CH367254A - Process for the preparation of monoazo dyes that are sparingly soluble in water - Google Patents
Process for the preparation of monoazo dyes that are sparingly soluble in waterInfo
- Publication number
- CH367254A CH367254A CH6106458A CH6106458A CH367254A CH 367254 A CH367254 A CH 367254A CH 6106458 A CH6106458 A CH 6106458A CH 6106458 A CH6106458 A CH 6106458A CH 367254 A CH367254 A CH 367254A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- water
- group
- parts
- monoazo dyes
- Prior art date
Links
- 239000000975 dye Substances 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 7
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title claims description 6
- 238000004043 dyeing Methods 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- -1 propionyloxy group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 3
- 150000008049 diazo compounds Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims 3
- 229920003023 plastic Polymers 0.000 claims 3
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000004922 lacquer Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 29
- 239000000835 fiber Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- VLMRGLCBIFWPGL-UHFFFAOYSA-N 2-chloro-4-methylsulfonylaniline Chemical compound CS(=O)(=O)C1=CC=C(N)C(Cl)=C1 VLMRGLCBIFWPGL-UHFFFAOYSA-N 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 229940081735 acetylcellulose Drugs 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920004934 Dacron® Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- VCSNPTXBUJEECX-UHFFFAOYSA-N 2,4-bis(methylsulfonyl)aniline Chemical compound CS(=O)(=O)C1=CC=C(N)C(S(C)(=O)=O)=C1 VCSNPTXBUJEECX-UHFFFAOYSA-N 0.000 description 1
- WNGFDYJEGYVMQZ-UHFFFAOYSA-N 2-amino-5-methylsulfonylbenzenesulfonic acid Chemical compound CS(=O)(=O)C1=CC=C(N)C(S(O)(=O)=O)=C1 WNGFDYJEGYVMQZ-UHFFFAOYSA-N 0.000 description 1
- YWQXPTOZAIEGIL-UHFFFAOYSA-N 2-amino-n-methyl-1,3-benzothiazole-6-sulfonamide Chemical group CNS(=O)(=O)C1=CC=C2N=C(N)SC2=C1 YWQXPTOZAIEGIL-UHFFFAOYSA-N 0.000 description 1
- MZMFEJWZHIUPSC-UHFFFAOYSA-N 2-amino-n-methyl-1,3-thiazole-5-sulfonamide Chemical group CNS(=O)(=O)C1=CN=C(N)S1 MZMFEJWZHIUPSC-UHFFFAOYSA-N 0.000 description 1
- RNUAVRNGQSIXMZ-UHFFFAOYSA-N 4-amino-n-ethyl-n-methylbenzenesulfonamide Chemical compound CCN(C)S(=O)(=O)C1=CC=C(N)C=C1 RNUAVRNGQSIXMZ-UHFFFAOYSA-N 0.000 description 1
- XJEVFFNOMKXBLU-UHFFFAOYSA-N 4-methylsulfonylaniline Chemical compound CS(=O)(=O)C1=CC=C(N)C=C1 XJEVFFNOMKXBLU-UHFFFAOYSA-N 0.000 description 1
- YEUFRAFORHUMLC-UHFFFAOYSA-N 5-methylsulfonyl-1,3-thiazol-2-amine Chemical compound CS(=O)(=O)C1=CN=C(N)S1 YEUFRAFORHUMLC-UHFFFAOYSA-N 0.000 description 1
- ZYHNHJAMVNINSY-UHFFFAOYSA-N 6-methylsulfonyl-1,3-benzothiazol-2-amine Chemical compound CS(=O)(=O)C1=CC=C2N=C(N)SC2=C1 ZYHNHJAMVNINSY-UHFFFAOYSA-N 0.000 description 1
- HBAKJBGOHINNQM-UHFFFAOYSA-N 9-benzylcarbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1CC1=CC=CC=C1 HBAKJBGOHINNQM-UHFFFAOYSA-N 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
- 229920000742 Cotton Polymers 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HTHKZOCCOVYKKI-UHFFFAOYSA-N dinaphthalen-1-ylmethanedisulfonic acid;sodium Chemical compound [Na].C1=CC=C2C(C(C=3C4=CC=CC=C4C=CC=3)(S(=O)(=O)O)S(O)(=O)=O)=CC=CC2=C1 HTHKZOCCOVYKKI-UHFFFAOYSA-N 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
- F02C7/26—Starting; Ignition
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung in Wasser schwer löslicher 1Vlonoazofarbstoffe Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung neuer, in Wasser schwer löslicher Monoazofarbstoffe der Formel
EMI0001.0004
R1 einen von Nitrogruppen und wasserlöslich machenden Gruppen freien Rest der Benzol-, Thiazol- oder Benzothiazolreihe, R" niedrigmolekulares Alkyl, Alkenyl, Cyanalkyl,
Halogenalkyl oder eine gegebenenfalls mono- oder disubstituierte Aminogruppe, R3 Wasserstoff oder einen gegebenenfalls durch Halogenatome, durch die Nitrilgruppe, die Acet- oxygruppe, die Propionyloxygruppe, die Methoxy- oder die Äthoxygruppe substituierten niedrig molekularen Alkylrest oder einen Arylrest,
x und y Wasserstoff oder zusammen die direkte C-C-Bindung bedeuten, und worin der Ring R4 weitere nicht wasserlöslich machende Substituen- ten tragen kann.
Das erfindungsgemässe Verfahren ist dadurch gekennzeichnet, dass man 1 Mol der Diazoverbin- dung aus einem Amin der Formel R,- O,S-R,-NH.= mit 1 Mol der Verbindung der Formel
EMI0001.0037
kuppelt. Die Kupplung der Diazoverbindungen mit den Azokomponenten erfolgt vorzugsweise in saurem, gegebenenfalls gepuffertem Medium.
Die neuen, in Wasser schwer löslichen Monoazo- farbstoffe ziehen zum Teil in Suspension auf synthe tische Polyamidfasern (z. B. Nylon, Perlon , Ril- san , eingetragene Schutzmarken), auf Celluloseester- fasern (z. B. Acetatkunstseide, Triacetatkunstseide), Polyvinylfasem, Polyacrylnitrilfasern, Terephthal- säureesterfasern (z.
B. Terylene , Dacron , einge tragene Schutzmarken) in brillanten gelben, orangen und roten Tönen auf. Ihre Färbungen zeichnen sich insbesondere durch hervorragende Licht-, Wasch-, Wasser-, Meerwasser-, Schweiss-, Plissier-, Bügel-, Thermofixier-, Rauchgas- und Chlorechtheit aus. Ausserdem sind sie weiss ätzbar. Die Farbstoffe reser vieren Baumwolle, Viskose und Wolle weitgehend und die Anschmutzungen lassen sich durch eine Be handlung mit Hydrosulfit reinigen.
Zum Teil sind die neuen Farbstoffe auch zum Färben von Lacken, Ölen, Kunstharzen und von künstlichen Fasern in der Masse geeignet.
Als Diazokomponenten sind insbesondere 1-Amino-benzol-4-sulfonsäuremethyl- und -dimethylamid, 1-Amino-4-methylsulfonyl-benzol, 1-Amino-2-halogen- bzw. -cyano-benzol- 4-sulfonsäuremethyl- und -dimethylamide, 1-Amino-2-halogen- bzw.
-cyano-4-methyl- sulfonyl-benzole, 1-Amino-2,4-bis-(methylsulfonyl)-benzol, 1-Amino-2-methylsulfonyl-benzol-4-sulfonsäure- methyl- und -dimethylamid, 1-Amino-4-methylsulfonyl-benzol-2-sulfonsäure- methyl- und -dimethylamid, 1-Amino-2,5-dihalogen-benzol-4-sulfonsäure- methyl- und -dimethylamide, 1-Amino-2,5-dihalogen-4-methylsulfonyl-benzole,
2-Amino-thiazol-5-sulfonsäuremethyl- und -dimethylamid, 2-Amino-5-methylsulfonylthiazol, 2-Aminobenzothiazol-6-sulfonsäuremethyl- und -dimethylamid, 2-Amino-6-methylsulfonyl-benzothiazol, 2-Amino-4-halogen-benzothiazol-6-sulfonsäure- methyl- und -dimethylamide sowie 2-Amino-4-halogen-6-methylsulfonyl- benzothiazole von Interesse.
In den nachfolgenden Beispielen sind unter Tei len Gewichtsteile und unter Prozenten Gewichts prozente zu verstehen; die Temperaturen sind in Cel siusgraden angegeben, und die Schmelzpunkte sind unkorrigiert. <I>Beispiel 1</I> 21 Teile 1-Amino-2-chlor-4-methylsulfonyl- benzol werden bei 60 in 130 Teilen konzentrierter Schwefelsäure gelöst. Durch Eintragen von 7 Teilen Natriumnitrit wird das Amin bei 60-70 diazotiert. Man rührt eine Stunde bei 60 nach und lädt die bräunliche Reaktionsmasse auf 500 Teile Eis und 200 Teile Wasser aus.
Man zerstört einen allfälligen Überschuss an salpetriger Säure mit 0,5 Teilen Amidosulfonsäure und vereinigt die erhaltene Diazo- lösung mit einer Lösung von 20 Teilen 9-Äthyl- carbazol in 200 Teilen Eisessig. Man rührt die erhal tene Suspension 24 Stunden lang bei Zimmertempe ratur, filtriert hierauf und trocknet den säurefrei gewaschenen Presskuchen.
Durch Umkristallisieren aus Äthanol erhält man den Farbstoff der Formel
EMI0002.0031
schmelzpunktrein (F. 150 ). Man erhält ein zum Fär ben geeignetes Präparat, indem man 35 Teile des Farbstoffes, 20 Teile dinaphthylmethandisulfonsaures Natrium, 20 Teile eines Fettalkoholsulfonats und 25 Teile Glaubersalz innig vermahlt.
Zum Färben von Polyesterfasern verfährt man wie folgt: Man bereitet ein Färbebad aus 0,5 Teilen des beschriebenen Färbepräparats, 10 Teilen emul- giertem Trichlorbenzol und 3000 Teilen Wasser zu. Man geht bei Zimmertemperatur mit 100 Teilen der Polyäthylenterephthalatfaser Dacron in das Bad ein, erhitzt dieses auf 100 und hält es während 60 Minuten bei Kochtemperatur. Hierauf wird das Färbegut aus der Flotte herausgenommen, mit Was ser gespült und getrocknet.
Die erhaltene rotstichig gelbe Färbung ist licht-, wasch-, sublimier- und plissierecht. Wolle wird relativ gut reserviert und die geringfügige Anschmutzung lässt sich mit Hydro- sulfit reinigen.
Zum Färben von Acetatkunstseide verfährt man wie folgt: Man bereitet ein Färbebad aus 1 Teil des beschriebenen Färbepräparats, 6 Teilen eines Fett- alkoholsulfonats und 3000 Teilen Wasser zu. Man geht bei Zimmertemperatur mit 100 Teilen Acetat kunstseide in das Bad ein, erwärmt dieses innerhalb von 1 Stunde auf 80 und hält es während einer Stunde bei 80 . Nach dieser Zeit ist der Färbeprozess beendigt. Man nimmt das Färbegut aus dem Bad heraus, spült es und trocknet es. Die erhaltene rot stichig gelbe Färbung ist licht-, rauchgas- und wasch echt und lässt sich weiss ätzen.
<I>Beispiel 2</I> 21 Teile 1 - Amino - 2 - chlor -4-methylsulfonyl- benzol werden, wie im Beispiel 1 angegeben, diazo- tiert und mit einer 60 warmen Lösung von 28 Tei len 9-Benzyl-carbazol in 500 Teilen Eisessig ver- einigt. Nach beendigter Kupplung filtriert man den ausgefallenen gelben Farbstoff ab, wäscht ihn mit Wasser neutral und trocknet ihn.
Er entspricht der Formel CH2 Cl \/N\ HsC-02S----\-N=N_ # und eignet sich zum Färben von Acetatkunstseide in der Masse: 100 Teile Acetylcellulose werden mit 280 Teilen Aceton und 20 Teilen Methanol ver mischt und über Nacht quellen gelassen. 1 Teil des Farbstoffs wird durch einfaches Schütteln in 60 Tei len Aceton gelöst und der Acetylcelluloselösung zu gegeben. Die Mischung wird auf 400 Teile eingeengt und hierauf in üblicher Weise in den Spinntopf ge presst und gesponnen.
Die erhaltenen Strängchen sind gelb gefärbt; die Färbungen sind ausgezeichnet licht-, wasch-, überfärbe-, alkalischchlor-, oxalsäure-, per- oxyd-, bleich-, rauchgas- und trockenreinigungsecht sowie hydrosulfitbeständig. Ähnliche Eigenschaften besitzt der Farbstoff
EMI0003.0001
<I>Beispiel 3</I> 21 Teile 1- Amino - 2 -chlor - 4 - methylsulfonyl- benzol werden, wie im Beispiel 1 angegeben,
diazo- tiert und mit einer Lösung von 20 Teilen N-Methyl- diphenylamin in 20 Teilen Eisessig vereinigt. Die Kupplung erfolgt augenblicklich. Der ausgefallene Farbstoff wird abfiltriert, säurefrei gewaschen und getrocknet.
Aus Benzol umkristallisiert schmilzt er bei 154 und besitzt die Formel
EMI0003.0017
Als Dispersionsfarbstoff färbt er Celluloseacetat-, synthetische Polyamid- und Polyesterfasern in oran gen Tönen mit sehr guten Licht-, Wasch-, Schweiss-, Meerwasser-, Sublimier- und Plissierechtheiten. Die erhaltenen Färbungen sind ätzbar. In Tabelle (I) sind weitere Farbstoffe zusammen gestellt, die in entsprechender Weise hergestellt wer den können und der Formel
EMI0003.0025
entsprechen:
<I>Tabelle (I)</I> Beispiel R2 R3 R5 RG X 1r Farbton der Färbung Nr. auf Acetatreyon 4 -NH-CH3 -CH 3 -Cl -H -H orange 5 N(CH3)2 -C3H7 -Cl -Cl -H 6 -NH-CH._ CH -OH OH -CH2 O-CO-CH3 Br H -H 7 -N(CH3)
2 -CH2 CN -Cl H H 8 -N(CH3)2 -CH2 CN -Cl -H direkte gelb Bindung 9 -NH-CH 3 -CH2 CN -Cl -C1<B> </B> 10 -CH2 CH. CN -H -Cl -H 11 -CH2 CH - CH2 -C2H5 -Cl -H <B> </B> > In Tabelle
(II) sind entsprechende Farbstoffe der Formel
EMI0003.0063
zusammengestellt.
EMI0004.0001
<I>Tabelle <SEP> (I1)</I>
<tb> Beispiel
<tb> R2
<tb> R3 <SEP> Rs <SEP> X <SEP> y
<tb> Farbton <SEP> der <SEP> Färbung
<tb> Nr. <SEP> auf <SEP> Acetatreyon
<tb> 12 <SEP> -CH3 <SEP> -CH3 <SEP> -H <SEP> -H <SEP> rosa
<tb> 13 <SEP> N(CH3)
2 <SEP> -H <SEP> -H <SEP> -H <SEP>
<tb> 14 <SEP> -CH3 <SEP> -CH2 <SEP> <B>Cl</B> <SEP> -CH3 <SEP> -H <SEP>
<tb> 15 <SEP> -CH3 <SEP> -H <SEP> -CF3 <SEP> -H <SEP>
<tb> 16 <SEP> -C3H7 <SEP> -H <SEP> -H <SEP> -H <SEP>
<tb> 17 <SEP> -CH3 <SEP> -CH3 <SEP> -H <SEP> direkte <SEP> rot
<tb> Bindung
<tb> 18 <SEP> -CH3 <SEP> -CH2 <SEP> CN <SEP> -H <SEP> <SEP>
<tb> 19 <SEP> -CH3 <SEP> -CH2 <SEP> O-CH3 <SEP> -CH3 <SEP> <SEP> Farbstoffe der Formel
EMI0004.0002
lassen sich in entsprechender Weise herstellen und besitzen folgende Eigenschaften:
EMI0004.0003
<I>Tabelle <SEP> (I11)</I>
<tb> <B>---------------</B>
<tb> BeNpiel
<tb> <B>1</B>
<tb> R2 <SEP> R <SEP> R, <SEP> X <SEP> 1. <SEP> Farbton <SEP> der <SEP> Färbung
<tb> auf <SEP> Acetatreyon
<tb> 20 <SEP> -C<B>13</B> <SEP> -H <SEP> -H <SEP> -H <SEP> rosa
<tb> 21 <SEP> -C<B>13</B> <SEP> -CH3 <SEP> -H <SEP> -H <SEP> >,
<tb> 22 <SEP> -CH3 <SEP> -CHZ <SEP> O-CO-C2H5 <SEP> -H <SEP> _H <SEP>
<tb> 23 <SEP> -CH3 <SEP> -CH3 <SEP> -H <SEP> direkte <SEP>
<tb> Bindung
<tb> 24 <SEP> -CH3 <SEP> -H <SEP> -Br <SEP> -H <SEP>
<tb> 25 <SEP> -CHS <SEP> C25 <SEP> -N02 <SEP> -H <SEP> violett
<tb> 26 <SEP> NH-CH3 <SEP> -H <SEP> -H <SEP> -H <SEP> rosa
<tb> 27 <SEP> N(CH3)2 <SEP> -CH3 <SEP> -H <SEP> -H <SEP>
<tb> 28 <SEP> NH-CH,
7 <SEP> CH2 <SEP> OH <SEP> -CH3 <SEP> -H <SEP> _H <SEP>
<tb> 29 <SEP> -NH-CH2 <SEP> CH.- <SEP> CH2 <SEP> -H <SEP> -H <SEP> H <SEP>
<tb> H360
<tb> 30 <SEP> -N(CH3)2 <SEP> -CH3 <SEP> -H <SEP> direkte <SEP>
<tb> Bindung
Process for the preparation of monoazo dyes which are sparingly soluble in water The present invention relates to a process for the preparation of new monoazo dyes of the formula which are sparingly soluble in water
EMI0001.0004
R1 is a radical of the benzene, thiazole or benzothiazole series free of nitro groups and water-solubilizing groups, R "low molecular weight alkyl, alkenyl, cyanoalkyl,
Haloalkyl or an optionally mono- or disubstituted amino group, R3 is hydrogen or a low molecular weight alkyl radical or an aryl radical optionally substituted by halogen atoms, by the nitrile group, the acetoxy group, the propionyloxy group, the methoxy or ethoxy group,
x and y denote hydrogen or together denote the direct C-C bond, and in which the ring R4 can carry further substituents which do not make water soluble.
The process according to the invention is characterized in that 1 mol of the diazo compound is obtained from an amine of the formula R, - O, S-R, -NH. = With 1 mol of the compound of the formula
EMI0001.0037
clutch. The coupling of the diazo compounds with the azo components is preferably carried out in an acidic, optionally buffered, medium.
The new monoazo dyes, which are sparingly soluble in water, are partly drawn in suspension onto synthetic polyamide fibers (e.g. nylon, Perlon, Rilsan, registered trademarks), on cellulose ester fibers (e.g. acetate rayon, triacetate rayon), Polyvinyl fibers, polyacrylonitrile fibers, terephthalic acid ester fibers (e.g.
B. Terylene, Dacron, registered trademarks) in brilliant yellow, orange and red tones. Their colorations are characterized in particular by their excellent light, washing, water, seawater, perspiration, pleating, ironing, heat setting, smoke gas and chlorine fastness. They can also be white-etched. The dyes largely reserve cotton, viscose and wool and the stains can be cleaned by treating them with hydrosulphite.
Some of the new dyes are also suitable for coloring paints, oils, synthetic resins and artificial fibers in bulk.
The diazo components are, in particular, 1-amino-benzene-4-sulfonic acid methyl- and dimethyl-amide, 1-amino-4-methylsulfonyl-benzene, 1-amino-2-halogen- or cyano-benzene-4-sulfonic acid methyl and dimethyl amides , 1-amino-2-halogen or
-cyano-4-methyl-sulfonyl-benzenes, 1-amino-2,4-bis- (methylsulfonyl) -benzene, 1-amino-2-methylsulfonyl-benzene-4-sulfonic acid, methyl and dimethyl amide, 1-amino -4-methylsulfonyl-benzene-2-sulfonic acid, methyl and dimethyl amide, 1-amino-2,5-dihalogenobenzene-4-sulfonic acid, methyl and dimethyl amides, 1-amino-2,5-dihalogen-4 -methylsulfonyl-benzenes,
2-Amino-thiazole-5-sulfonic acid methyl and dimethyl amide, 2-amino-5-methylsulfonylthiazole, 2-aminobenzothiazole-6-sulfonic acid methyl and dimethyl amide, 2-amino-6-methylsulfonyl-benzothiazole, 2-amino-4- Halogen-benzothiazole-6-sulfonic acid, methyl- and dimethylamides and also 2-amino-4-halogen-6-methylsulfonyl-benzothiazoles of interest.
In the following examples, parts are parts by weight and percentages are percentages by weight; temperatures are in degrees Celsius and melting points are uncorrected. <I> Example 1 </I> 21 parts of 1-amino-2-chloro-4-methylsulfonylbenzene are dissolved at 60 in 130 parts of concentrated sulfuric acid. The amine is diazotized at 60-70 by adding 7 parts of sodium nitrite. The mixture is stirred for one hour at 60 and the brownish reaction mass is loaded onto 500 parts of ice and 200 parts of water.
Any excess of nitrous acid is destroyed with 0.5 part of sulfamic acid and the resulting diazo solution is combined with a solution of 20 parts of 9-ethylcarbazole in 200 parts of glacial acetic acid. The suspension obtained is stirred for 24 hours at room temperature, then filtered and the acid-free washed press cake is dried.
Recrystallization from ethanol gives the dye of the formula
EMI0002.0031
pure melting point (F. 150). A preparation suitable for dyeing is obtained by thoroughly grinding 35 parts of the dye, 20 parts of sodium dinaphthylmethanedisulfonic acid, 20 parts of a fatty alcohol sulfonate and 25 parts of Glauber's salt.
The procedure for dyeing polyester fibers is as follows: A dye bath is prepared from 0.5 parts of the dye preparation described, 10 parts of emulsified trichlorobenzene and 3000 parts of water. 100 parts of the polyethylene terephthalate fiber Dacron are placed in the bath at room temperature, heated to 100 and kept at boiling temperature for 60 minutes. The dyed material is then removed from the liquor, rinsed with water and dried.
The reddish yellow coloration obtained is fast to light, washing, sublimation and pleating. Wool is relatively well reserved and the slightest soiling can be cleaned with hydrosulfite.
The procedure for dyeing acetate rayon is as follows: A dye bath is prepared from 1 part of the dye preparation described, 6 parts of a fatty alcohol sulfonate and 3000 parts of water. 100 parts of acetate rayon are added to the bath at room temperature, heated to 80 within 1 hour and kept at 80 for one hour. After this time the dyeing process is finished. The dyed material is taken out of the bath, rinsed and dried. The red, yellowish coloration obtained is light, smoke and washable and can be etched white.
<I> Example 2 </I> 21 parts of 1 - amino - 2 - chloro -4-methylsulfonylbenzene are, as indicated in Example 1, diazolated and treated with a 60 warm solution of 28 parts of 9-benzylcarbazole combined in 500 parts of glacial acetic acid. After the coupling has ended, the yellow dye which has precipitated is filtered off, washed neutral with water and dried.
It corresponds to the formula CH2 Cl \ / N \ HsC-02S ---- \ - N = N_ # and is suitable for dyeing acetate rayon in the mass: 100 parts of acetyl cellulose are mixed with 280 parts of acetone and 20 parts of methanol and mixed over Night swell. 1 part of the dye is dissolved in 60 Tei len acetone by simply shaking and added to the acetyl cellulose solution. The mixture is concentrated to 400 parts and then pressed and spun in the conventional manner in the spinning pot.
The strands obtained are colored yellow; the dyeings are extremely light, wash, over-dyeing, alkali chlorine, oxalic acid, peroxide, bleach, smoke gas and dry cleaning fast and hydrosulfite resistant. The dye has similar properties
EMI0003.0001
<I> Example 3 </I> 21 parts of 1- amino - 2-chloro - 4 - methylsulfonylbenzene are, as indicated in Example 1,
diazotized and combined with a solution of 20 parts of N-methyldiphenylamine in 20 parts of glacial acetic acid. The coupling is instantaneous. The precipitated dye is filtered off, washed free of acid and dried.
Recrystallized from benzene, it melts at 154 and has the formula
EMI0003.0017
As a disperse dye, it dyes cellulose acetate, synthetic polyamide and polyester fibers in orange tones with very good fastness to light, washing, perspiration, sea water, sublimation and pleating. The colorations obtained can be etched. In Table (I) other dyes are listed that can be prepared in a corresponding manner and the formula
EMI0003.0025
correspond:
<I> Table (I) </I> Example R2 R3 R5 RG X 1r shade of the dyeing no. On Acetatreyon 4 -NH-CH3 -CH 3 -Cl -H -H orange 5 N (CH3) 2 -C3H7 -Cl -Cl -H 6 -NH-CH._ CH -OH OH -CH2 O-CO-CH3 Br H -H 7 -N (CH3)
2 -CH2 CN -Cl H H 8 -N (CH3) 2 -CH2 CN -Cl -H direct yellow bond 9 -NH-CH 3 -CH2 CN -Cl -C1 <B> </B> 10 -CH2 CH. CN -H -Cl -H 11 -CH2 CH - CH2 -C2H5 -Cl -H <B> </B>> in table
(II) are corresponding dyes of the formula
EMI0003.0063
compiled.
EMI0004.0001
<I> Table <SEP> (I1) </I>
<tb> example
<tb> R2
<tb> R3 <SEP> Rs <SEP> X <SEP> y
<tb> Hue <SEP> of the <SEP> coloring
<tb> No. <SEP> on <SEP> Acetatreyon
<tb> 12 <SEP> -CH3 <SEP> -CH3 <SEP> -H <SEP> -H <SEP> pink
<tb> 13 <SEP> N (CH3)
2 <SEP> -H <SEP> -H <SEP> -H <SEP>
<tb> 14 <SEP> -CH3 <SEP> -CH2 <SEP> <B> Cl </B> <SEP> -CH3 <SEP> -H <SEP>
<tb> 15 <SEP> -CH3 <SEP> -H <SEP> -CF3 <SEP> -H <SEP>
<tb> 16 <SEP> -C3H7 <SEP> -H <SEP> -H <SEP> -H <SEP>
<tb> 17 <SEP> -CH3 <SEP> -CH3 <SEP> -H <SEP> direct <SEP> red
<tb> bond
<tb> 18 <SEP> -CH3 <SEP> -CH2 <SEP> CN <SEP> -H <SEP> <SEP>
<tb> 19 <SEP> -CH3 <SEP> -CH2 <SEP> O-CH3 <SEP> -CH3 <SEP> <SEP> dyes of the formula
EMI0004.0002
can be produced in a corresponding manner and have the following properties:
EMI0004.0003
<I> Table <SEP> (I11) </I>
<tb> <B> --------------- </B>
<tb> Example
<tb> <B> 1 </B>
<tb> R2 <SEP> R <SEP> R, <SEP> X <SEP> 1st <SEP> color <SEP> of the <SEP> color
<tb> on <SEP> Acetatreyon
<tb> 20 <SEP> -C <B> 13 </B> <SEP> -H <SEP> -H <SEP> -H <SEP> pink
<tb> 21 <SEP> -C <B> 13 </B> <SEP> -CH3 <SEP> -H <SEP> -H <SEP>>,
<tb> 22 <SEP> -CH3 <SEP> -CHZ <SEP> O-CO-C2H5 <SEP> -H <SEP> _H <SEP>
<tb> 23 <SEP> -CH3 <SEP> -CH3 <SEP> -H <SEP> direct <SEP>
<tb> bond
<tb> 24 <SEP> -CH3 <SEP> -H <SEP> -Br <SEP> -H <SEP>
<tb> 25 <SEP> -CHS <SEP> C25 <SEP> -N02 <SEP> -H <SEP> violet
<tb> 26 <SEP> NH-CH3 <SEP> -H <SEP> -H <SEP> -H <SEP> pink
<tb> 27 <SEP> N (CH3) 2 <SEP> -CH3 <SEP> -H <SEP> -H <SEP>
<tb> 28 <SEP> NH-CH,
7 <SEP> CH2 <SEP> OH <SEP> -CH3 <SEP> -H <SEP> _H <SEP>
<tb> 29 <SEP> -NH-CH2 <SEP> CH.- <SEP> CH2 <SEP> -H <SEP> -H <SEP> H <SEP>
<tb> H360
<tb> 30 <SEP> -N (CH3) 2 <SEP> -CH3 <SEP> -H <SEP> direct <SEP>
<tb> bond
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6106458A CH367254A (en) | 1958-06-26 | 1958-06-26 | Process for the preparation of monoazo dyes that are sparingly soluble in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6106458A CH367254A (en) | 1958-06-26 | 1958-06-26 | Process for the preparation of monoazo dyes that are sparingly soluble in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH367254A true CH367254A (en) | 1963-02-15 |
Family
ID=4523372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH6106458A CH367254A (en) | 1958-06-26 | 1958-06-26 | Process for the preparation of monoazo dyes that are sparingly soluble in water |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH367254A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2212755A1 (en) * | 1972-03-16 | 1973-09-20 | Cassella Farbwerke Mainkur Ag | HYDRO-INSOLUBLE MONOAZO DYES AND PROCESS FOR THEIR MANUFACTURING |
| US3787178A (en) * | 1972-02-28 | 1974-01-22 | American Aniline Prod | Polyester textile fibers dyed with thiazole or benzothiazole carbazole dyes |
| US3897203A (en) * | 1972-02-28 | 1975-07-29 | American Color & Chem | Carbazole dyestuffs |
| EP0035671A1 (en) * | 1980-02-28 | 1981-09-16 | CASSELLA Aktiengesellschaft | Water-insoluble azo dyestuffs, methods for their preparation and their use in dyeing and printing synthetic hydrophobic fibre materials |
-
1958
- 1958-06-26 CH CH6106458A patent/CH367254A/en unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787178A (en) * | 1972-02-28 | 1974-01-22 | American Aniline Prod | Polyester textile fibers dyed with thiazole or benzothiazole carbazole dyes |
| US3897203A (en) * | 1972-02-28 | 1975-07-29 | American Color & Chem | Carbazole dyestuffs |
| DE2212755A1 (en) * | 1972-03-16 | 1973-09-20 | Cassella Farbwerke Mainkur Ag | HYDRO-INSOLUBLE MONOAZO DYES AND PROCESS FOR THEIR MANUFACTURING |
| FR2176112A1 (en) * | 1972-03-16 | 1973-10-26 | Cassella Farbwerke Mainkur Ag | |
| EP0035671A1 (en) * | 1980-02-28 | 1981-09-16 | CASSELLA Aktiengesellschaft | Water-insoluble azo dyestuffs, methods for their preparation and their use in dyeing and printing synthetic hydrophobic fibre materials |
| US4431585A (en) * | 1980-02-28 | 1984-02-14 | Cassella Aktiengesellschaft | Water-insoluble azo dyestuffs, processes for their manufacture and their use for dyeing and printing synthetic hydrophobic fiber material |
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