JPH04217640A - Salicylic acid derivative and zinc salt thereof - Google Patents

Abstract

PURPOSE:To provide the subject new salicylic acid derivatives and zinc salts thereof capable of ready production with high purity in a high yield and at a low cost and useful as a colorant for basic dyes excellent in solvent resistance, especially oil resistance and plasticizer resistance. CONSTITUTION:Compounds of formula I (R is 1-4C alkyl; n is 2-4), e.g. 5-[p-2-p- methoxyphenoxyethoxy)cumyl]salicylic acid which can be obtained by reacting an alkyl halide derivative of formula II (X is halogen) with hydroxycumylsalicylic acid of formula III (R' is H, 1-4C alkyl or benzyl) or its ester in the presence of an alkali (e.g. NaOH) in a polar solvent (e.g. toluene) at 50-150 deg.C and, as necessary, hydrolyzing the resultant compound.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a novel salicylic acid derivative and its zinc salt useful as a coloring agent for colorless or light-colored basic dyes.

"Prior Art" Conventionally, recording materials that utilize a color reaction between a colorless or light-colored basic dye and an organic or inorganic coloring agent are well known. There is a heat-sensitive recording medium that is configured to obtain a recorded image using the following methods.

Recently, with the remarkable progress of thermal recording, its application fields and forms have diversified, and it is not only used as a recording medium for thermal facsimiles and thermal printers, but also as a recording medium for POS (Point
Its use in new applications such as labels (to of sales) is also rapidly increasing.

However, heat-sensitive recording materials generally have drawbacks such as background fogging and discoloration of recorded images due to the influence of solvents and the like. For this reason, packaging for stationery and office supplies such as water-based ink pens, oil-based ink pens, fluorescent pens, vermilion ink, adhesives, pastes, diazo developers, cosmetics such as hand creams, hair tonics, and milky lotions, and even vinyl chloride films, etc. It has the disadvantage that when it comes into contact with the material, the white paper part develops color or the colored part causes discoloration, which significantly reduces the commercial value.

In order to improve these drawbacks and increase the solvent resistance of heat-sensitive recording materials, bisphenol S derivatives (JP-A
7-210886, JP-A-58-82788, JP-A-58-166098, and JP-A-60-13852). However, even in heat-sensitive recording materials using these compounds, image storage stability,
In particular, stability against oil and plasticizers is not always sufficient.

``Problems to be Solved by the Invention'' The purpose of the present invention is to develop a novel salicylic acid derivative and its zinc salt that are extremely useful as coloring agents for basic dyes that have excellent solvent resistance, especially oil resistance and plasticizer resistance. It is in a place where we provide.

"Means for Solving the Problems" The present invention is a salicylic acid derivative represented by the following general formula [I] and a zinc salt thereof.

[In the formula, R represents a C1-4 alkyl group, and n is 2-4
indicates an integer. [Function] The salicylic acid derivative represented by the above chemical structural formula can be produced by a known synthesis method for salicylic acid derivatives, such as (i) a method by reacting hydroxycumyl salicylic acid or its ester with an alkyl halide derivative; (2) It can be easily produced in high yield, with high purity, and at a relatively low cost, by a method such as direct carboxylation of an alkali metal salt of a cumylphenol derivative under pressure of carbon dioxide gas.

More specifically, in the method (■) above, the following general formula [II
] and the alkyl halide derivative represented by the following general formula [I
By reacting hydroxycumyl salicylic acid or its ester represented by [II] in a polar solvent in the presence of an alkali, a salicylic acid derivative or its ester represented by the following general formula [IV] can be obtained; The desired salicylic acid derivative can be obtained by further hydrolysis.

[In the formula, X is a halogen atom, R' is a hydrogen atom, C1-
4 represents an alkyl group or a benzyl group, and R and n each have the above-mentioned meanings. ] Examples of the polar solvent used in the above reaction include acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl acetamide, dimethyl formamide, dimethyl sulfoxide, acetonitrile, and sulfolane, and examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methylate,
Examples include sodium ethylate, potassium methylate, potassium ethylate, and the like. The reaction temperature is usually 50-1
Performed at 50°C.

In the method (2) above, first, an alkyl halide derivative represented by the following general formula [II] and 4,4'-isopropylidenediphenol are mixed in a polar solvent in the same manner as in (2) above.
The reaction is carried out in the presence of an alkali to obtain a cumylphenol derivative represented by the following general formula [V]. Next, the obtained cumylphenol derivative was made into a sodium salt, and then reacted with carbon dioxide gas under heat and pressure to obtain the general formula [
A salicylic acid derivative represented by [I] can be obtained.

[In the formula, R, X, and n each have the above-mentioned meanings. ] Note that examples of the sodium source in the above reaction include sodium hydroxide, sodium metal, sodium carbonate, sodium methylate, and sodium ethylate.

The reaction may also be carried out in a solvent such as an aliphatic, alicyclic or aromatic hydrocarbon, or an aliphatic or aromatic ether.
Alternatively, it can be carried out without a solvent. The reaction temperature and pressure are generally 50 to 200°C and approximately 1 to 50 kg/cm2.

Further, the zinc salt of the salicylic acid derivative represented by the above general formula [I] can be synthesized by a known method. For example, the alkali metal salt of the corresponding salicylic acid derivative is mixed with zinc sulfate or chloride in water or alcohol. Obtained by salt exchange with zinc etc.

Specific examples of the salicylic acid derivative represented by the above general formula [I] include the following.

5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid, 5-[p-(2-p-ethoxyphenoxyethoxy)cumyl]salicylic acid, 5-[p-(2-p-n-propoxyphenoxy) ethoxy)cumyl]salicylic acid, 5-[p-(2-p-isopropoxyphenoxyethoxy)cumyl]salicylic acid, 5-[p-(2-p-tert-butoxyphenoxyethoxy)cumyl]salicylic acid, 5-[p- (3-p-methoxyphenoxypropoxy)
cumyl] salicylic acid, 5-[p-(3-p-isopropoxyphenoxypropoxy)cumyl]salicylic acid, 5-[p-(4-p-methoxyphenoxybutoxy)cumyl]salicylic acid, 5-[p-(4-p -Ethoxyphenoxyptoxy)cumyl]salicylic acid, 5-[p-(4-p-tert-butoxyphenoxybutoxy)cumyl]salicylic acid, 5-[p-(2-o-methoxyphenoxyethoxy)cumyl]salicylic acid, 5- [p-(2-m-methoxyphenoxyethoxy)cumyl] salicylic acid, 5-[p-(2-o-ethoxyphenoxyethoxy)cumyl] salicylic acid, 5-[p-(2-m-ethoxyphenoxyethoxy)cumyl] ]Salicylic acid, 5-[p-(3-m-methoxyphenoxypropoxy)
cumyl]salicylic acid, 5-[p-(4-m-methoxyphenoxybutoxy)cumyl]salicylic acid, 5-[p-(3-m-isopropoxyphenoxypropoxy)cumyl]salicylic acid, and the like.

"Example" The present invention will be described in more detail with reference to Examples below, but it is of course not limited to these.

Example 1 4-[p-(2
-p-methoxyphenoxyethoxy)cumyl]phenol 75.6 g (0.20 mol), diethylene glycol dimethyl ether 200 g, toluene 30 g, and 5
16.0 g (0.20 mol) of 0% aqueous sodium hydroxide solution was weighed out. The mixture was heated with stirring to remove water azeotropically.

After the dehydration was completed, the contents were transferred into a stainless steel autoclave, filled with carbon dioxide gas to a pressure of 20 kg/cm2, and reacted at 180°C for 3 hours.

After the reaction was completed, the autoclave was cooled, and after the temperature of the contents became 90° C. or less, the pressure was removed and the contents were transferred to a beaker. Boiling water and toluene were added to this, thoroughly stirred, and then allowed to stand, and the oil layer separated into the upper layer was removed. Next, dilute sulfuric acid was added to the remaining aqueous layer to make it acidic, and the precipitated crystals were filtered and dried.

The obtained crystals were recrystallized with ethanol, and the melting point was 145-1.
5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid at 46°C was obtained.

The yield was 85%.

Example 2 In Example 1, 4-[p-(2-p-methoxyphenoxyethoxy)cumyl]phenol was replaced with 4-[p-(2-p-methoxyphenoxyethoxy)cumyl]phenol.
[p-(2-p-isopropoxyphenoxyethoxy)
5-[p-(2-p-isopropoxyphenoxyethoxy)cumyl]salicylic acid was obtained in the same manner as in Example 1 except that cumyl]phenol was used. Melting point is 132-1
At 35°C, the yield was 82%.

Patent applicant Kanzaki Paper Co., Ltd.

Claims (1)

[Scope of Claims] [Claim 1] A salicylic acid derivative represented by the following general formula [I] and its zinc salt. [In the formula, R represents a C1-4 alkyl group, and n is 2-4
indicates an integer. [Claim 2] The salicylic acid derivative and its zinc salt according to claim (1), wherein the derivative is a compound represented by the following general formula [I']. [In the formula, R and n each have the above-mentioned meanings. [Claim 3] In the general formula [I'], n is 2 (
2) Salicylic acid derivatives and zinc salts thereof. Claim 4: The derivative is 5-[p-(2-p-methoxyphenoxyethoxy)cumyl]salicylic acid (
3) Salicylic acid derivatives and zinc salts thereof. 5. The salicylic acid derivative and zinc salt thereof according to claim 3, wherein the derivative is 5-[p-(2-p-isopropoxyphenoxyethoxy)cumyl]salicylic acid.