DE3625576A1 - Basic monoazo or disazo compounds containing sulfo groups - Google Patents

Abstract

Basic monoazo or disazo compounds which contain a sulfo group and which are metal-free or exist as 1:1 copper complexes conform, in the metal-free form, to the formula I <IMAGE> in which the individual symbols are as defined in Claim 1 and also their salts, including internal salts, and also solid and liquid formulations. The compounds (as water-soluble salts) and their formulations are used for the dyeing or printing of cationically colourable substrates such as organic hydroxyl- or nitrogen-containing textile substrates consisting of or containing cellulose, especially cotton, or leather or, in particular, paper. They are also suitable for colouring glass or glass products and can be used in addition for the production of inks in a manner known per se.

Description

The invention relates to basic ones containing a sulfonic acid group Monoazo or disazo compounds that are metal-free or as 1: 1 copper complexes are present, as well as salts thereof, processes for Preparation of these compounds and their use as dyes.

The invention accordingly relates to compounds of the formula I in metal-free form or in the form of the 1: 1 copper complex, wherein
n for 0 or 1,
R ₁ , independently of one another, is hydrogen, halogen, nitro, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl, -SO ₂ NR ₃ R ₄ , -CONR ₄ C ₆ H ₅ or -NHCOC ₆ H ₅ ,
R ₂ for hydrogen, hydroxy, halogen, nitro, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl or -NHCONR ₃ R ₄ ,
R ₃ , independently of one another, is hydrogen, C _1-4 alkyl or C _1-4 alkyl monosubstituted by hydroxy, halogen, cyano or C _1-4 alkoxy,
R ₄ , independently of one another, is hydrogen or C _1-4 alkyl,
Q, independently of one another, for C _2-6 alkylene, which can be interrupted by -O-, -S-or -N (R ₄ ) -, or for C _3-6 alkylene substituted by one or two hydroxyl groups or for - * NHCOCH ₂ -, where the atom marked * is bound to the -NR ₄ radical,
X for -NR ₅ R ₆ or -N⊕R ₇ R ₈ R ₉ An⊖,
R ₅ and R ₆ , independently of one another, are hydrogen, C _1-6 alkyl, C _2-6 alkyl monosubstituted by hydroxy or cyano; Phenyl or phenyl- C _1-4 alkyl, the phenyl radical of which is unsubstituted or has 1 to 3 substituents from the series consisting of chlorine, C _1-4 alkyl and C _1-4 alkoxy; or represent C _5-6 cycloalkyl which is unsubstituted or substituted by 1 to 3 C _1-4 alkyl groups, or R ₅ and R ₆ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring form, which includes 1 to 3 heteroatoms and which is unsubstituted or substituted by one to three groups from the series C _1-4 alkyl and C _2-4 alkyl monosubstituted by hydroxy or amino,
R ₇ and R ₈ , independently of one another, have one of the cyclic or non-cyclic meanings of R ₅ and R ₆ except hydrogen and
R _{9 is} C _1-4 alkyl or benzyl, or
R ₇ , R ₈ and R ₉ together with the N atom to which they are attached form a pyridinium group which is unsubstituted or substituted by one or two methyl groups, and
An⊖ stands for a non-chromophoric anion, and the salts of the compounds of the formula I, internal salts being included.

₂ bearing phenyl radical is located in the groups R ₁ and R Eineder groups R ₁ and R ₂ in the ortho-position to the radical = N-⁻CN Naphtholund provides a metallizable group such as hydroxy or C _1-4 alkoxy, or represents hydrogen or halogen cleavable , a compound of the formula I can also be in the form of a 1: 1 copper complex in which the copper is bonded via two oxygen bridges.

However, the compounds of the formula I are preferably metal-free. N is preferably 0. Metal-free compounds of the formula I in which n is 0 are particularly preferred.

Halogen generally preferably means fluorine, chlorine or bromine preferably chlorine or bromine, particularly preferably it means chlorine.  

Any alkyl or alkylene group provided in a compound of formula I. Unless otherwise stated, it can be linear or branched be.

Furthermore, in a hydroxyl- or alkoxy-substituted alkyl or alkylene group which is bonded to an N atom, the hydroxyl or alkoxy group is located on another atom than the C ₁ atom; in addition, in the case of disubstitution, two hydroxyl groups are not on the same carbon atom.

R ₁ or R ₂ as halogen preferably represents chlorine; as alkyl or alkoxy, it preferably contains 1 or 2 carbon atoms and in particular represents methyl or methoxy; as the acylamino group it is preferably acetylamino.

R ₃ as alkyl preferably contains 1 or 2 carbon atoms, more preferably it means methyl; as substituted alkyl it is preferably linear or branched C _1-3 alkyl and preferably contains a substituent from the series hydroxy, chlorine and cyano, of which hydroxy is particularly preferred.

R ₃ preferably represents R _3a , each R _3a , independently of one another, being hydrogen, methyl, ethyl or -CH ₂ CH ₂ OH; R ₃ particularly preferably represents hydrogen.

R ₄ as alkyl preferably means methyl. R ₄ preferably stands for R _4a , each R _4a independently of one another meaning hydrogen or methyl, particularly preferably R ₄ stands for hydrogen.

R ₁ preferably denotes R _1a , each R _1a , independently of one another, for hydrogen, chlorine, nitro, C _1-2 alkyl, C _1-2 alkoxy, -NHCOCH ₃ , -SO ₂ NR _3a R _4a , -CONR _4a C ₆ H ₅ or -NHCOC ₆ H ₅ ; more preferably R _1b , each R _1b , independently of one another, being hydrogen, chlorine, nitro, methyl, methoxy or -NHCOCH ₃ ; more preferably R _1c , where each R _{1c is} independently hydrogen, methyl or methoxy; R ₁ particularly preferably represents hydrogen.

R ₂ preferably denotes R _2a as hydrogen, hydroxy, C _1-2 alkyl, C _1-2 alkoxy, -NHCOCH ₃ or -NHCONH ₂ ; more preferably R _2b as hydrogen, hydroxy, C _1-2 alkyl or C _1-2 alkoxy; more preferably R _2c as hydrogen, methyl or methoxy. R ₂ particularly preferably denotes methoxy.

The sulfo group in the naphthol residue is preferably in 3-position and the substituted amino group preferably in 6 position.

If Q stands for branched alkylene, it preferably means a group

If the alkylene group is interrupted by a heteroatom, it preferably stands for - (CH ₂ ) _2-3 -Y- (CH ₂ ) _2-3 - with Y as -O- or -N (R _4a ) -; in particular it stands for - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -.

Q is preferably Q _a , each Q _a , independently of one another, C _2-4 alkylene, monohydroxy-substituted C _3-4 alkylene or the group - (CH ₂ ) _2-3 -Y- (CH ₂ ) _2-3 - means; more preferred for Q _b , each Q _b , independently of one another, - (CH ₂ ) _2-3 -, or - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -; particularly preferred for Q _c as - (CH ₂ ) _2-3 - or or if X ≠≠ NH ₂ , for Q _d as - (CH ₂ ) _2-3 -.

R ₅ or R ₆ as alkyl preferably represents C _1-4 alkyl, in particular methyl or ethyl. As substituted alkyl it is preferably ethyl or propyl monosubstituted by cyano or hydroxyl with the substituent in the 2- or 3-position.

In a phenyl or phenylalkyl group as R ₅ or R ₆ , the phenyl ring is preferably unsubstituted or substituted by one or two groups from the series chlorine, methyl and methoxy; the phenyl ring is even more preferably unsubstituted. Phenylalkyl is particularly preferably benzyl, the phenyl radical of which is unsubstituted.

A cycloalkyl group as R ₅ or R ₆ is preferably cyclohexyl; Alkyl-substituted cycloalkyl is preferably cyclohexyl substituted by one to three methyl groups.

If R ₅ and R ₆ form a ring together with the N atom to which they are attached, this ring preferably represents a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine radical. R is particularly preferred ₅ and R ₆ identical. R ₅ and R ₆ , independently of one another, preferably represent R _5a and R _6a in the meaning of hydrogen, C _1-6 alkyl, hydroxy-C _2-3 alkyl or benzyl, or R _5a and R _6a together with the N- Atom to which they are attached, a pyrrolidine, piperidine, morpholine, piprazine or N-methylpiperazine ring. More preferably they represent R _5b and R _6b , where R _5b and R _{6b are} identical and represent hydrogen, C _1-4 alkyl or 2-hydroxyethyl, or R _5b and R _6b together with the N atom to which they are attached form , a piperidine, morpholine, piperazine or N-methylpiperazine ring.

R ₅ and R ₆ are particularly preferably R _5c and R _6c , where R _5c and R _{6c are} identical and denote hydrogen, methyl or ethyl. R ₇ and R ₈ are preferably identical.

R ₇ and R ₈ , independently of one another, preferably represent R _7a and R _8a in the meaning of C _1-6 alkyl or hydroxy-C _2-3 alkyl, or R _7a and R _8a together with R ₉ and the N atom form to which R _7a , R _8a and R _{9 are} bound, an unsubstituted or substituted by one or two methyl groups pyridinium group.

They are more preferably R _7b and R _8b , where R _7b and R _{8b are} identical and are C _1-4 alkyl or 2-hydroxyethyl, or R _7b and R _8b form together with R ₉ and the N atom R _7b , R _8b and R _{9 are} bonded, a pyridinium group which is unsubstituted or monosubstituted by methyl. R ₇ and R ₈ are particularly preferably R _7c and R _8c , where R _7c and R _{8c are} identical and denote methyl or ethyl.

An alkyl group for R ₉ preferably denotes methyl or ethyl, in particular methyl. R ₉ preferably denotes R _9a as methyl, ethyl or benzyl, or R _9a together with R _7a and R _8a and the N atom to which R _7a , R _8a and R _{9a are} bonded forms a pyridinium group which is unsubstituted or through one or two methyl groups is substituted. It is more preferably R _9b as methyl, ethyl or benzyl, in particular methyl, or R _9b together with R _7b and R _8b and the N atom to which R _7b , R _8b and R _{9b are} bonded forms a pyridinium group which is unsubstituted or monosubstituted by methyl.

X preferably represents X _a as -NR _5a R _6a or -N⊕R _7a R _8a R _9a An⊖, more preferably X _b as -NR _5b R _6b or -N⊕R _7b R _8b R _9b An⊖, in particular preferred for X _c as -NR _5c R _6c .

Preferred compounds correspond to formula Ia in metal-free form and salts thereof, including internal salts.

Metal-free compounds of the formula Ia in which
(1) R _1b , independently of one another, stands for R _1c ;
(2) R _{1b represents} hydrogen and R _2c in the meaning of methoxy is in the o or p position (if n = 0), based on the azo group;
(3) those of (2), in which n is 0 and R _{2c is bonded} as methoxy in the o or p position, in particular in the o position, based on the azo group;
(4) -Q _b -X _{b represents} -Q _c -X _c ;
(5) those of (4), wherein -Q _b -X _{b is} -Q _d -X _c ;
(6) those from (1) to (4), in which -Q _b -NH _{2 are} -Q _c -NH ₂ and -Q _b -X _{b are} -Q _c -NH ₂ and these groups are -Q _c -NH _{2 are} identical.

In a compound of formula I the sulfone group is normally ionized and is present as SO ₃ ⊖. It forms an inner salt either with the basic amino group -Q-NH ₂ or with the basic amino group -QX. The amino group not included in the inner salt is capable of external salt formation, such as. B. of acid addition salts by reaction with suitable acids; as an acid, for example, dilute mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid, or preferably organic acids such as formic acid, acetic acid, methoxyacetic acid, lactic acid, citric acid, glycolic acid or methanesulfonic acid. X is a quaternary ammonium salt before, the anion An⊖ can be any non-chromophoric organic or inorganic anion, as is common, for example, in the field of basic dye chemistry. Suitable anions are e.g. B. chloride, bromide, iodide, lactate, acetate, propionate, citrate, oxalate, malate, maleate, succinate, methyl sulfate, ethyl sulfate and hydrogen sulfate.

The compounds of formula I are prepared by the diazonium salt of the amine of formula II, wherein R ₁ , R ₂ and n are as defined above, with a compound of the formula III, wherein R ₃ , R ₄ , Q and X are as defined above, and if desired, a metal-free compound of the formula I thus obtained is converted into the 1: 1 copper complex by reaction with a copper-donating compound.

Diazotization and coupling are analogous to methods known per se carried out. The coupling advantageously takes place in an aqueous medium a temperature range from 0 ° to 60 ° C, preferably at 20-50 ° C, and at a pH in the range 3-9, preferably at pH 4-6.

The conversion of a metal-free compound of the formula I, which bears hydrogen, halogen, hydroxy or C _1-4 alkoxy in an ortho position relative to the carbon atom of the group GruppeCN = N-naphthol, into the 1: 1 copper complex in a manner known per se, by allowing the metal-free compound of the formula I to act on the amount of a copper-donating compound corresponding to at least one equivalent of copper (based on one equivalent of monoazo compound).

For 1: 1 coppering, either the oxidative is expediently used Copper, preferably in a temperature range of 40-70 ° C and at pH 4-7 in the presence of copper (II) salts or with copper powder in Presence of hydrogen peroxide or another conventional oxidizing agent, on or preferably the demethylating copper in Presence of copper (II) salts, preferably in the pH range 2-6 at elevated to cooking temperature with the addition of metal acetates, or in the pH range from 6-11 at elevated to cooking temperature with addition of ammonia solution or aliphatic amines.

The compounds of formula I obtained can be known per se Be isolated from the reaction mixture.

Compounds of the formula I which contain free basic groups can by sales with one of the inorganic or organic acids wholly or only partially in a water-soluble Salt form are transferred.

The starting compounds, amines of the formula II are either known or can be obtained analogously to processes known per se from known starting materials. The compounds of the formula III are obtained by gradually replacing the chlorine atoms in cyanuric chloride, in the 1st and 2nd stages by reaction with the diamine of the formula IV and V, wherein R ₄ , Q and X are as defined above.

The 1st and 2nd stages can be contracted to one stage if identical diamine residues are to be introduced. Then you work Appropriately at temperatures of 0-30 ° C and preferably at pH 4-6.

If different diamine residues are to be introduced, the first Expediently chosen the stage diamine, which has a higher selectivity for condensation. For both stages, the usual ones Condensation temperatures applied, the reaction medium is appropriate acidic with a maximum pH of 7.

The final 3rd stage is the condensation with the aminonaphthol Component made at elevated temperature and a pH at 2-3.

The starting compounds of formulas IV and V are either known or can be analogous to known processes from known starting materials be preserved.

The compounds of formula I, in the form of the acid addition salts or as quaternary ammonium salts, are dyes; they are used for dyeing cationically dyeable materials such as uniform or copolymers of acrylic nitrile, acid modified Polyesters; Leather, cotton, bast fibers such as hemp, flax, sisal, Jute, coconut fiber and straw; Regenerated cellulose fibers, glass fibers and Paper.

The metal-free and metal-containing compounds according to the invention are used, for example, for dyeing or printing hydroxy group or nitrogen-containing organic substrates, such as fibers, threads or textiles made therefrom, which are made of cellulose material, e.g. B. Cotton, exist or contain them, according to known Methods. Cotton is preferably made using the usual pull-out method colored, for example from a long or short fleet and at Room to cooking temperature. The printing is done by impregnation with a printing paste, which is compiled according to a known method becomes.  

The compounds can also be used for dyeing or printing leather, also advantageous for low-affinity leather types, which are retanned vegetably were, as well as for coloring glass or glass products, the different can have chemical composition, per se known methods are used. In addition, the connections used in the manufacture of inks according to a known method will.

However, the compounds of the formula I are particularly suitable for Dyeing or printing paper, e.g. B. for the production of glued or unsized, wood-free or wood-containing paper in bulk like in the size press. But you can also use it to dye paper the immersion process. The dyeing and printing of Paper is made using known methods.

The dyeings and prints thus obtained and in particular the paper dyeings and paper prints show good fastness properties.

The compounds of formula I can also be in the form of coloring preparations be used. Processing in storage-stable liquid, preferably liquid-aqueous coloring preparations can be on well-known In this way, advantageously by dissolving in suitable solvents such as mineral acids or organic acids, e.g. B. hydrochloric acid, sulfuric acid, Phosphoric acid, formic acid, acetic acid, lactic acid, glycolic acid, Methanesulfonic acid and citric acid; furthermore formamide, Dimethylformamide, urea; Glycols and their ether, dextrin or Addition products of boric acid with sorbitol mixed with water are used, optionally with the addition of an auxiliary, e.g. B. a stabilizer. Such preparations can, for example prepared as described in French Patent No. 15 72 030 will.

A favorable composition of such liquid preparations is, for example, the following (parts mean parts by weight):
100 parts of a compound of formula I as an acid addition salt or as a quaternary ammonium salt,
0-10, preferably 0-1 parts of an inorganic salt,
1-100 parts of an organic acid such as formic, vinegar, lactic, citric acid etc.,
100-800 parts of water,
0-500 parts of a solubilizer (e.g. glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, hexylene glycol; glycol ethers such as methyl cellosolve, methyl carbitol, butyl polyglycol; urea; formamide and dimethylformamide).

Likewise, the compounds of formula I in a manner known per se are processed into solid, preferably granulated, dye preparations, advantageous by granulation as in the French patent No. 15 81 900.

A favorable composition for solid preparations is, for example, the following (parts mean parts by weight):
100 parts of a compound of formula I as an acid addition salt or as a quaternary ammonium salt,
0-10, preferably 0-1 parts of an inorganic salt,
0-800 parts of an adjusting agent (preferably non-ionic such as dextrin, sugar, glucose and urea).

The solid preparation can still contain up to 10% residual moisture to be available.

The compounds of formula I (in the corresponding salt form) good solubility properties, in particular they are notable for good solubility in cold water. Because of their high substantivity draw out the dyes practically quantitatively and thereby show good build ability. In the production of both glued and unsized Paper, the waste water is practically colorless or only marginal stained. The dyes can directly from the pulp, i. H. without  previous dissolution, added as dry powder or granules, without a decrease in the brilliance or a decrease in the Color yield occurs. The glued paper color shows compared to the unsized no starch drop. With the dyes can also in Soft water can be colored with full color yield. The dyes mottled on paper do not stain, they do not tend to two-sided paper and are largely insensitive to filler and pH Fluctuations.

The paper dyeings produced with the compounds of the formula I. are clear and brilliant and are characterized by remarkable light fastness out; after prolonged exposure the shade changes tone-in Volume. The colored papers show high fastness to bleeding, they are very good wet fastness not only against water but also against milk, Fruit juices, sweetened mineral water, tonic water, soapy water, saline, Urine etc .; they also have good alcohol fastness. Paper that has been colored with the new compounds is both oxidative as well as reductively bleachable, which is for the reuse of Waste and waste paper is important.

Fibers that contain wood pulp are described with the Dyes dyed in good and level quality. Furthermore, the dyes for the production of coated Find paper that is used in a manner known per se. Because of their tendency to pigmentation becomes a suitable filler, e.g. B. kaolin, stained with the dyes and with this mass Paper is given a one-sided surface coating. The compounds of formula I also show good combination behavior. The with the described dyes in combination with dyes, which have comparable coloring properties Dyes have good fastness properties.

The following examples serve to illustrate the invention. In the examples, all parts mean parts by weight or volume and all percentages by weight or volume, the temperatures are in Celsius degrees indicated.  

example 1

a) Diazotization
10.86 parts (0.088 mol) of 2-amino-1-methoxybenzene are introduced into 40 parts of ice and 25 parts of 30% hydrochloric acid. A solution consisting of 6.1 parts (0.088 mol) of sodium nitrite in 25 parts of water is added dropwise to this amine solution at 0-5 °.

b) Production of the coupling component
46 parts of 30% strength hydrochloric acid are added dropwise to a template consisting of 14.8 parts (0.2 mol) of 1,2-diaminopropane and 100 parts of ice in order to return the pH to the range 3 to 5. The temperature is set to 0-3 °, then 18.4 parts (0.1 mol) of cyanuric chloride are introduced. The mixture is homogenized by stirring.

During a reaction time of 4 to 5 hours, 53 parts 30% sodium hydroxide solution metered in so slowly that the pH at 5-5.5 is held. While adding the first half of the Sodium hydroxide solution (approx. 27 parts) must not have a temperature of 12 ° a pH of 5 should be maintained at the same time. When all of the sodium hydroxide has been added (end of reaction) a pH of 5.5 and a temperature of 25-30 ° should be reached be. The cloudy solution of the reaction product, which is not a monosubstituted Cyanuric chloride contains more, after the addition of Filter earth clarified.

The clear solution is mixed with 21.5 parts (0.09 mol) of 2-amino-5-hydroxy- naphthalene-7-sulfonic acid added. The suspension obtained is heated to 80 °, the pH with 13 parts of 30% sodium hydroxide solution is held at 2.2-2.6. After an hour at 80 ° the implementation is finished.  

c) clutch
The coupling component solution obtained under b) is cooled to 40-45 ° and mixed with 34 parts of sodium acetate, the pH rising to 4-5. At 40 ° the diazo solution obtained according to a) is then regularly added dropwise in 15 minutes and then 38 parts of 17% sodium hydroxide solution over two hours so that the pH rises to 5. The resulting dye suspension is then adjusted to pH 8-9 with sodium carbonate and filtered. The dye of the formula which is very soluble in dilute acids, preferably organic acids such as formic, lactic, acetic and methoxyacetic acid. The solution dyes paper in brilliant scarlet shades. The dyeings obtained have excellent light and wet fastness properties (against water, alcohol, milk, soapy water, sodium chloride solution, tonic water, urine, etc.) and have excellent behavior with regard to bilateral properties, and they are also easily bleachable.

Example 2

Manufacture of the coupling component
18.4 parts (0.1 mol) of cyanuric chloride are stirred in 20 parts of water and 50 parts of ice. At 0-5 ° a solution of 13 parts (0.1 mol) of 3-N, N-diethylaminopropylamine, 50 parts of ice and about 23 parts of 30% hydrochloric acid, which has a pH of 5 to 6, in 10 minutes dripped. Then the pH is adjusted to 6-6.5 with 20% sodium carbonate solution and kept at 0-5 ° for four hours. A white suspension of the monosubstituted cyanuric chloride is obtained.

An amine solution of pH 6 consisting of 6 parts (0.1 mol) is then Ethylenediamine, 40 parts of ice and approx. 20 parts of 30% hydrochloric acid in Added dropwise for 10 minutes. The pH is kept at 6 for ten hours held, during this time the temperature rises very slowly Room temperature (20-25 °).

The somewhat cloudy solution of the disubstituted cyanuric chloride is clarified by filtration and with 21.5 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid transferred. The mixture is heated to 80 ° and held there for one hour Temperature, the pH with 20% sodium carbonate solution always at 2.5 is held.

The coupling component thus produced is reacted with the diazo solution obtained in Example 1 under a) analogously to the method described in Step c) of Example 1. The dye of the formula which, dissolved in an organic acid, colors paper in a brilliant scarlet shade. The dyeings show very good light and wet fastness and are very bleachable.

Example 3-45

Analogously to the method described in Examples 1 and 2, further compounds of the formula I can be prepared using the appropriate starting materials. The compounds correspond to the formula (A) for which the symbols are listed in the following table. In the last column I, the shade of the color, as is obtained with these dyes on bleached cellulose, is given; it means:
a = scarlet
b = red
c = bluish red
d = yellow-orange.

The paper dyeings obtained have very good light and wet fastness properties and are easy to bleach.

In the table, An⊖ stands for an anion from the reaction medium.  

Table / compounds of the formula (A)

Example 46

The wet presscake obtained in Example 1 after the filtration, which corresponds to 52 parts of pure dye, is stirred in 500 parts of water and mixed with 20 parts of formic acid. The dye completely dissolves by heating to 80 °. The dye solution is evaporated to dryness, and the dye salt of the formula is obtained in powder form, which has good cold water solubility.

Instead of the formic acid used in Example 46, salt formation can be carried out also other organic acids such as lactic, acetic and methoxyacetic acid or mixtures thereof can be used.

The dyes of Examples 2-45 can be used in an analogous manner Acid addition salts are transferred.

Example 47

The moist press cake obtained according to Example 1 is at room temperature in a solution of 20 parts dextrin, 20 parts formic acid and 500 parts of water and dissolved by heating to 80 °. Atomized drying gives red granules, which dissolve in Dissolve the water very well and dye the paper in a scarlet shade.

Analogously, the dye salts of Examples 2-45 can be processed into granules will.  

Example 48

The moist press cake obtained according to Example 1 is divided into 20 parts Formic acid, 20 parts of lactic acid and 250 parts of water entered and dissolved while heating to 70 °. The solution is then at 20 Parts of ethylene glycol are added and then with the addition of a filter aid clarified. The filtrate is left at room temperature cool and adjust it to 520 parts with water. You get one Dye solution that can be kept for several months at room temperature and directly or after dilution with water to dye paper (in scarlet Nuance) can be used.

Analogously, the dye salts of Examples 2-45 can be converted into stable liquid aqueous dye preparations are processed.

Possible applications of the dyes described and the liquid aqueous coloring preparations are described in the following regulations illustrated:

Staining instructions A

In a Dutch company, 70 parts of chemically bleached sulfite cellulose made of softwood and 30 parts of chemically bleached sulfite cellulose Birchwood ground in 2000 parts of water. One sprinkles to this mass 0.2 part of the dye from Example 1 or 2 (as acid addition salt, e.g. B. according to Example 46) or are 2.0 parts of the liquid dye preparation according to example 48. After 20 minutes of mixing time made from paper. The absorbent obtained in this way Paper is colored scarlet in all cases. The wastewater is practically colorless.

Dyeing Instructions B

0.3 part of the dye powder from Example 1 or 2 (as acid addition salt according to Example 46) in 100 parts of hot water dissolved and cooled to room temperature. One gives the solution to 100 Parts of chemically bleached sulfite cellulose with 2000 parts  Water was ground in a Dutch. After mixing for 15 minutes is glued in the usual way with resin glue and aluminum sulfate. Paper made from this material shows one each scarlet shade and has good wastewater and wet fastness properties.

Staining instructions C

An absorbent paper web made of unsized paper is drawn at 40-50 ° through a dye solution of the following composition:
0.3 part of the dye from example 1 or 2 (as acid addition salt, for example according to example 46) or 3 parts of the liquid preparation from example 48,
0.5 parts starch and
99.0 parts water.

The excess dye solution is pressed off by two rollers. The dried paper web is colored scarlet red.

In an analogous manner as specified in regulations A to C can also with the dyes of Examples 3-45 or preparations thereof according to Example 47 or 48 are colored. The paper stains obtained have a high level of authenticity.

Dyeing Instructions D

0.2 parts of the dye from Example 1 as an acid addition salt, for. B. according to Example 46 are softened water at 40 ° in 4000 parts solved. 100 parts of pre-wetted cotton fabric are brought into the bathroom and heats to boiling temperature in 30 minutes. The bathroom will kept at boiling for one hour, taking from time to time Time the evaporated water is replaced. Then the coloring is made removed from the liquor, rinsed with water and dried. The Dye absorbs onto the fiber practically quantitatively; the dye bath is almost colorless. A scarlet color of good quality is obtained Light fastness and good wet fastness.  

Analogously, the dyes of Examples 2-45 for dyeing cotton be used.

Dyeing Instructions E

100 parts of freshly tanned and neutralized chrome grain leather in a fleet of 250 parts of water at 55 ° and 0.5 parts of the after Example 1 prepared dye (as acid addition salt) during Tumbled in the barrel for 30 minutes and in the same bath with 2 parts of one anionic fat lickers based on sulfonated tran based for another 30 Minutes treated. The leathers are dried in the usual way and mangled. You get no matter dyed leather in a scarlet shade.

Other low-affinity, vegetable retanned leather can also be used be dyed according to known methods.

The dyes of Examples 2-45 can be used in an analogous manner will.

Claims (20)

1. Compounds of formula I in metal-free form or in the form of the 1: 1 copper complex, wherein
n for 0 or 1,
R ₁ , independently of one another, is hydrogen, halogen, nitro, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl, -SO ₂ NR ₃ R ₄ , -CONR ₄ C ₆ H ₅ or -NHCOC ₆ H ₅ ,
R ₂ for hydrogen, hydroxy, halogen, nitro, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl or -NHCONR ₃ R ₄ ,
R ₃ , independently of one another, is hydrogen, C _1-4 alkyl or C _1-4 alkyl monosubstituted by hydroxy, halogen, cyano or C _1-4 alkoxy,
R ₄ , independently of one another, is hydrogen or C _1-4 alkyl,
Q, independently of one another, for C _2-6 alkylene, which can be interrupted by -O-, -S-or -N (R ₄ ) -, or for C _3-6 alkylene substituted by one or two hydroxyl groups or for - * NHCOCH ₂ -, where the atom marked * is bound to the -NR ₄ radical,
X for -NR ₅ R ₆ or -N⊕R ₇ R ₈ R ₉ An⊖,
R ₅ and R ₆ , independently of one another, are hydrogen, C _1-6 alkyl, C _2-6 alkyl monosubstituted by hydroxy or cyano; Phenyl or phenyl- C _1-4 alkyl, the phenyl radical of which is unsubstituted or carries 1 to 3 substituents from the series chlorine, C _1-4 alkyl and C _1-4 alkoxy; or represent C _5-6 cycloalkyl which is unsubstituted or substituted by 1 to 3 C _1-4 alkyl groups, or R ₅ and R ₆ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring form, which includes 1 to 3 heteroatoms and which is unsubstituted or substituted by one to three groups from the series C _1-4 alkyl and C _2-4 alkyl monosubstituted by hydroxy or amino,
R ₇ and R ₈ , independently of one another, have one of the cyclic or non-cyclic meanings of R ₅ and R ₆ except hydrogen and
R _{9 is} C _1-4 alkyl or benzyl, or
R ₇ , R ₈ and R ₉ together with the N atom to which they are attached form a pyridinium group which is unsubstituted or substituted by one or two methyl groups, and
An⊖ stands for a non-chromophoric anion, and the salts of the compounds of the formula I, internal salts being included. 2. Compounds according to claim 1, which are metal-free. 3. Compounds according to claim 1 or 2, wherein n is 0. 4. Compounds according to any one of claims 1 to 3, wherein R _{1 is} R _1a and each R _1a , independently of one another, is hydrogen, chlorine, nitro, C _1-2 alkyl, C _1-2 alkoxy, -NHCOCH ₃ , -SO ₂ NR _3a R _4a , -CONR _{4a is} C ₆ H ₅ or -NHCOC ₆ H ₅ , where R _{3a is} hydrogen, methyl, ethyl or 2-hydroxyethyl and R _{4a is} hydrogen or methyl. 5. Compounds according to any one of claims 1 to 4, wherein R _{2 is} R _2a is hydrogen, hydroxy, C _1-2 alkyl, C _1-2 alkoxy, -NHCOCH ₃ or -NHCONH ₂ . 6. Compounds according to claim 4 or 5, wherein R _{1 is} R _1b and each R _1b , independently of one another, is hydrogen, chlorine, nitro, methyl, methoxy or -NHCOCH ₃ , and R _{2 is} R _2b has the meaning of Hydrogen, hydroxy, C _1-2 alkyl or C _1-2 alkoxy. 7. Compounds according to any one of claims 1 to 6, wherein Q is Q _a and each Q _a , independently of one another, C _2-4 alkylene, monohydroxy-substituted C _3-4 alkylene or- (CH ₂ ) _2-3 -Y - (CH ₂ ) _2-3 - means where Y is -O- or -N (R _4a ) - and R _{4a is} hydrogen or methyl. 8. Compounds according to any one of claims 1 to 7, wherein X is X _a in the meaning of -NR _5a R _6a orN⊕R _7a R _8a R _9a An⊖, R _5a and R _6a , independently of one another, for hydrogen, C _1-6 alkyl, hydroxy-C _2-3 alkyl or benzyl, or
R _5a and R _6a together with the N atom to which they are attached form a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine ring,
R _7a and R _8a , independently, are C _1-6 alkyl or hydroxy-C _2-3 alkyl, and
R _{9a represents} methyl, ethyl or benzyl, or
R _7a , R _8a and R _9a together with the N atom to which they are attached form a pyridinium group which is unsubstituted or substituted by one or two methyl groups, and
An⊖ means a non-chromophoric anion. 9. Compounds according to claim 1, which of the formula Ia correspond, in metal-free form and their salts, including internal salts, wherein
n represents 0 or 1,
R _1b , independently of one another, hydrogen, chlorine, nitro, methyl, methoxy or -NHCOCH ₃ ,
R _{2c is} hydrogen, methyl or methoxy,
Q _b , independently of one another, - (CH ₂ ) _2-3 -, or - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -, and
X _b -NR _5b R _6b or -N⊕R _7b R _8b R _9b An⊖ mean
R _5b and R _6b , which are identical, represent hydrogen, C _1-4 alkyl or 2-hydroxyethyl, or R _5b and R _6b together with the N atom to which they are attached are a piperidine, morpholine, piperazine or form an N-methylpiperazine ring,
R _7b and R _8b , which are identical, are C _1-4 alkyl or 2-hydroxyethyl, and
R _{9b represents} methyl, ethyl or benzyl, or
R _7b , R _8b and R _9b together with the N atom to which they are attached form a pyridinium group which is unsubstituted or monosubstituted by methyl, and
An⊖ means a non-chromophoric anion. 10. A compound according to claim 9, wherein n is 0 and R _{1b is} hydrogen, and R _2c in the meaning of methoxy is bonded in the o- position based on the azo group. 11. A compound according to claim 9 or 10, wherein -Q _b -NH _{2 is} Q _c -NH ₂ and -Q _b -X _{b is} -Q _c -NH ₂ , the groups -Q _c -NH _{2 being} identical and Q _c for - (CH ₂ ) _2-3 - or stands. 12. A process for the preparation of compounds of the formula I, defined in claim 1, characterized in that the diazonium salt of the amine of the formula II, wherein R ₁ , R ₂ and n are as defined in claim 1, with a compound of formula III, wherein R ₃ , R ₄ , Q and X are as defined in claim 1, and, if desired, convert a metal-free compound of the formula I thus obtained into the 1: 1 copper complex by reaction with a copper-donating compound. 13. Containing storage-stable, liquid-aqueous dye preparation a compound of formula I defined in claim 1, in water soluble Salt form. 14. Solid, granulated dye preparation containing a compound of formula I defined in claim 1, in water-soluble salt form. 15. Process for dyeing or printing materials made from exist or contain cationically dyeable substrates, thereby characterized in that one defines with a compound of formula I. in claim 1, in water-soluble salt form or with a preparation colors or prints according to claim 13 or 14. 16. The method according to claim 15, for which as a substrate Paper, leather or textile material consisting of cellulose or this contains, is used. 17. The method according to claim 15 for coloring glass or products of glass.   18. The dyed or printed according to one of claims 15 to 17 Materials. 19. A process for the production of inks, characterized in that that a compound of formula I, defined in claim 1, used. 20. The inks produced according to claim 19.