DE2211663C3 - Azo dyes with 2,6-diaminopyrfdines as coupling components, process for their production and dye preparations - Google Patents
Azo dyes with 2,6-diaminopyrfdines as coupling components, process for their production and dye preparationsInfo
- Publication number
- DE2211663C3 DE2211663C3 DE19722211663 DE2211663A DE2211663C3 DE 2211663 C3 DE2211663 C3 DE 2211663C3 DE 19722211663 DE19722211663 DE 19722211663 DE 2211663 A DE2211663 A DE 2211663A DE 2211663 C3 DE2211663 C3 DE 2211663C3
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- amino
- red
- nitro
- chj
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic 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
- C07D213/02—Heterocyclic 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
- C07D213/04—Heterocyclic 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
- C07D213/60—Heterocyclic 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 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 ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic 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
- C07D213/02—Heterocyclic 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
- C07D213/04—Heterocyclic 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
- C07D213/60—Heterocyclic 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 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 ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic 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
- C07D213/02—Heterocyclic 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
- C07D213/04—Heterocyclic 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
- C07D213/60—Heterocyclic 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 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 ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic 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
- C07D213/02—Heterocyclic 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
- C07D213/04—Heterocyclic 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
- C07D213/60—Heterocyclic 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 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 ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
- C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
- C09B29/3639—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more amino groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/02—Disazo dyes
- C09B31/12—Disazo dyes from other coupling components "C"
- C09B31/14—Heterocyclic components
- C09B31/153—Heterocyclic components containing a six-membered ring with one nitrogen atom as the only ring hetero-atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/18—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group
- C09B43/20—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group with monocarboxylic acids, carbamic acid esters or halides, mono- isocyanates or haloformic acid esters
- C09B43/202—Aliphatic, cycloaliphatic, araliphatic carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
- C09B62/82—Azo dyes
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Description
NH-RNH-R
in der D der Rest einer Diazokomponente der Benzol-, Naphthalin-, Benztbiazol-, Benzisothiazol-, Thiazol-, Thiadiazol-, Thiophen-, Azobenzol- oder Anthrachinonreihe, X Cyan oder Carbonamid, einer der Reste R Phenyl und der andere Rest R Wasserstoff oder gegebenenfalls durch Hydroxy, Methoxy, Äthoxy, Hydroxyalkoxy mit 2 bis 4 C-Atomen, Metboxyäthoxy, Acyloxy mit 1 bis 4 C-Atomen oder Acyloxyalkoxy mit 2 bis 4 C-Atomen in der Alkoxygruppe sowie 1 bis 4 C-Atomen in der Acylgruppe substituiertes Alkyl mit 1 bis 6 C-Atomen sir 'in the D the remainder of a diazo component of the benzene, naphthalene, benztbiazole, benzisothiazole, Thiazole, thiadiazole, thiophene, azobenzene or anthraquinone series, X cyano or Carbonamide, one of the radicals R is phenyl and the other radical R is hydrogen or optionally by hydroxy, methoxy, ethoxy, hydroxyalkoxy with 2 to 4 carbon atoms, metboxyethoxy, acyloxy with 1 to 4 carbon atoms or acyloxyalkoxy with 2 to 4 carbon atoms in the alkoxy group as well 1 to 4 carbon atoms in the acyl group substituted alkyl with 1 to 6 carbon atoms sir '
2. Ein Verfahren zur Herste 70η Azo-2. A method of manufacturing 70η azo
farbstoffen der im Anspruch 1 ai»u -enen Formel, dadurch gekennzeichnet, daß man Diazoniumverbindungen von Aminen der allgemeinen Formeldyestuffs of the u -enen in claim 1 ai "formula, characterized in that the diazonium compounds of amines of the general formula
D — NH2 D - NH 2
mit Kupplungskomponenten der allgemeinen Formel zol-, Naphthalin-, BenztWazol-, Benzisothiazal-, Thiazol-, Thiadiazole, Thiophen-, Azobenzol- oder Anthrachinonreibe, X Cyan oder Carbonamid, einer der Reste R Phenyl und der andere Rest R Wasserstoff oder gegebenenfalls durch Hydroxy, Methoxy, Äthoxy, Hydroxyalkoxy mit 2 bis 4 C-Atomen, Methoxyäthoxy, Acyloxy mit 1 bis 4 C-Atomen oder Acyloxyalkoxy mit 2 bis 4 C-Atomen in der Alkoxygruppe sowie I bis 4 C-Atomen in der Acylgruppe substituiertes Alkyl mit 1 bis 6 C-Atomen sind, ein Verfahren zur Herstellung dieser Azofarbstoffe, das dadurch gekennzeichnet ist, daß man Diazoniumverbindungen von Aminen der allgemeinen Formelwith coupling components of the general formula zol-, naphthalene-, benztwazol-, benzisothiazal-, Thiazole, thiadiazole, thiophene, azobenzene or Anthraquinone grater, X cyano or carbonamide, one of the radicals R is phenyl and the other radical R is hydrogen or optionally by hydroxy, methoxy, ethoxy, hydroxyalkoxy with 2 to 4 carbon atoms, methoxyethoxy, Acyloxy with 1 to 4 carbon atoms or acyloxyalkoxy with 2 to 4 carbon atoms in the alkoxy group and I to 4 carbon atoms in the acyl group are substituted alkyl having 1 to 6 carbon atoms Process for the preparation of these azo dyes, which is characterized in that one diazonium compounds of amines of the general formula
D-NH,D-NH,
(II)(II)
mit Kupplungskomponenten der allgemeinen Formel CH3 with coupling components of the general formula CH 3
RHNRHN
(HI)(HI)
NHRNHR
RHNRHN
NHRNHR
4040
umsetzt und hydroxylgruppenhaltige Farbstoffe gegebenenfalls verestert, wobei in den Formeln D, X und R die im Anspruch 1 angegebenen Bedeutungen haben.reacted and hydroxyl-containing dyes optionally esterified, where in the formulas D, X and R have the meanings given in claim 1.
3. Farbstoffzubereitungen zum Färben von Polyamiden, Acrylnitrilpolymerisaten oder Polyestern, enthaltend neben üblichen Bestandteilen Azofarbstoffe gemäß Anspruch 1.3. Dyestuff preparations for dyeing polyamides, acrylonitrile polymers or polyesters, containing, in addition to the usual constituents, azo dyes as claimed in claim 1.
5555
Die Erfindung betrifft Azofarbstoffe mit 2,6-Dilinopyridinen als Kupplungskomponenten der allmeinen FormelThe invention relates to azo dyes containing 2,6-dilinopyridines as coupling components of the general formula
(D(D
6060
«5«5
der D der Rest einer Diazokomponente der Benumsetzt und hydroxylgruppenhaltige Farbstoffe gegebenenfalls verestert, wobei in den Formeln D, X und R die vorstehend angegebenen Bedeutungen haben, sowie Farbstoffzubereitungen zum Färben von Polyamiden, Acrylnitrilpolymerisaten oder Polyestern, enthaltend neben üblichen Bestandteilen die vorstehend genannten Farbstoffe.the D is the remainder of a diazo component which uses and hydroxyl-containing dyes, if appropriate esterified, where in the formulas D, X and R the meanings given above as well as dye preparations for dyeing polyamides, acrylonitrile polymers or polyesters, containing, in addition to the usual constituents, the aforementioned dyes.
Gegenüber nächstvergleichbaren aus der USA.-Patentschrift 2 029 315 und der deutschen Offenlegungsschrift 1917 278 bekannten Farbstoffen haben die neuen Farbstoffe in unvorhersehbarem Maße Vorteile in der Farbstärke, Lichtechtheit und Thermoibiierechtben.Compared to the next comparable from US Pat. No. 2,029,315 and the German Offenlegungsschrift 1917 278 known dyes have the new dyes in unpredictable Advantages in terms of color strength, lightfastness and thermal resistance.
Als Substituenten Tür die Reste D der Diazokomponenten sind beispielsweise zu nennen: in der Benzolreihe: Chlor, Brom, Nitro, Cyan, Trifluormethyl, Methylsuifonyl, Äthylsulfonyl, Phenylsulfonyl, Carbomethoxy, Carbobutoxy, Carbo-/i-methoxy-äthoxy, Carbo-/i-hydroxy-äthoxy, gegebenenfalls N-mono- oder N-disubstituiertes Carbon- oder Sulfonamid, Methyl, Äthyl, Methoxy oder Ätiioxy.The radicals D of the diazo components are used as substituents are to be mentioned for example: in the benzene series: chlorine, bromine, nitro, cyano, trifluoromethyl, Methylsulfonyl, ethylsulfonyl, phenylsulfonyl, carbomethoxy, carbobutoxy, carbo- / i-methoxy-ethoxy, Carbo- / i-hydroxy-ethoxy, optionally N-mono- or N-disubstituted carbon- or sulfonamide, methyl, ethyl, methoxy or etiioxy.
N-Substituenten der Carbon- oder Sulfonamide sind dabei z. B. Methyl, Äthyl, Propyl, Butyl, /ίί-Hydroxyäthyl, y- Hydroxy -propyl, /J-Methoxyäthyl, y-Methoxy-propyl oder y-Äthoxypropyl sowie das Pyrrolidid, Piperidid oder Morpholid.N-substituents of the carbon or sulfonamides are z. B. methyl, ethyl, propyl, butyl, / ίί-hydroxyethyl, y- hydroxy-propyl, / J-methoxyethyl, y-methoxypropyl or y-ethoxypropyl and the pyrrolidide, piperidide or morpholide.
In der Azobenzolreihe: Chlor, Brom, Nitro, Cyan, Methyl, Äthyl, Methoxy oder Äthoxy. In der Naphthalinreihe: Nitro, in den genannten heterocyclischen Reihen: Chlor, Brom, Nitro, Cyan, Methyl, Äthyl, Phenyl, Methoxy, Äthoxy, Methylmercapto, /i-Carbomethoxy-äthyl-mercapto, /7-Carboäthoxy-äthylmercapto, Carbomethoxy, Carboäthoxy, Acetyl, Methylsuifonyl oder Äthylsulfonyl.In the azobenzene series: chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy or ethoxy. In the naphthalene series: Nitro, in the named heterocyclic series: chlorine, bromine, nitro, cyano, methyl, ethyl, Phenyl, methoxy, ethoxy, methyl mercapto, / i-carbomethoxy-ethyl-mercapto, / 7-carboethoxy-ethyl mercapto, Carbomethoxy, carboethoxy, acetyl, methylsulfonyl or ethylsulfonyl.
Der Rest D leitet sich im einzelnen z. B. von folgenden Aminen ab: Anilin o-, m- oder p-Toluidin, o-, m- oder p-Nitroanilin, o-, m- oder p-Cyananilin, 2,4-Dicyananilin, o-, m- oder p-Chloranilin, o-, m- oder p-Bromanilin, 2,4,6-Tribromanilin, 2-Chlor-4 - nitroanilin, 2 - Brom - 4 - nitroanilin, 2 - Cyan-4 - nitroanilin, 2 - Methylsuifonyl - 4 - nitroanilin,The remainder D is derived in detail z. B. of the following Amines from: aniline o-, m- or p-toluidine, o-, m- or p-nitroaniline, o-, m- or p-cyananiline, 2,4-dicyaniline, o-, m- or p-chloroaniline, o-, m- or p-bromoaniline, 2,4,6-tribromaniline, 2-chloro-4 - nitroaniline, 2 - bromo - 4 - nitroaniline, 2 - cyano-4 - nitroaniline, 2 - methylsuifonyl - 4 - nitroaniline,
2-Methyl-4-nitroamlin, 2-Methoxy-4-nitroanilin, 4 - Chlor - 2 - nitroanilin, 4 - Methyl - 2 - nitroanilin, 4. Methoxy - 2 - aitroaniUn, 1 - Amino - 2 - triflnormetbyl - 4 - cWorbenzol, 2 - Chlor - 5 - amino - benzonitrii, 2 - Amino - 5 - cblorbenzonitril, 1 - Amino- 2 - nitrobenzol - 4 - sulfonsäure - η - butylamid oder .β-roetboxyäthylamid, 2,4 - Dinitroanilin, 2,4-Dinitro - 6 - cbloranilin, 2,4 - Dinitro - 6 - bromanilin, 2-methyl-4-nitroamline, 2-methoxy-4-nitroaniline, 4 - chloro - 2 - nitroaniline, 4 - methyl - 2 - nitroaniline, 4th methoxy - 2 - aitroaniUn, 1 - amino - 2 - triflnormetbyl - 4 - cWorbenzene, 2 - chloro - 5 - amino - benzonitrii, 2 - amino - 5 - chlorobenzonitrile, 1 - amino - 2 - nitrobenzene - 4 - sulfonic acid - η - butylamide or .β- roetboxyethylamide, 2,4 - dinitroaniline, 2,4 -Dinitro - 6 - cbloraniline, 2,4 - Dinitro - 6 - bromaniline,
2.4 - Dinitro - 6 - cyananilin, 1 - Amino - 2,4 - dinitro- benzol - 6 - methylsulfon, 2,6 - Dichlor - 4 - nitroanilin, 2,6-Dibrom-4-nitroanilin, 2-Chlor-6-brom-4-nitro- anilin, 2,6-picyan-4-nitroanilin, 2-Cyan-4-nitro- 6 - chloranilin, 2 - Cyan - 4 - nitro - 6 - bromanilin, 1-Aminobenzol-4-methylsulfon, 1 -Amino-2,6-dibrom - benzol - 4 - methylsulfon, 1 - Amino - 2,6 - di chlorbenzol-4-methylsulfon, 1 - Amino -2,4- dinitrobenzol-6-carbonsäure-methylester oder -/i-methoxyäthylester, 3,5-Dicbloranthranilsäure-propylester, 2.4 - dinitro - 6 - cyananiline, 1 - amino - 2,4 - dinitrobenzene - 6 - methylsulfone, 2,6 - dichloro - 4 - nitroaniline, 2,6-dibromo-4-nitroaniline, 2-chloro-6- bromo-4-nitro-aniline, 2,6-picyan-4-nitroaniline, 2-cyano-4-nitro- 6 - chloroaniline, 2 - cyano - 4 - nitro - 6 - bromaniline, 1-aminobenzene-4-methylsulfone, 1 -amino-2,6-dibromo-benzene-4-methylsulfone, 1-amino-2,6-dichlorobenzene-4-methylsulfone, 1 -amino-2,4-dinitrobenzene -6-carboxylic acid methyl ester or - / i- methoxyethyl ester, 3,5-dicbloranthranilic acid propyl ester,
3.5 - Dibromanthranilsäure - ρ - methoxyäthylestcr, N - Acetyl - ρ - phenylendiamin, 4 - Amino - acetophenon, 4- oder 1 -Amino-benzophcnon, 2- und 4-Aminodiphenylsulfon, 2-, 3- oder 4-Aminobenzoe- säure-methylester, -äthylester, -propylester, -butyl- ester, -isobutylester, -/i-methoxy-äthylester, -/f-äthoxy-äthylester, -methyl-diglykolester, -äthyl-digly» kolester, -methyl-triglykolester, -äthyl-triglykolester, -0-hydroxyäthylester, -/J-acetoxy-äthyiester, -p'-f^'-hy- droxy - äthoxy) - äthylester, -β - hydroxy - propylester, .γ - hydroxy - propylester, -<» - hydroxy - butylester, -ω - hydroxy - hexylester, 5 - Nitro - anthranilsäuremethylester, -isobui/kster, -methyl - diglykolester, -/i-methoxy-äthylester, -/J-butoxy-äthylester-, -,i-acetoxy - äthylester, 3 · oder 4 - Arriincphthalsäiire-, 5-Amino-isophthalsäure- oder Am ίο-terephthalsäure - di - methylester, -di - äthylester, -di - propylester, -di-butylester, 3- oder 4-Amino-benzoesaureamid, -methylamid, -propylamid, -butylamid, -iso- butylamid, -cyclohexylamid, -(i - äthyl - hexylamid. -v - methoxy - propylamid, -γ - äthoxy - propylamid. 2-, 3- oder 4-Aminobenzoesäure-dirnethylamid. -di- äthylamid, -pyrrolidid, -morpholid, N-methyl-N-,i-hy- droxy - äthylamid, 5 - Amino - isophthalsäurediamid. -bis-y-methoxy-propylamid, Aminoterephthalsiiurebis - diäthylamid, 3- oder 4 - Amino - phthalsäurc- imid, -β - hydroxy - äthylimid-, -;■-hydroxy-propylamid, 3 - Amino - 6 - nitro - phthalsäure - β - hydroxy- äthylimid, 2-, 3- oder 4-Aminobenzosulfonsäure- dimethylamid, -diäthylamid, -pyrrolidid, -morpholid, Methylsulfonsäure-2'-, -3'- oder -4 -amino-phenyl- ester, Äthylsulfonsäure - 2'-, -3'- oder -4' - amino- phenylester, Butylsulfonsaure-2'-, -3'- oder -4'-aminophenylester, Benzolsulfonsäure-2'-, -3'- oder 4'-amino- phenylester, 4 - Amino - naphthalsäure - äthylimid, -butylimid, -β - methoxy - äthylimid, -y - methoxypropylimid, 4- und 5 - Nitro-1-amino-naphthalin, 3.5 - Dibromoanthranilic acid - ρ - methoxyethyl ester, N - acetyl - ρ - phenylenediamine, 4 - amino - acetophenone, 4- or 1- amino benzophynone, 2- and 4-aminodiphenylsulphone, 2-, 3- or 4-aminobenzoic acid- methyl ester, ethyl ester, propyl ester, butyl ester, isobutyl ester, - / i-methoxy-ethyl ester, - / f-ethoxy -ethyl ester, -methyl-diglycol ester, -ethyl-digly » kolester, -methyl triglycol ester, -ethyl-triglycol ester, -0-hydroxyethyl ester, - / J-acetoxy-ethyl ester, -p'-f ^ '- hydroxy - ethoxy) - ethyl ester, -β - hydroxy - propyl ester, .γ - hydroxy - propyl ester, - <»- hydroxy - butyl ester, -ω - hydroxy - hexyl ester, 5 - nitro - anthranilic acid methyl ester, - isobui / kster, - methyl - diglycol ester, - / i-methoxy ethyl ester, - / I-butoxy ethyl ester, -, i acetoxy - ethyl ester, 3 * or 4 - Arriincphthalsäiire-, 5-amino -isophthalsäure- or on ίο-terephthalic acid - di - methylester, di - ethyl-di - propyl, di-butyl, 3- or 4-amino -benzoic acid amide, -methylamide, -propylamide, -butylamide, -isobutylamide , -cyclohexylamide, - (i- ethyl-hexylamide. -v - methoxy - propylamide, -γ - ethoxy - propylamide. 2-, 3- or 4-aminobenzoic acid dirnethylamide. -di-ethylamide, -pyrrolidide, -morpholide, N-methyl-N-, i- hydroxy - ethylamide, 5 - amino - isophthalic acid diamide. -bis-y-methoxy-propylamide, aminoterephthalsiiurebis - diethylamide, 3- or 4 - amino - phthalic acid imide, -β - hydroxy - ethylimide, -; ■ -hydroxy-propylamide, 3 - amino - 6 - nitro - phthalic acid - β - hydroxy ethyl imide, 2-, 3- or 4-aminobenzosulfonic acid dimethyl amide, diethyl amide, pyrrolidide, morpholide, methylsulfonic acid 2'-, -3'- or -4-aminophenyl ester, ethylsulfonic acid - 2 '-, -3'- or -4'-aminophenyl ester, butylsulfonic acid 2'-, -3'- or -4'-amino phenyl ester, benzenesulfonic acid 2'-, -3'- or 4'-amino phenyl ester, 4 - amino - naphthalic acid - ethylimide, -butylimide, -β - methoxy - ethylimide, -y - methoxy propylimide, 4- and 5 - nitro-1-amino-naphthalene,
2 - Amino - anthrachinon, 1 - Amino - 4 - chloranthra- chinon, 3- oder 4-Aminodiphenylenoxid, 2-Amino- benzthiazol, 2 - Amino - 6 - carbonsäure - methylesterbenzthiazoi, 2 - Amino - 6 - methyl - sulfonyl - benzthiazoL, 2 - Amino - 6 - cyanbenzthiazol, 2 - Amino-6-nitro-benzthiazol, 5,6- oder 6,7-Dichlor-2-aminobenzthiazol, 4-Amino-5-brom-7-nitro- 1,2-benzisothiazol, 3 - Amino - 5 - nitro - 2,1 - benzisothiazol, 2 - amino - anthraquinone, 1 - amino - 4 - chloranthraquinone, 3- or 4-aminodiphenylene oxide, 2-amino- benzothiazole, 2 - amino - 6 - carboxylic acid methyl ester benzthiazoi, 2 - amino - 6 - methyl - sulfonyl - benzthiazole, 2 - amino - 6 - cyanobenzothiazole, 2 - amino-6-nitro-benzothiazole, 5,6- or 6,7-dichloro-2-aminobenzothiazole, 4-amino-5-bromo-7-nitro-1,2 -benzisothiazole, 3 - amino - 5 - nitro - 2,1 - benzisothiazole,
3 - Amino - 5 - nitro - 7 - brom - 2,1 - benzisothiazol, 2-Amino-thiazol, 2-Amino-5-nitro-thiazol, 2-Amino- 4-methyl-thiazol-5-carbonsäure-äthylestcr, 2-Amino-4-methyl-5-acetyl-thiazol, 2-Amino-3-cyan-4-methyl- thiophen - 5 - carbonsäureester, 2 - Phenyl - 5 - amino- 1,3,4 - thiadiazol, 3 - Methylmercapto - 5 - aroino-1,2,4 - tbiadiazol, 3 - β · Carboraethoxy - äthylmercapto-5-amino-1,2,4-thiadiazol. 3 - Amino - 5 - nitro - 7 - bromo - 2,1 - benzisothiazole, 2-amino-thiazole, 2-amino-5-nitro-thiazole, 2-amino-4-methyl-thiazole-5-carboxylic acid ethyl ester, 2-amino- 4-methyl-5-acetyl-thiazole, 2-amino-3-cyano-4-methyl-thiophene - 5 - carboxylic acid ester, 2 - phenyl - 5 - amino- 1,3,4 - thiadiazole, 3 - Methylmercapto-5-aroino-1,2,4-tbiadiazole, 3- β- carboraethoxy-ethylmercapto-5-amino-1,2,4-thiadiazole.
Geeignete Diazokoroponenten der Aminoazoben-S zolreihe sind beispielsweise:Suitable diazo components of the aminoazoben S zol series are, for example:
4-Amijioazobenzol, 2',3-Dimethyl-4-aminoazo benzol, 3 '^-Dimethyl^aminoazobenzol,4-amijioazobenzene, 2 ', 3-dimethyl-4-aminoazo benzene, 3 '^ -Dimethyl ^ aminoazobenzene,
2,5-Dimethyl-4-aminoazobenzol,2,5-dimethyl-4-aminoazobenzene,
2-Methyl-5-methoxy-4-aminoazobenzol, 2-Methyl-4',5-diraethoxy-4-aminoazobenzol, 4'-Chlor-2-methyl-5-methoxy-4-aminoazooenzol, 4'-NitΓO-2-methyl-5-^lethoxy-4-aminoazobenzol,2-methyl-5-methoxy-4-aminoazobenzene, 2-methyl-4 ', 5-diraethoxy-4-aminoazobenzene, 4'-chloro-2-methyl-5-methoxy-4-aminoazooenzene, 4'-NitΓO-2-methyl-5- ^ lethoxy-4-aminoazobenzene,
rs 4'-Chlor-2-methyl-4-aminoazobenzol,
2,5-Dimethoxy-4-aminoazobenzol,
4'-ChloΓ-2,5-dimethoxy-4-aπlinoazobenzol,
4'-Nitro-2,5-dimethoxy-4-aminoazoben2ol,
4'-Chlor-2,5-dimethyl-4-amtnoazob<:2^y?: rs 4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-ChloΓ-2,5-dimethoxy-4-aπlinoazobenzol, 4'-nitro-2,5-dimethoxy- 4-aminoazoben2ol,
4'-chloro-2,5-dimethyl-4-amtnoazob <: 2 ^ y? :
4'-Methoxy-2,5-dimethyl-4-aminoazobenzol,
4'-Nitro-4-aminoazobenzol,
3,5-Dibrom-4-aminoazobenzol,
2,3'-Dichior-4-aminoazobenzol,
S-Methoxy^-aminoazobenzol.4'-methoxy-2,5-dimethyl-4-aminoazobenzene,
4'-nitro-4-aminoazobenzene,
3,5-dibromo-4-aminoazobenzene,
2,3'-dichloro-4-aminoazobenzene,
S-methoxy ^ aminoazobenzene.
Als Reste R sind neben Phenyl und WasserstoffThe radicals R are phenyl and hydrogen
ζ. B. zu nennen: die A'Jcylreste Methyl, Äthyl, Propylζ. B. to mention: the A'Jcylreste methyl, ethyl, propyl
oder Butyl, die Hydroxyalkylreste, ^-Hydroxyäthylor butyl, the hydroxyalkyl radicals, ^ -hydroxyethyl
oder -propyl, y-Hydroxypropyl, «j-Hydroxyhexyl, sowie die Reste der Formelnor propyl, γ-hydroxypropyl, γ-hydroxyhexyl, as well as the remains of the formulas
— CH, — CH, — O — CH, — CH2 — OH- CH, - CH, - O - CH, - CH 2 - OH
undand
-(CHj)3- O-(CH2)*-OH- (CHj) 3 - O- (CH 2 ) * - OH
die Alkoxyalkylreste /i-Methoxyäthyl, y-Methoxypropyl, 0-Äthoxyäthyl, y-Äthoxypropi5 oder der Rest der Formelthe alkoxyalkyl radicals / i-methoxyethyl, y-methoxypropyl, 0-ethoxyethyl, y-ethoxypropi5 or the rest the formula
(CH2I3OC2H4OCH3 (CH 2 I 3 OC 2 H 4 OCH 3
die Acyloxyalkylreste der Formeln
CH2-CH2-O-ACyI (CH2J3-O—Acylthe acyloxyalkyl radicals of the formulas
CH 2 -CH 2 -O-ACyI (CH 2 J 3 -O-acyl
CH,-CH-O-AcvlCH, -CH-O-Acvl
CH3 CH 3
ICH2),- O—Acyl
(C H2), — O—(C H2 )2 — O —AcylICH 2 ), - O-acyl
(CH 2 ), - O- (CH 2 ) 2 - O - acyl
oderor
(CH2)3—Ö—(CH2)4—O—Acyl
wobei Acyl beispielsweise(CH 2 ) 3 —O— (CH 2 ) 4 —O— acyl
where acyl is for example
CO-H CO-CH3 CO-CH2CiCO-H CO-CH 3 CO-CH 2 Ci
CO-CH2-CO-CH3 CO-CH=CH2 CO-CH 2 -CO-CH 3 CO-CH = CH 2
ist.is.
Bei der Herstellung der Farbstoffe der allgemeinen Formell erfolgt die Diazotierung der Amine wie üblich. Die Kupplung wird ebenfalls wie üblich in wäßrigem Medium, gegebenenfalls unter Zusatz von Lösungsmitteln, bei schwach- bis starksaurer Reak- 5 tion durchgeführtIn the preparation of the dyes of the general formula, the amines are diazotized as common. The coupling is also carried out as usual in an aqueous medium, optionally with the addition of Solvents, for weakly to strongly acidic reac- 5 tion carried out
Die Herstellung der Kupplungskomponenten der allgemeinen Formal IH ist im Prinzip in der deutschen Offenlegungsscbrift 2062 717 beschrieben, die Angaben dort gelten hier sinngemäß. ι οThe manufacture of the coupling components of the general formal IH is described in principle in the German Offenlegungsscbrift 2062 717, the Information there applies accordingly here. ι ο
Enthalten die erfindungsgemäßen Farbstoffe der Formel I eine Estergruppe in den Rest R, so kann die Herstellung der Verbindungen der Formel I im Prinzip nach dem angegebenen Verfahren erfolgen, wenn die entsprechende Estergruppe schon in der Kupp- 15 lungskomponente enthalten ist. In manchen Fällen ist es aber auch zweckmäßig, den Säurerest (Acyl) in den fertigen Farbstoff der Formel I einzuführen. Dazu eignen sich die freien Säuren, ihre Anhydride, Chloride oder Ester, wobei zweckmäßigerweise inerte 20 Verdünnungs- oder Lösungsmittel, wie Mono-, Dioder Trichlorbenzol, Tetrahydrofuran, Dioxan, Dimethylformamid, N-Methylpyrrolidon oder Pyridin Zugesetzt werden.If the dyes of the formula I according to the invention contain an ester group in the radical R, the compounds of the formula I can in principle be prepared by the process indicated if the corresponding ester group is already contained in the coupling component. In some cases, however, it is also expedient to introduce the acid radical (acyl) into the finished dye of the formula I. For this purpose, the free acids, their anhydrides, chlorides or esters are suitable, and advantageously 20 inert diluent or solvent, such as mono-, di- or trichlorobenzene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone or pyridine are.
Bei der Veresterung mit freien Säuren kann es von ^ Vorteil sein, anorganische oder organische Katalysatoren, z. B. HCl-Gas oder p-Toluolsulfonsäure, zujzusetzen und das entstehende Wasser aus dem Reaktionsgemisch durch Verdampfen entweichen zu lassen. Werden Säureanhydride oder -chloride zur Vereste- 30 rung eingesetzt, so können als Lösungsmittel in speziellen Fällen auch die betreffenden Säuren verwendet werden. So läßt sich die Umsetzung mit Acetanhydrid in Eisessig durchführen. Bei der Verwendung von Säurechloriden als Veresterungsmittel ist es von Vor- 35 teil, dem Reaktionsgemisch säurebindende Mittel hinzuzusetzen, z. B. Natriumcarbonat oder -acetat, Magnesiumoxid oder Pyridin. Als Veresterungsmittel »eien im einzelnen beispielsweise genannt: Ameisensäure, Essigsäure, Chloressigsäure sowie die Ester, 40 Anhydride oder Chloride dieser Säuren, weiterhin Chlorameisensäureäthylester oder Diketen.In the esterification of free acids, it may be advantageous ^, inorganic or organic catalysts, eg. B. HCl gas or p-toluenesulfonic acid, add and allow the water formed to escape from the reaction mixture by evaporation. If acid anhydrides or chlorides are used for the esterification, the relevant acids can also be used as solvents in special cases. For example, the reaction with acetic anhydride can be carried out in glacial acetic acid. When using acid chlorides as esterifying agents, it is advantageous to add acid-binding agents to the reaction mixture, e.g. B. sodium carbonate or acetate, magnesium oxide or pyridine. Examples of esterifying agents mentioned in detail are: formic acid, acetic acid, chloroacetic acid and the esters, anhydrides or chlorides of these acids, and also ethyl chloroformate or diketene.
Technisch besonders wertvoll sind Farbstoffe und Farbstoffgemische der allgemeinen Formel I aDyes and dye mixtures of the general formula I a are particularly useful industrially
4545
Y2 R1—HNY 2 R 1 -HN
NH-R1 NH-R 1
C2H4OCH3 C 2 H 4 OCH 3
oder C3H6OCH3 or C 3 H 6 OCH 3
C3H6OC2H5 C 3 H 6 OC 2 H 5
CH2CH2OCHOCH 2 CH 2 OCHO
CH2CH2CH2OCHOCH 2 CH 2 CH 2 OCHO
CH2CH2OCOCH3 CH 2 CH 2 OCOCH 3
CH2CH2OCH2Ch2OCHOCH 2 CH 2 OCH 2 Ch 2 OCHO
5050
in der Y Nitro, Cyan, Chlor, Brom, Carbomethoxy, 55 Carboäthoxy, Methylsulfonyl, Äthylsulfonyl, Methyl, Methoxy, Phenylazo, Y1 Wasserstoff, Nitro, Chlor, Brom, Cyan, Methyl, Methoxy, Carbomethoxy, Carbo= ithoxy, Methylsulfonyl oder Äthylsulfonyl und Y2 Wasserstoff, Chlor, Brom, Cyan, Methyl, Methoxy, 60 Carbom, hoxy oder Carboäthoxy, ein R1 Phenyl Und das andere ω-Hydroxyhexyl, /9-Hydroxyäthyl, ^-Hydroxypropyl, y-Hydroxypropyl oder einen Rest ier Formelnin Y nitro, cyano, chlorine, bromine, carbomethoxy, 55 carboethoxy, methylsulfonyl, ethylsulfonyl, methyl, methoxy, phenylazo, Y 1 hydrogen, nitro, chlorine, bromine, cyano, methyl, methoxy, carbomethoxy, carbo = ithoxy, methylsulfonyl or Ethylsulfonyl and Y 2 hydrogen, chlorine, bromine, cyano, methyl, methoxy, 60 carbom, hoxy or carboethoxy, one R 1 phenyl and the other ω-hydroxyhexyl, / 9-hydroxyethyl, ^ -hydroxypropyl, y-hydroxypropyl or a remainder ier Formulas
-(CH2J2-O-(CH2J2OH (CH2J3O(CH2J4OH- (CH 2 J 2 -O- (CH 2 J 2 OH (CH 2 J 3 O (CH 2 J 4 OH
Bei Farbstoffen mit Estergruppen sind solche mit bis 4 C-Atomen im Acylrest bevorzugtIn the case of dyes with ester groups, those with up to 4 carbon atoms in the acyl radical are preferred
Weiterhin sind besonders wertvoll die entsprechenden Farbstoffe, die als Diazokomponenten gegebenenfalls durch Nitro, Chlor, Brom, Cyan, Methyl, Methylmercapto, /j-Carbomethoxy-äthylmercapto, β - Carboäthoxy - äthylmercapto, Carbomethoxy, Carboäthoxy oder Acetyl substituiertes Benzthiazol, Benzisothiazol, Thiazol, Thiadiazol oder Thiophen enthalten.Furthermore, the corresponding dyestuffs, which are used as diazo components, are optionally substituted by nitro, chlorine, bromine, cyano, methyl, methyl mercapto, / j-carbomethoxy-ethyl mercapto, β- carboethoxy-ethyl mercapto, carbomethoxy, carboethoxy or acetyl-substituted benzothiazole, benzisothiazole, thiazole, benzisothiazole, Contain thiadiazole or thiophene.
Von den besonders wertvollen Diazokomponenten seien im einzelnen genannt:Some of the particularly valuable diazo components are:
4-Nitro-anilin,4-nitro-aniline,
2-Chlor-4-nitro-anilin,2-chloro-4-nitro-aniline,
2-Brom-4-nitro-aniIin,2-bromo-4-nitro-aniIine,
2 Cyan-4-nitro-anilin,2 cyano-4-nitro-aniline,
2-Methoxy-4-nitro-anilin,2-methoxy-4-nitro-aniline,
2-Amino-5-nitro-phenylsulfonsäuredimethylamid, 2-amino-5-nitro-phenylsulfonic acid dimethylamide,
2-Amino-5-nitro-phenylsuilbnsäure-butylamid, 2-Amino-5-nitΓO-phenylsulfonsäuΓe-2-Amino-5-nitro-phenylsulfuric acid-butylamide, 2-Amino-5-nitΓO-phenylsulfonic acid
/i-methoxy-äthylamid,
2-Amino-benzonitril,
3-Chlor-4-amino-benzonitril,
2-Chlor-5-amino-benzonitril,
2-Amino-5-chlor-benzonitril,
2.5-Dichlor-4-amino-benzonitril, 1 -Amino-2,4-dicyan benzol,
1 -Aminn^^-dicyan-e-chlor-benzoL
2-Chlor-4-amino-5-nitro-benzonitril,
2-Amino-3-chlor-5-nitro-benzonitril, 2-Amino-3-brom-5-nitro-bcnzonitril,
2,6-Dicyan-4-nitro-anilin,
2,5-Dichlor-4-nitroanilin,
2,o-Dichlor-4-nitro-anilin,
2,6-Dibron>4=nitro-anilin,
2-Chlor-6-brom-4-nitro-anilin,
2,4-Dinitro-anilin,
2,4-Dinitro-6-chlor-anilin,
2,4- Dinitro-6-brom-anilin,
2-Aniino-3,5-dinitro-benzonitril, l-Amino-4-nitrobenzol-2-niethylsulfon,
l-Amino-4-nitrobenzol-2-äthylsulfon, 4-MethyIsulfonyl-anilin,
l-Amino-2-chlorbenzol-4-methylsulfon, l-Amino-2,6-dibrombenzol-4-methylsuIfon,/ i-methoxy-ethylamide,
2-amino-benzonitrile,
3-chloro-4-aminobenzonitrile,
2-chloro-5-aminobenzonitrile,
2-amino-5-chlorobenzonitrile,
2.5-dichloro-4-aminobenzonitrile, 1-amino-2,4-dicyanobenzene,
1-Aminn ^^ - dicyan-e-chloro-benzoL 2-chloro-4-amino-5-nitro-benzonitrile, 2-amino-3-chloro-5-nitro-benzonitrile, 2-amino-3-bromo-5 -nitro-benzonitrile, 2,6-dicyano-4-nitro-aniline,
2,5-dichloro-4-nitroaniline,
2, o-dichloro-4-nitro-aniline,
2,6-dibron> 4 = nitro-aniline,
2-chloro-6-bromo-4-nitro-aniline, 2,4-dinitro-aniline,
2,4-dinitro-6-chloro-aniline,
2,4-dinitro-6-bromo-aniline,
2-aniino-3,5-dinitro-benzonitrile, l-amino-4-nitrobenzene-2-niethylsulphone, l-amino-4-nitrobenzene-2-ethylsulphone, 4-methylisulphonyl-aniline,
l-amino-2-chlorobenzene-4-methyl sulfone, l-amino-2,6-dibromobenzene-4-methyl sulfone,
l-Amino-2,6-dichlorbenzol-4-methylsulfon, 2- und 4-Amino-benzoesäureester, 2-Amino-5-nitro-benzoesäureester, 2-Amino-3-chloΓ-5-nitro-benzoesäureester, 2-Amino-3,5-dichlor-benzoesäureester, 2-Amino-3,5-dibrom-benzoesäureester, 2-Amino-3,5-dinitro-benzoesäure-methylesterl-amino-2,6-dichlorobenzene-4-methylsulfone, 2- and 4-amino-benzoic acid ester, 2-amino-5-nitro-benzoic acid ester, 2-amino-3-chloΓ-5-nitro-benzoic acid ester, 2-Amino-3,5-dichloro-benzoic acid ester, 2-amino-3,5-dibromo-benzoic acid ester, 2-amino-3,5-dinitro-benzoic acid methyl ester
oder -/J-methoxy-äthylester,
2-Amino-terephthalsäure-diäthylester, 4-Amino-azobenzol,
2,3'-Dimethyl-4-amino-azobenzol, 2',3-Dimethyl-4-amino-azobenzol, 2,5-Dimethyl-4-amino-azobenzol,or - / I-methoxy-ethyl ester, 2-amino-terephthalic acid-diethyl ester, 4-amino-azobenzene,
2,3'-dimethyl-4-amino-azobenzene, 2 ', 3-dimethyl-4-amino-azobenzene, 2,5-dimethyl-4-amino-azobenzene,
2-Methyl-5-mcthoxy-4-amino-azobenzol.2-methyl-5-methoxy-4-amino-azobenzene.
Von den besonders wertvollen heterocyclischen Diazokomponenten seien erwähnt:Of the particularly valuable heterocyclic diazo components are mentioned:
2-Amino-5-nitro-thiazol,2-amino-5-nitro-thiazole,
2-Amino-4-methyl-5-nitro-thiazol, Z-Amino-^methyl-thiazol-S-carbonsäureäthylester, 2-Amino-4-methyl-5-nitro-thiazole, Z-Amino- ^ methyl-thiazole-S-carboxylic acid ethyl ester,
2-Amino-5-phenyl-l,3,4-thiadiazol, S-Phenyl-S-amino-1,2,4-thiadiazol, S-Methyl-mercapto-S-amino-1,2,4-thiadiazol, S-Zf-Carbomethoxy-athylmercapto-S-amino-2-Amino-5-phenyl-1,3,4-thiadiazole, S-phenyl-S-amino-1,2,4-thiadiazole, S-methyl-mercapto-S-amino-1,2,4-thiadiazole, S-Zf-carbomethoxy-ethylmercapto-S-amino-
1,2,4-thiadiazol,
S-Zi-Carboathoxy-athylmercapto-S-amino-1,2,4-thiadiazole,
S-Zi-Carboathoxy-ethylmercapto-S-amino-
1,2.4-thiadiazol,
2-Amino-6-cyan-benzthiazol,
2-Amino-6-carbonsäuremethyl-esterbenzthiazol, 2-Amino-6-nitro-benzthiazol,
2-Amino-3-cyan-4-methyl-thiophen-5-carbonester,
1,2,4-thiadiazole,
2-amino-6-cyano-benzothiazole,
2-amino-6-carboxylic acid methyl ester benzothiazole, 2-amino-6-nitro-benzothiazole,
2-amino-3-cyano-4-methyl-thiophene-5-carbon ester,
3-Amino-5-nitro-2,l-benzisothiazol, S-Amino-S-nitro-T-chlor^l-benzisothiazol. S-Amino-S-nitro^-brom^.l-benzisothiazol, 4-Amino-7-nitro-l,2-benzisothiazol. 4-Amino-5-bΓom-l,2-benzisothiazol,3-Amino-5-nitro-2, l-benzisothiazole, S-amino-S-nitro-T-chloro ^ l-benzisothiazole. S-Amino-S-nitro ^ -bromo ^ .l-benzisothiazole, 4-Amino-7-nitro-1,2-benzisothiazole. 4-Amino-5-bΓom-l, 2-benzisothiazole,
l,2-benzisothiazol. 1,2-benzisothiazol, r-7-nitro-1,2-benzisothiazol.1,2-benzisothiazole. 1,2-benzisothiazole, r-7-nitro-1,2-benzisothiazole.
Die neuen Farbstoffe sind gelb bis blau und eignen sich zum Farben von Textilmaterialicn aus Acrylnitrilpolymerisaten, synthetischen Polyamiden, Celluloseestern, wie 2'.2- oder Triacetat, und insbesondere von synthetischen linearen Polyestern, wie PoIyäthylenglykolterephthalat oder chemisch analog aufgebauten Polymeren. Man erhält farbstarke Färbungen, die sich durch hervorragende Echtheiten auszeichnen. The new dyes are yellow to blue and are suitable for coloring textile materials made from acrylonitrile polymers, synthetic polyamides, cellulose esters such as 2 '. 2 - or triacetate, and in particular from synthetic linear polyesters, such PoIyäthylenglykolterephthalat or chemically analog based polymers. Strong dyeings are obtained which are distinguished by excellent fastness properties.
Die Angaben über Teile und Prozente beziehen sich in den folgenden Beispielen auf das Gewicht, wenn es nicht anders vermerkt istThe data on parts and percentages in the following examples relate to weight, if it is not otherwise noted
Ein Gemisch aus 187 Teilen 2,6-Dichlor-3-cyan-4-methyl-pyridin, 200 Teilen Isopropanol und 300 Teilen Anilin wird 8 Stunden bei ungefähr 90 bis 100° C gerührt. Dann läßt man erkalten und gießt das Gemisch unter Rühren in etwa 1500 Teile Wasser, Teile konzentrierte Salzsäure und 200 Teile Eis. Man rührt noch 1 Stunde, saugt den ausgefallenenA mixture of 187 parts of 2,6-dichloro-3-cyano-4-methyl-pyridine, 200 parts of isopropanol and 300 parts of aniline is 8 hours at about 90 to 100 ° C touched. Then it is allowed to cool and the mixture is poured into about 1500 parts of water while stirring, Parts of concentrated hydrochloric acid and 200 parts of ice. The mixture is stirred for a further 1 hour and the precipitated product is sucked off
Niederschlag der wahrscheinlichen Formel CH3 CNPrecipitation of the probable formula CH 3 CN
-NH VS-NH VS
ClCl
ab und wäscht ihn mit Wasser neutral. Nach dem Trocknen erhält man ungefähr 240 Teile eines farblosen Pulvers, das bei 135 bis 140°C schmilzt. 12,2 Teile dieses Pulvers werden mit 40 Teilen y-Hydroxy-propylamin 6 Stunden bei 145 bis 1600C gerührt. Dann läßt man erkalten, versetzt das Gemisch mit 100 Teilen Wasser und säuert mit Salzsäure auf einen pH-Wert von etwa 0 bis 1 an. Man erhält — gegebenenfalls unter Zusatz von etwas Eisessigand washes it neutral with water. After drying, about 240 parts of a colorless powder which melts at 135 to 140.degree. C. are obtained. 12.2 parts of this powder are stirred with 40 parts of γ-hydroxypropylamine at 145 to 160 ° C. for 6 hours. The mixture is then allowed to cool, 100 parts of water are added and the mixture is acidified to a pH of about 0 to 1 with hydrochloric acid. One receives - optionally with the addition of a little glacial acetic acid
m> oder Dimethylformamid — eine Lösung der Kupplungskomponente der wahrscheinlichen Formelm> or dimethylformamide - a solution of the coupling component the likely formula
NH -CH2 -CH -CH2- OHNH -CH 2 -CH -CH 2 - OH
Die Lösung (oder Suspension) dieser Kupplungskomponente wird durch Zugabe von Eis auf 0 bis 3°C abgekühlt und mit einer Diazoniumsalzlösung versetzt, die man wie folgt erhält:The solution (or suspension) of this coupling component is cooled to 0 to 3 ° C by adding ice and using a diazonium salt solution which can be obtained as follows:
6,9 Teile p-Nitroanilin werden mit ungefähr 30 Teilen konzentrierter Salzsäure (30%ig| und 80 Teilen Wasser versetzt, dann wird das Gemisch auf 0cC abgekühlt und in Anteilen mit 15 Raumteilen 23%iger Natriumnitritlösung versetzt. Man rührt 2 StundenApproximately 30 parts of concentrated hydrochloric acid (30% strength | and 80 parts of water) are added to 6.9 parts of p-nitroaniline, then the mixture is cooled to 0 ° C. and 15 parts by volume of 23% strength sodium nitrite solution are added. The mixture is stirred for 2 hours
^o nach, beseitigt einen gegebenenfalls vorhandenen Überschuß an salpetriger Säure wie üblich und filtriert. ^ o after, eliminates any existing Excess of nitrous acid as usual and filtered.
Das Tütrat wird zum Kupplungsgemisch gegeben und man fügt dann unter Rühren nach und nach so viel Natriumacetat oder Natronlauge zu, daß der pH-Wert des Kupplungsgemisches etwa 2 bis 3 beträgt. Falls das Gemisch schwer rührbar wird, kann Eiswasser zugesetzt werden. Nach beendeter Kupplung wird das Gemisch auf 70 bis 8O0C erhitzt,The filtrate is added to the coupling mixture and sufficient sodium acetate or sodium hydroxide solution is then gradually added with stirring so that the pH of the coupling mixture is about 2 to 3. If the mixture becomes difficult to stir, ice water can be added. After coupling the mixture to 70 to 8O 0 C is heated,
5» filtriert, mit Wasser gewaschen und getrocknet Man erhält ungefähr 20 Teile eines rotb*aunen Putvers der wahrscheinlichen Formel5 »filtered, washed with water and dried Man receives about 20 parts of a reddish brown putver the likely formula
60 NH-CH2-CH2-CH2-OH 60 NH-CH 2 -CH 2 -CH 2 -OH
das sich in Dimethylformamid mit noter Farbe lös und Polyäthylenterephthalgewebe in kräftigen, klarer scharlachroten Tönen mit hervorragenden Echtheit« färbt.which dissolves in dimethylformamide with a noticeable color and polyethylene terephthalmic fabric in strong, clearer scarlet tones with excellent fastness «colors.
Analog der beschriebenen Verfahnansweise könnet die foigcnden durch Diazo- und Kupphmgskompo nente charakterisierten Farbstoffe erhalten werden.Analogous to the procedure described, the following can be achieved by diazo and copper compo nente characterized dyes can be obtained.
409683/19409683/19
Beispiel Nr.Example no.
IOIO
13 14 1513 14 15
ί6ί6
1717th
18 19 2018 19 20
21 22 21 22
DiazokomponenteDiazo component
CNCN
NH,NH,
CNCN
Kupplungskomponente CH3 CNCoupling component CH 3 CN
-NH-/-NH- /
1010
CH2 CH^ CH2 Ο "CHjCH2 CH ^ CH2 Ο "CHj
CH 2 CH2 OH
CH2-CH2-CH2-OHCH 2 CH 2 OH
CH 2 -CH 2 -CH 2 -OH
CH2-CH-OHCH 2 -CH-OH
CH3 CH 3
CH2-CH2-O-CH2-CH2-OH
CH2-CH2-O-CH3 CH 2 -CH 2 -O-CH 2 -CH 2 -OH
CH 2 -CH 2 -O-CH 3
-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH2-CH-OH-CH 2 -CH-OH
CH3
-CH2-CH2-O-CH2-CH2-OHCH 3
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH2-CH2-OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH2-CH2-OH-CH 2 -CH 2 -OH
CH3
—CH2-CH2-O-CH2-CH2-CH 3
-CH 2 -CH 2 -O-CH 2 -CH 2 -
OHOH
-CH2-CH2-OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH2-CH-OH-CH 2 -CH-OH
CH3
-CH2-CH2-O-CH2-CH2-OHCH 3
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
Farbtonhue
RotstichiggelbReddish yellow
GoldgelbGolden yellow
RotstichiggelbReddish yellow
RotstichiggelbReddish yellow
Rotstichiggelb GelbReddish yellow yellow
Rotstichiggelb Rotstichiggelb Rotstichiggelb RotstichiggelbRed-tinged yellow Red-tinged yellow Red-tinged yellow Red-tinged yellow
RotstichiggelfcRotstichiggelfc
RotstichiggelbReddish yellow
GoldgelbGolden yellow
GoldgelbGolden yellow
GoldgelbGolden yellow
GoldgelbGolden yellow
Goldgelb Goldgelb GoldgelbGolden yellow golden yellow golden yellow
GoldgelbGolden yellow
GoldgelbGolden yellow
itit
Fortsetzung Continuation
1212th
Beispiel Nr.Example no.
DiazokomponenteDiazo component
23 24 25 2623 24 25 26
CNCN
BrBr
28 29 30 3128 29 30 31
32 33 3432 33 34
36 37 38 3936 37 38 39
41 42 43 4441 42 43 44
4545
46 4746 47
COOCH3 COOCH 3
ClCl
48 49 5048 49 50
CH2 CH2 OHCH 2 CH 2 OH
CH2 CH2 CH2 OH
-CH2-CH-OHCH 2 CH 2 CH 2 OH
-CH 2 -CH-OH
CHjCHj
-CH2-CHj-O-CH2-CHjOH-CH 2 -CHj-O-CH 2 -CHjOH
C H2 CH2~~ OH
-CHj-CH2-CH2-OHCH 2 CH 2 ~~ OH
-CHj-CH 2 -CH 2 -OH
CH2 CH2 O CHt CH2 OHCH 2 CH 2 O CHt CH 2 OH
-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OCOCHj-CH 2 -CH 2 -CH 2 -OCOCHj
OH
/
— CH,-CHOH
/
- CH, -CH
CHjCHj
-CH2 CH2-O-CH2-CH2-OH
-CH2-CH2-O-CHj
-CH2-CH2-CH2-O-CHj
-CH2-CH2OCHO-CH 2 CH 2 -O-CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CHj
-CH 2 -CH 2 -CH 2 -O-CHj
-CH 2 -CH 2 OCHO
-(CH2I6-OH- (CH 2 I 6 -OH
-CH2-CH2-OH
-CH2-CH2-CH2-OH
—CHj—CHj— 0 -CH2- CH2- OH
OH-CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CHJ-CHj- 0 -CH 2 - CH 2 - OH
OH
-CH2-CH-CH 2 -CH
CH3 CH 3
-CH2-CH2-CH2- 0-CH3
— CH j— CHj— CH2 - OCOCH3 -CH 2 -CH 2 -CH 2 - O-CH 3
- CH j - CH j - CH 2 - OCOCH 3
-CHj—CH2-OH
-CH2-CH2-CH2-OH
-CH2- CH2- O—CHj— CHj--CHj-CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 - CH 2 - O — CHj— CHj-
OHOH
Farbtonhue
Rotorange Scharlach Scharlach ScharlachRed-orange scarlet scarlet scarlet fever
Braunstichigscharlach Brownish scarlet fever
Rotorange Scharlach Scharlach ScharlachRed-orange scarlet scarlet scarlet fever
Orangeorange
ScharlachScarlet fever
ScharlachScarlet fever
ScharlachScarlet fever
Scharlach Scharlach ScharlachScarlet fever scarlet fever
Rotorangescharlach Reddish scarlet fever
ScharlachScarlet fever
Gelbstichigro Gelbstichigro Gelbstichigro FeuerrotYellowishro yellowishro yellowishro fiery red
FeuerrotFire red
Feuerrot FeuerrotFire Red Fire Red
Schurlach Scharlach ScharlachSchurlach scarlet fever scarlet fever
1313th
Beispiel Nr.Example no.
51 52 5351 52 53
56 57 5856 57 58
59 60 6159 60 61
62 63 6462 63 64
65 66 67 6865 66 67 68
69 70 7169 70 71
72 73 74 75 7672 73 74 75 76
DiazokomponenteDiazo component
OCH,OCH,
Ο,ΝΟ, Ν
NH2 NH 2
NO,NO,
NH,NH,
N=CN = C
NH,NH,
NH,NH,
COOCH«COOCH «
SO3CH.,SO 3 CH.,
CI-CI-
y/ V y / V
-NH2 -NH 2
Fortsetzungcontinuation
1414th
R,R,
-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
CH;-CH2—OH
-CH2-CH2-CH2-OHCH; -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
CH2-CH2-OH
-CH2-CH2-CH2-OH
-CH2-CH2-O- CH2-- CH2-OHCH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O- CH 2 - CH 2 -OH
CH2-CH2-OHCH 2 -CH 2 -OH
O NH2 O NH 2
-CH2-Ci-I2-OH-CH 2 -Ci-I 2 -OH
-CH2-CH2-CH3-OH-CH 2 -CH 2 -CH 3 -OH
-CH2-CH2-CH2-O-CH3 -CH 2 -CH 2 -CH 2 -O-CH 3
-CH2-CH2-OH-CH 2 -CH 2 -OH
- CH2- CH2- CH2- OH- CH 2 - CH 2 - CH 2 - OH
-CHi-CH2-O-CH2-CH2-OH-CHi-CH 2 -O-CH 2 -CH 2 -OH
CH2-CH2-OH
-CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH
-CH2-CH2-O-CH3 CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH -CH 2 -CH 2 -O-CH 3
Farbtonhue
Rot
Fiol
RotRed
Fiol
Red
Scharlach ScharlachScarlet fever
Rotstichiggclt Rotstichiggell· RotstichiggellRotstichiggclt Rotstichiggell · Rotstichiggell
Rotorange Rotorange RotorangeRed-orange red-orange red-orange
Orange Orange OrangeOrange orange orange
Orange ' vange Orange Orange Orange 'vange Orange Orange
Goldgelb Goldgelb GoldgelbGolden yellow golden yellow golden yellow
GoldgelbGolden yellow
Orangeorange
Orangeorange
Orangeorange
Orangeorange
„ 3"3
rortsctziingrortsctziing
fr.game
fr.
C2H5- OC -^J^-NHj■ LA
C 2 H 5 - OC - ^ J ^ -NHj
OH—CH 2 —CHj CHj OH
OH
H O I Ir x == /
HO
1 I 0031 I 003
1010
Tabelle 2 KupplungskomponenteTable 2 coupling component
CH3 CNCH 3 CN
Nr.example
No.
96
9795
96
97
<T>-NHjCOOCH 3
<T> -NHj
-CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
Rotstichiggelb
RotstichiggelbReddish yellow
Reddish yellow
Reddish yellow
99
10098
99
100
<J^NHjCN
<J ^ NHj
-CH2-CH2-CH2-OH
-CH2-CH2-CH2-O-CH2-CH2-Oh-CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 2 -Oh
Goldgelb
GoldgelbGolden yellow
Golden yellow
Golden yellow
!02
103101
! 02
103
C1-/~V>-NH2 CN
C1- / ~ V> -NH 2
-CH2-CH2-CH2-OH
-CH2-CHj-O-CHj-CH2-OH-CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CHj-O-CHj -CH 2 -OH
Goldgelb
GoldgelbGolden yellow
Golden yellow
Golden yellow
105
106104
105
106
— CH2- CHj— CHj— OH
—CH2-CHj—O —CHj—CH2-OHCH2 (~ 1 * 2 OH
- CH 2 - CH 1 - CH 1 - OH
-CH 2 -CHj-O-CHj-CH 2 -OH
Scharlach
ScharlachScarlet fever
Scarlet fever
Scarlet fever
108
109
110107
108
109
110
Br-\^S~ NH2
Br
Cl
O2N--^ "V-NH2 CN
Br- \ ^ S ~ NH 2
Br
Cl
O 2 N - ^ "V-NH 2
— CH2-CH2-0—CH2-CHj—OH
-CHj-CHj-CH2-OH
-CHj-CHj-O-CH2-CH2-OH-CH 2 -CHj-CH 2 -OH
- CH 2 -CH 2 -0-CH 2 -CHj-OH
-CHj-CHj-CH 2 -OH
-CHj-CHj-O-CH 2 -CH 2 -OH
scharlach
Braunstichii;-
scharlach
Rot
RotBrownish tinge
Scarlet fever
Braunstichii; -
Scarlet fever
Red
Red
112111
112
I
Cl--<;_>-NHjCF,
I.
Cl - <;_> - NHj
— CH2-CK2-0—CH2-CH2-OH-CH 2 -CHj-CH 2 -OH
- CH 2 -CK 2 -0-CH 2 -CH 2 -OH
GoldgelbGolden yellow
Golden yellow
22Π22Π
Fortsetzungcontinuation
DiazokomponenteDiazo component
NH,NH,
-CU1- CH2- OH
CH2-CH2-CH2-OH
-CH2-CH2-CH2-O-CH3 -CU 1 - CH 2 - OH
CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -O-CH 3
Farbtonhue
Orange
Orange
Orangeorange
orange
orange
24,4 Teile des Umsetzungsproduktes von Anilin mit 2,6-Dichlor-3-cyan-4-methylpyridin (s. Beispiel 1) werden mit 80 Teilen y-Methoxypropylamin 8 Stunden unter Druck bei 140 bis 1600C gerührt, dann läßt man erkalten, setzt 8 Teile 50%ige Natronlauge zu pnd destilliert überschüssiges y-Methoxy-propylamin lind Wasser ab. Der Rückstand wird mit 100 Teilen $5%iger Schwefelsäure 5 Stunden bei 1000C behandelt. Nach dem Erkalten gießt man das Gemisch in eine Mischung von etwa 500 Teilen Wasser, 600 Teilen Eis und 100 Teilen 50%iger Natronlauge. Zu dem auf 00C abgekühlten Gemisch, das die Kupplungskomponente der wahrscheinlichen Formel24.4 parts of the reaction product of aniline with 2,6-dichloro-3-cyano-4-methylpyridine (see Example 1) are stirred with 80 parts of γ-methoxypropylamine for 8 hours under pressure at 140 to 160 ° C., then left cool, 8 parts of 50% sodium hydroxide solution and excess γ-methoxypropylamine and water are distilled off. The residue is treated with 100 parts of 5% strength sulfuric acid at 100 ° C. for 5 hours. After cooling, the mixture is poured into a mixture of about 500 parts of water, 600 parts of ice and 100 parts of 50% sodium hydroxide solution. To the mixture cooled to 0 0 C, which is the coupling component of the probable formula
CONH,CONH,
NHNH
NH- CH2- CH,- CH:— O—CH3 NH-CH 2 -CH, -CH : -O-CH 3
enthält, gibt man dann in Anteilen eine Lösung von diazotiertem S-Amino-S-nitro^.l-benzisothiazol, die wie folgt hergestellt wird:contains, one then gives in proportions a solution of diazotized S-amino-S-nitro ^ .l-benzisothiazole, the is made as follows:
19,5 Teile 3-Amino-5-nitro-2,l-benzisothiazol werden unter Rühren bei 15 bis 25° C in Portionen zu ungefähr 75 bis 85 Teilen 96%iger Schwefelsäure gegeben und auf 0 bis 4° C abgekühlt. Dann tropft man bei dieser Temperatur 32,5 Teile 23%ige Nitrosylschwefelsäure zu. Die Diazotierung ist nach etwa 4stündigem Rühren bei 0 bis 5° C beendet. Nach dem Versetzten des Kupplungsgemisches mit der Diazoniumlösung wird der pH-Wert des Gemisches durch Zugabe eines säurebindenden Mittels wie Natriumacetat (oder Natronlauge) auf ungefähr 1,5 bis 2,5 erhöht. Um eine gute Rührung bei 0 bis 5° C zu erreichen, setzt man dabei zweckmäßigerweise Eis und Eiswasser zu. Nach beendeter Kupplung wird das Gemisch auf 60 bis 80° C erwärmt, der ausgefallene Farbstoff abgesaugt und mit heißem Wasser gewaschen. Nach dem Trocknen erhält man etwa 40 Teile eines schwarzen FarbstoiTpulvers der wahrscheinlichen Formel19.5 parts of 3-amino-5-nitro-2, l-benzisothiazole are with stirring at 15 to 25 ° C in portions of about 75 to 85 parts of 96% sulfuric acid given and cooled to 0 to 4 ° C. 32.5 parts of 23% strength nitrosylsulfuric acid are then added dropwise at this temperature to. The diazotization is complete after about 4 hours of stirring at 0 to 5 ° C. After this Adding the diazonium solution to the coupling mixture increases the pH of the mixture Adding an acid binding agent such as sodium acetate (or caustic soda) to about 1.5 to 2.5 elevated. In order to achieve good stirring at 0 to 5 ° C., it is expedient to use ice and ice water too. After the coupling has ended, the mixture is heated to 60 to 80 ° C., the precipitated one Sucked off dye and washed with hot water. After drying you get about 40 parts of a black coloring powder of the probable formula
122 Teile des Umsetzungsproduktes von Anilin mit 2,6-Dichlor-3-cyan-4-methylpyridin (s. Beispiel 1) werden mit 150 Teilen N-Methylpyrrolidon und ungefähr 1000 Teilen 25%igem Ammoniak 15 Stunden bei 1800C im Autoklav behandelt Nach dem Erkalten wird das ausgefallene Produkt der wahrscheinlichen Formel122 parts of the reaction product of aniline with 2,6-dichloro-3-cyano-4-methylpyridine (see Example 1) are treated with 150 parts of N-methylpyrrolidone and approximately 1000 parts of 25% ammonia for 15 hours at 180 ° C. in an autoclave After cooling, the precipitated product becomes the likely formula
NH,NH,
abfiltriert, mit Wasser gewaschen und getrocknet. Man erhält etwa 108 Teile eines farblosen Produktes.filtered off, washed with water and dried. About 108 parts of a colorless product are obtained.
22,4 Teile dieses Produktes werden in ungefähr 100 Teilen Eisessig gelöst, dann durch Zugabe von Eis auf 0 bis 2°C abgekühlt und mit etwas Amidosulfonsäure versetzt. Zu diesem Kupplungsgemisch gibt man bei 00C in Anteilen eine Lösung von diazotiertem 2-Amino-5-nitro-benzonitril, die wie folgt hergestellt wird:22.4 parts of this product are dissolved in approximately 100 parts of glacial acetic acid, then cooled to 0 to 2 ° C. by adding ice, and a little sulfamic acid is added. For this coupling mixture at 0 0 C is added in portions a solution of diazotized 2-amino-5-nitro-benzonitrile, which is prepared as follows:
16,3 Teile 2-Amino-5-nitro-benzonitril werden in Anteilen zu einem auf 00C abgekühlten Gemisch von ungefähr 90 Teilen 96%iger Schwefelsäure und 32,5 Teilen 23%iger Nitrosylschwefelsäure gegeben. Nach 4- bis 5stündigem Rühren bei 0 bis 4° C ist die Diazotierung beendet.16.3 parts of 2-amino-5-nitro-benzonitrile are added in portions to a cooled to 0 0 C mixture of about 90 parts of 96% sulfuric acid and 32.5 parts of 23% nitrosylsulfuric acid. After 4 to 5 hours of stirring at 0 to 4 ° C., the diazotization is complete.
Um die Kupplung rasch und vollständig durchzuführen, wird das Kupplungsgemisch — das mit Eis und Eiswasser verdünnt werden kann — bei 0 bis 5°C durch Zugabe von Natriumacetatlösung auf den pH-Wert von etwa 2,5 eingestellt. Nach beendeter Kupplung wird das Gemisch auf etwa 8O0C erhitzt der ausgefallene Farbstoff der wahrscheinlichen Formel In order to carry out the coupling quickly and completely, the coupling mixture - which can be diluted with ice and ice water - is adjusted to a pH of about 2.5 at 0 to 5 ° C. by adding sodium acetate solution. After coupling is complete the mixture is heated to about 8O 0 C the precipitated dyestuff of the probable formula
CNCN
O,NO, N
CH3 CH 3
CNCN
N=NN = N
NH-<NH- <
NO,NO,
NH,NH,
CONH,CONH,
N=NN = N
NH-CH2-CH2-CH2-O-CH3 NH-CH 2 -CH 2 -CH 2 -O-CH 3
das sich in Dimethylformamid mit blauer Farbe löst und Polyäthylentercphthalatgewebe in grünstichigbkiuen Tönen mit sehr guten Echtheiten färbt.which dissolves in dimethylformamide with a blue color and polyethylene terephthalate fabric in green tinted colors Dyes shades with very good fastness properties.
abfiltriert und mit heißem Wasser gewaschen. Mai erhält ungefähr 38 Teile eines dunkelbraunen Pulvers das sich in Dimethylformamid mit roter Farbe lös und Polyäthylenterephthalatgewebe mit vorzüglichei Echtheiten in kräftigen rosa bis roten Tönen färbt.filtered off and washed with hot water. Mai receives about 38 parts of a dark brown powder which dissolves in dimethylformamide with red color and polyethylene terephthalate fabric with excellent egg Dyes fastness properties in strong pink to red tones.
Analog zu der in den Beispielen 1, 116 und 11 beschriebenen Arbeitsweise lassen sich die in dei folgenden Tabellen durch Diazo- und Kupplungs komponente charakterisierten Farbstoffe herstellenAnalogous to that in Examples 1, 116 and 11 The procedure described in the following tables can be carried out using diazo and coupling produce component characterized dyes
2121
Tabelle KupplungskomponenteCoupling component table
CH3 CNCH 3 CN
2222nd
NH-R2 NH-R 2
i Nn
I .— Si Bcispi
i Nn
I.—
I I18 I.
I I18
ιCN
ι
120«119
120
—CH,-CH-OH
ιCH 2 -CH 2 -CH 2 -OH
-CH, -CH-OH
ι
Rosapink
pink
CH3 I.
CH 3
ιBr
ι
X^ ti 2 \^ii2 V-^rI 2 \Jt~i X ^ ti 2 \ ^ ii2 V- ^ rI 2 \ Jt ~ i
Beispiel Nr.Example no.
139 140 141 142139 140 141 142
143 144 145143 144 145
146 147 148146 147 148
149 150 151149 150 151
152 153152 153
154 155 156 157 156154 155 156 157 156
159 160 161 162159 160 161 162
163 164 165163 164 165
2323
211 663211 663
Fortsetzungcontinuation
2424
Diazokomponente CNDiazo component CN
ClCl
COOCH.,COOCH.,
O2N-/ >- NH2 O 2 N - /> - NH 2
O3NO 3 N
COOCH.,COOCH.,
NH,NH,
-NH2 -NH 2
COOCH2-CH, OCH3 COOCH 2 -CH, OCH 3
NONO
O2N-O 2 N-
BrBr
O2NO 2 N
BrBr
CH2-CH2-OH
-CH2-CH2-CH2-OH
CH2-CH-OHCH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
CH 2 -CH-OH
CH3 CH 3
-CH2-CH2-O-CH2-CH2-OH
"CHj C H 2 O
C2H5 -CH 2 -CH 2 -O-CH 2 -CH 2 -OH
"CHj CH 2 O
C 2 H 5
CH2-CH2-OHCH 2 -CH 2 -OH
CH2-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
CH2-CH2-O-CH2-CH2-OHCH 2 -CH 2 -O-CH 2 -CH 2 -OH
CH2-CH2-OHCH 2 -CH 2 -OH
CH2-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
CH2-CH2-O-CH2-CH2-OHCH 2 -CH 2 -O-CH 2 -CH 2 -OH
C-H2 OH2
— CH2-CH2 -CH2-OHC-H2 OH2
- CH 2 -CH 2 -CH 2 -OH
CH2-CH2-OHCH 2 -CH 2 -OH
CH2-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
CH2-CH2-O-CH2-CH2-OH
-CH2-CH2-O-CH3 CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 3
-CH2-CH2-OH
-CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH
-CH2-CH2-O-COCH3 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-COCH 3
-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH2-CH-OH-CH 2 -CH-OH
CH3
-CH2-CH2-O-CH2-CH2-OHCH 3
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
Farbtonhue
Rubin Rubin Rubin RubinRuby ruby ruby ruby
Rubin Rubin RubinRuby ruby ruby
Rot Rot RotRed red red
Rot Rot RotRed red red
Rot RotRed Red
RotRed
DunkelrotDark red
DunkelrotDark red
DunkelrotDark red
DunkelrotDark red
Braunstichigrot Braunstichigrol Braunstichigrol Braunstichigro]Brownish tint Brownish tinted Brownish tinted Brownish tinted brown]
Braunstichigro Braunstichigro BraunstichigrcBrownish tintro Brownish tintedro Brownish tinted color
BraunstichignBrown cast
IBr
I.
Nr.example
No.
L^n2 V^n2 V^n2 Un Cl-J CU CiJ OLJ
L ^ n 2 V ^ n 2 V ^ n 2 Un
L rt2 V_*il2 tHj v/ ^*ML rt 2 V_ * il 2 tHj v / ^ * M
ItIt
Fortsetzungcontinuation
Nr.example
No.
UlN ι T s α μ // \ s / ν
UlN ι T s
αI.
α
1~Γ12 ^rI, LtIi \J ^- ^ll-i
Il fll r ^ LJ / ~ Ί1 O C ^ CtI
1 ~ Γ1 2 ^ rI, LtIi \ J ^ - ^ ll-i
Il
OIl
O
ItO
It
OHI.
OH
2929
Fortsetzungcontinuation
3030th
208 209208 209
210 211210 211
DiazokomponenteDiazo component
NO2 NO 2
)>-NH2 Br)> - NH 2 Br
O2NO 2 N
NH,NH,
212 213212 213
214 215214 215
216 217 218 219216 217 218 219
220 221 222220 221 222
223 224223 224
NCNC
O,NO, N
R,R,
-(CH2Ij-OH
CH2-CH2-O-CH2-CH2-OH- (CH 2 Ij-OH
CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
CH2-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
CH2 CH2-O —CH2-CH2-OHCH 2 CH 2 -O -CH 2 -CH 2 -OH
CH2CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OHCH 2 CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
/ 1^·>2/ 1 ^> 2
\ V \ V
ClCl
NH, CH2-CH2-OHNH, CH 2 -CH 2 -OH
CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH
-(CH2)J-O-ICH2U-OHCH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
- (CH 2 ) JO-ICH 2 U-OH
CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH
-(CH2J3- O -(CH2J4- OH CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
- (CH 2 J 3 - O - (CH 2 J 4 - OH
Farbtonhue
Violett ViolettViolet violet
Scharlachrot ScharlachroScarlet Scarlet
Scharlachro ScharlachroScarlet scarlet
Gelbstichig GelbstichigYellowish Yellowish
CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
Rubin Rubin Rubin RubinRuby ruby ruby ruby
Violett Violett Violett Violet violet violet
Violett ViolettViolet violet
3131
I Ύ I Ύ
i 663i 663
Fortsetzungcontinuation
DiazokomponenteDiazo component
O2NO 2 N
Ο,Ν-Ο, Ν-
CH3- S-CH 3 - S-
SO2C2H5 SO 2 C 2 H 5
-NH,-NH,
-N-N
NH,NH,
IiIi
CH3O-C-C2H4-S-1 NCH 3 OCC 2 H 4 -S- 1 N
N JLN JL
CH,CH,
O2N-I: y'-NH, SO 2 NI: y'-NH, S.
OIi
O
CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
CH, CH, CH, OHCH, CH, CH, OH
j-CH-
j
LM2 pil
LM 2
CH3 CH 3
CH2CH2-OHCH 2 CH 2 -OH
CH2-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
CH2-CH2-O-CH2-CH2-OHCH 2 -CH 2 -O-CH 2 -CH 2 -OH
FarbionColor ion
Violett ViolettViolet violet
Rubinruby
Rotviolett Rotviolelt RotviolcttRed violet red violet red violet
3333
Beispiel Nr.Example no.
DiazokomponenteDiazo component
NO2 NO 2
CNCN
j ■ 252j ■ 252
■4-■ 4-
CH3 CNCH 3 CN
aN-4 1-NH,aN-4 1-NH,
253253
CH, CNCH, CN
C==C SC == C S
/' j/ 'j
CN HCN H
V NV N
A AA A
Fortsetzungcontinuation
-CH2-CH1-CH3-OH-CH 2 -CH 1 -CH 3 -OH
-CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
FarbionColor ion
RotRed
Violett
Violettviolet
violet
- CH; CH2-OH
-CH2- (H2-CH2-OH
-CHv-CH2-O-CH2-CH2-OH- CH ; CH 2 -OH
-CH 2 - (H 2 -CH 2 -OH
-CHv-CH 2 -O-CH 2 -CH 2 -OH
-CH1-CH2-CH2-OH-CH 1 -CH 2 -CH 2 -OH
Roistichigt Rotstichigt RotstichigtRoistichigt Rotstichigt Rotstichigt
BliiuBliiu
Tabelle 4
KupplungskomponenteTable 4
Coupling component
CH3 CN
■ζ V-NH-R1 CH 3 CN
■ ζ V-NH-R 1
Beispiel! Nr. :Example! No. :
254 255 256254 255 256
257 258 259 260 261 262 263257 258 259 260 261 262 263
DiazokomponenteDiazo component
BrBr
Ο2Ν-<ζ V- NH,Ο 2 Ν- <ζ V- NH,
CNCN
o2ro 2 r
S-NH, -CH2-CH2-OH
-CH2-CH2-CH2-OHS-NH, -CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
CH2-CH2-O-CH2-CH2-OHCH 2 -CH 2 -O-CH 2 -CH 2 -OH
H
-CH2-CH2-OHH
-CH 2 -CH 2 -OH
C H 2 O H 2 C H 2 O H
-CH2-CH2-O-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2OCHo
-(CH2),-OH CH 2 OH 2 CH 2 OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 OCHo
- (CH 2 ), - OH
l'arhli'il'arhli'i
Rot
Rot
RoIRed
Red
RoI
Rosapink
RotRed
Rosapink
DunkclroDarkclro
Rosapink
Rosapink
Dunkel roDark red
I ifI if
JcispielExample
3535
DiazokomponenteDiazo component
Fortsetzungcontinuation
3636
264 265264 265
SO2CH3 Ο,Ν-^^y-NH,SO 2 CH 3 Ο, Ν - ^^ y-NH,
266 267 268 269266 267 268 269
270270
271 272 273 274271 272 273 274
275275
CNCN
BrBr
CNCN
O,N-<^ V-NH, CiO, N - <^ V-NH, Ci
NO,NO,
O2N-V V NH2 SO1CH1 O 2 NV V NH 2 SO 1 CH 1
276 277276 277
278 279278 279
O2N x O 2 N x
s's'
_y V^NH,_y V ^ NH,
BrBr
O1N-<f -NHO 1 N- <f -NH
280 28!280 28!
282282
O2N-f W--:,,--NH,O 2 Nf W -: ,, - NH,
7--NH2 -CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OH7 - NH 2 -CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH2-CH2-OH
-CH2-CH2-CH2-OH
—CH-,-CH-OH-CH 2 -CH 2 -OH
-CH 2 -CH 2 -CH 2 -OH
- CH -, - CH-OH
CH3
— CH-r-CH,—0 — CH-,— CH-,—CH 3
- CH-r-CH, -0 - CH -, - CH -, -
-CH,-CH2- OH
-CH2-CH2-CH2-OH
-CH2-CH2-O-CJi2-CH1-OH
(CH2),-0-(CH2I4-OH-CH, -CH 2 - OH
-CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CJi 2 -CH 1 -OH
(CH 2 ), - 0- (CH 2 I 4 -OH
-CH1-CH--CH-.--OH-CH 1 -CH - CH -.-- OH
CH2-CH2-CH2-OH
CH,-CH, O- CH1-CH, OHCH 2 -CH 2 -CH 2 -OH
CH, -CH, O-CH 1 -CH, OH
CH2CH2CH, -OHCH 2 CH 2 CH, -OH
CH,- CH, - OCH,- CHv-OIICH, - CH, - OCH, - CHv-OII
-CH2-CH2-CH2-OH
CH2 CII2- O CH2 CH2 OH-CH 2 -CH 2 -CH 2 -OH
CH 2 CII 2 - O CH 2 CH 2 OH
-CH1-CH1-O-CH1-CH2-OH-CH 1 -CH 1 -O-CH 1 -CH 2 -OH
FarmenFarms
Rubin RubinRuby ruby
Rubin Rubin Rubin RubinRuby ruby ruby ruby
Rubinruby
Rubin Rubin Rubin RubinRuby ruby ruby ruby
Violettviolet
Rubin RubinRuby ruby
Violet l ViolettViolet l violet
Marineblau MarineblauNavy blue navy blue
Blaublue
Nr.No.
283283
284 285 286284 285 286
287 288287 288
289 290289 290
291 292291 292
3737
DiazokomponenteDiazo component
Nr.No.
293 294 29 S293 294 29 p
OjN-f V=T-^H:OjN-f V = T - ^ H:
NO2 NO 2
O2N-/ VO 2 N / V
NH1 NH 1
NO,NO,
O2N-<f^>— NH2 O 2 N- <f ^> - NH 2
ClCl
NO1 NO 1
CNCN
O7N-O 7 N-
COOCH.,COOCH.,
-NH1 22Π 663-NH 1 22Π 663
Fortsetzungcontinuation
3838
DiazokomponenteDiazo component
ClCl
Q2N-<f>— N H2 Q 2 N- <f> - NH 2
-CH2-CH3-O-CH2-CH2-OH-CH 2 -CH 3 -O-CH 2 -CH 2 -OH
-CH2-CH2-OH-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH2-CH2-CH1-OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -CH 1 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH2-CH2-CH2-OH
-CH1-CH1-O-CH1- CH1-OH-CH 2 -CH 2 -CH 2 -OH
-CH 1 -CH 1 -O-CH 1 - CH 1 -OH
Kupplungskomponente
CH3 CONH-Coupling component
CH 3 CONH-
NHNH
NH-R2 NH-R 2
-CH2-CH2-O-COCH3
-CH2-CH2-CH2-O-COCH3 -CH 2 -CH 2 -O-COCH 3
-CH 2 -CH 2 -CH 2 -O-COCH 3
CH2 CH2 0~ CH3 CH 2 CH 2 0 ~ CH 3
Farbtonhue
Blaublue
Dunkel rot Dunkelrot DunkelrotDark red dark red dark red
Violett ViolettViolet violet
Violett ViolettViolet violet
Rot RotRed Red
Farbtonhue
Rot Rot Rot RotRed red red red
297 298 299 300 301 302297 298 299 300 301 302
303 304 305 306 307 308303 304 305 306 307 308
309 310 311 312 313 314 315 316 317309 310 311 312 313 314 315 316 317
Beispiel Nr.Example no.
3939
BrI ^
Br
^-Γΐ2 *-Γΐ2 ^*"* 7. ^ ^-"3^ -Γΐ2 * -Γΐ2 ^ * "* 7. ^ ^ -" 3
N XA /
N
ClCl
O5NO 5 N
NH,NH,
Kupplungskomponente
CH3 CONH2
^V-NH-R1 Table 6
Coupling component
CH 3 CONH 2
^ V-NH-R 1
Rot
409683/198Red
Red
409683/198
-CH2-CH2-CH2- OH-CH 2 - CH 2 -CH 2 - OCOCH 3
-CH 2 -CH 2 -CH 2 - OH
328 329 330 331 3j2 333328 329 330 331 3j2 333
4141
CNCN
O2N-<f>-NH2 O 2 N- <f> -NH 2
BrBr
O7NO 7 N
τ-ΝΗ,τ-ΝΗ,
O2NO 2 N
NH,NH,
Fortsetzungcontinuation
4242
-CH2-CH2-Ch2-OCOCH3
CH2-CH2-CH2-OH
-CH2-CH2-O-CH2-CH2-OCOCh3
-CH2-CH2-O-CH2-CH2-OCHo-CH 2 -CH 2 -Ch 2 -OCOCH 3
CH 2 -CH 2 -CH 2 -OH
-CH 2 -CH 2 -O-CH 2 -CH 2 -OCOCh 3
-CH 2 -CH 2 -O-CH 2 -CH 2 -OCHo
-CH2-CH2-CH2-O-COCH3 -CH 2 -CH 2 -CH 2 -O-COCH 3
-CH3-CH2-O-CH2-CH2-OCHo-CH 3 -CH 2 -O-CH 2 -CH 2 -OCHo
-CH2-Ch2-O-CH2-CH2-O-COCH3 -CH 2 -Ch 2 -O-CH 2 -CH 2 -O-COCH 3
-CH2-CH2-CH2-O-COCH3 -CH 2 -CH 2 -CH 2 -O-COCH 3
-CH2-CH2-CH2-OCOCH2-COCh3 -CH 2 -CH 2 -CH 2 -OCOCH 2 -COCh 3
-CH2-CH2-CH2-OH-CH 2 -CH 2 -CH 2 -OH
-CH2-CH2-O-CH2-CH2-OH-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
-CH2-CH2-O-Ch2-CH2-OCHO-CH 2 -CH 2 -O-Ch 2 -CH 2 -OCHO
-CH2-Ch2-O-CH2-CH2-OCOCH3 -CH 2 -Ch 2 -O-CH 2 -CH 2 -OCOCH 3
-CH2-CH2-O-CH2-Ch2-OCHO
-CH2-CH2-O-CH2-Ch2-O-COCH3
-CH2-CH2-O-CH2-CH2-OH
-(CH2),-Ο—(CH2U- OH-CH 2 -CH 2 -O-CH 2 -Ch 2 -OCHO
-CH 2 -CH 2 -O-CH 2 -Ch 2 -O-COCH 3
-CH 2 -CH 2 -O-CH 2 -CH 2 -OH
- (CH 2 ), - Ο— (CH 2 U-OH
Farbtonhue
Blaustichigrot
Blaustichigrot
Blaustichigrot
BlaustichigrotBluish red
Bluish red
Bluish red
Bluish red
Violett
Violett
Violettviolet
violet
violet
-CH2-CH2-O-CH2-CH2-OCOCh3
-CH2-CH2-CH2-O-CH3 -CH 2 -CH 2 -O-CH 2 -CH 2 -OCOCh 3
-CH 2 -CH 2 -CH 2 -O-CH 3
Grünstichigblau Grünstichigblau Grünstichigblau Grünstichigblau Grünstichigblau GrünstichigblauGreenish blue Greenish blue Greenish blue Greenish blue Greenish blue Greenish blue
Grünstichigblau Grünstichigblau Grünstich'gblau GrünstichigblauGreenish blue Greenish blue Greenish blue Greenish blue
Grünstichigblau GrünstichicblauGreenish blue Greenish blue
Analog können die folgenden Farbstoffe hergestellt werden:The following dyes can be prepared analogously:
NHNH
RotRed
CH3OCH2CH2-N y= CH 3 OCH 2 CH 2 -N y =
NH-CH2-CH2-O-CH2-CH2-Oh
CH3 CNNH-CH 2 -CH 2 -O-CH 2 -CH 2 -Oh
CH 3 CN
N=NN = N
>--NH> - NH
NH-CH2-CH2-O-CH2-CH2-OhNH-CH 2 -CH 2 -O-CH 2 -CH 2 -Oh
BlaustichigrotBluish red
Fortsetzungcontinuation
4444
Nr.No.
Yn \=/N = N - <^ ^> - NH— \ 7 Orange
Yn \ = /
SΝ — Ν
S.
N=N-<CV-NH~y~\ Scharlach
Yn \=/
nh- ch2- ch2-o-ch2-ch2- oh\ /
N = N- <CV-NH ~ y ~ \ scarlet fever
Yn \ = /
nh- ch 2 - ch 2 -o-ch 2 -ch 2 - oh
Beispiel 344 11 Teile des Farbstoffs der FormelExample 344 11 parts of the dye of the formula
CNCN
CNCN
CH3 CH 3
20 filtriert den ausgefallenen Niederschlag der Formel20 filtered the deposited precipitate of the formula
CH3 CNCH 3 CN
O2N-f >—N=N-< >—NH-/>O 2 Nf> -N = N- <> -NH- />
H NH-CH2-CH2-O-C=OH NH-CH 2 -CH 2 -OC = O
(Beispiel 118) ab, wäscht ihn mit Wasser und trocknet. Man erhält ungefähr 11 Teile eines dunkelbraunen Pulvers, das(Example 118), washes it with water and dries. You get about 11 parts of a dark brown powder that
werden mit 100 Raumteilen Ameisensäure 4 Stunden sich in Dimethylformamid mit roter Farbe löst und unter Rückflußkühlung erhitzt. Nach dem Erkalten Poiyäthylenterephthalatgewebe in rosa bis roten Tönen letzt man unter Rühren ungefähr 100 Teile Wasser zu, 3S mit hervorragenden Echtheiten färbt.are with 100 parts by volume of formic acid and dissolve in dimethylformamide with a red color for 4 hours heated to reflux. After cooling, polyethylene terephthalate fabric in pink to red tones Finally, about 100 parts of water are added with stirring, 3S is dyed with excellent fastness properties.
Claims (1)
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722211663 DE2211663C3 (en) | 1972-03-10 | 1972-03-10 | Azo dyes with 2,6-diaminopyrfdines as coupling components, process for their production and dye preparations |
| CH321773A CH596263A5 (en) | 1972-03-10 | 1973-03-05 | |
| CS163973A CS178421B2 (en) | 1972-03-10 | 1973-03-07 | |
| IN502/CAL/73A IN139039B (en) | 1972-03-10 | 1973-03-07 | |
| US05/338,859 US4042578A (en) | 1972-03-10 | 1973-03-07 | Azo dyes having 2,6-diaminopyridine derivatives as coupling components |
| DD169311A DD106192A5 (en) | 1972-03-10 | 1973-03-08 | |
| GB1140873A GB1422650A (en) | 1972-03-10 | 1973-03-09 | Azo dyes having 2,6-diaminopyridine derivatives as coupling components |
| BE128597A BE796542A (en) | 1972-03-10 | 1973-03-09 | AZOIC DYES OBTAINED FROM COPULANTS CONSISTING OF 2,6-DIAMINOPYRIDINE DERIVATIVES |
| IT48707/73A IT979789B (en) | 1972-03-10 | 1973-03-09 | AZOCOLORANTS WITH 2, 6 DIAMMINOPYRIDINE DERIVATIVES AS COPULATION COMPONENTS |
| FR7308567A FR2187857B1 (en) | 1972-03-10 | 1973-03-09 | |
| SU1891749A SU521848A3 (en) | 1972-03-10 | 1973-03-09 | The method of obtaining 2,6-diaminopyridine azo dye |
| NL7303378A NL7303378A (en) | 1972-03-10 | 1973-03-09 | |
| JP48027651A JPS6139347B2 (en) | 1972-03-10 | 1973-03-10 | |
| US05/711,863 USRE29640E (en) | 1970-12-19 | 1976-08-05 | Certain substituted 2,6-diamino-4-methyl-nicotinitriles the corresponding nicotinamides and derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722211663 DE2211663C3 (en) | 1972-03-10 | 1972-03-10 | Azo dyes with 2,6-diaminopyrfdines as coupling components, process for their production and dye preparations |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2211663A1 DE2211663A1 (en) | 1973-09-20 |
| DE2211663B2 DE2211663B2 (en) | 1974-05-30 |
| DE2211663C3 true DE2211663C3 (en) | 1975-01-16 |
Family
ID=5838560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19722211663 Expired DE2211663C3 (en) | 1970-12-19 | 1972-03-10 | Azo dyes with 2,6-diaminopyrfdines as coupling components, process for their production and dye preparations |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE796542A (en) |
| DE (1) | DE2211663C3 (en) |
| IN (1) | IN139039B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2640576B2 (en) | 1975-10-29 | 1980-02-07 | Bayer Ag, 5090 Leverkusen | Use of sulfonic acid group-free azo dyes for dyeing and printing non-tanned cellulose and non-tanned cellulose-containing! Textile material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2832020C2 (en) * | 1978-07-21 | 1982-12-23 | Basf Ag, 6700 Ludwigshafen | Disazo dyes with pyridine coupling components, their preparation and use |
| DE3021294A1 (en) * | 1980-06-06 | 1981-12-24 | Basf Ag, 6700 Ludwigshafen | METHOD FOR COLORING COATING MASKS, ORGANIC SOLVENTS AND MINERAL OIL PRODUCTS, AND NEW DYES |
| EP0433693B1 (en) * | 1989-11-22 | 1994-02-02 | Hoechst Mitsubishi Kasei Co., Ltd. | Water-insoluble monoazo dyes and mixture thereof |
| JP3234004B2 (en) * | 1991-12-13 | 2001-12-04 | ダイスタージャパン株式会社 | Disperse dye mixture |
| DE19706245A1 (en) * | 1997-02-18 | 1998-08-20 | Basf Ag | Trifluoromethyl substituted azo dyes |
-
1972
- 1972-03-10 DE DE19722211663 patent/DE2211663C3/en not_active Expired
-
1973
- 1973-03-07 IN IN502/CAL/73A patent/IN139039B/en unknown
- 1973-03-09 BE BE128597A patent/BE796542A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2640576B2 (en) | 1975-10-29 | 1980-02-07 | Bayer Ag, 5090 Leverkusen | Use of sulfonic acid group-free azo dyes for dyeing and printing non-tanned cellulose and non-tanned cellulose-containing! Textile material |
Also Published As
| Publication number | Publication date |
|---|---|
| IN139039B (en) | 1976-05-01 |
| DE2211663B2 (en) | 1974-05-30 |
| BE796542A (en) | 1973-09-10 |
| DE2211663A1 (en) | 1973-09-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| 8330 | Complete disclaimer |