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DE2002893A1 - Pyrene compounds, their manufacture and use - Google Patents

Pyrene compounds, their manufacture and use

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Publication number
DE2002893A1
DE2002893A1 DE19702002893 DE2002893A DE2002893A1 DE 2002893 A1 DE2002893 A1 DE 2002893A1 DE 19702002893 DE19702002893 DE 19702002893 DE 2002893 A DE2002893 A DE 2002893A DE 2002893 A1 DE2002893 A1 DE 2002893A1
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formula
group
compounds
further substituents
alkyl
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German (de)
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Mueller Dr Curt
Zirngibl Dr Ulrich
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Sandoz AG
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Sandoz AG
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182Radicals derived from carboxylic acids
    • C07D295/185Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • C07C255/01Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/41Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/57Nitriles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/0033Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being bound through a sulfur atom
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00Systems containing at least three condensed rings
    • C07C2603/02Ortho- or ortho- and peri-condensed systems
    • C07C2603/40Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • C07C2603/50Pyrenes; Hydrogenated pyrenes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Description

KCiäKCiä

Dr. W. ScLu.. D\A I.-.g. P. WirtS Dr. W. ScLu .. D \ A I .-. G. P. WirtS

Dipi.-ina O. Dc.^-vibsrgDipi.-ina O. Dc. ^ - vibsrg

Dr. V. Schmi.-J-lv«. svarzikDr. V. Schmi.-J-lv «. svarzik

Dr. P. YvVnHoId, Df. D. Gudel Dr. P. YvVnHoId, Df. D. Gudel

6 Frankfurt/M., Gr. Eschenheimer Str. 326 Frankfurt / M., Gr. Eschenheimer Str. 32

SANDOZ AG . *SANDOZ AG. *

Basel / Schweiz Basel, Switzerland Case 15-303*»·Case 15-303 * »·

Pyrenverbindungen, ihre Herstellung und Verwendung.Pyrene compounds, their manufacture and use.

Gegenstand der Erfindung sind Pyrenverbindungen, die sich ausgezeichnet zum Färben oder Bedrucken von Pasern oder Fäden oder daraus hergestellten Materialien aus voll- oder halbsynthetischen, hydrophoben, hochmolekularen organischen Stoffen * eignen. The invention relates to pyrene compounds which are extremely suitable for dyeing or printing fibers or threads or materials made from them made from fully or semi-synthetic, hydrophobic, high molecular weight organic substances * .

Die neuen Verbindungen entsprechen der Formel The new compounds correspond to the formula

/A/ A

CH = C^ (I),CH = C ^ (I),

XCN X CN

worin A eine Cyangruppe, einen Acylrest oder ein gegebenen-wherein A is a cyano group, an acyl radical or a given

009831/1160009831/1160

falls weitere Substituenten tragendes heterocyclisches Ringsystem aromatischen Charakters bedeutet und der Pyrenkern weitere Substituenten tragen kann.if further substituents bearing heterocyclic Means ring system of aromatic character and the pyrene nucleus can carry further substituents.

Als Acylreste kommen insbesondere solche der Formeln -CO-R, -CO-OR, -CO-NR1R" oder -SO2-R in Betracht, wobeiParticularly suitable acyl radicals are those of the formulas -CO-R, -CO-OR, -CO-NR 1 R "or -SO 2 -R, where

wobei R einen gegebenenfalls weitere Substituenten tragenden aliphatischen, cycloaliphatischen oder aromatischen Rest,where R is an aliphatic, cycloaliphatic or aromatic which may carry further substituents Rest,

R1 und Rn unabhängig voneinander Wasserstoff oder R bedeuten,R 1 and R n are independently hydrogen or R,

und die Reste R1 und Rw zusammen mit dem an sie gebundenen Stickstoffatom gegebenenfalls einen Ring bilden können, der noch weitere Heteroatome, insbesondere -0-, -S- oder eine Gruppe -NR1- enthalten kann.and the radicals R 1 and R w together with the nitrogen atom bonded to them can optionally form a ring which can contain further heteroatoms, in particular -0-, -S- or a group -NR 1 -.

Bevorzugte aliphatische Reste sind Alkylreste, als cycloaliphatischer Rest ist der Cyclohexylrest und als aromatischer Rest der Phenyl- oder Naphthylrest bevorzugt.Preferred aliphatic radicals are alkyl radicals, the cyclohexyl radical is preferred as the cycloaliphatic radical and the phenyl or naphthyl radical is preferred as the aromatic radical.

Besonders geeignete heterocyclische Ringsysteme aromatischen Charakters sind z.B. Pyridyl-, Chinolyl-, Benzthiazolyl- und Benzimidazolylreste.Particularly suitable heterocyclic ring systems of aromatic character are, for example, pyridyl, quinolyl, benzthiazolyl and Benzimidazolyl radicals.

Als Substituenten an den aliphatischen Resten kommen z.B. Alkoxy-, Alkoxyalkoxy-, Cyan-, Rhodan-, Hydroxy-, Acyl- (wie oben beschrieben), Acyloxygruppen und Halogenatome in Betracht, Suitable substituents on the aliphatic radicals, for example alkoxy, alkoxyalkoxy, cyano, thiocyanate, hydroxy, acyl come (as described above), acyloxy groups and halogen atoms into consideration,

009831/1160009831/1160

die Cyclohexylreste können diese Substituenten und z.B. noch 'Alkyl- oder Alkoxyalkylgruppen tragen und die Kerne aromatischen Charakters können neben den erwähnten Substituenten z.B. noch Nitrogruppen tragen. Unter Halogenatomen sind vor allem die in Ihren Eigenschaften äusserst ähnlichen Chlor- und Bromatome gemeint. Alle Alkylreste sind im allgemeinen "niedrigraolekular", Aas heisst, sie enthalten 1,2,3 oder 4 Kohlenstoffatome.the cyclohexyl radicals can have these substituents and e.g. still 'Carry alkyl or alkoxyalkyl groups and the nuclei of aromatic character can, in addition to the substituents mentioned, e.g. Wear nitro groups. Among the halogen atoms are, above all, the chlorine and bromine atoms, which are extremely similar in terms of their properties meant. All alkyl radicals are generally "low molecular weight", Aas means that they contain 1, 2, 3 or 4 carbon atoms.

Bevorzugte Verbindungen der Formel (I) entsprechen der FormelPreferred compounds of the formula (I) correspond to the formula

CH - c' (II)·,CH - c '(II),

Nri No. i

worin R, «ine Gruppe der Formel -CN, -COR., -COOR3, -SO2Rwherein R, «a group of the formula -CN, -COR., -COOR 3 , -SO 2 R

«ine Alkyl-, Phenyl-, Nitrophenyl-, Toluyl-, Amino-, Alkylamino-, Dialkylamino-, Alkoxyalkylamino-, Aminotarbonylamino-, Phenylamlno-, Chlorphenylamino-, Bromphenylanlno-, Alkylphenylamlno-, Alkoxyphenyliftlno-, Nethoxyoarbonylphenylamlno-, Aethoxycarbonylphenylamino-, Naphthylamino-, Cyclohexylamino-, N-Fiperidyl- oder N-Morpholylgruppe und«Ine alkyl, phenyl, nitrophenyl, toluyl, amino, Alkylamino, dialkylamino, alkoxyalkylamino, aminotarbonylamino, phenylamino, chlorophenylamino, Bromophenylamino, alkylphenylamino, alkoxyphenylamino, nethoxyoarbonylphenylamino, ethoxycarbonylphenylamino, naphthylamino, cyclohexylamino, N-fiperidyl or N-morpholyl and

009831/1160009831/1160

R, eine Alkylgruppe, die durch eine Alkoxygruppe substituiert sein kann,R, an alkyl group which can be substituted by an alkoxy group,

bedeuten, wobei alle erwähnten Alkylreste 1,2,3 oder 4 Kohlenstoff atome enthalten.mean, where all mentioned alkyl radicals contain 1, 2, 3 or 4 carbon atoms.

Besonders bevorzugt sind unter den neuen Verbindungen diejenigen der FormelParticularly preferred among the new compounds are those of the formula

CNCN

CH β 'CH β '

worin R. einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeutet und Gemische aus Verbindungen dieser Formel.wherein R. denotes an alkyl radical having 1 to 4 carbon atoms and Mixtures of compounds of this formula.

Gemische aus 2 oder 3 Farbstoffen der Formel (I) oder, insbe-■ sondere, Formel (III) zeichnen sich in applikatorischer Hinsicht, durch besseres Zieh-, Aufbau- und Egalisiervermögen beim Ausziehverfahren und durch bessere Farbausbeute bzw. tiefere Färbungen beim sogenannten Thermosölverfahren aus.Mixtures of 2 or 3 dyes of the formula (I) or, in particular, formula (III) are distinguished from the application point of view by better drawing, build-up and leveling properties Exhaust process and through better color yield or deeper Discolouration in the so-called thermal oil process.

Die Herstellung der neuen Verbindungen erfolgt durch Kondensation eines Mol eines gegebenenfalls substituierten Pyrenaldehyds der FormelThe new compounds are prepared by condensation of one mole of an optionally substituted pyrenaldehyde of the formula

009831/1160009831/1160

CHO (IV)CHO (IV)

mit einem Mol einer Verbindung der Formelwith one mole of a compound of the formula

,CN, CN

wobei aber auch ein Ueberschuss der Verbindung der Formel (V)but also an excess of the compound of the formula (V)

bei der Reaktion vorhanden sein kann. M may be present in the reaction. M.

Die Umsetzung der Verbindungen der Formeln (IV) und (V) findet im allgemeinen in organischen Lösungsmitteln, vorzugsweise Alkoholen statt; als nicht limitative Beispiele seien Methanol, Aethanol, Propanol, Butanol, Pentanol, Hexanol, oder deren Isomere genannt, es eignen sich aber auch andere Lösungsmittel, z.B. Aether, Ester oder Amide, es seien genannt : Diisopropyläther, Dioxan, Tetrahydrofuran, Dimethoxyäthan, Diäthoxyäthan, Methoxyäthanol, Aethoxyäthanol, Aethylacetat, Dimethylformamid, ^ Dimethylacetamid, Dimethylsulfoxid oder bei den Reaktionsbedingungen noch flüssige Kohlenwasserstoffe.The reaction of the compounds of the formulas (IV) and (V) generally takes place in organic solvents, preferably Alcohol instead; non-limiting examples are methanol, ethanol, propanol, butanol, pentanol, hexanol, or their isomers but other solvents are also suitable, e.g. ethers, esters or amides, such as: diisopropyl ether, Dioxane, tetrahydrofuran, dimethoxyethane, diethoxyethane, Methoxyethanol, ethoxyethanol, ethyl acetate, dimethylformamide, ^ Dimethylacetamide, dimethyl sulfoxide or in the reaction conditions still liquid hydrocarbons.

Es ist vorteilhaft, in Gegenwart kleiner Mengen (bis etwa 10 Mol % auf Pyrenaldehyd bezogen) basischer, vorzugsweise organischer, Katalysatoren, z.B. Pyridin, Pyrrolidin, Piperidin und/ oder quaternärer Stickstoffbasen zu arbeiten, man kann aber auch anorganische Basen zugeben, z.B. KOH, wobei der pH-Wert der Lösung zwischen 8 und 10 gehalten werden soll.It is advantageous to work in the presence of small amounts (up to about 10 mol % based on pyrenaldehyde) of basic, preferably organic, catalysts, e.g. pyridine, pyrrolidine, piperidine and / or quaternary nitrogen bases, but you can also add inorganic bases, e.g. KOH, the pH of the solution should be kept between 8 and 10.

009831/1180'009831/1180 '

Die Reaktion erfolgt, gegebenenfalls unter Rühren, bei Temperatüren zwischen 40° und etwa 2000C in einem mit Rückflusskühler versehenen Gefäss, möglichst bei Siedetemperatur der Lösung, wobei aber auf die Dampfflüchtigkeit und die Beständigkeit der Katalysatoren und der Verbindungen der Formel (V) hingewiesen wird.The reaction is performed, optionally with stirring, at tempera doors between 40 ° and about 200 0 C in a vessel equipped with a reflux condenser vessel, preferably at the boiling point of the solution, but where and durability of the catalysts, and the compounds of formula (V) drawn to the vapor volatility will.

Die Reaktionsdauer beträgt im allgemeinen 2 bis 10 Stunden. Nach Beendigung der Reaktion und nach Abkühlen des Reaktionsgemisches wird der entstandene Niederschlag, gegebenenfalls nach Einengen, abgesaugt, gegebenenfalls z.B. mit Methanol und Wasser gewaschen, und getrocknet.The reaction time is generally 2 to 10 hours. After the reaction has ended and after the reaction mixture has cooled the precipitate formed, if necessary after concentration, is suctioned off, if necessary e.g. with methanol and Water washed, and dried.

Die so erhaltenen Farbstoffe eignen sich ausgezeichnet zum Färben oder Bedrucken von voll- oder halbsynthetischem Textilmaterial aus hydrophoben, hochmolekularen organischen Fasern, in brillanten, gelben oder grünstichig gelben Tönen.The dyes obtained in this way are extremely suitable for dyeing or printing fully or semi-synthetic textile material Made of hydrophobic, high molecular weight organic fibers, in brilliant, yellow or greenish yellow tones.

Es ist besonders vorteilhaft, die so erhaltenen neuen Farbstoffe vor ihrer Verwendung in Färbepräparate überzuführen. Die Verarbeitung zu Färbepräparaten erfolgt auf allgemein bekannte Weise, z.B. durch Mahlen in Gegenwart von Dispergler- und/oder Füllmitteln. Mit den gegebenenfalls im Vakuum oder durch Zerstäuben getrockneten Präparaten kann man, nach Zugabe von mehr oder weniger Wasser, in sogenannter langer oder kurzer Flotte färben, klotzen oder bedrucken.It is particularly advantageous to use the new dyes thus obtained to be converted into dye preparations before use. The processing to dye preparations is carried out in a generally known manner, e.g. by grinding in the presence of dispersing agents and / or fillers. With the preparations, which may have been dried in vacuo or by atomization, after the addition of more or less Dye, pad or print water in a so-called long or short liquor.

009831/1160009831/1160

Die Farbstoffe ziehen aus wässriger Suspension ausgezeichnet auf Textilmaterial aus voll- oder halbsynthetischen, hydrophoben« hochmolekularen organischen Stoffen auf. Besonders geeignet sind sie sum Färben oder Bedrucken von Textilmaterial aus linearen, aromatischen Polyestern, sowie aus Cellulose-2 1/2-aoetat, Cellulosetriacetat und synthetischen Polyamiden. Auch Polyolefine lassen sich mit ihnen färben.The dyes pull out of aqueous suspension excellently on textile material made of fully or semi-synthetic, hydrophobic « high molecular weight organic substances. They are particularly suitable for dyeing or printing textile material made of linear, aromatic polyesters, as well as from cellulose-2 1/2-aoetat, Cellulose triacetate and synthetic polyamides. They can also be used to color polyolefins.

Man färbt nach an sich bekannten, z.B. dem in der französischen Patentschrift 11° 1 4*5 571 beschriebenen Verfahren. Polyesterfasern können in Gegenwart von Carrlern bei Temperaturen zwi- sohen etwa 8O° und 1230C nach dem Ausziehverfahren gefärbt werden. Vorzüglich eignen sich die neuen Farbstoffe für die Applikation im Themosolverfahren. Nach diesem werden Polyesterfasern mit den wässrigen Dispersionen der neuen Farbstoffe geklotzt oder bedruckt und die erhaltene Imprägnierung bei etwa ]AO° bis 230° fixiert, z.B. mit Hilfe von Wasserdampf oder Luft. The dyeing is carried out according to the process known per se, for example the process described in French patent 11 ° 14 * 5 571. Polyester fibers can be in the presence of Carrlern at temperatures be- sohen about 8O ° and 123 0 C by the exhaust dyed. The new dyes are particularly suitable for application in the Thermosol process. After this, polyester fibers are padded or printed with the aqueous dispersions of the new dyes and the impregnation obtained is fixed at about] AO ° to 230 °, for example with the aid of steam or air.

Die erhaltenen brillanten, gelben Färbungen besitzen sehr gute Allgemelneohthjeiten ; besonders die Licht-, Wasch-, Schweiss-, Thermofixier-, Sublinler- und Plissierechtheit sind hervorzuheben. Bemerkenswert sind auch die Wollreserve, die Reduktionsstabilität (s.B. Sulfidechtheit), die Hydrolysenstabilität, die Beständigkeit gegenüber der Permanent-Press-Behandlung und die geringe Anfälligkeit gegenüber katalytischem Verschiessen (Catalytic Fading).The brilliant yellow colorations obtained have very good general properties; especially the light, washing, welding, Thermosetting, sublining and pleating fastness are to be emphasized. Also noteworthy are the wool reserve, the reduction stability (see e.g. sulfide fastness), the hydrolysis stability, the Resistance to permanent press treatment and low susceptibility to catalytic shooting (Catalytic fading).

009831/1160009831/1160

BAD ORIGINAL ;u BATH ORIGINAL ; u

In den folgenden Beispielen bedeuten die Teile Gewichtsteile und die Temperaturen sind in Celsiusgraden angegeben.In the following examples, the parts are parts by weight and the temperatures are given in degrees Celsius.

Beispiel 1example 1

10 Teile Pyrenaldehyd und 7 Teile Cyanacetanilid werden in Teilen absolutem Aethanol unter Zusatz von 0,3 Teilen Piperidin in einem mit Rückflusskühler versehenen Gefäss bei Siedetemperatur gehalten. Nach 10-stündiger Behandlung wird abgekühlt und der entstandene Niederschlag abgesaugt, mit etwas verdünntem Methanol gewaschen, getrocknet und gegebenenfalls gemahlen. Der erhaltene Farbstoff besitzt folgende Formel10 parts of pyrenaldehyde and 7 parts of cyanoacetanilide are used in Parts of absolute ethanol with the addition of 0.3 parts of piperidine in a vessel equipped with a reflux condenser at the boiling point held. After 10 hours of treatment, the mixture is cooled and the precipitate formed is filtered off with suction, with something diluted Washed methanol, dried and, if appropriate, ground. The dye obtained has the following formula

/CN/ CN

CH = Cf /—ν XO-NH-/ ) CH = Cf / —ν XO-NH- / )

Färbebeispiel Coloring example

7,0 Teile des nach Beispiel 1 erhaltenen Farbstoffs werden mit 4 Teilen dinaphthylmethandisulfonsaurem Natrium, 4 Teilen Natriumcetylsulfat und 5 Teilen wasserfreiem Natriumsulfat in einer Kugelmühle 30 Stunden zu einem feinen Pulver gemahlen.7.0 parts of the dye obtained in Example 1 are with 4 parts of sodium dinaphthylmethanedisulfonate, 4 parts of sodium cetyl sulfate and 5 parts of anhydrous sodium sulfate were ground to a fine powder in a ball mill for 30 hours.

0,3 Teile des so erhaltenen Färbenräparatfl werden mit wenig Wasser angeteigt und die erhaltene Suspension sodann durch ein Sieb einem 2 Teile Natriumlaurylsulfat in 4000 Teilen Wasser enthaltenden Färbebad zugesetzt. Das Flottenverhältnis beträgt hier 1:40, es kann jedoch innerhalb weiteren Grenzen verändert0.3 parts of the Därbenräparatfl thus obtained are with little Water made into a paste and the suspension obtained then through a sieve a 2 parts of sodium lauryl sulfate in 4000 parts of water containing dye bath added. The liquor ratio here is 1:40, but it can be changed within further limits

009831 /1180009831/1180

werden. Man gibt 100 Teile gereinigtes Polyesterfasermaterial bei 40-50° in das Bad, fügt 20 Teile einer Emulsion von o-Phenylphenol in Wasser zu, erwärmt das Bad auf 100° und färbt während 1-2 Stunden bei 95-100°. Das Färbegut wird hierauf gespült, geseift, erneut gespült und dann getrocknet. Die erhaltene grünstichig gelbe Färbung ist sehr lieht-, wasch-, thermofixier- und hydrolysebeständig.will. 100 parts of cleaned polyester fiber material are added to the bath at 40-50 °, and 20 parts of an emulsion of o-phenylphenol are added in water, heats the bath to 100 ° and colors for 1-2 hours at 95-100 °. The material to be dyed is then rinsed, soaped, rinsed again and then dried. The greenish yellow color obtained is very light, washable, thermosetting and hydrolysis resistant.

Setzt man im.Beispiel 1 anstelle der verwendeten 7 Teile Cyan- acetanilid die entsprechende molare Menge Cyanacettoluidid, -anisidid, -phenetidid, -chloranilid oder -bromanilid ein, erhält man auf gleiche Weise in sehr guten Ausbeuten die entsprechend substituierten Farbstoffe.If in Example 1, instead of the 7 parts used, cyanoacetanilide is used the corresponding molar amount of cyanoacetoluidide, anisidide, phenetidide, chloranilide or bromanilide the appropriately substituted dyes are obtained in the same way in very good yields.

Zur Darstellung von Färbstoffgemischen setzt man zwei oder mehrere verschieden substituierte Cyanacetanilide in den gewünschten Mischungsverhältnissen ein und verfährt ebenfalls wie im Beispiel 1 angegeben.Two or more are used to represent mixtures of dyes differently substituted cyanoacetanilides in the desired Mixing ratios and proceed as indicated in Example 1.

Beispiel 2Example 2

Man erhitzt 23 Teile Pyrenaldehyd in 200 Teilen Aethanol zum Sieden und fügt innerhalb von 15 Minuten bei dieser Temperatur eine Mischung aus 7,5 Teilen Malondlnitril, 10 Teilen Aethanol und 1 Teil Pyridin langsam zu. Nach zweistündigem Kochen am Rückflusskühler wird erkalten gelassen, der Rückstand abfiltriert und mit Methanol gewaschen. Nach dem Trocknen erhält man die Verbindung der Formel23 parts of pyrenaldehyde are heated in 200 parts of ethanol Boil and add within 15 minutes at this temperature slowly adding a mixture of 7.5 parts of malonditrile, 10 parts of ethanol and 1 part of pyridine. After two hours of cooking on The reflux condenser is allowed to cool, the residue is filtered off and washed with methanol. After drying, one obtains the compound of formula

C0SS31/116G BAD ORIGINAL'C0SS31 / 116G BATH ORIGINAL '

CH = CCH = C

/CN/ CN

die Polyesterfasermaterial in brillanten gelben Tönen mit ausgezeichneten Echtheiten färbt.the polyester fiber material dyes in brilliant yellow shades with excellent fastness properties.

Die folgende Tabelle enthält Beispiele weiterer Farbstoffe der Formel (I), die Polyesterfasermaterial in gelben Tönen färben. Diese Farbstoffe können nach der im Beispiel 1 angegebenen Methode hergestellt werden.The following table contains examples of other dyes of the formula (I) which dye polyester fiber material in yellow shades. These dyes can be prepared according to the method given in Example 1.

009831/1160 BADORfQJNAt.009831/1160 BADORfQJNAt.

TabelleTabel A\A \ Beispielexample ΛΛ Nr.No. ηη VjJPrevious year -CO-NH2 -CO-NH 2 44th -CO-NH-CO-NH2 -CO-NH-CO-NH 2 LfNLfN -CO-O-C2H5 -CO-OC 2 H 5 66th -CO-O-CH3 -CO-O-CH 3 77th -coQ)-coQ) 88th -CO-NH-Q-Cl-CO-NH-Q-Cl 99 -CO-NH-Q-O-CH3 -CO-NH-QO-CH 3 1010 -CO-Q-NO2 -CO-Q-NO 2 1111th -CONH-Q-OC2H5 -CONH-Q-OC 2 H 5 1212th -CONH-Q-CONH-Q OCH3 OCH 3 1515th -CONH-Q-CONH-Q OCH3 OCH 3 1414th 1515th -So2-Q-So 2 -Q 1616 -So2-CH3 -So 2 -CH 3 1717th -CONH-Q-CONH-Q 1818th -CONH-Q-CONH-Q ClCl

009831/1180009831/1180

Beispiel
Nr.
example
No.

21 -SO21 -SO

22 -CO-NH22 -CO-NH

25 -CO-NH-|^V^J25 -CO-NH- | ^ V ^ J

24 ""*24 "" *

25 -CO-O-C4H9 25 -CO-OC 4 H 9

26 -CO-NH26 -CO-NH

■Q■ Q

29 -COOC2H4OC4H9 29 -COOC 2 H 4 OC 4 H 9

31 -C0NH-O-C00CH^31 -C0NH-O- C00CH ^

55 -CONHCH,55 -CONHCH,

55 -coiOd55 -coiOd

56 -conh(ch2) och56 -conh (ch 2 ) och

57 -CONH-ZhN57 -CONH-ZhN

/CH, 38 -CON. 3 / CH, 38 -CON. 3

0 9 8J^ZI ISO0 9 8J ^ ZI ISO

Claims (6)

Patentansprüche
1. Verbindungen der Formel
Claims
1. Compounds of the formula
CH = C<" (I),CH = C <"(I), worin A eine Cyangruppe, einen Acylrest oder ein gegebenen-' falls weitere Substituenten tragendes heterocyclisoheswherein A is a cyano group, an acyl radical or a given- ' if further substituents carrying heterocyclisohes Ringsystem aromatischen Charakters bedeutet \ Ring system of aromatic character means \ und der Pyrenkern weitere Substituenten tragen kann.and the pyrene nucleus can carry further substituents.
2. Verbindungen gemäss Anspruch 1, der Formel2. Compounds according to claim 1, of the formula CNCN (II),(II), worin R, eine Gruppe der Formel -CN/ -COR2, -COOR.,, -SO R2, ä wherein R, a group of the formula -CN / -COR 2 , -COOR. ,, -SO R 2 , Ä oderor eine Alkyl-, Phenyl-, Nitrophenyl-, Toluyl-, Amino-, Alkylamino-, Dialkylamino-, Alkoxyalkylamino-, Aminocarbonylamino-, Phenylamino-, Chlorphenylamino-, Bromphenylamino-, Alkylphenylamino-, Alkoxyphenylamino-an alkyl, phenyl, nitrophenyl, toluyl, amino, alkylamino, dialkylamino, alkoxyalkylamino, aminocarbonylamino, Phenylamino, chlorophenylamino, bromophenylamino, alkylphenylamino, alkoxyphenylamino 008831/1160008831/1160 Methoxycarbonylphenylamino-, Aethoxycarbonylphenyl- amino-, Naphthylamine-, Cyclohexylamine-, N-Piperidyl- oder N-Morpholylgruppe und Methoxycarbonylphenylamino, ethoxycarbonylphenyl - amino, naphthylamine, cyclohexylamine, N- piperidyl or N-morpholyl group and R, eine Alkylgruppe, die durch eine Alkoxygruppe substituiert sein kann,R, an alkyl group which can be substituted by an alkoxy group, bedeuten, wobei alle erwähnten Alkylreste 1,2,3 oder 4 Kohlenstoff atome enthalten.mean, where all mentioned alkyl radicals 1, 2, 3 or 4 carbon contain atoms. 3. Verbindungen gemäss Anspruch 2, der Formel 3. Compounds according to claim 2, of the formula /CN
CH = C^
/ CN
CH = C ^
worin R4 einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeu tet. wherein R 4 denotes an alkyl radical having 1 to 4 carbon atoms.
4. Verfahren zur Herstellung von Verbindungen der Formel4. Process for the preparation of compounds of the formula CH = CQ (I),CH = CQ (I), XCN X CN worin A eine Cyangruppe, einen Acylrest oder ein gegebenenfalls weitere Substituenten tragendes heterocycli-wherein A is a cyano group, an acyl radical or an optionally carrying further substituents heterocyclic 009831 / 1 UO009831/1 UO sches Ringsystem aromatischen Charakters bedeutet und der Pyrenkern weitere Substituenten tragen kann, dadurch gekennzeichnet, dass man 1 Mol eines gegebenenfalls substituierten Pyrenaldehyds der Formelmeans a ring system of aromatic character and the pyrene nucleus can carry further substituents, characterized in that 1 mol of an optionally substituted pyrenaldehyde of the formula CHO (IV)CHO (IV) mit 1 Mol einer Verbindung der Formelwith 1 mole of a compound of the formula ,CN, CN (V)(V) kondensiert.condensed. 5. Verfahren zum Färben oder Bedrucken von Fasern oder Fäden oder daraus hergestellten Materialien aus voll- oder halbsynthetischen, hydrophoben, hochmolekularen organischen Stoffen mit einen oder mehreren Farbstoffen der Formel (I) gemäss Anspruch 1. '5. Process for dyeing or printing fibers or threads or materials made therefrom from fully or semi-synthetic, hydrophobic, high-molecular organic substances with one or more dyes of the formula (I) according to claim 1. ' 6. Die gemäss Anspruch 5 gefSrbten oder bedruckten Materialien.6. The materials dyed or printed according to claim 5. Dei? PatentanwaltDei? Patent attorney - Q 8 8 3 1 ,'1 t S 0- Q 8 8 3 1, '1 t S 0
DE19702002893 1969-01-28 1970-01-23 Pyrene compounds, their manufacture and use Pending DE2002893A1 (en)

Applications Claiming Priority (1)

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CH125169A CH505187A (en) 1969-01-28 1969-01-28 Process for the preparation of pyrene compounds

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DE2002893A1 true DE2002893A1 (en) 1970-07-30

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Country Link
JP (1) JPS4814642B1 (en)
CH (1) CH505187A (en)
DE (1) DE2002893A1 (en)
FR (1) FR2030201B1 (en)
GB (1) GB1273819A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122114A (en) 1975-02-10 1978-10-24 Xerox Corporation 1-Tricyanoinylpyrene

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51141836U (en) * 1975-05-08 1976-11-15

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122114A (en) 1975-02-10 1978-10-24 Xerox Corporation 1-Tricyanoinylpyrene

Also Published As

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JPS4814642B1 (en) 1973-05-09
FR2030201A1 (en) 1970-10-30
GB1273819A (en) 1972-05-10
FR2030201B1 (en) 1974-03-01
CH505187A (en) 1971-03-31

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