JPH0676560B2 - Pyrimidine compounds - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pyrimidine compound useful as a dye for use in heat-sensitive and pressure-sensitive recording materials, electric current recording display materials and the like.

2. Description of the Related Art The thermosensitive recording method is a method in which a color former and a developer are evenly dispersed and applied onto a support, and the mixture is heated and melted to develop a color. It is applied to a support as a microcapsule, superposed on a support coated with a color developer, and pressure is applied to break the microcapsule.
The two are brought into contact with each other to develop color. As the color former, leuco dyes such as triphenylmethane-based fluorane-based and phthalide-based dyes are used. Therefore, various properties such as whiteness of the background before coloring, coloring sensitivity, coloring density, light resistance after coloring, water resistance, solvent resistance, etc. are required for the color-developing agent. The above-mentioned dyes which are used as a mainstream with a small amount of agents have a color development accompanied by cleavage of a lactone ring, and no dye showing sufficient properties in water resistance has been found.

In addition, the energization record display method utilizes the property that a certain substance causes a redox reaction when a voltage is applied, and reversibly changes the light transmittance, and as a conventional substance such as an electrochromic substance. Are known to be inorganic transition metal oxides such as tungsten oxide and vanadium iridium hydroxide, and organic materials such as viologen derivatives, tetrathiofulvalene derivatives, fluorane compounds, and rare earth phthalocyanines are known. There is. Since the inorganic material forms the electrochromic layer by using a vacuum deposition technique such as vapor deposition or sputtering, it is not easy to obtain a uniform and flexible metal oxide layer over a wide area. The display color is limited to a specific color such as blue for tungsten oxide and blue black for iridium hydroxide. In addition, although it is possible to select a color tone with an organic substance, it is pointed out that the contrast of the color tone is weak and the response speed is slow, and the durability is insufficient, and these compounds are generally expensive compounds. .

Problems to be Solved by the Invention Water resistance after coloring as a color former for heat-sensitive and pressure-sensitive recording materials,
A dye (precursor) having excellent light resistance is required, and as an electrochromic substance for a current recording display material, an inexpensive dye having a high color value, a high color development response speed and durability is required.

Means for Solving Problems In order to obtain a color former which gives an image excellent in water resistance and light resistance as a heat-sensitive and pressure-sensitive recording material, and a durable electrochromic material having a fast response speed of an electric recording display material. As a result of intensive studies to obtain a substance, the present invention has been accomplished. That is, the present invention relates to formula (I), formula (II) or formula (III) [Wherein R ₁ represents a methyl group or an ethyl group, R ₂ R ₃ represents hydrogen,
Chlorine, methoxy group, ethoxy group, methyl group or (R ₄ and R ₅ are methyl group, ethyl group, cyanoethyl group, β-
A chloroethyl group or an alkoxyalkyl group having 3 to 4 carbon atoms is shown. ), X is chloro, -OY group, -SZ group or Indicates. However, Y represents a methyl group, an ethyl group, an allyl group, a benzyl group or a phenyl group, Z represents a β-hydroxyethyl group or a phenyl group, and W ₁ and W ₂ represent hydrogen, a butyl group, a benzyl group and γ-methoxy group. Propyl group, γ-ethoxypropyl group,-(CH ₂ ) ₅ -,-(CH ₂ ) _{4 in which} W ₁ and W ₂ are linked.
_{-, - C 2 H 4 OC} 2 H 4 - group or represents a phenyl group. Note that W ₁ , W ₂
Are not both hydrogen. ] Relates to a pyrimidine compound.

The inventors have found that pyrimidine compounds are excellent as color formers in heat-sensitive and pressure-sensitive recording methods, and as electrochromic materials in current-recording display.

Thus, the piperidine compound of formula (I) in the present invention is synthesized by the steps shown below.

That is, the pyrimidine compound of the formula (I) is obtained by condensing 7-dialkylamino-2-imino-coumarin-3-carbonamide with the benzaldehyde of the formula (III) in the presence of a catalytic amount of a base and then using an alkali to give a mutual reaction. The pyrimidone compound of the formula (II) synthesized by mutagenesis is used as a starting material. In the formula, R ₁ , R ₂ , R ₃ , Y, Z, W ₁ and W ₂ have the above meanings, and specific examples of the benzaldehydes (III) include benzaldehyde, 4-chlorobenzaldehyde, 4-methoxy- Benzaldehyde, 4-N, N-
Diethylamino-benzaldehyde, 4-N-methyl-
N-cyanoethylbenzaldehyde, 4-N-methyl-
4-N-β-chloroethylamino-2-methyl-benzaldehyde, 4,4-diethyl-2-ethoxy-benzaldehyde, 4-N, N-di (β-methoxyethyl) amino-benzaldehyde and the like can be mentioned.

In the formula (I), when X is chloro, that is, the formula (Ia)
The compound (1) is synthesized by reacting the pyrimidone compound (II) with phosphorus oxychloride at 80 to 120 ° C. in an inert organic solvent such as monochlorobenzene, dichlorobenzene and dimethylformamide.

In the formula (I), when X is —OY, that is, the compound of the group (Ib) is a pyrimidone compound of (II) such as an alkali in alcohol such as N is caustic soda, allyl bromide, benzyl chloride, dimethylsulfate, diethyl in the presence of caustic potash. An alkylating agent such as sulfuric acid or ethyl p-toluenesulfonic acid is allowed to act at the boiling point of the alcohol, or a chloropyrimidine compound (Ia) is added to a high-boiling organic solvent such as dimethylolamide or N-methylpyrrolidone in a carbonic acid. In the presence of potassium, caustic soda, and potassium hydroxide, phenol, bisphenol A, bisphenol S
Are synthesized at 80 to 120 ° C.

In the formula (I), when X is -SZ, that is, the compound of the formula (Ic) is added to the chloropyrimidine compound (Ia) in the presence of β-mercaptoethanol thiophenol and the like in the presence of sodium bicarbonate, soda ash, potassium carbonate and the like. It can be easily synthesized by reacting at 60-80 ° C.

In formula (I), X is In the case of the compound of formula (Id), the presence or absence of baking soda, sodium carbonate, potassium carbonate in the chlorpyrimidine compound (Ia) in a high-boiling organic solvent (for example, methyl cellosolve, ethyl cellosolve, glyme diglyme) It is synthesized by reacting dibutylamine, benzylamine, γ-methoxypropylamine, γ-ethoxypropylamine, pyrrolidine, piperidine, morpholine, aniline and the like at 80 to 130 ° C in the absence of the compound.

The pyrimidine compound of the formula (I) according to the present invention is a colorless or slightly colored compound, which is brought into contact with an acidic developer, that is, an electron acceptor, or an organic solvent containing a supporting electrolyte. When dissolved and energized, it develops red-orange to blue-green color, and is therefore a useful compound as a color former for pressure-sensitive and heat-sensitive recording materials and as an electrochromic substance for energized recording display materials.

The method of use is a known method, for example, in the thermosensitive recording method, the pyrimidine compound of the present invention is used as a color former, and a phenolic substance such as bisphenols is used as a developer.
Acid clay materials such as bentonite and zeolites are separately finely dispersed in an aqueous polyvinyl alcohol solution, mixed, coated on high quality paper and dried to obtain recording paper.
This recording paper is heated to 100 to 140 ° C by a thermal head etc., and when the color developer and the color developer are brought into melt contact with each other, the color is immediately developed, and a recorded image excellent in water resistance as compared with the known fluoran-based or phthalide-based color developing agent is obtained. You can get it.

Further, in the pressure-sensitive recording method, the pyrimidine compound (color former) of the present invention is dissolved in an oil agent such as KMC-113 (Kureha Chemical Co., Ltd., Diisopropylnaphthalene), and this is added to an aqueous solution of gelatin and arabic gum under stirring. After finely dispersing and emulsifying,
Acetic acid is added to adjust the pH to 4 to cause coacervation, and formalin is added to adjust the pH to 9 and the microcapsule film is cured by heating slightly. This is applied evenly to a high-quality paper and dried to give a colored paper. On the other hand, activated clay, acid clay, phenol resin, zinc 3,5-bis (α-methylbenzyl) salicylate, zinc toluenesulfonate, etc. are used as binders such as vinyl acetate, maleic anhydride copolymer (developing agent), etc. Disperse in, apply evenly on high-quality paper, and dry to make color paper. When both are overlaid and pressure is applied from above to break the capsule film and bring the color developer and the color developer into contact with each other, color is developed, and a recorded image with excellent light resistance is obtained as compared with the conventional phthalide-based or fluoran-based color developing agent. You can get it.

Further, the energization recording display method is as follows. First, a pyrimidine compound of the present invention and a supporting electrolyte such as tetrabutylammonium tosylate and sodium dodecylbenzenesulfonate are dissolved in a solvent such as dimethylformamide and acetonitrile dioxane to prepare a solution, which is an energization display device. Enclose in (cell). The cell has a transparent upper electrode and a lower electrode separated by about 0.1 to 0.5 mm via a spacer. Next, when a voltage is applied between both electrodes and electricity is applied, the material is oxidized to develop a color, and the electricity is applied in the opposite direction to erase the color. The pyrimidine-based compound of the present invention is rich in hue and has a characteristic of quick color development response.

EXAMPLES The present invention will be described in more detail by way of examples. In the examples, "part" means "part by weight".

Example 1 8.7 parts of a pyrimidine compound having the following structure (a) was stirred in 80 parts of chlorobenzene at 90 ± 3 ° C., and 5 parts of phosphorus oxychloride was added dropwise at the same temperature over 30 minutes. After stirring for 1 hour, 3 parts of phosphorus oxychloride was added dropwise over 30 minutes, and at 90 ± 5 ° C for 1 hour 10
Stir at 5-110 ° C for 1 hour. After cooling, 600 parts of water is added and chlorobenzene is azeotropically distilled off using steam. After cooling, the precipitated crystals are separated, washed thoroughly with water and dried.

A chloro-pyrimidine compound (II) having the following structure was obtained as pale yellow crystals. (Mp233-236 ℃ (decomposition)) When this compound was used as a color-developing agent in a pressure-sensitive recording method, an orange-red colored image having excellent light resistance was obtained.

Example 2 4.2 parts of a pyrimidine compound having the following structure (c) is dissolved in 50 parts of dimethylformamide, and 3.1 parts of phosphorus oxychloride is added dropwise at room temperature with stirring. It takes 30 minutes and gradually warms up to 80 ℃ 85
Stir for 45 minutes at ± 3 ° C. After cooling, pour into 300 parts of ice water, add caustic soda solution to neutralize until pH = 7, separate and wash with water.
The cake is dissolved in 50 parts of acetone and poured into 400 parts of ice water with stirring. When the precipitate is separated and dried, the following structure (d)
To obtain 4.0 parts of the pyrimidine compound. (Mp160-165
℃) When this compound was used as a color-developing agent in a pressure-sensitive recording method, a blue-green colored image having excellent light resistance was obtained.

Examples 3 to 6 According to Examples 1 and 2, a chlorpyrimidine compound (Ia) was obtained from the following pyrimidone compound (II).

Example 8 1.7 parts of the pyrimidone compound (a) described in Example 1 is added to 0.5 part of caustic potash in 25 parts of ethanol, and the mixture is stirred at 70-80 ° C for 30 minutes. 0.8 parts of allyl bromide is added dropwise at 70 ° C ± 2 ° C and stirred for 2 hours. Further, 0.8 part of allyl bromide is added dropwise and stirred for 3 hours. After cooling, separate the solution with ice water 400
The mixture was poured into 1 part and hydrochloric acid was added to adjust the pH to 3, and 15 parts of common salt was added to salt out. Separate the precipitate, wash with water and dry.

1.3 parts of a pyrimidine compound (e) having the following structure was obtained as an almost colorless powder.

(Mp206-208 (recrystallized from acetone)) When this compound was used as a color former in a pressure-sensitive recording method, a red colored image having excellent light resistance was obtained.

Examples 9 to 12 The following pyrimidine compound (II) was treated with the following alkylating agent in the same manner as in Example 8 to obtain the following pyrimidine compound (Ib).

Example 13 Chlorpyrimidine compound (d) 1.8 described in Example 2
Parts, 0.7 parts of bisphenol A and 0.4 parts of caustic potash are stirred in 20 parts of dimethylformamide at 90 ± 3 ° C. for 1 hour and 30 minutes. After cooling, pour into 300 parts of ice water, add 20 parts of salt and salt out. When separated and washed with water and dried, 2.0 parts of a pyrimidine compound having the following structure (f) was obtained. (Mp140-155 ℃) When this compound was used as a color former in a pressure sensitive recording method, a red colored image having excellent light resistance was obtained.

Examples 14 to 15 The following chloropyrimidine compounds (I-
The following phenols were allowed to act on a) to obtain the following pyrimidine compound (Ib).

Example 16 Chlorpyrimidine compound (ii) 1.9 described in Example 1
Parts, 0.5 parts of mercaptoethanol and 0.5 parts of potassium carbonate are refluxed in 30 parts of ethanol for 1 hour. 5 parts water and caustic soda
Add 0.2 parts and reflux for another 30 minutes. After cooling, the precipitated crystals are separated, washed with a small amount of ethanol and dried.

1.6 parts of a pyrimidine compound having the following structure (g) was obtained. (Mp165-167 ℃) When this compound was used as a color-developing agent in the pressure-sensitive recording method, a red colored image having good light resistance was obtained.

Example 17 Chlorpyrimidine compound (d) 2.1 described in Example 2
Parts, 0.6 parts of thiophenol, 0.5 parts of potassium carbonate, ethanol
Reflux for 1 hour in 20 parts.

After cooling, the precipitated crystals are separated, washed with a small amount of ethanol, and dried to obtain a pyrimidine compound of the following structure (CH) 2.0
Parts were obtained. (Mp162-164 ℃) Example 18 Chlorpyrimidine compound (ii) 1.9 described in Example 1
Part, aniline 1.0 part, methyl cellosolve 15 parts with stirring 110
Heat at ± 5 ° C for 2 hours.

After that, 25 parts of C ₂ H ₅ OH and 10 parts of water are added and cooled. The precipitated crystals were separated, washed with a small amount of ethanol and dried to obtain a pyrimidine compound having the following structure (i). (Mp103-
106 ° C) Examples 19 to 25 The following chlorpyrimidine compound (Ia) was reacted with the following amines in the same manner as in Example 18 to obtain the following pyrimidine compound (Ib).

Application Example 1 25 parts of the compound (ii) described in Example 1 and 25 parts of a 10% aqueous polyvinyl alcohol solution are ground with 50 parts of water in a ball mill for 24 hours to obtain a color developing solution. On the other hand, bisphenol A 30 parts, 10
% Polyvinyl alcohol aqueous solution (30 parts) and water (40 parts) are pulverized in a ball mill for 24 hours to obtain a color developer.

15 parts of the coloring liquid and 85 parts of the developing liquid were mixed and evenly coated on high-quality paper so that the dry weight would increase by 10%, and dried to obtain a thermal paper.

This thermal paper gave a dark orange-red color image when heated by a thermal head. The water resistance of the colored image was excellent.

Application Example 2 3 parts of the compound (chi) described in Example 17 is heated in 110 parts of KMC-113 (Kureha Chemical Co., Ltd., diisopropylnaphthalene), and 20 parts of gelatin which is substantially dissolved and 12 parts of arabic rubber are added to 20 parts of water.
Add 0 parts and heat to dissolve. The above KMC-113 solution was added with vigorous stirring, and the mixture was stirred for another 3 hours to give an emulsion.

To this, add 700 parts of water, adjust the pH to 4 by adding acetic acid to cause coacervation, cool to gel, add 50 parts of 30% formalin solution and then add caustic soda solution to pH. = 9 and heated to 40-50 ° C to harden the capsule film to obtain a coloring solution. The color-developing liquid thus obtained was uniformly applied to high-quality paper so that the weight increase upon drying was 10%, and dried to obtain a color-developing paper. On the other hand, vinyl acetate in 200 parts of water,
25% aqueous solution of sodium salt of maleic anhydride copolymer 50
Then, 20 parts of zinc oxide, 60 parts of kaolin, 10 parts of titanium oxide and 100 parts of zinc orthophenyl salicylate mud (10% dispersion) were added and dispersed, and 10 parts of styrene-butadiene latex was further added. In addition, dispersion was performed to obtain a color developing liquid. The dry weight of this developer is evenly distributed on high-quality paper,
It was applied to about 10% and dried to obtain a colored paper.

When the microcapsules were destroyed by pressure by superimposing them on each other, they immediately developed a blue-green color to give a color-developed image with excellent light resistance.

Application Example 3 2 parts of the compound (e) described in Example 8 and 2 parts of tetrabutylammonium tosylate as a supporting electrolyte were dissolved in 40 parts of DMF, and a part of this was enclosed in an empty cell shown in FIG. I got the device. Sweeping was performed while applying voltage by the potential regulation method shown in FIG. When the lower electrode 6 of the current-carrying display device was grounded and a positive voltage was applied to the upper electrode, a deep red color appeared near +2.0 V and near the upper electrode. When the voltage was swept in the opposite direction, the surface disappeared and became pale yellow near -1.8V.
The coloring and erasing period was about 0.4 seconds.

EFFECTS OF THE INVENTION A pyrimidine-based compound which gives a heat-sensitive and pressure-sensitive recorded image having excellent water resistance and light resistance, and which gives an energization display having a fast response speed was obtained.

[Brief description of drawings]

FIG. 1 shows an example of an electrochromic display device (ECD). FIG. 2 shows an example of a method for applying a voltage to the ECD. In FIGS. 1 and 2, 1 ... Transparent upper substrate 2 ... Transparent upper electrode 3 ... Solution containing EC substance and supporting electrolyte 4 ... Spacer 5 ... Porous white plate 6 ... Lower electrode 7 ... … Electricity indicator 8 …… Potentiometer 9 …… Cyclic wave oscillator

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B41M 5/30 C09B 11/02 7306-4H

Claims (1)

[Claims] 1. A formula (I), a formula (II) or a formula (III) [Wherein R ₁ is a methyl group or an ethyl group, R ₂ and R ₃ are hydrogen, chloro, methoxy group, ethoxy group, methyl group or (R ₄ and R ₅ are methyl group, ethyl group, cyanoethyl group, β-
A chloroethyl group or an alkoxyalkyl group having 3 to 4 carbon atoms is shown. ), X is chloro, -OY group, -SZ group or Indicates. However, Y represents a methyl group, an ethyl group, an allyl group, a benzyl group or a phenyl group, Z represents a β-hydroxyethyl group or a phenyl group, and W ₁ and W ₂ represent hydrogen, a butyl group, a benzyl group and γ-methoxy group. Propyl group, γ-ethoxypropyl group,-(CH ₂ ) ₅ -,-(CH ₂ ) _{4 in which} W ₁ and W ₂ are linked.
_{-, - C 2 H 4 OC} 2 H 4 - group or represents a phenyl group. Note that W ₁ , W ₂
Are not both hydrogen. ] A pyrimidine compound represented by: