JP2008231116A - 4,4"-DIHYDROXY-p-TERPHENYLS - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide novel 4,4"-dihydroxy-p-terphenyls having an asymmetrical molecular structure wherein its one terminal hydroxyphenyl group alone comprises a lower alkyl group, which is hence expected to have, for example, excellent solubility to an organic solvent. <P>SOLUTION: 4,4"-dihydroxy-p-terphenyls are represented by formula (I) wherein R represents a 1-4C alkyl group, and n is 2 or 3. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to novel 4,4 "-dihydroxy-p-terphenyls having an asymmetric structure having a lower alkyl group only on the hydroxyphenyl group at one end of the molecule. Such 4,4" according to the present invention. -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 for display elements and semiconductors.

  Conventionally, for 4,4 ″ -dihydroxy-p-terphenyls, for example, JP-A-1-168632 discloses 1,1,4,4-tetrakis (4- It is described that 4,4 ″ -dihydroxy-p-terphenyl can be obtained by producing (hydroxyphenyl) cyclohexane and cracking and dehydrogenating it. Japanese Patent Application Laid-Open No. 2-212449 discloses that a 4,4 "-compound is obtained by Grignard coupling of 4-methoxy-4'-bromobiphenyl and 4-methoxy-3-phenylmagnesium bromide and then demethylation. It is described that dihydroxy-3-phenyl-p-terphenyl can be obtained.

  However, a molecular structure such as 4,4 "-dihydroxy-p-terphenyl having a symmetrical molecular structure, or the above-mentioned 4,4" -dihydroxy-3-phenyl-p-terphenyl, Even if the structure is asymmetric, conventionally known dihydroxy terphenyls have problems such as limited solubility in solvents when used in fields such as synthetic resin raw materials and photoresist raw materials. There is. Therefore, in recent years, a novel 4,4 "-dihydroxy- having characteristics excellent in solubility in a solvent and can be used more effectively in various fields such as synthetic resin raw materials and photoresist raw materials. There is a strong demand for the development of p-terphenyls.

  The present invention has been made to meet the above-mentioned demand, and has an asymmetric molecular structure having a lower alkyl group only in one hydroxyphenyl group of a molecule, and thus, for example, to an organic solvent. It is an object of the present invention to provide novel 4,4 ″ -dihydroxy-p-terphenyls which are expected to be excellent in solubility.

  According to the invention, the general formula (I)

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

  The 4,4 ″ -dihydroxy-p-terphenyls according to the present invention have an asymmetric structure in which only a hydroxyphenyl group at one end of the molecule is substituted with a lower alkyl group, thus such an asymmetric structure. 4,4 ″ -dihydroxy-p-terphenyls are expected to be more soluble in organic solvents, for example, than 4,4 ″ -dihydroxy-p-terphenyls having a symmetrical structure. Further usefulness is expected as a raw material for synthetic resins such as liquid crystal polyester, polycarbonate, and polyurethane, and as a raw material for photoresists for display elements and semiconductors.

  The novel 4,4 "-dihydroxy-p-terphenyls according to the invention are represented by the general formula (I)

(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 above general formula (I), R represents an alkyl group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, propyl group. A propyl group or a butyl group, which may be linear or branched, and n is an integer of 1 to 3.

  Accordingly, 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, 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" -t-butyl-p-terphenyl, 4,4 " -Dihydroxy-2 "-t-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 "-Jihi Roxy-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 "- Examples include di-t-butyl-p-terphenyl, 4,4 "-dihydroxy-3", 5 "-di-isopropyl-p-terphenyl.

  Among these, particularly preferable specific examples include 4,4 "-dihydroxy-3" -methyl-p-terphenyl, 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-t-butyl-p-terphenyl, 4,4 “-Dihydroxy-3”, 5 ”-di-isopropyl-p-terphenyl and the like can be mentioned.

  Such 4,4 ″ -dihydroxy-p-terphenyls according to the present invention are represented, for example, by the general formula (II)

(Wherein, R represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3), preferably in the presence of an alkali catalyst. Can be obtained by pyrolysis and then subjecting the resulting reaction mixture to a dehydrogenation reaction.

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

  Accordingly, specific examples of hydroxyphenyl-substituted cyclohexylidene bisphenols represented by the general formula (II) include, 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) cycl Rhohexane, 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) cyclohexa And the like can be given.

  The hydroxyphenyl-substituted cyclohexylidene bisphenols represented by the above general formula (II), which are starting materials for the production of 4,4 ″ -dihydroxy-p-terphenyls according to the present invention, are disclosed in, for example, JP-A-2000-63308. As described in the publication, 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 hydroxyphenyl-substituted cyclohexylidenebisphenols may be performed in the absence of a catalyst, but is preferably performed in the presence of an alkali catalyst. The alkali catalyst is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and carbonates. Examples include alkali metal hydrogen carbonates such as sodium hydrogen and potassium hydrogen carbonate, alkali metal phenoxides such as sodium phenoxide and potassium phenoxide, alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide. it can. Of these, sodium hydroxide or potassium hydroxide is particularly preferably used.

  Thus, when an alkali catalyst is used, the alkali catalyst is usually 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the hydroxyphenyl-substituted cyclohexylidenebisphenols. It is used in the range. Although there is no restriction | limiting in particular in the usage form of a catalyst, From the point that preparation operation is easy, Preferably, it uses as a 50 to 50 weight% aqueous solution.

  Since the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidene bisphenols has a high melting point of the raw material hydroxyphenyl-substituted cyclohexylidene bisphenols and / or the reaction products resulting from the thermal decomposition, the hydroxyphenyl-substituted cyclohexylidene bisphenols In order to improve the liquidity at the thermal decomposition temperature, and further to prevent thermal polymerization of the reaction product due to the thermal decomposition, it is preferably carried out in the presence of a reaction solvent.

  The reaction solvent is not particularly limited as long as it is inert at the thermal decomposition temperature and does not distill from the reaction mixture. For example, triethylene glycol, tetraethylene glycol, pentaethylene glycol Polyethylene glycols such as, polypropylene glycols such as tripropylene glycol and tetrapropylene glycol, and polyhydric alcohols such as glycerin are used. Further, “Therm S” (manufactured by Nippon Steel Chemical Co., Ltd.) and “SK-OIL” (manufactured by Soken Chemical Co., Ltd.), which are commercially available organic heat transfer media, are also used.

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

  Thermal decomposition of hydroxyphenyl-substituted cyclohexylidenebisphenols is usually carried out at a temperature in the range of 150 to 300 ° C, preferably in the range of 180 to 250 ° C. This is because when the thermal decomposition temperature is too low, the reaction rate is too slow, while when the thermal decomposition temperature is too high, undesirable side reactions increase. The reaction pressure for thermal decomposition is not particularly limited, but is usually in the range of normal pressure to reduced pressure, for example, in the range of 1 to 760 mmHg gauge, preferably in the range of 30 to 50 mmHg gauge. is there.

  Under such reaction conditions, the thermal decomposition of 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 point at which the distillation of alkylphenols produced by the decomposition reaction ceases.

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

  In this way, 4,4 "-dihydroxy-p-terphenyls according to the invention are obtained by thermally decomposing hydroxyphenyl-substituted cyclohexylidenebisphenols and then subjecting the resulting reaction mixture to a dehydrogenation reaction. Can be obtained.

  Here, in the thermal decomposition of hydroxyphenyl-substituted cyclohexylidenebisphenols, when an alkali catalyst is used, an acid is added to the obtained reaction mixture to neutralize the alkali, and then the reaction mixture is subjected to crystallization filtration or the like. It is preferable to subject the neutralized reaction mixture to a dehydrogenation reaction without purification, from the viewpoint of simplifying the reaction process.

  The reaction mixture obtained by thermal decomposition of such hydroxyphenyl-substituted cyclohexylidenebisphenols is usually dehydrogenated in the presence of a dehydrogenation catalyst. As this dehydrogenation catalyst, a conventionally known dehydrogenation catalyst can be used. Thus, for example, Raney nickel, reduced nickel, nickel supported catalyst, etc., nickel catalyst, Raney cobalt, reduced cobalt, cobalt supported catalyst, etc., Raney copper, etc., copper catalyst, palladium oxide, palladium black, palladium such as palladium / carbon. Catalysts, platinum black, platinum catalysts such as platinum / carbon, rhodium catalyst, chromium catalyst, copper chromium catalyst, etc. are used. Among these, a platinum group catalyst such as palladium is particularly preferable, and a palladium catalyst is particularly preferably used.

  Such a dehydrogenation catalyst is usually 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the hydroxyphenyl-substituted cyclohexylidene bisphenol as a starting material. Used in a range.

  In this dehydrogenation treatment, a hydrogen acceptor may or may not be present. However, in order to obtain a target product with higher yield, it is preferable that a hydrogen acceptor is present. Such a hydrogen acceptor is not particularly limited, but for example, styrenes such as α-methylstyrene, nitrobenzene, methyl isobutyl ketone, phenol and the like are preferably used.

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

  The dehydrogenation treatment of the reaction mixture obtained by thermal decomposition of hydroxyphenyl-substituted cyclohexylidene bisphenols can be performed in the gas phase, but from the viewpoint of operability, it is preferably performed in the form of a solution, In that case, it is preferable to use a reaction solvent. As the reaction solvent, it is preferable to use the solvent used in the thermal decomposition reaction of the hydroxyphenyl-substituted cyclohexylidene bisphenol as it is from the viewpoint of simplifying the process. The reaction is preferably performed under normal pressure.

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

  After completion of dehydrogenation of the reaction mixture obtained by thermal decomposition of hydroxyphenyl-substituted cyclohexylidenebisphenols, the catalyst was separated from the obtained reaction mixture according to a conventional method, and then subjected to a method such as crystallization filtration. A crude product of 4,4 "-dihydroxy-p-terphenyls according to the present invention can be obtained, and if this is further purified again by a method such as crystallization filtration, it is highly purified. Goods can be obtained.

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

Example 1
(Production of 4-hydroxy-3 "-methyl-4" -hydroxy-p-terphenyl)
Thermal decomposition process 1- (4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane 50.2 g (0.129 mol), 48% aqueous sodium hydroxide 0.3 g and tetraethylene Glycol 26.3 g was charged into a reaction vessel (300 mL four-necked flask), and the inside of the reaction vessel was purged with nitrogen. Reaction was performed. The point of time when the distillate stopped distilling 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 to obtain 64.7 g of a hydrous oily reaction mixture.

Dehydrogenation step 60.0 g of α-methylstyrene and 3.5 g of 5% palladium / carbon supported catalyst (50 wt% water-containing product) were added to 64.7 g of the water-containing oily reaction mixture, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the temperature was raised to 165 ° C. under normal pressure, and the mixture was reacted for 3 hours with stirring.

  After completion of the reaction, 50 g of dimethylformamide was added to the resulting reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture, and the solvent was distilled off by distillation to obtain a distillation residue containing the target product. Methanol is added to the distillation residue to dissolve the residue, and water is further added, followed by crystallization and filtration. The obtained solid is dried to a purity of 99.1% (according to 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 (dd, 3H, J = 8.0 Hz, J = 3.2 Hz), 7.32 (dd, 1H, J = 10.2 Hz, J = 2.4 Hz) 7.41 (d, 1H, J = 2.4 Hz), 7.50 (d, 2H, J = 8.8 Hz), 7.58 (s, 4H), 9.48 (brs. 2H)

Example 2
(Production of 4-hydroxy-3 ", 5" -dimethyl-4 "-hydroxy-p-terphenyl)
Thermal Decomposition Step 1- (4-Hydroxyphenyl) -4,4-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane 83.2 g (0.200 mol) and 48% aqueous sodium hydroxide 0.4 g After charging 32 g of tetraethylene glycol into a reaction vessel (300 mL four-necked flask) and replacing the inside of the reaction vessel with nitrogen, the inside of the reaction vessel was reduced to a pressure of 40 mmHg and pyrolyzed at a temperature of about 210 ° C. for about 4 hours. Reaction was performed. The point of time when the distillate stopped distilling 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 neutralize it to about pH 6 to obtain 88.0 g of a hydrous oily reaction mixture.

Dehydrogenation step 90.0 g of α-methylstyrene and 0.56 g of 5% palladium / carbon supported catalyst (containing 50% by weight of water) were added to 88.0 g of the oily reaction mixture, and the reaction vessel was purged with nitrogen. The temperature was raised to 160 ° C. under normal pressure, and the reaction was allowed to proceed for 6 hours with stirring.

  After completion of the reaction, 96 g of dimethylformamide was added to the resulting reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture, and the solvent was distilled off by distillation to obtain a distillation residue containing the target product. Water is added to the distillation residue, crystallized and filtered, and isopropanol is added to the resulting solid to form a slurry, which is then crystallized and filtered again, and dried to obtain a purity of 98.1% (according to high performance liquid chromatography analysis). ) 4-hydroxy-3 ", 5" -dimethyl-4 "-hydroxy-p-terphenyl as white crystals. 1- (4-hydroxyphenyl) -4,4-bis (3 , 5-Dimethyl-4-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, 2H), 7.50 (d, 2H, J = 8.8 Hz), 7. 58 (s, 4H), 8.80 (brs, 2H)

Example 3
(Production of 4-hydroxy-3 "-isopropyl-4" -hydroxy-p-terphenyl)
Thermal decomposition process 1- (4-hydroxyphenyl) -4,4-bis (3-isopropyl-4-hydroxyphenyl) cyclohexane 29.3 g (0.0660 mol), 48% sodium hydroxide aqueous solution 0.2 g and tetraethylene 12.0 g of glycol was charged into a reaction vessel (300 mL four-necked flask), and the inside of the reaction vessel was purged with nitrogen, then the pressure inside the reaction vessel was reduced to 40 mmHg, and the temperature was about 210 ° C. for about 3 hours. Reaction was performed. The point of time when the distillate stopped distilling 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 neutralize it to about pH 6, and 33.6 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation step 33.6 g of α-methylstyrene and 0.2 g of 5% palladium / carbon supported catalyst (50 wt% water-containing product) were added to 33.6 g of the above water-containing oily reaction mixture. After purging with nitrogen, the temperature was raised to 160 ° C. under normal pressure, and the reaction was allowed to proceed for 4 hours with stirring.

  After completion of the reaction, 31.2 g of dimethylformamide was added to the resulting reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the 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 removed, the solvent was distilled off from the resulting oil layer, toluene was added, and crystallization was filtered, dried, and a purity of 99.0. % (By high-performance liquid chromatography analysis) of 4-hydroxy-3 "-isopropyl-4" -hydroxy-p-terphenyl was obtained as white crystals. The reaction yield based on the starting material 1- (4-hydroxyphenyl) -4,4-bis (3-isopropyl-4-hydroxyphenyl) cyclohexane was 81.2 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 = 6.8 Hz), 3.25 to 3.29 (m, 1H), 6.87 to 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 = 8.8 Hz), 7.61 (s, 4H) , 9.46 (brs, 1H), 9.56 (brs. 1H)

Example 4
(Production of 4-hydroxy-3 "-t-butyl-4" -hydroxy-p-terphenyl)
Thermal decomposition process 1- (4-hydroxyphenyl) -4,4-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane 25.0 g (0.0508 mol) and 48% sodium hydroxide aqueous solution 0.2 g After charging 10.0 g of tetraethylene glycol into a reaction vessel (300 mL four-necked flask) and replacing the inside of the reaction vessel with nitrogen, the pressure inside the reaction vessel was reduced to a pressure of 40 mmHg and the temperature was about 210 ° C. for about 3 hours. A thermal decomposition reaction was performed. The point of time when the distillate stopped distilling was regarded as the end point of the reaction.

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

Dehydrogenation step 24.5 g of α-methylstyrene and 0.2 g of 5% palladium / carbon supported catalyst (50 wt% water-containing product) were additionally added to 27.3 g of the water-containing oily reaction mixture, and the inside of the reaction vessel was purged with nitrogen. Thereafter, the temperature was raised to 160 ° C. under normal pressure, and the mixture was reacted for 4 hours with stirring.

  After completion of the reaction, 50 g of dimethylformamide was added to the resulting reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture, and the solvent was distilled off by distillation to obtain a distillation residue containing the target product. Methyl isopropyl ketone and water are added to this distillation residue, the aqueous layer is separated and removed, and the solvent is distilled off from the resulting oil layer. Then, a mixed solvent of toluene / cyclohexane is added, and crystallization is filtered. Then, 7.7 g of 4,4 ″ -dihydroxy-3 ″ -t-butyl-p-terphenyl having a purity of 97.1% (according to high performance liquid chromatography analysis) was obtained as white crystals. The yield based on 1- (4-hydroxyphenyl) -4,4-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane was 46.5 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, 1H, J = 8.4 Hz, 2.1 Hz), 7.44 (d, 1H) , J = 2.1 Hz), 7.52 (d, 2H, J = 8.4 Hz), 7.61 (s, 4H), 9.52 (s, 1H), 9.57 (s, 1H)

Claims (3)

Formula (I)

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, and n is 2 or 3). 4,4 ″ -dihydroxy-p-terphenyls represented by Formula (I)

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, n represents 2, and two Rs are both in the o-position of the hydroxy group.)
4,4 ″ -dihydroxy-p-terphenyls represented by 4-hydroxy-3 ", 5" -dimethyl-4 "-hydroxy-p-terphenyl.