EP0000346B1 - Composés quinoxaliniques, leur procédé de préparation et leur utilisation pour le blanchiment optique de matières organiques et les matières ainsi blanchies - Google Patents

Composés quinoxaliniques, leur procédé de préparation et leur utilisation pour le blanchiment optique de matières organiques et les matières ainsi blanchies Download PDF

Info

Publication number
EP0000346B1
EP0000346B1 EP78100253A EP78100253A EP0000346B1 EP 0000346 B1 EP0000346 B1 EP 0000346B1 EP 78100253 A EP78100253 A EP 78100253A EP 78100253 A EP78100253 A EP 78100253A EP 0000346 B1 EP0000346 B1 EP 0000346B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
denotes
chlorine
formula
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100253A
Other languages
German (de)
English (en)
Other versions
EP0000346A1 (fr
Inventor
Udo Dr. Eckstein
Hans Dr. Theidel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000346A1 publication Critical patent/EP0000346A1/fr
Application granted granted Critical
Publication of EP0000346B1 publication Critical patent/EP0000346B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
    • C07F9/650994—Six-membered rings having the nitrogen atoms in the positions 1 and 4 condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring

Definitions

  • non-chromophoric substituents are halogen, optionally substituted alkyl, optionally substituted alkenyl, aryl, aralkyl, optionally substituted alkoxy, alkoxycarbonyl, optionally substituted aminocarbonyl, cyano, alkylsulfonyl, alkoxysulfonyl, optionally substituted aminosulfonyl, acyl, acylamino, hydroxy, aryloxy, aralkyloxy, Alkenyloxy, aryloxycarbonyl, aralkyloxycarbonyl, carboxy or acyloxy.
  • Alkyl is in particular C 1 -C 4 -alkyl, which can be monosubstituted by hydroxy, C 1 -C 4 -alkoxy, cyano, carboxy, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, chlorine or bromine or trifluoromethyl.
  • Alkenyl is in particular C 2 -C 5 alkenyl, which can be monosubstituted by hydroxy, C 1 -C 4 alkoxy, cyano, carboxy, C 1 -C 4 alkoxycarbonyl, chlorine or bromine.
  • Halogen is especially fluorine, chlorine and bromine, preferably chlorine.
  • Aryl is in particular phenyl optionally substituted by C 1 -C 4 alkyl, trifluoromethyl, chlorine, bromine carboxy, cyano, C 1 -C 4 alkoxycarbonyl or C 1 -C 4 alkoxy.
  • Aralkyl is in particular phenyl-C 1 -C 4 -alkyl, which can be substituted by chlorine, methyl or methoxy in the phenyl core.
  • Cycloalkyloxy is especially cyclopentyloxy and cyclohexyloxy.
  • Acyl is especially C 1 -C 4 alkylcarbonyl, Ci-C 4 alkylsulfonyl, optionally substituted by methyl, methoxy or chlorine-substituted benzoyl or optionally substituted by methyl, methoxy or chlorine-substituted benzenesulfonyl.
  • aminocarbonyl and aminosulfonyl radicals are, in particular, C 1 -C 4 alkyl, phenyl or phenyl C 1 -C 4 alkyl optionally substituted by methyl, methoxy or chlorine.
  • solvents for example hydrocarbons such as toluene or xylene or alcohols such as methanol, ethanol, isopropanol, butanol, glycol, glycol ethers such as 2-methoxyethanol; Hexanol, cyclohexanol, cyclooctanol, furthermore ethers such as diisopropyl ether, dioxane, tetrahydrofuran, furthermore formamides or N-methylpyrrolidone.
  • Dipolar organic solvents such as dimethylformamide and dimethyl sulfoxide are particularly suitable.
  • Strongly basic compounds are suitable as condensing agents, such as alkali or alkaline earth metal hydroxides, alkali or alkaline earth amides and alkali or alkaline earth metal alcoholates, for example potassium hydroxide, sodium hydroxide, potassium tert-butoxide, sodium amide or sodium methylate, furthermore the alkali compounds of dimethyl sulfoxide and alkali metal hydroxide and optionally alkali metal hydroxide . It is preferably carried out in the temperature range from 0 to 100 ° C.
  • the organic materials in question can be in a wide variety of processing states (raw materials, semi-finished or finished products) and physical states. They can be in the form of a wide variety of shaped structures, i.e. H. so z. B. predominantly three-dimensionally expanded bodies such as blocks, plates, profiles, pipes, injection moldings or various workpieces, chips or granules, foams; predominantly two-dimensional bodies such as films, foils, lacquers, tapes, coatings, impregnations and coatings or predominantly one-dimensional bodies such as threads, fibers, flakes, bristles, wires.
  • processing states raw materials, semi-finished or finished products
  • physical states can be in the form of a wide variety of shaped structures, i.e. H. so z.
  • B. predominantly three-dimensionally expanded bodies such as blocks, plates, profiles, pipes, injection moldings or various workpieces, chips or granules, foams; predominantly two-dimensional bodies such as films, foils, lacquers, tapes, coating
  • Said materials can also exist in unshaped states in the most varied of homogeneous and inhomogeneous forms of distribution and physical states, e.g. B. as powders, solutions, emulsions, dispersions, latices (examples: lacquer solutions, polymer dispersions, brine, jelly, putty, pastes, waxes, adhesives and fillers, etc.).
  • Fiber materials can be in the form of endless threads, staple fibers, flakes, extrudates, textile threads, yarns, twists, non-woven fabrics, felts, wadding, flocking structures, or as textile fabrics or textile composites, knitted fabrics, and as paper, cardboard or paper pulp, etc.
  • the compounds to be used according to the invention are also important for the treatment of textile organic materials, in particular textile fabrics. If fibers, which can be in the form of staple fibers or endless fibers, in the form of strands, fabrics, knitted fabrics, nonwovens, flocked substrates or composites, are to be tinted white according to the invention, this is advantageously done in an aqueous medium in which the compounds in question are in finely divided form (Suspension, optionally solution). If necessary, dispersants can be added during the treatment, such as. B.
  • soaps polyglycol ether of fatty alcohols, fatty amines or alkylphenols, cellulose sulfite waste liquor or condensation products of optionally alkylated naphthalenesulfonic acids with formaldehyde. It proves particularly useful to work in neutral, weakly alkaline or acid bath. It is also advantageous if the treatment is carried out at elevated temperatures of approximately 50 to 100 ° C., for example at the boiling point of the bath or in the vicinity thereof (approximately 90 ° C.). Solutions in organic solvents are also suitable for the refinement according to the invention, as is practiced in dyeing practice in the so-called solvent dyeing (pad heat-fixing application, pull-out dyeing process in drum dyeing machines), for example for polyamide and polyester substrates.
  • solvent dyeing pad heat-fixing application, pull-out dyeing process in drum dyeing machines
  • the new white toners to be used according to the invention can furthermore be added to or incorporated into the materials before or during their shaping.
  • they can be added to the molding compound or injection molding compound in the production of films, foils, tapes or moldings dissolve, disperse or otherwise ensure a homogeneous fine distribution in the spinning mass or before spinning.
  • the whiteners can also be added to the starting substances, reaction mixtures or intermediates for the production of fully or semi-synthetic organic materials, i.e. also before or during the chemical reaction, for example in the case of polycondensation (also including precondensates), in the case of polymerization (also including prepolymers) or one Polyaddition.
  • the new whiteners can of course also be used wherever organic materials of the type indicated above are combined with inorganic materials in any form (typical examples: detergents, white pigments in organic substances).
  • the new white-tinting substances are characterized by particularly good heat resistance, light fastness and migration resistance.
  • the amount of new white toners to be used according to the invention can vary within wide limits. Even with very small quantities, in certain cases e.g. B. those of 0.001 wt .-%, a clear and durable effect can be achieved. However, amounts of up to about 0.5% by weight and more can also be used. For most practical purposes, amounts between 0.01 and 0.2% by weight are preferably of interest.
  • the compounds of the formula given at the outset can be used as scintillators, for various purposes of a photographic nature, such as for electrophotographic reproduction or for supersensitization.
  • the combined treatment is advantageously carried out with the help of appropriate, stable preparations.
  • Such preparations are characterized in that they contain white-tinting compounds of the general formula given at the outset, as well as dispersants, detergents, carriers, dyes, pigments or finishing agents.
  • the heat treatment in the dry state is then advantageously carried out at temperatures between 120 and 225 ° C., for example by heating in a drying chamber, by ironing in the specified temperature interval or also by treatment with dry, superheated steam.
  • the drying and dry heat treatment can also be carried out immediately one after the other or combined in a single operation.
  • the dimethoxyphosphonomethyl compound of the formula used is manufactured in the following way:
  • a solution of 1 mol of sodium methylate in 1 liter of methanol is added dropwise to a suspension of 106.5 g (0.5 mol) of 2,3-dichloro-6-methylquinoxaline in 1 liter of methanol at 20 to 30 ° C. in the course of one hour.
  • the mixture is stirred at 40 ° C. for 5 hours and the solvent is distilled off in vacuo.
  • the residue is mixed with 1 liter of water and filtered off after cooling. 95.6 g (94% of theory) of colorless crystals with a melting point of 81 ° C. and recrystallized from methanol of 81 to 82 ° C. are obtained.
  • 2- (4-Formylphenyl) benzoxazole was prepared in a known manner by bromination of 2-tolylbenzoxazole and subsequent reaction with hexamethylenetetramine in acetic acid.
  • the compound is purified by recrystallization from dimethylformamide.
  • the compound of the formula is obtained in an analogous manner from the compound of the formula (7) by reaction with a) aniline and b) sodium ethylate in the form of yellow crystals, which are recrystallized from chlorobenzene and show a strong blue fluorescence in dimethylformamide.
  • the aldehyde of the formula also becomes analogous with the melting point 186 ° C in 65% yield.
  • Example 7 Analogously to Example 7, the compound of the formula is obtained from the aldehyde (28) and the corresponding phosphonate as yellow crystals, which are recrystallized from xylene and fluoresce greenish blue in dimethylformamide.
  • Example 7 Analogously to Example 7, the compound of the formula is obtained from 2,3-dimethoxy-6-formylquinoxaline and 5,6-dimethoxy-2- (4-diethoxyphosphonomethylphenyl) -2H-benzotriazole as pale yellow crystals that show blue fluorescence in dimethylformamide.
  • Example 1 the compound of the formula is obtained from 5-biphenylyl-2- (4-formylphenyl) -1,3,4-oxdiazole and 2,3-dibutoxy-6-diethoxyphosphonomethylquinoxaline in 80% yield in the form of light yellow crystals, which are recrystallized from xylene and fluoresce reddish blue in dimethylformamide.
  • the compound of the formula is obtained from 2,3-diethoxy-6-formyl-quinoxaline and 2-methoxy-4-formylbenzoic acid as pale yellow crystals, which show a reddish blue fluorescence in dimethylformamide.

Claims (7)

1. Colorants fluorescents, caractérisés en ce qu'ils répondent à la formule:
Figure imgb0067
dans laquelle
X et Y représentent de l'hydrogène, un halogène, un groupe alkyle, aralkyle, alcényle, hydroxy, amino, alkoxy, aralkoxy, cycloalkoxy, aryloxy, alkylmercapto, alkylamino, dialkylamino, morpholino, pipéridino, pi- pérazino, pyrrolidino, acylamino, arylamino,
Q est un atome d'hydrogène ou un groupe pyrazo- le-1-yle, oxazole-2-yle, benzoxazole-2-yle, naphtoxa- zole-2-yle, 1,2,4-oxadiazole-5-yle, 1,3,4-oxadiazole-2-yle, isoxazole-3-yle, isoxazole-5-yle, thiazole-2-yle, benzothiazole-2-yle, 1,3,4-thiadiazole-2-yle, imidazo- le-2-yle, benzimidazole-2-yle, 1,2,3-triazole-2-yle, 1,2,3-triazole-4-yle, 1,2,4-triazole-3-yle, 1,2,4-triazo- le-5-yle, 1,3,5-triazine-2-yle, 2H-benzotriazole-2-yle, 2H-naphtotriazole-2-yle, 1,2,3,4-tétrazole-5-yle, 1,2,3,4-tétrazole-1-yle, benzo[b]-furanne-2-yle, naph- to[2,1]-furanne-2-yle, benzo[b]-thiophène-2-yle, naphto[2,1-b]-thiophène-2-yle, pyrimidine-2-yle, pyridine-2-yle, quinazoline-4-yle ou quinazoline-2-yle, et
n est égal à 1 ou 2, les substituants X, Y, Q et les autres restes cycliques pouvant encore porter d'autres substituants non chromophores classiques pour des azurants optiques.
2. Colorants fluorescents suivant la revendication 1, caractérisés en ce que n est égal à 1.
3. Colorants fluorescents suivant la revendication 1, caractérisés en ce qu'ils répondent à la formule :
Figure imgb0068
X1 et Y1 représentent de l'hydrogène, du chlore, un groupe alkylamino en C1 à C4, di-(alkyle en C1 à C4)-amino, morpholino, pipéridino, phénylamino éventuellement substitué par un radical méthyle, méthoxy ou chloro, ou un reste de formule:
Figure imgb0069
R1 est un atome d'hydrogène ou de chlore ou un groupe alkyle en C1 à C4, alkoxy en C1 à C4, (alkoxy en C1 à C4)-carbonyle ou cyano,
R2 est un atome d'hydrogène ou un groupe alkyle en C1 à C4, benzyle ou phényle,
q est un nombre entier ayant une valeur de 0 à 7 et Q1 est un radical chloro, bromo, cyano, carboxy, (alkoxy en C1 à C4)-carbonyle ou un reste de formule :
Figure imgb0070
Figure imgb0071
R3 représente de l'hydrogène, du chlore, un groupe alkyle en C1 à C4, phényl-(alkyle en C1 à C3), cyclohexyle, phényle, alkoxy en C1 à C4, (alkyle en C1 à C4)-sulfonyle, (alkoxy en C1 à C4)-carbonyle, cyano ou carboxy ou forme avec R4 un noyau 1-cyclopenté- nique, 1-cyclohexénique ou benzénique condensé, substitué le cas échéant par 1 à 4 groupes méthyle,
R4 représente de l'hydrogène, du chlore ou un groupe méthyle ou forme avec R3 un noyau 1-cyclopenténique, 1-cyclohexénique ou benzénique condensé, éventuellement substitué par 1 à 4 groupes méthyle,
R5 est un groupe alkyle en C1 à C4, phényle ou styryle ou forme avec R6 un noyau benzénique condensé éventuellement substitué par un groupe alkyle en C1 à C4, un groupe alkoxy en Ci à C4 ou du chlore, ou un noyau naphtalénique condensé,
R6 représente de l'hydrogène, un groupe alkyle en C1 à C4 ou un groupe phényle ou forme avec R5 un noyau benzénique condensé, éventuellement substitué par un groupe alkyle en C1 à C4, un groupe alkyle en C1 à C4, un groupe alkoxy en C1 à C4 ou du chlore, ou un noyau naphtalénique condensé,
R7 est un groupe phényle éventuellement substitué par un radical alkyle en C1 à C4, alkoxy en C1 à C4, (alkoxy en C1 à C4)-carbonyle, cyano ou chloro ou un groupe styryle, biphénylyle ou naphtyle,
R8 est un atome d'hydrogène, un groupe alkyle en C1 à C4, alkoxy en Ci à C4, (alkoxy en Ci à C4)-carbonyle, cyano, ou un reste benzoxazole-2-yle éventuellement substitué par un radical (alkoxy en Ci à C4)-carbonyle, cyano ou chloro,
Z représente un atome d'oxygène ou de soufre ou un groupe NR9 et
Rg est un atome d'hydrogène ou un groupe alkyle en C1 à C4, acétyle, benzoyle, benzyle ou phényle.
4. Colorants fluorescents suivant la revendication 3, caractérisés en ce qu'ils répondent à la formule :
Figure imgb0072
R10 est un groupe alkyle en C1 à C4,
R11 est un atome d'hydrogène ou un groupe cyano,
r est un nombre entier égal à 0, 1 ou 2,
Q2 est un reste de formule:
Figure imgb0073
R12 représente de l'hydrogène, du chlore, un groupe alkyle en C1 à C4, phényl-(alkyle en C1 à C3), cyclohexyle, phényle, alkôxy en C1 à C4, (alkyle en C1 à C4)-sulfonyle, (alkoxy en C1 à C4)-carbonyle, cyano ou carboxy et
R5, R6 et R7 ont les définitions données dans la revendication 3.
5. Procédé de production de colorants fluorescents suivant la revendication 1, caractérisé en ce qu'il consiste à condenser ou bien un composé phosphono de formule:
Figure imgb0074
(dans laquelle
X et Y ont les définitions données dans la revendication 1, le noyau benzénique pouvant porter d'autres substituants non chromophores, et
R,3 et R14 représentent un groupe alkoxy en C1 à C4, cycloalkoxy en C5 ou C6, phényle ou phénoxy), avec un aldéhyde de formule:
Figure imgb0075
(dans laquelle
Y et n ont les définitions données dans la revendication 1 et le noyau benzénique peut porter d'autres substituants non chromophores), ou bien
un composé phosphono de formule:
Figure imgb0076
(dans laquelle
Q, R13 et R14 et n ont les définitions données dans la revendication 1 et le noyau benzénique peut porter d'autres substituants non chromophores) avec un aldéhyde de formule:
Figure imgb0077
(dans laquelle
X et Y ont les définitions données dans la revendication 1 et le noyau benzénique peut porter des substituants non chromophores),
dans des solvants organiques, en présence d'agents basiques de condensation.
6. Procédé d'azurage optique de matières organiques de haut poids moléculaire, synthétiques, semi-synthétiques et naturelles, caractérisé en ce qu'il consiste à utiliser les colorants fluorescents suivant la revendication 1.
7. Des matières organiques de haut poids moléculaire synthétiques, semi-synthétiques et naturelles azurées optiquement avec les colorants fluorescents suivant la revendication 1.
EP78100253A 1977-07-07 1978-06-28 Composés quinoxaliniques, leur procédé de préparation et leur utilisation pour le blanchiment optique de matières organiques et les matières ainsi blanchies Expired EP0000346B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2730644 1977-07-07
DE19772730644 DE2730644A1 (de) 1977-07-07 1977-07-07 Fluoreszenz-farbstoffe

Publications (2)

Publication Number Publication Date
EP0000346A1 EP0000346A1 (fr) 1979-01-24
EP0000346B1 true EP0000346B1 (fr) 1980-01-09

Family

ID=6013331

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100253A Expired EP0000346B1 (fr) 1977-07-07 1978-06-28 Composés quinoxaliniques, leur procédé de préparation et leur utilisation pour le blanchiment optique de matières organiques et les matières ainsi blanchies

Country Status (4)

Country Link
US (1) US4184977A (fr)
EP (1) EP0000346B1 (fr)
JP (1) JPS5417933A (fr)
DE (2) DE2730644A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297234A (en) * 1979-05-17 1981-10-27 Ciba-Geigy Corporation Benzoxazolyl-stilbenes
US4346016A (en) * 1980-04-23 1982-08-24 Ciba-Geigy Corporation 6-Styrylquinoxalines, and their use as fluorescent brighteners
JPH0636370B2 (ja) * 1984-01-24 1994-05-11 日本電信電話株式会社 リチウム二次電池用電解液
WO2000056274A1 (fr) * 1999-03-23 2000-09-28 Pyramid Productions, Inc. Composition colorante pour le corps
US6723445B2 (en) 2001-12-31 2004-04-20 Canon Kabushiki Kaisha Organic light-emitting devices
JP4780372B2 (ja) * 2005-03-02 2011-09-28 独立行政法人産業技術総合研究所 キノキサリンジオン誘導体及びその製造方法並びにその用途

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH484918A (de) * 1965-10-28 1970-01-31 Ciba Geigy Verfahren zur Herstellung heterocyclischer, Aethylendoppelbindungen enthaltender Verbindungen
CH540247A (de) * 1967-04-21 1973-09-28 Ciba Geigy Ag Verfahren zur Herstellung von heterocyclischen, Asthylendoppelbindungen enthaltenden Verbindungen
US3684729A (en) * 1969-10-02 1972-08-15 Robert J Tuite Brightener compositions
BE758359A (fr) * 1969-11-03 1971-04-16 Bayer Ag Eclaicissants de la serie des oxadiazolylstyrylbenzotriazols
US3872114A (en) * 1971-02-05 1975-03-18 Hoechst Ag Benzofurane derivatives, process for their manufacture and their use as optical brighteners
GB1457400A (en) * 1972-11-20 1976-12-01 Pfizer Pharmaceutical compositions containing 2-substituted quinoxa lines
CH305975A4 (fr) * 1975-03-11 1977-08-15

Also Published As

Publication number Publication date
EP0000346A1 (fr) 1979-01-24
US4184977A (en) 1980-01-22
JPS5417933A (en) 1979-02-09
DE2857515D1 (en) 1980-02-14
DE2730644A1 (de) 1979-01-25

Similar Documents

Publication Publication Date Title
DE1594834B1 (de) Optische Aufhellmittel
US4167628A (en) Novel benzoxazole compounds
EP0003784A1 (fr) Composés de distyryle, leur préparation et leur application comme produits de blanchiment et matière colorante pour lasers
DE1294923B (de) Optische Aufhellmittel
EP0136259B1 (fr) Hétérocyclyl-4-styryl-4' biphényles
EP0030917B1 (fr) Agents de blanchiment optique de la série des bistyrylbenzènes, procédé pour leur préparation et leur utilisation
DE1594861B2 (de) Verfahren zum stufenweisen Blei chen von Cellulosematerial
EP0000346B1 (fr) Composés quinoxaliniques, leur procédé de préparation et leur utilisation pour le blanchiment optique de matières organiques et les matières ainsi blanchies
DE2712686C2 (de) 4-Triazinyl-4'-benzoxazolyl- bzw. 4'-phenyl-stilben-derivate
DE1794400C3 (de) Verwendung von 4,4'-disubstituierten Stilbenderivaten als optische Aufhellungsmittel
DE2535612A1 (de) Neue stilbenverbindungen
DE2535613A1 (de) Neue stilbenverbindungen
EP0009095B1 (fr) Dérivés de la 1.3.4-oxadiazole-2-one, procédés pour leur préparation et leur utilisation comme azurants optiques
EP0002042A1 (fr) Composés diaminés de 1,3,5-triazinylstilbène, leur procédé de préparation et leur emploi comme azurants optiques
EP0020298B1 (fr) Composés benzoxazolyl-stilbène, procédé pour leur préparation et leur utilisation comme azurants optiques pour matières organiques
DE2309614A1 (de) Azolverbindungen, verfahren zu deren herstellung und deren verwendung
DE2331444A1 (de) Neue styryl-benzoxazole, verfahren zu deren herstellung und ihre verwendung als optische aufhellungsmittel
DE2650456A1 (de) Fluoreszenzfarbstoffe
DE2060288A1 (de) Neue Bis-aroxazolyl-Verbindungen,Verfahren zu deren Herstellung und deren Verwendung
DE2535615A1 (de) Verfahren zur herstellung von styrolderivaten, neue styrolderivate und deren verwendung als optische aufhellmittel
DE2609421A1 (de) Neue benzoxazol-styryle
CH532629A (de) Verfahren zum optischen Aufhellen mit neuen Bis-aroxazolyl-Verbindungen
DE2712409A1 (de) Neue 4-(v-triazolyl)-styrylverbindungen
EP0022491A1 (fr) Composés stilbéniques, procédé pour leur préparation et leur utilisation comme agents de blanchiment optique
DE2554027A1 (de) Neue triazolverbindungen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): CH DE FR GB

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): CH DE FR GB

REF Corresponds to:

Ref document number: 2857515

Country of ref document: DE

Date of ref document: 19800214

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19830701

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840526

Year of fee payment: 7

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19850228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19870303

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881117

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19890622

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19900630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT