CH280731A - Process for the preparation of a copper-containing disazo dye. - Google Patents
Process for the preparation of a copper-containing disazo dye.Info
- Publication number
- CH280731A CH280731A CH280731DA CH280731A CH 280731 A CH280731 A CH 280731A CH 280731D A CH280731D A CH 280731DA CH 280731 A CH280731 A CH 280731A
- Authority
- CH
- Switzerland
- Prior art keywords
- copper
- dye
- releasing agent
- process according
- carried out
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052802 copper Inorganic materials 0.000 title claims description 11
- 239000010949 copper Substances 0.000 title claims description 11
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000975 dye Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000004699 copper complex Chemical class 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001880 copper compounds Chemical class 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
- 239000000243 solution Substances 0.000 description 2
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 azo copper complex Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000001335 demethylating effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000725 suspension Substances 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
- C09B45/28—Disazo or polyazo compounds containing copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Verfahren zur Herstellung eines kupferhaltigen Disazofarbstoffes. Es wurde gefunden, dass man zu einem wertvollen, kupferhaltigen Disazofarbstoff ge- langt, wenn man auf einen Disazofarbstoff der Formel
EMI0001.0006
unter solchen Bedingungen kupferabgebende Mittel einwirken lässt, dass eine Aufspaltung der -0-Alkylgi-uppen unter Bildung des Bis- (o,o'-dioxy azokupferkomplexes) erfolgt.
Der neue Farbstoff bildet ein schwärz lielies Pulver, das sieh in Wasser mit rötlich- blauer Farbe löst und Baumwolle aus natrium- sulfatlialtigem Bade in reinen rötlichbraunen Tönen von hoher Lichteehtheit färbt.
Die beim vorliegenden Verfahren als Aus gangsstoffe dienenden Disazofarbstoffe der obigen Formel, welche zweckmässig in Form eines Alkalisalzes verwendet werden, können erhalten werden, indem man ein tetrazotiertes 3,3'-Dialkoxy-4,4'-diaminodiphenyl, vorzugs weise tetrazotiertes 3,3'-Dimethoxy-4,4'-di- aininodiphenyl beidseitig mit 2-(4'-Carboxy- tnetlioxy phenyl) -amino-5 - oxynaphtlialin-7-sul- fonsäure kuppelt.
Die Behandlung mit kupferabgebenden Mitteln erfolgt in der Weise, dass unter Auf spaltung der -0-Alkylgruppen der Bis-(o,o'- dioxyazokupferkoniplex) entsteht. Methoden, die zu einer solchen entalkylierenden Kupfe run- führen, sind allgemein bekannt.
Beson- ders bewährt hat sieh zum Beispiel das Ver- fahren, wonach unter Verwendung von Kup- fertetramminkomplexen in Gegenwart oder Abwesenheit von überschüssigem Ammoniak die Kupferung während einer bis mehrerer Stunden in der Nähe von 100 in wässerigem Medium durchgeführt wird. Als sehr vorteil haft erweist sich auch das Verfahren der schweizerischen Patentschrift Nr.261365, wo nach in Gegenwart von Oxyalkylaminen, ins besondere Äthanolamin bzw. der sich davon ableitenden Kupferkomplexe, gearbeitet wird.
Die Kupferung kann aber auch mit Kupfer acetat bzw. einer Mischung von Kupfersulfat und Natriumacetat durehgeführt werden, in dem man das Reaktionsgemiseh oder den pri mär entstehenden Kupferkomplex, in welchem die Alkoxygruppen noch nicht aufgespalten worden sind, einige Stunden in trockenem Zustand bei Temperaturen über 100 behan delt.
Beispiel.: 24,4 Teile Dianisidin werden in 200 Teilen Wasser mit 25 Teilen 30 11/oiger Salzsäure ge löst, darnach mit weiteren 25 Teilen 30 /oiger Salzsäure versetzt und bei 0 bis 2 mit. 14 Tei len Natriumnitrit tetrazotiert. Die klare Lö- sung von 80 Teilen 2-(4'-Carboxymethoxyphe- nyl)-amino-5-oxynaphthalin-7-sulfonsäure und 50 Teilen wasserfreiem Natriumcarbonat in 650 Teilen Wasser fliessen.
Nach einigen Stun den erwärmt man die Suspension des entstan denen Disazofarbstoffes auf 60 , gibt etwa 1.00 Teile Natriumchlorid zu und filtriert den nun ausbefällten Farbstoff ab.
Die erhaltene Farbstoffpaste wird mit 9 wenig Wasser zu einer dicklichen Paste an- geteigt, mit der Lösung von 56 Teilen krist. Kupfersulfat und 50 Teilen krist. Natrium acetat in 500 Teilen MTasser versetzt und 10 Stunden verrührt. Darnach dampft man die Paste unter Vakuum ein und hält am Ende des Eindampfens 6 Stunden bei 125 bis 128 .
Man erhält dadurch die Kupferverbindung des o,o'- Dioxyazofarbstoffes als trockenes schwärz- liches Pulver, das zweckmässig mit 2 bis 5 % des Gewichtes mit wasserfreiem Natriumearbo- nat versetzt wird.
Die entmethylierende Kupferung der nach den obigen Angaben erhaltenen Farbstoffpaste kann auch in wässeriger Lösung erfolgen, in dem man die Parbstoffpaste in 4000 Teilen M asser löst, mit 55 Teilen krist. Kupfersulfat, 1.00 Teilen konz. Ammoniak und 25 Teilen hIonoäthanolamin versetzt und 12 bis 15 Stun den unter Rüekfl.uss kocht.
Mit 200 Teilen Natriumchlorid fällt man die so erhaltene Kupferverbindung des o,o'-Dioxyazofarbstof- fes aus, filtriert und trocknet.
Process for the preparation of a copper-containing disazo dye. It has been found that a valuable, copper-containing disazo dye is obtained by using a disazo dye of the formula
EMI0001.0006
lets copper-releasing agents act under such conditions that splitting of the -0-alkyl groups with formation of the bis (o, o'-dioxy azo copper complex) takes place.
The new dye forms a blackish-white powder that dissolves in water with a reddish-blue color and dyes cotton from sodium sulphate bath in pure reddish-brown shades of high lightness.
The disazo dyes of the above formula which are used as starting materials in the present process and which are conveniently used in the form of an alkali salt can be obtained by adding a tetrazotized 3,3'-dialkoxy-4,4'-diaminodiphenyl, preferably tetrazotized 3,3 '-Dimethoxy-4,4'-di-ainodiphenyl couples on both sides with 2- (4'-carboxy tnetlioxy phenyl) -amino-5-oxynaphthalene-7-sulphonic acid.
The treatment with copper-releasing agents takes place in such a way that the bis (o, o'-dioxyazokupferkoniplex) is formed with splitting of the -0-alkyl groups. Methods which lead to such dealkylating copper are generally known.
For example, the method according to which coppering is carried out for one to several hours in an aqueous medium using copper tetrammine complexes in the presence or absence of excess ammonia has proven particularly successful. The process of Swiss patent specification No. 261365, which is used in the presence of oxyalkylamines, in particular ethanolamine or the copper complexes derived therefrom, has also proven to be very advantageous.
The coppering can also be carried out with copper acetate or a mixture of copper sulfate and sodium acetate, in which the reaction mixture or the primarily resulting copper complex in which the alkoxy groups have not yet been split, for a few hours in a dry state at temperatures above 100 treated.
Example .: 24.4 parts of dianisidine are dissolved in 200 parts of water with 25 parts of 30% hydrochloric acid, then a further 25 parts of 30% hydrochloric acid are added and, at 0 to 2, with. 14 parts sodium nitrite tetrazotized. The clear solution of 80 parts of 2- (4'-carboxymethoxyphenyl) -amino-5-oxynaphthalene-7-sulfonic acid and 50 parts of anhydrous sodium carbonate in 650 parts of water flow.
After a few hours, the suspension of the disazo dye formed is heated to 60, about 1.00 part of sodium chloride is added and the dye which has now precipitated out is filtered off.
The dye paste obtained is made into a thick paste with a little water, with the solution of 56 parts of crystalline. Copper sulfate and 50 parts of crystalline. Sodium acetate is added in 500 parts of water and stirred for 10 hours. The paste is then evaporated in vacuo and, at the end of the evaporation, is kept at 125 to 128 hours for 6 hours.
This gives the copper compound of the o, o'-dioxyazo dye as a dry, blackish powder to which 2 to 5% by weight of anhydrous sodium carbonate is expediently added.
The demethylating coppering of the dye paste obtained according to the above information can also be carried out in aqueous solution by dissolving the dye paste in 4000 parts of water, with 55 parts of crystalline. Copper sulfate, 1.00 parts conc. Ammonia and 25 parts of hionoethanolamine are added and cooked under reflux for 12 to 15 hours.
The copper compound of the o, o'-dioxyazo dye thus obtained is precipitated with 200 parts of sodium chloride, filtered and dried.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH277658T | 1949-08-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH280731A true CH280731A (en) | 1952-01-31 |
Family
ID=4481343
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH280732D CH280732A (en) | 1949-08-05 | 1949-08-05 | Process for the preparation of a copper-containing disazo dye. |
| CH277658D CH277658A (en) | 1949-08-05 | 1949-08-05 | Process for the preparation of a copper-containing disazo dye. |
| CH280731D CH280731A (en) | 1949-08-05 | 1949-11-10 | Process for the preparation of a copper-containing disazo dye. |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH280732D CH280732A (en) | 1949-08-05 | 1949-08-05 | Process for the preparation of a copper-containing disazo dye. |
| CH277658D CH277658A (en) | 1949-08-05 | 1949-08-05 | Process for the preparation of a copper-containing disazo dye. |
Country Status (4)
| Country | Link |
|---|---|
| CH (3) | CH280732A (en) |
| DE (1) | DE889662C (en) |
| FR (1) | FR1023892A (en) |
| GB (1) | GB674707A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2816102A (en) * | 1953-02-12 | 1957-12-10 | Ciba Ltd | Metalliferous azo dyestuffs |
| BE541338A (en) * | 1954-09-17 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE515468C (en) * | 1929-02-19 | 1931-01-09 | I G Farbenindustrie Akt Ges | Process for the preparation of ª ‰ -Naphthylaminophenoxyfettsaeuren |
| GB333573A (en) * | 1929-05-10 | 1930-08-11 | Ig Farbenindustrie Ag | Process for the manufacture of substantive ª¤-carboxyazo dyestuffs containing copper |
| GB352956A (en) * | 1930-04-14 | 1931-07-14 | Ig Farbenindustrie Ag | Process for the manufacture of substantive dyeing disazo dyestuffs containing copper |
-
1949
- 1949-08-05 CH CH280732D patent/CH280732A/en unknown
- 1949-08-05 CH CH277658D patent/CH277658A/en unknown
- 1949-11-10 CH CH280731D patent/CH280731A/en unknown
- 1949-11-28 DE DEC211A patent/DE889662C/en not_active Expired
-
1950
- 1950-07-27 GB GB18845/50A patent/GB674707A/en not_active Expired
- 1950-07-31 FR FR1023892D patent/FR1023892A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE889662C (en) | 1953-09-14 |
| GB674707A (en) | 1952-06-25 |
| CH280732A (en) | 1952-01-31 |
| FR1023892A (en) | 1953-03-25 |
| CH277658A (en) | 1951-09-15 |
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