JPS5993754A - Chromogen bis-quinazoline compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to chromogenic bis-quinazoline compounds, processes for their preparation and their use as color formers in pressure- or heat-sensitive recording materials.

The novel suquinaprine compound according to the present invention is represented by the following general formula (1).

In the formula, Q means a direct bond, an aliphatic or cycloaliphatic hydrocarbon group having at most 8 carbon atoms, -CO-, -S- or -502-, and Y is a couplingable means a residue of a compound, and iA and BXD are each independently unsubstituted or cyano, nitro, halokene, lower alkyl, phenyl, benzyl,
Substituted by lower alkoxy or lower alkoxycarbonyl.

Lower alkyl and lower alkoxy in the definition of the substituents of the above bis-quinazoline compound usually mean a group or group component having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and the lower alkyl group is, for example, methyl, ethyl, n
The lower alkoxy group is, for example, methoxy, ethoxy, isopropoxy or tert-butoxy.

Q is located at a para position with respect to the pixel atom.

When Q is an aliphatic hydrocarbon, it preferably means an alkylene group or an alkylidene group. In this case, the radicals contain up to 8 carbon atoms and may be straight-chain or branched. Preferably, the alkylene group has 1 to 41111 carbon atoms. For example -CH2-.

-CH2CH□-1-CI(2CH2CH2-, -CH
It is a group such as 2-CH-CH2-1CH3 -CH2CH2CH2CH2-. The alkyritene groups are ethylidene, pyropylidene, isopropylidene, butylidene, and 5ec-butylidene. When Q is a cycloaliphatic group, a large hydroxide group, it is a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group or especially a cyclohexylidene group. The cycloaliphatic group may have one or more methyl groups.

Preferably Q means an aliphatic or cycloaliphatic group, in particular methylene or an alkyritene group having at most 41 secondary carbon atoms, isopropylidene, butylidene or cyclohexylidene.

Examples of the couplingable group represented by Y include the following.

optionally N-monosubstituted or N,N-disubstituted aniline or naphthylamine, N to unsubstituted or N
-Substituted indole, indo-line, carbazole, tetrahydrocarbazole, dihydro I+- or tetrahydro-quinoline, shihensylamito, benzmorpholine or phenylvirazoline, many U:N
, N-substituted aniline or N-substituted tetrahydroquinoline.

The mono- or polynuclear carbonaceous or heterocyclic couplingable compounds may also be mono- or polycyclicly substituted. In this case, C-substitutions other than those include, for example, halokene, hydroxyl, cyanide, nitro, lower alkyl, lower alkoxy, lower alkoxycarbonyl, acyl having a total of 8 carbon atoms, lower alkyl, etc. Carbonyl, alkylene, cycloalkyl, hensyl or phenyl are considered, with non-N-substituted and U7 preferably c
, Cl2-alky, C3Cl2-alkenyl or hensyl are contemplated, the latter group also being substituted by, for example, cyano, halokene, nitro, lower alkyl, lower alkoxy or lower alkoxy sulfonyl.

The alkyl group and the alkylnon group may be linear or branched. Examples include methyl, ethyl, D-
Propyl, isopropyl, n-butyl, t-butyl, 5
ec-butyl, amyl, isoamyl, n-hexinosu
2-ethylhexyl, inoctyl, n-octyl, decyl or n-dodecyl and allyl, 2-methylallyl, 2-ethylallyl, 2-butenyl or octenyl.

Paacyl is especially formyl, lower alkylcarbonyl such as acetyl or propionyl or benzoyl. Other acyl groups are further exemplified by lower alkylsulfonyl such as methylsulfonyl or ethylsulfonyl and phenyl. It may be substituted with halokene, methyl, methoxy or ethoxy.

Preferably, rings A and BXD are not further substituted.

If "further substituted", the substituent is in particular halokene, lower alkyl or lower alkoxy, and may be further substituted, for example by chlorine, methyl, impropyl, t-butyl or methoxy. Preferably each 1 or 21161 substituents may be present on each benzene ring. As possible substituents for the benzene rings B and D, methyl and t-butyl and phenyl or pencil are considered.

A preferable chromogenic histoquinasoline compound within the scope of the present invention is represented by the following formula (2).

In the formula, A, BXD and Q have the above-described meanings, and C YI is a 1-minophenyl group of the above formula or a hydrogenated heterocyclic group of the following formula (in the above formula, Xl and alkyl, cycloalkyl, phenyl, pencil or halogen, nitro, cyano, lower alkyl, lower alkoxy or (substituted by lower alkoxycarbonyl) or
i and X2 together with the nitrogen atom to which they are bonded form a 5- or 6-membered, preferably saturated heterocyclic group; means lower alkoxycarbonyl, Z means alkyl, cycloalkyl or hensyl having at most 8 carbon atoms substituted with hydrogen or unsubstituted or substituted with halokene, cyano or lower alkoxy; and ring E may be substituted, substituted, or substituted with 16 by cyano, halokene, lower alkyl such as methyl or lower alkoxy such as methoxy, and ring G may be hydrogenated and 5-membered. is a 6-membered complex term, which ring optionally has further heteroatoms such as oxygen, sulfur or nitrogen as ring members and is unsubstituted or halokene, cyanide, hydroxy. , lower alkyl, lower alkoxy, "5-06-cycloalkyl", "pencil" or "C5-06-alkylene" means C5-06-alkylene which may be mono- or multiple, especially double, C-substituted depending on the type of substituents.

When Xl and X2 represent an alkyl group, it may be linear or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 5ec-
Butyl, amyl, isoamyl, n-hexyl, 2-ethylhexyl, n~octyl9, isooctyl or n-
It's Dodecyl.

If the alkyl radicals Xl and X2 are substituted, the 1d-substituted alkyl radicals are in particular cyanoalkyl, haloalkyl, hydroxyalkyl or alkoxyalkyl having preferably 2 to 4 carbon atoms in total. Examples thereof include β-cyanoethyl, β-chloroethyl, -β-hydroxyethyl, β-methoxyethyl, and β-ethoxyethyl.

The cycloalkyl group represented by Xl and X2 is cyclopentyl or cyclohexyl.

When Xl and X2 mean substituted benzyl or phenyl groups, preferred substituents are, for example, halogen, cyano, methyl, methoxy or carbomethoxy. Examples of such araliphatic and aromatic groups include methylhensyl, chlorpencyl, cyanophenyl, tolyl, xylyl, chlorphenyl, methoxyphenyl or carbomethoxyphenyl.

When Xl and X2 together with their common nitrogen atom form a heterocyclic group, it is, for example, pyrrolidino, piperidino, pipecoline, mol-o-lino, thiomorpholino or piperazino, such as N-methylpiperazino.

Preferred heterocyclic groups by NXlX2 are pyrrolidino, piperidino or morpholino.

Xl and X2 each independently represent lower alkyl, benzyl, phenyl, lower alkylphenyl or lower alkoxyphenyl. X3 preferably means hydrogen, chlorine, methyl, methoxy or ethoxy.

It's great that WE is unreplaced. However, if it is substituted with a methyl group, that would be great too.

The ring G is preferably a 6-membered ring, and is particularly preferably C-substituted by 1.2 to 3 methyl groups.

Z is preferably lower alkyl, Hensyl or β-cyanoethyl.

Among the bis-quinapurine compounds of formula (2), those in which Y represents a group of formula (2a) are preferred.

The practically important chromogen bis-quinapurine compound has the following formula (
3).

In the formula, Ql means a direct bond, a linear or branched alkylene group or an alkyritene group or a cyclohexylidene group having at most 8, preferably at most 4 carbon atoms, and Y2 is An aminophenyl group of the formula, a 5-indoline group of the formula, a tetrahydroquinolinyl group of the formula, a tetrahydroquinolinyl group of the formula T1 or a benzmorpholino group of the formula (in each of the above formulas, and X5 each independently mean lower alkyl, cyano-lower alkyl, hensyl, phenyl, lower alkylphenyl or lower alkoxyphenyl, or X4 and forming pyrrolidino, piperidino or morpholino, X6 is hydrogen, halokene, lower alkyl or lower alkoxy, Zl is hydrogen, C,-C8-alkyl, C2-C6-alkoxyalkyl, β-cyanethyl or benzyl, T is hydrogen, haloken, lower alkyl, lower alkoxy,
C, C,, -acylamino or phenyl, T1 and T2 are hydrogen, halogen, hydroxy,
lower alkyl or lower alkoxy and T1, T2, T3, T4 each mean hydrogen, lower alkyl, cycloalkyl or Hensyl, or (Vl and T2) i or (Va and T4) - together means alkylene, and the term Al z B1
, DI may be independently unsubstituted or substituted with one or two substituents selected from the group consisting of cyano, halokene, lower alkyl, phenyl and lower alkoxy.

In the bisuquinasoline compound of formula (3), T2 is of the formula (
3a) which means an aminophenyl group is preferred.

In this case, X4 and X5 are lower alkyl or benzyl. X6 is preferably hydrogen. Ql is preferably in the para position to the ○ one atom and means alkylene or alkylidene, preferably having at most 4 carbon atoms, especially isopropyritine or butylidene. It is also very important that Ql is a cyclohexylidene group. Preferably, ring A1 is unsubstituted. The Hensen rings B1 and Dl are unsubstituted or substituted with methyl and/or t-butyl to form formulas (4) and (
5), Q2 trJ, a linear or branched alkylene radical or alkylidene having at most 4 carbon atoms, or cyclohexylidene, X7 and X8 respectively lower alkyl, β-cyanoethyl, benzyl means phenyl or -NX7X8 means piperidino, X91fi, hydrogen, methyl, methoxy or ethoxy, Z2 is alkyl having 1 to 8 carbon atoms, β-cyanoethyl or pencil, T3, ■5, v6 respectively lower alkyl, especially methyl or ethyl, T4 trJ, hydrogen or methyl, W means halokene, methyl, methoxy or especially hydrogen, and 'J B 2 and D2 are unsubstituted or methyl, methoxy, t - 1 selected from the group consisting of methyl
-1: Substituted with as many as two substituents.

Of particular interest are his-quinazoline compounds of formula (5) in which Q2 means phthyritin or especially impropylidene. X7 and X8 are preferably benzyl or especially lower alkyl.

The halogen in the compounds having the above-mentioned substituents in formulas (1) to (5) is, for example, fluorine, bromine or chlorine.

According to the invention, the suquinazoline compound of formula (1) is obtained by adding 1 mole of a his-phenol compound of the formula (wherein B, DXQ have the meanings given above) to a compound of the formula (wherein A and Y have the meanings given above). and Hatd, meaning a halokene such as hydrogen, fluorine or preferably chlorine) with 2 moles of a 4-halocene quinasoline compound.

The reaction between the compound of formula (6) and the compound of formula (7) can be carried out using an alkali metal hydroxide, an alkali metal carbonate, a tertiary nitrogen base/
Kotoe is prepared in the presence of an acid binder such as pyridine or a trialkylamine, and optionally in the presence of a quaternary ammonium salt such as tetrabutylammonium bromide, an organic solvent or an aqueous-organic biphasic solution. It is carried out in a medium at reflux temperature.

As solvents, the following may be considered, for example:

Alicyclic or aromatic hydrocarbons such as cyclohexane, benzene, toluene, and xylene; Chlorinated hydrocarbons such as chloroform, ethylene chloride, and chlorhenzene; Ethers such as diethyl ether and glycol dimethyl ether; cyclic ethers such as dioxane and tetrahydrofuran; and dimethylformamide, diethylformamide, dimethylsulfoxide or acetonitrile.

Bisphenol compounds of formula (6) which can be used as starting materials for the reaction with quinazoline compounds of formula (7) are disclosed, for example, in US Pat. No. 3,244,550, appendix.

Examples of bisphenols useful as starting materials for formula (6) are shown below.

2.4'-methylene diphenol, 4,4'-methylene diphenol, 2.2'-methylene diphenol, 4
, 14. / (1// , ] // -butylidene)-diphenol, 4 + 4' -5ec-butylidene diphenol, 4,7I'-isopropylidene diphenol, 4,4' -isopropylidene-bis-(
2-methylphenol), 4. +4'-cyclopentylidene diphenol, 4,4'-cyclohexylidene diwenol, 2,2'-methylenedi-p-cresol,
4,4'-methylene di〇-talesol, 4,4'-methylene-bis-(2-pencylphenol), 2,2'
-methylene-his-(4-mo-butylphenol), 2
゜2'-methylene-bis-(4-t-pentylphenol), 2,2'-methylene-his-(4-chlorophenol), 4,4'-methylene-his=(2-chlorophenol), 4 .4'-C1''-methyl-n-hexylidene)-diphenol, 4.,4/(1//
, t//-phthylidene)-bis-(2-t-phthyl-5-methylphenol), 2,2'-methylene-bis(4-phenyl-phenol), 4,4'-methylene-his(2-phenyl -phenol), /1.4. '
-thiodiphenol, 4,4'-sulfonyldiphenol, 2,2'-diphenol, 3,3'-diphenol, 4,/I'-diphenol, 4,4'-dihydroxybenzophenone or 2,2'-diphenol '-Dihydroxybenzophenone.

The starting material of formula (7) can be produced, for example, by the following method.

A 2-amino-benzoic acid amide of formula (9) is reacted with an aldehyde of formula (9) Y-CHO to form a compound of formula The hydroxyl group present is replaced by a herokene atom using, for example, phosphorus oxychloride in dichlorobenzene or thionyl chloride in dimethylformamide to form the starting material of formula (7). The obtained 4-halokenquinasoline compound can be used without isolation.

The oxidation of the reaction product of formula 00 to the 4-quinazolone compound of formula (1) is carried out using an oxidizing agent. Suitable mono-oxidizing agents are chromium monate, dichromate, chlorate, chlorite, peroxides such as hydrogen peroxide, hydrogen oxide, manganese dioxide, lead dioxide, molecular oxygen, air, perboric acid. salts, permanganates, nitrites, chlorine, bromine and especially floranil or bisulfites.

The best results with respect to the yield and purity of the 4-quinazolone compounds obtained are achieved when chloranie is used as the oxidizing agent.

There are environmental advantages if the oxidation is carried out using sodium hydrogen sulfate. This oxidizing agent is used to synthesize 5-synthesizers (11,35
The quinazolone compound of formula (11) can be obtained with high purity and good yield by a method similar to that described in P. (1981).

4-halokenquinasorin compound of formula (7), formula (Jl)
The 4-quinazolone compounds and their preparation are described, for example, in European Patent Publication No. 1+1B No. 33716.

Bisuquinasorines of formulas (1) to (5) are usually colorless or only slightly colored.

When this color former is brought into contact with an acidic color developer, ie, an electron acceptor, it develops a deep yellow or orange color. This color is extremely light-fast and especially sublimation-fast. This compound may therefore be combined with one or more other known color formers such as 3,3-(bis-aminophenyl)-phthalide, 3-indolyl-3-aminophenyl-
Asaphthalide, 3,3-(bis-indolyl-)phthalide, 3-aminofluorane, 2,6-diamitufluorane, leucoolamine, spiropyran, spiropyran,
It is an extremely valuable compound in combination with chromenoindole, phenoxyazine, phenothiazine, carpanylmethane or other triarylmethane leuco dyestuffs to obtain blue, gray or black colors.

The tomato nasolines of formulas (1) to (5) exhibit excellent color strength, sublimation fastness and light fastness both on phenolic substrates and also especially on activated clay. The compounds are particularly suitable as rapid color formers for use in heat-sensitive or especially pressure-sensitive recording materials, which may be 1i royalties, recording materials, etc.

The pressure-sensitive recording material includes at least one sheet containing at least 1 fffl of a color forming agent of formulas (1) to (5) and 1 ml of electron acceptors as a color developer dissolved in an organic solvent, for example. .

Typical examples of color developers for this purpose are activated clay materials such as acpulgite, acid clay, bentonite, montmorillonite, activated clay/acid-activated bentonite or montmorillonite, as well as zeolite, halloysite, silicon dioxide, aluminum oxide, Aluminum sulfate, aluminum phosphate, zinc chloride, activated kaolin or any other suitable clay. Other color developers include acid-reactive organic compounds such as optionally unsubstituted or ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts, and also acidic polymers such as phenolic polymers, alkylphenol acetylene resins, Maleic rosin resins or partially or fully hydrolyzed polymers of maleic anhydride with styrene, ethylene or vinyl methyl ether or carboxypolymethylene; mixtures of these polymeric compounds can also be used. Particularly preferred color developers are acidic clays, lead salicylates, and condensation products of p-substituted phenols and formaldehyde. This condensation product is 1■I1
．． May contain lead.

The developer may additionally contain other ultraviolet-absorbing auxiliary substances, such as silica gel or 2-(2-hydroxyphenyl)benzotriazole, which are not themselves reactive or have little or no reactivity. It can also be used in combination with other agents. Examples of such pigments include talc, titanium dioxide, zinc oxide, white paper, clays such as kaolin, and organic pigments such as urea-formaldehyde condensation products (with a BET surface area of 2 to
75 n? /g) or a melamine-formaldehyde condensation product.

The Mizumoto colorant leaves a colored mark at the point of contact with the electron acceptor. In order to prevent the color former contained in the pressure-sensitive recording material from inadvertently developing color before use, the color former and the electron acceptor are generally separated. This is conveniently achieved by incorporating the color former into a foam-like, sponge-like or honeycomb-like structure.

Preference is generally given to encapsulating the color former in microcapsules that are rupturable by pressure.

Color development occurs at the point when the capsule is crushed, for example by pressing with a pencil, thereby transferring the color former solution to the adjacent sheet coated with the electron acceptor. This color results from the then produced pigments that absorb in the visible region of the electromagnetic spectrum.

Preferably, the color former is encapsulated in the form of a solution dissolved in an organic solvent. Suitable solvents are preferably non-volatile solvents and are exemplified by the following.

Polyhalogenated paraffins or diphenyls such as chlorparaffin, monochlordiphenyl or trichlordiphenyl, tricresyl phosphate, di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene, trichloroethyl phosphate, aromatic compounds such as pensylphenyl ether, hydrocarbon oils For example paraffin or kerosene, such as isopropyl, isobutyl, sec-butyl or tert-butyl
L7 Kylated diphenyl, naphthalene-sweet or terphenyl derivatives, henzylated toluene, terphenyl, partially hydrogenated terphenyls, hensylated xylenes, mono- or tetramethylated diphenylalkanes or other chlorinated or hydrogenated condensations Aromatic hydrocarbons. Mixtures of different solvents are also often used. In particular, in order to obtain optimum solubility of the color reservoir, for rapid and concentrated color development and for obtaining a viscosity favorable for microencapsulation, paraffin oil or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyls are combined. A mixture made of

The capsule wall can be formed by coacervation forces in addition to the droplets of the color former solution. In this case, the capsule material may consist of gelatin and gum arabic, for example.

This is described, for example, in US Pat. No. 2,800,457. Capsules can also preferably be formed from aminoplasts or modified aminoplasts by polycondensation. British Patent No. 989
No. 264, No. 1156725, No. 1301052 and No. 1355], and No. 24. Furthermore, microcapsules formed by interfacial polymerization, for example from polyesters, polycarbonates, polysulfonamides, polysulfonates, especially polyamides or polyurethanes, are also suitable.

Microcapsules containing color formers of formulas (1) to (5) can be used for producing various types of known pressure-sensitive copying materials. In this case, the differences between the various recording material systems lie primarily in the arrangement of the capsules, the type of color-forming reactant or developer and/or the type of support.

One of the most interesting configurations is that the encapsulated color former is present in the form of one layer on the back side of the transfer sheet, and the color developer is present in the form of one layer on the front side of the transfer sheet. It is.

According to another configuration, the microcapsules containing the color former and the color developer are present in one or more layers in one and the same sheet or in a paper pulp. let

Preferably, the capsules are fixed onto the support material using a suitable binder. Since paper is the most preferred supporting material, the binder in this case is primarily a paper coating agent, such as arabic com, polyhinyl alcohol, hydroxymethylcellulose, casein, methylcellulose, dextrin, starch or starch derivatives or heavy Combined latex etc. are considered. Examples of polymer latexes are butadiene-styrene copolymers or acrylic homopolymers or copolymers.

Paper includes not only plain paper made of cellulose fibers, but also
Papers are also used in which cellulose fibers are (partially or completely) replaced by synthetic polymer fibers.

The compounds of formulas (1) to (5) can also be used as coloring agents in heat-reactive recording materials. Recording materials of this type usually contain at least one layer support, a color former, an electron acceptor and optionally further a binder.

Thermoresponsive recording systems include, for example, thermal recording media, thermal copying materials, thermal recording, copying paper, and the like. These systems are used for recording information in, for example, electronic meters, cameras, teleprinters, teletypes, or recording and measuring devices such as ILL" 5. Image formation (marking) is performed using a heated pen. It can also be performed manually.

Another method of thermal marking is using a laser beam.

The heat-reactive material i';+ is one in which the color former is dissolved or dispersed in the binder layer and the developer is dissolved or dispersed in the binder as a second layer. Another arrangement is to disperse both the color former and developer in one layer.When the binder is softened by heat in a specific area, the color former is dispersed at the location where the heat is applied. The desired color develops immediately upon contact with an electron acceptor (color developer).

As the color developer, the same electron acceptor as that used in pressure-sensitive recording paper is suitable. Examples of color developers include the mineral clays already mentioned above and in particular phenolic resins or phenolic compounds, such as those described, for example, in DE 1251.348. In particular, 4-t~
Butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, α-naphthol, β-naphthol, 4-hydroxybenzoic acid methyl ester, 4-
Hydroxyacetophenone, 2,2'-dihydrobutyric acid, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-his-(2=methylphenol), 2,2'-methylene-his~ (4-phenylphenol), 4.4'-his-(hydroxyphenyl)-valeric acid, 2.2'-methylene-his-(4-
phenylphenol), hydroquinone, pyrogallol, phlorochrysin, p-, m-1o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid,
Boric acid and organic dicarboxylic acids such as fatty acids such as tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid, and succinic acid.

It is advantageous to use meltable film-forming binders for the production of thermoreactive recording materials. The binder is usually water-soluble, while the bisquinaprine and developer are water-soluble or insoluble. The binder must be capable of dispersing and fixing the color forming agent and developer at room temperature.

When exposed to heat, the binder softens or melts,
Then, the color forming agent comes into contact with the color developer and becomes colored. Examples of water-soluble or at least water-wettable binders are hydrophilic polymers such as polyhinyl alcohol, polyacrylic monomers, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyacrylamide, polyvinylpyrrolidone, seratin or starch.

If the color former and developer are present in two separate layers, water-insoluble binders, ie binders soluble in non-polar or very weakly polar solvents, can be used. For example, natural rubber, synthetic rubber, chlorinated combs, alkyd resins, polystyrene, styrene/butadiene copolymers, polymethyl acrylate, ethylcellulose, nitrocellulose and polyvinyl carboxylates can be used. However, it is preferable to have a structure in which the color former and the color developer are contained in J layers in the water-soluble binder.

The thermally responsive layer may contain pond additives. For example, talc, titanium dioxide, sp-lead oxide,
Aluminum hydroxide, calcium carbonate (e.g. white)
, clay, or even organic pigments such as urea-formaldehyde polymers. To ensure that color development occurs only within a limited temperature range, additives such as urea, thiourea, Schiff'nilthiourea, acetamide, acetanilide, stearamide, phthalic anhydride, metal stearates, and phthalate nitrile are used. It is also possible to add materials or other suitable substances which induce simultaneous melting of the color forming agent and the color developer. Precisely, thermocouple recording materials include carnauba wax, paraffin wax,
Contains wax such as polyethylene wax.

Examples of the present invention are shown below. Percentages in Example 1f+j are by weight unless otherwise specified.

Example 1 1.2-Dichlorobenzene i in 50.9] 50
'G to dissolve quinazolone compound 26.5I of the following formula.

This solution was then cooled to 90-95'''C.
Phosphorus oxychloride i in 30 minutes at a temperature of 5.3
,! Add l/ dropwise. The reaction mixture is stirred at this temperature for 1 hour. This results in a dark red 4-chloro-
A solution of 2-(4'-dimethylaminophenyl)-quinazolone compound is obtained.

Add this solution to sodium hydroxide solution (50 parts) 64! ! 4.4'-Isopropyritine diphenol (phenol A containing hydrogen) ], ],, 4 g and 2 g of tetraphytylammonium firomide! It (3 to Shu liquid
Inject in 0 minutes. The reaction is then boiled under reflux for 1 hour, and the dichlorobenzene is removed by steam distillation. At this time, the product precipitates, so it is separated at 50°C, washed with water and methanol, and then heated to 80°C.
Dry in vacuum. Thus, 331 g of his-quinazoline compound of the following formula is obtained.

Maximum reflection wavelength of bis-quinasoline compound (paper coated with acid viscosity
ximurn) exists at 465 nm.

This coloring agent produces a yellow color with excellent light fastness and brightness in acidic clay.

Example 2 In place of the quinazolone compound of formula (1) in Example 1, 1,000-1
293 g of a quinazolone compound of formula j12 was used.

Other operations were carried out in exactly the same manner as in Example 1 to obtain 342 g of a bis-quinasoline compound of the following formula.

(The melting point of the sample recrystallized from toluene/methanol is 14
The temperature was 7-150°C.

The maximum reflection wavelength on paper coated with acid clay is 470.
It is nm.

This color former produces a yellow color on CI clay, and the color is extremely lightfast and! It has excellent hardness.

Example 3 The inpropyritense phenol compound in Example 1 was replaced with 19.2 g of hisphenol compound of the following formula/
ξ.

H3 Other operations were carried out in the same manner as in Example 1 to obtain a bis-quinasoline compound of the following formula] 7.29.

Melting point is 145-160°C.

The maximum reflection wavelength on paper coated with acidic clay is 4-65 nm.
Met.

This color former produces a yellow color with excellent light fastness and A-color fastness on acidic clay.

Analogously to Example 1, the his-quinazoline compounds of the following formulas shown in the following table were prepared using the corresponding starting materials.

(CH3)2 Example 12 The compound is heated to 6()°C. This mixture was heated to 60°C for 1
and hold the product for 4 hours with sodium bisulfite.
Add 69 g of a 0% aqueous solution, and then stir at reflux for 2 hours at 6°C to convert to tM. After cooling to room temperature, the precipitated product is filtered off, washed with ethanol and dried. This gives the quinasolone compound 1.9.9 of formula (IV) with a melting point of 215-219°C.

Example 13: Preparation of pressure-sensitive copying paper A solution of 3 g of the bis-quinazoline compound of formula (21) dissolved in a mixture of 80 g of partially hydrogenated terphenyl and 17 g of kerosene is mixed with gelatin in a manner known per se. Microencapsulated by coacervation using gum arabic, mixed with a starch solution and spread on a sheet of paper. Acid-reactive hentonite as a color developer is applied to the front side of the second paper sheet. The first paper sheet and the second paper sheet coated with a color developer are placed one on top of the other so that their coated surfaces are adjacent to each other. Applying pressure by hand or with a typewriter on the first paper sheet immediately produces a deep yellow copy on the developer coated second paper sheet. This yellow copy has excellent sublimation fastness and l1 light fastness.

Even when other coloring agents of formulas (22) to (25) obtained in the above production examples are used, correspondingly deep, sublimation-fast and light-fast yellow copies are achieved.

Example I4 In place of the bis-quinazoline compound of formula (21) used in Example 13, a mixture having the following composition is used.

3.3-bis-(4'-dimethylaminophene-6
-dimethylaminophthalide...12g1 N-)'thylcarbazo'-3-yl-bis-(4'
-N-methyl-N-phenylaminophenyl-)methane...1211 His-quinazoline compound of formula (2J)...1.5 g, 3.3-his=(N-p-octyl-27-methyl Indole-3'-yl-)phthalide

...0.4 g.

The song was pressure-sensitive recorded by performing the same operation as in Example 13.
” Manufacture thorns. When this pressure-sensitive recording material is written by hand or with a typewriter, a dark and light-resistant black copy is obtained.

Example 15 1 g of His-quinapurine compound of formula (22) was added to 1 g of toluene.
．． 79, and into this solution, with stirring, add 12 g of polyvinyl acetate, 8 g of calcium carbonate, and 2 g of titanium dioxide.
Add g.

The resulting suspension is diluted with toluene in a weight ratio of 1:1 and applied to a thickness of 10 μm on a paper sheet using a knife. Overlay this sheet with a second paper sheet. This second paper sheet had on its back side 1 part amide wax, 1 part stearin wax, 1 part zinc chloride.
A mixture consisting of 1.5 g/m" was applied at a coating weight of 3 g/m".

When pressure was applied to the sheet according to the first rule by hand or with a Tights 0 lighter, the sheet that had been coated with the coloring agent immediately developed a deep, sublimation-fast and light-fast yellow color.

Example I6: Preparation of heat-sensitive recording material 4.4'-Impropyritine diphenol (bisphenol A) 32,9. Distearylamide of ethylenecyamine 3.84. 38 g of kaolin, 20 g of polyvinyl alcohol hydrolyzed with 881-4 and 500 g of water
ml is placed in a whole mill and ground to a particle size of approximately 5 μm. In a second ball mill, 3 g of polyvinyl alcohol hydrolyzed with 9.88% t of compound 6 of formula (2I) and 60 ml of water were added to obtain a particle size of about 3μ.
Grind until m.

The above two dispersions were combined and coated on one paper sheet at a dry coverage of 5.5 g/m'.

When a heated ballpoint pen is brought into contact with this paper, a bright yellow color develops, and the resulting color has excellent sublimation fastness and light fastness.

Other color-forming agents of formulas (22) to (25) were used, and a dark solid yellow color was also produced on the platform.

Example 17 2.7 g of the suquinaprine compound of formula (22), 24 g of N-phenyl-N'-(1-hydroxy-2゜2.2-1-lichloroethyl)-urea, 16 stearic acid amide
g, hydrolyzed to 88%; chopped polyvinyl alcohol 59. ? and 58 m7 of water! The mixture is placed in a ball mill and ground until the particle size is 2 to 5 μm. This suspension is applied to a paper sheet at a dry coverage of 5.5 g/m'. When a heated hole pen was brought into contact with this paper, a bright yellow color was obtained that was bright and stable under one light.

Claims (1)

[Scope of Claims] 1 An aliphatic or cycloaliphatic hydrocarbon group of the formula (wherein Q is a direct bond and has at most 8 carbon atoms), -CO-, -S-S-8O2 -, Y means a residue of a compound capable of coupling, and rings A, B, and D are each independently unsubstituted or cyano, nitro, halokene, lower alkyl, phenyl, pencil,
Chromogenic his-quinazoline compounds (substituted by lower alkoxy or lower alkoxycarbonyl). 2. Y in formula (1) is a compound of the formula (2) in which XI and alkyl, cycloalkyl, phenyl, benzyl or phenyl substituted by halogen, nitro, cyano, lower alkyl, lower alkoxy or lower alkoxycarbonyl; together with the nitrogen atom to which they are attached they form a 5- or 6-membered cyclic group, X3 means hydrogen, halogen, nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl; Z means hydrogen or alkyl having at most 8 carbon atoms substituted by haloken, cyano, lower alkoxy, cycloalkyl or pencil, and ring E is unsubstituted. is substituted with cyanogen, halogen, lower alkyl or lower alkoxy, ring G is a hydrogenated 5-membered -tA2id, 6-membered nitrogen heterocycle, and is unsubstituted or substituted with halogen. , cyan, hydroxy, lower alkyl, lower alkoxy, C
5-C6-cycloalkyl, pencil or C3-C6
- 1'' selected from alkylene: ) or substituted with two or more same or different groups. Chromogen and soukinapurine compound. 3. Chromogen and soukinapurine compound according to claim 2, characterized in that Y in formula (1) means a group of formula (2a). 4. Claim 3, characterized in that Xl and X2 in 2a) each independently represent lower alkyl, hensyl, fluorine, lower alkylphenyl, or lower alkoxyphenyl. A chromogenic bis-quinapurine compound. 5. Claims characterized in that in formula (1) K and Y mean formula (2b) in which ring G is a six-membered atom-containing abdominal ring. Chromogen bis-quinazoline compound according to item 2. 6 Y in formula (1) means a group of formula (2b) in which Z is lower alkyl, pencil or β-cyanoethyl. A chromogenic suquinazoline compound according to claim 2.7. A patent suquinazoline characterized in that Q in formula (1) means an aliphatic aliphatic or cycloaliphatic hydrocarbon group. Compound. 8. Formula [wherein Ql means a direct bond, a linear or branched alkylene moiety or alkylidene group or cyclohexylidene group having at most 8 carbon atoms, Y2 is an amino group of the formula phenyl group, 5-indoline group of formula 1, tetrahydroquinolinyl group of formula, tetrahydroquinolinyl group of formula Zl, or benzomorpholino group of formula and lower alkyl, cyano-
means lower alkyl, pencil, phenyl, lower alkylphenyl or lower alkoxyphenyl, or X4 and X5 together with the nitrogen atom to which they are attached means pyrrolidino, piperidino or morpholino, X6 is hydrogen, halogen, Lower alkyl or lower alkoxy, Zl is hydrogen, C2-C6-alkoxyalkyl, β-cyanoethyl or Hensyl, T is hydrogen, halogen, lower alkyl, lower alkoxy,
C1-C4-acylamino or phenyl, TI and T2 each mean hydrogen, halokene, hydrochloride, lower alkyl or lower alkoxy, and vl, V2, V3, V4 respectively hydrogen, lower alkyl, cycloalkyl or hensyl Or (Vz and V2) or (■3 and V4) means both -
and rings AI, BI, and XDI are each independently unsubstituted or one or two substituents selected from the group consisting of cyanohalokene, lower alkyl, phenyl, and lower alkoxy. T4 means hydrogen or methoxy; W means hydrogen, halogen, methyl or methoxy;
and rings B2 and D2 are unsubstituted or substituted with one or two substituents selected from the group consisting of methyl, methoxy and tert-methyl. A chromogenic bis-quinazoline compound. 18, formula) (wherein Q stands for a direct bond, an aliphatic or cycloaliphatic hydrocarbon radical having at most 8 carbon atoms, -CO-, -S- or -802-, and Y means a residue of a compound that can be coupled, and 1AXB, D are each independently unsubstituted or cyan, nitro, halokene, lower alkyl, phenyl, benzyl,
Pressure-sensitive or heat-sensitive, characterized in that it comprises a support containing or coated with at least one bis-quinapurine compound (substituted by lower alkoxy or lower alkoxy carbonyl) as a coloring agent. Recording materials. 19. Claim 18, characterized in that the bis-quinapurine compound is dissolved in an organic solvent and the recording material further contains at least one solid state electron acceptor.
Pressure-sensitive recording materials as described in Section. 20. The pressure-sensitive recording material according to claim 19, wherein the bis-quinazoline compound is encapsulated in microcapsules. 21, characterized in that the conjugated bis-quinazoline compound is present in the form of one layer on the back side of the transfer sheet, and the electron acceptor is present in the form of one layer on the front side of the transfer sheet. A pressure-sensitive recording material according to claim 20. 22 Bis-quinazoline compounds are used for seed selection or other purposes.
2. The pressure-sensitive recording monthly according to item 18 between Σ. 23. Claim 18, characterized in that at least one layer contains at least one bis-quinazoline color former, at least one electron acceptor and at least one bond. The heat-sensitive recording material described. 24, the formula (wherein Q means a direct bond, an aliphatic or cycloaliphatic hydrocarbon group having at most 8 carbon atoms, -CO-, -S- or -3O2-, and Y represents a cup and 4hX BX D are each independently unsubstituted or substituted by cyano, nitro, halokene, lower alkyl, phenyl, benzyl, lower alkoxy or 1-degree alkoxycarbonyl. In the method for producing bis-quinazoline 11 compound of the formula A bis-quinazoline compound characterized in that it is reacted with a 4-halokenquinazoline compound (wherein A and Y have the meanings given in claim 1 and Ha/ means halokene) manufacturing method.