JPH09323965A - New phenylacetic acid derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a developer capable of making reversible color development of heat-sensitive coloring matter. SOLUTION: This new compound is shown by formula I (R is a 12-20C straight-chain or branched saturated or unsaturated alkyl), e.g. 4-(4'- octadecyloxybenzoylamino)phenylacetic acid. The compound of formula I is obtained by reaction of a 4-alkoxybenzoic acid halide of formula II (X is a halogen) with a 4-aminophenylacetic acid or its alkyl ester of formula III (R' is H or a lower alkyl) to form the objective 4-(4'-alkyloxybenzoylamino) phenylacetic acid or its alkyl ester (in the case of the latter, the ester is then hydrolyzed). Since the color developed by this compound as a developer vanishes extremely rapidly on heating, repetition of reversible color development and color fading clan be made using this new compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phenylacetic acid derivative.

[0002]

The present invention is a novel compound and the applicant is unaware of the existence of its prior art.

[0003]

An object of the present invention is to provide a new compound. This novel compound is useful as a developer capable of reversibly developing a color of a thermosensitive dye.

[0004]

According to the present invention, there is provided the following general formula [1]:

Embedded image (In the formula, R has 12 to 20 carbon atoms, preferably 14 to 18 carbon atoms.
Is a linear or branched, saturated or unsaturated alkyl group).

The compound of the present invention is obtained, for example, by reacting a halide of 4-alkoxybenzoic acid represented by the following general formula [2] with 4-aminophenylacetic acid represented by the following general formula [3] or its alkyl ester. By doing so, 4- (4′-alkyloxybenzoylamino) phenylacetic acid represented by the following general formula [4] or an alkyl ester thereof is obtained. In the case of the alkyl ester, it is then hydrolyzed. The compound of the present invention can be obtained.

[0006]

Embedded image (In the formula, R is the same as above, R'is a hydrogen atom or a lower alkyl group, generally an alkyl group having 2 to 5 carbon atoms, X is a halogen, and M is an alkali metal salt.)

As R, dodecyl, tridecyl,
Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 2-dodecenyl, 2-tridecenyl, 2-tetradecenyl, 2
-Pentadecenyl, 2-hexadecenyl, 2-heptadecenyl, 2-octadecenyl, 2-methylpentadecyl, 2-methylhexadecyl, 2-methylheptadecyl, 2-ethylpentadecyl, 2-ethylhexadecyl, 2-ethylheptadecyl , 2-methyloctadecyl, 2-methylnonadecyl, and the like. Examples of the lower alkyl group of R'include methyl, ethyl, propyl, butyl and the like.

The compound of the present invention is useful as a developer for various electron-donating heat-sensitive dyes (so-called leuco dyes), and the color developed by the developer of the present invention is erased very quickly by heating. Since it has the characteristic of coloring, the color-forming composition containing the color developer and the thermosensitive dye of the present invention exhibits reversibility in which coloring and decoloring are repeated by heating and cooling, as shown in FIG.

In order to develop the color of the color-forming composition, the color-developed state can be maintained by, for example, heating to a temperature condition where the color is developed by a thermal head and then rapidly cooling. In order to decolorize this, there is a method of heating it once and then slowly cooling it, and a method of holding it at a temperature slightly lower than the coloring condition, whereby either one of the dye or the developer is crystallized. It is considered that the color is erased by the formation of the two or by the phase separation between the two.

The color developer of the present invention is used in a proportion of 1 mol or more, preferably 1.5 mol or more, relative to 1 mol of the color-developing agent, but generally about 5 to 10 times by mol is preferable.

The heat-sensitive dye to which the developer of the present invention can be applied is not particularly limited as long as it is a heat-sensitive dye. For example, JP-A-51-121035, JP-A-51-21037, JP-A-51-21038, 55-115448, 5
No. 5-115449, No. 55-115450, No. 55
-115451, 55-115452, 55-
No. 115456, No. 57-167979, No. 58-1
No. 57779, No. 60-8364, No. 60-2758
No. 9, phthalide dyes described in each publication; thiofluorane dyes described in JP-A-59-148695; JP-A-59-199757; EP-A-124377; -371
No. 58, No. 63-109086, No. 63-14536
No. 6, fluorene dyes, triarylmethane dyes, diphenylmethane dyes, thiazine dyes, spiro dyes, and the like.

Specific dye names include the following. That is, as the fluorene-based dye, 2-dibenzylamino-6-diethylaminofluoran, 2-anilino-6-diethylaminofluoran,
2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-cyclohexylmethylaminofluoran, 2-o-chloroanilino-6
-Diethylaminofluoran, 2-m-chloroanilino-6-diethylaminofluoran, 2- (3,4-dichloroanilino) -6-diethylaminofluoran, 2-
Octylamino-6-diethylaminofluorane, 2-
Dihexylamino-6-diethylaminofluoran, 2
-M-trifluoromethylanilino-6-diethylaminofluoran, 2-butylamino-3-chloro-6-diethylaminofluoran, 2-ethoxyethylamino-3
-Chloro-6-diethylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, 2-
Diphenylamino-6-diethylaminofluoran, 2
-Anilino-3-methyl-6-diphenylaminofluoran, 2-phenyl-6-diethylaminofluoran,
3- (4'-phenylaminophenylamino) -6-methyl-7-chlorofluoran, 3- (4'-phenylaminophenylamino) -7-methylfluoran, 3-
[4 '-(4 "-methoxyphenylamino) phenylamino] -5,6-benzofluoran, 3- [4'-
(4 "-methoxyphenylamino) phenylamino]-
6-chlorofluorane, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -6-methyl-7-chlorofluoran, 3- [4'-(4" -phenylaminophenylamino) Phenylamino] -7-methylfluoran, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -6-benzylfluoran, 3- [4'-(4" -phenylaminophenylamino) Phenylamino] -7-cycloalkylfluoran, 3- [4 ′-(4 ″ -phenylaminophenylamino) phenylamino] -7-chlorofluoran, 3-
[4 '-(4 "-phenylaminophenylamino) phenylamino] -6-chlorofluoran, 3- [4'-
(4 "-phenylaminophenylamino) phenylamino] -5,7-dichlorofluoran, 3- [4'-
(4 "-phenylaminophenylamino) phenylamino] -7-sec-octylfluoran, 3- [4'-
(4 "-phenylaminophenylamino) phenylamino] -7-phenylfluoran, 3- [4 '-(4"-
Phenylaminophenylamino) phenylamino]-
6,7-dimethylfluoran, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -5
6-benzofluoran, 3- [4 '-(4 "-phenylaminophenylamino) phenylamino] -7,8-benzofluoran, 3- [4'-(4" -phenylaminophenylamino) -2 '-Methylphenylamino] -6
-Methyl-7-chlorofluoran, 3- [4 '-(4 "
-Phenylaminophenylamino) phenylamino]-
7-methoxyfluoran, 3- [4 '-(4 "-phenylamino-3" -methoxy-6 "-methylphenylamino) phenylamino] -7-chlorofluoran, 3-
[4 '-(4 "-phenylamino-3" -methylphenylamino) -2'-methylphenylamino] -6-methyl-7-chlorofluoran, 3- [4'-(4 "-phenylaminophenyl Amino) -2 ', 6'-dichlorophenylamino) -7-methylfluoran, 2-methyl-
6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2,3-dimethyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 3-
Methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-chloro-3-methyl-6
p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2,3-dimethyl-6-p- (p-phenyl Aminophenyl) aminoanilinofluoran, 3-methyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-chloro-3-methyl-6-p- (p-phenylaminophenyl) amino Anilinofluoran and the like, as triarylmethane compounds, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet lactone), 3,3-bis (p-
Dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,3-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole- 3-yl) phthalide and the like, as diphenylmethane compounds,
4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N
-2,4,5-trichlorophenyl leuco auramine and the like; thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzyl leucomethylene blue; spiro compounds such as 3-methyl-spiro-dinaphthopyran and 3- Ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran,
3-benzylspiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like.

[0013]

The present invention will be described below with reference to examples.
The present invention is not limited to this.

Example 1 Synthesis of the following formula 4- (4'-octadecyloxybenzoylamino) phenylacetic acid

Embedded image 1.72 g (4.
(4 mmol) 4-octadecyloxybenzoic acid and 1.0 ml of dimethylformamide are added, and the mixture is stirred at room temperature. 0.35 ml of thionyl chloride was added to 4.0 m
A solution of 1-l, 2-dichloroethane dissolved therein was added dropwise over 5 minutes, and the mixture was heated under reflux for 1 hour. After leaving overnight,
Recovery of the solvent leaves 4-octadecyloxybenzoyl chloride. 30 ml of 1,2 to this residue
-Add dichloroethane and stir with heating. When the residue has dissolved, heating is discontinued, 0.79 g (4.4 mmol) of ethyl 4-aminophenylacetate are added and 0.81 ml of triethylamine is added to 5 ml of 1 ml with vigorous stirring.
The solution diluted with 2-dichloroethane is added dropwise over 15 minutes. The reaction liquid becomes an emulsion at first, but gradually becomes a transparent liquid and becomes an emulsion again as the reaction progresses. After completion of the dropping, the mixture is heated and refluxed for 1 hour. When 30 ml of ethanol is added to the residue obtained after recovering the solvent and heated, a transparent liquid is obtained. After cooling, the precipitated crude ethyl 4- (4'-octadecyloxybenzoylamino) phenylacetate was collected by filtration,
Wash with ethanol, water and ethanol again. 1.
76 g (yield 72%). Recrystallization from ethanol gives short needle crystals with a melting point of 111.5-113.5 ° C. 1.
11 g (2.0 mmol) of the above ester is added to 40 ml of ethanol and heated to reflux. Once the ester has dissolved, a solution of 0.113 g potassium hydroxide in 5 ml 20% ethanol is added dropwise over 30 minutes with stirring. Immediately, the potassium salt precipitates. After completion of dropping, the mixture is heated under reflux with stirring for 1 hour. After cooling, the precipitated potassium salt is collected by filtration and washed with ethanol, water and then ethanol. The potassium salt is added to 25 ml of acetic acid, and the mixture is heated and stirred. When the potassium salt is dissolved, heating is stopped and the mixture is allowed to cool. The precipitated 4- (4'-octadecyloxybenzoylamino) phenylacetic acid is collected by filtration and washed with water. 80ml
Recrystallized from ethanol, mp 162.5-16
Fine crystals of 4.5 ° C. are obtained. 0.90 g (yield
86%)

Mass spectrum M / Z 523 (M ⁺ , 7%), 478 (4), 375
(3), 374 (25), 373 (88), 151
(5), 139 (21), 138 (29), 123
(3), 122 (8), 121 (100), 120
(4), 111 (4), 106 (6), 104 (3). IR spectrum (cm ⁻¹ ) 3343, 3046, 2954, 2918,
2850, 1718, 1688, 1645, 1607,
1579, 1532, 1517, 1472, 1418,
1306, 1257, 1171, 1037, 1021,
939, 845, 813, 771, 761, 719, 6
49.

Example 2 The thermosensitive dye 3-diethylamino-6-methyl-7-chlorofluorane obtained in Example 1 with respect to 2 parts by weight of 4-
A thermosensitive recording liquid having a thickness of 8 parts by weight of (4'-octadecyloxybenzoylamino) phenylacetic acid, 12 parts by weight of vinyl chloride-vinyl acetate copolymer, 45 parts by weight of methyl ethyl ketone, and 43 parts by weight of toluene was prepared.
Wire coating was performed on a PET film of μm to obtain a reversible thermosensitive recording medium having a thickness of 8 μm. This product develops red color with a thermal head and disappears when slowly cooled,
When cooled rapidly, it remained red. Even if the heating and slow cooling were repeated 10 times, there was no change in the color-decolored state.
The color developer of the present invention had a much faster decoloring rate than the conventionally known color developer composed of bis (hydroxyphenyl) acetic acid.

The embodiments of the present invention will be listed below. 1. The following general formula [1]

Embedded image (In the formula, R represents a straight-chain or branched, saturated or unsaturated alkyl group having 12 to 20 carbon atoms). 2. The following general formula [1]

[Chemical 6] (In the formula, R has 12 to 20 carbon atoms, preferably 14 to 18 carbon atoms.
A straight-chain or branched, saturated or unsaturated alkyl group), which is a phenylacetic acid derivative. 3. The following general formula [2]

[Chemical 7] (Wherein R is a straight-chain or branched, saturated or unsaturated alkyl group having 12 to 20 carbon atoms, and X is halogen), and a halide of 4-alkoxybenzoic acid represented by the following general formula [3]

Embedded image (In the formula, R'is a hydrogen atom or a lower alkyl group)
By reacting with 4-aminophenylacetic acid or an alkyl ester thereof represented by the following general formula [4]

Embedded image (In the formula, R and R ′ are the same as above), 4- (4′-alkyloxybenzoylamino) phenylacetic acid or its alkyl ester is obtained, and when R ′ is an alkyl group, this is The following general formula [1] can be obtained by hydrolysis.

Embedded image A method for producing a phenylacetic acid derivative represented by the formula (wherein R is the same as above).

[0018]

[Effect] According to the present invention, a novel phenylacetic acid derivative can be provided. INDUSTRIAL APPLICABILITY The compound of the present invention is useful as a developer for a thermosensitive dye, and a thermosensitive coloring composition using the same can reversibly repeat coloring and decoloring.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a process of reversible color development-erasing.

Claims (1)

[Claims] [Claim 1] The following general formula [1] (In the formula, R represents a straight-chain or branched, saturated or unsaturated alkyl group having 12 to 20 carbon atoms).