JP2002308808A - New 4,4"-dihydroxy-p-terphenyl - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new 4,4"-dihydroxy-p-terphenyl having an asymmetric molecular structure having a lower alkyl group only in the hydroxyphenyl group of one terminal of molecule thereof and expected to be excellent, for example, in the solubility in an organic solvent. SOLUTION: This new 4,4"-hydroxy-p-terphenyl is represented by formula (1) (wherein, R is a 1-4C alkyl group and n is an integer of 1-3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to novel 4,4 "-dihydroxy-p-terphenyls having an asymmetric structure having a lower alkyl group only at the hydroxyphenyl group at one terminal of the molecule. Such 4,
4 "-dihydroxy-p-terphenyls can be expected to be useful as raw materials for synthetic resins such as liquid crystal polyesters, polycarbonates and polyurethanes, and as raw materials for photoresists such as display elements and semiconductors.

[0002]

2. Description of the Prior Art Conventionally, 4,4 "-dihydroxy-p-terphenyls are disclosed in, for example, JP-A-1-16886.
No. 32,1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane is produced from 1,4-cyclohexanedione and phenol, and this is decomposed and dehydrogenated to give 4,4 ″ -dihydroxy. It is described that -p-terphenyl can be obtained.
JP-A-2-212449 discloses that 4-methoxy-4'-bromobiphenyl and 4-methoxy-3-phenylmagnesium bromide are subjected to Grignard coupling, followed by demethylation to give 4,4 "-.
It is described that dihydroxy-3-phenyl-p-terphenyl can be obtained.

However, such as 4,4 "-dihydroxy-p-terphenyl, which has a symmetrical molecular structure, and the above 4,4" -dihydroxy-3.
Even if the molecular structure is asymmetric, such as -phenyl-p-terphenyl, conventionally known dihydroxy terphenyls may be used in the fields of synthetic resin materials, photoresist materials, etc. There is a problem that the solubility in water is limited. Accordingly, in recent years, a novel 4,4 ″ -dihydroxy- compound having excellent properties in solubility in a solvent, which can be more effectively used in various fields such as a synthetic resin material and a photoresist material. There is a strong demand for the development of p-terphenyls.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in order to meet the above-mentioned demands, and has an asymmetric molecular structure having a lower alkyl group only at one terminal hydroxyphenyl group of the molecule. Thus, for example, it is an object of the present invention to provide novel 4,4 "-dihydroxy-p-terphenyls which are expected to have excellent solubility in organic solvents.

[0005]

According to the present invention, the compound represented by the general formula (I)

[0006]

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(Wherein, R represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3).
4 "-dihydroxy-p-terphenyls are provided.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The novel 4,4 "-dihydroxy-p-terphenyls according to the invention have the general formula (I)

[0009]

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(Wherein R represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3).

In the 4,4 "-dihydroxy-p-terphenyls represented by the general formula (I), R represents an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group,
It is an ethyl group, a propyl group or a butyl group, and the propyl group or the butyl group may be linear or branched. N is an integer of 1 to 3.

Therefore, preferred specific examples of the 4,4 "-dihydroxy-p-terphenyls according to the present invention include, for example, 4,4" -dihydroxy-3 "-methyl-p-terphenyl and 4,4"-. Dihydroxy-2 "-methyl-
p-terphenyl, 4,4 "-dihydroxy-3" -ethyl-p-terphenyl, 4,4 "-dihydroxy-
2 "-ethyl-p-terphenyl, 4,4" -dihydroxy-3 "-n-propyl-p-terphenyl, 4,
4 "-dihydroxy-2" -n-propyl-p-terphenyl, 4,4 "-dihydroxy-3" -isopropyl-p-terphenyl, 4,4 "-dihydroxy-2"-
Isopropyl-p-terphenyl, 4,4 "-dihydroxy-3" -n-butyl-p-terphenyl, 4,4 "
-Dihydroxy-2 "-n-butyl-p-terphenyl, 4,4" -dihydroxy-3 "-isobutyl-p-
Terphenyl, 4,4 "-dihydroxy-2" -isobutyl-p-terphenyl, 4,4 "-dihydroxy-
3 "-s-butyl-p-terphenyl, 4,4" -dihydroxy-2 "-s-butyl-p-terphenyl, 4,
4 "-dihydroxy-3" -tert-butyl-p-terphenyl, 4,4 "-dihydroxy-2" -tert-butyl-p
-Terphenyl, 4,4 "-dihydroxy-3", 6 "
-Dimethyl-p-terphenyl, 4,4 "-dihydroxy-3", 5 "-dimethyl-p-terphenyl, 4,
4 "-dihydroxy-2", 3 ", 6" -trimethyl-
p-terphenyl, 4,4 "-dihydroxy-2",
3 ", 5" -trimethyl-p-terphenyl, 4,4 "
-Dihydroxy-3 "-isopropyl-6" -methyl-
p-terphenyl, 4,4 "-dihydroxy-3" -isopropyl-5 "-methyl-p-terphenyl, 4,
4 "-dihydroxy-3" -t-butyl-6 "-methyl-p-terphenyl, 4,4" -dihydroxy-3 "-
t-butyl-5 "-methyl-p-terphenyl, 4,
4 "-dihydroxy-3", 5 "-di-t-butyl-p
-Terphenyl, 4,4 "-dihydroxy-3", 5 "
-Di-isopropyl-p-terphenyl and the like.

Of these, particularly preferred specific examples are 4,4 "-dihydroxy-3" -methyl-p-terphenyl and 4,4 "-dihydroxy-3" -ethyl-.
p-terphenyl, 4,4 "-dihydroxy-3" -isopropyl-p-terphenyl, 4,4 "-dihydroxy-3" -t-butyl-p-terphenyl, 4,4 "-
Dihydroxy-3 ", 5" -dimethyl-p-terphenyl, 4,4 "-dihydroxy-3" -isopropyl-
5 "-methyl-p-terphenyl, 4,4" -dihydroxy-3 ", 5" -di-tert-butyl-p-terphenyl, 4,4 "-dihydroxy-3", 5 "-di-isopropyl -P-terphenyl and the like.

The 4,4 "-dihydroxy-p-terphenyls according to the present invention have, for example, the general formula (I)
I)

[0015]

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Wherein R is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3; a hydroxyphenyl-substituted cyclohexylidenebisphenol represented by the formula: Pyrolyzes in the presence of
Then, the obtained reaction mixture can be obtained by subjecting it to a dehydrogenation reaction.

In such a method, in the hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the general formula (II), which is a starting material, R is the same as that in the general formula (I).

Accordingly, as specific examples of the hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the general formula (II), for example, 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4) -Hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (2-methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3,5 -Dimethyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3,6-dimethyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4 -Bis (2,3,5-trimethyl-4-hydroxyphenyl) cyclohexane, 1- (4
-Hydroxyphenyl) -4,4-bis (2,3,6-
Trimethyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-ethyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis ( 2-ethyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-isopropyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-
Bis (2-isopropyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,
4-bis (3-isobutyl-4-hydroxyphenyl)
Cyclohexane, 1- (4-hydroxyphenyl)-
4,4-bis (2-isobutyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl)
-4,4-bis (3-t-butyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (2-t-butyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-isopropyl-6-methyl-4-hydroxyphenyl) cyclohexane, 1- (4
-Hydroxyphenyl) -4,4-bis (3-t-butyl-5-methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-t-butyl-6) -Methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl)
-4,4-bis (3,5-di-t-butyl-4-hydroxyphenyl) cyclohexane and the like can be mentioned.

The 4,4 "-dihydroxy-p according to the invention
The hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the above general formula (II), which are starting materials for the production of terphenyls, are described in, for example, JP-A-2000-6.
As described in Japanese Patent No. 3308, it can be easily obtained by reacting 4- (4-hydroxyphenyl) cyclohexanone with a substituted phenol in the presence of an acid catalyst.

The thermal decomposition of the above hydroxyphenyl-substituted cyclohexylidenebisphenols may be carried out in the absence of a catalyst, but is preferably carried out in the presence of an alkali catalyst. The alkali catalyst is not particularly limited, for example, sodium hydroxide, potassium hydroxide, alkali metal hydroxides such as lithium hydroxide,
Alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal phenoxides such as sodium phenoxide and potassium phenoxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc. And alkaline earth metal hydroxides. Among these, sodium hydroxide or potassium hydroxide is particularly preferably used.

As described above, when an alkali catalyst is used, the alkali catalyst is usually used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the hydroxyphenyl-substituted cyclohexylidenebisphenol. Used in the range of 10 parts by weight. The form of use of the catalyst is not particularly limited, but from the viewpoint of easy charging operation, preferably
Used as an aqueous solution of 10 to 50% by weight.

In the thermal decomposition of the above hydroxyphenyl-substituted cyclohexylidenebisphenols, the hydroxyphenyl-substituted cyclohexylidenebisphenols as raw materials and / or the reaction products obtained by the thermal decomposition thereof have a high melting point. It is preferably carried out in the presence of a reaction solvent in order to improve the liquidity of the denbisphenols at the thermal decomposition temperature, and to prevent thermal polymerization of the reaction products due to the thermal decomposition.

The reaction solvent is not particularly limited as long as it is inert at the pyrolysis temperature and does not distill from the reaction mixture.
Triethylene glycol, tetraethylene glycol,
Polyethylene glycols such as pentaethylene glycol, polypropylene glycols such as tripropylene glycol and tetrapropylene glycol, and polyhydric alcohols such as glycerin are used. In addition, commercially available organic heat mediums such as "Therm S" (manufactured by Nippon Steel Chemical Co., Ltd.) and "SK-OIL" (manufactured by Soken Chemical Co., Ltd.) are also used.

Such a solvent is used in an amount of usually 10 to 150 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the hydroxyphenyl-substituted cyclohexylidenebisphenol used.

The thermal decomposition of hydroxyphenyl-substituted cyclohexylidenebisphenols is usually from 150 to 300
C., preferably at a temperature in the range of 180 to 250.degree. If the thermal decomposition temperature is too low, the reaction rate is too low, while if the thermal decomposition temperature is too high, undesirable side reactions increase. The reaction pressure of the thermal decomposition is not particularly limited, but is usually in a range from normal pressure to reduced pressure, for example, 1 to 760 mmHg.
Gauge range, preferably 30-50 mmHg gauge.

Under such reaction conditions, the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols is usually completed in about 1 to 6 hours. The end point of the thermal decomposition reaction can be, for example, the time point at which the distillation of the alkylphenols generated by the decomposition reaction stops.

According to a preferred embodiment, the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenol is carried out, for example, by charging a hydroxyphenyl-substituted cyclohexylidenebisphenol, an alkali catalyst and a solvent such as tetraethylene glycol into a reaction vessel, 190-
The stirring is performed at 220 ° C. under a pressure of 30 to 50 mmHg gauge for about 3 to 6 hours while distilling off the alkylphenols generated by the decomposition reaction.

In this way, the hydroxyphenyl-substituted cyclohexylidenebisphenols are pyrolyzed and then the resulting reaction mixture is subjected to a dehydrogenation reaction to give the 4,4 "-dihydroxy-p-p- according to the invention. Terphenyls can be obtained.

Here, when an alkali catalyst is used in the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols, an acid is added to the obtained reaction mixture to neutralize the alkali, and then the reaction mixture is crystallized. It is preferable to subject the reaction mixture after the neutralization to a dehydrogenation reaction without performing purification such as filtration from the viewpoint of simplification of the reaction process.

The reaction mixture obtained by the thermal decomposition of such hydroxyphenyl-substituted cyclohexylidenebisphenols is usually subjected to a dehydrogenation treatment in the presence of a dehydrogenation catalyst. As this dehydrogenation catalyst, a conventionally known dehydrogenation catalyst can be used. Therefore,
For example, Raney nickel, reduced nickel, nickel catalysts such as nickel-supported catalysts, Raney cobalt, reduced cobalt, cobalt catalysts such as cobalt-supported catalysts, copper catalysts such as Raney copper, palladium oxide, palladium black, palladium /
Palladium catalyst such as carbon, platinum black, platinum /
A platinum catalyst such as carbon, a rhodium catalyst, a chromium catalyst, a copper-chromium catalyst and the like are used. Among these,
Particularly, a platinum group catalyst such as palladium is preferable, and a palladium catalyst is particularly preferably used.

Such a dehydrogenation catalyst is generally used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the starting material, hydroxyphenyl-substituted cyclohexylidenebisphenols.
0 parts by weight, preferably in the range of 0.2 to 10 parts by weight.

In the dehydrogenation treatment, a hydrogen acceptor may or may not be co-present, but it is preferable to co-exist with a hydrogen acceptor in order to obtain a desired product in a higher yield. Examples of such a hydrogen acceptor include, but are not particularly limited to, styrenes such as α-methylstyrene, nitrobenzene, methyl isobutyl ketone, and phenol.

The dehydrogenation of the reaction mixture obtained by the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols is usually carried out at a temperature in the range of 100 to 250 ° C., preferably 130 to 200 ° C. Is

The dehydrogenation treatment of the reaction mixture obtained by thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols can be carried out in the gas phase, but from the viewpoint of operability, it is preferably carried out in the form of a solution. It is preferable to use a reaction solvent. As the reaction solvent, the solvent used in the thermal decomposition reaction of the hydroxyphenyl-substituted cyclohexylidenebisphenol is preferably used as it is from the viewpoint of simplification of the process. The reaction is preferably performed under normal pressure.

Under such reaction conditions, the dehydrogenation treatment of the reaction mixture obtained by pyrolysis of the hydroxyphenyl-substituted cyclohexylidenebisphenols is usually completed in about 3 to 6 hours, and 4 "
-Dihydroxy-p-terphenyls are usually provided in a yield of about 75% or more, based on the starting hydroxyphenyl substituted cyclohexylidenebisphenols.

After completion of the dehydrogenation treatment of the reaction mixture obtained by thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols, the catalyst is separated from the resulting reaction mixture according to a conventional method, and then subjected to crystallization filtration and the like. By the method, a crude product of the 4,4 "-dihydroxy-p-terphenyls according to the present invention can be obtained, and if necessary, it can be purified again by a method such as crystallization filtration. , High purity products can be obtained.

[0037]

According to the present invention, 4,4 "-dihydroxy-
The p-terphenyls have an asymmetric structure in which a lower alkyl group is substituted only in the hydroxyphenyl group at one terminal of the molecule, and thus 4,4 "-dihydroxy-p-type having such an asymmetric structure. Terphenyls are expected to have, for example, better solubility in organic solvents than symmetrical 4,4 ″ -dihydroxy-p-terphenyls, and include liquid crystal polyesters, polycarbonates,
Further usefulness is expected as a raw material for synthetic resins such as polyurethane and the like, and a raw material for photoresist such as display elements and semiconductors.

[0038]

The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Example 1 (4-hydroxy-3 "-methyl-4" -hydroxy-
Production of p-terphenyl) Pyrolysis step 1- (4-hydroxyphenyl) -4,4-bis (3-
Methyl-4-hydroxyphenyl) cyclohexane 5
0.2 g (0.129 mol), 0.3 g of a 48% aqueous sodium hydroxide solution and 26.3 g of tetraethylene glycol
Into a reaction vessel (300 mL four-necked flask), and the inside of the reaction vessel is purged with nitrogen.
The thermal decomposition reaction was performed at a reduced pressure of 0 mmHg at a temperature of about 210 ° C. for about 4 hours. The point at which no distillate was distilled was regarded as the end point of the reaction.

After completion of the reaction, 50% was added to the obtained reaction mixture.
An aqueous acetic acid solution was added to neutralize the solution to about pH 6, and 64.7 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation Step To 64.7 g of the above water-containing oily reaction mixture, 60.0 g of α-methylstyrene and 3.5 g of a 5% palladium / carbon supported catalyst (50% by weight water-containing product) were additionally added, and the inside of the reaction vessel was added. After purging with nitrogen, the temperature was raised to 165 ° C. under normal pressure, and the reaction was carried out for 3 hours with stirring.

After completion of the reaction, 50 g of dimethylformamide was added to the obtained reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture,
The solvent was distilled off by distillation to obtain a distillation residue containing the target substance. Methanol is added to the distillation residue to dissolve the residue, water is further added, and then crystallization filtration is performed. The obtained solid is dried to a purity of 99.1% (by high performance liquid chromatography analysis). 30.5 g of 4,4 "-dihydroxy-3" -methyl-p-terphenyl was obtained as white crystals. The yield based on 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane was 85.8 mol%.

Melting point: 251.4 ° C. Molecular weight: 277 (M ⁺ ) (by mass spectrometry) Proton NMR (400 MHz, solvent DMSO-d)
(Δ (ppm): 2.19 (s, 3H), 6.86 (d
d, 3H, J = 8.0 Hz, J = 3.2 Hz), 7.3
2 (dd, 1H, J = 10.2 Hz, J = 2.4H
z), 7.41 (d, 1H, J = 2.4 Hz), 7.5
0 (d, 2H, J = 8.8 Hz), 7.58 (s, 4
H), 9.48 (brs. 2H)

Example 2 (Production of 4-hydroxy-3 ", 5" -dimethyl-4 "-hydroxy-p-terphenyl) Pyrolysis step 1- (4-hydroxyphenyl) -4,4-bis (3 ,
83.2 g (0.200 mol) of 5-dimethyl-4-hydroxyphenyl) cyclohexane, 0.4 g of a 48% aqueous sodium hydroxide solution and 32 g of tetraethylene glycol
Into a reaction vessel (300 mL four-necked flask), and the inside of the reaction vessel is purged with nitrogen.
The thermal decomposition reaction was performed at a reduced pressure of 0 mmHg at a temperature of about 210 ° C. for about 4 hours. The point at which no distillate was distilled was regarded as the end point of the reaction. After completion of the reaction, a 50% aqueous acetic acid solution was added to the obtained reaction mixture to neutralize it to about pH 6, and 88.0 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation Step 98.0 g of α-methylstyrene and 5% palladium / carbon supported catalyst (50
0.56 g of a water-containing product (wt.% By weight) was added, and the inside of the reaction vessel was purged with nitrogen. Then, the temperature was raised to 160 ° C. under normal pressure, and the reaction was carried out with stirring for 6 hours.

After completion of the reaction, 96 g of dimethylformamide was added to the obtained reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture,
The solvent was distilled off by distillation to obtain a distillation residue containing the target substance. Water was added to the distillation residue, crystallization filtration was performed, and the obtained solid was slurried by adding isopropanol. Then, crystallization filtration was performed again, followed by drying, and purity of 98.1% (by high performance liquid chromatography analysis). )) 4-Hydroxy-
47.4 g of 3 ", 5" -dimethyl-4 "-hydroxy-p-terphenyl were obtained as white crystals. 1- (4-hydroxyphenyl) -4,4-bis (3,5-dimethyl-4-) The yield based on (hydroxyphenyl) cyclohexane was 81.7 mol%.

Melting point: 231 ° C. (DSC method) Molecular weight: 291 (M ⁺ ) (by mass spectrometry) Proton NMR (400 MHz, solvent DMSO-d)
(Δ (ppm): 2.25 (s, 6H), 6.88
(D, 2H, J = 8.0 Hz), 7.25 (s, 2
H), 7.50 (d, 2H, J = 8.8 Hz), 7.5
8 (s, 4H), 8.80 (brs, 2H)

Example 3 (Production of 4-hydroxy-3 "-isopropyl-4" -hydroxy-p-terphenyl) Thermal decomposition step 1- (4-hydroxyphenyl) -4,4-bis (3-
29.3 g (0.0660 mol) of isopropyl-4-hydroxyphenyl) cyclohexane, 0.2 g of a 48% aqueous sodium hydroxide solution and tetraethylene glycol 1
2.0 g was charged into a reaction vessel (300 mL four-necked flask), and the inside of the reaction vessel was replaced with nitrogen. Then, the pressure inside the reaction vessel was reduced to 40 mmHg. Was done. The point at which no distillate was distilled was regarded as the end point of the reaction. After completion of the reaction, a 50% aqueous acetic acid solution was added to the resulting reaction mixture to give
After neutralization to a certain extent, 33.6 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation Step To 33.6 g of the above water-containing oily reaction mixture, 31.2 g of α-methylstyrene and 0.2 g of a 5% palladium / carbon supported catalyst (50% by weight water-containing product) were additionally added to the reaction vessel, and the reaction was carried out. After replacing the inside of the container with nitrogen, the temperature was 160
The temperature was raised to ° C., and the reaction was carried out for 4 hours with stirring.

After completion of the reaction, 31.2 g of dimethylformamide was added to the obtained reaction mixture and mixed. After this,
The palladium / carbon catalyst was filtered off from this mixture, and the solvent was distilled off by distillation to obtain a distillation residue containing the target product. Methyl isobutyl ketone and water were added to the distillation residue, the aqueous layer was separated, and the solvent was distilled off from the obtained oil layer. Toluene was added, crystallization filtration was performed, and drying was performed, and purity was 99.0. % (By high performance liquid chromatography analysis) of 4-hydroxy-3 "-isopropyl-4"-
16.5 g of hydroxy-p-terphenyl were obtained as white crystals. The reaction yield of the starting material, 1- (4-hydroxyphenyl) -4,4-bis (3-isopropyl-4-hydroxyphenyl) cyclohexane, was 81.
It was 2 mol%.

Melting point: 179 ° C. (DSC method) Molecular weight: 305 (M ⁺ ) (by mass spectrometry) Proton NMR (400 MHz, solvent DMSO-d)
(Δ (ppm): 1.24 (d, 6H, J = 6.8H
z), 3.25-3.29 (m, 1H), 6.87-
6.90 (m, 3H), 7.33 (dd, 1H, J =
8.4 Hz, J = 2.0 Hz), 7.43 (d, 1H,
J = 2.4 Hz), 7.52 (d, 2H, J = 8.8H)
z), 7.61 (s, 4H), 9.46 (brs, 1
H), 9.56 (brs. 1H)

Example 4 (Production of 4-hydroxy-3 "-tert-butyl-4" -hydroxy-p-terphenyl) Pyrolysis Step 1- (4-hydroxyphenyl) -4,4-bis (3-
25.0 g (0.0508 mol) of t-butyl-4-hydroxyphenyl) cyclohexane, 0.2 g of a 48% aqueous sodium hydroxide solution and tetraethylene glycol10.
0 g was charged into a reaction vessel (300 mL four-necked flask), the inside of the reaction vessel was replaced with nitrogen, and then the pressure inside the reaction vessel was reduced to 40 mmHg, and the thermal decomposition reaction was performed at a temperature of about 210 ° C. for about 3 hours. Was. The point at which no distillate was distilled was regarded as the end point of the reaction.

After completion of the reaction, 50% was added to the obtained reaction mixture.
An aqueous acetic acid solution was added to neutralize the solution to a pH of about 6, and 27.3 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation Step To 27.3 g of the above water-containing oily reaction mixture, 24.5 g of α-methylstyrene and 0.2 g of a 5% palladium / carbon-supported catalyst (50% by weight water-containing product) were additionally added, and the inside of the reaction vessel was added. After purging with nitrogen, the temperature was raised to 160 ° C. under normal pressure, and the reaction was carried out for 4 hours with stirring.

After completion of the reaction, 50 g of dimethylformamide was added to the obtained reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture,
The solvent was distilled off by distillation to obtain a distillation residue containing the target substance. Methyl isopropyl ketone and water were added to the distillation residue, the aqueous layer was separated and removed, and the solvent was distilled off from the obtained oil layer. Then, a mixed solvent of toluene / cyclohexane was added, and the mixture was subjected to crystallization filtration. Is dried to a purity of 97.1%
(By high performance liquid chromatography analysis) 4,
7.7 g of 4 "-dihydroxy-3" -t-butyl-p-terphenyl were obtained as white crystals. 1- (4-hydroxyphenyl) -4,4-bis (3-t-butyl-4-
The yield based on (hydroxyphenyl) cyclohexane is 4
It was 6.5 mol%.

Melting point: 180.5 ° C. (DSC method) Molecular weight: 317 (M ⁻ ) (by mass spectrometry) Proton NMR (400 MHz, solvent DMSO-d)
(Δ (ppm): 1.42 (s, 9H), 6.89
(T, 3H, J = 8.4 Hz), 7.34 (dd, 1
H, J = 8.4 Hz, 2.1 Hz), 7.44 (d, 1
H, J = 2.1 Hz), 7.52 (d, 2H, J = 8.
4Hz), 7.61 (s, 4H), 9.52 (s, 1
H), 9.57 (s, 1H)

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hiroyasu Ohno 2-115 Kozaiga, Wakayama City F-term in Honshu Kagaku Kogyo Co., Ltd. F-term (reference) 4H006 AA01 AB46 FC52 FE13

Claims (1)

[Claims] 1. A compound of the general formula (I) (Wherein, R represents an alkyl group having 1 to 4 carbon atoms;
Is an integer of 1 to 3. 4,4 "-dihydroxy-p-terphenyls represented by the formula: