JPH02145563A - Phenol compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is phenyl, benzyl or naphthyl which may have alkyl, cycloalkyl, aryl, alkenyl, alkoxy, acyl, halogen, OH, etc., as a substitutent). EXAMPLE:1-(4-Hydroxyphenylthio)-3-phenoxy-2-propanol. USE:A material for heat-sensitive recording paper or an antibacterial agent. PREPARATION:The compound of formula I is produced by reacting a compound of formula II with a compound of formula III in an aprotic solvent (e.g. benzene compound, ether, halogen-containing compound or ester) preferably in the presence of a basic catalyst or in the absence of catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel phenol compound having a thioether bond, and more specifically to thermal paper materials,
This invention relates to novel phenolic compounds useful as antibacterial agents.

[Prior art and its sections Ml Recently, in the field of information recording, various recording methods have been researched, developed, and put into practical use. Among them, heat-sensitive or pressure-sensitive recording materials require complicated processes such as development and fixing. It has the advantages of being able to record in a short time with a relatively simple device without any processing, does not generate noise, and is relatively inexpensive, and is used for computer output, printers such as calculators, and medical measurement. It is widely used in recorders, facsimiles, automatic ticket vending machines, labels, copying machines, etc.

The basic principle of these recording methods is that the dye changes into a colored substance through chemical contact between an electron-donating colorless dye and an electron-accepting compound. A colored image can be obtained by heating with a thermal pen, laser light, etc., or by pressing with a pencil, etc.

As the above-mentioned electron-accepting compound (generally called a color developer), various compounds having a phenolic 01-1 group have been proposed (for example, Japanese Patent Publication No. 40-9309, Japanese Patent Publication No. 43-4160, Japanese Patent Publication No. 45-14039, Japanese Patent Publication No. 5129830, Japanese Patent Publication No. 56-14
Publication No. 4193, etc.). Usually bisphenol compounds and 4
-Hydroxybenzoic acid esters and the like are in practical use.

Desirable properties of these color developers include: (1) Reacts with the 71i child-donating colorless dye to give a high-density colored image.

(2) The color image is stable, and there is little fading due to aging, moisture, light, oil, etc.

(3) Low water solubility.

(4) No sublimability.

(5) It is easy to manufacture industrially and can be obtained at a high yield and purity at a relatively low cost.

However, with the conventional materials mentioned above, for example, thermal responsiveness is low, and sufficient color density cannot be obtained during high-speed recording, or the density of the color image decreases over time after recording. However, there were problems such as surface precipitation of a white powdery substance called so-called powder blowing.

As a method of compensating for such defects, there is a method using a sensitizer or a stabilizer.
Although these methods are disclosed in Japanese Patent Publication No. 036, Japanese Patent Application Laid-open No. 53-39139, etc., the effect of improving performance is insufficient, the color image disappears due to sebum, etc., the color density decreases, etc. This results in secondary problems.

[Objective of the Invention] The object of the present invention is to solve the above-mentioned problems, and to provide a method which, when used in combination with an electron-donating colorless dye, has high color development sensitivity, and provides a color image with high environmental resistance after color development. The object of the present invention is to provide a compound from which a recording material with sufficient stability can be obtained.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventors found that heat-sensitive Alternatively, it has been discovered that a recording material suitable as a pressure-sensitive recording material, particularly a heat-sensitive recording material, can be obtained, and the present invention has been achieved.

That is, the present invention provides optionally substituted alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, acyloxy group, a halogen atom, or a hydroxyl group, and n represents an integer of 0 to 3. ] The present invention provides a phenol compound represented by the following.

Specific examples of compounds represented by formula (1) are shown below.
However, the present invention is not limited to these. hydroxyphenoquine) ~2-propatur, I-(4-hydroquinphenylthio)-3
-(3-hydroxyphenoxy)-2-propatol,
1-(4-Hydroquinophenylthio)-3-(2-hydroxyphenoquine)2-propatool, 1-(4-hydroxyphenylthio)-3-(3,4-dihydroxyphenoquine)2-propatool Tool, 1-(4-hydroquinphenylthio)-1-(2,4-dihydroquinphenoxy)-2-propatool, I-(4-hydroxyphenylthio)-3-(4-methoxyphenoxy)-2 [J panol, I-(4-hydroxyphenylthio)-3-(
3-methoxyphenoxy)-2-propertool, 1-(
4-hydroxyphenylthio)3-(3,4-dimethoxyphenoxy)-2-probanol, 1(4-hydroxyphenylthio)-3-(3,5-dimethoxyphenoxy)-2-propanol, 1-( 4-hydroxyphenylthio)3-(2,3-dimethoxyphenoxy)-2-
Propatool, I-(4-hydroxyphenylthio)3
-(4-ethoxyphenoxy)-2-propertool,!
-(4-hydroxyphenylthio)-3(3-n-butoxyphenoxy)-2-propatur, 1-(4-hydroxyphenylthio)-3-(4acetylphenoxy)
-2-propatur, 1(4-hydroxyphenylthio)-3-(3-propionylphenoxy)-2-propatur, 1(4-hydroxyphenylthio)-3-(4
-benzoylphenoxy)-2~propertool, 1-(
4-hydroxyphenylthio)-3-(4-acetoxyphenoxy)-2-propatur, 1-(4-hydroxyphenylthio)-3-(3-propionyloxyphenoxy)-2-propatur, 1-(4 -hydroxyphenylthio)-3-(4-chlorophenoxy)-2-propatur, '1-(4-hydroxyphenylthio)-3
-(3-chlorophenoxy)-2-propertool, 1-
(4-hydroxyphenylthio)-3-(2-chlorophenoxy)-2-propatur, I-(4-hydroquinophenylthio)-3-(2,3-dichlorophenoxy)
-2-propatur, 1-(4-hydroxyphenylthio)-1-(2,4-dichlorophenoxy)-2-propatur, 1-(4-hydroxyphenylthio)3-(
2,5-dichlorophenoxy)-2-7' lovanol,
1-(4-hydroxyphenylthio)-3-(2,6-
dichlorophenoxy)-2-propatur, I-(4-
Hydroxyphenylthio)-3-(3,4-dichlorophenoxy)-2-propatur, I-(4-hydroxyphenylthio)-3(3,5-dichlorophenoxy)-
2-propatol, 1-(4-hydroquinphenylthio)-3-(4bromophenoxy)-2-propatol,
I-(4-hydroxyphenylthio')-3-(3-bromophenoxy)-2-propatur, 1-(4-hydroxyphenylthio)-3-(2-bromophenoxy)2
-Propatur, I-(4-hydroquinphenylthio)
-3-(2,4-dibromophenoxy)2-propatur, 1-(4-hydroxyphenylthio)-3-(3,
5-dibromophenoxy)-2propertool, I-(4
-hydroxyphenylthio)-3-(2,3,4-trichlorophenoxy)2-propanol, 1-(4-hydroxyphenylthio)-3-(2,3,5-)dichlorophenoxy)-2-propanol Tool, I-(4-hydroxyphenylthio)-3-(2,3,6-trichlorophenoxy)-2-propatool, 1-(4-hydroxyphenylthio)-3-(2,4,6-trichloro phenoxy)-2-propatur, I-(4-hydroxyphenylthio)-3-(2,4,6-tribromophenoxy)
-2-propatur, I-(4-hydroxyphenylthio)-3-(4-methylphenoxy)-2propatur, 1-(4-hydroxyphenylthio)-3-(3-methylphenoxy)-2- Propatur, 1-(4-hydroxyphenylthio)-3-(2-methylphenoxy)
-2-propatur, 1-(4-hydroquinphenylthio')-3-(3,4 dimedylphenoxy)-2-propatur, ■(4-hydroxyphenylthio)-3-(
2,4-methylphenoxy)-2-propertool, 1-
(4-hydroxyphenylthio)-3-(4-t-butylphenoquine)-2-propatur, 1-(4-hydroxyphenylthio)-3-(4-phenoxyphenoxy)
-2-propatur, 1-(4-hydroxyphenylthio)-3-(3-phenoxyphenoxy)-2-propatur, 1-(4-hydroxyphenylthio)-3-(
4-phenylphenoxy)-2 propatool, 1-(4
-hydroxyphenylthio)-3-(3-phenylphenoxy)-2-propatur, 1(4-hydroxyphenylthio)3-(2-methoxycarbonylphenoxy)
-2propatur, I-(4-hydroxyphenylthio)-3-(4-ethoxycarbonylphenoquine)2-propatur, 1-(4-hydroxyphenylthio)-3
-(3,4-dimethoxycarbonylphenoxy)-2-
propatool, 1-(4-hydroxyphenylthio)-
3-benzyloxy-2propatur, 1-(4-hydroxyphenylthio)-3-(p-chlorobenoloxy)-2-propatur,! -(4-hydroxyphenylthio)3-(2-naphthyloquino)-2-propatol, -(4-hydroxyphenylthio)-3-(+naphthylokino)-2-propatol, and the like.

In addition to being used as the electron-accepting compound of the present invention as a color developer for heat-sensitive recording materials, this novel compound (1) was confirmed to have physiological activities such as antibacterial activity.

The phenol compound of the present invention can be easily and almost quantitatively synthesized by the following reaction.

This reaction proceeds with good yield in any organic solvent, regardless of whether it is protic or aprotic, but it is particularly preferable to use aprotic solvents such as Hensen's, ether, halogen, and ester. or proceed. In this reaction, only the diol part reacts with a selectivity of almost 100%,
And only the carbons on the outside of the epoxy ring from the gludinol side react. In order to promote the reaction, an acid catalyst (eg, sulfonic acid, hydrochloric acid, etc.), a basic catalyst (eg, pyridine, sodium hydroxide, etc.), or a metal salt may be used. When considering the selectivity of the reaction, a basic catalyst or no catalyst is preferred.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

All parts and percentages shown in the examples are by weight.

Synthesis Examples 1 to 13 [Synthesis of 1-(4-hydroxyphenylthio)-2-7' lovanols] A solution of 0.05 mol of 4-hydroxythiophenol in toluene (50d) was stirred at room temperature in a nitrogen atmosphere. A solution of 0.0525 mol of various grindyl ether compounds in toluene (10 mR) was added dropwise over 5 minutes. After stirring at room temperature for 1 hour, the mixture was heated and refluxed for 6.5 hours, and then allowed to cool to room temperature. The precipitated crystals were collected by filtration and washed with toluene/hexane to obtain a product. The properties of the obtained product are shown in Table 1, and the NMR data are shown in Table 2.

Application example! [Liquid A] 10 parts of 3-N-methyl-N-cyclo to quinylamino-6-methyl 7-anilic fluorane 10% polyvinyl alcohol 20 parts aqueous solution - [Liquid 13] Synthesis example! Compound obtained in: 10 parts Calcium carbonate 10 parts 10% polyvinyl alcohol 10 parts Aqueous solution A and B were each separately atomized with a sand mill until the average particle size was 3μ or less, and then 1 part of A and B were A coating solution was prepared by mixing three parts. This coating] Two parts tsubo fi15
Coated on commercially available high-quality paper of 0g/cm' (coating: solid content 6g
/m')L. After drying, smoothing treatment was performed using a super calender to obtain a heat-sensitive recording material.

Application example 2 As an electron-accepting compound, 1-(4
A heat-sensitive recording material was obtained in the same manner as in Application Example I except that -hydroxyphenylthio)-3-(4-tbutylphenoxy)-2-propanol was used.

Application examples 3 to 6 Application examples 1 except for using the electron-accepting compounds shown in Table 3
A heat-sensitive recording material was obtained in the same manner as above.

Rusekshi! - A heat-sensitive recording material was obtained in the same manner as in Application Example 1, except that benzene 4-hydroxybenzoate was used instead of the 2-propatol compound.

Taste [Liquid C] Bisphenol A 10 parts 10% polyvinyl alcohol 20 parts Aqueous solution [Liquid D] Stearamide 10 parts Calcium carbonate 10 parts 1O% polyvinyl alcohol
The 10-part aqueous solutions C and D were separately atomized using a sand mill until the average particle size was 3 μ or less, and then Application Example 11? A coating liquid was prepared by mixing 1 part of liquid A, 3 parts of liquid C, and 5 parts of liquid D. Using this coating liquid, a heat-sensitive recording material was obtained in the same manner as in Application Example 1.

Comparative Example 3 A heat-sensitive recording material was obtained in the same manner as in Comparative Example 2, except that p-benzylbiphenyl was used instead of stearamide.

The heat-sensitive recording materials obtained on each side above were evaluated for color development sensitivity and color image stability in the following manner. The results are shown in Table 4.

(Evaluation method) ■Color development sensitivity Using a dynamic color development test device manufactured by Daikane Electric Co., Ltd., color was developed at a printing energy of 0.45 mJ/dot, and the color density was measured using a Macbeth rLD~918 type densitometer (manufactured by Macbeth Co., Ltd.). ) was measured.

■ Colored image stability ■ The colored sample prepared in
After using the device for one month in H), the color density was measured again, and the retention rate of the density was calculated.

Table-4 Comparative example! =Benzyl 4-hydroxybenzoate Comparative Example 2;
Bisphenol A Comparative Example 3: Bisphenol A As is clear from the table, the heat-sensitive recording material of the present invention has 0
．． Despite the low printing energy of 45 mJ/dot, it showed very excellent color development sensitivity, and the stability of the color image was also significantly superior to that of the comparative example.

Application Example 7 Table 5 shows the evaluation results of the compounds shown in Application Example as antibacterial agents.

1. Test method: Agar plate diffusion method (disk method) Prepare a 5% ethanol solution of the test substance, and add 40 μg of each to a disk (thick paper disk, diameter 8 flm).
After drying with ethanol, place on an SCD agar medium coated with 0.1 ml of bacterial cell suspension (10'/ml), and culture at 30°C for 2 days. The inhibition zone (inhibition zone of the transparent part that occurs around the area) was determined. The higher this value, the greater the antibacterial effect.

■, Test strain Gram-positive bacteria 1, 5 taphylococcus aureus
Staphylococcus aureus 2, St, epiderIIlid
is one of the resident bacteria on the skin ■, the phenol compound of the test subject Thimble invention 4 points Control compound 1, TCC (trichlorocarboanilide) 2, MP (
Methylparaben) Table 5 As described above, the phenol compound of the present invention exhibited antibacterial activity superior to commercially available antibacterial agents such as TCC and Ml).

[Effects of the Invention] The phenol compound of the present invention exhibited excellent color development sensitivity and stability of color images, which are desirable as heat-sensitive recording materials.

It can also be applied as an antibacterial agent.

Claims (1)

[Claims] 1. Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is shown. However, Z is an optionally substituted alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, It represents an acyloxy group, a halogen atom, or a hydroxyl group, and n represents an integer of 0 to 3. ] A phenolic compound represented by.