JP5380008B2 - Tetrakis (hydroxymethylphenol) and its formylated derivatives tetrakis (formylphenol) - Google Patents

Description

  The present invention relates to novel tetrakis (hydroxymethylphenol) s and further to novel tetrakis (formylphenol) s which may be derived by formylation of such compounds.

  In recent years, raw materials such as epoxy resins for electronic parts and photosensitive resists have been required to be further improved in terms of reactivity and heat resistance in response to microfabrication technology. There is a need for raw material compounds. Polynuclear poly (hydroxymethylphenol) s as such compounds, and polynuclear poly (formylphenol) s that may be derived by formylization using these as raw materials are hydroxyl groups that are highly reactive with the phenyl nuclei at the molecular terminals. And a hydroxymethyl group or a formyl group, and selection of the central structure is relatively easy in the production of the compound, so that it is suitable as a raw material compound for meeting further improvement demands. In particular, as a structure having high reactivity and heat resistance, tetrakis (hydroxymethylphenol) or tetrakis (formylphenol) having two phenol groups having one hydroxymethyl group or formyl group in two cyclohexyl rings at the molecular end. Was found to be a novel compound having a structure meeting such a requirement, and the present invention was completed.

  Conventionally, polynuclear hydroxymethylphenols having a hydroxymethyl substituent at the hydroxyphenyl group at the molecular end include, for example, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bis (3,5-dihydroxy Bisphenol such as methylphenol), tetrakisphenol such as 2,2-bis [4,4-cyclohexylidenebis (4-hydroxy-3,5-dihydroxymethylphenyl)] propane (Patent Document 1), 1- [α- Methyl-α- (3′-hydroxymethyl-5′-methyl-4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (3 ″ -hydroxymethyl-5 ″ -methyl-4) '' -Hydroxyphenyl) ethyl] benzene (Patent Document 2) and some compounds such as pentamethylolated tetraphenol (Patent Document 3: Example 9) It is known.

However, there is no known tetrakis (hydroxymethylphenol) in which one hydroxymethyl group is bonded to each of two hydroxyphenyl groups bonded to the same carbon atom of each terminal cyclohexyl ring of the central biscyclohexane or cyclohexane skeleton. .
Conventionally, polynuclear phenols having a formyl group as a nuclear substituent on the hydroxyphenyl group at the molecular end include 1- [α-methyl-α- (3-formyl-5-methyl-4-hydroxyphenyl) ethyl]. Several compounds such as tris (hydroxyformylphenyl) compounds (Patent Document 4) such as -4- [α, α-bis (3-formyl-5-methyl-4-hydroxyphenyl) ethyl] benzene are known. However, a formyl group may be further bonded to two hydroxyphenyl groups bonded to the same carbon atom of each of the terminal cyclohexyl rings of biscyclohexyl, which may be derived by formylation of tetrakis (hydroxymethylphenol) as described above. Tetrakis (formylphenol) is not known.

Japanese Patent Laid-Open No. 2003-300923 JP 2003-3000922 A JP 2006-117899 A International Publication No. 2007/142353

  Accordingly, it is an object of the present invention to provide novel tetrakis (hydroxymethylphenol) s and novel tetrakis (formylphenol) s which may be derived by formylation of such compounds.

The novel compounds according to the present invention are tetrakis (hydroxymethylphenol) s represented by the following general formula (1).
General formula (1)
(In the formula, Ra and Rb each independently represents an alkyl group having 1 to 8 carbon atoms, k and j represent 0 or an integer of 1 to 4, and R ₁ represents an alkyl group having 1 to 8 carbon atoms. Or an alkoxyl group having 1 to 8 carbon atoms, n represents an integer of 0 or 1 to 3, X represents a single bond or a divalent linking group, and m represents an integer of 0 or 1.)

Another novel compound that may be derived by formylating the above tetrakis (hydroxymethylphenol) according to the present invention is a tetrakis (formylphenol) represented by the following general formula (2).
General formula (2)
(In the formula, Ra, Rb, k, j, R ₁ , n, X and m are the same as those in the general formula 1.)

In the tetrakis (hydroxymethylphenol) represented by the general formula (1),
In the formula, Ra and Rb each independently represent an alkyl group having 1 to 8 carbon atoms, k and j represent 0 or an integer of 1 to 4, and R ₁ represents an alkyl group having 1 to 8 carbon atoms or An alkoxyl group having 1 to 8 carbon atoms, n represents an integer of 0 or 1 to 3, X represents a single bond or a divalent linking group, and m represents an integer of 0 or 1.

In R a, R b, R ₁ , the alkyl group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and is a linear alkyl group or a branched chain having 3 to 8 carbon atoms. And a cyclic alkyl group having 3 to 8 carbon atoms. The alkoxyl group having 1 to 8 carbon atoms in R ₁ is preferably an alkoxyl group having 1 to 4 carbon atoms, and is a linear alkoxyl group or a branched alkoxyl group having 3 to 8 carbon atoms. And a cyclic alkoxyl group having 3 to 8 carbon atoms. Preferable Ra and Rb are the same as each other and each is an alkyl group having 1 to 4 carbon atoms. Preferred R ₁ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms. is there. Further, preferable k and j are both 0 or 1, and preferable n is 1.
Specifically, for example, as a linear alkyl group and a branched alkyl group having 3 to 8 carbon atoms, methyl group, ethyl group, isopropyl group, tert-butyl group, sec-butyl group, isobutyl group, The n-hexyl group, t-octyl group, n-dodecyl group, and cyclic alkyl group having 3 to 8 carbon atoms include cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, linear alkoxyl group, and 3 to 3 carbon atoms. Examples of the branched alkoxy group of 8 include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, and examples of the cyclic alkoxyl group having 3 to 8 carbon atoms include a cyclohexyloxy group and a cyclopentyloxy group.

In the general formula (1), the hydroxyl group is preferably 4-position or 2-position, more preferably 4-position with respect to the bonding position of the cyclohexyl group and the phenyl group. When the hydroxyl group is 4-position, the hydroxymethyl group is The 3-position is preferred, and when the hydroxyl group is the 2-position, the hydroxymethyl group is preferably the 3-position or the 5-position.
Accordingly, a preferred hydroxymethylphenol group is represented by, for example, the following general formula (3).
General formula (3)
(Wherein R ₁ is the same as that of general formula 1)

Moreover, in General formula (1), X shows a single bond or a bivalent coupling group. When X is a divalent linking group, X is a saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, specifically, a linear saturated hydrocarbon group or a branched saturated hydrocarbon group. Examples thereof include a hydrogen group and a cyclic saturated hydrocarbon group which may have a substituent. Specifically, for example, methylene group, 1,2-ethylene group, 1,3-propylene group, ethylethylene group, pentamethylene group and other alkylene groups, 1-methyl-methylidene group, 2,2-propylidene group, Alkylidene groups such as 1-methyl-2,2-hexylidene group, 1-ethyl-2,2-hexylidene group, 2,2-butylidene group, 1-isopropyl-2,2-propylidene group, cyclohexane-1,4- And cycloalkylene groups such as diyl group and 5-methyl-cyclohexane-1,3-diyl group.
M represents an integer of 0 or 1. When m = 1, the 4,4′-position is preferred with respect to the bonding position of the phenyl group.

Therefore, the following central group represented by the general formula (1)
As, preferably,
Specifically,
If m is 0,
When m is 1 and X is 0,
When m is 1 and X is a divalent linking group,
(In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 19 carbon atoms as the sum of R ₃ + R _4. )
Is mentioned. As the saturated hydrocarbon group for R ₃ and R ₄ , both or at least one is preferably a primary or secondary alkyl group, and a chain or branched alkyl group is particularly preferable. R ₃ and R ₄ preferably have 1 to 9 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

Therefore, as tetrakis (hydroxymethylphenol) represented by the general formula (1), specifically, for example,
1,1,4,4, -tetrakis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) cyclohexane,
4,4,4′4′-tetrakis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) -1,1′-bicyclohexane,
Bis {4,4-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) cyclohexyl} methane,
2,2-bis {4,4-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) cyclohexyl} propane,
Etc.

  The tetrakis (hydroxymethylphenol) represented by the general formula (1) of the present invention is not particularly limited in its production method. For example, it is similar to the method described in JP-A-2003-300922. It can be manufactured by a method. Specifically, a tetrakisphenol represented by the following general formula (4) corresponding to the tetrakis (hydroxymethylphenol) of the present invention is directly used as a raw material, and this is water or water and organic in the presence of a base. Obtained after reacting 1 to 10 times, preferably 1.5 to 5 times, the amount of formaldehyde in a mixed solvent with the solvent in the theoretical amount (4 mol parts relative to 1 mol part of tetrakisphenol). It can be obtained by neutralizing the reaction product obtained.

General formula (4)
(In the formula, Ra, Rb, k, j, R ₁ , n, X and m are the same as those in the general formula (1).)

The raw material tetrakisphenols represented by the general formula (4) can be prepared by, for example, alicyclic diketones and phenols in the presence of an acid catalyst, as in the method described in JP-A-62-84035. It can be obtained by reacting.
In the reaction of the raw material tetrakisphenol with formaldehyde, when formaldehyde is used in the tetrakisphenol above the theoretical amount of 10 times, the formaldehyde greatly exceeds the theoretical amount in the reaction, and the process economy is reduced. . On the other hand, when the tetrakisphenol is used in an amount less than the theoretical amount, a large amount of di- and trihydroxymethyl group-substituted products and unreacted raw material tetrakisphenol remain unpreferable.

In the above-described production method, as the formaldehyde, a commercially available formalin aqueous solution can be used as it is, and paraformaldehyde and trioxane that act in the same manner as formaldehyde in the presence of water can be used. Among these, formalin is used. It is preferable.
Examples of the basic catalyst include alkali metal hydroxides and acetates such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides and acetates such as calcium hydroxide, and pyridine. And tertiary amines such as trimethylamine and tributylamine. Of these, sodium hydroxide, potassium hydroxide, and the like are particularly preferably used.
In the present invention, such a basic catalyst is used in the range of 0.1 to 5 times equivalent, preferably 0.1 to 2 times equivalent to the hydroxyl group of the tetrakisphenol.

In the present invention, the reaction between the tetrakisphenols and formaldehyde in the presence of the basic catalyst is usually carried out in an aqueous solvent or a mixed solvent of water and an organic solvent. The solvent is usually used in a range of about 1 to 5 times, preferably about 2 to 3 times by weight with respect to the tetrakisphenols as the raw material.
Examples of the organic solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, and ethylene glycol as long as the solubility of the basic catalyst and the raw material tetrakisphenol in the mixed solvent is not impaired. Alcohol solvents such as ethylene glycol monomethyl ether, diethylene glycol, carbitol, and water-soluble organic solvents such as tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are used.
The above reaction is usually performed at a temperature in the range of 0 to 60 ° C., preferably 20 to 50 ° C., usually for 1 to 72 hours, preferably about 4 to 16 hours.
In the condensation reaction of the tetrakisphenols with formaldehyde in the presence of a basic catalyst, the reaction product obtained is a mixture of hydroxymethyl group adducts to the aromatic nucleus at the end of the tetrakisphenols. Depending on the amount of basic catalyst used, some or all of these are present as alkali salts in the reaction mixture. Although the reaction varies depending on conditions such as the type and mixing ratio of an organic solvent such as an alcohol or the like in an aqueous solvent or mixed solvent used in the reaction, the amount of the solvent used, the type and amount of the basic catalyst used, It is a reaction.

Therefore, according to the present invention, in order to separate and recover the desired reaction product from the obtained reaction mixture, the obtained reaction mixture is cooled after the completion of the reaction, and an aromatic hydrocarbon is used as an extraction solvent. After adding an organic solvent that does not mix with water, such as aliphatic alcohols, aliphatic ketones, and esters, or a mixture thereof to the reaction mixture, an acidic compound such as an organic acid or an inorganic acid, or a mixture thereof. An aqueous solution is added to neutralize the entire reaction mixture, the aqueous layer is separated, and the reaction product is extracted into the organic layer. Subsequently, the organic layer thus obtained is concentrated if necessary, and then cooled, and thus the precipitated solid content is filtered off to obtain the desired tetrakis (hydroxymethylphenol) s. it can.
Further, according to the present invention, after neutralizing the reaction mixture, an extraction solvent such as aromatic hydrocarbon, aliphatic alcohol, aliphatic ketone, ester or the like may be added thereto. In particular, according to the present invention, after completion of the reaction, the impurities separated from the reaction mixture at the initial stage of neutralization of the obtained reaction mixture are previously extracted and removed with the extraction solvent, and then the reaction product is extracted from the aqueous layer. If the organic layer is extracted using a solvent and the organic layer is treated as described above, a higher-purity target product can be obtained.

The compound according to the present invention obtained by the method as described above is usually solid at room temperature and can be advantageously used for various applications.
In particular, the compound according to the present invention corresponds to a tetrakis (hydroxymethylphenol) compound by using this as a raw material, further reacting it with hexamethylenetetramine in the presence of an acid, and then hydrolyzing the reaction product. A tetrakis (formylphenol) compound can be obtained.

  For example, 2,2-bis {4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexyl} propane is hydroxylmethylated to give 2,2-bis {4,4-bis (4-hydroxy-3-hydroxy). Methyl-5-methylphenyl) cyclohexyl} propane, which is then formylated to give 2,2-bis {4,4-bis (3-formyl-4-hydroxy-5-methylphenyl) cyclohexyl} propane The reaction is shown by the reaction formula.

1) Hydroxymethylation
Reaction formula 1
2) Formylation
Reaction formula 2

Next, tetrakis (formylphenol) which may be derived from the above tetrakis (hydroxymethylphenol), which is another novel compound of the present invention, is represented by the following general formula (2).
General formula (2)
In the formula, Ra, Rb, k, j, R ₁ , n, X and m are the same as those in the general formula 1.

Accordingly, in the formula, Ra and Rb each independently represents an alkyl group having 1 to 8 carbon atoms, k and j represent 0 or an integer of 1 to 4, and R ₁ represents an alkyl group having 1 to 8 carbon atoms. A group or an alkoxyl group having 1 to 8 carbon atoms, n represents an integer of 0 or 1 to 3, X represents a single bond or a divalent linking group, and m represents an integer of 0 or 1.
In R a, R b, R ₁ , the alkyl group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and is a linear alkyl group or a branched chain having 3 to 8 carbon atoms. And a cyclic alkyl group having 3 to 8 carbon atoms. The alkoxyl group having 1 to 8 carbon atoms in R ₁ is preferably an alkoxyl group having 1 to 4 carbon atoms, and is a linear alkoxyl group or a branched alkoxyl group having 3 to 8 carbon atoms. And a cyclic alkoxyl group having 3 to 8 carbon atoms. Preferable Ra and Rb are the same as each other and each is an alkyl group having 1 to 4 carbon atoms. Preferred R ₁ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms. is there. Further, preferable k and j are both 0 or 1, and preferable n is 1.
Specific examples of the alkyl group and alkoxyl group are the same as those described in the general formula (1).
In the general formula (2), the hydroxyl group is preferably 4-position or 2-position, more preferably 4-position with respect to the bonding position of the cyclohexyl group and the phenyl group. When the hydroxyl group is 4-position, the formyl group is 3 The position is preferred, and when the hydroxyl group is at position 2, the formyl group is preferably at position 3 or 5.

Accordingly, a preferred formylphenol group is represented by the following general formula (5) corresponding to the general formula (3), for example.
General formula (5)
(Wherein R ₁ is the same as that of general formula (1))

In the general formula (2), X is the same as defined in the general formula (1), and X is a single bond or a divalent linking group. When X is a divalent linking group, X is a saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, specifically a linear saturated hydrocarbon group or a branched chain. Examples thereof include a saturated hydrocarbon group and a cyclic saturated hydrocarbon group which may have a substituent. Specific examples of such X are the same as the examples shown in the general formula (1).
M represents an integer of 0 or 1. When m = 1, the 4,4′-position is preferred with respect to the bonding position of the phenyl group.

Therefore, as tetrakis (formylphenol) represented by the general formula (2), specifically, for example,
1,1,4,4, -tetrakis (3-formyl-4-hydroxy-5-methylphenyl) cyclohexane,
4,4,4′4′-tetrakis (3-formyl-4-hydroxy-5-methylphenyl) -1,1′-bicyclohexane,
Bis {4,4-bis (3-formyl-4-hydroxy-5-methylphenyl) cyclohexyl} methane,
2,2-bis {4,4-bis (3-formyl-4-hydroxy-5-methylphenyl) cyclohexyl} propane,
Etc.

  The tetrakis (formylphenol) represented by the general formula (2) of the present invention is not particularly limited in its production method, but for example, produced by a method similar to the method described in WO2007 / 139191. can do. Specifically, the tetrakis (hydroxymethylphenol) phenol of the present invention corresponding to the tetrakis (formylphenol) of the present invention is directly used as a raw material, and this is reacted with hexamethylenetetramine in the presence of an acid (first step) ) And then hydrolyzing the reaction product (second step), a tetrakis (formylphenol) compound corresponding to the tetrakis (hydroxymethylphenol) compound can be obtained.

(First step)
In the production method of the present invention, when the tetrakis (hydroxymethylphenol) represented by the general formula (1) is reacted with hexamethylenetetramine in the presence of an acid, the acid used is trifluoroacetic acid, trichloro Examples include halogenated organic carboxylic acids such as acetic acid, tribromoacetic acid, monofluoroacetic acid, monochloroacetic acid, and fluorobenzoic acid, organic carboxylic acids such as acetic acid and formic acid, and inorganic weak acids such as boric acid. Liquid halogenated organic carboxylic acids are preferred.
The amount of acid used in the reaction varies depending on the type of acid, but the range of the amount added or the preferred amount of acid varies, but is usually 0.1% per mole of tetrakis (hydroxymethylphenol). It is the range of about -100 mol times, Preferably it is the range of about 1-50 mol times, More preferably, it is the range of about 10-40 mol times.
Further, the form of hexamethylenetetramine is not limited. For example, hexamethylenetetramine produced by adding ammonia and formaldehyde, which are raw materials of hexamethylenetetramine, to the reaction system may be used.
The amount of hexamethylenetetramine is not particularly limited as long as it is 4 mol times or more with respect to 1 mol of tetrakis (hydroxymethylphenol) represented by the above general formula (2), but preferably 4 to 10 mol times. The range is more preferably 4.2 to 6 mole times.
In the reaction, a solvent may or may not be used. It is not particularly necessary if the reaction raw material can be dissolved and the reaction composition can be dissolved. However, if the acid used or the melting point of the raw material is high, the reaction liquid is high at the reaction temperature, and the stirring is difficult. preferable.
Examples of the solvent used include ethers such as ether, diethyl ether and tetrahydrofuran, aliphatic esters such as ethyl acetate and n-butyl acetate, alkyl alcohols such as methanol, ethanol, butanol and cyclohexanol, toluene, xylene and ethylbenzene. Aromatic hydrocarbons such as these or mixtures thereof.
In the reaction, there is no limitation on the charging method and order of the reaction raw materials, and the method and order may be appropriately selected according to the properties of the raw materials used.
The reaction temperature is preferably in the range of 0 to 110 ° C, more preferably in the range of 50 to 90 ° C. The reaction pressure is in the range of slightly reduced pressure to slightly increased pressure, preferably about normal pressure.

(Second step)
In the production method of the present invention, the reaction intermediate product obtained in the first step is hydrolyzed to obtain the target tetrakis (formylphenol) represented by the general formula (2).
In the hydrolysis reaction, it is preferable to use the reaction product mixture with the hexamethylenetetramine as it is from the viewpoints of reaction efficiency and yield improvement. In the reaction, an acid catalyst is preferably used. As a catalyst to be used, the acid contained in the reaction product mixture used in the reaction with hexamethylenetetramine may be used as it is as a hydrolysis catalyst, or may be newly added. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic sulfones such as p-toluenesulfonic acid, and organic carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid. The amount of the acid is usually in the range of 0.1 to 100 moles, preferably in the range of about 1 to 20 moles per mole of tetrakis (hydroxymethylphenol). Further, in the hydrolysis reaction, the amount of water in the reaction composition is not particularly limited as long as the reaction can be smoothly carried out, but usually with respect to 1 mol of the raw material tetrakis (hydroxymethylphenol), It is in the range of 4 to 160 mol times, preferably in the range of 40 to 100 mol times.
The reaction temperature is preferably in the range of 0 to 100 ° C, more preferably in the range of 50 to 80 ° C. The reaction pressure is in the range of slightly reduced pressure to slightly increased pressure, preferably about normal pressure.
After completion of the reaction, the target crude product or purified product can be obtained in good yield from the obtained reaction completion mixture according to a known method. For example, if the target product in the reaction completion mixture is precipitated as crystals, the target product may be filtered off as it is, and if it is not precipitated as crystals, a poor solvent is added to the reaction completion mixture to precipitate the target product. It may be separated. At that time, neutralization of the acid catalyst in the reaction completion mixture with alkaline water is not always necessary. For example, when an acid catalyst is used, an appropriate amount necessary for neutralizing the acid catalyst in the reaction completion mixture is used. After neutralizing to about pH 5-7 by adding alkaline water such as aqueous sodium hydroxide solution, separation and precipitation of the target product, for example, water such as toluene, xylene, methyl isobutyl ketone, or ether can be separated. The aqueous layer is separated by adding a solvent, and the oil layer is washed with water. After the solvent is distilled off from the obtained oil layer, the solvent is added to the crystal, and the target crystal is obtained by crystallization and filtration. . If the purity of the crystal is low, the above recrystallization operation may be further performed once to plural times as necessary.

Since the tetrakis (hydroxymethylphenol) compound of the present invention has four aromatic rings in one or two cyclohexyl rings in the same molecule, it is excellent in heat resistance, lipophilicity, water absorption resistance and the like. It has four phenolic hydroxyl groups and four phenolic hydroxymethyl groups bonded to each other, so it has a wide variety of reactivity, and can be used as a modifier for phenolic resins, as a raw material for photoresists, and as a raw material for reaction intermediates. Is possible. In particular, it is useful as a raw material compound for efficiently synthesizing a tetrakis (formylphenol) compound by reaction with hexamethylenetetramine.
In addition, the tetrakis (formylphenol) compound that may be derived from the tetrakis (hydroxymethylphenol) compound, which is another compound of the present invention, similarly has two aromatic rings on each of the two cyclohexyl rings in the same molecule. It has excellent heat resistance, lipophilicity, water absorption resistance, etc., and since it has four phenolic hydroxyl groups and four phenolic aldehyde groups bonded to each of these four aromatic rings, it is rich in various reactivity and intermediate reaction. It can be used in a wide range of applications as a body material. In particular, by using this as a raw material, for example, by using a reaction product with phenol as a material, a material having improved heat resistance (high glass transition temperature), low dielectric constant, water resistance, moisture absorption resistance, etc. It is possible to obtain.

Example (Example 1)
Synthesis of 2,2-bis {4,4-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) cyclohexyl} propane;
After charging 1020.0 g (4.08 mol) of 16% aqueous sodium hydroxide solution into a 5 L four-necked flask and substituting the reaction vessel with nitrogen, 2,2-bis {4,4-bis ( 4-hydroxy-5-methylphenyl) cyclohexyl} propane (538.0 g, 0.85 mol) was added, followed by stirring for 1 hour. Next, 947.1 g (11.05 mol) of 35% aqueous formaldehyde solution was added with stirring at 25-30 ° C. over 2 hours to carry out the reaction. Thereafter, the reaction was carried out at 30 ° C. for 5 hours with stirring.
After completion of the reaction, the mixture was cooled to 10 ° C., 550.8 g of methyl ethyl ketone was added dropwise over 20 minutes, and 1280.0 g of methyl isobutyl ketone was added. Thereafter, 661.8 g of 17.5% hydrochloric acid aqueous solution was added for neutralization, the temperature was raised to 30 ° C., and the mixture was allowed to stand for 10 minutes, and the aqueous layer was extracted. Thereafter, 640.0 g of water was added and stirred, and then the aqueous layer was removed. From the obtained oil layer, 1021.5 g of the solvent was distilled off at 45 ° C. under reduced pressure, and 1280.0 g of toluene was added and cooled to precipitate crystals. The precipitated crystals were separated by filtration to obtain 870.2 g of crude crystals.
Thereafter, 960.0 g of the obtained crude crystal, 960.0 g of methyl ethyl ketone, 1700.0 g of methyl isobutyl ketone, and 800 g of water were charged into a 5 L four-necked flask, and the temperature was raised to 45 ° C. to dissolve the crystal. The layer was extracted, and 1470.5 g of the solvent was distilled off from the obtained oil layer at 45 ° C. under reduced pressure (crystals were deposited in the middle), cooled to 20 ° C., filtered and dried, and 224.8 g of the desired white powder. (Purity of 93.3% by high performance liquid chromatography) was obtained. The white powder was confirmed to be the target compound by proton NMR analysis. The yield based on the raw material tetrakisphenol was 35.1%.

1H-NMR measurement (400 MHz, solvent: DMSO-d6)

Example 2
Synthesis of 2,2-bis {4,4-bis (3-formyl-4-hydroxy-5-methylphenyl) cyclohexyl} propane;
After charging 461.7 g (4.05 mol) of trifluoroacetic acid into a 3 L four-necked flask and replacing the reaction vessel with nitrogen, 83.3 g (0.594 mol) of hexamethylenetetramine was added at about 30 ° C. 60, 11.7 g (0.135 mol) of 2,2-bis {4,4-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) cyclohexyl} propane (methylol) obtained in Example 1 was The reaction was carried out with stirring for 1 hour 30 minutes. Thereafter, the reaction was further carried out at 80 ° C. with stirring for 16 hours.
251.5 g of water was added to the obtained reaction completion liquid, and a hydrolysis reaction was performed at 60 ° C. for 1 hour. A viscous solid precipitated during the hydrolysis. 201.2 g of toluene and 301.8 g of methyl isobutyl ketone were added to this mixed solution, and the mixture was heated to 70 ° C. and dissolved, and then left to stand to extract the aqueous layer. Thereafter, neutralization was performed with 444.8 g of a 16% aqueous sodium hydroxide solution, and crystals were precipitated during cooling. After cooling to 20 ° C., the precipitate was filtered off to obtain 104.0 g of crude crystals.
Thereafter, the obtained crude crystals and 1814.0 g of tetrahydrofuran were charged into a 3 L four-necked flask, heated to 60 ° C. to dissolve the crystals, and then 1449.0 g of solvent was distilled off under normal pressure. Crystals precipitated in the middle. 240.0 g of water and 144.0 g of acetone were added to the residual liquid, cooled to 20 ° C., filtered and dried to obtain 71.2 g (purity of 96.2% by high performance liquid chromatography) as a target product. The yellow powder was confirmed to be the target compound by proton NMR analysis. The yield based on the methylol body was 70.8%.

1H-NMR measurement (400 MHz, solvent: DMSO-d6)

Claims (2)

Tetrakis (hydroxymethylphenol) s represented by the following general formula (1)

(In the formula, Ra and Rb each independently represents an alkyl group having 1 to 8 carbon atoms, k and j represent 0 or an integer of 1 to 4, and R ₁ represents an alkyl group having 1 to 8 carbon atoms. Or an alkoxyl group having 1 to 8 carbon atoms, n is an integer of 0 or 1 to 3, X is a single bond or a chain saturated hydrocarbon group having 1 to 20 carbon atoms , and m is 0 or Indicates an integer of 1.) Tetrakis (formylphenol) s represented by the following general formula (2) General formula (2)
(In the formula, Ra, Rb, k, j, R ₁ , n, X and m are the same as those in the general formula 1.)