CH476077A - Process for the production of azo dyes - Google Patents
Process for the production of azo dyesInfo
- Publication number
- CH476077A CH476077A CH101460A CH101460A CH476077A CH 476077 A CH476077 A CH 476077A CH 101460 A CH101460 A CH 101460A CH 101460 A CH101460 A CH 101460A CH 476077 A CH476077 A CH 476077A
- Authority
- CH
- Switzerland
- Prior art keywords
- amino group
- azo dyes
- group
- amino
- parts
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 13
- 239000000987 azo dye Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 20
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000006193 diazotization reaction Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- -1 amino compound Chemical class 0.000 claims description 3
- 150000008049 diazo compounds Chemical class 0.000 claims description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 3
- 238000001465 metallisation Methods 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- IQCQWQDFHQPFIT-UHFFFAOYSA-N 3,8-diaminonaphthalene-1,5-disulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 IQCQWQDFHQPFIT-UHFFFAOYSA-N 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000975 dye Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 2
- 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
- 150000004699 copper complex Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- UFHNERYKYRKIOJ-UHFFFAOYSA-N 3-acetamido-8-aminonaphthalene-1,5-disulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C2=CC(NC(=O)C)=CC(S(O)(=O)=O)=C21 UFHNERYKYRKIOJ-UHFFFAOYSA-N 0.000 description 1
- NEECEUZBAHTVIN-UHFFFAOYSA-N 4-amino-3-chlorobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1Cl NEECEUZBAHTVIN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000008053 sultones Chemical group 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/16—Trisazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/44—Preparation of azo dyes from other azo compounds by substituting amine groups for hydroxyl groups or hydroxyl groups for amine groups; Desacylation of amino-acyl groups; Deaminating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Azofarbstoffen Die Erfindung betrifft ein Verfahren zur Herstellung von Azofarbstoffen, welches dadurch gekennzeichnet ist, dass man (a) eine Diazoverbindung eines Amins der Formel Y-R-NH,
worin Y einen zur Aminogruppe orthoständigen metall- komplexbildenden Substituenten und R den Rest einer oder ein Molteil einer solchen Aminoverbindung und ein Molteil einer andersartigen aminogruppenhaltigen Ver bindung mit polyfunktionellen Acylierungsmitteln an der 6ständigen Aminogruppe derart umsetzt, dass sich zwischen je zwei Aminoverbindungen ein Brückenglied ausbildet.
Die Stufe (c) des Verfahrens läuft demnach nach folgendem Schema ab:
EMI0001.0019
Diazokomponente bedeutet, mit 1,6-Diaminonaphthalin- -4,8-disulfonsäure in 2-Stellung kuppelt, (b) die 6ständige Aminogruppe der Kupplungs komponente vor oder nach der Kupplung acyliert, (c) die l ständige Aminogruppe nunmehr oder als letz ten Verfahrensschritt durch Diazotieren und Verkochen in eine OH-Gruppe überführt, (d) die 6ständige Aminogruppe durch Verseifen wiederherstellt und (e)
zwei Molteile gleicher oder verschiedener so er haltener Aminoverbindungen der Formel
EMI0001.0033
In den Formeln bedeuten R den Rest einer Diazo- kornponente, die Y in o-Stellung zur Azobrücke gebun den enthält, und Y einen metallkomplexbildenden Substi- tuenten, d.h. z.B. eine Hydroxyl-,
eine Carboxyl- oder eine heterocyclisch gebundene NH-Gruppe, oder aber einen Rest, der unter den Bedingungen der nichtoxidie- renden Metallisierung in eine metallkomplexbildende Gruppe übergeführt wird, beispielsweise eine Alkoxy- oder eine Carbonsäureestergruppe oder Halogen.
Man kann auch so vorgehen, dass zunächst die in 6-Stellung befindliche Aminogruppe acyliert wird und anschliessend die Kupplung und Umwandlung der 1- ständigen Aminogruppe in eine Oxygruppe erfolgt.
Die weitere Umsetzung der nach den geschilderten Verfahren erhältlichen Zwischenstufen erfolgt nach Ab spaltung des Acylrestes durch Umwandlung der 6stän- digen Aminogruppe in ein mindestens zwei Stickstoff atome enthaltendes Brückenglied durch Umsetzung der Aminogruppe in Gegenwart einer zweiten Aminokom- ponente mit polyfunktionellen Acylierungsmitteln.
Die für die Durchführung des neuen Verfahrens er- forderlichen Schritte lassen sich in gewissem Umfang in der Reihenfolge vertauschen. So kann beispielsweise die Diazotierung und Verkochung der in 1-Stellung be findlichen Aminogruppe auch nach der Umsetzung mit den polyfunktionellen Acylierungsmitteln erfolgen.
Werden Diazotierung und Verkochung der in 1-Stel- lung befindlichen Aminogruppe als erste Stufe durchge führt, d.h. vor der Kupplung, so gelangt man zu 1-Oxy- -6-acylamino-naphthalin-4,8-disulfonsäuren und damit zu Ausgangsprodukten für die weiter erforderlichen Schritte des Verfahrens.
Eine weitere Variante wird dadurch ermöglicht, dass man die z. B. als erste Stufe durchgeführte Verkochung so leiten kann, dass dabei das Sulton entsteht:
EMI0002.0017
Vom Amino-sulton ausgehend lassen sich nun die Schritte, die zur Umwandlung der Aminogruppe in ein mindestens zwei Stickstoffatome enthaltendes Brücken glied erforderlich sind, zuerst durchführen. Die hydroly tische Aufspaltung des Sultonrings, Kupplung zur Oxy- gruppe und Metallisierung können dann als letzte Stu fen erfolgen.
<I>Beispiel</I> Die Lösung von 36,2 Gewichtsteilen (0,1 Mol) 1- -Amino - 6 - acetylaminonaphthalin - 4,8 - disulfonsäure in 1000 Volumenteilen Wasser wird mit 25 Gewichtsteilen Natriumacetat und anschliessend mit der Diazoverbin- dung aus 20,8 Gewichtsteilen 2-Chlor-l-aminobenzol-4- sulfonsäure bei 0 versetzt.
Nach beendeter Kupplung wird die Reaktionslösung durch Zugabe von Salzsäure auf pH 1 gebracht, der Farbstoff mit Natriumchlorid ab geschieden und isoliert.
Die so erhaltene Farbstoffpaste wird in 1000 Vo- lumteilen Wasser verrührt, schwach sodaalkalisch ge- stellt, mit 70 Volumteilen 10%iger Natriumnitritlösung und anschliessend mit 100 Volumteilen 50%iger Schwe felsäure versetzt.
Nach beendeter Diazotierung wird die Reaktionslösung auf ca. 80 erhitzt und bei dieser Tem peratur so lange gehalten, bis die Verkochung beendet ist. Dann wird das Reaktionsprodukt mit Natriumchlo- rid abgeschieden, isoliert und in üblicher Weise in den Kupferkomplex übergeführt.
Nach alkalischer Versei fung der Acetylaminogruppe erhält man den Kupfer komplex-Farbstoff der Formel
EMI0002.0055
Die Paste wird sodaalkalisch in 700 Volumteilen Was ser gelöst und durch Einheiten von Phosgen in die soda- alkalisch gehaltene Lösung in den Harnstoff überge- führt. Man erhält einen Farbstoff, der getrocknet ein dunkles Pulver darstellt, das sich in Wasser mit rot violetter Farbe löst und Baumwolle in rotviolettem Farb ton färbt.
Process for the production of azo dyes The invention relates to a process for the production of azo dyes, which is characterized in that (a) a diazo compound of an amine of the formula Y-R-NH,
where Y is a metal complex-forming substituent ortho to the amino group and R is the remainder of one or a molar part of such an amino compound and a molar part of a different type of amino group-containing compound with polyfunctional acylating agents on the 6-position amino group in such a way that a bridge member is formed between every two amino compounds.
Step (c) of the process therefore proceeds according to the following scheme:
EMI0001.0019
Diazo component means coupling with 1,6-diaminonaphthalene--4,8-disulfonic acid in the 2-position, (b) the 6-position amino group of the coupling component is acylated before or after the coupling, (c) the 1-position amino group is now or last Process step converted into an OH group by diazotization and boiling, (d) the 6-position amino group is restored by saponification and (e)
two molar parts of the same or different amino compounds of the formula thus obtained
EMI0001.0033
In the formulas, R denotes the remainder of a diazo component which contains Y bound in the o-position to the azo bridge, and Y denotes a metal complex-forming substituent, i.e. e.g. a hydroxyl,
a carboxyl or a heterocyclically bonded NH group, or a radical which, under the conditions of non-oxidizing metallization, is converted into a metal complex-forming group, for example an alkoxy or a carboxylic ester group or halogen.
It is also possible to proceed in such a way that the amino group in the 6-position is first acylated and then the coupling and conversion of the 1-position amino group into an oxy group takes place.
The further implementation of the intermediate stages obtainable by the process described takes place after cleavage of the acyl radical by converting the 6-position amino group into a bridge member containing at least two nitrogen atoms by reacting the amino group in the presence of a second amino component with polyfunctional acylating agents.
The order of the steps required to carry out the new method can to a certain extent be reversed. For example, the diazotization and boiling of the amino group in the 1-position can also take place after the reaction with the polyfunctional acylating agents.
If diazotization and boiling of the amino group in the 1-position are carried out as the first stage, i.e. before the coupling, 1-oxy-6-acylamino-naphthalene-4,8-disulfonic acids and thus starting materials for the further steps of the process are obtained.
Another variant is made possible by the fact that the z. B. can conduct the boiling carried out as the first stage so that the sulton is created:
EMI0002.0017
Starting from the amino sultone, the steps required to convert the amino group into a bridging member containing at least two nitrogen atoms can now be carried out first. The hydrolytic splitting of the sultone ring, coupling to the oxy group and metallization can then take place as the last stages.
<I> Example </I> The solution of 36.2 parts by weight (0.1 mol) 1- -amino-6-acetylaminonaphthalene-4.8-disulfonic acid in 1000 parts by volume of water is mixed with 25 parts by weight of sodium acetate and then with the diazo compound manure from 20.8 parts by weight of 2-chloro-1-aminobenzene-4-sulfonic acid was added at 0.
After the coupling has ended, the reaction solution is brought to pH 1 by adding hydrochloric acid, and the dye is separated off with sodium chloride and isolated.
The dye paste obtained in this way is stirred in 1000 parts by volume of water, made slightly alkaline with soda, 70 parts by volume of 10% sodium nitrite solution and then 100 parts by volume of 50% sulfuric acid are added.
When the diazotization is complete, the reaction solution is heated to about 80 and kept at this temperature until the boiling has ended. The reaction product is then precipitated with sodium chloride, isolated and converted into the copper complex in the usual way.
After alkaline saponification of the acetylamino group, the copper complex dye of the formula is obtained
EMI0002.0055
The paste is dissolved soda-alkaline in 700 parts by volume of water and converted into urea by units of phosgene in the soda-alkaline solution. A dye is obtained which, when dried, is a dark powder which dissolves in water with a red-violet color and dyes cotton in a red-violet color tone.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH898569A CH476809A (en) | 1959-02-14 | 1960-01-29 | Process for the production of azo dyes |
| CH1408468A CH491176A (en) | 1959-02-14 | 1960-01-29 | Process for the production of azo dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF27709A DE1117235B (en) | 1959-02-14 | 1959-02-14 | Process for the production of azo dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH476077A true CH476077A (en) | 1969-07-31 |
Family
ID=7092564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH101460A CH476077A (en) | 1959-02-14 | 1960-01-29 | Process for the production of azo dyes |
Country Status (3)
| Country | Link |
|---|---|
| CH (1) | CH476077A (en) |
| DE (1) | DE1117235B (en) |
| NL (1) | NL6602947A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2033989C2 (en) * | 1969-07-18 | 1985-05-09 | Ciba-Geigy Ag, Basel | Storage-stable concentrated solutions of metal complexes of azo or azo-azomethine dyes and their uses |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE528166C (en) * | 1927-10-08 | 1931-06-26 | Chemische Ind Ges | Process for the production of metal-containing azo dyes |
-
1959
- 1959-02-14 DE DEF27709A patent/DE1117235B/en active Pending
-
1960
- 1960-01-29 CH CH101460A patent/CH476077A/en not_active IP Right Cessation
-
1966
- 1966-03-07 NL NL6602947A patent/NL6602947A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE1117235B (en) | 1961-11-16 |
| NL6602947A (en) | 1966-07-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |