JP2641002B2 - Diphenyl sulfone compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a recording material using an electron-donating colorless dye and an electron-accepting compound, for example, 3,3'- useful as an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials. It relates to a diphenyl-4-hydroxy-4'-substituted hydroxydiphenylsulfone compound.

[0002]

2. Description of the Related Art Various phenolic compounds are known as electron-accepting compounds for pressure-sensitive recording materials and heat-sensitive recording materials. All of them are known as color density, color sensitivity, unprinted area preservability, and printed area preservation ( Weather resistance, chemical resistance, etc.). For example, when 4-isopropoxy-4'-hydroxydiphenylsulfone disclosed in Japanese Patent Publication No. 3-54555 is used for thermal recording paper, it exhibits high color density and sensitivity, but is written with a magic marker, highlighter, or the like. As a result, the unprinted portion was colored or the printed image disappeared, and the chemical resistance was insufficient.

When bis- (3-phenyl-4-hydroxyphenyl) sulfone disclosed in JP-A-2-266981 is used for heat-sensitive recording paper, the color-forming sensitivity is low, and it is difficult to write with a magic pen or a fluorescent pen. Although no decoloration of the image was shown, the unprinted portion was colored, and if hand cream or the like was attached, the image was immediately decolored, and the color sensitivity and chemical resistance were insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a color density,
An object of the present invention is to provide a phenolic compound which simultaneously satisfies the color development sensitivity, preservability of an unprinted portion, preservability of a printed portion (weather resistance, chemical resistance, etc.).

[0005]

The object of the present invention is to provide a phenolic compound represented by the following general formula (1):
Achieved by 3'-diphenyl-4-hydroxy-4'-substituted hydroxydiphenylsulfone compounds. General formula (1)

[0006]

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In the formula, R represents an alkoxy group, an aryl group, or an alkyl group which may be substituted with an aryloxy group.

The alkyl group represented by R may be linear, branched or form a ring, and is preferably a group having 1 to 25 carbon atoms, more preferably a group having 1 to 18 carbon atoms. Particularly, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, normal amyl group, isoamyl group, normal hexyl group, cyclohexyl group, normal heptyl group, normal octyl group, normal Nonyl, normal decyl, lauryl and stearyl groups are preferred.

The alkoxy group which may be substituted on the alkyl group represented by R may be linear, branched or form a ring, and is preferably a group having 1 to 10 carbon atoms. Groups 1-6 are preferred. In particular, a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, an isobutoxy group, a secondary butoxy group, a normal amyloxy group, an isoamyloxy group, a normal hexyloxy group, and a cyclohexyloxy group are preferable.

The aryl group which may be substituted with the alkyl group represented by R is preferably a group having 6 to 14 carbon atoms.
Apart from this carbon number, the aromatic ring may further have a substituent. As the aryl group, a phenyl group, a naphthyl group and an anthracenyl group are particularly preferred. As a substituent which may be present on the aromatic ring, an alkyl group, an alkoxy group,
An aryl group, an aryloxy group, and a halogen atom are preferable, and particularly, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal amyl group, an isoamyl group, a normal hexyl group, a methoxy group, and an ethoxy group Group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, secondary butoxy group, normal amyloxy group, isoamyloxy group, phenyl group, phenoxy group, fluorine atom, chlorine atom and bromine atom are preferable.

The aryloxy group which may be substituted by the alkyl group represented by R is preferably a group having 6 to 10 carbon atoms. Apart from this carbon number, the aryloxy group may further have a substituent on the aromatic ring. Is also good. As the aryloxy group, a phenyloxy group and a naphthyloxy group are particularly preferred. As the substituent which may be present on the aromatic ring, an alkyl group, an alkoxy group, an aralkyloxy group, an aryl group, an aryloxy group, and a halogen atom are preferable, and in particular, a methyl group, an ethyl group, a normal propyl group, and isopropyl Group, normal butyl group, isobutyl group, normal amyl group, isoamyl group, normal hexyl group, cyclohexyl group, methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, isobutoxy group, secondary butoxy group, normal amyl Preferred are an oxy group, an isoamyloxy group, a phenyl group, a cumyl group, a benzyloxy group, a phenyloxy group, a fluorine atom, a chlorine atom, and a bromine atom.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The compounds of the present invention can be easily synthesized with reference to known synthetic methods. For example, bis- (3-phenyl-4-hydroxyphenyl) sulfone is used without solvent or
Water, protic solvents such as alcohols, aprotic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, polar solvents such as acetonitrile, ethyl acetate, acetone, toluene, hexane, benzene,
In a non-polar solvent such as ether, a halogen-containing solvent such as dichloromethane or chloroform, or a mixed solvent thereof (may be a two-layer system), sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, hydrogencarbonate In the presence of a binder such as potassium, magnesium hydroxide or calcium hydroxide, without additives, or with the addition of additives such as quaternary ammonium salts and alkali halides, the corresponding alkyl group, aralkyl group, aryloxyalkyl group Is reacted at 0 to 150 ° C. for 0.5 to 24 hours. Next, the reaction mixture is poured into ice water and subjected to liquid separation operation with an organic solvent for extraction or purification by recrystallization or silica gel column chromatography to obtain the desired compound.

As another synthesis method, for example, the corresponding 4
Alkyl-aralkyl, aralkyl, aryloxyalkyl ether of -hydroxy-3-phenylbenzenesulfonyl chloride and orthophenylphenol with aluminum chloride,
In the presence of a binder such as iron chloride, zinc chloride, and sulfuric acid, in a solvent such as no solvent or in a solvent such as dichloromethane, dichloroethane, nitrobenzene, and carbon disulfide, and reacted at a reaction temperature of -10 to 150 ° C for 0.5 to 24 hours, Usually, the target compound can be obtained by treating with ice-cooled hydrochloric acid and, if necessary, purifying by recrystallization, silica gel column chromatography or the like.

[0024]

【Example】

Example 1 Synthesis of Compound of Specific Example (1) In 20 ml of dimethylacetamide, 10 g of bis- (3-phenyl-4-hydroxyphenyl) sulfone, 4.28 g of potassium carbonate, and 4.4 g of methyl iodide were added, and the mixture was added at 40 ° C. for 6 hours. Stirred for hours. After cooling, the reaction mixture was poured into ice water, salt and ethyl acetate were added, and the mixture was stirred for 1 hour. The ethyl acetate layer was concentrated and purified by silica gel column chromatography to obtain the target compound. 133-136 ° C.

Example 2 Synthesis of Compound of Specific Example (2) 10 g of bis- (3-phenyl-4-hydroxyphenyl) sulfone, 3.38 g of ethyl bromide, and 2.75 g of 48% NaOHaq were added to 40 ml of methanol, and the mixture was added with 40 g of methanol.
Stirred at C for 6 hours. After cooling, the mixture was treated in the same manner as in Example 1 to obtain the desired compound. Melting point 169-172 [deg.] C.

Example 3 Synthesis of Compound of Specific Example (3) 30 g of bis- (3-phenyl-4-hydroxyphenyl) sulfone and 10.5 g of normal propyl bromide were added to 171 ml of water and stirred at 50 ° C. Next, 84.7 g of a 20% by weight aqueous sodium carbonate solution was added dropwise at 50 ° C. over 2 hours, followed by stirring at 70 ° C. for 3 hours. After cooling,
The pH was adjusted to 7.5 with hydrochloric acid, filtered, washed with water and dried to obtain crude crystals. Recrystallization from isopropyl alcohol gave the desired compound. Melting point 172-175 [deg.] C.

Example 4 Synthesis of Compound of Specific Example (4) 48.2 g of bis- (3-phenyl-4-hydroxyphenyl) sulfone, 18.5 g of isopropyl bromide and 22.2 g of potassium carbonate were added to dimethylformamide 20
The mixture was added to 0 ml and stirred at a temperature of 100 to 120 ° C for 4 hours. Dimethylformamide was distilled off under reduced pressure, 200 ml of chloroform and 200 of water were added to the residue to dissolve it, and a small amount of sulfuric acid was added to adjust the pH of the aqueous layer to 5.0, followed by liquid separation. After the chloroform layer was washed with 100 ml of water, chloroform was distilled off, and the residue was recrystallized from toluene to obtain the desired compound. 153-156 ° C.

Example 5 Synthesis of the compound of the specific example (9) 8 g of sodium hydroxide and 25 g of water were added and dissolved. Then, 40 g of bis- (3-phenyl-4-hydroxyphenyl) sulfone was added and dissolved by heating. After the liquid temperature was 70 ° C., 16.5 g of normal amyl bromide was added dropwise over 1 hour.
Stirring was further continued at 65-72 ° C for 12 hours. Toluene was added to the reaction solution, and the diether was extracted and removed from the toluene layer. Ethyl acetate was added to the aqueous layer for extraction, and the desired product was extracted into the ethyl acetate layer. Neutralize the ethyl acetate layer with dilute hydrochloric acid,
After washing with water, the residue obtained by evaporating the solvent was recrystallized from toluene to obtain the desired compound. 140-143 ° C.

Example 6 Synthesis of Compound of Specific Example (11) 2 g of sodium hydroxide, 2.0 g of sodium bromide, 12 g of water
g, bis- (3-phenyl-4-hydroxyphenyl)
After 10 g of sulfone was charged and dissolved, 16.5 g of normal hexyl bromide was added dropwise at 70 ° C. for 1 hour. The reaction and treatment were conducted in the same manner as in Example 5 to obtain the desired compound. 138-141 ° C.

Examples 7 to 17 Table 1 below shows compounds synthesized by the same method as in Example 2 and their melting points.

[0031]

[Table 1]

Example 18 Synthesis of the compound of the specific example (9) 3-phenyl-4 in 40 ml of 1,2-dichloroethane
-Normal amyloxyphenylsulfonyl chloride (9.66 g), 4.73 g of aluminum chloride and 4.85 g of orthophenylphenol were added, and the mixture was stirred at room temperature for 12 hours. The reaction solution was poured into a mixture of ice and diluted hydrochloric acid, and the organic layer was repeatedly washed with water and dried. The solvent was distilled off, and the residue was recrystallized from ethanol to obtain the desired compound. Melting point 140-
143 ° C.

Claims (1)

(57) [Claims] 1. A 3,3'-diphenyl-4-hydroxy-4'-substituted hydroxydiphenylsulfone compound represented by the following general formula (1). General formula (1) In the formula, R represents an alkyl group which may be substituted with an alkoxy group, an aryl group, or an aryloxy group.