DE1204764B - Process for the preparation of water-soluble basic azo dyes - Google Patents
Process for the preparation of water-soluble basic azo dyesInfo
- Publication number
- DE1204764B DE1204764B DEB62067A DEB0062067A DE1204764B DE 1204764 B DE1204764 B DE 1204764B DE B62067 A DEB62067 A DE B62067A DE B0062067 A DEB0062067 A DE B0062067A DE 1204764 B DE1204764 B DE 1204764B
- Authority
- DE
- Germany
- Prior art keywords
- water
- alkyl
- preparation
- soluble basic
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000000987 azo dye Substances 0.000 title description 4
- 150000001412 amines Chemical class 0.000 claims description 6
- -1 alkyl radical Chemical group 0.000 claims description 5
- 125000000320 amidine group Chemical group 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 150000002081 enamines Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical class NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims description 3
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical class C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 2
- 239000002168 alkylating agent Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000981 basic dye Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XMXLBDNVSIHRRA-UHFFFAOYSA-N 4,5-dimethyl-1,3-thiazol-2-amine Chemical compound CC=1N=C(N)SC=1C XMXLBDNVSIHRRA-UHFFFAOYSA-N 0.000 description 2
- KZHGPDSVHSDCMX-UHFFFAOYSA-N 6-methoxy-1,3-benzothiazol-2-amine Chemical compound COC1=CC=C2N=C(N)SC2=C1 KZHGPDSVHSDCMX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- MIHADVKEHAFNPG-UHFFFAOYSA-N 2-Amino-5-nitrothiazole Chemical compound NC1=NC=C([N+]([O-])=O)S1 MIHADVKEHAFNPG-UHFFFAOYSA-N 0.000 description 1
- YJTBHWXNEMGNDC-UHFFFAOYSA-N 2-amino-1,3-thiazole-5-carbonitrile Chemical compound NC1=NC=C(C#N)S1 YJTBHWXNEMGNDC-UHFFFAOYSA-N 0.000 description 1
- 229940018167 2-amino-5-nitrothiazole Drugs 0.000 description 1
- PYSJLPAOBIGQPK-UHFFFAOYSA-N 4-phenyl-1,3-thiazol-2-amine Chemical compound S1C(N)=NC(C=2C=CC=CC=2)=C1 PYSJLPAOBIGQPK-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- DBZBJLJYSYHKJO-UHFFFAOYSA-N 6-chloro-4-methyl-1,3-benzothiazol-2-amine Chemical compound CC1=CC(Cl)=CC2=C1N=C(N)S2 DBZBJLJYSYHKJO-UHFFFAOYSA-N 0.000 description 1
- KOYJWFGMEBETBU-UHFFFAOYSA-N 6-ethoxy-1,3-benzothiazol-2-amine Chemical compound CCOC1=CC=C2N=C(N)SC2=C1 KOYJWFGMEBETBU-UHFFFAOYSA-N 0.000 description 1
- DZWTXWPRWRLHIL-UHFFFAOYSA-N 6-methyl-1,3-benzothiazol-2-amine Chemical compound CC1=CC=C2N=C(N)SC2=C1 DZWTXWPRWRLHIL-UHFFFAOYSA-N 0.000 description 1
- DNXIQMQGKSQHPC-UHFFFAOYSA-N 7-methoxy-3,4,5,6-tetrahydro-2h-azepine Chemical compound COC1=NCCCCC1 DNXIQMQGKSQHPC-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MQYXHJAHYXZKML-UHFFFAOYSA-N n'-(3-methylphenyl)ethane-1,2-diamine Chemical compound CC1=CC=CC(NCCN)=C1 MQYXHJAHYXZKML-UHFFFAOYSA-N 0.000 description 1
- GCGMQDJOIHALPF-UHFFFAOYSA-N n'-methyl-n'-phenylethane-1,2-diamine Chemical compound NCCN(C)C1=CC=CC=C1 GCGMQDJOIHALPF-UHFFFAOYSA-N 0.000 description 1
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 150000003673 urethanes Chemical class 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung wasserlöslicher basischer Azofarbstoffe Es wurde gefunden, daß man neue wasserlösliche basische Azofarbstoffe der allgemeinen Formel erhält, worin R einen Alkylrest, X und Y nichtionogene Substituenten, insbesondere Bestandteile eines gegebenenfalls selbst durch nichtionogene Gruppen substituierten o-kondensierten Benzolrings, A den zweiwertigen Rest eines zur Kupplung befähigten Amins oder Enamins, dessen Stickstoffatom über einen Alkyl- und/oder Arylrest mit der cyclischen Amidingruppierung verbunden ist, ZO das Anion einer anorganischen oder organischen ein-oder mehrbasischen Säure und n eine der ganzen Zahlen von 3 bis 7 bedeutet, wenn ma'n Amine oder Enamine, deren Stickstoffatom über einen Alkyl- und/oder Arylrest mit einer cyclischen Amidingruppierung verbunden ist, mit diazotierten 2-Aminothiazolen oder 2-Aminobenzthiazolen kuppelt und die erhaltenen Azofarbstoffe mit alkylierenden Mitteln in die Farbsalze der oben angegebenen Formel umwandelt.Process for the preparation of water-soluble basic azo dyes It has been found that new water-soluble basic azo dyes of the general formula can be obtained where R is an alkyl radical, X and Y are nonionic substituents, in particular constituents of an o-condensed benzene ring optionally substituted by nonionic groups, A is the divalent radical of an amine or enamine capable of coupling, the nitrogen atom of which is via an alkyl and / or aryl radical the cyclic amidine group, ZO is the anion of an inorganic or organic mono- or polybasic acid and n is one of the integers from 3 to 7 , if amines or enamines whose nitrogen atom is via an alkyl and / or aryl radical with a cyclic amidine grouping is coupled with diazotized 2-aminothiazoles or 2-aminobenzothiazoles and converts the azo dyes obtained with alkylating agents into the color salts of the formula given above.
Für das neue Verfahren sind z. B. folgende diazotierbare Amine brauchbar: 2-Aminothiazol, 2-Amino-4,5-dimethylthiazol, 2-Amino-4-phenylthiazol, 2-Amino-4-(3'-nitro)-phenylthiazol, 2-Amino-5-nitrothiazol, 2-Amino-5-cyanthiazol, 2-Aminobenzthiazol, 2-Amino-6-methylbenzthiazol, 2-Amino-6-methoxybenzthiazol, 2-Amino-6-äthoxybenzthiazol, 2-Amino-4-methyl-6-chlorbenzthiazol.For the new method are z. B. the following diazotizable amines can be used: 2-aminothiazole, 2-amino-4,5-dimethylthiazole, 2-amino-4-phenylthiazole, 2-amino-4- (3'-nitro) -phenylthiazole, 2-amino-5-nitrothiazole, 2-amino-5-cyanthiazole, 2-aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-ethoxybenzthiazole, 2-amino-4-methyl-6-chlorobenzothiazole.
Als Kupplungskomponenten lassen sich die nach dem Verfahren von R. E. B e n s o n und T. L. C a i r n s, J. Amer. Chem. Soc., 70 (1948), S. 2115, hergestellten Umsetzungsprodukte von Lactim-0-alkyläthern mit Aminen oder Enaminen verwenden, z. B. N-Phenyläthylendiamin, N-(3-Methylphenyl)-äthylendiamin, N-Methyl-N-phenyl-äthylendiamin, N-Athyl-N'-(3-methoxy-phenyl)-äthylendiamin, N-(2-Hydroxy-äthyl)-N'-(2-methoxy-5-methylphenyl)-äthylendiamin, N-Butyl-N'-phenyl-1,3-diaminopropanol-(2), N-(ß-Aminopropyl)-diphenylamin, N-(ß-Aminoäthyl)-4-äthoxy-diphenylamin, 4 - (V - Aminopropyl) - aminodiphenylamin, 1-(V-Aminopropyl)-2-methylindol und 1-(y-Aminopropyl)-3-hydroxy-1,2,3,4-tetrahydrochinolin.The coupling components which can be used according to the method of R. E. Benson and TL C airn s, J. Amer. Chem. Soc., 70 (1948), p. 2115, use prepared reaction products of lactim-0-alkyl ethers with amines or enamines, z. B. N-phenylethylenediamine, N- (3-methylphenyl) ethylenediamine, N-methyl-N-phenyl-ethylenediamine, N-ethyl-N '- (3-methoxyphenyl) ethylenediamine, N- (2-hydroxy- ethyl) -N '- (2-methoxy-5-methylphenyl) -ethylenediamine, N-butyl-N'-phenyl-1,3-diaminopropanol- (2), N- (ß-aminopropyl) -diphenylamine, N- ( ß-aminoethyl) -4-ethoxy-diphenylamine, 4 - (V - aminopropyl) - aminodiphenylamine, 1- (V-aminopropyl) -2-methylindole and 1- (y-aminopropyl) -3-hydroxy-1,2,3 , 4-tetrahydroquinoline.
Die neuen Farbstoffe eignen sich zum Färben und Bedrucken sehr verschiedenartiger Stoffe, wie z. B. Fasern aus tannierter Baumwolle, Celluloseacetat, Polyamiden, -urethanen und -estern. Ferner lassen sich mit ihrer Hilfe, insbesondere auf Polymerisaten und Mischpolyrnerisaten des Acrylnitrils bzw. Dicyanäthylens sehr echte Färbungen herstellen.The new dyes are suitable for dyeing and printing in a wide variety of ways Substances such as B. fibers made of tannin cotton, cellulose acetate, polyamides, urethanes and esters. They can also be used, in particular on polymers and mixed polymers of acrylonitrile or dicyanethylene very fast colorations produce.
Gegenüber bekannten Farbstoffen, die keine Amidingruppierung besitzen, zeichnen sich die neuen Farbstoffe durch deutlich verbesserte Wasserlöslichkeit aus; insbesondere besitzen sie- gegenüber vergleichbaren Farbstoffen der französischen Patentschrift 1 145 235 einen reineren Farbton und besserc Naßechtheitseigenschaften, wie Wasch-, Potting-und Uberfärbeechtheit. Ferner bewirkt die Amidingruppe in vielen Fällen eine sehr erwünschte bathochrome Verschiebung des Farbtons.Compared to known dyes which do not have an amidine group, the new dyes are distinguished by significantly improved water solubility; in particular, have seven over comparable dyes French Patent 1,145,235 a cleaner shade and besserc wet fastness properties, such as wash, potting and Uberfärbeechtheit. Furthermore, the amidine group brings about a very desirable bathochromic shift in the hue in many cases.
Die im folgenden Beispiel genannten Teile sind Gewichtsteile.The parts mentioned in the following example are parts by weight.
B e i s p i e 1 18 Teile 2-Amino-6-methoxybenzthiazol werden in üblicher Weise mit Nitrosylschwefelsäure diazotiert und mit einer schwefeisauren, wäßrigen Lösung von 26 Teilen. des Kondensationsproduktes von Caprolactim-O-methyläther und N-Methyl-N-(3-methyl)-phenyläthylendiamin gekuppelt. Man neutralisiert nach beendeter Kupplung mit wäßriger Natriumhydroxydlösung, saugt ab und wäscht auf dem Filter nach. Der getrocknete Farbstoff wird in 250 Teilen Dimethylformamid gelöst und unter Rühren mit 13,5 Teilen Dimethylsulfat versetzt. Man erwärmt auf 90 bis 100'C, bis eine violettblaue Lösung entstanden ist und gießt in 2000 Teile Wasser aus. Durch Zugabe von. Natriumchlorid wird das Farbsalz abgeschieden, isoliert und getrocknet. Man erhält in guter Ausbeute den Farbstoff der Formel Er löst sich in Wasser mit violettblauer Farbe und färbt Fasern aus Polyacrylnitril oder Acrylnitril enthaltenden Mischpolymerisaten in sehr echten, rotstichigblauen Tönen.B ice p e 1 18 parts of 2-amino-6-methoxybenzothiazole are diazotized with nitrosylsulfuric acid in a conventional manner and with a schwefeisauren aqueous solution of 26 parts. of the condensation product of caprolactim-O-methyl ether and N-methyl-N- (3-methyl) -phenylethylenediamine coupled. After the coupling has ended, it is neutralized with aqueous sodium hydroxide solution, filtered off with suction and washed on the filter. The dried dye is dissolved in 250 parts of dimethylformamide, and 13.5 parts of dimethyl sulfate are added while stirring. The mixture is heated to 90 to 100 ° C. until a violet-blue solution has formed and it is poured into 2000 parts of water. By adding. Sodium chloride, the color salt is deposited, isolated and dried. The dye of the formula is obtained in good yield It dissolves in water with a violet-blue color and dyes fibers made of polyacrylonitrile or copolymers containing acrylonitrile in very real, reddish-blue tones.
Auf entsprechende Weise lassen sich unter anderem folgende Farbstoffe herstellen, die ebenfalls echte Färbungen auf acrylnitrilhaltigen Fasern ergeben (die auf diesen Fasern erhältlichen Farbtöne sind mit angegeben): In a corresponding manner, the following dyes, among others, can be produced, which also produce true colorations on acrylonitrile-containing fibers (the colors available on these fibers are also indicated):
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB62067A DE1204764B (en) | 1957-12-04 | 1957-12-04 | Process for the preparation of water-soluble basic azo dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB62067A DE1204764B (en) | 1957-12-04 | 1957-12-04 | Process for the preparation of water-soluble basic azo dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1204764B true DE1204764B (en) | 1965-11-11 |
Family
ID=6973442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB62067A Pending DE1204764B (en) | 1957-12-04 | 1957-12-04 | Process for the preparation of water-soluble basic azo dyes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1204764B (en) |
-
1957
- 1957-12-04 DE DEB62067A patent/DE1204764B/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1644103B2 (en) | BASIC CATIONIC AZO DYES | |
| DE1204764B (en) | Process for the preparation of water-soluble basic azo dyes | |
| DE918634C (en) | Process for the production of dye-fast dyeings on acetyl cellulose and linear polyamides or polyurethanes | |
| DE1150163B (en) | Process for the preparation of water-soluble yellow monoazo dyes | |
| DE2623251A1 (en) | DISPERSE MONOAZO DYES | |
| DE1544450B2 (en) | Process for the preparation of water-insoluble monoazo dyes | |
| DE1644092A1 (en) | Process for the preparation of water-insoluble azo dyes | |
| DE1153840B (en) | Process for the preparation of water-insoluble azo dyes | |
| DE2015350C3 (en) | Monoazo compounds sparingly soluble in water, process for their preparation and their use for dyeing or printing | |
| DE1088631B (en) | Process for the preparation of diazapolymethine dyes | |
| DE2116315A1 (en) | Azo compounds | |
| DE634211C (en) | Process for the production of azo dyes | |
| DE653116C (en) | Process for the production of water-insoluble azo dyes | |
| DE2158774C3 (en) | Dispersion monoazo dyes and process for their preparation | |
| DE1904190A1 (en) | Monoazo compounds, their preparation and use | |
| DE1544452A1 (en) | Process for the preparation of water-soluble azo dyes | |
| DE1644167C3 (en) | ||
| DE1644103C3 (en) | Azo basic cationic dyes | |
| DE666478C (en) | Process for the production of azo dyes | |
| DE1241922B (en) | Process for the preparation of monoazo dyes | |
| DE859185C (en) | Process for the preparation of monoazo dyes | |
| DE745413C (en) | Process for the preparation of monoazo dyes | |
| DE1544582C (en) | Copper-containing disazo dyes and process for the preparation of kupferhal term disazo dyes | |
| DE513763C (en) | Process for the preparation of disazo dyes suitable for coloring acetyl cellulose | |
| DE1619394A1 (en) | Process for dyeing and printing polymers or copolymers made of acrylonitrile or asymmetrical dicyanaethylene with azo dyes |