| PATENT ASSIGNEE'S COUNTRY | Germany |
| UPDATE | 08.99 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 31.08.99 |
| PATENT TITLE |
Process for the preparation of triphendioxazine dyestuffs amidated on both sides, and novel triphendioxazine dyestuffs |
| PATENT ABSTRACT |
According to the invention, a process for the preparation of triphendioxazines systemetrically or asymmetrically amidated on both sides comprises reducing a triphendioxazine chromophore, which is optionally already amidated on one side, to give the leuco form end amidating and re-oxidizing the leuco form. Products amidated on both sides are obtained in this manner with a high yield and product quality. Novel triphendioxazine dyestuffs are furthermore prepared in this manner. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 15.07.97 |
| PATENT FOREIGN APPLICATION PRIORITY DATA | This data is not available for free |
| PATENT REFERENCES CITED | Hisao Nishi et al., "A New Synthesis of Triphenodithiazines and Triphenodithiazinequinoes", Bulletin of the Chemical Society of Japan, Bd. 56, Nr. 5, May 1983, Tokyo Japan, pp. 1482-1486 XPOO2026132. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
We claim: 1. A triphendioxazine compound of the formula ( 7) ##STR75## in which R.sub.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl, which is optionally substituted by 1 or 2 substituents selected from the group consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, sulfato and sulfo; R.sub.2 has one of the meanings of R.sub.1 ; X.sub.1 is halogen, hydrogen, C.sub.1 -C.sub.6 -alkyl, phenyl, phenoxy or C.sub.1 -C.sub.4 -alkoxy; X.sub.2 has one of the meanings of X.sub.1 ; M is hydrogen or an alkali metal and Z.sub.1 and Z.sub.2 are the following combinations (7a) to (7e): ##STR76## in which A.sup.10 and A.sup.30 are each cyanoamino; A.sup.20 and A.sup.40 are fluorine or chlorine, or are a compound of the formulae ##STR77## in which L is hydroxyl, sulfo, carboxyl or sulfato; U.sub.2 is a chemical bond, methylene, --O--, --NH--, >N(CH.sub.2).sub.2 OH, --S-- or --SO.sub.2 -- and y is the number 1 or 2; ##STR78## in which W.sub.1 is C.sub.2 -C.sub.6 -alkylene; Q.sub.1 is fluorine, chlorine, amino, C.sub.1 -C.sub.4 -alkoxy, phenoxy, or pyridyl, which is optionally substituted by carboxyl or aminocarbonyl, or cyanoamino; Y.sup.7 is .beta.-sulfatoethyl, .beta.-chloroethyl or vinyl; R.sub.40 is hydrogen, C.sub.1 -C.sub.4 -alkyl, phenyl or sulfophenyl; A.sub.4 is one of the radicals ##STR79## and A.sub.3 is fluorine, chlorine, amino or cyanoamino; or in which Y.sup.7, R.sub.4, A.sub.4 and A.sub.3 have the abovementioned meanings and Q.sub.1 is cyanoamino and W.sub.1 is phenylene; ##STR80## in which R.sub.40, Q.sup.1 and Y.sup.7 are defined as above; alk is ethylene or propylene; and Z.sub.1 ' is C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.2 -C.sub.4 -alkenylcarbonyl, aminocarbonyl, C.sub.1 -C.sub.6 -alkylaminocarbonyl, C.sub.6 -aryl-amirocarbonyl, C.sub.6 -arylsulfonyl or C.sub.6 -aryicarbonyl, which are optionally substituted by hydroxyl, cyano, sulfo carboxyl, sulfato, acetylamino or SO.sub.2 Y.sup.7 ; ##STR81## in which R.sub.40, Y.sup.7 and Z.sub.1 ' are defined as above; ##STR82## in which Y.sup.7 is defined as above and Z.sub.11 ' has one of the meanings of Z.sub.1 ' or Z.sub.11 ' is one of the radicals ##STR83## in which Hal is fluorine or chlorine. 2. A triphendioxazine compound of the formula (7) ##STR84## in which R.sub.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl, which is optionally substituted by 1 or 2 substituents selected from the group consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, sulfato and sulfo; R.sub.2 has one of the meanings of R.sub.1 ; X.sub.1 is halogen, hydrogen, C.sub.1 -C.sub.6 -alkyl, phenyl, phenoxy or C.sub.1 -C.sub.4 -alkoxy; X.sub.2 has one of the meanings of X.sub.1 ; M is hydrogen or an alkali metal and Z.sub.1 and Z.sub.2 are the combination of (7f); ##STR85## in which Z.sub.11 ' is Z.sub.1 ', C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.2 -C.sub.4 -alkenylcarbonyl, aminocarbonyl, C.sub.1 -C.sub.6 -alkylaminocarbonyl, C.sub.6 -aryl-aminocarbonyl, C.sub.6 -arylsulfonyl or C.sub.6 -arylcarbonyl, which are optionally substituted by hydroxyl, cyano, sulfo, carboxyl, sulfato, acetylamino or SO.sub.2 Y.sup.7 ; or Z.sub.11 ' is one of the radicals ##STR86## Y.sup.7 is .beta.-sulfatoethyl, .beta.-chloroethyl or vinyl; B.sub.1 is hydrogen, chlorine, fluorine, trichloromethyl, trifluoromethyl or methylsulfonyl; B.sub.2 is hydrogen, chlorine, methyl, methylsulfonyl or fluorine and B.sub.3 is hydrogen, cyano, fluorine or chlorine, with the proviso that at least one of the radicals B.sub.1 or B.sub.2 is a leaving group selected from the group consisting of fluorine, chlorine and methylsulfonyl. 3. The compound as claimed in claim 1, wherein R.sub.1 and R.sub.2 are hydrogen. 4. The compound as claimed in claim 1, wherein X.sub.1 and X.sub.2 are chlorine. 5. The compound as claimed in claim 1, wherein M is hydrogen. 6. The compound as claimed in claim 1, wherein the compound is of the formula ##STR87## 7. The compound as claimed in claim 6, wherein M is hydrogen. 8. A method of dyeing or printing fiber materials of cellulose, polyamides, proteins or mixtures of said fiber materials comprising the step of contacting said fiber materials with a triphendioxazine compound as claimed in claim 1. 9. The method as claimed in claim 8, wherein the dyeing or printing takes place in the presence of 0 to 20 grams of an electrolyte salt per liter of dye solution. 10. A method of dyeing or printing fiber materials of cellulose, polyamides, proteins or mixtures of said fiber materials comprising the step of contacting said fiber materials with a triphendioxazine compound as claimed in claim 2. 11. The method as claimed in claim 10, wherein the dyeing or printing takes place in the presence of 0 to 20 grams of an electrolyte salt per liter of dye solution. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
DESCRIPTION Process for the preparation of triphendioxazine dyestuffs amidated on both sides, and novel triphendioxazine dyestuffs The present invention lies in the field of triphendioxazine textile dyestuffs. Triphendioxazines are tinctorially strong dyestuffs which are suitable both as direct dyestuffs and as reactive dyestuffs. However, the corresponding dyestuff hydrolysates are often difficult to wash out, and the levelness of the dyeings is unsatisfactory. Dioxazines amidated on both sides have already been described frequently in the technical literature (for example U.S. Pat. No. 4,933,446, U.S. Pat. No. 5,486,607 and U.S. Pat. No. 3,883,523). However, the compounds amidated on one side are frequently chiefly formed in the procedures described, often in contrast to the statements made, or the products described as being amidated on both sides are formed only in unsatisfactory yields. Thus, the compounds amidated on one side are royal blue, while the compounds amidated on both sides are violet or very reddish-tinged blue. It is furthermore known that an increasingly redder product is formed with excess amidating agents (U.S. Pat. No. 3,883,523), from which partial double amidation can be concluded, although this is achieved selectively in the rarest of cases. Moreover, customary methods to date for preparation of such triphendioxazine dyestuffs, for example U.S. Pat. No. 5,486,607, U.S. Pat. No. 5,272,267, U.S. Pat. No. 5,438,137 and U.S. Pat. No. 4,933,446, give yields and product qualities which are in need of improvement. "Amidated triphendioxazine compounds" in the present Application means those compounds in which the exocyclic nitrogen atoms of the triphendioxazine chromophore are bonded with an acyl radical, an aminocarbonyl radical, a sulfonyl radical or a nitrogen-containing heteroaromatic radical. The object of the present invention was to provide a process for the preparation of triphendioxazine dyestuffs which overcomes the disadvantages of the prior art in respect of yield and product quality. Another object of the present invention was to provide an advantageous method for the preparation of triphendioxazines amidated on both sides. Another object of the invention was to provide novel triphendioxazine dyestuffs, in particular those having a violet or reddish-tinged blue shade. It has been found that the objects mentioned are achieved, surprisingly, by reduction of the triphendioxazine chromophore, which is optionally already amidated on one side, to the leuco form, amidation at the stage of the leuco form and reoxidation. The invention relates to a process for the preparation of triphendioxazine compounds of the formula (1) ##STR1## in which R.sub.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl, which can be substituted by 1 or 2 substituents from the series consisting of hydroxyl, C.sub.1 -C.sub.4 -alkoxy, sulfato or sulfo; R.sub.2 has one of the meanings of R.sub.1 ; E is sulfo, carboxyl, C.sub.1 -C.sub.4 -alkylsulfonyl or a radical SO.sub.2 Y, in which Y is vinyl or CH.sub.2 CH.sub.2 V, in which V is hydroxyl, or is a leaving group from the series consisting of sulfato, phosphate, thiosulfato or halogen, such as chlorine; or is --SO.sub.2 NR.sub.3 R.sub.4 or --CONR.sub.3 R.sub.4, in which R.sub.3 is hydrogen, phenyl, or C.sub.1 -C.sub.4 -alkyl, which can be substituted by hydroxyl, carboxyl, sulfo, sulfato or a radical SO.sub.2 Y, R.sub.4 has one of the meanings of R.sub.3, or, together with R.sub.3 and N, forms a 5- or 6-membered heterocyclic radical, which can be interrupted by 1 to 3 further heteroatoms from the series consisting of N, O and S; X.sub.1 is halogen, such as chlorine or bromine, in particular chlorine, hydrogen, C.sub.1 -C.sub.6 -alkyl, such as methyl, ethyl or isopropyl, phenyl, phenoxy or C.sub.1 -C.sub.4 -alkoxy; X.sub.2 has one of the meanings of X.sub.1 ; V.sub.1 is hydrogen, sulfo, methoxy, methyl or halogen, such as chlorine; V.sub.2 has one of the meanings of V.sub.1 ; and Z.sub.1 and Z.sub.2 are identical or different and are an acyl radical, an unsubstituted, alkylated or arylated aminocarbonyl radical, a sulfonyl radical or a nitrogen-containing heteroaromatic radical, which comprises reducing a compound of the formula (2) ##STR2## in which T is hydrogen, Z.sub.1 or Z.sub.2, to give a compound of the formula (3) ##STR3## reacting this with a reactive derivative on which the radical Z.sub.1 and/or Z.sub.2 is based, to give a compound of the formula (4) ##STR4## and subsequently oxidizing this to give the triphendioxazine compound of the formula (1). It is known from Bull. Chem. Soc. Jpn. 56 (1983), 1482 that 9,13-dichorotriphendioxazines can be dehalogenated in the 9- and 13-positions with tin in polyphosphoric acid. However, instead of the dehatogenation expected from knowledge of the prior art, surprisingly, a reduction to the leuco base takes place if the reaction according to the invention is carried out in an aqueous medium in the presence of reducing agents. The reduction is completely reversible, and the triphendioxazine color base is obtained again by oxidation. E is preferably sulfo, --SO.sub.2 --CH.sub.2 CH.sub.2 --OSO.sub.3 M, --SO.sub.2 --CH.dbd.CH.sub.2, --SO.sub.2 --CH.sub.2 CH.sub.2 Cl or --SO.sub.2 --CH.sub.2 CH.sub.2 OH. X.sub. and X.sub.2 are referably chlorine. V.sub.1 is preferably hydrogen. V.sub.2 is preferably hydrogen or sulfo, in particular hydrogen. R.sub.1 and R.sub.2 are preferably hydrogen. R.sub.3 is preferably hydrogen, methyl or phenyl. The radicals Z.sub.1 and Z.sub.2 are preferably C.sub.1 -C.sub.6 -alkylcarbonyl, C.sub.2 -C.sub.4 -alkenylcarbonyl, C.sub.6 -arylcarbonyl, aminocarbonyl, C.sub.1 -C.sub.6 -alkylaminocarbonyl, di-(C.sub.1 -C.sub.6)-alkylaminocarbonyl, C.sub.6 -arylaminocarbonyl or C.sub.6 -arylsulfonyl, in which the alkyl and aryl radicals can be substituted by 1 to 3, preferably 1, identical or different substituents from the series consisting of SO.sub.2 Y, sulfo, carboxyl, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkyl, cyano, halogen, acylamino, such as acetylamino, and nitro. In the case where Z.sub.1 and/or Z.sub.2 are a nitrogen-containing heterocyclic radical, heterocycles from the series consisting of the triazines, pyrimidines and quinoxalines are preferred. Particularly preferred radicals here are those of the formulae (5a) to (5d) ##STR5## in which p is 0 or 1, preferably 0; A.sub.1 is chlorine, fluorine, C.sub.1 -C.sub.4 -alkoxy, phenoxy, hydroxyl, amino, cyanamino or pyridinyl which is optionally substituted by carboxyl or aminocarbonyl, or a radical NR.sub.7 R.sub.8, wherein R.sub.7 is hydrogen, C.sub.1 -C.sub.4 -alkyl, which can be substituted by 1 or 2, preferably 1, identical or different substituents from the series consisting of hydroxyl, sulfo, sulfato and carboxyl, or phenyl, which can be substituted by 1 to 3 identical or different substituents from the series consisting of methoxy, methyl, halogen, sulfo or carboxyl, R.sub.8 is hydrogen or C.sub.1 -C.sub.4 -alkyl, which can be substituted by 1 to 2, preferably 1, substituents from the series consisting of hydroxyl, sulfo, sulfato and carboxyl, or R.sub.7 and R.sub.8, together with the N atom, form a saturated 5- to 7-membered heterocyclic radical, which can also contain 1 or 2 others of the hetero groups N, O, S and/or SO.sub.2, for example piperidine, morpholine, pyrrolidine, piperazine, thiomorpholine or thiomorpholine dioxide, in particular morpholine; A.sub.2 has one of the meanings of A.sub.1 and is, in particular, chlorine, fluorine or cyanoamino; A.sub.1 has one of the meanings of A.sub.1 ; U is a bridge member from the series consisting of --NH--C.sub.1 -C.sub.6 -alkylene-NH--, --NH--C.sub.6 -arylene-NH--, in which arylene can be substituted by 1 or 2 sulfo, carboxyl, methyl and/or methoxy radicals, ##STR6## B.sub.1 is hydrogen, chlorine, fluorine, trichloromethyl, trifluoromethyl or methylsulfonyl; B.sub.2 is hydrogen, chlorine, methyl, methylsulfonyl or fluorine; and B.sub.3 is hydrogen, cyano, fluorine or chlorine, with the proviso that at least one of the radicals B.sub.1 or B.sub.2 is a leaving group from the series consisting of chlorine, fluorine and methylsulfonyl. The bridge member U is particularly preferably a radical of the formula --NH--CH.sub.2 --CH.sub.2 --NH--, --NH--(CH.sub.2).sub.3 --NH--, ##STR7## The abovementioned radical NR.sub.7 R.sub.8 is particularly preferably a structure of the formulae (6a) to (6d) ##STR8## in which U.sub.2 is a chemical bond, --CH.sub.2 --, --O--, --NH--, >N--(CH.sub.2).sub.2 OH, --S-- or --SO.sub.2 --; y is 1 or 2; M is hydrogen or an alkali metal, such as Li, Na or K, and L is hydroxyl, sulfo, sulfato or carboxyl. Z.sub.1 and Z.sub.2 furthermore preferably represent a fiber-reactive radical of the formula (5e) ##STR9## in which Q is halogen, such as chlorine or fluorine, hydroxyl, cyanoamino or a radical NR.sub.30 --W--SO.sub.2 Y; W is C.sub.2 -C.sub.6 -alkylene, which can be interrupted by a hetero group O, S, NH or SO.sub.2 ; phenylene, which can be substituted by methoxy or sulfo; or aralkylene, such as --CH.sub.2 -phenylene or -phenylene--CH.sub.2 --; R.sub.30 is hydrogen, C.sub.1 -C.sub.4 -alkyl, phenyl, which can be substituted by a sulfo group, or the radical --W.sub.1 --SO.sub.2 Y, in which W.sub.1 is C.sub.2 -C.sub.6 -alkyl, and Y has one of the abovementioned meanings. Particularly preferably, W is --(CH.sub.2).sub.2 --, --(CH.sub.2).sub.3 --, --(CH.sub.2).sub.2 O--(CH.sub.2).sub.2 --, 1,4-phenylene or 1,3-phenylene and R.sub.30 is hydrogen, methyl or phenyl. The radical NR.sub.30 --W--SO.sub.2 Y is particularly preferably one of the formulae defined below ##STR10## in which Y.sup.1 is vinyl, .beta.-hydroxyethyl, .beta.-chloroethyl or .beta.-sulfatoethyl. Particularly preferred radicals Z.sub.1 and Z.sub.2 are ##STR11## in which x is 2 or 3; y is 1 or 2; U.sub.2 has one of the abovementioned meanings; L is hydroxyl, sulfo, carboxyl or sulfato; Y.sup.1 has one of the abovementioned meanings; Hal is chlorine or fluorine, and M is hydrogen or an alkali metal. Examples of the radical NR.sub.30 --W--SO.sub.2 Y are N-phenyl-3-(.beta.-sulfatoethylsulfonyl)-propylamino, N-methyl-2-(.beta.-sulfatoethylsulfonyl)-ethylamino, N-phenyl-2-(.beta.-sulfatoethylsulfonyl)-ethylamino, 3-(.beta.-sulfatoethylsulfonyl)-propylamino, bis-{3-(.beta.-sulfatoethylsulfonyl)-propyl}-amino, bis-{2-(.beta.-sulfatoethylsulfonyl)-ethyl}-amino, bis-{3-(.beta.-chloroethylsulfonyl)-propyl}-amino, bis-{2-(.beta.-chloroethylsulfonyl)-ethyl}-amino, N-phenyl-3-(vinylsulfonyl)-propylamino, N-phenyl-2-(vinyisulfonyl)-ethylamino, 3-(vinylsulfonyl)-propylamino, bis-{3-(vinylsulfonyl)-propyl}-amino, bis-{2-(vinylsulfonyl)-ethyl}-amino, 3-(.beta.-sulfatoethylsulfonyl)-phenylamino, 4-(.beta.-sulfatoethylsulfonyl)-phenylamino, 2-methoxy-5-(.beta.-sulfatoethylsulfonyl)-phenylamino, 2,5-dimethoxy-4-(.beta.-sulfatoethylsulfonyl)-phenylamino and 2-methoxy-5-methyl-4-(.beta.-sulfatoethylsulfonyl)-phenylamino. Examples of radicals of the formula Z.sub.1 and/or Z.sub.2 are phenylsulfonyl, 4-methylphenylsulfonyl, 4-acetylaminosulfonyl, phenylaminocarbonyl, aminocarbonyl, benzoyl, 2-carboxybenzoyl, 4-carboxybenzoyl, 3-(.beta.-chloroethylsulfonyl)-benzoyl, 3-nitrobenzoyl, 4-nitrobenzoyl, acetyl, propionyl, 2-carboxy-acryloyl, 2-carboxy-propionyl, 2,4-dichloro-triazin-6-yl, 2-(2'-sulfophenyl)amino-4-chloro-triazin-6-yl, 2-(3'-sulfophenyl)amino-4-chloro-triazin-6-yl, 2-(4'-sulfophenyl)amino-4-chloro-triazin-6-yl, 2-(2',5'-disulfophenyl)amino-4-chloro-triazin-6-yl, 2-cyanoamino-4-chloro-triazin-6-yl, 2-phenoxy-4-chloro-triazin-6-yl, 2-methoxy-4-chloro-triazin-6-yl, 2-amino-4-chloro-triazin-6-yl, 2-(.beta.-sulfoethyl)amino-4-chloro-triazin-6-yl, 2-(N-.beta.-sulfoethyl-N-methyl-)amino-4-chloro-triazin-6-yl, 2-(.beta.-sulfoethyl)amino-4-fluoro-triazin-6-yl, 2-(N-.beta.-sulfoethyl-N-methyl-)amino-4-fluoro-triazin-4-yl, bis-{2,4-(.beta.-sulfoethyl)amino}-triazin-6-yl, bis-{2,4-(.beta.-hydroxyethyl)amino}-triazin-6-yl, 2,4-dicyanoamino-triazin-6-yl, 2-(.beta.-sulfoethyl)amino-4-cyanoamino-triazin-6-yl, 4-fluoro-2-{N-phenyl-2'-(.beta.-sulfatoethyl)sulfonyl-ethyl-amino}-triazin- 6-yl, 4-fluoro-2-{N-phenyl-3'-(.beta.-sulfatoethyl)sulfonyl-propyl-amino}-triazin -6-yl, 4-fluoro-2-{N-methyl-2'-(.beta.-sulfatoethyl)sulfonyl-ethyl-amino}-triazin- 6-yl, 4-fluoro-2-{3'-(.beta.-sulfatoethyl)sulfonyl-propyl-amino}-triazin-6-yl, 4-chloro-2-{N-phenyl-2'-(.beta.-sulfatoethyl)sulfonyl-ethyl-amino}-triazin- 6-yl, 4-chloro-2-{N-phenyl-3'-(.beta.-sulfatoethyl)sulfonyl-propyl-amino}-triazin -6-yl, 4-chloro-2-{N-methyl-2'-(.beta.-sulfatoethyl)sulfonyl-ethyl-amino}-triazin- 6-yl, 4-chloro-2-{3'-(.beta.-sulfatoethyl)sulfonyl-propyl-amino}-triazin-6-yl, 4-cyanoamino-2-{N-phenyl-2'-(.beta.-sulfatoethyl)sulfonyl-ethyl-amino}-tria zin-6-yl, 4-cyanoamino-2-{N-phenyl-3'-(.beta.-sulfatoethyl}-sulfonyl-propyl-aminor-tr iazin 4-chloro-2-{4'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl, 4-cyanoamino-2-{4'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl 4-chloro-2-{3'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl, 4-cyanoamino-2-{3'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl 4-chloro-2-{2'-methoxy-5'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-triaz in-6-yl 4-cyanoamino-2-{2'-methoxy-5'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-t riazin-6-yl, 4-fluoro-2-{4'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl, 4-fluoro-2-{4'-(.beta.-sulfatoethyl)sulfonyl-phenyl-amino}-triazin-6-yl, 2,4-difluoro-pyrimidin-6-yl, 2,4-difluoro-5-chloro-pyrimidin-6-yl, 2,4,5-trichloro-pyrimidin-6-yl, 2-fluoro-5-chloro-pyrimidin-6-yl, 5-cyano-2,4-dichloro-pyrimidin-6-yl, 2-methylsulfonyl-4-methyl-5-chloro-pyrimidin-6-yl, 2-fluoro-4-methyl-5-chloro-pyrimidin-6-yl, 5-chloro-4-fluoropyrimidin-6-yl, 4,5-difluoro-2-trifluormethyl-pyrimidin-6-yl, 2,5-dichloro-4-fluoro-pyrimidin-6-yl, 2-fluoro-4,5-dichloro-pyrimidin-6-yl, 4-fluoropyrimidin-6-yl, 2-fluoropyrimidin-6-yl, and 2-fluoro-5-chloro-pyrimidin-6-yl. In the process according to the invention for the preparation of the triphendioxazine compounds of the formula (1) mentioned, which are amidated on both sides, the compound of the formula (2) is first reduced to give the compound of the formula (3). The reduction can be carried out with hydrogen in the presence of a catalyst, such as palladium, platinum or nickel, at temperatures of 40 to 90.degree. C., or by non-noble metals, such as tin or zinc, in the presence of an acid, preferably a mineral acid, such as, for example, hydrochloric acid or sulfuric acid, at temperatures of 10 to 50.degree. C. Preferably, the reduction is carried out with sodium dithionite in water, in particular at pH values of 6 to 9, preferably 6.5 to 7.5, and temperatures of 15 to 45.degree. C., preferably 20 to 30.degree. C. The reducing agent is expediently employed in a 2- to 6-fold molar amount, based on the compounds of the formula (2). The compounds of the formula (3) are novel and the invention likewise relates to them. The compounds of the formula (3) are stable in air in an acidic medium and can be isolated as solids by filtration with suction. In a neutral medium, the process is expediently carried out under an inert gas, for example a nitrogen atmosphere. The compounds of the formula (3) thus obtained are reacted with a corresponding amidation component under an inert gas atmosphere in water, in a solvent, such as dimethylformamide, dimethylacetamide or N-methyl-pyrrolidone, or in a water/solvent mixture, or in water containing auxiliaries, such as, for example, .epsilon.-caprolactam, urea, surfactants, solvents of the abovementioned type and other water-miscible solvents, such as acetone or methyl ethyl ketone, to give compounds of the formula (4), the radicals Z.sub.1 and/or Z.sub.2 defined above being introduced. The said amidation components are compounds from the series consisting of organic or inorganic acid halides, such as carboxylic acid or sulfonic acid chlorides, anhydrides, such as carboxylic acid or sulfonic acid anhydrides, isocyanates, carbonic acid esters, such as chlorocarbonic acid esters or carbonic acid diesters, ureas, carbamic acid chlorides, carboxylic acid esters, sulfonic acid esters and electron-depleted N-containing heterocyclic compounds which contain leaving groups, such as, in particular, halotriazines or halopyrimidines. In the case where the amidation component is a carboxylic acid chloride, the reaction is advantageously carried out at pH values of 3 to 9, preferably 4 to 8, and temperatures of 0 to 80.degree. C., preferably 20 to 50.degree. C. Carboxylic acid chlorides are, for example, benzoyl chloride, 3- or 4-nitrobenzoyl chloride, chloroacetyl chloride, acetyl chloride, propionyl chloride or 3-(.beta.-chloroethylsulfonyl)-benzoyl chloride. In the case where the amidation component is an acid anhydride, the reaction is advantageously carried out at pH values of 3 to 9, preferably 4 to 8, and temperatures of 30 to 100.degree. C., preferably 40 to 60.degree. C. Carboxylic acid anhydrides are, for example, acetic anhydride or cyclic carboxylic acid anhydrides, such as, in particular, succinic anhydride, maleic anhydride or phthalic anhydride. In the case where the amidation component is urea or a urea derivative, the reaction is advantageously carried out in the urea (derivative) melt or in a high-boiling solvent, such as N-methylpyrrolidone or dimethylacetamide, at temperatures of 120 to 180.degree. C. In the case where the amidation component is a carbamic acid chloride, such as Cl--CO--NHC.sub.2 H.sub.5, the reaction is advantageously carried out in water at pH values of 4 to 7 and temperatures of 40 to 95.degree. C. In the case where the amidation component is a carboxylic acid ester, such as ethyl acetate, the reaction is advantageously carried out in water or a water/solvent mixture at temperatures of 90 to 150.degree. C. and in the presence of acid or Lewis acid catalysts. In the case where the amidation component is a sulfonic acid ester, such as para-methylphenyl-SO.sub.2 --OC.sub.2 H.sub.5, the reaction is advantageously carried out in water at pH values of 2 to 5 and temperatures of 80 to 150.degree. C. In the case where the amidation component is a 2,4-difluoro-triazine compound, the reaction is advantageously carried out at pH values of 3 to 9, preferably 4 to 8, and temperatures of 0 to 60.degree. C., preferably 0 to 40.degree. C. In the case where the amidation component is a 2,4-dichloro-triazine compound, the reaction is advantageously carried out at pH values of 3 to 10, preferably 4 to 8, and temperatures of 20 to 100.degree. C., preferably 30 to 80.degree. C. In the case where the amidation component is a monochloro-triazine compound, the reaction is advantageously carried out at pH values of 3 to 9, preferably 4 to 8, and temperatures of 50 to 100.degree. C., preferably 60 to 90.degree. C. In the case where the amidation component is a monofluoro-triazine compound, the reaction is advantageously carried out at pH values of 3 to 9, preferably 4 to 8, and temperatures of 40 to 90.degree. C., preferably 50 to 70.degree. C. In the case where the amidation component is a di- or trifluoro-pyrimidine compound, the reaction is advantageously carried out at pH values of 3 to 9, preferably 4 to 8, and temperatures of 0 to 60.degree. C., preferably 20 to 40.degree. C. In the case where the amidation component is a carbonic acid derivative, for example an isocyanate, a chlorocarbonic acid ester or a carbonic acid ester, the reaction is advantageously carried out at pH values of 4 to 8, preferably 5 to 7, and temperatures of 20 to 60.degree. C., preferably 25 to 40.degree. C. In the case where the amidation component is a sulfonyl chloride, the reaction is advantageously carried out at pH values of 4 to 8, preferably 5 to 7, and temperatures of 20 to 60.degree. C., preferably 25 to 40.degree. C. Sulfonyl chlorides are, for example, 4-methylphenyl-sulfonyl chloride, phenylsulfonyl chloride or 4-(acetylamino)phenylsulfonyl chloride. If several possibilities for the preparation of the same products are described, the reaction with acid chlorides is the preferred procedure. The molar ratios of amounts for the preparation of compounds of the formula (4) amidated symmetrically on both sides are: compound of the formula (3) where T=H to amidation component 1:2 to 1:6, preferably 1:2 to 1:3. Mixed condensation reactions (3).fwdarw.(4) for the preparation of asymmetric dioxazines, i.e. Z.sub.1 differs from Z.sub.2, can be carried out by reacting the compound of the formula (2) where T=H with an approximately 1:1 mixture of the amidation components corresponding to the radicals Z.sub.1 and Z.sub.2 The asymmetric product is obtained here as a mixture with the two symmetric condensation products. A better and therefore preferred procedure, however, is the reaction of that compound of the formula (3) in which T=Z.sub.1 with the amidation component corresponding to the radical Z.sub.2. Considerably purer uniform products are obtained in this reaction than in the mixed condensation reaction, which is a particular advantage of the process variant according to the invention. For the reaction of a compound of the formula (3) where T=Z.sub.1 with the amidation component Z.sub.2, the said amidation component is employed in a molar ratio of 1:1 to 1:3, preferably 1:1 to 1:2, to the compound of the formula (3). The compounds of the formula (4) are novel and the invention likewise relates to them. The compounds of the formula (4) are converted into the compounds of the formula (1) by oxidation. This oxidation can be carried out by atmospheric oxygen at pH values of 6 to 10, or by addition of an oxidizing agent, such as hydrogen peroxide or an alkali metal peroxodisulfate, at pH values of 4 to 7 and 20 to 60.degree. C., preferably 25 to 40.degree. C. The amount of oxidizing agent added is expediently 2 to 6 molar equivalents, based on the compound of the formula (4). It is surprising that, in spite of an additional reduction and oxidation step, the process according to the invention gives considerably higher yields and better product qualities than according to the prior art. Particularly preferred triphendioxazine compounds of the formula (1) are those of the formula (1a) ##STR12## in which M is Na, K or Li. Particularly preferred triphendioxazine compounds of the formula (1) are those which correspond to the formula (7a) ##STR13## in which R.sub.1, R.sub.2, X.sub.1, X.sub.2 and M have one of the abovementioned meanings; A.sup.10 is the radical of a C.sub.1 -C.sub.4 -aliphatic amine, which can be substituted by sulfo, hydroxyl or carboxyl, or the radical of a C.sub.6 - or C.sub.10 -aromatic amine, which can be substituted by SO.sub.2 Y, 1 or 2 methoxy groups and/or 1 or 2 sulfo groups, or cyanoamino; A.sup.20 is halogen or has one of the meaning of A.sup.10 ; A.sup.30 has one of the meanings of A.sup.10 ; and A.sup.40 has one of the meanings of A.sup.10 or is halogen. Such dyestuffs are known in some cases from U.S. Pat. No. 5,272,267, U.S. Pat. No. 5,438,137, U.S. Pat. No. 5,456,726 and U.S. Pat. No. 5,486,607 and are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. The procedure described in the present invention is advantageous in respect of the yield and purity of these dyestuffs. Dyestuffs of the formula (7a) in which both the radicals A.sup.10 and A.sup.30 are --NH--arylene--SO.sub.2 Y, and both the radicals A.sup.20 and A.sup.40 are fluorine, chlorine, --NH--(CH.sub.2).sub.2 --SO.sub.3 H or --NH-phenylene-(SO.sub.3 H).sub.1-2 or are a radical --NH-arylene--SO.sub.2 Y are already known from U.S. Pat. No. 5,272,267, U.S. Pat. No. 5,438,137 and Japanese Patent Application No. 02238063, and are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. The procedure described in the present invention is particularly advantageous in respect of the yield and purity of these dyestuffs. Dyestuffs of the formula (7a) in which both the radicals A.sup.10 and A.sup.30 are the radical of a sulfonated phenylamine, such as --NH-phenylene-(SO.sub.3 H).sub.1-2, and both the radicals A.sup.20 and A.sup.40 are fluorine or chlorine are already known from U.S. Pat. No. 3,883,523 and are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. The procedure described in the present invention is particularly advantageous in respect of the yield and purity of these dyestuffs. Those dyestuffs of the formula (7a) in which both the radicals A.sup.10 and A.sup.30 are cyanoamino and the two radicals A.sup.20 and A.sup.40 are fluorine, chlorine or are a radical of the formula ##STR14## in which M, L, y and U.sub.2 have one of the abovementioned meanings, are novel and the present invention therefore relates to them. Those dyestuffs of the formula (7a) in which both the radicals A.sup.10 and A.sup.30 are N(aryl)--(CH.sub.2).sub.2-3 --SO.sub.2 Y and both radicals A.sup.20 and A.sup.40 are fluorine or chlorine are already known from U.S. Pat. No. 5,405,947 and U.S. Pat. No. 5,484,458 and are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. The procedure described in the present invention is particularly advantageous in respect of the yield and purity of these dyestuffs. Particularly preferred dyestuffs of the formula (1) are furthermore those dyestuffs in which the radicals Z.sub.1 and Z.sub.2 have different meanings, for example the compound of the formula (7b) ##STR15## in which R.sub.1, R.sub.2, X.sub.1, X.sub.2, W and M have one of the abovementioned meanings; R.sub.40 is hydrogen, C.sub.1 -C.sub.4 -alkyl, phenyl or sulfophenyl; Q.sub.1 is fluorine, chlorine, amino, C.sub.1 -C.sub.4 -alkoxy, phenoxy, or pyridinyl, which can be substituted by carboxyl or aminocarbonyl, or cyanoamino; Y.sup.7 is .beta.-sulfatoethyl, .beta.-chloroethyl or vinyl; A.sub.3 is fluorine, chlorine, cyanoamino or amino; and A.sub.4 is one of the following radicals ##STR16## in which M, U.sub.2, y and L have one of the abovementioned meanings. Those dyestuffs of the formula (7b) in which the radical Q.sub.1 is cyanoamino and at the same time W is phenylene are particularly preferred. They are novel and the invention therefore relates to them. Those dyestuffs of the formula (7b) in which the radical W is C.sub.2 -C.sub.6 -alkylene and Q.sub.1 has one of the abovementioned meanings are likewise particularly advantageous. They are novel and the invention therefore relates to them. The dyestuffs of the formula (7b) are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. Those dyestuffs of the formula (7b) in which Q.sub.1 is halogen and W is phenylene are already known in some cases from U.S. Pat. No. 5,272,267 and U.S. Pat. No. 5,438,137. The procedure described in the invention is advantageous in respect of the yield and purity of these dyestuffs. Particularly preferred dyestuffs of the formula (1) are furthermore the asymmetric dyestuffs of the formula (7c) ##STR17## in which R.sub.1, R.sub.2, R.sub.40, X.sub.1, X.sub.2, Q.sup.1, Y.sup.7 and M have one of the abovementioned meanings; alk is ethylene or propylene; and Z.sub.1 ' is C.sub.1 -C.sub.4 -alkylcarbonyl, C.sub.2 -C.sub.4 -alkenylcarbonyl, aminocarbonyl, C.sub.1 -C.sub.6 -alkylaminocarbonyl, C.sub.6 -arylaminocarbonyl, C.sub.6 -arylcarbonyl or C.sub.6 -arylsulfonyl, which can be substituted by hydroxyl, cyano, sulfo, sulfato, carboxyl, acetylamino or SO.sub.2 Y.sup.7. Z.sub.1 ' is, for example, acetyl, .beta.-carboxyacryloyl, .beta.-carboxypropionyl, 3-(.beta.-chloroethylsulfonyl)-benzoyl, phenylsulfonyl, 4'-methylphenylsulfonyl, benzoyl or 2- or 4-carboxybenzoyl. Dyestuffs of the formula (7c) are novel and the invention therefore relates to them. They are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. Particularly preferred dyestuffs of the formula (1) are furthermore the asymmetric dyestuffs of the formula (7d) ##STR18## in which R.sub.1, R.sub.2, R.sub.40, Y.sup.7, Z.sub.1 ', X.sub.1, X.sub.2 and M have one of the abovementioned meanings. Dyestuffs of the formula (7d) are novel and the invention therefore relates to them. They are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. Particularly preferred dyestuffs of the formula (1) are furthermore the asymmetric dyestuffs of the formula (7e) ##STR19## in which R.sub.1, R.sub.2, X.sub.1, X.sub.2, Y.sup.7 and M have one of the abovementioned meanings; Z.sub.11 ' has one of the meanings of Z.sub.1 '; or in which Z.sub.11 ' is one of the radicals ##STR20## in which M, y, U.sub.2, Hal and L have one of the abovementioned meanings. Dyestuffs of the formula (7e) are novel and the invention therefore relates to them. They are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. Particularly preferred dyestuffs of the formula (1) are, furthermore, the asymmetric dyestuffs of the formula (7f) ##STR21## in which B.sub.1, B.sub.2, B.sub.3, R.sub.1, R.sub.2, X.sub.1, X.sub.2 and M have one of the abovementioned meanings and Z.sub.11 ' has one of the meanings given under (7e). Dyestuffs of the formula (7f) are novel and the invention therefore relates to them. They are suitable, for example, as reactive dyestuffs for dyeing cellulose fibers. Particularly preferred dyestuffs of the formula (7f) are those in which B.sub.1 and B.sub.2 are in each case fluorine. The present invention therefore relates to triphendioxazine compounds of the formula (7) ##STR22## comprising the dioxazine compounds described above as novel and defined in claim 10. The dyestuffs according to the invention are suitable for dyeing and printing fiber materials. Suitable fiber materials are cellulose fibers, such as cotton, viscose or chemically modified cellulose, polyamides, such as polyamide 6 or polyamide 6,6, or protein fibers, such as wool or silk, or blend fabrics comprising at least one of the abovementioned fiber materials, such as cotton/polyester blend fabric or cotton/polyamide blend fabric. The dyestuffs can be applied to cellulose fibers as direct dyestuffs or reactive dyestuffs, suitable dyeing processes being exhaustion or pad-dyeing processes, such as the short-time pad-batch process or the pad-steam process, but particularly preferably exhaustion processes. The dyestuffs can be applied to polyamide or protein fibers as acid dyestuffs or reactive dyestuffs. Dyestuffs of the formula (1) in which at least one of the radicals Z.sub.1 and Z.sub.2 is a reactive group from the pyrimidine series are particularly tinctorially strong and are distinguished by very good fastnesses to washing. Accompanying white laundry is stained only very little during washing. This finding is particularly surprising, since triphendioxazines to date have only moderate fastness to washing. The suitability of the dyestuffs according to the invention for dyeing processes in which very small amounts of salt, for example sodium chloride or sodium sulfate, are applied is likewise remarkable, amounts of salt to 50 to 80 g/l being customary in reactive dyeing, and even so-called low-salt dyestuffs in any case requiring 20 to 40 g/l of salt. A loss of tinctorial strength is usually suffered with reduced amounts of salt, i.e. for ecological reasons the dyestuffs are used for dyeing under conditions which do not correspond to their optimum. Surprisingly, it has now been found that the tinctorial strength which can be achieved for the triphendioxazines of the formula (1) according to the invention in which at least one of the radicals Z.sub.1 or Z.sub.2 is a reactive group from the pyrimidine series is almost independent of the amount of salt, i.e. the amount of salt employed can be reduced drastically without a loss of tinctorial strength. The invention therefore likewise relates to such a particularly ecologically advantageous dyeing process with a greatly reduced amount of salt of 0 to 20, preferably 5 to 15, grams of electrolyte salt per liter of dye solution, not taking into account alkaline electrolyte introduced by the dyeing alkali, such as, for example, sodium hydroxide or sodium carbonate, preferably at dyeing temperatures of 40 to 90.degree. C. in the exhaustion process. |
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