DE2656781A1 - PROCESS FOR THE PRODUCTION OF AMINO-GROUP-CONTAINING AZOMETAL COMPLEX DYES - Google Patents
PROCESS FOR THE PRODUCTION OF AMINO-GROUP-CONTAINING AZOMETAL COMPLEX DYESInfo
- Publication number
- DE2656781A1 DE2656781A1 DE19762656781 DE2656781A DE2656781A1 DE 2656781 A1 DE2656781 A1 DE 2656781A1 DE 19762656781 DE19762656781 DE 19762656781 DE 2656781 A DE2656781 A DE 2656781A DE 2656781 A1 DE2656781 A1 DE 2656781A1
- Authority
- DE
- Germany
- Prior art keywords
- dye
- amino
- complex dyes
- production
- group
- 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.)
- Granted
Links
- 239000000975 dye Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 7
- 239000000434 metal complex dye Substances 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 239000000987 azo dye Substances 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- 159000000000 sodium salts Chemical class 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- -1 aliphatic alcohols Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- HGWQOFDAUWCQDA-UHFFFAOYSA-N 4-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(O)=CC=C(S(O)(=O)=O)C2=C1 HGWQOFDAUWCQDA-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003610 charcoal Substances 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
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 2
- ZFRBZRZEKIOGQI-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound C1=CC(O)=C2C(N)=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 ZFRBZRZEKIOGQI-UHFFFAOYSA-N 0.000 description 2
- VVPHSMHEYVOVLH-UHFFFAOYSA-N 6-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(O)=CC=C21 VVPHSMHEYVOVLH-UHFFFAOYSA-N 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 2
- WKWVTNARZXNZQY-UHFFFAOYSA-N azanide;copper(1+) Chemical compound [Cu]N WKWVTNARZXNZQY-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- TZBROGJRQUABOK-UHFFFAOYSA-N 4-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 TZBROGJRQUABOK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- BJUKBQYOYJOPDS-UHFFFAOYSA-N [O-][N+]([Cu])=O Chemical compound [O-][N+]([Cu])=O BJUKBQYOYJOPDS-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010626 work up procedure Methods 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
- C09B45/48—Preparation from other complex metal compounds of azo 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
- C09B43/08—Preparation of azo dyes from other azo compounds by reduction
-
- 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
- C09B45/01—Complex metal compounds of azo dyes characterised by the method of metallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
Zentralbereich Patente, Marken und LizenzenCentral area of patents, trademarks and licenses
500 Leverkusen, Bayerwerk500 Leverkusen, Bayerwerk
My-dbMy-db
Verfahren zur Herstellung aminogruppenhaltiger AzometallkomplexfarbstoffeProcess for the preparation of amino groups Azo metal complex dyes
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von aminogruppenhaltigen Azometallkomplexfarbstoffen welches dadurch gekennzeichnet ist, daß man nitrogruppenhaltige Azometallkomplexfarbstoffe in polaren Lösungsmitteln in Gegenwart katalytischer Mengen einer Schwermetallverbindung mit Hydrazin behandelt.The present invention relates to a method of production of amino-containing azo metal complex dyes which is characterized in that one contains nitro-groups Azo metal complex dyes in polar solvents in the presence of catalytic amounts of a heavy metal compound with hydrazine treated.
Die Reduktion wird bei Temperaturen von etwa 40 - 1200C, vorzugsweise 50 - 1000C, durchgeführt. Sie verläuft mit stöchiometrischen Mengen Hydrazin, d.h. 1,5 Mol pro Mol Nitrogruppe. Im allgemeinen arbeitet man mit einem Überschuß von 5 - 15 $· Auch ein Überschuß von 50 % ist nicht von Nachteil.The reduction is conducted at temperatures of about 40-120 0 C, preferably 50-100 0 C is performed. It proceeds with stoichiometric amounts of hydrazine, ie 1.5 moles per mole of nitro group. In general, an excess of $ 5-15 is used. Even a 50 % excess is not a disadvantage.
Geeignete Lösungsmittel sind beispielsweise Wasser - insbesondere für sulfonsäuregruppenhaltige Farbstoffe -, Alkohole, insbesondere niedere aliphatische Alkohole, Äther und andere polare organische Lösungsmittel. Im allgemeinen verwendet man ein Lösungsmittel, in dem der Farbstoff möglichst gut löslich ist.Suitable solvents are, for example, water - in particular for dyes containing sulfonic acid groups -, alcohols, in particular lower aliphatic alcohols, ethers and other polar organic solvents. Generally one uses a Solvent in which the dye is as soluble as possible.
Der pH-Wert der Reaktionsmischung wird zweckmäßigerweise bei etwa 4-9, vorzugweise zwischen 7 und 9 gehalten.The pH of the reaction mixture is expediently kept at about 4-9, preferably between 7 and 9.
809825/0U1809825 / 0U1
Le A 17 665Le A 17 665
Geeignete Schwermetallverbindungen sind beispielsweise die Schwermetallsalze die das Metall in einer durch Hydrazin reduzierbaren Oxydationsstufe enthalten wie Fe-(IIl)- und Cu-(ll)-Salze.Suitable heavy metal compounds are, for example, the heavy metal salts which contain the metal in an oxidation stage that can be reduced by hydrazine, such as Fe (III) and Cu (II) salts.
Geeignete Salze dieser Art sind beispielsweise PeCl3, Fe2(SO4)5, CuCl2, CuSO4.Suitable salts of this type are, for example, PeCl 3 , Fe 2 (SO 4 ) 5 , CuCl 2 , CuSO 4 .
Die Schwermetallverbindungen werden in Mengen von etwa 0,1-1 Mol fo, bezogen auf zu reduzierenden Farbstoff, eingesetzt.The heavy metal compounds are used in amounts of about 0.1-1 mol fo, based on the dye to be reduced.
Torzugsweise wird die Reduktion in Gegenwart eines inerten Adsorbens durchgeführt.Preferably, the reduction is carried out in the presence of an inert adsorbent carried out.
Geeignete inerte Adsorbentien sind beispielsweise Aktivkohlen wie Α-Kohle, Tierkohle, Holzkohle, Aluminiumoxide, Siliciumdioxid-Gele und Materialien auf Cellulosebasis (z. B. "Celite" R), vergleiche Römpp, Chemie Lexikon, 1966, S. 73·Suitable inert adsorbents are, for example, activated carbons such as Α charcoal, animal charcoal, charcoal, aluminum oxides, silicon dioxide gels and cellulose-based materials (e.g. "Celite" R), see Römpp, Chemie Lexikon, 1966, p. 73 ·
Die Trägermaterialien werden in Mengen von etwa 10 - 100 g, vorzugsweise 20 - 50 g, pro Mol zu reduzierendem Farbstoff eingesetzt.The carrier materials are used in amounts of about 10-100 g, preferably 20-50 g, used per mole of dye to be reduced.
Im allgemeinen führt man die Reduktion in der Weise durch, daß man zu einer Lösung oder Suspension des Farbstoffes in einem geeigneten Lösungsmittel, die außerdem eine Schwermetallverbindung und gegebenenfalls ein Trägermaterial enthält, bei erhöhter Temperatur langsam Hydrazin, vorzugsweise in Form von Hydrazinhydrat, zusetzt und bis zur Beendigung der Reduktion auf erhöhter Temperatur hält.In general, the reduction is carried out in such a way that to a solution or suspension of the dye in a suitable solvent, which also contains a heavy metal compound and optionally contains a carrier material, slowly adding hydrazine, preferably in the form of hydrazine hydrate, at elevated temperature, and up to holds at elevated temperature to complete the reduction.
Nach dem erfindungsgemäßen Verfahren kann man sowohl 1:1- als auch 1:2-Metallkomplexfarbstoffe reduzieren.The process according to the invention can be used both 1: 1 and Reduce 1: 2 metal complex dyes.
Das Verfahren eignet sich ganz besonders zur Reduktion von Metallkomplexfarbstoffen der Formeln (l) und (il).The process is particularly suitable for the reduction of metal complex dyes of formulas (l) and (il).
809825/0U1809825 / 0U1
Le A 17 665 - 2 - Le A 17 665 - 2 -
O2N'O 2 N '
N=N KN = N K
(C0)m0-Me-0(C0) m 0-Me-0
(D(D
D = aromatisch-carbocyclische DiazokomponenteD = aromatic-carbocyclic diazo component
K = aromatisch-carbocyclische oder aromatisch-heterocyclische KupplungskomponenteK = aromatic-carbocyclic or aromatic-heterocyclic coupling component
Me = Cu, Ni, Co, Cr, Pe m = 0 oder 1
η = 0 - 4Me = Cu, Ni, Co, Cr, Pe m = 0 or 1
η = 0 - 4
O2N-B-N=N-KO 2 NBN = NK
(CO)1nO-Cu-O(CO) 1n O-Cu-O
-(SO3H)- (SO 3 H)
(II)(II)
m = 0 oder 1
P - 2, 3, 4m = 0 or 1
P - 2, 3, 4
Die aminogruppenhaltigen Farbstoffe z.B. finden Verwendung zur Herstellung von Reaktivfarbstoffen, wobei die Aminogruppe mit einer Eeaktivkomponente acyliert wird.The amino group-containing dyes, for example, are used for the production of reactive dyes, the amino group with a Active component is acylated.
Le Le A A. 17 17th 661661
809825/0U1809825 / 0U1
57>4 S des Natriumsalzes des Farbstoffs der Formel57> 4 S of the sodium salt of the dye of the formula
,0-Cu-O, O-Cu-O
SO3HSO 3 H
werden mit 150 ml Wasser, 4OO mg Eisen-III-chlorid und 2,4 g Aktivkohle
versetzt und auf 1000C erhitzt. Der pH-Wert wird auf 8,5 eingestellt
und bei diesem pH innerhalb von 30 Minuten 8 ml Hydrazinhydrat
zugetropft. Man rührt 1 Stunde bei 1000C nach, filtriert
heiß und fällt im FiItrat in üblicher Weise bei pH 4>5 mit Kochsalz
den Farbstoff aus.
Man erhält den Farbstoff der Formel (Ka-SaIz)are mixed with 150 ml of water, 4OO mg of ferric chloride and 2.4 g of activated carbon and heated to 100 0 C. The pH is adjusted to 8.5 and, at this pH, 8 ml of hydrazine hydrate are added dropwise over the course of 30 minutes. It is stirred for 1 hour at 100 0 C after, filtered hot and falls in FiItrat in a conventional manner at pH 4> 5 with saline from the dye.
The dye of the formula (Ka-Salz) is obtained
in Form eines braunroten Pulvers.in the form of a brown-red powder.
Der Farbstoff findet Verwendung als Zwischenprodukt für die Herstellung von Reaktivfarbatoffen. Verwendet man an Stelle von Eisen-III-chlorid 400 mg Kupfer-II-sulfat (5H2O) oder an Stelle von Aktivkohle 2,5 g Aluminiumoxid oder 3 S Silicagel, erhält man gleiche Ergebnisse.The dye is used as an intermediate for the production of reactive dyes. If 400 mg of copper (II) sulfate (5H 2 O) is used instead of iron (III) chloride or 2.5 g of aluminum oxide or 3 S silica gel instead of activated carbon, the same results are obtained.
In gleicher Weise werden die Kupferkomplexazofarbetoffe reduziert, die anstelle der 6-Hydroxy-2-naphthalinsulfonsäure die 3-Hydroxy-2,7-naphthalindisulfonsäure, 4-Hydroxy-l-naphthalinsulfonsäure oder 4-Amino-5-hydroxy-l,3-naphthalindisulfonsäure als Kupplungskomponente enthalten.In the same way, the copper complex azo dyes are reduced, instead of 6-hydroxy-2-naphthalenesulfonic acid, 3-hydroxy-2,7-naphthalenedisulfonic acid, 4-hydroxy-1-naphthalenesulfonic acid or 4-Amino-5-hydroxy-1,3-naphthalenedisulfonic acid as coupling component contain.
809825/0U1809825 / 0U1
Le A 17 663 - 4 - Le A 17 663 - 4 -
62,4 S des Natriumsalzes des Farbstoffes der Formel62.4 S of the sodium salt of the dye of the formula
HO3SHO 3 S
O3HO 3 H
werden in 300 ml Wasser mit 2,4 g Aktivkohle und 250 mg Eisen-III-chlorid auf 800C erwärmt und der pH-Wert auf 8 gestellt. Innerhalb 30 Minuten werden 10 ml Hydrazinhydrat zugegeben u.6 Std. bei 800C gehalten. Man arbeitet wie in Beispiel 1 auf. Nach dem Trocknen erhält man den Aminokupferkomplex-azofarbstoff in Form eines schwarzbraunen Pulvers. are heated to 80 ° C. in 300 ml of water with 2.4 g of activated carbon and 250 mg of iron (III) chloride and the pH is adjusted to 8. Over 30 minutes 10 ml of hydrazine hydrate added u.6 hrs. At 80 0 C are maintained. Work up as in Example 1. After drying, the amino copper complex azo dye is obtained in the form of a black-brown powder.
In gleicher Weise wird der Kupferkomplexfarbstoff reduziert, der
anstelle der 4-Hydroxy-l-naphthalinsulfonsäure die 4-Amino-5-hydroxy-1.3-naphthalindisulfonsäure
enthält (vgl. Beispiel 3)·In the same way, the copper complex dye is reduced, the
instead of 4-hydroxy-1-naphthalenesulphonic acid, it contains 4-amino-5-hydroxy-1,3-naphthalenedisulphonic acid (see Example 3)
74>2 g des Natriumsalzes des Farbstoffs74> 2 g of the sodium salt of the dye
0 Cu 0 NH2 0 Cu 0 NH 2
SO3HSO 3 H
O3HO 3 H
werden mit 300 mg Eisen-III-chlorid in 500 ml Wasser auf 9O0C erwärmt
und innerhalb 40 Minuten mit 12 ml Hydrazinhydrat bei einem
pH-Wert von 8.5 versetzt. Man hält weitere 4 Stunden bei 900C. Man
arbeitet wie in Beispiel 1 auf und erhält nach dem Trocknen den reduzierten Azofarbstoff als blauschwarzes Pulver.are heated with 300 mg of iron (III) chloride in 500 ml of water to 9O 0 C and within 40 minutes with 12 ml of hydrazine hydrate at a
pH value of 8.5 added. It is kept at 90 ° C. for a further 4 hours. The procedure is as in Example 1 and, after drying, the reduced azo dye is obtained as a blue-black powder.
Le A 17 665Le A 17 665
809825/0141809825/0141
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87,6 g des Farbstoffs der Formel87.6 g of the dye of the formula
HO3S 0 Cu 0HO 3 S 0 Cu 0
SO3HSO 3 H
SO3HSO 3 H
als Natriumsalz werden in 300 ml Wasser mit 2,4 g Akivkohle und 250 mg FeCl3-OH2O auf 500C erwärmt und der pH-Wert auf 8 gestellt. Innerhalt» 30 Minuten werden 8 ml Hydrazinhydrat zugegeben und dann 1 Stunde bei 900C nachgerührt. Es wird in üblicher Weise aufgearbeitet. Nach -dem Trocknen erhält man den Amino-kupferkomplex-azofarbstoff als schwarzviolettes Pulver.as the sodium salt in 300 ml of water with 2.4 g of FeCl 3 and 250 Akivkohle -OH O 2 mg to 50 0 C is heated and the pH-value. 8 8 ml of hydrazine hydrate are added within 30 minutes and the mixture is then stirred at 90 ° C. for 1 hour. It is worked up in the usual way. After drying, the amino-copper complex-azo dye is obtained as a black-violet powder.
In gleicher Weise werden die Nitro-kupferkomplex-azofarbstoffe reduziert, die anstelle der 4-Hydroxy-2.7-naphthalindisulfonsäure als Kupplungskomponente die 4-Hydroxy-l-naphtalinsulfonsäure, 3-Hydroxy-2.7-naphthalindisulfonsäure, 6-Hydroxy-2-naphthalinsulfonsäure oder 4_Amino-5-hydroxy-1.3-naphthalindisulfonsäure enthalten.The nitro-copper complex-azo dyes are reduced in the same way, instead of 4-hydroxy-2.7-naphthalenedisulfonic acid as Coupling component 4-hydroxy-l-naphthalene sulfonic acid, 3-hydroxy-2.7-naphthalenedisulfonic acid, Contain 6-hydroxy-2-naphthalenesulphonic acid or 4_amino-5-hydroxy-1,3-naphthalenedisulphonic acid.
73»5 S des Natriumsalzes des Azofarbstoffes von Beispiel 3 als Eisenkomplex werden in 450 ml Wasser mit 2,2 g Aktivkohle und 400 mg FeCl3^H2O auf 9O0C erhitzt und bei einem pH-Wert von 9»5 innerhalb 30 Minuten mit 9 nil Hydrazinhydrat versetzt. Nach weiteren 1 1/2 Stunden bei 900C wird heiß geklärt und in üblicher Weise isoliert. Man erhält den Farbstoff der Formel (Na73 »5 S of the sodium salt of the azo dye of Example 3 as the iron complex are O heated to 9O 0 C in 450 ml of water with 2.2 g of activated carbon and 400 mg of FeCl 3 ^ H 2 and at a pH value of 9» 5 within 30 Minutes with 9 nil hydrazine hydrate. After a further 11/2 hours at 90 ° C., it is clarified while hot and isolated in the customary manner. The dye of the formula (Na
0 Fe—0 NH2 0 Fe-0 NH 2
in Form eines schwarzbraunen Pulvers.in the form of a black-brown powder.
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Le A 17 663 - 6 - Le A 17 663 - 6 -
Beispiel 6 43 Example 6 43
60 g des Azofarbstoffes der Formel60 g of the azo dye of the formula
SO3HSO 3 H
als Na-SaIz werden in 4OO ml Wasser "bei pH 7 und 8O0C gelöst. Es werden 2 g Aktivkohle und 250mgPeCl3*6H20 zugegeben. Unter Einhalten von pH 7 gibt man innerhalb 30 Minuten 8 ml Hydrazinhydrat zu und hält danach noch weitere 2 Stunden bei 8O0C und pH 7· Man isoliert den reduzierten Farbstoff in üblicher Weise und erhält nach dem Trocknen ein hellbraunes Pulver.as Na salt mL of water "at pH in 4OO dissolved 7 and 8O 0 C. There are 2 g activated charcoal and 250mgPeCl 3 * 6H 2 0 was added. Under maintaining of pH 7 is added ml of hydrazine hydrate in 30 minutes 8 and holds thereafter for a further 2 hours at 8O 0 C and pH 7 · are isolated the reduced dye in a conventional manner and, after drying, a light brown powder.
0,1 Mol des Farbstoffes der Formel0.1 mol of the dye of the formula
ale 1:2-Chrom-Komplexale 1: 2 chromium complex
werden in 1000 ml Wasser mit 4,8 g Aktivkohle und 500 mg FeCl2* 6H2O bei pH 8 auf 1000C erhitzt und innerhalb 1 Stunde mit 24 ml Hydrazinhydrat versetzt. Man kocht weitere 8 Stunden am Rückfluß. Der reduzierte Farbstoff wird wie üblich isoliert, er stellt nach dem Trocknen ein rotbraunes Pulver dar. 6H are heated in 1000 ml of water with 4.8 g of activated carbon and 500 mg FeCl 2 * 2 O at pH 8 to 100 0 C and added over 1 hour with 24 ml of hydrazine hydrate. The mixture is refluxed for a further 8 hours. The reduced dye is isolated as usual; after drying it is a red-brown powder.
809825/0U1809825 / 0U1
Le A 17 663 - 7 - Le A 17 663 - 7 -
26.5673126.56731
Beispiel 8 λ« Example 8 λ «
0,1 Mol des Farbstoffes der Formel0.1 mol of the dye of the formula
HO H^-SO2CH3 HO H ^ -SO 2 CH 3
als 1:2-Chrom-Komplexas a 1: 2 chromium complex
werden mit 5 g Aktivkohle und 600 mg FeCl3^oH2O bei pH 8,5 in
1200 ml Wasser suspendiert und zum Sieden erhitzt. Es werden
innerhalb 45 Minuten 24 ml Hydrazinhydrat zugegeben und weitere
6.5 Stunden am Rückfluß gekocht.are with 5 g activated charcoal and 600 mg FeCl 3 ^ oH 2 O at pH 8.5 in
Suspended 1200 ml of water and heated to boiling. It will
added 24 ml of hydrazine hydrate within 45 minutes and more
Boiled under reflux for 6.5 hours.
Es wird wie üblich aufgearbeitet. Nach dem Trocknen erhält man den 1:2-Chromkomplex des Aminoazofarbstoffes als olivschwarzes Pulver.It is worked up as usual. After drying, one obtains the 1: 2 chromium complex of the aminoazo dye as an olive black powder.
0,1 Mol des 1:1-Chromkomplexes des Farbstoffes der Formel0.1 mol of the 1: 1 chromium complex of the dye of the formula
werden in 350 ml 2.4 g Aktivkohle und 250 mg FeCl3^oH2O auf Siedetemperatur
erhitzt. Bei pH 8 werden innerhalb 30 Hinuten 16 ml
Hydrazinhydrat zugegeben und weitere 5 Stunden bei Siedetemperatur gehalten. Man arbeitet wie in Beispiel 1 beschrieben auf und erhält
nach dem Trocknen ein violettschwarzes Pulver des 1:1-Chromkomplex
des Aminoazofarbstoffes.are heated to boiling temperature in 350 ml 2.4 g activated charcoal and 250 mg FeCl 3 ^ oH 2 O. At pH 8, 16 ml are added within 30 minutes
Hydrazine hydrate was added and the mixture was kept at boiling temperature for a further 5 hours. It is worked up as described in Example 1 and, after drying, a violet-black powder of the 1: 1 chromium complex of the aminoazo dye is obtained.
Le A 17 665 - β - Le A 17 665 - β -
809825/0U1809825 / 0U1
ACfACf
0,1 Mol des 1:2-Chromkomplexes des Farbstoffes der Formel0.1 mol of the 1: 2 chromium complex of the dye of the formula
HO3SHO 3 S
werden mit 5 g Aktivkohle und 500 mg FeCl3 6H2O in 1200 ml Wasser zum Sieden erhitzt und bei pH 8,5 innerhalb 45 Minuten mit l6 ml Hydrazinhydrat versetzt. Man kocht 6 Stunden am Rückfluß. Nach dem Filtrieren wird das Filtrat auf pH 6 gestellt und die Fällung mit NaCl vervollständigt. Nach dem Trocknen erhält man den 1:2-Chromkomplex des Aminoazofarbstoffes als fast schwarzes Pulver.are heated to boiling with 5 g of activated charcoal and 500 mg of FeCl 3 6H 2 O in 1200 ml of water, and 16 ml of hydrazine hydrate are added at pH 8.5 within 45 minutes. It is refluxed for 6 hours. After filtering, the filtrate is adjusted to pH 6 and the precipitation with NaCl is completed. After drying, the 1: 2 chromium complex of the aminoazo dye is obtained as an almost black powder.
Le A 17 663Le A 17 663
80982~5/0U180982 ~ 5 / 0U1
Claims (6)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762656781 DE2656781C2 (en) | 1976-12-15 | 1976-12-15 | Process for the preparation of azo metal complex dyes containing amino groups |
| IN385/DEL/77A IN147252B (en) | 1976-12-15 | 1977-11-11 | |
| GB5160277A GB1554088A (en) | 1976-12-15 | 1977-12-12 | Process for the preparation of azo metal complex dyestuffs containing amino groups |
| CH1532477A CH626111A5 (en) | 1976-12-15 | 1977-12-13 | Process for preparing amino-containing azo metal complex dyes |
| JP14892477A JPS5374529A (en) | 1976-12-15 | 1977-12-13 | Method of making azo metal complex dye containing amino group |
| BR7708297A BR7708297A (en) | 1976-12-15 | 1977-12-14 | PROCESS FOR THE PREPARATION OF AZOIC METAL COMPLEX DYES CONTAINING AMINO GROUPS |
| ES465042A ES465042A1 (en) | 1976-12-15 | 1977-12-14 | Process for the preparation of azo metal complex dyestuffs containing amino groups |
| FR7737740A FR2374383A1 (en) | 1976-12-15 | 1977-12-14 | PROCESS FOR PREPARING DYES CONSISTING OF METAL COMPLEXES OF AZOIC COMPOUNDS CARRYING AMINO GROUPS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762656781 DE2656781C2 (en) | 1976-12-15 | 1976-12-15 | Process for the preparation of azo metal complex dyes containing amino groups |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2656781A1 true DE2656781A1 (en) | 1978-06-22 |
| DE2656781C2 DE2656781C2 (en) | 1985-02-21 |
Family
ID=5995592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19762656781 Expired DE2656781C2 (en) | 1976-12-15 | 1976-12-15 | Process for the preparation of azo metal complex dyes containing amino groups |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5374529A (en) |
| BR (1) | BR7708297A (en) |
| CH (1) | CH626111A5 (en) |
| DE (1) | DE2656781C2 (en) |
| ES (1) | ES465042A1 (en) |
| FR (1) | FR2374383A1 (en) |
| GB (1) | GB1554088A (en) |
| IN (1) | IN147252B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6008330A (en) * | 1998-02-18 | 1999-12-28 | Bayer Aktiengesellschaft | Process for the preparation of aminodiarylazo compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1514670A (en) * | 1975-11-28 | 1978-06-21 | Bayer Ag | Removing 4-coupled products from azo dyestuffs derived from 1-naphthol series coupling components |
-
1976
- 1976-12-15 DE DE19762656781 patent/DE2656781C2/en not_active Expired
-
1977
- 1977-11-11 IN IN385/DEL/77A patent/IN147252B/en unknown
- 1977-12-12 GB GB5160277A patent/GB1554088A/en not_active Expired
- 1977-12-13 CH CH1532477A patent/CH626111A5/en not_active IP Right Cessation
- 1977-12-13 JP JP14892477A patent/JPS5374529A/en active Pending
- 1977-12-14 ES ES465042A patent/ES465042A1/en not_active Expired
- 1977-12-14 FR FR7737740A patent/FR2374383A1/en active Granted
- 1977-12-14 BR BR7708297A patent/BR7708297A/en unknown
Non-Patent Citations (1)
| Title |
|---|
| NICHTS-ERMITTELT * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6008330A (en) * | 1998-02-18 | 1999-12-28 | Bayer Aktiengesellschaft | Process for the preparation of aminodiarylazo compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| BR7708297A (en) | 1978-08-15 |
| DE2656781C2 (en) | 1985-02-21 |
| IN147252B (en) | 1980-01-05 |
| FR2374383B1 (en) | 1981-12-24 |
| FR2374383A1 (en) | 1978-07-13 |
| GB1554088A (en) | 1979-10-17 |
| CH626111A5 (en) | 1981-10-30 |
| JPS5374529A (en) | 1978-07-03 |
| ES465042A1 (en) | 1978-09-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition | ||
| 8339 | Ceased/non-payment of the annual fee |