GB1589915A - Process for the manufacture of triphenodioxazine compounds - Google Patents
Process for the manufacture of triphenodioxazine compounds Download PDFInfo
- Publication number
- GB1589915A GB1589915A GB4720976A GB4720976A GB1589915A GB 1589915 A GB1589915 A GB 1589915A GB 4720976 A GB4720976 A GB 4720976A GB 4720976 A GB4720976 A GB 4720976A GB 1589915 A GB1589915 A GB 1589915A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sulphophenyl
- amino
- parts
- persulphate
- oleum
- 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.)
- Expired
Links
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
- C09B19/00—Oxazine dyes
- C09B19/02—Bisoxazines prepared from aminoquinones
Description
(54) A PROCESS FOR THE MANUFACTURE OF
TRIPHENODIOXAZINE COMPOUNDS
(71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial
Chemical House, Millbank, London SW1P 3JF a British Company do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a new process for the manufacture of triphenodioxazine compounds.
It is known that such sompounds can be made by the cyclisation of 2,5-diarylaminobenzoquinone compounds with the aid of condensation agents, sulphuric acid and oleum being particularly well-known in this connection. However it is frequently found, especially where the arylamino substituents contain sulphonic acid groups, that cyclisation is difficult to effect with these agents, and that the use of elevated temperatures and/or high strength oleum is necessary, as a result of which sulphonation of the aryl nuclei takes place.
It has now been found that the addition of an inorganic persulphate to the reaction medium enables cyclisations in oleum to be effected under milder conditions than are otherwise the case i.e. using a lower strength oleum or a lower temperature than is necessary in the absence of persulphate.
As inorganic persulphates which may be used, there may be mentioned more especially sodium, potassium and ammonium persulphates.
The oleum used preferably contains from 5% to 30% by weight of SO, and reaction is preferably effected at from 0--600C, using from 1 to 3 moles of the persulphate per mole of the dianilinobenzoquinone.
As examples of 2,5-diarylaminobenzoquinones which may be used, there may be mentioned compounds of the formula:
in which X is H, CH3 or, preferably, Cl, and R is an aromatic radical having the NH group linked to a benzene nucleus, which may be further substituted or may form part of a fused cyclic system, e.g. a naphthyl, carbazolyl or fluorenyl radical.
Thus R may, for example, be a benzene nucleus containing substituents such as alkyl, e.g. methyl, halogen, e.g. Cl or Br, CO2H, SO,11, acylamino e.g. acetylamino NH2, alkylamino, anilino, alkoxy, aryloxy, benzyl, phenylethyl, phenylvinyl, phenylurea, arylthio; any alkyl groups or benzene nucleus in these substituents can itself be substituted, more especially by SO,H and NH,.
As specific examples of R, there may be mentioned:
4-amino-3 -sulphophenyl
3 -amino-4-sulphophenyl, 4-(4-amino-3 -sulphoanilino)-3-sulphophenyl 4-(3-amino-4-sulphoanilino)-3-sulphophenyl 4-(2-aminoethylamino)-3-sulphophenyl
4-ethylamino-3-sulphophenyl
4hydroxyethylamino-3 -sulphophenyl
4-sulphoethylamino-3 -sulphophenyl 6-amino-1,5-disulphonaphth-3-yl 4-(4-amino-3,6-disulphoanilino)-3 -sulphophenyl 4-benzylamino-3-sulphophenyl, and
4-phenoxy-3 -sulphophenyl
The triphenodioxazines which contains SO,H groups are useful as dyestuffs for wool and nylon, whilst those which in addition contain amino groups can be converted to reactive dyes by reaction with halogeno heterocyclic compounds, such as cyanuric chloride or tri- or tetra-chloropyrimidine.Reactive dyestuffs of this type are described, e.g. in U.K. Specifications Nos. 1,349,513, 1,368,158 and 1,450,746.
The new process has the advantage of enabling cyclisation to take place under milder conditions than are necessary using other oxidising agents or operating in monohydrate (100% sulphuric acid). A further advantage in the case of compounds of formula 1 which are assymetrically substituted is that ring-closure appears to be preferentially directed to one ortho position so that the mixtures inevitably obtained in such cases are less complex than in previously described methods.
The invention is illustrated by the following examples in which parts and percentages are by weight.
Example 1.
137 Parts of 2,5-bis(4-amino-3-sulphophenylamino)-3,6-dichlorobenzoquinone are added with stirring to 3,030 parts of 10% oleum, the temperature being maintained below 250C. The mixture is then heated to 400C. and 125.5 parts of ammonium persulphate added over 1 1/2 hours at 40,10C. After being held for a further hour at 40+ 1 oC, the reaction mixture is poured on to approximately 2,000 parts of ice-water so that the temperature does not rise above 50C. The resulting mixture is neutralised to pH 7.0 by addition of approximately 3,600 parts of aqueous ammonia solution (S.G. 0.88).The crude product is filtered off, washed with water, redissolved in 50,000 parts of water and the solution screened to remove a small amount of insoluble material. 1,200 parts of sodium chloride are dissolved with stirring in the filtrates.
The resulting precipitate is filtered off yielding 236 parts of an aqueous paste containing 101 parts of 3,10-diamino-6,1 3-dichlorotriphendioxazine-4, ll-disulphonic acid as a sodium salt.
Example 2.
31.8 Parts of 2,5-bis[4-(2-aminoethylamino)-3-sulphophenylamino]-3,6-dichloro- benzoquinone are added over 15 minutes with stirring to 318 parts of 20% oleum at 20-250C. 22.8 Parts of ammonium persulphate are then added in 7 equal portions at hourly intervals and the mixture stirred for a further hour, the temperature being maintained throughout at 2O300C. The reaction mixture is poured on to approximately 500 parts of ice so that the temperature of the drown-out does not rise above 200C. The drown-out is adjusted to pH 9.0 by addition of approximately 440 parts of aqueous ammonia solution (S.G. 0.88).The product is filtered off and washed with standard sodium chloride solution to yield 122 parts of an aqueous paste containing 24.9 parts of 3,10-bis-(2-aminoethylamino)-6,13-dichlorotriphendioxazine-4,11-disul- phonic acid and approximately 3 parts of a second blue triphendioxazine derivative probably differing only in the position of the sulphonic acid groups.
Example 3.
22.8 parts of 2,5-his [4-(4-amino-3-sulphoanilino)-3-sulphophenylamino] -3,6- dichlorobenzoquinone magnesium salt are added over 20 minutes with stirring to 447 parts of 5% oleum at 20-250C. 11.4 parts of ammonium persulphate are then added over 30 minutes and the mixture stirred for a further 2 hours, the temperature being maintained throughout at 20-250C. The reaction mixture is poured on to 1,500 parts of crushed ice and the resulting precipitate is filtered off under vacuum and washed with 10 parts of cold water.The filter cake is dissolved in a solution of approximately 8.5 parts of sodium hydroxide in 620 parts of water sufficient to give a final pH of 7.0. 100 Parts of potassium acetate are then dissolved in this solution, the precipitate formed is filtered off, redissolved in water, reprecipitated by addition of potassium acetate, filtered off and washed with ethanol 740P. The filter cake is reslurried in 800 parts of ethanol 740P, filtered off, washed with ethanol 740P, and dried at 100 C. to yield 17.2 parts of a potassium salt of 3,10-bis(4-amino-3-sulphoanilino)-6,13-dichlorotriphendioxazine-4,11-disulphonic acid.
The following table describes the yield of 3,10-bis-(2-aminoethylamino)-6,13dichlorotriphenodioxazine disulphonic acid when 2,5-bis-[4-(2-aminoethylamino)-3sulphophenylamino]-3,6-dichlorobenzoquinone (31.8 parts) was cyclised in a similar manner to Example 2, but using a variety of process conditions as detailed in the table.
Oleum Oleum Reaction Reaction Ammonium Yield of 3,10-bis-(2-aminoethyl
Example Strength Charge Temp. Time Persulphate amino)-6,13-dichlorotriphen
No. (% free SO3) (pts.) ( C) (hours) Usage (pts.) dioxazine disulphonic acid (pts.) 4 0 636 55-60 2 22.8 17.1 5 10 636 40 4 22.8 22.5 6 5 477 20-25 23 22.8 28.3 7 15 318 20-25 8 22.8 30.3 8 0 636 20-25 23 13.7 18.4 9 0 318 20-25 5 28.5 16.5 10 20 318 20-25 5 16.5 23.4 11 10 477 20-25 19 17.1 20.7 12 10 477 50 3.5 17.1 17.4 13 10 477 50 5 11.4 16.1 14 0 636 40 4 34.2 12.8
Claims (8)
1. A process for the manufacture of triphenodioxazine compounds by treatment of a 2,5-diarylaminobenzoquinone compound with oleum containing an inorganic persulphate.
2. A process as claimed in claim 1 wherein the inorganic persulphate is sodium, potassium or ammonium persulphate.
3. A process as claimed in claim 1 or claim 2 wherein the oleum used contains from 5% to 30% by weight of SO3.
4. A process as claimed in any of claims 1 to 3 wherein the treatment is carried out at a temperature of from 0--600C.
5. A process as claimed in any of claims 1 to 4 wherein the amount of persulphate used is from 1 to 3 moles per mole of the dianilino benzoquinone.
6. A process as claimed in any of claims 1 to 5 wherein the 2,5-diarylamino benzoquinone used is a compound of the formula:
wherein R is an aromatic radical.
7. A process as claimed in claim 6 wherein R is chosen from 4-amino-3-sulphophenyl, 3-amino-4-sulphophenyl, 4-(4-amino-3-sulphoanilino)-3 -sulphophenyl, 4-(3amino-4-sulphoanilino)-3-sulphophenyl, 4-(2-aminoethylamino)-3 -sulphophenyl, 4ethylamino-3-sulphophenyl, 41P-hydroxyethylamino-3-sulphophenyl, 4-fi-sulphoethyl amino-3-sulphophenyl, 6-amino-1,5-disulphonaphth-3-yl, 4-(4-amino-3,6-disulphoanilino)-3-sulphophenyl, 4-benzylamino-3-sulphophenyl, and 4-phenoxy-3-sulphophenyl.
8. A process as claimed in claim 1 substantially as herein described with reference to and as illustrated by any of the Examples.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB4720976A GB1589915A (en) | 1977-10-07 | 1977-10-07 | Process for the manufacture of triphenodioxazine compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB4720976A GB1589915A (en) | 1977-10-07 | 1977-10-07 | Process for the manufacture of triphenodioxazine compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1589915A true GB1589915A (en) | 1981-05-20 |
Family
ID=10444149
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB4720976A Expired GB1589915A (en) | 1977-10-07 | 1977-10-07 | Process for the manufacture of triphenodioxazine compounds |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB1589915A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0141359A2 (en) * | 1983-11-04 | 1985-05-15 | Bayer Ag | Process for preparing triphenyldioxazine compounds |
EP0170838A2 (en) * | 1984-06-27 | 1986-02-12 | Bayer Ag | Reactive dyes of the dioxazine-type, their preparation and use |
EP0292906A2 (en) * | 1987-05-27 | 1988-11-30 | Hoechst Aktiengesellschaft | Process for the preparation of Triphendioxazine compounds |
EP0298916A1 (en) * | 1987-07-07 | 1989-01-11 | Ciba-Geigy Ag | Process for preparing triphene dioxazines |
EP0400429A2 (en) * | 1989-05-31 | 1990-12-05 | BASF Aktiengesellschaft | Process for the preparation of triphendioxazines |
US5194607A (en) * | 1990-06-27 | 1993-03-16 | Basf Aktiengesellschaft | Reactive dyes with a triphendioxazine chromophore |
EP0694588A1 (en) | 1994-07-26 | 1996-01-31 | Bayer Ag | Triphendioxazine reactive dyes, preparation and use thereof |
-
1977
- 1977-10-07 GB GB4720976A patent/GB1589915A/en not_active Expired
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0371469B2 (en) * | 1983-11-04 | 1991-11-13 | Bayer Ag | |
JPS60112855A (en) * | 1983-11-04 | 1985-06-19 | バイエル・アクチエンゲゼルシヤフト | Manufacture of triphendioxazine compounds |
EP0141359A3 (en) * | 1983-11-04 | 1986-03-12 | Bayer Ag | Process for preparing triphenyldioxazine compounds |
EP0141359A2 (en) * | 1983-11-04 | 1985-05-15 | Bayer Ag | Process for preparing triphenyldioxazine compounds |
EP0170838A2 (en) * | 1984-06-27 | 1986-02-12 | Bayer Ag | Reactive dyes of the dioxazine-type, their preparation and use |
EP0170838A3 (en) * | 1984-06-27 | 1986-02-26 | Bayer Ag | Reactive dyes |
US4604459A (en) * | 1984-06-27 | 1986-08-05 | Bayer Aktiengesellschaft | Triphendioxazine reactive dyestuffs |
EP0292906A2 (en) * | 1987-05-27 | 1988-11-30 | Hoechst Aktiengesellschaft | Process for the preparation of Triphendioxazine compounds |
EP0292906A3 (en) * | 1987-05-27 | 1989-03-22 | Hoechst Aktiengesellschaft | Process for the preparation of triphendioxazine compounds |
US4886880A (en) * | 1987-07-07 | 1989-12-12 | Ciba-Geigy Corporation | Process for the preparation of triphendioxazines |
EP0298916A1 (en) * | 1987-07-07 | 1989-01-11 | Ciba-Geigy Ag | Process for preparing triphene dioxazines |
EP0400429A2 (en) * | 1989-05-31 | 1990-12-05 | BASF Aktiengesellschaft | Process for the preparation of triphendioxazines |
EP0400429A3 (en) * | 1989-05-31 | 1991-11-27 | BASF Aktiengesellschaft | Process for the preparation of triphendioxazines |
US5194607A (en) * | 1990-06-27 | 1993-03-16 | Basf Aktiengesellschaft | Reactive dyes with a triphendioxazine chromophore |
EP0694588A1 (en) | 1994-07-26 | 1996-01-31 | Bayer Ag | Triphendioxazine reactive dyes, preparation and use thereof |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed | ||
PCNP | Patent ceased through non-payment of renewal fee |