CH564592A5 - Yellow-red-green-blue-black vat dyes - for dyeing/printing cellulosics,polymers,in cosmeti s,lacquers,crayons,etc - Google Patents

Abstract

Title cpds. have the formula (I): a-A-NHCO-RZ-X-B (I) (where A is a polycyclic quinone which can be vatted, X is O or S; B is a 6-membered heterocycle contg. 2 or 3 N atoms, opt. contg. other carbocycles linked by condensn.; R is an aromatic gp. to which is fixed the substituent - X-B in pos. O- or in to the amide gp.; Z is H or -X-B; a is H or -NHCO-R-X-B). They are prepd. by condensing a cpd. of formula (III): a' - A-NHCO-RZXH (III) (where a' is H or - NHCORZ'XH, Z' being H or XH) with a coloured or colourless reactant of formula (IV) B-Y1Y2Y3 (IV) (where Y1-Y3 are substits. at least one of which is easily cleaved, e.g. halogen and esp. Cl or Br or methyl (sulphonyl). In an example a yellow dye is obtd. by reacting the reaction product from 1 mol. cyanaryl chloride with 2 mol. 1-aminoanthraquinone, with salicyloylaminoanthraquinone.

Description

  

  
 



   The present invention relates to the preparation of new vat dyes of the general formula
EMI1.1
 wherein
A = connectable polycyclic quinone,
X = oxygen or sulfur,
B = 6-membered heterocycle with 2 to 3 nitrogen atoms which optionally contains further fused carbocyclic rings.



   R = aromatic radical on which the -X-B substituent is in the o or m position to the amide group.



   Z = hydrogen or -X-B a = hydrogen or
EMI1.2

A special group of such dyes are those of the formula
EMI1.3
 wherein
K = -NH-Aryl-NH-, -X-Aryl-X-, -NH-Aryl-N = N-Aryl-NH-,
O-Aryl-N = N-ArylOrn -NH-Aryl-CH = CH-Aryl-NH-, O-ArylCH = CH-Aryl4-, -NH-Anthraquinonyl-NH- and where A, B, R, Z and X mean the same as above.



   B is preferably the radical of a heterocyclic compound of the general formula
EMI1.4
 wherein X1 denotes the group = N- or = C-, where Rl represents a hydrogen atom or a substituent such as e.g. a halogen atom, a nitro, cyano, -COCI or alkyl group, such as. B. denotes the methyl group, or the general formula
EMI1.5
 where the radicals of formulas (3) and (4), as indicated by the dashed line, may contain a fused carbocyclic ring, preferably a benzene ring.



   Residues of polycyclic quinones, such as e.g. Indanthrones, pyranthrones, dibenzanthrones, but especially phthaloylacridones and especially anthraquinones.



   The aromatic radical R preferably represents a benzene or naphthalene radical. Preferred dyes are those in which B is derived from a radical from the pyrimidine, pyridazine, quinazoline, quinoxaline, phthalazine or, in particular, 1,3,5 triazine series. These radicals B have one of the 2 of the following substituents: halogen, alkyl, aryl, aryloxy, arylamino, O-aryl-N = N-aryl, -NH-aryl-N = N-aryl, -O-aryl-CH = CH -Aryl, -NH-aryl-CH = CH-aryl -NH-A1, -X-A1, where X has the meaning given and A3 is a polycyclic quinone that can be linked.

  Here and below, aryl radicals are primarily understood to mean unsubstituted phenyl, naphthyl or diphenyl radicals substituted with chlorine, bromine, low molecular weight alkyl and alkoxy groups, and halogen means chlorine, bromine or fluorine.



   These substituents occur mainly in the following combinations: a) Both substituents correspond to the formula -NH-A1.



   b) A substituent is a halogen atom, a low molecular weight, i.e. H. An alkyl group containing up to 4 carbon atoms or an aryl group and the other a linkable group A linked via an -NH-, -O- or -S- bridge.



   c) One substituent is a halogen atom, a low molecular weight alkyl group, an aryl radical or a radical of a connectable, polycyclic quinone A1 bonded via an -NH-, 0 or + bridge, and the other is a radical of the formula -X-R-CONH-A.



   d) One substituent corresponds to the formula -X-R-X-B <X-R-CO-NH-A
X-RCO-NwA and the other is -X-R-CONH-A.



   The substitution possibilities d) and e) only occur if a is a hydrogen atom, i.e. if the radical A has only one amino group which can be acylated with the acid chloride of an aromatic hydroxy or mercaptocarboxylic acid.



   e) If the radical B is derived from a heterocyclic carboxylic acid chloride or sulfonic acid chloride, it can contain a viable radical A1 bonded via an amide bridge instead of an amino group. In this case, the second substituent on B is preferably a halogen atom.



   Particularly colored products are those compounds whose dye molecule contains only one or at most two groups of the formula -X-R-CONH-A per triazine radical.



   The symbol B thus preferably denotes a 1,3,5 triazine radical of the formula
EMI1.6
  where a) y1 = -NH-A, or -X-A, y2 = -NH-A1 or-X-A1 b) y1 = halogen, low molecular weight alkyl, aryl,
Aryloxy, arylamino, phenylazophenylamino, phenylazophenyloxy, stilbenyloxy, stilbenyl amino y2 = -X-A1 -NH-A1; c) yX = halogen, -NH-A1 or -X-A1, y2 = -X-R-CONII-A; d) y1 = -X-R-CONH-A
EMI2.1
 and where A, A ,, K, X and R have the meanings given in formula (1) and (2) and the possibilities listed under c) and d) only occur if in formula (1) a = hydrogen.



   Furthermore, B can also be a radical of the formula
EMI2.2
 mean in which
R1 = hydrogen, halogen, low molecular weight alkyl,
Aryl, nitro or cyano and a) y1 and y2 = -X-R-CO-NH-A b) y1 = halogen y2 = -CO-NH-A1 or
EMI2.3

R1 and y'2 together form a benz ring optionally substituted by a group of the formula -CO-NH-A1, and y1 = halogen, low molecular weight alkyl, aryl, arylamino, -NH-A1 or -X-A1.



   Examples of such dyes are:
EMI2.4


<tb> <SEP> n <SEP> 0 <SEP> - <SEP> Tr <SEP> - <SEP> 0
<tb> <SEP> Nil <SEP> d <SEP> CO
<tb> <SEP> <SEP> CH3 <SEP> CH30 <SEP>
<tb> where <SEP> -Tr- <SEP> is the <SEP> remainder <SEP> of the <SEP> formula <SEP> 9¯ <SEP> 0 <SEP> - <SEP> Tr <SEP>
<tb> <SEP> l2 \ N <SEP> | <SEP> on
<tb> <SEP> CO <SEP> (Wt
<tb> means. <SEP> ei) J <SEP> B <SEP> (¸
<tb> <SEP> NH, <SEP> IS
<tb> <SEP> R <SEP>) oOÄy
<tb> <SEP> oil <SEP> 0
<tb> <SEP> 00113 <SEP> CO- <SEP> OH3
<tb>
EMI3.1
 Other such dyes in which A and At are polycyclic quinone radicals that can be coupled are:
EMI3.2
  
EMI4.1

Because of their interesting hues, those dyes which contain at least two different connectable radicals, e.g.

  Compounds of the above formulas in which A and A1 are different radicals; especially preferred.

 

   There can also be two reactive components, e.g. B. 2 triazine rings can be linked by bifunctional compounds such as diamines and dyhydroxy compounds, as in the following formulas:
EMI4.2
 More such bridge members are z. B.
EMI4.3

EMI4.4




   The dyes of the formula (1) are prepared by condensation of a compound of the formula
XH āA-NHCO-R <(5) z where A, R and X are the same as above, a 'is hydrogen or a radical of the formula -NHCO-R <XH and Z' is hydrogen or -XH, with a colorless one or colored heterocyclic reactive component of the formula
EMI4.5
   wherein B has the meaning given and Y1, Y2 and Y3 are substituents, of which at least one is an easily cleavable radical, such as. B. is a halogen atom, preferably chlorine or bromine, or a methylsulfonyl group.



   For the preparation of dyes of the formula (2) one starts from a reactive component of the formula
EMI5.1
 from, where K has the meaning given and B, Y1 and Y2 are the same as above.



   Furthermore, one or two of the substituents Y1, Y2 and Y3 can be an aromatic radical bonded via an -NH-, -O- or -S- bridge, e.g. an aryloxy or arylamino radical or a group of the formula -NH-A3, -X-A1 or -CO-NH-A1. The introduction of these substituents is also done by condensation by adding component B, the two to 3 reactive groups, e.g. Halogen atoms or an acid chloride group contains, reacts with the corresponding amino, hydroxy or mercapto compounds.



  These substituents are preferably introduced into radical B before the condensation with the aromatic hydroxy or mercapto compound of the formula (5). But it is also possible to do this afterwards. So z. B. 2,4,6-trichloro 1,3,5-triazine is first reacted with one or two equivalents of the compound of formula (5) and the product obtained is then reacted with two or one mole of an amino group-containing quinone, e.g. of a 1-aminoanthraquinone are condensed.



   The representation can also take place in such a way that triazines or pyrimidines which contain removable substituents, e.g.



  Halotriazines, are reacted with a hydroxyl or mercapto compound in a molar ratio of 1: 1 and, after subsequent replacement of two removable substituents of the triazine or pyrimidine by amino groups, with polycyclic aromatic compounds that can be linked which contain removable substituents, e.g. Halanthraquinones, are condensed. By combining two different kinds of linkable connections, you can get valuable mixed tones.



   According to the general formulas (5), (6) and (7), the combination ratios of the hydroxy or



  Mercapto compound (5) to reactive component (6) or (7) vary as desired within the limits 4: 1, 3: 1, 2: 1, 1: 1, 1: 2, 1: 3 and 1: 4. The ratio is preferably chosen so that the dye molecule contains only one or at most two radicals of the formula -X-R-CONH-A per heterocyclic radical B.



   The condensation reactions are conveniently carried out in an inert solvent and in the presence of an acid-binding agent, such as. B. sodium carbonate, sodium acetate, dimethylformamide or with the advantage of a tentiary amine, preferably pyridine.



   The media for the reaction, depending on the type and sequence, are aqueous systems (e.g. water / acetone) or organic solvents with a boiling point of over 100 C, such as nitrobenzene, di- or trichlorobenzenes, dimethylaniline, N-methylpyrrolidine, pyridine etc. or possibly phenol in question.



   If 2,4,6 trichloro-1,3,5-triazine is used as the heterocyclic compound, it is advantageous to work in a high-boiling solvent, for example nitrobenzene, dichlorobenzene, naphthalene or phenol, since the third substituent of the triazine radical is relatively difficult to replace .



  Reaction temperatures of over 100 are advantageously chosen. The replacement of the third substituent in the triazine ring can also be made easier by adding small amounts of an aromatic sulfonic acid, such as benzene, p-toluene or, in particular, m-nitrobenzenesulfonic acid.



   It can be advantageous if a stream of air or nitrogen is passed through the reaction mixture temporarily or for the entire duration of the reaction. The dyes according to the invention can also contain sulfo groups.



  Occasionally, products that attract the fibers are better obtained if dyes free of sulfo groups are sulfated afterwards using one of the customary processes.



   The reactive components of the formula (6) or (7) originate e.g. from the pyridazine, quinazoline, quinoxaline, phthalazine or preferably from the pyrimidine or 1, 3,5-triazine series.



   The suitable compounds of the triazine series preferably correspond to the formula
EMI5.2
 wherein
A) Y'i is a halogen atom and Y'2 and Y'3 are each radicals of the formula -x-A1 or -NH-A1 or b) Y'1 is a halogen atom, Y'2 is a low molecular weight alkyl, an aryl , Aryloxy, arylamino radical, the radical of a hydroxyazo or aminoazo compound or of a hydroxy or aminostilbene and Y'3 is a radical of the formula -X-A1 or -NH-A1 or c) Y'1 and Y'2 are halogen atoms and Y'3 is a low molecular weight alkyl, aryl, aryloxy or arylamino radical or the radical of an amino or hydroxyazo compound,

   of an amino or hydroxystilbene or a radical of the formula -NH-A1 or -X-A1 or d) Y'1 and Y'2 are halogen atoms and Y'3 is a radical of the formula
EMI5.3

  <SEP> galogenic
<tb> <SEP> öw: en
<tb> lial <SEP> halogen
<tb> is or e) Y'1, Y'2 and Y'3 are halogen atoms and where X, A1 and K are the same as above.

 

   Such compounds are e.g. B. 2,4,6-trichloro-1,3,5-triazine or 2,4,6-tribromo-1, 3,5-triazine, 2,4,6-trimethanesulfonyl 1,3,5-triazine, 4,6-dichloro-1,3,5-triazines which are substituted in the 2-position by an aryl or alkyl radical, e.g. B. a phenyl, methyl or ethyl radical, or by the radical of an aliphatic or aromatic mercapto or hydroxyl bond bonded via the sulfur atom, or in particular by the radical of an aromatic amino compound bonded via the nitrogen atom, e.g. of an aminoanthraquinone.



   Further examples of such reactive components are the compounds of the following formulas, in which the symbol Tr always denotes a 1,3,5-triazinyl radical:
EMI6.1
  
EMI7.1
 where Rt and R2 are hydrogen, benzoylamino or phenyl mercapto radicals.
EMI7.2




   Reactive components of the quinazoline and pyrimidine series are, for example:
2,4-dichloroquinazoline and its derivatives which, instead of the one chlorine atom, contain an aromatic radical preferably bonded via an amino bridge, e.g. B. carry an anilido group or the remainder of an aminoanthraquinone. Monochloroquinazolines which have an aryl (e.g. phenyl, toluyl, diphenyl) or low molecular weight alkyl radical in the 2-position. 2,4,6 trichloro- or 2,4,6-tribromopyrimidine and their derivatives, the z. B. in the 5-position a cyano, nitro, methyl, ethyl, carbamide, sulfamide, carbomethoxy, carbalkoxy, acyl (e.g. benzoyl, acetyl or propionyl), alkenyl (e.g. allyl or chlorovinyl -), or a substituted alkyl (e.g.

  Carboxymethyl, chloromethyl or bromomethyl) group, 2,4,5,6-tetrachloro- or 2,4,5,6-tetrabromopyrimidine, 2,6-dichloro- or 2,6-dibromo-4-carboethoxypyrimidine 2,4,5-trichloropyrimidine 5-nitro-6-methyl-2,4-dichloropyrimidine 2,4-dichloropyrimidine-5-sulfonic acid 2,4-dichloro-5-chloromethyl-6-methyl-pyrime 2,4-dibromo- S-bromomethyl-6-methylpyrimidine 2,4-dichloro-5-chloromethylpyrimidine 2,4-dibromo-5-bromomethylpyrimidine 2,5,6-trichloro-4-methylpyrimidine 2,6-dichloro-4-trichloromethylpyrimidine or especially 2-methanesulphonyl -4,5-dichloro-6-methylpyrimidine 2,4-dimethanesulfonyl-5-chloro-6-methylpyrimidine and in particular the reaction products of 2,6-dichloropyrimidine-4- or -5-carboxylic acid chloride 2,6-dichloropyrimidine-4- or -5-sulfonic acid chloride 2,6-dibromopyrimidine-4- or -5-carboxylic acid or sulfonic acid chloride

   2,4-dichloroquinazoline carbonic or sulfonic acid chloride with aromatic, preferably viable amino compounds.



   Suitable compounds of the quinazoline and pyrimidines preferably correspond to the formula
EMI7.3
 where R1 is hydrogen, a halogen atom, in particular chlorine, a cyano, nitro or low molecular weight alkyl group or an aryl radical. The substituents Y "1, Y" 2 and Y "3 are either all halogen atoms, in particular chlorine, or one of them is a radical of the formula -CONH-A1 or
EMI7.4

In addition, R1 and Y "3 can together form a fused, preferably aromatic ring, for example a benzene ring, which can be unsubstituted or which bears a radical of the formula -CO-NH-A1.

  In this case, one of Y 1 and Y "2 is a halogen atom and the other is halogen, low molecular weight alkyl, aryl, arylamino, -NH-A1 or -X-A1. Examples of such reactive components are:
EMI7.5

The anthraquinonyl radical can be substituted or replaced by another groupable radical, in particular by a 3,4-phthaloylacridone radical
EMI8.1

Suitable reactive components of the pyridazine, quinoxaline or phthalazine series are, for.

  B. 3,6-dichloropyridazine, tetrachloropyridazine or the reaction products of acid chlorides of this series, such as 3, 6-dichloropyridazine-5-caronic acid chloride 4,5-dichloropyridazone (6) -yl-propionic acid chloride 4, S-dichloro-1-phenylpyridazone- carbonic or sulfonic acid chloride 4,5-dichloropyridazone propionic acid chloride 1, 4-dichlorophthalazine carbonic or sulfonic acid chloride 2,3-dichloroquinoxaline carbonyl or sulfonic acid chloride with aromatic, viable radicals.



   As linkable radicals, in particular for the groups designated with A and A, residues of linkable polycyclic quinones are possible. The term quinone that can be linked includes those chromophores that are reduced to a so-called



  Leuco form or vat, which has a better affinity for natural or regenerated cellulose fibers than the non-reduced form, and which can be returned to the original chromophoric system by oxidation. No polycyclic quinones of the 1-amino-4arylaminoanthraquinone-2-sulfonic acid type are used in the present process, because they can be reduced, but are chemically modified so strongly by the reduction that they no longer fit into the original chromophoric system get convicted.



   The following are examples of polycyclic quinones that can be linked:
Perylentetracarbonsäureamide, especially the phenylimides, anthrapyrimidines, anthrapyridones, Isothiazolanthrone, Chinazolinanthrachinone, Oxazolanthrachinone, Thiazolanthrachinone, Oxdiazolanthrachinone, Anthrachinonyltriazole, Pyrazolanthrachinone, Dipyrazolanthronyle, Pyrazinoanthrachinone, Azabenzanthrone, indanthrones, Thioxanthonanthrachinone, anthrimides Anthrimidcarbazole, dihydroacridines, anthanthrones, pyranthrones, flavanthrones, Acedianthrone and especially Anthraquinone acridones and the anthraquinones themselves, which not only include derivatives with pure 9,10-dioxoanthracene rings, but also those with thiophanthrone residues and the like, as well as anthraquinone compounds which have 9,10-dioxoanthracene rings.

  Preferred radicals are the 3,4-phthaloylacridones bound in the 2- or 8-position and the anthraquinones bound in the 1- or 2-position. All these radicals can carry the substituents customary for vat dyes. Such substituents are, for example: halogen atoms, in particular chlorine, fluorine or bromine, alkyl, alkoxy, aryl, aryloxy, aralkyl, aralkoxy, carbalkoxy, arylamino, alkyl mercapto, aryl mercapto, cyano and thiocyano groups. By alkyl is meant in particular radicals with 14 carbon atoms, by aryl in particular radicals such as phenyl, toluyl, chlorophenyl, methoxyphenyl or naphthyl radicals and with aralkyl especially the benzyl radical.



  The acyl and acylamino groups are also particularly important substituents. The term acyl mainly comprises residues of low molecular weight alkanecarboxylic or sulfonic acids and residues of carboxylic or sulfonic acids of the benzene series, where the benzene nucleus can be unsubstituted or substituted by halogen, low molecular weight alkyl or alkoxy residues, or aryl residues. The term acyl also includes residues of low molecular weight alkyl carbonic acid monoesters or sulfur or carbonic acid monoamides.

  Examples of such acyl and acylamino radicals are: benzoyl, p-chlorobenzoyl, p-phenylbenzoyl, benzenesulphonyl, toluenesulphonyl, acetyl, acetylamino, ethoxycarbonyl, ethoxycarbonylamino, unsubstituted or low-molecular-weight alkylamido groups, aralkyl or aryl groups and substituted sulfonamido groups, and substituted sulfonamide groups such as NH2-CO-NH- or (CH3) 2N-CO-NH-.



   The starting product of the formula (5) required in the process according to the invention is obtained by reacting an aromatic hydroxyl or mercaptocarboxylic acid chloride with amino compounds of the vettable quinones mentioned.



  As suitable starting compounds of the formula A-NH2 or



  A1NH2 are for example:
1-aminoanthraquinone
1-amino-4-methoxyanthraquinone 1-amino-4-acetylaminoanthraquinone 1-amino-4-benzoylamino-anthraquinone 1-amino-4- (p-toluenesulfonylamino) anthraquinone 1-amino-4- (p-chlorobenzoylamino) anthraquinone
1-amino-4-anilido-anthraquinone 1 -amino-4- [p- (N, N-dimethylsulfamido) -benzoylamino] anthraquinone 1-amino-4-phenyl mercapto-anthraquinone 1 -amino-4- (4 '-phenyl- benzoylamino) anthraquinones, as well as the corresponding 1-aminoanthraquinones, which are substituted in the 5- or 8-position instead of in the 4-position
1,4-diaminoanthraquinone
1-amino-2-chloroanthraquinone, 1 -amino-3-chloroanthraquinone, 2-amino-3-chloroanthraquinone, 1 -amino-5-chloranthraquinone, 2-amino-4-chloroanthraquinone, 1-amino-4-chloroanthraquinone, 1 - Amino-6-chloroanthraquinone,

   1-amino-8-chloroanthraquinone, 1-amino-3-chloro-6-methylanthraquinone, 1-amino-6,7-dichloroanthraquinone, 2-amino-3,4-phthaloylacridone, 1,4-diamino-2-acetylaminoanthraquinone, Aminoanthrapyrimidines, 1-aroylamino-4- or -5-aminoanthraquinone, 1,4-diamino-2-acetylanthraquinone, 1-amino-7-chloranthraquinone, 1-amino-2-methyl-3-chloranthraquinone, 4-aminoanthraquinone-2, 1 (N) -acridone, 4,4'-, 4,5'- or 5,5'-diamino-1,1'-dianthrimidcarbazole, aminopyranthrone, mono- and diaminoacedianthrone, aminoisodibenzanthrone, aminodibenzanthrone, aminoanthanthrone, aminoflavanthrone, aminopyranthrone, 4-,

   5- or 8-amino-1,1'-dianthrimide carbazole, 4- or 5-amino-5 '-b enzoylamino-dianthrimide carbazole, 4-amino-4 ¯benzoylamino-dianthnmidcarbazole, aminodibenzpyrenquinone, also mono- and diaminotrianthrimide carbazole, e.g.

   the 8 ', 8 "diamino-1 1,4,1" -trianthrimidecarbazole, furthermore perylenetetracarboxylic acid-di- (p- or m-aminophenyl) -imd, the compounds of the formulas
EMI9.1
  (X = 0 or S) and
EMI9.2
 and those of the formula
EMI9.3
   wherein one of the symbols R1 is a hydrogen atom and the other is a group of the formula - (- NH-CO-R4-) n¯1-NH2n = 1 or 2, one of the symbols R2, R3 is a halogen atom, an alkoxy, aryloxy, aryl mercapto - or acylamino group, in particular a benzoylamino group, such as the chlorine, methyl, sulfo or fluorobenzoylamino groups and the unsubstituted C6H5-CO group itself, the other of the symbols R2,

   R3 and R, represent a hydrogen or halogen atom where one of the symbol pairs R2R2, R3R3 or RsR5 together form a group
EMI9.4
 may mean, and R4 is an arylene radical, preferably the
Benzene series, means.



   Suitable carboxylic acid chlorides of aromatic hydroxy or mercapto compounds are preferably derived from carboxylic acids of the benzene or naphthalene series. In addition to the hydroxyl or mercapto groups, they can contain other substituents, e.g. Halogen atoms, low molecular weight alkyl, aralkyl, especially benzyl, aryl, especially phenyl, aryloxy, acyl or acylamino. Examples of such carboxylic acids are: salicylic acid thiosalicylic acid 2-hydroxy-5-chlorobenzoic acid 2-hydroxy-3-methyl-benzoic acid 2-hydroxy-4,5- or 6-methyl-benzoic acid 2,4-dihydroxy-benzoic acid 2,5-dihydroxybenzoic acid 3 - Hydroxybenzoic acid 1 - Hydroxybenzoic acid 1 - Hydroxy-2-naphthoic acid 3-hydroxy-2-naphthoic acid or compounds of the formula
EMI9.5

The colorations obtained with the dyes according to the invention are distinguished by vivid, clear nuances.



  Particularly noteworthy are the advantageous application properties. According to the present process, u. a. Dyes, the application of which is largely independent of temperature. The application can be carried out by the most varied of processes, for example by exhaust or pad-dying processes, e.g. the pad jig process, the pad steam or the cold dwell process.



  It is also noteworthy that good dye yields are obtained in all application processes and that a large part of the dyes can be synthesized in almost theoretical yield after the preparation according to the invention. A particular advantage is that the range of variation in the color shades is very large, so that practically all color shades can be produced with the dyes according to the invention.



   The products obtained according to the process are suitable for dyeing and printing a wide variety of materials, in particular for dyeing and printing fibers made from natural and regenerated cellulose in the presence of reducing agents, such as e.g. Dithionite. The dyeings obtained are distinguished by very good wet fastness, in particular soda boiling and chlorine fastness, and good to very good light fastness.



   The new compounds can also be used as pigments. Thanks to their favorable properties, they can be used for a wide variety of pigment applications, e.g. in finely divided form for dyeing rayon and viscose or cellulose ethers or esters or super polyamides or super polyurethanes or polyesters in the spinning mass, as well as for the production of colored lacquers or lacquer formers, solutions or products made from acetyl cellulose, nitrocellulose, natural resins or synthetic resins such as poly merization resins or condensation resins, e.g. B. aminoplasts, alkyl resins, phenoplasts, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins.

  They can also be used advantageously in the production of colored pencils, cosmetic preparations or laminating plates.



  Among the compounds according to the invention are u. a. also pigment dyes, which are characterized by their excellent migration behavior in fabrics coated with polyvinyl chloride.



   In the following examples, the parts always mean
Parts by weight, the temperatures are given in degrees Celsius and the symbol -Tr- means the remainder of the formula
EMI10.1

example 1
5.6 parts of the reaction product of 1 mole of cyanuric chloride with 2 moles of 1-aminoanthraquinone are heated in 80 parts of nitrobenzene together with 3.5 parts of sylicyloylaminoanthraquinone in the presence of 0.3 part of pyridine to 205-210 ° C. with stirring. The reaction mixture is kept at this temperature for 12 hours, a stream of nitrogen being passed through it continuously or intermittently.



   The mixture is then allowed to cool, the insoluble dye is isolated by filtration, the filter material is washed with nitrobenzene and then with methanol and dried in vacuo. The dye obtained corresponds to the formula
EMI10.2
 and dyes cotton using the usual vat dyeing processes in intense yellow shades with good fastness properties.



   Example 2
1.85 parts of the reaction product of 1 mole of cyanuric chloride with 1 mole of 1-aminoanthraquinone are in 60 parts of nitrobenzene together with 3.5 parts of salicyloylamino-anthraquinone in the presence of 0.2 part of pyridine for 45 minutes.



  heated to boiling.



   The mixture is allowed to cool to room temperature and worked up as described in Example 1. The isolated dye of the formula
EMI10.3
  dyes cotton, linen or regenerated cellulose in intensive, golden yellow tones using the usual vat dyeing processes.



   From the starting materials mentioned in the table below, further dyes can be prepared in accordance with the invention which have the color shades given in the last column.
EMI11.1


<tb>

 

  Example <SEP> reactive component <SEP> Hydroxy- <SEP> or <SEP> color
<tb> <SEP> O <SEP> OCH <SEP> Mercapto connection
<tb> <SEP> II
<tb> <SEP> O <SEP> NH
<tb> <SEP> o <SEP> NO
<tb> <SEP> CO- <SEP> Ni
<tb> 3 <SEP> Tr- <SEP> C <SEP> 9 <SEP> red-orange
<tb> <SEP> O <SEP> tJII
<tb> <SEP> Ü <SEP> 6
<tb> <SEP> o <SEP> STILL,
<tb> <SEP> R <SEP> HS / 0
<tb> <SEP> R
<tb> <SEP> CW <SEP> HS4)
<tb> <SEP> 6 <SEP> CO-NO
<tb> <SEP> NR <SEP> 9
<tb> 4 <SEP> 1 <SEP> 1 <SEP> red-orange
<tb> <SEP> Tr- <SEP> C1 <SEP> 6
<tb> <SEP> Q <SEP> s
<tb> <SEP> 6 <SEP> $ 1
<tb> <SEP> NO
<tb> <SEP> HO <SEP> HO
<tb> <SEP> CO-NI
<tb> <SEP> I <SEP> 9
<tb> <SEP> NH <SEP> <
<tb> 5 <SEP> 1 <SEP> gray
<tb> <SEP> Tr- <SEP> Cl
<tb> <SEP> 9
<tb> <SEP> 0
<tb> <SEP> 0
<tb> <SEP> N9
<tb> <SEP> H <SEP> U
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI12.1


<tb>

   <SEP> 2 <SEP> moles
<tb> <SEP> Ü <SEP> NRCO
<tb> <SEP> 6 <SEP> ITH <SEP> pg; <SEP> yellow
<tb> <SEP> Tr- <SEP> C1 <SEP> CO-NHb
<tb> <SEP> box
<tb> <SEP> 6
<tb> <SEP> Cl <SEP> 2 <SEP> Mol
<tb> <SEP> C1 <SEP> - <SEP> Tr <SEP> - <SEP> Cl
<tb> <SEP> 7 <SEP> 110 <SEP> blue
<tb> <SEP> 7
<tb> <SEP> CO-NIl
<tb> <SEP> 0
<tb> <SEP> d
<tb> <SEP> vC '
<tb> <SEP> CIii / C) (<SEP> 110 <SEP> - <SEP> $ 1
<tb> <SEP> II <SEP> I
<tb> 8 <SEP> g <SEP> yellow
<tb> il '<SEP> - <SEP> Cl <SEP> CO-I
<tb> <SEP> NR <SEP> yellow
<tb> <SEP> CaO
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI13.1


<tb> <SEP> Tr <SEP> - <SEP> Cl
<tb> 9 <SEP>) <SEP> ()) <SEP> HO <SEP> Y <SEP> I
<tb> <SEP> (¸ <SEP> yellow
<tb> <SEP> 6
<tb> <SEP> Cl <SEP> Cl.

  <SEP> 4 <SEP> moles
<tb> <SEP> Tr- <SEP> O-0- <SEP> Q
<tb> <SEP> HD
<tb> lo <SEP> al <SEP> Cl <SEP> yellow
<tb> <SEP> CO <SEP> <SEP> b <SEP> H
<tb> <SEP> o
<tb> <SEP> 6
<tb> <SEP> Cl <SEP> -Tr- <SEP> Cl <SEP> HO
<tb> <SEP> 9 <SEP> H <SEP> ¸
<tb> R <SEP> lTH <SEP> C0NX
<tb> 1 <SEP> blue
<tb> 6
<tb> <SEP> NO
<tb> <SEP> Ö <SEP> 110
<tb> <SEP> 12 <SEP> TH <SEP> CO- <SEP> Nil <SEP> green
<tb> <SEP> 9
<tb> <SEP> W
<tb> <SEP> (f <SEP> (NH
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI14.1


<tb> <SEP> r <SEP> NH-OC4Cl
<tb> <SEP> II <SEP> I <SEP> CO-NHo
<tb> <SEP> Nil <SEP> 0
<tb> <SEP> 13 <SEP> 1 <SEP> I;

  <SEP> olive green
<tb> <SEP> Tr-C1 <SEP> Od <SEP> H6
<tb> <SEP> O <SEP> 1IH
<tb> <SEP> t
<tb> <SEP> Cl
<tb> <SEP> 0
<tb> <SEP> CO <SEP> CG'NH41
<tb> 14 <SEP> 6r1-Cl <SEP> OH <SEP> olive green
<tb> <SEP> Cr-C1
<tb> <SEP> 0 <SEP> PH
<tb> <SEP> O <SEP> n
<tb> <SEP> HN '
<tb> <SEP> / C <SEP> cO <SEP> sH
<tb> 15 <SEP> () HC <SEP> 0-NR0 <SEP> blue-green
<tb> 15 <SEP> 1 <SEP> II
<tb> <SEP> "= d
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI15.1


<tb> <SEP> 0lo <SEP> 81R
<tb> <SEP> Q <SEP> 0 <SEP> CO <SEP> -7HII
<tb> <SEP> NO
<tb> trCl <SEP> O <SEP> yellow
<tb> <SEP> NO
<tb> <SEP> y
<tb> <SEP> 016
<tb> <SEP>) 3 <SEP> 2 <SEP> Mol
<tb> 17 <SEP> 2 <SEP> Nol <SEP> green
<tb> <SEP> NKLTr-C1
<tb> <SEP> Cl
<tb> <SEP> oCONHo
<tb> <SEP> Clb <SEP> OH
<tb> <SEP> NT
<tb> ¸ <SEP> I <SEP> OH
<tb> <SEP>) CO-NO
<tb> 18 <SEP> Tr-Cl <SEP> O <SEP> Cl
<tb> <SEP>

   oCO <<SEP>
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI16.1


<tb> <SEP> OH
<tb> <SEP> 0: <SEP> b ,. <SEP>
<tb>



  19 <SEP> SCOk <SEP> yellow
<tb> <SEP> Tr-C1
<tb> <SEP> 0 <SEP> i <SEP> N-S
<tb> <SEP> OH <SEP> 0
<tb> <SEP> OCO <SEP> T <SEP> 11 <SEP> $ <SEP> 1 i
<tb> <SEP> II
<tb> 20 <SEP> H <SEP> 6 <SEP> golden yellow
<tb> <SEP> Tr-Cl
<tb> <SEP> NH
<tb> <SEP> CO- <SEP> NO
<tb> <SEP> 'II
<tb> <SEP> ö {i; O (¸; yROII
<tb> <SEP> 6 <SEP> NH <SEP> 6
<tb> 21 <SEP> Tr-Cl <SEP> blue-gray
<tb> <SEP> o <SEP> NH
<tb> <SEP> II
<tb> <SEP> i¸i;

  ;O
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI17.1

  <SEP> 0 <SEP> OH
<tb> <SEP> t0 <SEP> gCOdW
<tb> <SEP> ¸ <SEP>) rCy
<tb> <SEP> NH <SEP> li <SEP> s
<tb> 22 <SEP> t \ r-Cl <SEP> gray-blue
<tb> <SEP> 1pj
<tb> <SEP> 'i1
<tb> <SEP> Cl <SEP> OH
<tb> <SEP> II <SEP> -C1 <SEP> b-c <SEP> 0IiO
<tb> 23 <SEP> <SEP> IyH <SEP> CX) <SEP> yellow
<tb> <SEP> O <SEP> N'R <SEP> ¸
<tb> <SEP> li <SEP> NH <SEP> o <SEP> NH
<tb> <SEP> W) <SEP> C> -co
<tb> <SEP> Cl
<tb> <SEP> OH
<tb> <SEP> HD0 <SEP> & Oll
<tb> 24 <SEP> C;

  ; l'NR <SEP> IY (<SEP> blue-green
<tb> <SEP> 1 l <SEP> H
<tb> <SEP> 0
<tb>
Example 25 5.3 parts of the monochlorotriazine product of the formula
EMI18.1
 prepared by heating molar amounts of 2-phenyl-4,6dichloro-1,3,5-triazine with 2-amino-3,4-phthaloylacridone in N-methylpyrrolidone, are heated to boiling with 4 parts of thiosalicyloylaminoanthraquinone in 100 parts of nitrobenzene for 2 hours. After cooling to room temperature, the precipitated dye is of the formula
EMI18.2
 isolated by filtration, washed with nitrobenzene and dried. It dyes cotton and regenerated cellulose in blue shades with very good fastness properties.



   Example 26
4.1 parts of the acetylation product of perylenetetracarboxylic acid di- (p-aminophenyl-imide) with salicyloyl chloride of the formula
EMI18.3
 are refluxed for 14 hours with 8.0 parts of the monochlorotriazine product from 1 mol of cyanuric chloride with 2 mol of 1-amino-4-benzoylaminoanthraquinone in 150 parts of nitrobenzene with the addition of 0.1 part of pyridine and a stream of nitrogen being passed through. After cooling, the excreted dye becomes of the formula
EMI18.4
 isolated by filtration, washed with nitrobenzene, then methanol and dried in vacuo at 8e100 ". It dyes cotton and regenerated cellulose by the usual vat dyeing processes in bluish red shades of excellent levelness and very good fastness properties.



   Example 27
24 parts of salicylamino-5-benzoylaminoanthraquinone are mixed with 31 parts of the condensation product of 1 mole of cyanuric chloride and 2 moles of 1-amino-4-methoxyanthraquinone in 500 parts of dry nitrobenzene with the addition of 1.5 parts of pyridine and 5.5 parts of dusty sodium carbonate for 6 hours 145 to 150 ". After cooling to 40", the precipitated dye is isolated by filtration with nitrobenzene, then methanol and finally washed neutral with 500 warm water and dried in vacuo
The orange dye of the formula obtained in this way
EMI19.1
 dyes cotton and regenerated cellulose in brilliant orange shades with excellent fastness properties and application properties.



   If in this example the 24 parts of 1-salicyloylamino-5-benzoylaminoanthraquinone are replaced by 26 parts of 1- (2 3'-oxynaphtoylamino) -5-benzoylaminoanthraquinone, a dye with similarly good properties is obtained.



   Example 28
16 parts of the chlorotriazine derivative, obtained from 1 mol
Cyanuric chloride and 2 moles of 1-amino-5-benzoylamino-anthraquinone are mixed with 3.6 parts of 1- (3 ', 5'-dioxybenzoylamino) anthraquinone in 150 parts of nitrobenzene with the addition of 0.2
Share pyridine and pass through a stream of nitrogen 16
Condensed hours at reflux.



   The dye suspension is on after cooling
Room temperature, as described in Example 26, worked up. The dye of the formula thus obtained
EMI19.2
 dyes cotton and regenerated cellulose in golden yellow shades with very good fastness properties and excellent application properties.

 

   The 1- (3 ', 5'-dioxybenzoylamino) anthraquinone used in this example can be obtained, for example, from the corresponding 1- (3', 5'-diacetoxy) derivative by saponification of the acetoxy groups using 87% strength sulfuric acid 5-10 can be obtained in practically theoretical yield.



   Further properties can be produced in accordance with the invention from the starting materials mentioned in the tables below, the symbol -Tr- denoting the triazinyl radical and the dyes having the color shades given in the last column.



  Example reactive component hydroxyl or color shade
Mercapto connection
EMI20.1


<tb> <SEP> OH <SEP> OH
<tb> <SEP> tNH <SEP> $} CO-I <SEP> Hll
<tb> <SEP> 29 <SEP> 2 <SEP> Mol <SEP> Tr-Cl <SEP> INH <SEP> golden yellow
<tb> <SEP> 011 <SEP> CO
<tb> <SEP> ¸II
<tb> <SEP> CO-NHO <SEP> IO-% CONH
<tb> <SEP> SX13
<tb> <SEP> 6 <SEP> NR <SEP> 6
<tb> <SEP> 30 <SEP> 2 <SEP> Mol <SEP> Tr-Ol <SEP> (9 <SEP> olive
<tb> <SEP> II <SEP> I
<tb> <SEP> CIJ
<tb> <SEP> OWCO-NHO
<tb> <SEP> CO-NHO
<tb> <SEP> OH <SEP> 2 <SEP> Mol
<tb> <SEP> C <SEP> CONH0
<tb> 31 <SEP> al <SEP> O <SEP> olive green
<tb> <SEP> R <SEP> II <SEP> 1 <SEP> olive green
<tb> <SEP> Cl <SEP> 0
<tb> <SEP> 0
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI21.1


<tb> 32 <SEP> y¸ <SEP> 2 <SEP> Mol <SEP> black
<tb> 32 <SEP> C
<tb> <SEP> NR <SEP> iy)
<tb> <SEP> Cl-Tr-Cl
<tb> <SEP> tA0 <SEP>

   ssCOX
<tb> <SEP> ¸CO <SEP> Y'1R
<tb> 33 <SEP> 1 <SEP> Cl-CO
<tb> <SEP> green
<tb> <SEP> Tr-Cl
<tb> <SEP> o <SEP> 2 <SEP> NH
<tb> <SEP> 2 <SEP> Mol
<tb> <SEP> o
<tb> <SEP> II <SEP> 2 <SEP> Mol
<tb> <SEP> Cl <SEP> 2 <SEP> Mol
<tb> <SEP> NO <SEP> o <SEP> NH-Tr <SEP> NR9
<tb> <SEP> NH-Tr
<tb> 34 <SEP> 9 <SEP> Cl <SEP> <SEP> brown
<tb> <SEP> IN <SEP> Cj <SEP> do
<tb> <SEP> o <SEP> 1 l
<tb> <SEP> 11
<tb> <SEP> 6
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI22.1


<tb> <SEP> C1 <SEP> O
<tb> <SEP> oCO-NHO <SEP> il
<tb> <SEP> I <SEP> O-NRO <SEP> (¸)
<tb> <SEP> C9? <SEP> O <SEP> I <SEP> ONR
<tb> <SEP> 35 <SEP> 0 <SEP> NH <SEP> yellow
<tb> <SEP> 2 <SEP> Mol <SEP> Tr-Cl <SEP> CO
<tb> <SEP> luH
<tb> <SEP> 1 <SEP> V-OH
<tb> <SEP> CO- <SEP> HO
<tb> <SEP> oiii4P
<tb> <SEP> -CO-HO <SEP> YNIHCO
<tb> <SEP> 36 <SEP> 2 <SEP> Mol <SEP> Tr-Cl

   <SEP> Ct <SEP> O <SEP> yellow olive
<tb> <SEP> 2 <SEP> moles <SEP> Tr-C1 <SEP> H
<tb> <SEP> o <SEP> kH
<tb> <SEP> II
<tb> <SEP> o
<tb> <SEP> II <SEP> II
<tb> 37 <SEP> W
<tb> 37 <SEP> Mol <SEP> O <SEP> red
<tb> <SEP> 2 <SEP> Mol <SEP> 1 <SEP> 0 <SEP> CO
<tb> <SEP> HN <SEP> ZIP
<tb> <SEP> co-Äii
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI23.1


<tb> <SEP> Cl
<tb> <SEP> O <SEP> NH-OC-O <SEP> n
<tb> <SEP> CO
<tb> 38 <SEP> b <SEP> NH <SEP> HN <SEP> O <SEP> red
<tb> <SEP> NR <SEP> IN
<tb> <SEP> Tr-CjL <SEP> TNHOCK <SEP>>
<tb> <SEP> NH-OC O
<tb> <SEP> t <SEP> H <SEP> HO);

  <SEP> O
<tb> 39 <SEP> 11 <SEP> 0 <SEP> RO <SEP> 0-Nil0 <SEP> yellow
<tb> <SEP> O <SEP> Tr-Cl <SEP> II
<tb> <SEP> 0 <SEP> I <SEP> CC9
<tb> <SEP> 11 <SEP> NR <SEP> 011 <SEP> NR
<tb> <SEP> Ï <SEP> <So
<tb> <SEP> o
<tb> <SEP> CCg <SEP> C1-CONH9OH
<tb> <SEP> CO
<tb> 40 <SEP> NH <SEP> olive green
<tb> <SEP> Tr-C1
<tb> <SEP> H <SEP> WITHOUT <SEP> O
<tb> <SEP> y
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI24.1


<tb> <SEP> O <SEP> o
<tb> <SEP> II <SEP> CXCONH
<tb> <SEP> 1 <SEP> "<SEP> 0 <SEP> yellow
<tb> <SEP> <SEP> NH <SEP> all
<tb> 41 <SEP> Tr-Cl <SEP> OC <SEP> yellow
<tb> <SEP> <SEP> NH <SEP> \ OH
<tb> <SEP> II <SEP> V <SEP> WH
<tb> <SEP> d <SEP> ¸
<tb> <SEP> B <SEP> 11
<tb> <SEP> 0
<tb> <SEP> N = N
<tb> <SEP> Oy
<tb> <SEP> 110 $ <SEP> moles
<tb> <SEP> 2 <SEP> Mol
<tb> <SEP> <SEP> H <SEP> HN-CO <SEP> CO-NH
<tb> 42 <SEP> TrCl <SEP> (t) e

   <SEP> e <SEP> °) <SEP> blue-green
<tb> <SEP> II <SEP> ROJ
<tb> <SEP> 110 <SEP> NR <SEP> (
<tb> <SEP> 0% <SEP> · <SEP> ¸
<tb> <SEP> 9 <SEP> CH3 <SEP> HO / Cio, l
<tb> <SEP> 03, <SEP> 0
<tb> <SEP> 43 <SEP> Tr-Cl <SEP> Cm
<tb> 43 <SEP> Tr-Cl <SEP> CO-NR
<tb> <SEP> O <SEP> ss <SEP> II <SEP> orange
<tb> <SEP> 0
<tb> <SEP> <SEP> FCH3
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI25.1


<tb> <SEP> o <SEP> NH-OC <SEP> ClCONR
<tb> <SEP> | <SEP> J'OH
<tb> <SEP> 2 <SEP> 2 <SEP> Mol <SEP> 1 l <SEP> OllNHO
<tb> 44 <SEP> 011R <SEP> red
<tb> <SEP> red
<tb> <SEP> Tr-Cl <SEP> OC-NH
<tb> <SEP> N1H <SEP> OC-NR
<tb> <SEP> 9
<tb> <SEP> l'OssNH- <SEP> <<SEP> CA
<tb> <SEP> <SEP> NH-OC <SEP> 4
<tb> <SEP> 9 <SEP> Cl <SEP> O <SEP> STH-OC <SEP> 9
<tb> <SEP> Cl <SEP> 3
<tb> 45 <SEP> Tr-Cl <SEP> 0 <SEP> yellow
<tb> <SEP> o <SEP> AH
<tb> <SEP> II <SEP>

   I.
<tb> <SEP> 0 <SEP> 1
<tb> <SEP> oil
<tb> <SEP> 0
<tb> <SEP> O <SEP> C1 <SEP> C14OH
<tb> <SEP> yCl <SEP> CO
<tb> <SEP> O <SEP> NH <SEP> o <SEP> NH
<tb> 46 <SEP> 11 <SEP> grain
<tb> <SEP> Tr-Cl <SEP> oO
<tb> <SEP> o <SEP> NH <SEP> U <SEP> Y <SEP> ss <SEP> O
<tb> <SEP> 1 <SEP> t
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI26.1


<tb> <SEP> o <SEP> Ii
<tb> <SEP> II <SEP> 3 <SEP> HD
<tb> <SEP> <SEP> NH,

   <SEP> orange
<tb> <SEP> Tr-Cl
<tb> <SEP> O <SEP> PH <SEP> (z)
<tb> <SEP> II <SEP> t
<tb> <SEP> 3
<tb> <SEP> 0
<tb> <SEP> 2 <SEP> 2 <SEP> moles <SEP> RAW
<tb> <SEP> I
<tb> 48 <SEP> 0 <SEP> NH <SEP> I <SEP> II <SEP> olive
<tb> <SEP> Fr-Cl <SEP> 00
<tb> <SEP> O <SEP> NH
<tb> <SEP> II
<tb> <SEP> 0
<tb> <SEP> OR
<tb> <SEP> O <SEP> 4 <SEP> o <SEP> HN-CO <SEP> t
<tb> <SEP> 2
<tb> <SEP> 2 mol <SEP> OH
<tb> <SEP> ll <SEP> NO
<tb> 49 <SEP> ir-Cl <SEP> blue-gray
<tb> <SEP> 1 l <SEP> aH
<tb> <SEP> 0
<tb> <SEP> HN <SEP> |
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI27.1

  <SEP> C1 <SEP> 0
<tb> <SEP> 50 <SEP> Cit <SEP> 3 <SEP> yellow-brown
<tb> <SEP> t <SEP> \ <SEP> O <SEP>
<tb> <SEP> Cl- <SEP> -CO
<tb> <SEP> VC <SEP> /
<tb> <SEP> cl
<tb> <SEP> II-V
<tb> <SEP> 51 <SEP> 06I \ I <SEP> blue
<tb> <SEP> HN / <SEP> C1
<tb> <SEP> 0
<tb> <SEP>

   sN
<tb> <SEP> II <SEP> 1
<tb> <SEP> NR-OC "-0 <SEP> 0-01
<tb> 52 <SEP> HD0
<tb> <SEP>} Ü11 <SEP> OC <SEP> 0 <SEP> yellow
<tb> 52 <SEP> C <SEP> '<SEP> L,
<tb> <SEP> o <SEP> CO <SEP> O <SEP> IH
<tb> <SEP> cO
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI28.1


<tb> <SEP> Cl <SEP> 0
<tb> O <SEP> NH-OC- <SEP> O <SEP> t <SEP> OC-NR.r <SEP> red
<tb> <SEP> II <SEP> 3 <SEP> C <SEP> "- <SEP>
<tb> <SEP> NH <SEP> II
<tb> <SEP> CO <SEP> HN <SEP>
<tb> <SEP> CO
<tb> <SEP> 4 <SEP> OC- <SEP> o <SEP> Cl
<tb> <SEP> ruC-C1
<tb> OC <SEP> 1 \ NC.

  <SEP> C1
<tb> 54 <SEP> yl <SEP> b, <SEP> OC-NHO
<tb> <SEP> 1
<tb> <SEP> RK
<tb> HN <SEP> OC-NIIn
<tb> 55 <SEP> 0 <SEP>) <SEP> &num; <SEP> yellow
<tb> <SEP> NH-OC- <SEP> O <SEP> o <SEP> CO-HN
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI29.1


<tb> <SEP> 0 <SEP> 0
<tb> <SEP> <SEP> 2 <SEP> moles <SEP> g
<tb> <SEP> Cc,
<tb> 56 <SEP> o <SEP> NH <SEP> BN <SEP> L <SEP> yellow
<tb> <SEP> Tr-Cl <SEP> ROO% CCR2DRO
<tb> <SEP> NO
<tb> <SEP> 01
<tb> <SEP> o
<tb> <SEP> O <SEP> OGH, <SEP> O <SEP> C1
<tb> <SEP> II <SEP> I <SEP> C1
<tb> <SEP> III <SEP> ¸ <SEP> ¸
<tb> 57 <SEP> <SEP> 0 <SEP> NU <SEP> NU
<tb> 57 <SEP> 1
<tb> <SEP> Tr-Cl <SEP> 0001100 <SEP> orange
<tb> <SEP> 112011
<tb> <SEP> o <SEP> NH
<tb> <SEP> II
<tb> <SEP> 6 <SEP> OCH3
<tb>
Example 58
34 parts of 2-amino-3,4-phthaloylacridone are slurried in 300 parts of dry nitrobenzene.

   The solution of 19 parts of cyanuric chloride in 100 parts of nitrobenzene is added with thorough stirring and the temperature is increased to 140-145 ". After 3 hours, the evolution of hydrogen chloride is weaker and only 25.2 parts of 5-aminoisothiazolanthrone are added and the temperature is increased to 190-195 9 Strong evolution of hydrogen chloride occurs again and the suspension gradually turns green-olive. After 3 hours, the mixture is cooled to 100 "and the asymmetric monochlorotriazine product obtained in olive leaves is isolated by filtration. It is washed with hot nitrobenzene, then with methanol and dried in vacuo at 1100
Analysis: The. N = 13.9% found. N = 13.6%
The. S = 4.5% found. S = 4.8%
The. Cl = 5.0% found.

  Cl = 5.2%
7 parts of this monochlorotriazine derivative are suspended in 100 parts of nitrobenzene, 3.5 parts of 1-salicylolylaminoanthraquinone and 0.1 part of pyridine are added and the mixture is refluxed for 10 hours. After cooling, the color becomes
EMI29.2


<tb> substance <SEP> of the <SEP> formula <SEP>
<tb> <SEP>, HNV
<tb> <SEP> / 4 <SEP> ob
<tb> <SEP> Tr-NH
<tb> <SEP> u <SEP> CONTHO
<tb> <SEP> fCOgt
<tb> <SEP> f
<tb> <SEP> 0
<tb> isolated by filtration, washed with nitrobenzene, then methanol and dried at 100 "in vacuo.



   The dye obtained in this way dyes cotton and regenerated cellulose in strong olive tones with very good fastness properties and application properties.



   From the starting materials mentioned in the table below, further asymmetric dyes with 3 different vettable anthraquinoid radicals can be prepared in the manner according to the invention.



  Example reactive component hydroxyl or color shade
Mercapto connection
EMI30.1


<tb> <SEP> OC <SEP> OH
<tb> <SEP> NR <SEP> CONH0
<tb> 59 <SEP> ¸; <SEP> v <SEP> bordo
<tb> <SEP> WITHOUT
<tb> <SEP> Tr-Cl
<tb> <SEP> BN
<tb> <SEP> II
<tb> <SEP> Cli
<tb> <SEP> OC- (7
<tb> <SEP> NH <SEP> OH
<tb> <SEP> CONR
<tb> 60 <SEP> t) <SEP> W <SEP> red-brown
<tb> <SEP> Tr-Cl
<tb> <SEP> NHo <SEP> d
<tb> <SEP> 1
<tb> <SEP> 3
<tb> Example reactive component hydroxyl or color shade
Mercapto connection
EMI31.1


<tb> <SEP> SH <SEP> O
<tb> <SEP> 0ss0 <SEP>) CONR
<tb> 61 <SEP> RO <SEP> Ï <SEP> olive
<tb> <SEP> olive
<tb> <SEP> Tr-Cl
<tb> <SEP> NH
<tb> <SEP> y
<tb> <SEP> HN <SEP> OK
<tb> <SEP> 0
<tb> <SEP> RNo <SEP> II
<tb> <SEP> 0
<tb> <SEP> 62 <SEP> O <SEP> green
<tb> <SEP> Tr-Cl
<tb> <SEP> NH
<tb> <SEP> 8
<tb> <SEP> li
<tb> <SEP> 0
<tb> Example reactive component hydroxy or

   hue
Mercapto connection
EMI32.1


<tb> <SEP> n <SEP> OH
<tb> <SEP> 41 <SEP> d1
<tb> <SEP> 0
<tb> 63 <SEP> Tr-Cl <SEP> yellow-green
<tb> <SEP> o
<tb> <SEP> 0
<tb> <SEP> I <SEP> o
<tb> <SEP> RN
<tb> <SEP> OCç
<tb> <SEP> OH
<tb> <SEP> lolBt <SEP> to <SEP> CO <SEP>
<tb> 1 <SEP> II
<tb> <SEP> ii
<tb> <SEP> 64 <SEP> (<SEP> X <SEP> 1l <SEP> blue-green
<tb> <SEP> 6 '<SEP> 0
<tb> <SEP> NO
<tb> <SEP> tr-NH <SEP> 9
<tb> <SEP> v <SEP> UV
<tb> <SEP> 0
<tb> <SEP> OH
<tb> <SEP> R
<tb> <SEP> NH <SEP> X <SEP> green-yellow
<tb> <SEP> NR <SEP> II
<tb> <SEP> Tr-Cl <SEP> II
<tb> <SEP> 0 <SEP> NR <SEP> N
<tb> <SEP> + <SEP> Cl
<tb> textile dyeing
1 part of dye is vat with 10 parts by volume of 360Be 'sodium hydroxide solution and 5 parts of sodium hydrosulfite in 200 parts of water at 50 to 70 degrees.

  The above stock vat is added to a dyebath which contains, in 2000 parts of water, 5 parts by volume of sodium hydroxide solution of 36 "Be and 3.7 parts of sodium hydrosulfite, and 100 parts of cotton are added at 40. After 10 minutes, 15 parts of sodium chloride are added to, after 20 minutes another 15 parts and stains at 40 for 45 minutes.



  The cotton is then squeezed off, oxidized and finished as usual.



  Pigment coloring
5 parts of the dye mentioned in Example 20 are mixed with 95 parts of dioctyl phthalate and ground in a ball mill until the dye particles are smaller than 3 u.



   0.8 part of this dioctyl phthalate paste is mixed with 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate and 0.1 part of cadmium stearate and then rolled out on a two-roll mill at 140 "for 5 minutes.

 

   A yellow-colored material with good migration properties and good lightfastness is obtained.



   If the reaction products of Examples 28, 34, 41 or 45 are used instead of the above-mentioned dye and the rest of the procedure is the same, materials with similarly good migration and lightfastness properties are obtained.



  Paint coloring
40 parts of a nitrocellulose lacquer, 2.375 parts of titanium dioxide and 0.125 part of the dye from Example 3 are ground for 16 hours in a rod mill. The paint obtained in this way is applied in a thin layer to an aluminum foil. It gives an orange coloration of excellent lightfastness.



   Orange or red paint colors with similarly good lightfastnesses are obtained when using the dyes according to Example 27 or 37.

 

Claims (1)

PATENT CLAIM Process for the preparation of vat dyes of the general formula EMI33.1 wherein A = connectable polycyclic quinone, X = oxygen or sulfur, B = 6-membered heterocycle with 2 to 3 nitrogen atoms, which optionally contains further fused carbocyclic rings, and is optionally substituted, R = aromatic radical in which the -X-B substituent is in the o or m position to the amide group, Z = hydrogen or -X-B, a = hydrogen or EMI33.2 characterized in that a hydroxy or mercapto compound of the formula H-X a'A-NHCO-R <(5), Z 'where A, R and X are the same as above, a' is hydrogen -NHCO-R <or a radical of the formula -NHCO-Rc z, and Z 'is hydrogen or -X-H, with a colorless or colored heterocyclic reactive component of the formula EMI33.3 where B has the meaning given and Yo, Y2 and Y3 are substituents, at least one of which is an easily split off radical, condensed. SUBCLAIMS 1. The method according to claim, characterized in that if the radical B in formula (6) contains further cleavable groups, it is reacted further with polycyclic quinones or aromatic compounds which contain condensable groups. 2. The method according to claim and dependent claim 1, characterized in that one of a reactive component of the formula EMI33.4 emanates from what K = -NH-aryl-NH-, -X-aryl-X, NH-aryl-N = N aryl-NH-, -O-aryl-N = N-aryl-O, -NH-aryl-CH = CH -Aryl-NH-, -O-Aryl-CH = CH-Aryl-O-, -NH-Anthraquinonyl-NH-, and in which B, Y3 and Y2 are as indicated Have meaning. 3. The method according to claim and dependent claim 1, characterized in that one of hydoxy or mercapto compounds of the formula X-H a'-ANHrn-R <and starts from heterocyclic reactive radicals of the formula given which have at least one easily split off halogen atom and optionally one or two of the following substituents: Halogen, alkyl, aryl, aryloxy, arylamino, -NH-aryl- N = N-aryl, -O-aryl-N = N-aryl, -NH-aryl-CH = CH- aryl, -O-aryl-CH = CH-Aryl, -NH-A1, -X-A1, -NH- -CONHAt or CO-NH-A1, where X, R, A, Z 'and a' are the same as above and A1 is a linkable polycyclic quinone, where A and Al can be the same or different. 4. The method according to claim and dependent claim 1, characterized in that one of reactive components of the formula EMI33.5 starts, where a) Y '= halogen, Y'2 and Y'3 = -X-A1 or -NH-A1; b) Y'l = halogen, = = low molecular weight alkyl, aryl, aryloxy, Arylamino, phenylazophenylamino, phenylazo phenyloxy, stilbenyloxy, stilbenylamino, -X-A1 or -NH-A1; c) Y ', and Y'2 = halogen, Y'3 = low molecular weight alkyl, aryl, aryloxy, acylamino, phenylazophenylamino, phenylazo phenyloxy, stilbenyloxy, stilbenylamino, -X-A1 or -NH-A1; ; d) Y'1 and Y'2 = halogen 1 = EMI34.1 e) Y'3, Y'2 and Y'3 = halogen, and in which X, A and K have the meanings given for formula (1) and (7). 5. The method according to dependent claim 4, characterized in that the hydroxy or mercapto compound is reacted with the reactive component in a ratio such that one or at most two radicals of the form] -X-R-CONH-A are introduced per triazinyl radical. 6. The method according to claim and dependent claim 1, characterized in that one of reactive components of the formula EMI34.2 emanates from what R1 = hydrogen, halogen, low molecular weight alkyl, aryl, nitro or cyano and Y "1, Y" 2 and Y ", halogen or one of them is a radical of the formula CO-NH-A1 or -NH- -CO-NH-A1 , or where R1 and Y3 together form a benz ring optionally substituted by a group of the formula -CO-NH-A1, one Y "is halogen and the other is halogen, low molecular weight alkyl, aryl, arylamino, -NH-A1 or -X-A1 is where A1 is a linkable radical. 7. The method according to claim and dependent claim 1, characterized in that the heterocyclic reactive component on the one hand with a hydroxy or mercapto compound of the formula A-NHCO-R-X-H and on the other hand with a quinone of the formula H2N-A1 or X-A1, where A and A1 are different linkable radicals. 8. The method according to claim and dependent claim 1, characterized in that one starts from a hydroxy or mercapto compound of the formula given in which R is a benzene or naphthalene radical which may be substituted by low molecular weight alkyl, aralkyl, aryl, acyl, acylamino or halogen can. 9. The method according to claim and dependent claim 1, characterized in that one starts from compounds of the formulas given in which the linkable radicals A and A1 are different, optionally substituted anthraquinon-1-yl-, anthraquinon-2-yl-, 3, 4 -Phthaloylacridon-2-yl or 3,4-phthaloylacridon-8-yl radicals. 10. The method according to dependent claim 9, characterized in that one starts from compounds in which the anthraquinone or phthaloylacridone radical is substituted with halogen, low molecular weight alkyl, aryl, alkoxy, aryloxy, aryl mercapto, arylamino and, in particular, acylamino and acyl. 11. The method according to claim and dependent claim 1, characterized in that a compound of the formula EMI34.3 with a triazine of the formula EMI34.4 in which U = low molecular weight alkyl, aryl, -NH-A1, -O-A1, where A and A1 are linkable radicals, condensed in a ratio of 2: 1. 12. The method according to claim and dependent claim 1, characterized in that a compound of the formula EMI34.5 with a triazine of the formula EMI34.6 in which U '= low molecular weight alkyl, aryl, halogen or -NH-A1 and in which A and A1 are viable radicals, in a ratio of 1: 1. 13. The method according to claim and dependent claim 1, characterized in that a connection of the EMI34.7 with a reactive component of the formula EMI35.1 where K '= -NH-aryl-NH-, -O-aryl-O-, EMI35.2 EMI35.3 EMI35.4 is, and where A is the same as above, in a ratio of 4: 1. 14. The method according to claim and dependent claim 1, characterized in that an inert gas stream is passed through the mixture during the condensation.