EP0000346A1 - 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

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Publication number
EP0000346A1
EP0000346A1 EP78100253A EP78100253A EP0000346A1 EP 0000346 A1 EP0000346 A1 EP 0000346A1 EP 78100253 A EP78100253 A EP 78100253A EP 78100253 A EP78100253 A EP 78100253A EP 0000346 A1 EP0000346 A1 EP 0000346A1
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EP
European Patent Office
Prior art keywords
alkyl
hydrogen
formula
chlorine
phenyl
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Granted
Application number
EP78100253A
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German (de)
English (en)
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EP0000346B1 (fr
Inventor
Udo Dr. Eckstein
Hans Dr. Theidel
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Bayer AG
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Bayer AG
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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 Table
    • 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

  • the invention relates to fluorescent dyes, processes for their preparation and their use for whitening organic materials.
  • non-chromophoric substituents are halogen, optionally substituted alkyl, optionally substituted alkenyl, aryl, aralkyl, optionally substitutedx 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, -C 4 alkyl substituted by hydroxy, C 1 -C 4 alkoxy, cyano, carboxy, C 1 -C 4 alkoxycarbonyl, aminocarbonyl, chloro or bromo may be mono-substituted 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 optionally substituted by C, -C 4 alkyl, trifluoromethyl, chlorine, bromine, carboxy, cyano, C 1 -C 4 -alkoxycarbonyl or C 1 -C 4 -alkoxy-substituted phenyl.
  • Aralkyl is in particular phenyl-C 1 -C 4 -alkyl, which can also be substituted by chlorine, methyl or methoxy in the phenyl nucleus.
  • Cycloalkyloxy is especially cyclopentyloxy and cyclohexyloxy.
  • Acyl is especially C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkylsulfonyl, benzoyl optionally substituted by methyl, methoxy or chlorine or benzenesulfonyl optionally substituted by methyl, methoxy or chlorine.
  • substituents of the aminocarbonyl and aminosulfonyl radicals there are in particular C 1 -C 4 alkyl, if appropriate phenyl or phenyl-C 1 -C 4 -alkyl substituted by methyl, methoxy or chlorine in question.
  • 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 .
  • the compounds according to the invention are suitable for whitening a wide variety of synthetic, semisynthetic and natural organic high-molecular materials, as are indicated individually below.
  • Polyesters saturated (eg polyethylene terephthalate) or unsaturated (eg maleic acid dialcohol polycondensates and their crosslinking products with polymerizable vinyl monomers), unbranched and branched (also based on higher alcohols, such as alkyd resins); Polyamides (e.g. hexamethylenediamine adipate), maleate resins, melamine resins, phenolic resins,
  • Aniline resins furan resins, carbamide resins or their precondensates and analog products, polycarbonates, silicone resins and others.
  • polyaddition products such as polyurethanes (crosslinked and uncrosslinked), epoxy resins.
  • Semi-synthetic organic materials such as Cellulose esters or mixed esters (acetate, propionate), nitrocellulose, cellulose ethers, regenerated cellulose (viscose, copper ammonia cellulose) or their after-treatment products, casein plastics.
  • Natural organic materials of animal or vegetable origin for example based on cellulose or proteins, such as wool, cotton, silk, bast, jute, hemp, skins and hair, leather, wood mass in finely divided form, natural resins (such as rosin, in particular lacquer resins) Rubber, gutta-percha, balata, as well as their after-treatment and modification products (e.g. through hardening, crosslinking or grafting), degradation products (e.g. through hydrolysis, depolymerization), products obtainable through modification of reactive groups (e.g. through acylation, halogenation, crosslinking, etc.).
  • natural resins such as rosin, in particular lacquer resins
  • Rubber gutta-percha, balata
  • degradation products e.g. through hydrolysis, depolymerization
  • products obtainable through modification of reactive groups e.g. through acylation, halogenation, crosslinking, etc.
  • the organic materials in question can be in a wide variety of processing states (raw materials, semi-finished or finished products) and physical states. You can once in the form of ver a wide variety of shaped structures are present, that is to say, for example, predominantly three-dimensionally extended bodies such as blocks, plates, profiles, pipes, injection moldings or a wide variety of 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.
  • the said materials can also be in unshaped states in the most varied of homogeneous and inhomogeneous distribution forms and aggregate states, for example as powders, solutions, emulsions, dispersions, latices (examples: lacquer solutions, polymer dispersions, brine, jelly, putty, pastes, waxes, Adhesives and fillers etc.).
  • Fiber materials can be present, for example, as endless threads, staple fibers, flakes, stranded goods, textile threads, yarns, twists, non-woven fabrics, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics, as well 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 present as 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 present in finely divided form (suspension, optionally solution).
  • dispersants can be added during the treatment, such as soaps, polyglycol ethers of fatty alcohols, fatty amines or alkylphenols, cellulose sulphite waste liquor or condensation products of optionally alkylated naphthalenesulphonic 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 deformation.
  • they can be added to the molding compound or injection molding compound in the production of films, foils, tapes or moldings, or they can be dissolved, dispersed or otherwise used in the spinning compound before spinning ensure homogeneous fine distribution.
  • 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 white toners 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 the 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. of 0.001% by weight, 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 procedure is expediently such that these fibers are mixed with the aqueous dispersions of the white toners at temperatures below 75 ° C, e.g. at room temperature, impregnated and subjected to a dry heat treatment at temperatures above 100 ° C, where it is generally advisable to previously the fiber material at a moderately elevated temperature, e.g. dry at least 60 ° C to about 100 ° C.
  • 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 suspension of 106.5 g (0.5 mol) of 2,3-dichloro-6-methylquinoxaline in 1 liter of methanol is added dropwise at 20 to 30 ° C. a solution of 1 mol of sodium methylate in 1 liter of methanol within 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 1 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.
  • a mixture is dispensed in portions at 60 ° C. within 20 minutes at 60 ° C. to a solution of 40.8 g (0.2 mol) of 2,3-dimethoxy-6-methyl-quinoxaline and 0.2 g of dibenzoyl peroxide in 300 ml of anhydrous carbon tetrachloride 35.6 g (0.2 mol) of N-bromosuccinimide and 0.2 g of azoisobutyronitrile and stirred at the reflux temperature for 4 hours.
  • the succinimide is then filtered off, the filter cake is washed with hot carbon tetrachloride and the filtrate is evaporated to almost dryness.
  • the residue is filtered off and washed with petroleum ether (40 to 80 ° C.). 41.4 g (73% of theory) of bromomethyl compound, mp. 149 ° 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.
  • Chlorobenzene gives pale yellow crystals, the solution of which in dimethylformamide shows an intense reddish blue fluorescence.
  • 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 0 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-diethoxyphosponomethylphenyl) -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.
  • 36 g of 30 are added dropwise to a solution of 31.2 g (0.1 mol) of 2,3-dimethoxy-6-dimethoxyphosphonomethylquinoxaline and 18.2 g (0.1 mol) of 4-formylbiphenyl in 200 ml of dimethylformamide in 20 minutes % sodium methylate solution and allowed to stir at 50 ° C for 5 hours. Then diluted with 100 ml of methanol and adjusted to pH 4 to 5 with acetic acid.
  • the compound of the formula is obtained from 2,3-diethoxy-6-formylquinoxaline and 2-methoxy-4-formylbenzoic acid as pale yellow crystals, which show a reddish blue fluorescence in dimethylformamide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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 true EP0000346A1 (fr) 1979-01-24
EP0000346B1 EP0000346B1 (fr) 1980-01-09

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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
EP1162936B1 (fr) * 1999-03-23 2011-07-13 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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2206951A1 (fr) * 1972-11-20 1974-06-14 Pfizer

Family Cites Families (6)

* 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
CH603881B5 (fr) * 1975-03-11 1978-08-31 Ciba Geigy Ag

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2206951A1 (fr) * 1972-11-20 1974-06-14 Pfizer

Also Published As

Publication number Publication date
EP0000346B1 (fr) 1980-01-09
US4184977A (en) 1980-01-22
JPS5417933A (en) 1979-02-09
DE2730644A1 (de) 1979-01-25
DE2857515D1 (en) 1980-02-14

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