butanol was charged, and after replacing with hydrogen, the reaction was carried out while maintaining the reaction temperature of 120 ° C./hydrogen pressure of 0.4 MPa while stirring. However, hydrogen absorption stopped at about 20% of the theoretical absorption. This indicates that the 1,4-conjugate is difficult to hydrogenate compared to the 1,3-conjugate of the present invention, and bis (4-oxocyclohexyl) cannot be easily obtained.
When the autoclave was opened at room temperature, white crystals were precipitated and the reaction solution was solidified. The white crystals did not dissolve in polar solvents such as tetrahydrofuran, dimethyl sulfoxide, N, N-dimethylformamide.

Claims (2)

General formula (1)
General formula (1)
(In the formula, X represents a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, R ₁ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 0 to 4. The bis (4-oxocyclohexyl) compound represented by this. General formula (2)
General formula (2)
(In the formula, R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₁ , X and n are the same as those in the general formula (1).) The tetrakisphenol compound represented by these.