JPH046186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, R is a phenyl group substituted with two or more alkyl groups, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylene group, a phenyl group substituted with a halogen atom, or a naphthyl group, a fluorenyl group, or a terphenyl group. The present invention relates to a novel monosulfonylquinone derivative represented by an anthranyl group, an aralkyl group, a cycloalkyl group, or an alkyl group. The compound represented by the general formula () is new,
Similar compounds include only R is a phenyl group, and

The compound of the formula is only described in the Weilstein Handbook. The present inventors have discovered that the quinone derivative represented by the general formula () has the formula () (In the formula, X, Y, and Z are the same or different aromatic residues that may have substituents, aromatic heterocyclic residues, or β-styryl groups, and at least one amino acid residue in the molecule) A cationic dye () that is colored by quickly oxidizing a compound represented by (having a group) The present invention has been completed based on the discovery that the following can be produced. The compound represented by the general formula () is produced by reacting 1,4-benzoquinone () with sulfinic acid () to form sulfonylhydroquinone (), which is then oxidized by an appropriate method. are synthesized. In the reaction of formula (1), the yield at each step is good. The sulfinic acid used in this reaction is
o-xylene sulfinic acid, m-xylene sulfinic acid, p-xylene sulfinic acid, p-cyclohexylbenzenesulfinic acid, p-chlorobenzenesulfinic acid, p-bromobenzenesulfinic acid, indan-β-sulfinic acid Acid, tetralin-β-sulfinic acid, naphthalene-α-sulfinic acid, naphthalene-β-sulfinic acid, 4-methoxybenzenesulfinic acid, 4-phenoxybenzenesulfinic acid, ethanesulfinic acid, butanesulfinic acid, cyclohexylsulfinic acid Acid, dodecyl sulfinic acid, benzyl sulfinic acid, α
Examples include, but are not limited to, -anthraquinone sulfinic acid, β-anthraquinone sulfinic acid, terphenyl-4-sulfinic acid, and fluorene-2-sulfinic acid. The reaction between 1,4-benzoquinone and sulfinic acids is easily carried out in an aqueous solution. In the final stage of the oxidation reaction, compounds such as nitrogen tetroxide, lead tetraacetate, silver oxide, lead peroxide, nickel peroxide, manganese dioxide or trimanganese tetroxide are used, although manganese dioxide is usually used frequently. Although the compound of the present invention has a simple structure, it exhibits the unexpected performance of rapidly oxidizing the methine compound represented by the general formula (), and is capable of producing pressure-sensitive copies using oxidation coloring systems using methine compounds. This is a group of compounds that are extremely useful as color developers for paper or thermal recording paper. That is, a color developing sheet coated on a support by various methods known in the pressure-sensitive copying paper and heat-sensitive recording paper industries contains microcapsules containing oil droplets in which a methine compound represented by the general formula () is dissolved. The microcapsules are destroyed by applying pressure while facing the coated support, and the methine-based compound comes into contact with the compound of the present invention, thereby quickly oxidizing and coloring the methine-based compound to the corresponding hue, creating a robust colored image. Form. The color images obtained in this way have better light fastness and water fastness compared to the color images on pressure-sensitive copying paper of the currently widely used acid-base color systems (e.g. crystal violet lactone and activated white). Because of its outstanding durability and fastness to chemicals, extremely stable colored images can be obtained, leading to an increase in the reliability of pressure-sensitive copying paper. Similarly, a new monosulfonylquinone derivative of the general formula () and a methine compound are held on the same support together with a polymeric binder, and a chemical reaction (color development) is caused by heating contact using a thermal head, etc., which is the so-called thermosensitive recording. As for paper, to obtain a recording paper that has excellent storage stability under various conditions compared to a heat-sensitive recording paper that uses a normal acid-base coloring system (for example, bisphenol A and crystal violet lactone). I can do it. Table 1 shows examples of the novel quinone derivatives of the present invention, but the present invention is not limited thereto.

【table】

[Table] The present invention will be explained in detail with reference to Examples below. The text middle part means the weight part. Example 2-(3',4'-dimethylphenylsulfonyl)
Synthesis with -1,4-benzoquinone [Table 1 Compound No. 1] 23 parts of 3,4-dimethylbenzenesulfinic acid was dissolved in 300 parts of water under heating, and when 10 parts of concentrated hydrochloric acid was added and stirred, the system becomes itchy due to precipitation of free sulfuric acid. Heat 10 parts of 1,4-benzoquinone with 200 parts of water,
When the completely dissolved quinone is added all at once to the above-mentioned sulfuric acid separation solution and stirring is continued under heating, the yellow color of the quinone rapidly decolorizes, and the addition reaction product 2-
3′,4′-dimethylphenylsulfonyl)-hydroquinone precipitates out. Stirring was carried out at 90°C for 30 minutes, and then the crude 2-
(3',4'-dimethylphenylsulfonyl)-hydroxine was obtained. Recrystallization from xylene or orthodichlorobenzene gave white crystals with a melting point of 225-227°C. Add 10 parts of this crude hydroquinone to manganese dioxide.
40 parts of benzene and 50 parts of benzene were stirred for 6 hours while heating on a boiling water bath, and the water generated during this time was distilled off azeotropically with the benzene. Then, the hot manganese dioxide is filtered off and washed with hot benzene. The liquid and washing liquid were mixed and concentrated, 50 parts of ligroin was added, and the mixture was cooled to obtain pale yellowish brown crystals. Recrystallize the crystals by heating and dissolving them in benzene, adding a small amount of ligroin, and cooling.
2-(3',4'-dimethylphenylsulfonyl)-1,4-benzoquinone was obtained as pale yellow crystals with a melting point of 152-153°C. The yield of quinone was 60% of the crude hydroquinone. The elemental analysis values of the obtained quinone were as follows. Elemental analysis value (%) C H S Calculated value 60.86 4.38 11.60 Actual value 60.99 4.23 11.40 Compounds 2-17 listed in Table 1 were all synthesized by a method similar to the above example, and all The analytical values were in good agreement with the calculated values. Reference Examples Example of pressure-sensitive copying paper using sulfonylquinone of the present invention Example of pressure-sensitive copying paper developer sheet using 2-β-naphthylsulfonyl-1,4-benzoquinone (Compound No. 4 in Table 1) (solid content (parts by weight)) Kaolin 85 Calcium carbonate 15 Sulfonylquinone 2... Styrene-butadiene latex used as an aqueous dispersion
6... Oxidized starch 6... Prepare a water-based paint with a solid content of 40 wt% and a weight composition for use as an aqueous solution, and apply it onto high-quality paper using a Meyer bar so that the dry coating amount is 6 g/ ^m2 . A pressure-sensitive copying paper developer sheet (lower paper) was created. Separately, 1.5 wt. A top paper for pressure-sensitive copying paper coated with capsules was prepared, and when the coated sides of the top paper and bottom paper were placed facing each other and the coated sides of the top paper and bottom paper were pressed against each other with an electric typewriter, a blue colored image was quickly obtained. The colored image showed excellent fading resistance against light, exposure, and contact with solvents, etc. In contrast, commercially available blue-colored pressure-sensitive paper using p-phenylphenol-formaldehyde polymer as a developer Colored images are easily erased by contact with light and solvents.

Claims (1)

[Claims] 1 General formula () (In the formula, R is a phenyl group substituted with two or more alkyl groups, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylene group, an aryloxy group, an alkylene group, or a phenyl group substituted with a halogen atom, or Naphthyl group, fluorenyl group, terphenyl group, anthranyl group,
A novel monosulfonylquinone derivative represented by an aralkyl group, a cycloalkyl group, or an alkyl group.