DE4315031B4 - Basic sulfo-containing disazo compounds - Google Patents

Abstract

die als freie Säure oder in Salzform vorliegen, worin
jeder der Reste R₁ bis R₄ unabhängig voneinander für Wasserstoff, Halogen, Hydroxy, C_1-4Alkyl, C_1-4Alkoxy, -NHCOC_1-4Alkyl oder -NHCONH₂ steht,
jeder der Reste R₁ bis R₄ unabhängig voneinander für Wasserstoff, Halogen, Hydroxy, C_1-4Alkyl, C_1-4Alkoxy, -NHCOC_1-4Alkyl oder -NHCONH₂ steht,
jeder der Reste X₁ bis X₄ unabhängig voneinander eine aliphatische, cycloaliphatische oder heterocyclische Aminogruppe bedeutet, die mindestens zwei Stickstoffatome enthält, mit der Massgabe, dass jede dieser Aminogruppen ein protonierbares oder quaternäres Ammoniumion und mindestens eine dieser Aminogruppen eine primäre Aminogruppe aufweist, und
X₅ für eine aliphatische, cycloaliphatische oder heterocyclische Aminogruppe, die mindestens zwei Stickstoffatome enthält, wovon eines protonierbar ist oder ein quaternäres Ammoniumion darstellt, oder für eine aromatische Diaminogruppe steht, dessen endständige Aminogruppe den Rest

jedes X₆ und X₇ unabhängig voneinander für eine aliphatische, cycloaliphatische oder heterocyclische Aminogruppe steht, die mindestens zwei Stickstoffatome enthält, wovon eines protonierbar...Compounds of the formula I,

which are present as free acid or in salt form, in which
each of R ₁ to R _{4 is} independently hydrogen, halogen, hydroxy, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl or -NHCONH ₂ ,
each of R ₁ to R _{4 is} independently hydrogen, halogen, hydroxy, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl or -NHCONH ₂ ,
each of X ₁ to X ₄ independently represents an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, with the proviso that each of these amino groups has a protonatable or quaternary ammonium ion and at least one of these amino groups has a primary amino group, and
X _{5 represents} an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, one of which is protonatable or represents a quaternary ammonium ion, or represents an aromatic diamino group whose terminal amino group is the radical

each X ₆ and X _{7 is} independently an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, one of which is protonatable,

Description

The Invention relates to basic sulfo-containing disazo compounds, which are metal-free, and acid addition salts of which, methods of making these compounds, their use as dyes and their processing into dyeing preparations.

Out DE 34 40 777 A1 are sulfo-containing, basic azo compounds known.

die in Form der freien Säure oder als Salz vorliegen, worin
jeder der Reste R₁ bis R₄ unabhängig voneinander für Wasserstoff, Halogen, Hydroxy, C_1-4Alkyl, C_1-4Alkoxy, -NHCOC_1-4Alkyl oder -NHCONH₂ steht,
jeder der Reste X₁ bis X₄ unabhängig voneinander eine aliphatische, cycloaliphatische oder heterocyclische Aminogruppe bedeutet, die mindestens zwei Stickstoffatome enthält, mit der Massgabe, dass jede dieser Aminogruppen ein protonierbares oder quaternäres Ammoniumion und mindestens eine dieser Aminogruppen eine primäre Aminogruppe aufweist, und
X₅ für eine aliphatische, cycloaliphatische oder heterocyclische Aminogruppe, die mindestens zwei Stickstoffatome enthält, wovon eines protonierbar ist oder ein quaternäres Ammoniumion darstellt, oder für eine aromatische Diaminogruppe steht, dessen endständige Aminogruppe den Rest

jedes X₆ und X₇ unabhängig voneinander für eine aliphatische, cycloaliphatische oder heterocyclische Aminogruppe steht, die mindestens zwei Stickstoffatome enthält, wovon eines protonierbar ist oder ein quaternäres Ammoniumion darstellt,
deren Säureadditionssalze sowie Gemische davon.The invention therefore relates to compounds of the formula I,

which are in the form of the free acid or in the form of a salt, in which
each of R ₁ to R _{4 is} independently hydrogen, halogen, hydroxy, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl or -NHCONH ₂ ,
each of X ₁ to X ₄ independently represents an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, with the proviso that each of these amino groups has a protonatable or quaternary ammonium ion and at least one of these amino groups has a primary amino group, and
X _{5 represents} an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, one of which is protonatable or represents a quaternary ammonium ion, or represents an aromatic diamino group whose terminal amino group is the radical

each X ₆ and X ₇ independently represent an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, one of which is protonatable or represents a quaternary ammonium ion,
their acid addition salts and mixtures thereof.

The number of the radicals X ₁ to X _5, which have a primary amino group is preferably 2-4; more preferably, X ₅ does not contain a primary amino group.

The substituents of the benzene rings R ₁ and R ₂ as well as R ₃ and R _{4 are} preferably para-elastic to one another according to the following arrangement:

R ₁ and R _{3 are} preferably R _1a and R _3a , which independently of one another are hydrogen, methyl, methoxy, -NHCOCH ₃ or -NHCONH ₂ ; and R ₂ and R _{4 are} preferably R _2a and R _4a , which are independent of each other is hydrogen, methyl or methoxy. More preferably, R ₁ and R _{3 are} R _1b and R _3b , which are independently hydrogen, methyl or methoxy, and R ₂ and R _{4 are} hydrogen; particularly preferably, each of the radicals R ₁ to R _{4 is} hydrogen.

The Sulfo group in the Naphthylresten is preferably in the 3-position.

R₅ Wasserstoff oder C_1-4Alkyl,
Q C_2-6Alkylen, durch Hydroxy mono- oder disubstituiertes C_3-6Alkylen oder durch -O-, -S- oder -N(R₅)- unterbrochenes C_4-6Alkylen, und
Z -NR₆R₇ oder -^⊕NR₈R₉R₁₀ An^⊝ bedeuten, worin
R₆ und R₇ unabhängig voneinander für Wasserstoff, C_1-6Alkyl, durch Hydroxy, C_1-4Alkoxy oder Cyano monosubstituiertes C_2-6Alkyl; Phenyl oder Phenyl(C_1-4alkyl), deren Phenylring unsubstituiert oder durch 1 bis 3 Substituenten aus der Reihe Halogen, C_1-4Alkyl und C_1-4Alkoxy substituiert ist, oder für unsubstituiertes oder durch 1 bis 3 C_1-4Alkylgruppen substituiertes C_5-6Cycloalkyl stehen, oder
-NR₆R₇ für Pyrrolidino, Piperidino, Morpholino oder für den Rest

steht, worin R₁₁ Wasserstoff, C_1-4Alkyl oder durch Hydroxy oder Amino monosubstituiertes C_2-4Alkyl bedeutet, R₈ und R₉ unabhängig voneinander für C_1-6Alkyl, durch Hydroxy, C_1-4Alkoxy oder Cyano monosubstituiertes C_2-6Alkyl, Phenyl oder Phenyl(C_1-4alkyl), deren Phenylring unsubstituiert oder durch 1 bis 3 Substituenten aus der Reihe Halogen, C_1-4Alkyl und C_1-4Alkoxy substituiert ist, oder für unsubstituiertes oder durch 1 bis 3 C_1-4Alkylgruppen substituiertes C_5-6Cycloalkyl, und
R₁₀ für C_1-4Alkyl oder Benzyl, oder

oder -N(R₁₁)- bedeutet, oder für eine Pyridiniumgruppe stehen, die unsubstituiert oder durch eine oder zwei Methylgruppen substituiert ist,
An^⊝ ein nicht-chromophores Anion, und
R₁₂ durch Amino oder Hydroxy monosubstituiertes C_2-4Alkyl bedeuten.The amino group defined for the radicals X ₁ to X ₇ is preferably a residue

R _{5 is} hydrogen or C _1-4 alkyl,
QC _2-6 alkylene, C _3-6 alkylene monosubstituted or disubstituted by hydroxy or -O-, -S- or -N (R ₅ ) - interrupted C _4-6 alkylene, and
Z is -NR ₆ R ₇ or - ^⊕ NR ₈ R ₉ R ₁₀ An ^⊝ , in which
R ₆ and R ₇ are each independently hydrogen, C _1-6 alkyl, C _2-6 alkyl monosubstituted by hydroxy, C _1-4 alkoxy or cyano; Phenyl or phenyl (C _1-4 alkyl) whose phenyl ring is unsubstituted or substituted by 1 to 3 substituents selected from halogen, C _1-4 alkyl and C _1-4 alkoxy, or unsubstituted or by 1 to 3 C _{1 4} alkyl groups substituted C _5-6 cycloalkyl, or
-NR ₆ R ₇ for pyrrolidino, piperidino, morpholino or for the rest

wherein R _{11 is} hydrogen, C _1-4 alkyl or C _2-4 alkyl monosubstituted by hydroxy or amino, R ₈ and R _{9 are} independently C _1-6 alkyl, monosubstituted by hydroxy, C _1-4 alkoxy or cyano C _2-6 alkyl, phenyl or phenyl (C _1-4 alkyl), the phenyl ring of which is unsubstituted or substituted by 1 to 3 substituents selected from halogen, C _1-4 alkyl and C _1-4 alkoxy, or unsubstituted or substituted 1 to 3 C _1-4 alkyl groups substituted C _5-6 cycloalkyl, and
R _{10 is} C _1-4 alkyl or benzyl, or

or -N (R ₁₁ ) -, or stand for a pyridinium group which is unsubstituted or substituted by one or two methyl groups,
An ^{⊝ is} a non-chromophoric anion, and
R ₁₂ is amino or hydroxy monosubstituted C _2-4 alkyl.

In In the present specification, halogen is preferably fluorine, Chlorine or bromine, more preferably chlorine or bromine; especially preferred it means chlorine.

Provided unless otherwise specified, any alkyl or alkyl group provided Alkylene group be linear or branched.

In a hydroxy- or alkoxy-substituted alkyl or alkylene group, which is bound to nitrogen, is the hydroxy or Alkoxy group preferably on a carbon atom which does not directly to the Nitrogen atom is bonded. Wearing the alkylene group is two hydroxy groups, these are preferred not on the same carbon atom, and preferably not on two adjacent ones C-atoms.

In an alkylene chain interrupted by -O-, -S- or -N (R ₅ ) -, which is bonded to nitrogen, the heteroatom is preferably located on a carbon atom which is not linked directly to this nitrogen atom.

R ₅ is preferably R _5a as hydrogen or methyl.

Q as linear alkylene is preferably - (CH ₂ ) _n - with n = 2 or 3;
Q as hydroxy-substituted alkylene is preferably

worin das markierte C-Atom an -N(R₅)- gebunden ist.Q as branched alkylene preferably means a group

wherein the labeled C atom is attached to -N (R ₅ ) -.

If the alkylene group is interrupted by a heteroatom, it is preferably - (CH ₂ ) _n -Y- (CH ₂ ) _n -, in which n is 2 or 3 and Y is -O- or -N (R _5a ) -.

oder -(CH₂)₂-NH-(CH₂)₂- ; insbesondere bevorzugt für Q_c als -(CH₂)_n- oder

worin n und Y wie oben definiert sind und das markierte C-Atom an -N(R₅)- gebunden ist.Q is preferably Q _a as C _2-4 alkylene, monohydroxy-substituted C _3-4 alkylene or - (CH ₂ ) _n -Y- (CH ₂ ) _n -; more preferably Q _b as - (CH ₂ ) _n -,

or - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -; especially preferred for Q _c as - (CH ₂ ) _n - or

wherein n and Y are as defined above and the labeled C atom is attached to -N (R ₅ ) -.

worin R_11a für Wasserstoff, Methyl, 2-Hydroxyäthyl oder 2-Aminoäthyl steht;
mehr bevorzugt R_6b und R_7b, wobei R_6b und R_7b identisch sind und Wasserstoff, Methyl, Aethyl oder 2-Hydroxyäthyl oder -NR_6bR_7b Piperidino, Mor pholino oder

bedeuten.R ₆ and R ₇ independently of one another are preferably R _6a and R _7a as hydrogen, C _1-4 alkyl, C _2-3 hydroxyalkyl or benzyl, or -NR _6a R _7a as piperidino, morpholino or

wherein R _{11a is} hydrogen, methyl, 2-hydroxyethyl or 2-aminoethyl;
more preferably R _6b and R _7b , wherein R _6b and R _{7b are} identical and are hydrogen, methyl, ethyl or 2-hydroxyethyl or -NR _6b R _7b piperidino, morpholino or

mean.

Particularly preferably R ₆ and R _{6c are} R _6c and R _7c , which are identical and denote hydrogen, methyl or ethyl.

R ₈ and R ₉ are preferably R _8a and R _9a in the meaning of methyl or ethyl, which are preferably identical;
R ₁₀ is preferably R _10a as methyl, ethyl or benzyl;
or - ^⊕NR _8a R _9a R _{10a represents} a pyridinium ring which is unsubstituted or substituted by one or two methyl groups.

Z is preferably Z _a as -NR _6a R _7a or - ^⊕NR _8a R _9a R _10a An ^⊝ ; more preferably Z _b as -NR _6b R _7b or - ^⊕ NR _8a R _9a R _10a An ^⊝ ; in particular Z _c as -NR _6c R _7c .

R ₁₂ is preferably R _12a as amino-monosubstituted C _2-4 alkyl; in particular, it is 2-aminoethyl.

mehr bevorzugt X_1b bis X_4b als Rest -NH-Q_b-Z_b oder

noch mehr bevorzugt X_1c bis X_4c als -NH-Q_c-Z_c oder

Meist bevorzugt stehen X₁ bis X₄ unabhängig voneinander für X_1d bis X_4d als -NH-(CH₂)_n-NR_6dR_7d,

worin n für 2 oder 3 und R_6d und R_7d für Methyl oder Aethyl stehen und die gleiche Bedeutung haben.

mehr bevorzugt X_5b als -NH-(CH₂)_n-Z_b', worin n für 2 oder 3 steht und Z_b' eine der Bedeutungen von Z_b jedoch unabhängig davon hat ausgenommen -NH₂; insbesondere bevorzugt steht X₅ für X_5c als -NH-(CH₂)_n-NR_6dR_7d, worin n wie oben definiert ist, und R_6d und R_7d Methyl oder Aethyl bedeuten und identisch sind.The X residues ₁ to X ₄ independently of one another preferably X _1a to X _4a

more preferably X _1b to X _4b as the radical -NH-Q _b -Z _b or

even more preferably X _1c to X _4c as -NH-Q _c -Z _c or

Most preferably X ₁ to X _{4 are} independently of one another X _1d to X _4d as -NH- (CH ₂ ) _n -NR _6d R _7d ,

wherein n is 2 or 3 and R _6d and R _{7d are} methyl or ethyl and have the same meaning.

more preferably X _5b is -NH- (CH ₂ ) _n -Z _b ', wherein n is 2 or 3 and Z _b ' has one of the meanings of Z _b but is independent of -NH ₂ ; most preferably X _{5 is} X _5c as -NH- (CH ₂ ) _n -NR _6d R _7d , wherein n is as defined above, and R _6d and R _{7d are} methyl or ethyl and are identical.

worin die Reste R_1b, R_3b und X_1b bis X_5b wie oben definiert sind mit der Massgabe, dass mindestens zwei der Reste X_1b bis X_4b unabhängig voneinander für

stehen. Preferred compounds of the formula I correspond to the formula Ia,

wherein the radicals R _1b , R _3b and X _1b to X _{5b are} as defined above with the proviso that at least two of the radicals X _1b to X _4b independently of one another

stand.

• (1) X_1b bis X_4b für X_1c bis X_4c stehen mit der Massgabe, dass mindestens zwei der Reste X_1c bis X_4c unabhängig voneinander
  
• (2) X_1b bis X_4b für X_1d bis X_4d Stehen mit der Massgabe, dass mindestens zwei der Reste X_1d bis X_4d
  
  oder
  
• (3) solche von (2), worin mindestens zwei der Reste X_1d-X_4d für
  
• (4) X_5b für X_5c steht;
• (5) solche von (1) bis (4), worin R_1b und R_3b beide für Wasserstoff stehen.

More preferred are compounds of the formula Ia wherein

• (1) X _1b to X _4b for X _1c to X _4c are provided with the proviso that at least two of X _1c to X _4c independently
  
• (2) X _1b to X _4b for X _1d to X _4d with the proviso that at least two of X _1d to X _4d
  
  or
  
• (3) those of (2) wherein at least two of X _1d -X _{4d are}
  
• (4) X _{5b is} X _5c ;
• (5) those of (1) to (4) wherein R _1b and R _{3b are} both hydrogen.

The anion An ^⊝ present in the quaternary ammonium salts defined for X ₁ to X ₅ may be any non-chromophoric organic or inorganic anion, as is customary in the field of basic dye ^chemistry , for example. Suitable anions include, for example, chloride, bromide, lactate, acetate, propionate, citrate, oxalate, malate, maleate, succinate, methylsulfate, ethylsulfate and bisulfate.

In a compound of formula I, the sulfo groups are normally ionized and can form internal salts with the basic amino groups in X ₁ to X ₅ . Amino groups which are not present as internal salts form acid addition salts by reaction with suitable acids. Suitable acids are, 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.

mit einem Amin der Formel X₅-H umsetzt, worin R₁ bis R₄ und X₁ bis X₅ wie oben definiert sind.The compounds of the formula I are prepared by reacting a compound of the formula II

with an amine of the formula X ₅ -H, wherein R ₁ to R ₄ and X ₁ to X _{5 are} as defined above.

beidseitig diazotiert und mit mindestens 2 Mol einer Verbindung der Formel IV,

worin R₁ bis R₄, X₁, X₂ und X₅ wie oben definiert sind, kuppelt.Compounds of the formula I in which X _{1 is} identical to X ₃ and X _{2 is} X ₄ and the sulfo group in the naphthyl radicals is either in the 3 or 4 position can also be prepared by reacting 1 mol of a compound of the formula III

Diazotized on both sides and with at least 2 moles of a compound of formula IV,

wherein R ₁ to R ₄ , X ₁ , X ₂ and X _{5 are} as defined above, coupling.

The condensation of a compound of formula II with the amine X ₅ -H is conveniently carried out at temperatures around 95 ° C. The diazotization of a compound of formula III is carried out according to conventional methods; as well as the coupling with a compound of formula IV, which preferably takes place at pH 6-8.

The Isolation of a compound of formula I can in the usual way done by failures of the dye from the reaction solution, filtering and drying. Furthermore, the resulting compound of the formula I by addition of acid also be obtained in the form of a ready-to-use solution.

The starting compounds of the formulas II, III and IV and the amines X ₅ -H are either known or can be prepared analogously to processes known per se using known starting materials, ie by appropriate condensation and coupling reactions starting from cyanuric chloride, in which the stepwise exchange the chlorine atoms on the triazine ring are carried out in a manner known per se, as is customary when replacing the first (at temperatures of 0-5 ° C.), second (at temperatures of 40-60 ° C.) and third (at temperatures around 95 ° C.) Chloratoms is applied.

The Compounds of formula I, in the form of the acid addition salts or as quaternary Ammonium salts, are dyes; they find use for To dye or printing on cationically dyeable materials such as uniform or copolymers of acrylonitrile, acid-modified polyesters; Leather, cotton, bast fibers such as hemp, flax, sisal, jute, coconut fibers and straw; Cellulose regenerated fibers, glass fibers and paper.

The invention Compounds in the form of their water-soluble salts are preferred Use for dyeing or printing hydroxy or nitrogen-containing organic Substrates. They are used, for example, for dyeing or printing fibers, Threads or textiles made from natural or synthetic Polyamides or natural or regenerated cellulosic material, e.g. Cotton, persist or these contain, according to known methods; Cotton becomes preferably dyed by the exhaust process, for example, from long or short liquor and at room to cooking temperature.

The Printing is done by impregnation with a printing paste, which compiled according to known methods becomes.

The new connections can also for dyeing or printing leather, preferably chrome-tanned leathers, be used according to methods known per se. In addition, the Dyes in the production of inks according to known per se Method be used.

Especially However, the compounds of formula I are suitable for dyeing or Printing on paper, e.g. For the preparation of mass-dyed, glued or unsized ones Paper. But you can also for coloring used by paper after the dipping process or in the size press become. Dyeing and printing on paper is done by known methods. The respectively obtained dyeings and prints (especially on paper) show good use fastness.

The Compounds of the formula I can also in the form of dyeing preparations be used. This application form is particularly useful in dyeing Paper preferred. Processing into stable liquid, preferably aqueous, concentrated dyeing preparations can in a generally known manner, advantageously by dissolving in suitable solvents optionally with the addition of an adjuvant, e.g. a hydrotropic Compound or a stabilizer. Of particular advantage is the production possibility such stable, aqueous-concentrated preparations in the course of the dye synthesis itself without intermediate isolation of the Dye.

A favorable composition of such liquid preparations is, for example, the following (parts are parts by weight): 100 parts a compound of the formula I as an acid addition salt or as a quaternary ammonium salt, 0-10, preferably 0-1 parts an inorganic salt, 100-800 parts Water and 0-500 parts a solubilizer (eg 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).

The liquid aqueous Preparations are stable and over longer Time storable.

The Compounds of formula I (in appropriate salt form) good solubility properties, in particular they are characterized by good cold water solubility. As a result of her high substantivity draw the dyes virtually quantitatively and show it a good build capacity. In the production of glued as well as unsized paper the wastewater practically colorless or only slightly stained. The dyes may be the Paper pulp directly, i. without previous dissolution, as dry powder or Granules are added without causing a reduction in brilliance or decrease in color yield occurs. The sized paper dyeing shows across from the unsized no starch waste. Using the dyes can also in soft water with full color yield colored become. The dyes do not mottle on paper dyed, they do not tend for paper two-sidedness and are largely insensitive to filler and pH fluctuations.

The with the compounds of formula I prepared paper dyeings are characterized by good lightfastness; after a longer exposure changes the nuance tone-on-tone. The dyed Papers show high bleeding fastness, they are very good wetfast not only against water, but also against milk, fruit juices, sweetened mineral water, Tonic water, soapsuds, saline, urine etc .; also own they have good alcohol fastness. Paper that with the new connections colored is bleachable both oxidatively and reductively, indicating reuse of scrap and waste paper is of importance. Fibers, the groundwood are described with the dyes described in good and level quality colored.

The Compounds of formula I also show a good combination behavior. The dyes described in combination with dyes, the comparable dyeing Have properties, obtained dyeings have good fastness properties.

The The following examples serve to illustrate the invention. Provided Unless otherwise indicated, all parts mean in the examples Parts by weight and all percentages by weight; the temperatures are in degrees Celsius.

example 1

enthält, werden nach bekannten Methoden tetrazotiert und bei pH 6 auf 43,6 Teile (0,08 Mol) der Verbindung der Formel (1b)

gekuppelt. Der entstandene blaue Farbstoff fällt aus und wird abfiltriert. Nach dem Trocknen erhält man 60 Teile des Farbstoffs der Formel (1c)

300 parts of a hydrochloric acid aqueous solution containing 0.0366 mole of a compound of the formula (1a)

are tetrazotized by known methods and at pH 6 to 43.6 parts (0.08 mol) of the compound of formula (1b)

coupled. The resulting blue dye precipitates and is filtered off. After drying, 60 parts of the dye of the formula (1c) are obtained.

you stirred The dye in 890 parts of demineralized water and adds 50 parts by volume formic acid added. The result is a ready-stable dye solution, the Paper in reddish-blue tones colors. The Wastewater is colorless; the wet and light fastness of the obtained paper dyeings are excellent.

The Preparation of the starting material, compounds of the formula (1a) and (1b), analogously to methods known per se.

For example, the compound (1a) can be obtained as follows:
Stir 1 mole of cyanuric chloride in water and ice and add 2 moles of 4-aminoacetanilide, the condensation reaction being carried out in stages, first at a temperature of 0-10 °, which is gradually increased to 60 °. After the reaction has ended, 2 mol of diethylaminopropylamine are added and the temperature is raised to 90-95.degree. When the third chlorine is reacted in the cyanuric chloride, the acetyl groups are removed by acid saponification, whereby the compound (1a) is obtained.

The Compound (1b) can be prepared, for example, as follows: 2 moles of 1,2-diaminopropane are stirred in ice and water and with hydrochloric acid to pH 3-5 set. After that adds Add 1 mole of cyanuric chloride and the temperature within 5 Hours from 0 ° to 25-30 ° rise. The pH is doing with dilute sodium hydroxide solution kept at 5.5. After the reaction is complete, add 0.9 Mol 1-amino-8-hydroxynaphthalene-3,6-disulfonic add and warmed up at 80-90 °. Man holds it the pH with diluted Sodium hydroxide at 2-3. After one hour, the reaction is complete, taking the compound of the formula (1b) results.

Becomes instead of 2 moles of 1,2-diaminopropane, first with 1 mole of diethylaminopropylamine and then reacted with 1 mole of 1,2-diaminopropane, to obtain a the compound (1b) analogous compound, the Triazinylring two carries different amino groups.

Examples 2-12

Analogous the method described in Example 1 can be carried out using appropriate Starting materials further compounds of formula I prepared which are listed in Table 1 below.

für welche in Tabelle 1 die Variablen angeführt sind.These compounds have the formula (A),

for which in Table 1 the variables are given.

The Dyes of Examples 2-12 to dye Paper in reddish-blue tones with good light and wet fastness.

In the following Tables 1 and 2 to X ₅ is used as radicals X _1, the following groups:

Table 1 / Compounds of the formula (A)

Example 13

werden mit 0,01 Mol Cyanurchlorid bei 0–5° kondensiert, danach mit 0,01 Mol einer Verbindung der Formel (13b)

bei 40–60° umgesetzt und schliesslich mit Diäthylaminopropylamin bei 95° kondensiert. Man erhält so den Farbstoff der Formel (13c)

mit welchem Papier in rotstichig-blauen Tönen gefärbt wird.0.01 mol of a compound of the formula (13a)

are condensed with 0.01 mol of cyanuric chloride at 0-5 °, then with 0.01 mol of a compound of formula (13b)

reacted at 40-60 ° and finally condensed with Diäthylaminopropylamin at 95 °. This gives the dyestuff of the formula (13c)

with which paper is dyed in reddish-blue tones.

The obtained paper dyeings show good light and wet fastness.

Examples 14-23

für welche in Tabelle 2 die Variablen angeführt sind.Analogous to the method described in Example 13 further compounds of formula I can be prepared when using the appropriate starting materials, which are listed in the following Table 2. They correspond to the formula (B),

for which in Table 2 the variables are given.

The Compounds of Examples 14-23 to dye Paper in blue tones with good fastnesses.

Table 2 / Compounds of the formula (B)

Example 24

enthalten, innerhalb von 20 Minuten bei pH 4–5 und einer Temperatur von 5–15° zulaufen. Sobald die Kondensationsreaktion beendet ist, werden 55 Teile 4-Aminoacetanilid zugegeben. Man erwärmt auf 95° und hält zwei bis drei Stunden bei dieser Temperatur, wobei der pH-Wert mit Natronlauge bei 3,5 gehalten wird. Nach dieser Zeit sind nur noch weniger als 5% 4-Aminoacetanilid nachweisbar. Die Lösung wird mit 200 Volumteilen 30%iger Salzsäure versetzt und zehn Stunden bei 80° gerührt. Nach dieser Behandlung sind die Acetylschutzgruppen abgespalten. Die erhaltene Lösung wird auf Raumtemperatur abgekühlt und klärfiltriert. Es resultieren 1800 Volumteile einer salzsauren Lösung, die 106 Teile der Verbindung der Formel (24b)

enthält.33.8 parts of cyanuric chloride are stirred in 150 parts of ice and 150 parts of water. 849 parts by volume of a hydrochloric acid aqueous solution containing 60.6 parts of the compound of the formula (24a) are then

within 20 minutes at pH 4-5 and a temperature of 5-15 °. Once the condensation reaction is complete, 55 parts of 4-aminoacetanilide are added. The mixture is heated to 95 ° and held for two to three hours at this temperature, the pH is maintained at 3.5 with sodium hydroxide solution. After this time, only less than 5% 4-aminoacetanilide be detected. The solution is mixed with 200 parts by volume of 30% hydrochloric acid and stirred at 80 ° for ten hours. After this treatment, the acetyl protecting groups are split off. The resulting solution is cooled to room temperature and clarified by filtration. This results in 1800 parts by volume of a hydrochloric acid solution containing 106 parts of the compound of formula (24b)

contains.

enthält. Der Farbstoff ist in Gegenwart von Säure, wie mit Ameisen-, Essig- oder Milchsäure, sehr gut löslich, er färbt Papier in rotstichig-blauen Tönen. Die Färbungen zeichnen sich durch perfekte Abwasser- und Nassechtheiten aus.216 parts by volume of this solution are mixed with ice and tetrazotized with 11 parts by volume of a 4N sodium nitrite solution. Subsequently, 12 parts of the compound of formula (1b) are entered; The pH is made alkaline with sodium carbonate first to 6, then with sodium hydroxide solution. The resulting dye suspension is filtered off and washed with water. After drying, 47 parts of a dark powder containing 31 parts of the dye of formula (24c) are obtained.

contains. The dye is very soluble in the presence of acid, such as with formic, acetic or lactic acid, it dyes paper in reddish-blue tones. The dyeings are characterized by perfect sewage and wet fastness.

The Compound of formula (24a) can be prepared as follows: 2 Mole of 1,2-diaminopropane are stirred in ice and water and with hydrochloric acid to pH 3-5 set. After that adds 1 mol of cyanuric chloride and allowed while five hours stir at a pH of 5.5. Then 1 mole of 4-acetaminoanilide is added and the temperature set to 70 °. By adding dilute Sodium hydroxide solution, the pH is maintained at 3-3.5. After being determined Condensation is added 500 volumes of 30% hydrochloric acid, and it will further stirred at 70-75 °. To Two hours the saponification is over.

On analogous manner as described in Example 1, the dyes of the Examples 2-24 with the addition of the appropriate amount of water and formic acid in ready to use Dye solutions are transferred.

Instead of the formic acid used can for the Salt formation also includes other organic acids such as lactic, acetic and methoxyacetic or mixtures of these acids including formic acid be used.

application options the dyestuffs described which are solid as acid addition salt Mold or as ready-to-use aqueous solution can be used are illustrated in the following provisions A to E.

Dyeing Procedure A

In a dutchman be 70 parts of chemically bleached softwood sulfite cellulose and 30 parts of chemically bleached birchwood sulfite cellulose Milled in 2000 parts of water. To this mass is sprinkled 0.2 parts of the dye of Example 1 (as an acid addition salt) or is 2.0 parts of the dye solution according to Example 1 to. After 20 minutes of mixing time from paper is made. The absorbent paper obtained in this way is reddish-blue colored. The wastewater is colorless.

Dyeing Procedure B

0.3 Parts of the dye powder from Example 1 (as acid addition salt) are in 100 parts of hot water dissolved and cooled to room temperature. The solution are added to 100 parts chemically bleached sulfite, the was ground with 2000 parts of water in a Dutchman. After 15 Minutes of mixing is on usual Type with resin glue and aluminum sulfate glued. Paper made from this Material is produced, shows a reddish-blue shade and has good light, sewage and wet fastness properties.

Dyeing Procedure C

An absorbent paper web of unsized paper is drawn at 40-50 ° through a dye solution of the following composition: 0.3 parts of the dyestuff from Example 1 (as acid addition salt) or 3 parts of the dye solution according to Example 1, 0.5 parts Strength and 99.2 parts (or 96.5 parts) Water.

The excess dye solution becomes pressed by two rollers. The dried paper web is reddish-blue colored.

On analogous manner as stated in the regulations A to C, can also be dyed with the dyes of Examples 2-24. The obtained paper dyeings have a high level of authenticity.

Dyeing Procedure D

0.2 Parts of the dye from Example 1 as an acid addition salt are in 4000 parts of softened water solved at 40 °. you Brings 100 pieces of pre-wetted cotton fabric into the bath and heated to boiling temperature in 30 minutes. The bathroom will be during a Hour kept at boiling temperature, from time to time the evaporated water is replaced. Then the coloring is off the fleet taken out, rinsed with water and dried. The dye draws practically quantitatively on the fiber; the dyebath is nearly colorless. You get a reddish-blue color of good light fastness and good wet fastness.

Analogous can the dyes of Examples 2-24 to dye be used by cotton.

Dyeing instruction E

100 Parts are freshly tanned and neutralized chrome grain leather in a fleet of 250 parts water of 55 ° and 0.5 parts of the example 1 prepared dye (as acid addition salt) during 30 Drummed for a few minutes in the barrel and in the same bath with 2 parts of an anionic The fat liquor is treated on a sulphonated tran basis for a further 30 minutes. The leathers are in the usual Type dried and prepared. You get no matter dyed leather in reddish blue Nuance.

Further low affinity, vegetable retanned leathers may also be known Dyed methods become.

On analogous manner can be stained with the dyes of Examples 2-24.

Claims (17)

Compounds of the formula I,

which are present as free acid or in salt form, wherein each of R ₁ to R _{4 is} independently hydrogen, halogen, hydroxy, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl or -NHCONH ₂ each of R ₁ to R _{4 is} independently hydrogen, halogen, hydroxy, C _1-4 alkyl, C _1-4 alkoxy, -NHCOC _1-4 alkyl or -NHCONH ₂ , each of X ₁ to X ₄ independently represents an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, with the proviso that each of these amino groups has a protonatable or quaternary ammonium ion and at least one of these amino groups has a primary amino group; _{5 represents} an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, one of which is protonatable or represents a quaternary ammonium ion, or represents an aromatic diamino group whose terminal amino group is the radical

each X ₆ and X ₇ independently represent an aliphatic, cycloaliphatic or heterocyclic amino group containing at least two nitrogen atoms, one of which is protonatable or a quaternary ammonium ion, their acid addition salts and mixtures thereof. Compounds according to claim 1, wherein 2-4 of the radicals X ₁ to X _{5 have} a primary amino group. Compounds according to claim 2, wherein X ₅ does not contain a primary amino group. Compounds according to any one of claims 1-3, wherein the phenyl substituents R ₁ and R ₂ as well as R ₃ and R _{4 are} paramagnetic to each other according to the arrangement

wherein R ₁ and R _{3 are} R _1a and R _3a independently of one another are hydrogen, methyl, methoxy, -NHCOCH ₃ or -NHCONH ₂ , and R ₂ and R _{4 are} R _2a and R _4a , which independently of one another are hydrogen , Methyl or methoxy. Compounds according to claim 4, wherein R ₁ and R ₃ independently of one another are hydrogen, methyl or methoxy, and R ₂ and R _{4 are} both hydrogen. Compounds according to any one of claims 1-5, wherein each X ₁ to X _{7 is} independently a radical

in which R _{5 is} hydrogen or C _1-4 alkyl, Q C _2-6 alkylene, by hydroxy mono- or disubstituted C _3-6 alkylene or by -O-, -S- or -N (R ₅ ) - interrupted C _4-6 alkylene, and Z is -NR ₆ R ₇ or - ^⊕ NR ₈ R ₉ R ₁₀ An ^⊝ , wherein R ₆ and R _{7 are} independently hydrogen, C _1-6 alkyl, by hydroxy, C _1-4 alkoxy or cyano monosubstituted C _2-6 alkyl; Phenyl or phenyl (C _1-4 alkyl) whose phenyl ring is unsubstituted or substituted by 1 to 3 substituents selected from halogen, C _1-4 alkyl and C _1-4 alkoxy, or unsubstituted or by 1 to 3 C _{1 4} alkyl groups substituted C _5-6 cycloalkyl, or -NR ₆ R _{7 is} pyrrolidino, piperidino, morpholino or the radical

wherein R _{11 is} hydrogen, C _1-4 alkyl or C _2-4 alkyl monosubstituted by hydroxy or amino, R ₈ and R _{9 are} independently C _1-6 alkyl, C _2-6 alkyl, phenyl or phenyl (C _1-4 alkyl) monosubstituted by hydroxy, C _1-4 alkoxy or cyano, their phenyl ring unsubstituted or from 1 to 3 Substituents from the series halogen, C _1-4 alkyl and C _1-4 alkoxy substituted, or unsubstituted or substituted by 1 to 3 C _1-4 alkyl groups C _5-6 cycloalkyl, and R _{10 is} C _1-4 alkyl or benzyl, or

or -N (R ₁₁ ) -, or is a pyridinium group which is unsubstituted or substituted by one or two methyl groups, An ^{⊝ is} a non-chromophoric anion, and R ₁₂ is amino or hydroxy monosubstituted C _2-4 alkyl. Compounds according to claim 6, wherein each of X ₁ to X _{4 is} X _1d to X _4d , which are independently -NH- (CH ₂ ) _n -NR _6d R _7d ,

or

and X _{5 is} X _5c , wherein X _{5c is} -NH- (CH ₂ ) _n -NR _6d R _{7d is} independently of X _1d to X _4d , wherein n is 2 or 3 and R _6d and R _{7d are} methyl or Aethyl stand and have the same meaning. Compounds according to any one of claims 1-3, of the formula Ia

R _1b and R _3b independently of one another are hydrogen, methyl or methoxy, and each of the radicals X _1b to X _{4b is} independently -NH-Q _b -Z _b or

where Q _{b is} - (CH ₂ ) _n -,

or - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ - wherein n is 2 or 3 and the labeled C atom is attached to -NH; and Z _{b is} -NR _6b R _7b or - ^⊕NR _8a R _9a R _10a An ^⊝ in which R _6b and R _{7b are} identical and denote hydrogen, methyl, ethyl or 2-hydroxyethyl, or -NR _6b R _7b piperidino, Morpholino or

with R _11a as hydrogen, methyl, 2-hydroxyethyl or 2-aminoethyl; R _8a and R _{9a are} identical and are methyl or ethyl, and R _{10a is} methyl, ethyl or benzyl or - ^⊕ NR _8a R _9a R _{10a forms} a pyridinium group which is unsubstituted or substituted by one or two methyl groups, An ^⊝ a non-chromophoric anion means; X _{5b is} -NH- (CH ₂ ) _n -Z _b 'wherein n is 2 or 3 and Z _b ' has one of the meanings of Z _b , but independently, except -NH ₂ ; with the proviso that at least two of the radicals X _1b to X _4b independently of one another

or acid addition salts thereof. Compounds according to claim 8, wherein X _1b to X _{4b are} X _1d to X _4d , which independently of one another are -NH- (CH ₂ ) _n -NR _6d R _7d ,

or

where n is 2 or 3 and R _{7d is} methyl or ethyl and are identical; and X _5b for X _5c is -NH- (CH ₂ ) _n -NR _6d R _7d , wherein n, R _6d and R _{7d are} as defined above but independently. Compounds according to claim 8 or 9, wherein R _1b and R _{3b are} both hydrogen. Process for the preparation of compounds of the formula I defined in claim 1, characterized in that a compound of the formula II,

wherein R ₁ to R ₄ and X ₁ to X _{4 are} as defined in claim 1, with an amine of formula X ₅ -H, wherein X _{5 is} as defined in claim 1, reacted. A process for the preparation of compounds of the formula I defined in claim 1, wherein X _{1 is} identical to X ₃ and X _{2 is} X ₄ and the radicals X ₁ to X _{4 are} as defined in claim 1, and the sulfo group in the naphthyl radicals is present either in 3- or in the 4-position, characterized in that 1 mol of a compound of formula III

wherein R ₁ to R ₄ and X _{5 are} as defined in claim 1, Diazotized on both sides and with at least 2 moles of a compound of formula IV

wherein X ₁ and X _{2 are} as defined in claim 1, coupling. Use of the compounds of formula I defined in claim 1 in water-soluble Salt form for the preparation of storage-stable, liquid-aqueous dyeing preparations. Use of the compounds of formula I defined in claim 1 or the storage-stable, liquid-aqueous dyeing preparations according to claim 13 for dyeing or printing on materials that are cationically dyeable Substrates exist or contain these. Use according to claim 14, wherein the dyeable material a hydroxy or nitrogen containing organic substrate is. Use according to claim 15, wherein as substrate Paper is used. Use of the compounds of formula I defined in claim 1 for the preparation of inks.