JPS58122964A - Fluoran compound and production thereof - Google Patents

Abstract

NEW MATERIAL:Fluoran compounds of formulaIwherein R1 is (alkyl-substd., halogen-substd.) phenyl; R2 is a 1-8C alkyl; R3 is a 1-10C (alkoxy) alkyl, phenylalkyl; R4 is a 1-10C (alkoxy)alkyl, cycloalkyl, furylalkyl, or R3 and R4 may be combined together with -CH< group to form a ring; benzene ring A may be substituted with halogen. USE:Couplers for pressure-sensitive or heat-sensitive recording paper. The compounds are colorless, but develop black tone when contacted with an acidic material. PREPARATION:A compound of formula II is reacted with a compound of formula III in the presence of a dehydration-condensation agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel fluoran compound and a method for producing the same. .

More specifically, the present invention is based on the general formula (Il [wherein R+ is an alkyl group or a phenyle group which may be substituted with halogen, R2 is a 5-alkyl group having 1 to 8 carbon atoms, and Rsl is a carbon number 1N10
When talking about alkyl, an alkoxyalkyl group represents a phenylalkyl group.

R4 is an alkyl group with a JR prime number of 1 to IO, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a cycloalkoxyalkyl group, a cycloalkoxyalkoxyalkyl group, a phenylarekoxyalkyl group, a phenylalkoxyalkoxyalkyl group, a phenylalkyl group group, phenoxyalkoxyalkyl group, cyanoalkyl group, phenylrea! Reki t base, Ashi! Represents a rare frekyl group, a cyanoalkyl group, a calebamidoalkyl group, a furyloxyalkyl group, a tetrahydrofuryloxyalkyl group, or a tetrahydrofuryloxyalkyl group, R
The lerphenyl group contained in 3 or R4 may be substituted with an alkyl group or a halogen. Wait, R3 and R4 together with -CH are cycloalkyl 6-? may form a tetralinyl group, a tetralinyl group or an indanyl group. Benzene &A may be directly converted with NO10. ] A fluoran compound represented by the following and a method for producing the same.

Pressure sensitivity 6 that applies a coloring reaction caused by contact between an almost uncolored electron-donating substance and an almost uncolored Kame-accepting substance
1. The number of recording paper and thermal recording paper is increasing with the development of the current information age. In general, pressure-sensitive 6 self-recording paper is made by emulsifying an electron-based white pigment (hereinafter referred to as F-shaping) into a self-propelled bath additive, emulsifying it into a few ε molecules, and then microcapsulating it with a polymer compound such as gelatin. It consists of an upper paper coated with this material on a support, and a lower paper coated with an electron-accepting substance (hereinafter referred to as a color developer) on the support, with the coated surfaces of the two facing each other. This is a recording method in which the microcapsules are destroyed by application of writing pressure, hammering pressure, etc., the color forming agent inside the capsules is released, and the color forming agent is transferred to the surface of the color developing agent, causing a color reaction to occur and obtaining a multiple image.

In addition, in heat-sensitive recording paper, the color forming agent and color developer are supported in a binder (for example, a monomolecular substance such as polyvinyl alcohol) together with a solid flux, if necessary, so that they do not come into contact with each other. The most common type is one provided on a support, in which at least one of the fluxing agent, color forming agent, or color developer is melted by heating, and the color forming agent and the color developing agent 11 come into contact, causing a color reaction and forming a recorded image. This is a method of pitching that can be achieved.

In addition, in the case of electrically conductive heat-sensitive self-recording paper, a conductive agent containing a conductive agent is provided between the support and the coloring agent (containing a coloring agent, a color developer, and a melting lamp if necessary) to reduce the heating pressure. This is an 8I2 recording method in which the force is increased, thereby generating heat and producing a dark-colored reaction to obtain a recorded image.

Progress has been made in the development of pigments that can produce black images using a single coloring agent, but there are still problems in terms of hue, fastness, self-coloring property,
At present, no dye has been found that produces a black image that is satisfactory in all respects including cost.

The present invention is based on the fact that the fluoran derivative represented by the general formula (I) itself is a white crystal with no coloration, or that it develops a black tone when it comes into contact with an acidic substance, has light resistance and water resistance of 6+, and has " We have discovered that this dye is useful as a coloring agent for pressure-sensitive or heat-sensitive recording paper with strong fastness.

The fluoran compound of the present invention can be produced, for example, as follows.

(~ General formula (11) [In the formula, R1, R2, and nucleus N have the above meanings.] A compound represented by the general formula (IID 9- [In the formula, R is a droplet or a carbon number 1 ~4 alkyl group, R3 and R4 have the meaning of t(jl MU2).

] The compound represented by 15 to 9 in the presence of a dehydrating table field.
The reaction is allowed to take place at around 0°C for several hours to several tens of hours.

Next, after injecting it into water, it is made into an alkaline juice, and if necessary, it is further heat-treated to obtain slightly colored white crystals.

This is separated from P, dried, and then crystallized as P1 by the general formula (I
) is obtained as white crystals.

Here, the compound represented by the general formula (]1) and the general formula θ
Sulfuric acid, phosphoric acid, polyphosphoric acid, etc. can be used as the dehydrating agent when synthesizing the compound of general formula (I) from compound No. 10, but sulfuric acid with 85% to 100% is used.

Further, as the recrystallization solvent, toluene, monochlorobenzene, chloroform, methyl isobutyl ketone, methyl esterosolve, isobutanoIO-nol, isopropanol, dioxane, ethylene glyco-a dimethyl ether, etc. are used.

Pressure-sensitive or heat-sensitive recording paper can be produced by using one or more of the six dyes prepared in this manner, or by using them in combination with other dyes.

The fluorane conductor represented by the general formula (I) of the present invention is a compound itself, and this compound (
The recording paper used for expenditures is also a Choki. And general formula (1) 1
The represented fluoran derivative contains chlorine as an adjunct group at the 6th position, and at the same time, it is special that it is bonded to a tertiary carbon at the 7th position. The recording paper obtained by using a fluoran derivative with such an innovative and unique chemical structure as a coloring agent develops a deep black color, and has excellent storage stability, long-lasting color development, and water resistance. It is especially grave.

In other words, when using this coloring agent, there was less discoloration due to light on the capsule-coated paper (in case of pressurized paper), and the luminescence of the colored image was weaker (in case of C-thermal paper, there was less discoloration due to the light of uncolored paper). It has the great advantage of being less likely to be colored by light or 1m tM, and less likely to develop new colors due to temperature and humidity of the colored image, or to discolor or fade due to light.Also, it has the great advantage of producing multiple colors (applied to Takenori recording paper, but coloring does not occur when heated). It produces multiple colors without mixing colors and is stable during storage.

Furthermore, this color former has a feature of extremely high dissolution resistance in organic solvents used in the production of pressure-sensitive recording paper.

Next, it is used in the production of the I-leolane compound of the present invention.
Examples of compounds represented by the general formula include the following.

2-(4'-N-mena freanilino-2'-hydroxybenzoyl)-benz: fFJf&2-(4'-N-ethylanilino-2'-hydroxybenzoyl)-benz),
i h acid 2-(4'-N-methyl-p-4 luidino 2
'-Hydroxybenzoyl)-benzoic acid 2-(4'-N
=Ethyl-p-toluidino-2'-hydroxybenzoyl)-benzo-2-14'-N-ethyl-〇-toluidino-27-hydroxybenzoy! )-benzoic acid 2-(
4'-(N-ethyl-N-1)-chlororefunilylamino)-2'-hydroxybenzoyl)-benzoic acid 2'-(4'-N-butyl-p-biluidino 2'-
hydroxybenzoyl)-benzoic acid 2-(4'-(N-ethyl-N-9-butylepheni!reamino)-2'-hydroxybenzoyl)-benzoic acid Also, compounds represented by general formula (11) For example, the following can be given.

13- 14- - l O- -17- 16- -■ 8- -19- Some examples of the fluoran compound represented by the general formula CI) of the present invention will now be described. The hue was the same as that of Shirikage I and Ju.

20- -22- Hereinafter, the present invention will be specifically explained with reference to Examples.

In the text, Miyako represents Denkobu.

Example 1 (Synthesis of compound of k82) amt acid ta moiety + C2-(4'-N-methyl-I)
1.82 parts of -toluidino-2'-hydroxybenzoyl)benzoic acid and 1.18 parts of 2-chloro-4-hydroxyN-cyclohexylaniline (melting point 116-117°C) were dissolved at 30°C or below. , and then stirred at 30° C. for 48 hours to complete the reaction.

Next, the mixture was poured into 100 volumes of ice water, 16 parts of 28% aqueous ammonia was added to make it alkaline, and the precipitate formed was collected from house to house. After washing with 200 parts of warm water, dry. ,l'
2.8 parts of 8-(N-methylerol-toluidino)-6
-Chloro-7-cyclohexylaminofluorane was obtained. This product was recrystallized from isopropyl alcohol-I to obtain 37.9 parts of white crystals each having a temperature of 218 to 219.5°C.

Elemental analysis, mass spectrum, NMR spec23- It was confirmed that this structure was present.

Example 2' (Synthesis of compound l?al) In Example 1, 2-(4'-N-methyl f-p-toluidino-2'
-hydroxybenzoyl) instead of 2-(
A similar procedure was carried out using 1.88 parts of 4'-N-ethyl-p-toI raysinoic acid (2'-hydroxybenzoyl)benzoic acid.

2.8kan: 8-(N-ethyl-p-toluidino)-
6-chlorof-rea-cyclohexylaminofluorane was attached. This product was recrystallized from isopropyladalecol to obtain white crystals with a melting point of 187-188°C.

Example 3 (Synthesis of Compound 5) 98% sulfur, 2-(4'-N-ethyl-1) in the fita part
1.88 parts of 2'-hydroxybenzoyl)benzoic acid and 2-chloro-4-hydroxy-N
-isopropylaniline (melting point 80-81°C) 0.98
After that, the mixture was stirred at 80°C for 48 hours, and the reaction was completed after 24 hours.

The same procedure as in Example 1 was repeated 1' to obtain 3-(N-ethyl-p-toluidino)-6-chloro-isopropyl-reaminofluorane. This was recrystallized from isopropyl alcohol to give white crystals with a melting point of 159-160°C.

Example 4 (Synthesis of compound of 7Q 22) 95% sulfuric acid 1
8 parts, 2-(4'-N-ethyl-p-toluidino-21
-Hydroxybenzoyl)benzoic acid 1.88 parts and 2-chloroI-4-hydroxy-N-41'-methyI-2
'-acetylethyl)aniline (8 points 62-64℃>
1. The procedure was as in Example 1 using 4 parts of t.

3-(N-ethyl-p-toluidino)-6-chloro-7
-(1'-methyl-21-acetyl leethylamino)
Fluorane was obtained. White crystals with a melting point of 151-154°C are formed by internal crystallization from isopropital alcohol.

Example 5 (8 samples of compound I1) 98% sulfuric acid 18%, 2-(4'-N-methyl-1)-1
-I Reishino 2'-hydroxybenzoyl) 1.88 parts of acid, 2-crotale-4-hydroxy-N-(1
'-Methyl-2'-methoxyethyl)aniline (melting point 8
Example 1 and same compound 1 using 1.08 parts (2-83°C)
I operated this. 8-(N-Ethyl-1)-1-luidino)-6-chloro-7-(1'-methoxyethyl-2'-methoxyethylolean was obtained. This was recrystallized from isopropyladalecol. , melting point 149~
1 fathom of white crystals at 152℃.

Example 6 (Synthesis of compound A, 2) 11 parts of 98% sulfur, 18 parts of 2-(4'-N-niF-ru-p-belayzino-21-hydroxybenzoyl)benzoic acid containing 1.8 parts
The same procedure as in Example 1 was carried out using 8 parts and 1.06 parts of 2-chloro-4-hydroxy-N-cyclopentylaniline (melting point 68-69°C).

8-(N-ethyl-p-toluidino-6-chloro-7-
Add cyclopentylaminofluorane. This was recrystallized from isopropyl alcohol with a melting point of 200-2.
Wait for white crystals at 02℃.

Example 7 (Synthesis of compound h6) 13 parts of 98% sulfuric acid, 1.
88 parts and 2-chloro-4-hydroxy-N-(biethylpropylene)aniline (boiling point 120-121°C/1
．． 2 parts 1gHf) 1.07 me Example 1 for toilet shite%
I operated the meeting in the same way. 3-(N-ethyl-p-toluidino)-6-chloro-7-(1'-ethyl leprovira ε
)) Obtained fluorane. This was recrystallized from isopropyl alcohol hexane to obtain white crystals with a melting point of 128-iaoC.

Example 8 (Synthesis of the compound of Oboro 9) 219 parts of 94% sulfuric acid, 2-(4'-N-27-1, L, -p-to-t-reicino-21-hydroxyhexyl)benzoic acid 1 .88 parts and 2-chloro-4-hydroxy-N-(1',8'-dimethyl I-levutyl)
The same procedure as in Example 1 was carried out using 1.14 parts of aniline (64-65° 5°C per point). 8-(N-ethyl-
p-toIreicino6-chloroleir-(1').

Wait for 3'-dimethyl-levtylamino) fluorane. This was recrystallized from isopropyl alcohol and hexane to obtain white crystals with a melting point of 184-186°C.

Example 9 2-(4'-N-ethyl-p-toluidino-2'-hydroxybenzoyl) rest M1.
88 parts of 2-chloride and 1.25 parts of 4-methoxy N-cyclohexylaniline were dissolved at 30°C or lower, and the mixture was heated at 30°C.
The mixture was stirred and kept warm for 48 hours. Next, the mixture was poured into 200 volumes of ice water, made alkaline by adding 25% sodium chloride solution, heated to 60°C, heated to 28°C, kept warm for 1 hour, and the precipitate was washed separately with water. After drying the cake, open the opening IL/' of II-IJ j=.
<3-(N-ethyl-p-toluidino) by boiling with nozene and diluting with isopropyl alcohol after cooling.
-6-chloro-7-ditarohekizyla epsilon Ileolano was obtained. Isopropi! Recrystallization from real alcohol gave white crystals of 1144- and those obtained by the method of Example 2.

129 Completed - Procedural amendment 1, Indication of the case 1987 Patent Application No. 4498 2, Name of the invention (-, Fluoran compound and its manufacturing method 3, Relationship with the Nagisa case to be amended Patent applicant Higashi Ward, Osaka City 5-15 Kitahama (209) Sumitomo Chemical Co., Ltd. Representative Takeshi Tokata 4, Agent 5-15-6 Kitahama, Higashi-ku, Osaka, Contents of amendment (1) Line 2 from the bottom of page 23 of the specification, r37.9 copies”
Correct the statement to read "1.9 copies."

10

Claims (2)

[Claims] (1) General formula (11 [In the formula, R1 is an alkyl group or a phenyl group optionally substituted with halogen, R2 is an alkyl group having 1 to 8 carbon atoms, and RI+ is an alkyl group having 1 to 10 carbon atoms. , an alkoxyalkyl group or a phenylalkyl group. R4 is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms,
Lekyl group, Arekoxyalkyl group, cycloalkoxyadarekyl group, cycloarekoxyalkoxyalkyl group, phenylalkoxyalkyl group,
Phenylalkoxyalkoxyalkyl group, phenoxyalkyl group, phenoxydialkoxyatarekyl group, cycloalkyl group, Hunini realkyl group, azilarylyl group, cyanoalkyl group, carbamidoalkyl group,
Represents a furyl alkyl group, a furyl realekyloxyalkyl group, a tetrahydrofuryl realyl At or a tetrahydrofuryl realekyloxyalkyl group, and R
The phenyl group contained in 3 or R4 may be substituted with an alkyl group or a halogen. Also, R3 and R4
may be combined with bar CH, to form a cycloalkyl group, a tetralinyl group or an indanyl group. The benzene nucleus N may be substituted with a halogen.] A fluoran compound represented by the following. (2) General formula ([1) [In the formula, R1 represents an allekyl group or a phenyl group which may be substituted with a halogen, R2 represents an allekyl group having 61 to 8 carbon atoms, and the benzene nucleus A is a halogen. May be replaced. ], a compound represented by the general formula [wherein R3 is an alkyl group having 1 to 10 carbon atoms, an alkoxylalkyl group, or a phenylalkyl group, and R4 is an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group,
Recoxia! lexoxyalkyl group, cycloalkoxyalkyl group, cycloalkoxyalkoxyalkyl group, phenylalkoxyamelyl group, phenyl realkoxyalkoxyalkyl group, phenoxyadarekyl group, phenoxyalkoxyalkyl group, cyanoalkyl group , represents a phenylalkyl group, an azila I-rekyl group, a cyanoalkyl group, a carboamide alkyl group, a furyl alkyl M, a furyl alkyloxyalkyl group, a tetrahydrofuryl alkyl group or a tetrahydrofuryl realkyloxyalkyl group, and is included in R3 or R4. The phenyl group may be substituted with an alkyl group or a halogen. Further, R3 and R4 may be combined with -CH to form a cycloalkyl group, a tetralinyl group or an indanyl group. R represents hydrogen or an alkyl group having 1 to 4 carbon atoms. ] General formula (1) characterized by reacting with a compound represented by the following in the presence of dehydration:
Association R4+nuclear N has the above meaning. ] A method for producing a fluoran compound shown in