JPH06107665A - Bislactone compound and its production - Google Patents

Abstract

PURPOSE:To provide a new compound having excellent storability, light- resistance and chemical resistance as an electron-donative colorless dye for recording materials such as heat-sensitive paper, pressure-sensitive paper and light and pressure-sensitive paper. CONSTITUTION:The compound of formula I [R1 and R2 are H, (substituted) alkyl or aryl; R3 is single bond or bivalent group; R4 to R6 are H, acyl, alkyl, alkoxy, halogen, nitro or aryll, e.g. the compound of formula II. The compound of formula I can be produced by reacting a 3,3'-dimethoxydiphenyl compound of formula III with a 2-hydroxybenzoylbenzoic acid compound of formula IV.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention, as an electron-donating colorless dye for recording materials such as thermal paper, pressure-sensitive paper, and light-sensitive pressure-sensitive paper, exhibits high storage stability and excellent light resistance and chemical resistance. A bislactone compound and a method for producing the same are provided.

[0002]

2. Description of the Related Art Recording materials using an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, thermal paper, photosensitive pressure-sensitive paper and the like. For example British Patent 214
0449, 21659593, 2166882, 2
174504, U.S. Pat.
20, JP-B-60-23992, JP-A-57-1798.
36, the same 60-123556, the same 60-123557,
Details are the same as 61-230134. The recording material should have (1) sufficient color density and color sensitivity, (2) no fog, (3) sufficient fastness of the color body after color development, 4) Color hue is proper and suitability for copying machines, (5) S / N ratio is high, and (6) Coloring material has sufficient chemical resistance. In recent years, with the speeding up of recording systems and the diversification of requirements, research has been earnestly conducted to improve these characteristics. The present inventors have found that the characteristics of the recording material are significantly improved by incorporating a unique device into the electron-donating colorless dye.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a bislactone compound which is thermally stable, has low solubility, excellent storage stability, and excellent light resistance, and a method for producing the same.

[0004]

The above object has been achieved by developing a bislactone compound represented by the general formula (1). General formula (1)

[0005]

[Chemical 4]

In the formula, R ₁ and R ₂ represent a hydrogen atom, an optionally substituted alkyl group or an aryl group, R ₃ represents a single bond or a divalent group, and R _{4 to} R ₆ represent a hydrogen atom or an acyl group. Represents a group, an alkyl group, an alkoxy group, a halogen atom, a nitro group, or an aryl group.

The compound of the general formula (1) is obtained by reacting the 3,3'-dimethoxyphenyl compound of the general formula (2) with 2-hydroxybenzoylbenzoic acid of the general formula (3). To be General formula (2)

[0008]

[Chemical 5]

R₃Represents a single bond and a divalent group, for example
For example, alkylene, alkenylene, -CO ₂-, -SO₂
-, -S-, -O-, -CONH-, or general formula (4).
R represents a linking group represented by₇Is a hydrogen atom, al
Represents a kill group, an aryl group, an acyl group, X is —CO—,
-SO₂-, -CONH-, -CO₂-, N is 0 or 1
Represents General formula (4)

[0010]

[Chemical 6]

R ₄ is a hydrogen atom, an acyl group, an alkyl group,
It represents an alkoxy group, an aryloxy group, a halogen atom, a nitro group, or an aryl group. General formula (3)

[0012]

[Chemical 7]

In the formula, R ₁ and R ₂ represent a hydrogen atom, an optionally substituted alkyl group, a phenyl group, an aryl group such as a naphthyl group, and these are an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, It may have a substituent such as a nitro group or an aryl group. The alkyl group represents a saturated or unsaturated alkyl group or cycloalkyl group, which may have a substituent such as an aryl group, an alkoxy group, an aryloxy group, a halogen atom or a cyano group. Among the substituents represented by R ₁ and R ₂ in the formula, hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and 6 carbon atoms
To 12 aryl groups are preferable, and these may be substituted with a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an acyl group, a cyano group, a pyridyl group, a furfuryl group or the like. R ₁ and R ₂ may combine with each other to form a 5- or 6-membered ring. R _{5 to} R ₆ represent a hydrogen atom, an acyl group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, or an aryl group.

The electron-donating colorless dye according to the present invention has a low solubility in an organic solvent, and has an advantage of rapidly developing a color when brought into contact with an electron-accepting substance. The colored dye is remarkably stable as compared with the dyes generated from the existing color formers, and hardly discolors due to long-term light irradiation or heating, which is particularly advantageous from the viewpoint of long-term storage of records. Further, the stability of the color forming agent is excellent, it does not cause deterioration even after long-term storage and has a sufficient color forming ability, and it has a performance close to ideal as a color forming agent for recording materials such as pressure sensitive paper and thermal paper.

Specific examples of the raw material to be used in the present invention include 3,3'-dimethoxydiphenyl and 3,3'-
Dimethoxydiphenylamine, 3,3'-dimethoxydiphenylmethylamine, 3,3'-dimethoxydiphenyl-N-phenoxyacetylamine, 3,3'-dimethoxydiphenyl-N-hexylamine, 3,3'-dimethoxydiphenyl-N- Methanesulfonylamine,
3,3′-dimethoxydiphenyl-Np-toluenesulfonylamine, 3,3′-dimethoxybenzophenone, 3,3′-dimethoxydiphenylsulfone, N,
N-bis-3-ethoxyphenyl-N-phenylurea, N-phenyl-N'-3,3'-dimethoxydiphenylurea, N-hexyl-N'-3,3'-dimethoxydiphenylurea and the like can be mentioned. It is represented by the general formula (2). General formula (2)

[0016]

[Chemical 8]

Specific examples of 4-substituted amino-2-hydroxybenzoylbenzoic acid include 2-hydroxy-4-dibutylaminobenzoylbenzoic acid and 2-hydroxy-4.
-Diethylaminobenzoylbenzoic acid, 2-hydroxy-4-N-ethyl-p-toluidino-benzoylbenzoic acid, 2-hydroxy-4-N-ethyl-N-isobutyl-benzoylbenzoic acid, 2-hydroxy-4-N- Ethyl-N-tetrahydroxyfurfurylmethyl-benzoylbenzoic acid, 2-hydroxy-4-N-ethyl-N-isoamyl-benzoylbenzoic acid, 2-hydroxy-4-
N-propyl-N-γ-ethoxypropyl-benzoylbenzoic acid, 2-hydroxy-4-N-ethyl-N-β-
Phenoxyethyl-benzoylbenzoic acid, 2-hydroxy-4-N-ethyl-N-γ-p-ethylphenoxypropyl-benzoylbenzoic acid, 2-hydroxy-4-N
-Ethyl-N-cyclohexylamino-benzoylbenzoic acid and the like are mentioned and represented by the general formula (3). General formula (3)

[0018]

[Chemical 9]

The compound of the present invention includes the 3,3'-dimethoxydiphenyl compound represented by the general formula (2) and the general formula (3).
The compound of formula (2) and the compound of formula (3) are preferably used in an acidic solvent in a molar ratio of 1: 2 to 1: 2.2. These are -10 to 5
React at 0 ° C. for 2-8 hours. When the acidic solvent is sulfuric acid, it is 60% or more, preferably 80 to 100%. Higher acid concentrations are effective to keep the reaction liquid. Mixtures of other acidic condensation solvents such as sulfuric acid and oleum, phosphoric anhydride, polyphosphoric acid and certain Lewis acids such as zinc chloride, phosphorus oxychloride may also be used. Sulfuric acid is a preferred condensation solvent because of its low cost, ease of handling and relative volatility, the reaction can be easily cooled and diluted in ice water, and then the reaction product can be directly processed. As the recrystallization solvent, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as monochlorobenzene, dichlorobenzene and chloroform, and alcohols such as methanol, ethanol and propanol are used.

Another method is to synthesize a bislactone compound from 3,3'-dimethoxydiphenyl and 4-substituted amino-2-hydroxybenzoylbenzoic acid by the above method and then introduce various substituents. Examples of the raw material for the substituent to be introduced include alkyl iodides such as methyl iodide, ethyl iodide, butyl iodide and octyl bromide, benzyl chloride, arylalkyl halides such as 1-phenyl-2-bromoethane, 1- Aryloxy halides such as phenoxy-2-bromoethane, 1-phenoxy-2-bromopropane, 4-methoxyphenoxy-2-bromoethane, acetyl chloride, benzoyl chloride, 4-
Acid halides such as chlorobenzoyl chloride, 4-nitrobenzoyl chloride, 3,5-dinitrobenzoyl chloride, benzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride, 2,4-dinitrobenzenesulfonyl chloride, 4-toluylbenzenesulfonyl chloride, 4 -Nitrobenzenesulfonyl chloride, 2-naphthylsulfonyl chloride, 4-
Methanesulfonylbenzenesulfonyl chloride, 2,
4-dichlorobenzenesulfonyl chloride, 2,4-
Dimethoxybenzenesulfonyl chloride, 4-pentanoylbenzenesulfonyl chloride, 1-butanesulfonyl chloride, 4-methoxybenzenemethanesulfonyl chloride, 8-octanebenzenesulfonyl chloride, 4-cyanobenzenesulfonylbenzenesulfonyl chloride, 4-phenylureidobenzenesulfonyl chloride And the like sulfonyl acid halides and the like. Examples of the catalyst include alkali catalysts such as sodium hydroxide, potassium hydroxide and calcium carbonate, sodium hydride and the like. Examples of the reaction solvent include N, N-dimethylformamide, N, N-dimethylacetamide, ether, tetrahydrofuran and the like. 3,3 '
The ratio of -dimethoxydiphenyl and 4-substituted amino-2-hydroxybenzoylbenzoic acid is preferably 1: 1 to 1: 1.5 molar equivalent, and the reaction temperature is preferably 20 to 50 ° C. Specific examples of the compound of the present invention are shown below.

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

Examples will be shown below, but the present invention is not limited to these examples.

[0026]

【Example】

(Example 1) Synthesis of compound represented by specific example (1) 0.1 mol of 3,3'-dimethoxydiphenylamine and 2-
Hydroxyl-4-N-ethyl-p-toluidino-benzoylbenzoic acid (0.22 mol) is added to an ice-cooled mixture of concentrated sulfuric acid (80 cc) and fuming sulfuric acid (20 cc), and the mixture is stirred at room temperature for 2 hours and then at 30 ° C. Next, the product was isolated by pouring the mixture into ice-alkali water in which twice the molar equivalent of sodium hydroxide was dissolved while stirring. By column chromatography using silica gel with acetonitrile / chloroform as a developing solvent, the target product having a melting point of 231 ° C. shown in Specific Example (1) which exhibits a purple color when contacted with BPA (bisphenol A) was obtained. (Example 2) Synthesis of compound shown in specific example (2) 40 cc of N, N-dimethylformamide dehydrated with molecular sieves and sodium hydride (60% dispersion)
(in mineral oil, manufactured by Aldrich Co.) 0.5 g was stirred at room temperature, and 10 g of the compound obtained in Example 1 was stirred therein.
Added. After stirring for 1 hour, 2.5 g of ethyl iodide was slowly added dropwise, and the mixture was stirred at 50 ° C for 5 hours. Water and chloroform were added to the reaction solution for extraction, and acetonitrile /
By column chromatography using silica gel with chloroform as a developing solvent, the target product having a melting point of 217 ° C., which is shown in Specific Example (2) and exhibits a purple color upon contact with BPA, was obtained.

Example 3 Synthesis of Compound Represented in Specific Example (3) Benzoyl chloride was used in place of ethyl iodide in Example 2. Other than the same method as in Example 2, melting point 2 shown in specific example (3) exhibiting a bluish purple color upon contact with BPA.
The desired product at 42 ° C was obtained. (Example 4) Synthesis of compound shown in specific example (4) 4-Chloro-benzoyl chloride was used instead of ethyl iodide in Example 2. Other than the above, the same procedure as in Example 2 was carried out to obtain a target product having a melting point of 205 ° C., which was shown in specific example (4) and had a blue-violet color upon contact with BPA. (Example 5) Synthesis of compound represented by specific example (5) Benzenesulfonyl chloride was used instead of ethyl iodide in Example 2. Otherwise the same method as in Example 2,
The target product having a melting point of 269 ° C., which is shown in specific example (5) and exhibits a blue color upon contact with BPA, was obtained. (Example 6) Synthesis of compound shown in specific example (6) Instead of ethyl iodide in Example 2, 4-chloro-benzenesulfonyl chloride was used. Other than the above, the same procedure as in Example 2 was carried out to obtain the target product having a melting point of 262 ° C., which is shown in specific example (6) and exhibits a blue color upon contact with BPA. (Example 7) Synthesis of compound shown in specific example (7) Instead of ethyl iodide in Example 2, 4-nitro-benzenesulfonyl chloride was used. Other than the above, the same procedure as in Example 2 was carried out to obtain the target product having a melting point of 253 ° C., which is shown in specific example (7) and exhibits a blue color when contacted with BPA.

─────────────────────────────────────────────────── ───Continued from the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B41M 5/30

Claims (2)

[Claims] 1. A bislactone compound represented by the general formula (1): In the formula, R ₁ and R ₂ represent a hydrogen atom, an optionally substituted alkyl group or an aryl group, R ₃ represents a single bond or a divalent group, and R _{4 to} R ₆ represent a hydrogen atom, an acyl group or an alkyl group. Represents a group, an alkoxy group, a halogen atom, a nitro group, and an aryl group. 2. The bislactone according to claim 1, wherein 3,3′-dimethoxydiphenyl represented by the general formula (2) is reacted with 2-hydroxybenzoylbenzoic acid represented by the general formula (3). Method for producing compound. General formula (2) In the formula, R ₃ represents a single bond or a divalent group, and R ₄ represents a hydrogen atom, an acyl group, an alkyl group, an alkoxy group, a halogen atom, a nitro group or an aryl group. General formula (3) In the formula, R ₁ and R ₂ represent a hydrogen atom, an optionally substituted alkyl group and an aryl group, and R _{5 to} R ₆ represent a hydrogen atom, an acyl group, an alkyl group, an alkoxy group, a halogen atom, a nitro group and an aryl group. Represents