JP2618410B2 - Method for producing aromatic hydroxy compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel aromatic hydroxy compound and a method for producing the same. More specifically, p-halogenonitrobenzene and the compound of the general formula (I) in a molar ratio of 1 to 1.2 with respect to p-halogenonitrobenzene (Wherein X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -C
_{(CF 3) 2 -, -} CO -, - S -, - SO -, - shows a or a divalent -O- - SO _2. Wherein X may be directly bonded by a single bond) and a dialkali metal salt of a biphenol represented by the formula (II): (Wherein X has the same meaning as in formula (I)).

The aromatic hydroxy compound represented by the general formula (II) is a novel compound, has not been produced before, and its use is not known.

However, due to its structure, it is a compound useful as a raw material for high molecular compounds and as an intermediate raw material for dyes, pigments, agricultural and pharmaceutical products.

(Prior Art) Hitherto, many methods for producing 4-nitrodiphenyl ethers from phenols and p-halogenonitrobenzene have been known. As a method of reacting only one of the two hydroxyl groups of biphenols with p-halogenonitrobenzene, an example using hydroquinone having two hydroxyl groups on one benzene ring is known (Gov. Pat. 2,
157,781), and no compound having a monovalent phenol bonded by a linking group represented by X as in the general formula (I) of the present invention has been known at all.

(Problems to be Solved by the Invention) An object of the present invention is to provide a novel aromatic hydroxy compound represented by the above general formula (II), which is useful as a raw material for a polymer and various intermediates, and to obtain this compound. It is to provide a method of manufacturing at a high rate.

(Means for Solving the Problems) The present inventors have conducted intensive studies in order to achieve the above-described problems. As a result, when 1 to 1.2 equivalents and 1 equivalent of p-halogenonitrobenzene of a dialkali metal salt of a bisphenol represented by the above general formula (I) are condensed in an aprotic polar solvent, surprisingly, The present inventors have found that a novel aromatic hydroxy compound represented by the formula (II) can be produced in good yield, and completed the present invention.

The novel compounds of the present invention include, specifically, 4-hydroxy-4 '-(4-nitrophenoxy) biphenyl,
Hydroxy-4 '-(4-nitrophenoxy) diphenylmethane, 2- (4-hydroxyphenyl) -2- [4
-(4-nitrophenoxy) phenyl] propane, 2-
(4-hydroxyphenyl) -2- [4- (4-nitrophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane, 4-hydroxy-4 '-(4-nitrophenoxy) benzophenone , 4-hydroxy-4 '-(4-
Nitrophenoxy) diphenyl sulfide, 4-hydroxy-4 '-(4-nitrophenoxy) diphenyl sulfoxide, 4-hydroxy-4'-(4-nitrophenoxy) diphenyl sulfone, 4-hydroxy-4'-
(4-Nitrophenoxy) diphenyl ether and the like are exemplified.

The raw material used in the method of the present invention is a compound represented by the general formula (I)
Are bisphenols and p-halogenonitrobenzene.

Specific examples of bisphenols include 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl)- 1,1,1,3,
3,3-hexafluoropropane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide,
4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether and the like can be mentioned.

Specific examples of p-halogenonitrobenzene include p-fluoronitrobenzene, p-chloronitrobenzene, p-bromonitrobenzene, p-iodonitrobenzene, and the like, and p-chloronitrobenzene is frequently used industrially.

The amounts of these starting compounds used are in the range of 1.0 to 1.2 mole ratio of bisphenols to p-halogenonitrobenzene.

The base used in the method of the present invention is an alkali metal oxide, hydroxide, hydride or alkoxide, preferably an alkali metal hydroxide. Specifically, sodium oxide, lithium oxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium hydride, potassium t-butoxide, sodium methoxide, sodium ethoxide, and the like are used. Sodium hydroxide and potassium hydroxide are used. The amount of these bases to be used is usually 1.8 to 2.0 times the molar amount of the raw material biphenols.

In this reaction, quaternary ammonium salts, quaternary phosphorus salts, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cribate, nitrogen-containing linear polyethers, polyethylene glycol and alkyl ethers thereof Such a phase transfer catalyst, copper powder and copper salt may be added as a reaction accelerator.

In the method of the present invention, an aprotic polar solvent is used as a reaction solvent. As the reaction solvent, specifically,
N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, 1-methyl-2-
Pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, N, N, N ', N'-tetramethylurea, hexamethylphosphotriamide and 1,3-dimethyl-3,4,5,6-tetrahydro- 2- (1H) -pyrimidine and the like.

The use amount of these solvents is not particularly limited, but usually,
A range of 1 to 10 times the weight of the raw material is sufficient.

Although the method for carrying out the reaction is not particularly limited, usually, a predetermined amount of a bisphenol, a base, and a solvent are charged to prepare an alkali metal salt of the bisphenol in advance, and then p-halogenonitrobenzene is used as a solid or in a solvent. Add in a solution dissolved in.

Water generated in the reaction system when an alkali metal oxide, hydroxide, or the like is used as the base can carry out the reaction without particular removal.

The reaction temperature is usually 20 to 240 ° C, preferably 60 to 160 ° C.
And the reaction time is in the range of 1 to 10 hours.

The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography, or the like.

After completion of the reaction, the reaction solution is discharged into water as it is, and acidified by adding hydrochloric acid to obtain a crude product of an intended product. This crude product can be further recrystallized or further purified as an alkali metal salt.

[Action and effect]

The present invention provides a novel aromatic hydroxy compound, and according to the present invention, a novel aromatic hydroxy compound can be easily produced at a high yield according to the method.

(Examples) Hereinafter, the method of the present invention will be described more specifically with reference to examples.

Example 1 In a reaction flask equipped with a stirrer, thermometer, and cooling tube,
186.2 g (1.1 mol) of 4,4'-dihydroxybiphenyl and 1,
Charge 931.0 g of 3'-dimethyl-2-imidazolidinone, raise the temperature while passing nitrogen, and dissolve at 60 ° C. This was charged with 91.7 g (2.2 mol) of 96% sodium hydroxide, heated, and stirred at 100 to 120 ° C for 2 hours. After lowering the internal temperature to 80 ° C or less, 157.5 g (1.0 mol) of p-nitrobenzene
Was dissolved in 236.3 g of 1,3'-dimethyl-2-imidazolidinone dropwise at 80 to 90 ° C. over 2 hours, and further stirred at the same temperature for 2 hours.

After the completion of the reaction, the reaction solution is cooled, discharged into ice water 2.4,
When 137.7 g of 5% hydrochloric acid aqueous solution was added dropwise, yellow crystals precipitated.
This was filtered, washed and dried to obtain 4-hydroxy-4'-nitrophenoxybiphenyl.

Yield 240.0 g (Yield 78.0%) mp 260-262 ° C Elemental analysis (C ₁₈ H ₁₃ NO ₄ ) Calculated value of CHN (%) 70.35 4.26 4.56 Analytical value (%) 70.85 4.00 4.72 IR (KBr, cm ^-1) 3425: hydroxyl group 1590, 1340: nitro group 1240: ether bond Examples 2-3 and Comparative Example 1 Except that the solvent or the base was changed, the same operation as in Example 1 was performed, and the results in Table 1 were obtained. .

Example 4 In a reaction flask equipped with a stirrer, thermometer, and cooling tube,
2,2-bis (4'-hydroxyphenyl) propane 100.4
g (0.44 mol) and 1,3-dimethyl-2-imidazolidinone
Charge with 502 g, raise the temperature while passing nitrogen, and dissolve at 60 ° C. After charging 51.4 g (0.88 mol) of 96% sodium hydroxide, the mixture was heated and stirred at 100 to 120 ° C for 2 hours.
After lowering the internal temperature to 80 ° C or lower, p-nitrobenzene 63.0
g (0.4 mol) in 1,3-dimethyl-2-imidazolidinone 9
A solution dissolved in 4.5 g was added dropwise at 80 to 90 ° C. over 2 hours,
The mixture was further stirred at the same temperature for 2 hours.

After the completion of the reaction, the reaction solution is cooled, discharged into ice water 1.2,
When 45.9 g of 5% aqueous hydrochloric acid was added dropwise, yellow crystals precipitated. This was filtered, washed and dried to obtain 2- (4-hydroxy-phenyl) -2- [4- (4-nitrophenoxy) phenyl] propane.

Yield 107 g (76.5% yield) mp 118-120 ° C Elemental analysis (C ₂₁ H ₁₉ NO ₄ ) Calculated value for CH N (%) 72.19 5.48 4.01 Analytical value (%) 72.43 5.61 3.76 IR (KBr, cm ^-1 ) 3420: hydroxyl group 1340: nitro group 1240: ether bond Examples 5 to 6 and Comparative Example 2 The same operation as in Example 4 was performed except that the solvent or the base was changed, and the results in Table 2 were obtained.

Claims (1)

(57) [Claims] (1) p-halogenonitrobenzene and the compound of the formula (I) in a molar ratio of 1 to 1.2 with respect to the same. [Wherein X is a divalent hydrocarbon group having 1 to 10 carbon atoms, -C
_{(CF 3) 2 -, -} CO -, - S -, - SO -, - SO 2 - or an divalent group -O-. X may be directly bonded by a single bond], wherein the compound is condensed with a dialkali metal salt of a biphenol represented by the following general formula (II): [Wherein X has the same meaning as in formula (I)].