DE1105540B - Process for the preparation of diazapolymethine dyes - Google Patents
Process for the preparation of diazapolymethine dyesInfo
- Publication number
- DE1105540B DE1105540B DEB53945A DEB0053945A DE1105540B DE 1105540 B DE1105540 B DE 1105540B DE B53945 A DEB53945 A DE B53945A DE B0053945 A DEB0053945 A DE B0053945A DE 1105540 B DE1105540 B DE 1105540B
- Authority
- DE
- Germany
- Prior art keywords
- dyes
- alkyl
- radical
- diazapolymethine
- alkyl 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
- 239000000975 dye Substances 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- -1 alkyl radical Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002081 enamines Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000007800 oxidant agent 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 125000005853 β-dimethylaminoethyl group Chemical group 0.000 description 2
- GJRLBGNXSJZXMF-UHFFFAOYSA-N 3-(2-phenylindol-1-yl)propan-1-amine Chemical compound C=1C2=CC=CC=C2N(CCCN)C=1C1=CC=CC=C1 GJRLBGNXSJZXMF-UHFFFAOYSA-N 0.000 description 1
- BHHICRFDCVVASL-UHFFFAOYSA-N 3-(3,4-dihydro-2h-quinolin-1-yl)propan-1-amine Chemical compound C1=CC=C2N(CCCN)CCCC2=C1 BHHICRFDCVVASL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 150000008043 acidic salts Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- HGZSNEQFBNVKTM-UHFFFAOYSA-N n',n'-diethyl-n-(3-methoxyphenyl)ethane-1,2-diamine Chemical compound CCN(CC)CCNC1=CC=CC(OC)=C1 HGZSNEQFBNVKTM-UHFFFAOYSA-N 0.000 description 1
- UBOPQEUFWPCPRA-UHFFFAOYSA-N n',n'-dimethyl-n-(3-methylphenyl)ethane-1,2-diamine Chemical compound CN(C)CCNC1=CC=CC(C)=C1 UBOPQEUFWPCPRA-UHFFFAOYSA-N 0.000 description 1
- AIIUZOINSAAJMM-UHFFFAOYSA-N n,n'-dimethyl-n'-phenylethane-1,2-diamine Chemical compound CNCCN(C)C1=CC=CC=C1 AIIUZOINSAAJMM-UHFFFAOYSA-N 0.000 description 1
- BXEFFCMWYFJKBI-UHFFFAOYSA-N n,n,n'-triethyl-n'-phenylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)C1=CC=CC=C1 BXEFFCMWYFJKBI-UHFFFAOYSA-N 0.000 description 1
- RELMAMSEALKTTC-UHFFFAOYSA-N n,n,n'-trimethyl-n'-phenylethane-1,2-diamine Chemical compound CN(C)CCN(C)C1=CC=CC=C1 RELMAMSEALKTTC-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003756 stirring Methods 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
- C09B27/00—Preparations in which the azo group is formed in any way other than by diazotising and coupling, e.g. oxidation
-
- 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
- C09B44/20—Thiazoles or hydrogenated thiazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung von Diazapolymethinfarbstoffen Es wurde gefunden, daß man Diazapolymethinfarbstoffe der allgemeinen Formel erhält, in der R einen Alkylrest, R, ein Wasserstoffatom oder einen Alkylrest, R, ein Wasserstoffatom, einen Alkyl-, Aralkyl- oder Arylrest, wobei die Alkylreste R1 und R2 direkt oder über ein Heteroatom miteinander verbunden sein können, X und Y nichtionogene Substituenten, insbesondere Bestandteile eines gegebenenfalls weiter substituierten o-kondensierten Benzolringes, A den zweiwertigen Rest eines zur Kupplung befähigten Amins oder Enamins, dessen Aminogruppe über einen Alkylrest mit der Gruppe verbunden ist, und Z das Anion einer anorganischen oder organischen ein- oder mehrbasischen Säure bedeuten, wenn man auf Amine oder Enamine der allgemeinen Formel in der A, R1 und R, die oben angegebene Bedeutung haben, nach dem Verfahren der Patentschrift 963176 in 3-Stellung alkylierte Thiazolon-2-hydrazone oder Benzthiazolon-2-hydrazone gleichzeitig mit Oxydationsmitteln einwirken läßt.Process for the preparation of diazapolymethine dyes It has been found that diazapolymethine dyes of the general formula in which R is an alkyl radical, R is a hydrogen atom or an alkyl radical, R is a hydrogen atom, an alkyl, aralkyl or aryl radical, where the alkyl radicals R1 and R2 can be connected to one another directly or via a heteroatom, X and Y are nonionic Substituents, in particular constituents of an optionally further substituted o-condensed benzene ring, A the divalent radical of an amine or enamine capable of coupling, its amino group via an alkyl radical with the group is connected, and Z is the anion of an inorganic or organic monobasic or polybasic acid when looking at amines or enamines of the general formula in which A, R1 and R, which have the meaning given above, are allowed to act simultaneously with oxidizing agents by the process of patent specification 963176 in the 3-position alkylated thiazolone-2-hydrazones or benzthiazolone-2-hydrazones.
Für die Herstellung der Farbstoffe brauchbare Hydrazone sind beispielsweise: 3-Methyl-4-phenylthiazolon-2-hydrazon, 3-Methylbenzthiazolon 2-hydrazon, 3 Äthylbenzthiazolon-2-hydrazon, 3-Methyl-6-methoxybenzthiazolon-2-hydrazon, 3-Methyl-6-chlorbenzthiazolon-2-hydrazon, 3-Methyl-6-phenylaminobenzthiazolon-2-hydrazon, 3-Methyl-6-acetylaminobenzthiazolon-2-hydrazon.Hydrazones which can be used for the preparation of the dyes are, for example: 3-methyl-4-phenylthiazolone-2-hydrazone, 3-methylbenzthiazolone-2-hydrazone, 3-ethylbenzthiazolone-2-hydrazone, 3-methyl-6-methoxybenzthiazolon-2-hydrazone, 3-methyl-6-chlorobenzthiazolon-2-hydrazone, 3-methyl-6-phenylaminobenzothiazolone-2-hydrazone, 3-methyl-6-acetylaminobenzothiazolone-2-hydrazone.
Als Azokomponenten können beispielsweise verwendet werden: N,N-Dimethyl-N'-(3-methylphenyl)-äthylendiamin, N,N-Diäthyl-N'-(3-methoxyphenyl)-äthylendiamin, N,N'-Dimethyl-N'-phenyläthylendiamin, N,N,N'-Triäthyl-N'-phenyläthylendiamin, N,N-Di-ß-oxäthyl-N'-methyl-N'-phenyläthylendiamin, N,N-Dimethyl-N'-ß-oxäthyl-N'-phenyläthylendiamin, N,N-Dimethyl-N'-ß-oxäthyl-N'-phenyl-1,3-diaminopropan, N,N-Dimethyl-N'-äthyl-N'-phenyl-1,3-diaminopropanol-2, N-Butyl-N-(ß-piperidinoäthyl)-3-amino-l-methylbenzol, N-(ß-.Diäthylaminoäthyl)-diphenylamin, N-(ß-Dimethylaminoäthyl)-4-äthoxydiphenylamin, 4-[(ß-Dimethylaminoäthyl)-amino]-diphenylamin, 1-(y-Aminopropyl) 2-phenyl-indol, 1-(y-Aminopropyl)-1,2,3,4-tetrahydrochinolin.The azo components that can be used are, for example: N, N-dimethyl-N '- (3-methylphenyl) ethylenediamine, N, N-diethyl-N '- (3-methoxyphenyl) ethylenediamine, N, N'-dimethyl-N'-phenylethylenediamine, N, N, N'-triethyl-N'-phenylethylenediamine, N, N-di-ß-oxethyl-N'-methyl-N'-phenylethylenediamine, N, N-dimethyl-N'-ß-oxäthyl-N'-phenylethylenediamine, N, N-dimethyl-N'-ß-oxethyl-N'-phenyl-1,3-diaminopropane, N, N-dimethyl-N'-ethyl-N'-phenyl-1,3-diaminopropanol-2, N-butyl-N- (ß-piperidinoethyl) -3-amino-1-methylbenzene, N- (ß-diethylaminoethyl) -diphenylamine, N- (ß-dimethylaminoethyl) -4-ethoxydiphenylamine, 4 - [(ß-Dimethylaminoethyl) -amino] -diphenylamine, 1- (γ-aminopropyl) 2-phenyl-indole, 1- (γ-aminopropyl) -1,2,3,4-tetrahydroquinoline.
Die Farbstoffe sind in Form ihrer der eingangs gegebenen Formel entsprechenden neutralen Salze gut wasserlöslich. Insbesondere zeigen die sauren Salze, die durch Anlagerung eines Moleküls einer anorganischen Säure an die externe Aminogruppe entstehen, eine Löslichkeit in Wasser, die höher ist als die Wasserlöslichkeit vergleichbarer, bekannter Farbstoffe ohne Aminogruppe außerhalb des farbgebenden Systems. Die Farbstoffe eignen sich zum Färben sehr verschiedener Materialien, wie tannierte Baumwolle, Celluloseacetat, lineare Polyamide, Urethane und Ester. Insbesondere auf Polymerisaten und Mischpolymerisaten aus Acrylnitril bzw. Dicyanäthylen erhält man sehr echte Färbungen.The dyes are in the form of their formula corresponding to the formula given at the beginning neutral salts readily soluble in water. In particular, the acidic salts show that by Addition of a molecule of an inorganic acid to the external amino group occurs, a solubility in water that is higher than the water solubility of comparable ones, known dyes without an amino group outside the coloring system. The dyes are suitable for dyeing very different materials, such as tannin cotton, Cellulose acetate, linear polyamides, urethanes and esters. In particular on polymers and copolymers of acrylonitrile or dicyanethylene are very real Colorations.
Aus der französischen Patentschrift 1 145 235 sind Diazapolymethinfarbstoffe bekannt, die keine Aminogruppe außerhalb des farbgebenden Systems enthalten. Diesen bekannten Farbstoffen gegenüber zeichnen sich die nach der Erfindung erhältlichen Diazapolymethinfarbstoffe durch wesentlich bessere Überfärbeechtheiten, insbesondere auf Polyacrylnitrilfasern, aus.French Patent 1,145,235 discloses diazapolymethine dyes known that contain no amino group outside of the coloring system. This one Compared to known dyes, those obtainable according to the invention stand out Diazapolymethine dyes due to significantly better over-dyeing fastness, in particular on polyacrylonitrile fibers.
Die in dem Beispiel genannten Teile sind Gewichtsteile.The parts mentioned in the example are parts by weight.
Beispiel Zu einer Lösung von 22 Teilen 3-Methylbenzthiazolon-2-hydrazon-hydrochlorid
in 300 Teilen Wasser fügt man eine Lösung von 18 Teilen N,N,N'-Trimethyl-N'-phenyläthylendiamin
in
100 Teilen Methanol und tropft bei gewöhnlicher Temperatur unter Rühren 240 Teile
einer 35°/oigen wäßrigen Eisen (III)-chloridlösung und gleichzeitig 160 Teile einer
50%igen Natriumacetatlösung ein. Nach der Umsetzung gibt man 40 Teile einer 5 n-Salzsäure
und 200 Teile einer gesättigten wäßrigen Kaliumchloridlösung hinzu. Der abgeschiedene
Farbstoff wird filtriert, mit Kaliumchloridlösung gewaschen und bei 50° C im Vakuum
getrocknet. Man erhält 41 Teile eines Farbstoffes der Formel
der sich in Wasser mit blauvioletter Farbe löst und Polyacrylnitrilfasern aus schwefelsaurem
Bad in sehr echten rotstichigblauen Tönen färbt. In entsprechender Weise können
die folgenden Farbstoffe erhalten werden, die ebenfalls echte Färbungen auf Polyacrylnitril
ergeben:
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB53945A DE1105540B (en) | 1957-10-24 | 1957-10-24 | Process for the preparation of diazapolymethine dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB53945A DE1105540B (en) | 1957-10-24 | 1957-10-24 | Process for the preparation of diazapolymethine dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1105540B true DE1105540B (en) | 1961-04-27 |
Family
ID=6970435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB53945A Pending DE1105540B (en) | 1957-10-24 | 1957-10-24 | Process for the preparation of diazapolymethine dyes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1105540B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2206362A1 (en) * | 1972-11-10 | 1974-06-07 | Bayer Ag | |
| US4225490A (en) * | 1971-06-17 | 1980-09-30 | Sandoz Ltd. | Heterocyclyl-azo-phenyl dyes having a cationic group linked through a branched alkylene chain to the nitrogen atom of the coupling component radical |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1145235A (en) * | 1954-12-15 | 1957-10-23 | Geigy Ag J R | Water soluble dyestuff salts and method for preparing such salts |
-
1957
- 1957-10-24 DE DEB53945A patent/DE1105540B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1145235A (en) * | 1954-12-15 | 1957-10-23 | Geigy Ag J R | Water soluble dyestuff salts and method for preparing such salts |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4225490A (en) * | 1971-06-17 | 1980-09-30 | Sandoz Ltd. | Heterocyclyl-azo-phenyl dyes having a cationic group linked through a branched alkylene chain to the nitrogen atom of the coupling component radical |
| FR2206362A1 (en) * | 1972-11-10 | 1974-06-07 | Bayer Ag |
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