JPS5965053A - Benzoic acid derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is methyl or ethyl). EXAMPLE:o-(4-N-n-Butyl-methylamino-2-hydroxybenzoyl)benzoic acid. USE:Useful as a preparation raw material of a fluoran compound, which has excellent properties as a chromogen for the recording material of pressure-sensitive copying paper, heat-sensitive recording paper, etc. PROCESS:The compound of formula I can be prepared by reacting the m-amino- phenol derivative of formula II with phthalic anhydride in the absence of solvent or in an inert organic solvent such as toluene, xylene, etc. under heating. The amount of phthalic anhydride is 1-2mol per 1mol of the compound of formula II. The compound of formula II can be obtained by alkylating m-butylaminophenol derived from m-aminophenol or resorcinol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to benzoic acid derivatives represented by the general formula (in which R represents a methyl group or an ethyl group);
--- (wherein R is the same as above) A process for producing the above-mentioned benzoic acid derivatives, which involves reacting an m-amine phenol derivative represented by the formula (in which R is the same as above) with phthalic anhydride, The present invention aims to produce a new benzoic acid derivative that can be used as a raw material for producing a fluoran compound that exhibits excellent performance as a chromogen for use in recording materials such as copy paper, R&thermal recording paper, etc.

The benzoic acid derivative currently used in large quantities as a raw material for fluoran compounds is 0-(4-diethylamino-2-hydroxybenzoyl)benzoic acid, and among the fluoran compounds produced using this compound as a raw material, for example, 3-diethylamino-6 -Methyl-
7-Phenylaminofluorane is widely used as a chromogen that develops a black color when it comes into contact with an electron-accepting substance such as clay or bisphenol A in pressure-sensitive copying paper or heat-sensitive recording paper. However, when this fluoran compound is used in thermal recording paper, for example, it is unsatisfactory in terms of the whiteness of the background of the thermal recording paper, its light resistance, and the speed of color development in high-speed facsimile machines. is requested.

The present invention provides benzoic acid derivatives that can be used as raw materials for fluoran compounds that have been improved from such unsatisfactory points. N-butelumebuamino)-6-methyl-7
-phenylaminofluor 2-3- (N-butyl-ethylamino)-6-methyl-7
-Quenylaminofluora/ All of these satisfy the desire for improvements to the compound proboscis of formula (Jll).

A sabbatical for the misfiring fJl'l #! The m-amine phenol derivative represented by the general formula (where Rtri is the same as above), which is a raw material for producing the conductor preventive material, can be produced according to various routes as described below. where X represents the T gene and R-X' represents a methylating agent or an ethylating agent. Synthesize phenol and then alkylate it with an alkylating agent to form the general formula (If
), route A involves reacting m-7<nophenol with butyl halide. Bromine or iodine is preferred as the halogen. Route B proceeds by thermally reacting butylamine with the hydrochloride of stone-amine phenol or by thermally reacting the hydrochloride of butylamine with m-7 minophenol. At this time, the presence of anhydrous zinc chloride is effective in making the reaction proceed smoothly. 0
The route is to drop butylamine into resorcinol heated to 160-180°C. At this time, the reaction is accelerated by the presence of a Lewis acid catalyst such as anhydrous zinc chloride or anhydrous zinc chloride.

The m-butylaminophenol obtained by these methods is treated with a methylating agent or an ethylating agent such as dimethyl sulfate, diethyl sulfate, methyl halogenide, ethyl halide (2), and AX or iodine is preferred as the halogen. ,
D-) Methyl luenesulfonate, p-) Luenesulfo/
General formula (II) by reacting with ethyl acid etc.
An m-aminophenol derivative represented by is obtained.

Routes D and E follow the course of forming m-methylaminophenol or m-ethylaminephenol from m-aminophenol or resorcinol and then butylating it. A methylating or ethylating agent is reacted with the methylating or ethylating agent.The above-mentioned substance is used as the methylating or ethylating agent.When using p-) luenesulfonic acid ester, a basic solvent such as pyridine is used. It is preferable to use a mixed solvent of an inert solvent and a basic solvent such as toluene or chlorine. Route E involves a heating reaction between methylamine or ethylamine and m-aminophenol hydrochloride, or a heating reaction between methylamine hydrochloride or ethylamine salt and m-aminophenol. In these cases, the presence of anhydrous zinc chloride in the chamber is effective in order to allow the reaction to proceed smoothly. The path of F is 160°
The reaction is carried out by bubbling methylamine or ethylamine vapor into the resorcinol heated to ~200°C or in an autoclave. At this time, the reaction is promoted by the presence of a Lewis acid catalyst such as anhydrous zinc chloride or anhydrous magnesium chloride.

Bromine or iodine is preferred as the butyl halide and halogen for m-methylaminephenol or In-ethylaminophenol obtained by these reactions.

) to obtain the m-aminophenol derivative of formula (1).

Route G involves heating reaction of butylmethylamine or butylethylamine with m-aminone enol hydrochloride, or heating reaction of butylmethylamine hydrochloride or butylethylamine hydrochloride with m-aminophenol.

In these reactions, the presence of anhydrous zinc chloride is effective in facilitating the reaction.

Route H involves dropping butylmethylamine or butylethylamine into resorcinol heated to 160° to 200°C. At this time, the reaction is promoted by a Lewis acid catalyst such as anhydrous zinc chloride or anhydrous magnesium chloride.

By these methods, a benzoic acidic conductor expressed by the general formula (wherein R is methyl or ether) is prepared by reacting 9m-aminone enol with phthalic anhydride. is the general formula (II
) m-aminophenol derivative and 1 to 2 molar ratio of phthanolic anhydride without solvent, ttf toluene, xylene, perchlorene, chlorocene, tricrene,
This is achieved by heating in an inert organic solvent such as tetrachloroethane.

In this case, it is not preferable to use an excessive amount of the m-amine phenol derivative because it produces a colored fluoran derivative as a by-product.

The female zoic acid spinner obtained by the present invention has a general formula (wherein R1 is a hydrogen atom, a lower alkyl group, a halogen atom, an amino group, an acylamino group, a monobenzylamino group,
or dibenzylamino group, 2, R2 represents a hydrogen atom, a lower alkyl group, an alkoxy group, or a halogen atom, and R3 represents a hydrogen atom, a lower alkyl group, an alkoxy group, )) a rogen atom, a phenyl group, an amine group , lower monoalkylamino group, lower dialkylamino group, monobenzylamino group, dibenzylamino group, acylamino group, cyclohexylamino group, N-cyclohexyl-N
-benzylamino &, N-lower alkyl-N-phenylamino group, phenylamino group, and phenylamino group optionally substituted with lower alkyl, halogen atom, alkoxy, diphenyl optionally substituted with similar nucleus A phenol derivative represented by a methylamino group or a naphthylmethylamino group (R5 represents a hydrogen atom or a lower alkyl group) or α- or β-naphthols, which may have a substituent, in 70 to 98% sulfuric acid. by reacting at a suitable temperature between 0 and 150°C to obtain the general formula (wherein R+R1tR2 and R5 are the same as above)
A fluorane derivative of the formula (X represents an i-group on the naphthalene nucleus) is obtained.

Example 1 13° OF m-M-H-butyl-methylaminophenol and 13° of phthalic anhydride in 100 d of toluene. After heating and refluxing for 6 hours with stirring, toluene 50- was distilled off, and Improvil alcohol 5-5 was added to the residue.
o- was added. The precipitate was collected, dried again with inpropyl alcohol, and 0-(,zu-N-n-butyl-
Methylamino-2-hydroxybenzoyl)benzoic acid 2
2.8j' (yield 70.0%) with a melting point of 12a2-129
．． Obtained as pale yellow crystals at 8°C.

Example 2 1 a5 p of m-N-n-butyl-ethylaminophenol and 16.5 t of phthalic anhydride were added to 100 d of toluene, and heated under reflux for 6 hours with stirring. Hereinafter, almost the same operation as in Example 1 was carried out to obtain 0-(4-N-n-butyl-ethylamino-2-hydroxybenzoyl)benzoic acid 26, IP (yield: 76.4%), with a melting point of 112.2~ 11
Soaked as pale yellow fine crystals at 3.2°C.

Reference Example 1 m-N-rl-butylaminophenol used in Example 1 was synthesized as follows.

m-aminophenol 109P in methanol 400d
and 54 jl of anhydrous sodium carbonate, and while stirring,
At a temperature of ~20 tl, n-butyl iodide 1849 was added dropwise over t5 hours, and stirring was continued at the same temperature for 8 hours.
The sodium iodide produced was filtered off. Methanol was distilled off from the mother liquor, the residue was extracted with toluene and washed with warm water, the toluene was distilled off, and the residue was distilled under reduced pressure (124~
b recombined to form m-n-butylaminophenol 111P (
67.3) was obtained as white granular crystals with a melting point of 6t1 to 62.8°C.

Thus obtained 9m-n-butylaminophenol i6. Dissolve sP in 100ml of toluene, add 10ml of water, and dissolve 1ml of dimethyl sulfate at a temperature of 50 to 60°C while stirring.
a9p was added dropwise. After continuing stirring at the same temperature for 1 hour, it was cooled to around 20'C, and a caustic sorter aqueous solution was added.
The U was adjusted to approximately a5, and the mixture was heated under reflux for 1 hour and then separated, the toluene layer was washed with warm water, and the toluene was distilled off. The residue was distilled under reduced pressure and 109-b m-N-n-butyl-methylaminophenol 13jl
(yield 72.6ts) was obtained as a pale yellow viscous liquid.

Reference example 2 Resorcinol 55P and anhydrous zinc chloride 6P are combined L, 1
80-200℃ (7) m U K 7J [l Heat L
While stirring, n-butylamine 45P was added dropwise to the mixture at the same temperature. Furthermore, while maintaining the same temperature can 1
The reaction was continued for an hour, and after cooling, 200% of toluene was added and stirred with heating to extract the generated m-n-butylaminophenol into toluene. After washing with warm water, the toluene was distilled off and m-n- Butylaminophenol 5a6p
(Yield 71g6) was obtained.

16.5 jl of this m-n-butylaminophenol and 17.2 jl of ethyl iodide were mixed with 100 mJ of methyl cellosolve.
After adding 6.1 F of anhydrous sodium carbonate to the mixture and heating under reflux for 9 hours with stirring, insoluble materials were removed. The methylseron rub was distilled off, the residue was extracted with toluene, the extract was washed with warm water, the toluene was distilled off, and then distilled under reduced pressure (108-b Le-ethylaminophenol 17.5F (yield 9 [L)
5) was obtained as a pale yellow viscous liquid.

Reference Example 6 (Production of fluorane derivative) O-(4-N-n-butyl-methylamino-2-
Hydroxybenzoyl)benzoic acid 8, OjI and 4-
6.7 p of ethoxy-2-methyldiphenylamine was added to 40 p of concentrated sulfuric acid, and after continued stirring at room temperature for 48 hours, the mixture was poured into ice water to collect the precipitate t['. The cake was dispersed in water, made alkaline by adding caustic soda solution and filtered. Recrystallize the cake with isopropyl alcohol to obtain 3-(N-n-butyl-methylamine) represented by the formula
-6-methyl-7-phenylaminofluorane 9.9
l! (Yield 82.5% from benzoic acid derivative) was obtained as pale yellow fine crystals with a melting point of 15a9-159.5°C.

In addition, the above benzoic acid derivative 111KO-(4-N=
n-butyl-ethylamino-2-hydroxy)benzoic@
Using a6jl, perform almost the same operation as above to obtain the formula (■
3-(N-n-butyl-etheramino)-
3P on 6-methyl-7-phenylaminofluorane H (
Yield 81.9t) from benzoic acid derivative with melting point 18t
Obtained as pale yellow fine crystals at 2-182.6°C.

Patent applicant: Nippon Sokako Co., Ltd.

Claims (1)

[Scope of Claims] 1) A benzoic acid derivative represented by the general formula (in the formula, Rt-J represents a methyl group or an ethyl group). 2) A general formula (in the formula, R represents the above-mentioned A method for producing a benzoic acid derivative represented by