CH370503A - Process for the production of new water-soluble azo dyes - Google Patents
Process for the production of new water-soluble azo dyesInfo
- Publication number
- CH370503A CH370503A CH6145558A CH6145558A CH370503A CH 370503 A CH370503 A CH 370503A CH 6145558 A CH6145558 A CH 6145558A CH 6145558 A CH6145558 A CH 6145558A CH 370503 A CH370503 A CH 370503A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- quaternization
- carried out
- water
- alkyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 13
- 239000000987 azo dye Substances 0.000 title claims description 7
- -1 azo compound Chemical class 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 238000004043 dyeing Methods 0.000 claims description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 3
- 125000002950 monocyclic group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims description 2
- 229940008406 diethyl sulfate Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000002825 nitriles Chemical group 0.000 claims description 2
- 238000005956 quaternization reaction Methods 0.000 claims 6
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 244000172533 Viola sororia Species 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 3
- HOQAPVYOGBLGOC-UHFFFAOYSA-N 1-ethyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CC HOQAPVYOGBLGOC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- GCMNJUJAKQGROZ-UHFFFAOYSA-N 1,2-Dihydroquinolin-2-imine Chemical compound C1=CC=CC2=NC(N)=CC=C21 GCMNJUJAKQGROZ-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NEKVNWJRLIKKJA-UHFFFAOYSA-N 1-propyl-9h-carbazole Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CCC NEKVNWJRLIKKJA-UHFFFAOYSA-N 0.000 description 1
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical compound SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 description 1
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- USYCQABRSUEURP-UHFFFAOYSA-N 1h-benzo[f]benzimidazole Chemical compound C1=CC=C2C=C(NC=N3)C3=CC2=C1 USYCQABRSUEURP-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
- LVQFHDAKZHGEAJ-UHFFFAOYSA-M 4-methylbenzenesulfonate Chemical compound [CH2]C1=CC=C(S([O-])(=O)=O)C=C1 LVQFHDAKZHGEAJ-UHFFFAOYSA-M 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 1
- LSZJZNNASZFXKN-UHFFFAOYSA-N 9-propan-2-ylcarbazole Chemical compound C1=CC=C2N(C(C)C)C3=CC=CC=C3C2=C1 LSZJZNNASZFXKN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C09B44/00—Azo dyes containing onium groups
- C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
- C09B44/103—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system characterised by the coupling component being a heterocyclic compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung neuer wasserlöslicher Azofarbstoffe Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung neuer wasserlöslicher Azo- farbstoffe der Formel
EMI0001.0006
worin Y+ den Rest einer gegebenenfalls durch nichtionogene Substituenten substituierten mono- oder poly- cyclischen heterocyclischen Diazokomponente,
welche mindestens ein quaterniertes Ringstick- stoffatom enthält, R2 Wasserstoff, einen gegebenenfalls durch nicht- ionogene Substituenten substituierten Arylrest, oder einen gegebenenfalls durch Halogen, Nitril, Hydroxy, -O-CO--Alkyl, -O-CO-Aralkyl, -0-C0 Aryl, -0-C0 NH-Alkyl,
-0-C0 NH-Aralkyl, -0-C0 NH Aryl oder niedrigmolekulares Alkoxy substituierten niedrigmolekularen Alkylrest und X- ein Anion bedeuten, oder von Derivaten von solchen Farb stoffen, bei denen die Ringe A und B weitere nicht- ionogene Substituenten tragen.
Die neuen wasserlöslichen Azofarbstoffe dienen zum Färben und Bedrucken von Gebilden aus Poly- merisaten mit mehr als 80% Acrylnitril, beispiels- weise Polyacrylnitril, z. B.
Orion (eingetragene Schutzmarke), und Copolymeren aus 95 % Acryl- nitril und 5 0/a Vinylacetat bzw. Methylacrylat bzw. Methyhnethacrylat in kräftigen Tönen, welche gute Licht-, Wasch-, Schweiss-, Sublimier-, Plissier-, Bügel-, Wasser-, Meerwasser- und Bleichechtheiten besitzen.
Einige der beschriebenen Farbstoffe zeichnen sich durch besonders gutes Egalisieren aus, eine Eigen schaft, die den meisten basischen Farbstoffen abgeht. Graue basische Farbstoffe, wie sie verfahrensgemäss hergestellt werden können, sind bis anhin nicht be kannt gewesen. Baumwolle, Viscose und Polyester- fasern werden reserviert, zum Teil besitzen die neuen Farbstoffe eine gute Wollreserve.
Sie eignen sich zum Teil auch zum Färben von Polyacrylnitril in der Masse in licht-, wasch- und schweissechten Tönen. Zum Teil sind auch diejenigen Abkömmlinge, welche eine gute Löslichkeit in organischen Lösungsmitteln besitzen, auch zum Färben von Ölen, Lacken, plasti schen Massen, Kunststoffen und Fasern, welche aus organischen Lösungsmitteln versponnen werden, in der Masse geeignet.
Beispielsweise werden Acetatkunstseide und Polyacrylnitrilfasern in der Masse in orangen bis blauen Tönen gefärbt, welche sehr gute Echtheits eigenschaften aufweisen.
Das erfindungsgemässe Verfahren ist dadurch gekennzeichnet, dass man 1 Mol einer wasserunlös lichen Azoverbindung der Formel
EMI0001.0095
worin R1 den Rest einer gegebenenfalls durch nicht- ionogene Substituenten substituierten mono- oder polycyclischen heterocyclischen Diazokomponente, welche mindestens ein tertiäres Ringstickstoffatom enthält, bedeutet, bzw.
die entsprechenden Derivate mit mindestens 1 Mol eines Quaternisierungsmittels umsetzt. Als Diazokomponenten Rl- NH, sind z. B.
die Aminoderivate eines gegebenenfalls durch nicht- ionogene Gruppen substituierten Thiazols, Benzo- thiazols, eines höher kondensierten Thiazols, eines Pyrazols, Cinnolins, Imidazols, Triazols, Tetrazols, Oxazols, Thiodiazols, Benzimidazols, Naphthimid- azols,
Indazols, Pyridins oder Chinolins geeignet.
Die Umsetzung des wasserunlöslichen Azofarb- stoffes mit dem Alkylierungsmittel erfolgt in einem inerten Lösungsmittel oder gegebenenfalls in wäss riger Suspension und bei erhöhter Temperatur und in gegebenenfalls gepuffertem Medium.
Geeignete Alkylierungsmittel sind z. B. die Ester starker Mineralsäuren und organischer Sulfonsäuren, Alkylchloride und -bromide, Aralkylhalogenide, Di- alkylsulfate und gegebenenfalls substituierte Benzol- sulfonsäureester wie Methyl-, Äthyl-, Propyl-, n-Butylester der Benzolsulfonsäure, 2- oder 4-Methyl- benzolsulfonsäure,
4-Chlor-benzolsulfonsäure oder 4 Nitro-benzolsulfonsäure.
Die Abtrennung der gebildeten wasserlöslichen Produkte kann nach einer der üblichen Grundopera tionen wie z. B. Filtration, Einengen des Lösungs mittels, Fällung aus dem Lösungsmittel mit einem geeigneten Medium erfolgen.
Als Anionen sind sowohl organische wie anorga nische Anionen geeignet, wie z. B. die Formiat-, Acetat-, Oxalat-, Lactat-ionen oder die Chlorid-, Bromid-, Iodid-, Methylsulfat-, Äthylsulfat-, Sulfat-, Bisulfat-, Benzolsulfonat-, 4-Methyl-benzolsulfonat-, 4-Chloro-benzolsulfonat-ionen.
Ebenfalls geeignet sind wasserlösliche Doppel salzverbindungen der Farbstoffbasen mit gewissen anorganischen Salzen wie z. B. Zinkchlorid.
Im folgenden Beispiel sind unter Teilen Gewichts teile und unter Prozenten Gewichtsprozente zu ver stehen; die Temperaturen sind in Celsiusgraden an gegeben und die Schmelzpunkte sind unkorrigiert. <I>Beispiel</I> 30,6 Teile der wasserunlöslichen Azoverbindung der Formel
EMI0002.0075
werden in 500 Teilen Chlorbenzol aufgeschlämmt und unter starkem Rühren bei 1000 mit 15 Teilen Dimethylsulfat tropfenweise versetzt.
Die rote Lösung schlägt langsam nach blauviolett um und der qua- ternierte Farbstoff scheidet sich in harten Kristallen aus und wird nach Beendigung der Reaktion abfil- triert und getrocknet.
Zwecks Reinigung kann das erhaltene dunkle Pulver in heissem Wasser gelöst werden und mit Natriumchlorid wieder ausgefällt werden. Man erhält auf diese Weise einen gereinigten Farbstoff, welcher sich in Schwefelsäure mit gelber und in Wasser mit violetter Farbe löst und Polyacrylnitrilfasern aus wässriger Suspension wie in der Spinnmasse in violet ten Tönen von sehr guten Echtheitseigenschaften anfärbt.
Das Färben kann z. B. wie folgt geschehen: Man verpastet 1 Teil des nach Beispiel erhältli chen Farbstoffes mit wenig kaltem weichem Wasser. Die Paste wird in 4000 Teile Wasser eingerührt und die Lösung wird mit verdünnter Essigsäure auf den pH-Wert 5-6 eingestellt. In dieses Färbebad bringt man bei 30 100 Teile Orion 42 (eingetragene Schutzmarke) ein; man erhitzt das Färbebad inner halb von 30 Minuten zum Sieden und hält es während 1 Stunde auf Siedetemperatur. Das gefärbte Orion wird aus der Flotte herausgenommen, mit Wasser gespült und getrocknet.
Die erhaltene Färbung besitzt eine gute Lichtechtheit und gute Nassechtheiten.
Farbstoffe von ähnlichen Eigenschaften werden erhalten, wenn man entsprechend obigem Beispiel die folgenden wasserunlöslichen Azoverbindungen alky- liert:
EMI0002.0098
Diazokomponente <SEP> Kupplungskomponente <SEP> Alkylierungsmittel <SEP> Farbe <SEP> der <SEP> Färbungen <SEP> auf
<tb> Polyacrylnitrilfasern
<tb> 2-Amino-thiazol <SEP> N-Methyl-carbazol <SEP> Dimethylsulfat <SEP> violett
<tb> >, <SEP> N <SEP> Propyl-carbazol <SEP> <SEP>
<tb> ,
> <SEP> N-Isopropyl-carbazol <SEP> <SEP>
<tb> <SEP> N-2'-Hydroxy-äthyl-carbazol <SEP> <SEP>
<tb> " <SEP> N-2'-Cyan-äthyl-carbazol <SEP> <B> <SEP> </B>
<tb> N-2'-Chlor-äthyl-carbazol <SEP> <SEP>
EMI0003.0001
Diazokomponente <SEP> Kupplungskomponente <SEP> <U>A</U>lkylierungsmittel <SEP> Farbe <SEP> der <SEP> Färbungen <SEP> auf
<tb> 1 <SEP> Polyacrylnitrilfasern
<tb> 2-Amino-thiazol <SEP> N-2'-Acetoxy-äthyl-carbazol <SEP> Dimethylsulfat <SEP> violett
<tb> <SEP> LV-2'-Propionyloxy-äthyl-carbazol <SEP> <B> <SEP> </B>
<tb> <SEP> hT-2'-Benzoxy-äthyl-carbazol <SEP>
<tb> <SEP> N-2'-äthylcarbaminsaures <SEP>
<tb> Äthylcarbazol
<tb> <SEP> N-2'-phenylcarbaminsaures <SEP> <SEP>
<tb> Athylcarbazol
<tb> <SEP> N-2'-Methoxy-äthyl-carbazol <SEP> <B> <SEP> </B>
<tb> <SEP> IV-2'-Athoxy-äthyl-carbazol <SEP> <SEP>
<tb> <SEP> hT-1'-Methyl-2'-hydroxy- <SEP> <SEP>
<tb> äthyl-carbazol
<tb> <SEP> IN-Benzyl-carbazol <SEP>
<tb> 2-Amino-benzothiazol <SEP> N-Äthyl-carbazol <SEP> <SEP> blau
<tb> 2-Amino-6-methyl- <SEP> <B> <SEP> </B> <SEP>
<tb> benzothiazol
<tb> 2-Amino-6-methoxy- <SEP> <SEP> <B> <SEP> </B>
<tb> benzothiazol
<tb> 2 <SEP> Amino-6-äthoxy- <SEP> <SEP> <B> <SEP> </B>
<tb> benzothiazol
<tb> 2-Amino-pyridin <SEP> > > <SEP> violett
<tb> 2-Amino-chinolin <SEP> <SEP> <SEP>
<tb> 2-Amino-5-methyl- <SEP> <B>D <SEP> <SEP> </B>
<tb> thiazol
<tb> 2-Amino-triazol <SEP> <SEP> <SEP> rot
<tb> 2-Amino-benzimidazol <SEP> <SEP> <SEP> violett
<tb> 2-Amino-6-methyl- <SEP> <B> <SEP> <SEP> </B>
<tb> oxazol
<tb> 2-Amino-6-methoxy- <SEP> <B>D <SEP> D <SEP> </B>
<tb> oxazol
<tb> 2-Amino-thiazol <SEP> <SEP> Diäthylsulfat <SEP>
<tb> <B>
<SEP> </B> <SEP> Benzylchlorid <SEP>
<tb> <SEP> <SEP> 4-Methyl-benzol- <SEP>
<tb> sulfonsäure propylester
<tb> <SEP> <SEP> Butyljodid <SEP>
<tb> 2-Amino-6-methoxy- <SEP> IV-2'-Cyan-äthyl-carbazol <SEP> Dimethylsulfat <SEP> blau
<tb> benzothiazol
<tb> <SEP> IV-Äthyl-3-acetylamino-carbazol <SEP> @ >
Process for the preparation of new water-soluble azo dyes The present invention relates to a process for the preparation of new water-soluble azo dyes of the formula
EMI0001.0006
wherein Y + is the radical of a mono- or polycyclic heterocyclic diazo component optionally substituted by non-ionic substituents,
which contains at least one quaternized ring nitrogen atom, R2 is hydrogen, an aryl radical which is optionally substituted by non-ionic substituents, or an aryl radical which is optionally substituted by halogen, nitrile, hydroxy, -O-CO-alkyl, -O-CO-aralkyl, -0- C0 aryl, -0-C0 NH-alkyl,
-0-C0 NH-aralkyl, -0-C0 NH aryl or low-molecular-weight alkoxy-substituted low-molecular-weight alkyl radical and X- mean an anion, or of derivatives of those dyes in which the rings A and B carry further non-ionic substituents.
The new water-soluble azo dyes are used for dyeing and printing structures made of polymers with more than 80% acrylonitrile, for example polyacrylonitrile, e.g. B.
Orion (registered trademark), and copolymers made of 95% acrylonitrile and 5 0 / a vinyl acetate or methyl acrylate or methyl methacrylate in strong tones, which are good for light, washing, welding, sublimation, pleating, ironing, Have fastness to water, seawater and bleach.
Some of the dyes described are characterized by particularly good leveling, a property that most basic dyes lack. Gray basic dyes, as they can be produced according to the process, have not been known to date. Cotton, viscose and polyester fibers are reserved; some of the new dyes have a good reserve of wool.
Some of them are also suitable for dyeing polyacrylonitrile in bulk in shades which are fast to light, wash and perspiration. In some cases, those derivatives which have good solubility in organic solvents are also suitable in the mass for dyeing oils, paints, plastic masses, plastics and fibers that are spun from organic solvents.
For example, acetate rayon and polyacrylonitrile fibers are dyed in the mass in orange to blue tones, which have very good fastness properties.
The process according to the invention is characterized in that 1 mol of a water-insoluble azo compound of the formula
EMI0001.0095
where R1 is the radical of a mono- or polycyclic heterocyclic diazo component which is optionally substituted by non-ionic substituents and which contains at least one tertiary ring nitrogen atom, or
reacting the corresponding derivatives with at least 1 mol of a quaternizing agent. As diazo components Rl-NH, z. B.
the amino derivatives of a thiazole, benzothiazole, a more highly condensed thiazole, a pyrazole, cinnoline, imidazole, triazole, tetrazole, oxazole, thiodiazole, benzimidazole, naphthimidazole, optionally substituted by nonionic groups,
Indazole, pyridine or quinoline suitable.
The reaction of the water-insoluble azo dye with the alkylating agent takes place in an inert solvent or, if appropriate, in aqueous suspension and at an elevated temperature and, if appropriate, in a buffered medium.
Suitable alkylating agents are e.g. B. the esters of strong mineral acids and organic sulfonic acids, alkyl chlorides and bromides, aralkyl halides, dialalkyl sulfates and optionally substituted benzenesulfonic acid esters such as methyl, ethyl, propyl, n-butyl esters of benzenesulfonic acid, 2- or 4-methylbenzenesulfonic acid ,
4-chloro-benzenesulfonic acid or 4-nitro-benzenesulfonic acid.
The separation of the water-soluble products formed can after one of the usual basic operations such. B. Filtration, concentration of the solution means, precipitation from the solvent with a suitable medium.
As anions, both organic and inorganic anions are suitable, such as. B. the formate, acetate, oxalate, lactate ions or the chloride, bromide, iodide, methyl sulfate, ethyl sulfate, sulfate, bisulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4- Chlorobenzenesulfonate ions.
Also suitable are water-soluble double salt compounds of the dye bases with certain inorganic salts such as. B. zinc chloride.
In the following example, parts are parts by weight and percentages are percentages by weight; the temperatures are given in degrees Celsius and the melting points are uncorrected. <I> Example </I> 30.6 parts of the water-insoluble azo compound of the formula
EMI0002.0075
are suspended in 500 parts of chlorobenzene and, with vigorous stirring at 1000, 15 parts of dimethyl sulfate are added dropwise.
The red solution slowly turns blue-violet and the quaternized dye separates out in hard crystals and is filtered off and dried after the reaction has ended.
For cleaning purposes, the dark powder obtained can be dissolved in hot water and reprecipitated with sodium chloride. In this way, a purified dye is obtained which dissolves in sulfuric acid with a yellow color and in water with a violet color and dyes polyacrylonitrile fibers from aqueous suspension as in the spinning material in violet shades of very good fastness properties.
The dyeing can e.g. B. done as follows: 1 part of the dye obtainable according to the example is pasted with a little cold soft water. The paste is stirred into 4000 parts of water and the solution is adjusted to pH 5-6 with dilute acetic acid. 100 parts of Orion 42 (registered trademark) are introduced into this dyebath at 30; the dyebath is heated to the boil within 30 minutes and kept at the boiling temperature for 1 hour. The colored Orion is removed from the liquor, rinsed with water and dried.
The dyeing obtained has good lightfastness and good wetfastness.
Dyes with similar properties are obtained if the following water-insoluble azo compounds are alkylated according to the above example:
EMI0002.0098
Diazo component <SEP> Coupling component <SEP> Alkylating agent <SEP> Color <SEP> of the <SEP> colors <SEP> on
<tb> polyacrylonitrile fibers
<tb> 2-Amino-thiazole <SEP> N-Methyl-carbazole <SEP> Dimethyl sulfate <SEP> violet
<tb>>, <SEP> N <SEP> Propyl-carbazole <SEP> <SEP>
<tb>,
> <SEP> N-isopropyl-carbazole <SEP> <SEP>
<tb> <SEP> N-2'-hydroxy-ethyl-carbazole <SEP> <SEP>
<tb> "<SEP> N-2'-cyano-ethyl-carbazole <SEP> <B> <SEP> </B>
<tb> N-2'-chloro-ethyl-carbazole <SEP> <SEP>
EMI0003.0001
Diazo component <SEP> Coupling component <SEP> <U> A </U> alkylating agent <SEP> color <SEP> of the <SEP> colors <SEP>
<tb> 1 <SEP> polyacrylonitrile fibers
<tb> 2-Amino-thiazole <SEP> N-2'-acetoxy-ethyl-carbazole <SEP> dimethyl sulfate <SEP> violet
<tb> <SEP> LV-2'-propionyloxy-ethyl-carbazole <SEP> <B> <SEP> </B>
<tb> <SEP> hT-2'-Benzoxy-ethyl-carbazole <SEP>
<tb> <SEP> N-2'-ethylcarbamic acid <SEP>
<tb> ethyl carbazole
<tb> <SEP> N-2'-phenylcarbamic acid <SEP> <SEP>
<tb> Ethylcarbazole
<tb> <SEP> N-2'-methoxy-ethyl-carbazole <SEP> <B> <SEP> </B>
<tb> <SEP> IV-2'-ethoxy-ethyl-carbazole <SEP> <SEP>
<tb> <SEP> hT-1'-methyl-2'-hydroxy- <SEP> <SEP>
<tb> ethyl-carbazole
<tb> <SEP> IN-Benzyl-carbazole <SEP>
<tb> 2-Amino-benzothiazole <SEP> N-Ethyl-carbazole <SEP> <SEP> blue
<tb> 2-Amino-6-methyl- <SEP> <B> <SEP> </B> <SEP>
<tb> benzothiazole
<tb> 2-Amino-6-methoxy- <SEP> <SEP> <B> <SEP> </B>
<tb> benzothiazole
<tb> 2 <SEP> Amino-6-ethoxy- <SEP> <SEP> <B> <SEP> </B>
<tb> benzothiazole
<tb> 2-Amino-pyridine <SEP>>> <SEP> violet
<tb> 2-amino-quinoline <SEP> <SEP> <SEP>
<tb> 2-Amino-5-methyl- <SEP> <B> D <SEP> <SEP> </B>
<tb> thiazole
<tb> 2-Amino-triazole <SEP> <SEP> <SEP> red
<tb> 2-Amino-benzimidazole <SEP> <SEP> <SEP> violet
<tb> 2-Amino-6-methyl- <SEP> <B> <SEP> <SEP> </B>
<tb> oxazole
<tb> 2-Amino-6-methoxy- <SEP> <B> D <SEP> D <SEP> </B>
<tb> oxazole
<tb> 2-Amino-thiazole <SEP> <SEP> Diethyl sulfate <SEP>
<tb> <B>
<SEP> </B> <SEP> Benzyl chloride <SEP>
<tb> <SEP> <SEP> 4-methyl-benzene- <SEP>
<tb> sulfonic acid propyl ester
<tb> <SEP> <SEP> butyl iodide <SEP>
<tb> 2-Amino-6-methoxy- <SEP> IV-2'-cyano-ethyl-carbazole <SEP> dimethyl sulfate <SEP> blue
<tb> benzothiazole
<tb> <SEP> IV-ethyl-3-acetylamino-carbazole <SEP> @>
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6145558A CH370503A (en) | 1958-07-07 | 1958-07-07 | Process for the production of new water-soluble azo dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6145558A CH370503A (en) | 1958-07-07 | 1958-07-07 | Process for the production of new water-soluble azo dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH370503A true CH370503A (en) | 1963-07-15 |
Family
ID=4523651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH6145558A CH370503A (en) | 1958-07-07 | 1958-07-07 | Process for the production of new water-soluble azo dyes |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH370503A (en) |
-
1958
- 1958-07-07 CH CH6145558A patent/CH370503A/en unknown
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