EP0159295B1 - Composés bis-quinazoliniques chromogènes, procédé pour leur préparation et leur utilisation comme précurseur de colorant dans des matériaux d'enregistrement sensibles à la pression ou à la chaleur - Google Patents

Composés bis-quinazoliniques chromogènes, procédé pour leur préparation et leur utilisation comme précurseur de colorant dans des matériaux d'enregistrement sensibles à la pression ou à la chaleur Download PDF

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EP0159295B1
EP0159295B1 EP85810163A EP85810163A EP0159295B1 EP 0159295 B1 EP0159295 B1 EP 0159295B1 EP 85810163 A EP85810163 A EP 85810163A EP 85810163 A EP85810163 A EP 85810163A EP 0159295 B1 EP0159295 B1 EP 0159295B1
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formula
halogen
radical
lower alkyl
hydrogen
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EP0159295A2 (fr
EP0159295A3 (en
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Rudolf Zink
Ian John Dr. Fletcher
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Novartis AG
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Ciba Geigy AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes

Definitions

  • the present invention relates to chromogenic bis-quinazoline compounds, processes for their preparation and their use as color formers in pressure-sensitive or heat-sensitive recording materials.
  • Chromogenic mono-quinazoline compounds are known from EP-A-33716 which are substituted in the 2-position by a 4-aminophenyl group and in the 4-position by an aryloxy group.
  • Lower alkyl and lower alkoxy in the definition of the radicals of the bis-quinazoline compounds are those groups or group components which have 1 to 5, preferably 1 to 3, carbon atoms, such as, for. B. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or amyl or methoxy, ethoxy, isopropoxy or tert-butoxy.
  • Q represents the meaning of an aliphatic radical, in particular an alkylene group which is optionally substituted by halogen atoms, especially chlorine.
  • the alkylene group can contain 2 to 8 carbon atoms and can be straight-chain or branched.
  • the alkylene group preferably has 2 to 5 carbon atoms. For example, it is the
  • the aliphatic hydrocarbon residue can be interrupted by oxygen atoms and thus the rest of a polyalkylene glycol, such as. B. represent polyethylene glycol, polypropylene glycol or polybutylene glycol.
  • Q advantageously means the rest of the formula wherein m are 1 to 9, particularly 1 to 3 and s 1 to 5, preferably 1 or 2.
  • Q means z.
  • B the 1,2-cyclopentylene group, the 1,2-cyclohexylene group, the 1,3-cyclohexylene group, the 1,4-cyclohexylene group or
  • cycloaliphatic radicals can have one or two methyl groups.
  • Q can be used as an araliphatic radical, for example represent.
  • Q is preferably the aliphatic or cycloaliphatic radical, in particular alkylene having 2 to 4 carbon atoms and especially ethylene.
  • Ring A is preferably not further substituted. If it has substituents, it is primarily by halogen, lower alkyl or lower alkoxy z. B. further substituted by chlorine, methyl, isopropyl, tert-butyl or methoxy. There may advantageously be 1 or 2 substituents per benzene ring.
  • the substituents X, and X 2 represent alkyl groups, they may be straight or branched. Examples of such alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, n-hexyl, 2-ethyl-hexyl, n-octyl, isooctyl or n-dodecyl.
  • alkyl radicals in X and X 2 are substituted, it is primarily cyanoalkyl, haloalkyl, hydroxyalkyl or alkoxyalkyl, the alkyl parts preferably having 2 to 4 carbon atoms, such as, for. B. ⁇ -cyanoethyl, ⁇ -chloroethyl, ⁇ -hydroxyethyl, ⁇ -methoxyethyl or ⁇ -ethoxyethyl.
  • cycloalkyl in the meaning of X 1 and X 2 are cyclopentyl or preferably cyclohexyl.
  • the cycloalkyl radicals can contain one or more C 1 -C 4 -alkyl radicals, preferably methyl groups. They preferably have a total of 5 to 10 carbon atoms.
  • Preferred substituents in the benzyl and phenyl group of X 1 and X 2 are e.g. B. halogens, cyano, methyl, methoxy or carbomethoxy.
  • Examples of such araliphatic or aromatic radicals are methylbenzyl, chlorobenzyl, cyanophenyl, tolyl, xylyl, chlorophenyl, methoxyphenyl or carbomethoxyphenyl.
  • X 1 and X 2 together with the common nitrogen atom represent a heterocyclic radical, this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino, such as, for. B. N-methylpiperazino.
  • Preferred heterocyclic radicals for NX, X 2 are pyrrolidino, piperidino or morpholino.
  • X and X 2 are , independently of one another, preferably lower alkyl, benzyl, phenyl, lower alkylphenyl or lower alkoxyphenyl.
  • X 3 preferably denotes hydrogen, chlorine, methyl, methoxy or ethoxy.
  • Ring B is preferably unsubstituted. However, it can advantageously have a methyl group.
  • the ring D is preferably six-membered and especially C-substituted by 1, 2 or 3 methyl groups.
  • Z is preferably lower alkyl, benzyl or ⁇ -cyanoethyl.
  • Y 1 represents an aminophenyl radical of the formula (3a) are preferred.
  • X 4 and X 5 are lower alkyl or benzyl.
  • X 6 is preferably hydrogen.
  • Q 1 is preferably alkylene with 2 to 4 carbon atoms and in particular ethylene or propylene.
  • Q 1 is preferably also ⁇ CH 2 CH 2 ⁇ O ⁇ CH 2 CH 2 - or the cyclohexylene radical.
  • the ring A 1 is preferably unsubstituted.
  • the N-substituent Z 1 is in particular benzyl, ⁇ -cyanoethyl or Alkyl of 1 to 8 carbon atoms, e.g. B. n-octyi, n-butyl, isopropyl or especially methyl or ethyl.
  • V 1 and V 2 ) or (V 3 and V 4 ) together mean alkylene, they advantageously have 4 or 5 carbon atoms and form a cyclopentane or cyclohexane ring with the carbon atoms connecting them.
  • bis-quinazoline compounds of the formula (5) in which Q 2 is C 2 -C 4 -alkylene, preferably propylene or especially ethylene or is also ⁇ CH 2 CH 2 ⁇ O ⁇ CH 2 ⁇ CH 2 - .
  • X 7 and X 8 are preferably benzyl or especially lower alkyl.
  • W and T 4 are preferably hydrogen.
  • Halogen in compounds with the above substituents in formulas (1) to (5) means, for example, fluorine, bromine or preferably chlorine.
  • the bis-quinazoline compounds of the formula (1) according to the invention are prepared by adding 1 mol of a diol compound of the formula where Q has the meaning given, with 2 moles of a 4-haloquinazoline compound of the formula wherein A and Y have the meaning given and Hal halogen, such as. B. bromine, fluorine or preferably chlorine.
  • reaction of the compound of formula (6) with the compound of formula (7) is conveniently carried out in the presence of an acid-binding agent, such as. B. an alkali metal hydroxide, alkali metal carbonate, a tertiary nitrogen base, such as. As pyridine or trialkylamines, and preferably in the presence of a quaternary ammonium salt such as. B. tetrabutylammonium bromides, optionally in an organic solvent or in an aqueous-organic two-phase medium and at reflux temperature.
  • an acid-binding agent such as. B. an alkali metal hydroxide, alkali metal carbonate, a tertiary nitrogen base, such as. As pyridine or trialkylamines, and preferably in the presence of a quaternary ammonium salt such as. B. tetrabutylammonium bromides, optionally in an organic solvent or in an aqueous-organic two-phase medium and at reflux temperature.
  • solvents examples include cycloaliphatic or aromatic hydrocarbons, such as. B. cyclohexane, benzene, toluene or xylene; Chlorinated hydrocarbons, such as B. chloroform, ethylene chloride or chlorobenzenes especially dichlorobenzene; Ethers such as B. diethyl ether or glycol dimethyl ether; cyclic ethers, such as. B. dioxane or tetrahydrofuran; as well as dimethylformamide, diethylformamide, dimethyl sulfoxide or acetonitrile.
  • cycloaliphatic or aromatic hydrocarbons such as. B. cyclohexane, benzene, toluene or xylene
  • Chlorinated hydrocarbons such as B. chloroform, ethylene chloride or chlorobenzenes especially dichlorobenzene
  • Ethers such as B. diethyl ether or glycol dimethyl
  • diols used as starting materials of the formula (6) are:
  • the starting materials of the formula (7) can be prepared by, for example, a 2-amino-benzoic acid amide of the formula with an aldehyde of the formula to a 1,2,3,4-tetrahydro-quinazolone (4) compound of the formula converts this into a compound of the formula oxidized, then the hydroxyl group on the heterocyclic ring of the quinazoline system by a halogen atom, e.g. B. replaced by phosphorus oxychloride in dichlorobenzene or thionyl chloride in dimethylformamide to form the starting material of formula (7).
  • the 4-haloquinazoline compound obtained can be used without being isolated.
  • oxidizing agents are e.g. B. chromates, bichromates, chlorates, chlorites, peroxides, e.g. B. hydrogen peroxide, manganese dioxide, lead dioxide, molecular oxygen, air, perborates, permanganates, nitrites, chlorine, bromine and especially chloranil or bisulfites.
  • 4-haloquinazoline compounds of the formula (7) and 4-quinazolone compounds of the formula (13) and their preparation are, for. B. described in European Patent Publication No. 33716.
  • the bis-quinazolines of the formulas (1) to (5) are normally colorless or at most weakly colored.
  • these color formers are mixed with a preferably acidic developer, e.g. H. an electron acceptor, they result in intense yellow or orange shades that are excellent lightfast and above all sublimation resistant. They are therefore also very valuable in a mixture with one or more other known color formers, e.g. B.
  • 3,3- (bis-aminophenyl) phthalides 3,3- (bis-aminophenyl) phthalides, 3-indolyl-3-aminophenyl-azaphthalides, 3,3- (bis-indolyl -) - phthalides, 3-aminofluoranes, 2,6-diaminofluoranes, leucoauramines , Spiropyrans, spirodipyrans, chromenoindoles, phenoxazines, phenothiazines, monoquinazolines, carbazolylmethanes or other triarylmethane leuco dyes to give blue, gray or black colors.
  • the bis-quinazolines of formulas (1) to (5) show excellent color intensity, sublimation and light fastness both on phenolic substrates and especially on activated clays. They are particularly suitable as rapidly developing color formers for use in a heat-sensitive or, in particular, pressure-sensitive recording material, which can be both copying and registration material.
  • a pressure sensitive material consists of at least one pair of sheets that contain at least one color former of the formulas (1) to (5) dissolved in an organic solvent and an electron acceptor as developer.
  • Typical examples of such developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, such as. B. acid activated bentonite or montmorillonite, also zeolite, halloysite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, activated kaolin or any clay.
  • Other developers are acidic organic compounds, such as. B. optionally ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts, and also an acidic polymer material such. B.
  • a phenolic polymer an alkylphenol acetylene resin, a maleic rosin resin, or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene.
  • Particularly preferred developers are acid clays, zinc salicylates or the condensation products of p-substituted phenols with foramaldehyde. The latter can also contain zinc.
  • the developers can also with other, in itself unreactive or less reactive pigments or other auxiliaries such as silica gel or UV adsorbers, such as. B. 2- (2-hydroxyphenyl) benzotriazoles mixed.
  • pigments are: talc, titanium dioxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, e.g. B. urea-formaldehyde condensates (BET surface 2-75 m 2 / g) or melamine-formaldehyde condensation products.
  • the color former provides a colored marking at the points where it comes into contact with the electron acceptor.
  • these are usually separated from the electron acceptor. This can conveniently be achieved by incorporating the color formers into foam, sponge or honeycomb structures.
  • the color formers are preferably enclosed in microcapsules which can usually be broken by pressure.
  • the color former solution When the capsules are broken by pressure, for example using a pencil, the color former solution is transferred to an adjacent sheet coated with an electron acceptor, thereby producing a colored area. The color results from the dye formed, which absorbs in the visible range of the electromagnetic spectrum.
  • the color formers are preferably encapsulated in the form of solutions in organic solvents.
  • suitable solvents are preferably non-volatile solvents, for example polyhalogenated paraffin or diphenyl, such as chlorinated paraffin, monochlorodiphenyl or trichlorodiphenyl, furthermore tricresyl phosphate, di-n-butyl phthalate, di-octyl phthalate, trichlorobenzene, trichloroethyl phosphate, aromatic ethers, such as benzylphenyl ether such as paraffin or kerosene, e.g. B.
  • Mixtures of various solvents in particular mixtures of paraffin oils or kerosene and diisopropyinaphthaiine or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.
  • the capsule walls can be formed evenly around the droplets of the color former solution by coacervation forces, the encapsulation material e.g. B. may consist of gelatin and gum arabic, as z. B. is described in U.S. Patent 2,800,457.
  • the capsules can preferably also be formed from an aminoplast or modified aminoplast by polycondensation, as described in British Patents 989, 264, 1 156 725, 1 301 052 and 1 355 124.
  • microcapsules which are formed by interfacial polymerization, such as. B. capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
  • the color formers of the formulas (1) to (5) containing microcapsules can be used to produce pressure-sensitive copying materials of various known types.
  • the different systems differ essentially from each other in the arrangement of the capsules, the color reactants and the carrier material.
  • the encapsulated color former is present in the form of a layer on the back of a transfer sheet and the electron acceptor is in the form of a layer on the front of a receiver sheet.
  • microcapsules containing the color former and the developer are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
  • the capsules are preferably attached to the carrier by means of a suitable binder.
  • this binder is primarily paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch or starch derivatives or polymer latices.
  • the latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.
  • the compounds of formulas (1) to (5) can also be used as color formers in a thermoreactive recording material.
  • This usually contains at least one layer support, a color former, an electron acceptor and optionally also a binder and / or wax.
  • Thermoreactive recording systems include e.g. B. heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, e.g. B. in electronic computers, remote printers, teleprinters or in recording devices and measuring instruments, such as. B. electrocardiograph used.
  • the imaging (marking) can also be done manually with a heated spring.
  • Another device for producing markings by means of heat is laser beams.
  • thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in a binder layer and the developer is dissolved and dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer.
  • the binder is softened by heat in specific areas and at these points where heat is applied the color former comes into contact with the electron acceptor and the desired color develops immediately.
  • developers are the clay minerals already mentioned and especially phenolic resins, or also phenolic compounds, as described for example in DE-PS 12 51 348, e.g. B. 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, a-naphthol, ⁇ -naphthol, 4-hydroxy-diphenyl-sulfone, 4-hydroxybenzoic acid methyl ester or benzyl ester, 4-hydroxyacetophenone, 2,2 ' -Dihydroxy-diphenyl, 4,4'-isopropylidene diphenoi, 4,4'-isopropylidene-bis- (2-methylphenol), 2,2-methylene-bis- (4-phenylphenol), 4,4'-bis- (hydroxyphenyl ) -valeric acid, hydroquinone, pyrogallol, phloroglucin, p-, m
  • Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water soluble, while the bis-quinazolines and developer are sparingly soluble or insoluble in water. The binder should be able to disperse and fix the color former and developer at room temperature.
  • Water-soluble or at least water-swellable binders are e.g. B. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or esterified corn starch.
  • hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin, starch or esterified corn starch.
  • water-insoluble binders e.g. H. binders soluble in non-polar or only weakly polar solvents, such as e.g. B. natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
  • B. natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
  • the preferred arrangement is one in which the color former and the developer are contained in one layer in a water-soluble binder.
  • thermoreactive layers can contain further additives.
  • these layers for. B. talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate (e.g. chalk), clays or organic pigments, such as. B. urea-formaldehyde polymers.
  • substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearic acid amide, phthalic anhydride, metal stearates, such as, for.
  • Thermographic recording materials preferably contain waxes, e.g. B. carnauba wax, montana wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
  • waxes e.g. B. carnauba wax, montana wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
  • the solution is added dropwise to a suspension of 3.1 g of ethylene glycol, 100 g of sodium hydroxide solution (50%) and 1 g of tetrabutylammonium bromide.
  • the suspension is then stirred under reflux for one hour and then 150 ml of water are added at 90.degree.
  • the xylene phase is separated and washed several times with hot water.
  • the xylene phase is then allowed to cool with stirring and 100 g of methanol are added at 35.degree.
  • the maximum reflectance of this bis-quinazoline compound on acid-coated paper is 464 nm.
  • the red reaction solution of the compound of the formula is stirred at 85-90 ° C for 1 hour.
  • the solution is then added dropwise to a suspension of 1.6 g of ethylene glycol, 30 g of sodium hydroxide solution (50%) and 1 g of tetrabutylammonium bromide.
  • the emulsion is stirred for 2 hours at 90-95 ° C., the toluene phase is separated, this is washed with water and the product is precipitated in crystalline form by adding 80 g of methanol at 40 ° C. Filtration at 15 ° C., washing with methanol and drying give 10.1 g of a practically colorless bishinazoline compound of the formula
  • Recrystallization from toluene / isopropyl alcohol 7: 3 gives the pure product with a melting point of 228-229 ° C.
  • This color former develops a yellow color with good light fastness on acid clay.
  • the color former is also characterized by excellent sublimation fastness.
  • a solution of 3 g of the bis-quinazoline compound of the formula (21) in 80 g of partially hydrogenated terphenyl and 17 g of kerosene is microencapsulated in a manner known per se with gelatin and gum arabic by coacervation, mixed with starch solution and spread on a sheet of paper.
  • a second sheet of paper is coated on the front with acid-activated bentonite as a color developer.
  • the first sheet and the paper coated with color developer are placed on top of each other with the coatings adjacent. Writing by hand or with the typewriter on the first sheet exerts pressure, and an intense yellow copy develops on the sheet coated with the developer, which is excellent in sublimation and lightfastness.
  • 1 g of the bis-quinazoline compound of the formula (21) is dissolved in 17 g of toluene. 12 g of polyvinyl acetate, 8 g of calcium carbonate and 2 g of titanium dioxide are added to this solution with stirring. The suspension obtained is diluted in a weight ratio of 1: 1 with toluene and spread on a sheet of paper using a 10 ⁇ m doctor blade. A second sheet of paper is placed on this sheet of paper, the underside of which has been coated at a coating weight of 3 g / m 2 with a mixture consisting of 1 part of an amide wax, 1 part of a stearic wax and 1 part of zinc chloride. By writing by hand or with a typewriter on the top sheet, pressure is exerted and an intense, sublimation and lightfast yellow color develops on the sheet coated with the color formers.
  • the two dispersions are combined and coated onto a paper with a dry application weight of 5.5 g / m 2 .
  • a paper with a dry application weight of 5.5 g / m 2 By touching the paper with a heated ballpoint pen, an intense yellow color is obtained, which has excellent sublimation and light fastness.
  • Intense and lightfast yellow colors can also be obtained using any of the other color formers of formula (22) given in Preparation Examples 2-15.

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Claims (22)

1. Dérivés bis-quinazoliniques chromogènes de formule
Figure imgb0066
dans laquelle le cycle A est non substitué ou substitué par un ou des groupes cyano, nitro, halogéno, alkyle inférieur, phényle, benzyle, alcoxy inférieur ou alcoxycarbonyle inférieur,
Q représente un radical aliphatique de poids moléculaire 28 à 450, éventuellement substitué par des atomes d'halogène ou interrompu par des atomes d'oxygène, ou un radical cycloaliphatique ou araliphatique contenant au maximum 10 atomes de carbone et
Y représente le groupe de formule
Figure imgb0067
ou de formule
Figure imgb0068
dans lesquelles
X, et X2 représentent chacun, indépendamment l'un de l'autre, un hydrogène, un groupe alkyle de 12 atomes de carbone au maximum, non substitué ou substitué par un ou des groupes halogéno, hydroxy, cyano ou alcoxy inférieur, un groupe cycloalkyle, phényle, benzyle, ou un groupe phényle ou benzyle substitué par un ou des groupes halogéno, nitro, cyano, alkyle inférieur, alcoxy inférieur ou alcoxycarbonyle inférieur, ou bien X, et X2 forment ensemble, avec l'atome d'azote auquel ils sont liés, un radical hétérocyclique à 5 ou 6 chaînons,
X3 représente un hydrogène, un halogène, ou un groupe alkyle inférieur, alcoxy inférieur ou alcoxycarbonyle inférieur et
Z représente un hydrogène ou un groupe alkyle de 8 atomes de carbone au maximum, non substitué ou substitué par un ou des groupes halogéno, cyano ou alcoxy inférieur, un groupe cycloalkyle ou benzyle, et le cycle B est non substitué ou substitué par un ou des groupes cyano, halogéno, alkyle inférieur, alcoxy inférieur, acylamino en C,-C4 ou phényle et le cycle D est un hétérocycle azoté hydrogéné à 5 ou 6 chaînons, qui contient le cas échéant un autre hétéroatome en tant que chaînon du cycle et est non substitué ou, selon la nature des substituants mono- ou poly-substitué sur les atomes de carbone par des halogènes, des groupes cyano, hydroxy, alkyle inférieur, alcoxy inférieur, cycloalkyle, en C5-C6, benzyle ou alkylène en C3-C6.
2. Dérivés bis-quinazoliniques selon la revendication 1, caractérisés en ce que, dans la formule (1) Y représente le groupe de formule (2a).
3. Dérivés bis-quinazoliniques selon la revendication 2, caractérisés en ce que, dans la formule (2a), X, et X2 représentent chacun, indépendamment l'un de l'autre, un groupe alkyle inférieur, benzyle, phényle, (alkyle inférieur)-phényle ou (alcoxy inférieur)-phényle.
4. Dérivés bis-quinazoliniques selon la revendication 1, caractérisés en ce que, dans la formule (1), Y représente le groupe de formule (2b) dans laquelle Z représente un groupe alkyle inférieur, benzyle ou bêta-cyanoéthyle.
5. Dérivés bis-quinazoliniques selon l'une des revendications 1 et 4, caractérisés en ce que, dans la formule (1), Y représente le groupe de formule (2b) dans laquelle le cycle D est à 6 chaînons.
6. Dérivés bis-quinazoliniques selon l'une des revendications 1 à 5, caractérisés en ce que, dans la formule (1), Q représente un radical aliphatique ou cycloaliphatique, en particulier un radical alkylène en C2-C4.
7. Dérivés bis-quinazoliniques selon la revendication 1, caractérisés en ce qu'ils répondent à la formule
Figure imgb0069
dans laquelle Q1 représente un groupe alkylène à chaîne droite ou ramifiée en C2-Ca, de préférence en C2-CS, ou un groupe ―(CH2CH2O)m1―CH2CH2―
Y1 représente un groupe aminophényle de formule
Figure imgb0070
un groupe 5-indolinyle de formule
Figure imgb0071
un groupe tétrahydroquinoléinyle de formule
Figure imgb0072
un groupe tétrahydroquinoléinyle de formule
Figure imgb0073
ou un groupe benzomorpholino de formule
Figure imgb0074
dans lesquelles formules
m, a une valeur de 1 à 3,
X4 et X5 représentent chacun, indépendamment l'un de l'autre, un groupe alkyle inférieur, cyano- alkyle inférieur, benzyle, phényle (alkyle inférieur)-phényle ou (alcoxy inférieur)-phényle, ou bien
X4 et X5 forment ensemble, avec l'atome d'azote auquel ils sont liés, un cycle pyrrolidino, pipéridino ou morpholino,
Xe représente un hydrogène, un halogène, ou un groupe alkyle inférieur ou alcoxy inférieur,
Z1 représente un hydrogène, ou un groupe alkyle en C1-C8, alcoxyalkyle en C2-C6, bêta-cyanoéthyle ou benzyle,
T représente un hydrogène, un halogène, ou un groupe alkyle inférieur, alcoxy inférieur, acylamino en C1-C4 ou phényle,
T1 et T2 représentent chacun un hydrogène, un halogène, ou un groupe hydroxy alkyle inférieur ou alcoxy inférieur et
V1, V2, V3 et V4 représentent chacun un hydrogène, ou un groupe alkyle inférieur, cycloalkyle en CS-C6 ou benzyle, ou bien (V1 et V2) ou (V3 et V4) forment ensemble, respectivement, un groupe alkylène en C3-C6, et
le cycle A1 est non susbstitué ou porte un ou deux substituants choisis parmi les groupes cyano, halogéno, alkyle inférieur, phényle et alcoxy inférieur.
8. Dérivés bis-quinazoliniques selon la revendication 7, caractérisés en ce que, dans la formule (3) Y1 représente un groupe de formule (3a).
9. Dérivés bis-quinazoliniques selon la revendication 8, caractérisés en ce que, dans la formule (3a) X4 et X5 représentent des groupes alkyle inférieur ou benzyle et X6 un hydrogène.
10. Dérivés quinazoliniques selon l'une des revendications 7 à 9, caractérisés en ce que, dans la formule (3), Q1 représente un groupe alkylène en C2-C4, plus particulièrement un groupe propylène ou éthylène.
11. Dérivés bis-quinazoliniques selon l'une des revendications 7 à 10, caractérisés en ce que, dans la formule (3), le cycle A1 est non substitué.
12. Dérivés bis-quinazoliniques selon la revendication 7, caractérisés en ce que, dans la formule (3), Y1 représente le groupe de formule (3d).
13. Dérivés bis-quinazoliniques selon la revendication 1 ou 7, caractérisés en ce qu'ils répondent à la formule
Figure imgb0075
dans laquelle
Q2 représente un groupe alkylène à chaîne droite ou ramifiée en C2-C4,
Figure imgb0076
Figure imgb0077
X7 et X8 représentent des groupes alkyle inférieur ou benzyle, ou bien -NX7XB représente un groupe pipéridino,
X9 représente un hydrogène, ou un groupe méthyle, méthoxy ou éthoxy et
W représente un hydrogène, un halogène, ou un groupe méthyle ou méthoxy.
14. Dérivés bis-quinazoliniques selon la revendication 13, caractérisés en ce que, dans la formule (5), Q2 représente un groupe alkylène en C2-C4 ou un groupe ―CH2CH2―O―CH2CH2―, X7 et X8 représentent des groupes alkyle inférieur et X9 et W représentent des atomes d'hydrogène.
15. Dérivés bis-quinazoliniques selon la revendication 1 ou 7, caractérisés en ce qu'ils répondent à la formule
Figure imgb0078
dans laquelle
Q2 représente un groupe alkylène à chaîne droite ou ramifiée en C2-C4 ou un groupe ―CH2CH2―O―CH2CH2―,
Z2 représente un groupe alkyle en C1-C8, bêta-cyanoéthyle ou benzyle,
T3, V5 et V6 représentent chacun un groupe alkyle inférieur,
T4 représente un hydrogène ou un groupe méthyle et
W représente un hydrogène, un halogène, ou un groupe méthyle ou méthoxy.
16. Dérivés bis-quinazoliniques selon la revendication 15, caractérisés en ce que, dans la formule (4), Z2 représente un groupe alkyle inférieur, T3, V5 et V6 représentent des groupes méthyle et T4 et W représentent des atomes d'hydrogène.
17. Procédé de préparation des dérivés bis-quinazoliniques de formule (1) donnée dans la revendication 1, caractérisé en ce que l'on fait réagir 1 mole d'un diol de formule
Figure imgb0079
dans laquelle Q a les significations indiquées dans la revendication 1, avec 2 moles d'une 4- halogénoquinazoline de formule
Figure imgb0080
dans laquelle A et Y ont les significations indiquées dans la revendication 1 et Hal représente un halogène.
18. Utilisation d'un dérivé bis-quinazolinique de formule indiquée dans l'une des revendications 1 à 16 en tant qu'agent chromogène dans un matériau d'enregistrement sensible à la pression ou sensible à la chaleur.
19. Matériau d'enregistrement sensible à la pression, caractérisé en ce qu'il contient dans son système de réactifs pour couleur, en tant qu'agent chromogène, au moins un dérivé bis-quinazolinique selon l'une des revendications 1 à 16 et au moins un accepteur d'électrons solide, le dérivé bis-quinazolinique étant en solution dans un solvant organique et encapsulé dans des microcapsules.
20. Matériau d'enregistrement sensible à la pression selon la revendication 19, caractérisé en ce que le dérivé bis-quinazolinique encapsulé est présent sous forme d'une couche sur le verso d'une feuille de transfert et l'accepteur d'électrons est présent sous forme d'une couche sur le recto de la feuille réceptrice.
21. Matériau d'enregistrement sensible à la pression selon l'une des revendications 19 et 20, caractérisé en ce que le dérivé bis-quinazolinique est contenu conjointement avec un ou plusieurs autres agents chromogènes.
22. Matériau d'enregistrement sensible à la chaleur, caractérisé en ce qu'il contient, dans au moins une couche, au moins un dérivé bis-quinazolinique selon l'une des revendications 1 à 16, un accepteur d'électrons solide et, le cas échéant, un liant et/ou une cire.
EP85810163A 1984-04-18 1985-04-12 Composés bis-quinazoliniques chromogènes, procédé pour leur préparation et leur utilisation comme précurseur de colorant dans des matériaux d'enregistrement sensibles à la pression ou à la chaleur Expired EP0159295B1 (fr)

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JP (1) JPS60233065A (fr)
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ES (1) ES542331A0 (fr)
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US4766211A (en) * 1985-09-06 1988-08-23 Ciba-Geigy Corporation Chromogenic quinazolines
DE3905339A1 (de) * 1989-02-22 1990-09-06 Basf Ag Chinolin-4-carbonsaeurederivate und deren verwendung
US5326766A (en) * 1992-08-19 1994-07-05 Dreikorn Barry A 4-(2-(4-(2-pyridinyloxy)phenyl)ethoxy)quinazoline and analogues thereof
GB9522233D0 (en) * 1995-10-31 1996-01-03 Wiggins Teape Group The Limite Pressure-sensitive copying paper
RU2702751C1 (ru) * 2019-03-28 2019-10-11 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Производные пиримидина, обладающие модуляторной активностью по отношению к рецепторам амра-типа

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US3340260A (en) * 1962-12-03 1967-09-05 Ciba Geigy Corp 4-amino-pyrimidines
US3574210A (en) * 1967-07-13 1971-04-06 Squibb & Sons Inc 2,4-disubstituted-6-nitro-and 6-a minoquinazolines
US3637693A (en) * 1968-07-12 1972-01-25 Du Pont Hydroxyarylquinazolines and their use as uv-absorbers
US3931179A (en) * 1974-03-06 1976-01-06 Sandoz Inc. N,N-Bis(4-Quinazolinyl)alkanediamines
US3998951A (en) * 1974-03-13 1976-12-21 Fmc Corporation Substituted 2-arylquinazolines as fungicides
US4011323A (en) * 1974-03-18 1977-03-08 Sandoz, Inc. Bi-4-[1-(quinazolinyl-4)piperidyls] and bis{4-[1-(quinazolinyl-4)piperidyl]alkanes}
US4306065A (en) * 1979-12-19 1981-12-15 A. H. Robins Company, Incorporated 2-Aryl-4-substituted quinazolines
FI70036C (fi) * 1980-01-31 1986-09-12 Ciba Geigy Ag Kromogena kinazolinfoereningar
JPS57204031A (en) * 1981-06-09 1982-12-14 Ricoh Co Ltd Heat development type diazo copying material
CH657131A5 (de) * 1982-04-22 1986-08-15 Ciba Geigy Ag Chromogene dihydrochinazoline und ihre herstellung und verwendung.
GB8329361D0 (en) * 1983-11-03 1983-12-07 Wiggins Teape Group Ltd Record material

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YU64385A (en) 1988-02-29
ES8602770A1 (es) 1985-12-16
EP0159295A2 (fr) 1985-10-23
FI87070C (fi) 1992-11-25
EP0159295A3 (en) 1986-10-08
FI87070B (fi) 1992-08-14
JPH0524904B2 (fr) 1993-04-09
JPS60233065A (ja) 1985-11-19
US4668966A (en) 1987-05-26
DE3568733D1 (en) 1989-04-20
ES542331A0 (es) 1985-12-16
FI851493L (fi) 1985-10-19

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