DE3516809A1 - Basic compounds, their preparation and use - Google Patents

Abstract

Compounds of the formula <IMAGE> in which the azo group is preferably bonded in the 3- or 4-position and the sulpho group is preferably bonded in the ortho-position to the azo group, and B is a di- or trivalent bridge member, X is hydrogen or alkyl-(C1-4), R is hydrogen, -NH2, a (1-4C)-alkyl or (5-6 C)-cycloalkyl radical which can be substituted by 1 to 3 (1-4 C)-alkyl radicals, or a phenyl, benzyl or phenylethyl radical whose phenyl radicals can be substituted by a methyl, ethyl, methoxy or ethoxy substituent, the substituents T and M are customary per se, it being possible for the groups B, T and M to carry cationic groups and the number of the basic groups in the molecule to be >/= 3, the preparation of the compounds of the formula (I) and their use as dyes.

Description

Basic compounds, their preparation and use

The present invention relates to compounds of the formula in which the azo group is preferably bonded in the 3- or 4-position and the sulfo group is preferably bonded in the ortho position to the azo group, and B is a divalent or trivalent bridging member, X is hydrogen or alkyl- (C1,4), R is hydrogen, -NH2, a (1-4C) -alkyl, (5-6C) -cycloalkyl radical which can be substituted by 1 to three (1-4C) -alkyl radicals, or a phenyl, benzyl or phenylethyl radical, the phenyl radicals of which by one or two Methyl, ethyl, methoxy or ethoxy can be substituted, d 2 or 3 t 0 or 1, T hydrogen, halogen, CN, -COOR4, -CONR5R6, -S02NR5R6 or mean, Ac means an optionally substituted acyl radical and preferably Ac1, ie -CO-alkyl (C14), -CO-alkylene (C4) -halogen, -CO-alkylene- (C1-4) -CN, -CO-alkylene ( C1-4) -OCH3, -S02-aryl, Ra hydrogen, methyl, halogen, methoxy, cyano, -CONH2, M hydrogen, -NR11R12, (1-4C) -alkyl, hydroxy (2-4C) -alkyl, (1-4C) -alkoxy- (1-4C) -alkyl, (5-6Ci-cycloalkyl, phenyl- (1-3C) -alkyl, -R1-NH-Ro, -V1-NR13R14 or -V- R13R14R15, an anion, R1 an alkylene or alkenylene radical optionally interrupted by one or two heteroatoms, a phenylene or cyclohexylene radical, Ro a radical of the formula q 0 or 1, R2 a radical of the formula -CO- (CH2) 1-3-Z b) or hydrogen, R3 hydrogen, a (1-4C) -alkyl radical, -NR5R6 or -CONR5R6, R4 a (1-6C) -alkyl- or phenyl- (1- 3C) -alkyl radical, R5 and R6 independently of one another hydrogen or (1-4C) -alkyl, R7 (1-4C) -alkyl, R8 hydrogen or (1-4C) -alkyl, Rg -S-, -0- or - N-R5, R10 an aliphatic, cycloaliphatic, aromatic or heterocyclic amine or hydrazine radical in which the N atom is bonded to the C atom of the triazinyl radical, and the aliphatic, cycloaliphatic, aromatic or heterocyclic amine or hydrazine radical protonatable and / or quaternary N atoms, Q halogen, OH, -NH2, (1-4C) -alkyl, (1-4C) -alkoxy, phenyl or R10, Z a radical -NR11R12 or -R13R14R15Ri) R11 and R12 independently of one another Hydrogen, unsubstituted (1-6C) -alkyl, (2-6C) -alkyl substituted by OH, CN or halogen, phenyl- (1-3C) -alkyl, whose phenyl radical has 1 to 3 substituents from the chlorine series, (1 -4C) -alkyl or (1-4C) -alkoxy can, unsubstituted or substituted by 1 to 3 (1-4C) -alkyl groups (5-6C) -cycloalkyl, R13 and R14 independently of one another have one of the meanings of R11 and R12, where in the radical -V1-NR13R14 one of the radicals R13 and R14 and preferably both radicals and in the radical - R13R14R15 AO both radicals R13 and R14 are different from hydrogen, R15 is a (1-4C) -alkyl radical which is optionally substituted by phenyl, R16 is hydrogen, halogen, (1-4C) -alkyl, (1- 4C) alkoxy or nitro, V a (2-6C) -alkylene radical which is optionally substituted by OH, which can be interrupted by -N (1-4C) alkyl, or (2-6C) -alkenylene radical, V1 a (1-6C) ) -Alkylene or (2-6C) -alkenylene radical, where the radicals R5 and R6, or R11 and R12, or R13 and R14 together with the N atom bonded to them are a saturated heterocyclic ring and R13, R14 and R15 together with the nitrogen atom attached to it can form a pyridine ring, and the pyridine and the saturated heterocyclic ring can be formed by one, two or three (1-4C) -alkyl groups can be substituted, the number of basic groups in molecule # 3 and the compounds of formula I must carry at least two -SO3H groups.

R preferably denotes R ', ie methyl, ethyl, phenyl, benzyl or cyclohexyl and preferably methyl, T preferably denotes T1, ie hydrogen, -CN, or -CONR'sR'6 and preferably T2, ie hydrogen, CN or All alkyl radicals with at least 2C atoms can be straight-chain or branched.

Ac preferably denotes Ac1 and preferably Ac2, i.e. -CO-alkylene- (C1 4) -halogen, in which halogen is chlorine or bromine and preferably chlorine, and -CO-alkylene (C14) -CN or -CO-alkylene- (C1-C4) -OCH3 and preferably Ac3, i.e.

-CO-alkylene (C14) Cl, preferably -CO-CH2Cl.

Aryl means optionally substituted phenyl or naphthyl, preferably phenyl.

X preferably denotes X ', i.e. hydrogen or methyl, M denotes preferably M ', i.e. hydrogen, -CH3, -C2H5, -C2H40H, cyclohexyl, benzyl, - (CH2) 1-3-NR'13R'14, - (CH2) 2-3- + NR'13R'14R'15A- or -R'1-NHR'o, and preferably M ", i.e. hydrogen, - (CH2) 1-3-NR'13R'14, - (CH2) 2-3- + NR'13R'14R'15 AO CH3, C2Hs, benzyl or -R'1-NHR ' , and preferably M "', i.e.

Hydrogen, - (CH2) 1-3-NR "13R" 14, - (CH2) 23 R "13R1114R1115 3 or -R "1-NHR" o, R1 preferably denotes R'1, i.e. a straight-chain or branched one (2-8C) -alkylene radical or a meta- or para-phenylene radical, preferably R "j, i.e. 1,2 ethylene, linear or branched 1,3-propylene or meta- or para-phenylene.

Ro preferably denotes R'o, ie a radical of the formula and preferably a radical R110, ie a radical of the formula where R2 is defined below, R161 is hydrogen, chlorine, methyl or methoxy, and q is zero or 1.

R2 preferably denotes R'2, ie a radical of the formula -CO- (CH2) 1 ~ 2-Z1 - b) or hydrogen, preferably R2, ie hydrogen or or -COCH2-Z2, R3 preferably denotes R'3, ie, independently of one another, denotes hydrogen, methyl, ethyl, -NH2, -N (CH3) 2, -CON (CH3) 2 or -CON (C2H5) 2 R5 or R6 preferably R'5 or R'6 ie independently of one another hydrogen, methyl or ethyl.

R8 preferably denotes R'8, ie hydrogen or methyl Q preferably denotes Q1, ie chlorine, -OH, -NH2, -NR'5 OCH3, mono (1-4C) -alkylamino, di- (1-2C) -alkylamino, monohydroxy- (2-4C) -alkylamino, bis-hydroxy (2-4C) -alkyl] -amino or R'10, preferably Q2, ie R'10, R10 preferably denote R'10, ie independently of one another wherein Rx is a (1-12C) -alkyl radical interrupted by one and / or more groups of the formula -NR'5- or -NR7R7- A-, optionally substituted by OH, -NHCOCH2-Z1, -CHCONH-V-Z1, - V-Z1, -V-Arylen-ZO, -Arylen-ZO, or Rx and R'5 together with the N atom bonded to them are a radical Å3, ZO -N (CH3) 2, -N (C2H5) 2, -N (CH3) 3, -N (C2H5) 3 AO or a radical -CONH-V0-Z1, -NHCO-V0-Z1, -CO-V0-Z1 -SO2NH-V0-Z1, -V0-Z1 or -NHNH-COCH2-Z1, where the arylene radical bonded to Z0 is replaced by halogen, OH, NO2, (1-4C) -alkyl or (1-4C ) -Alkoxy can be substituted, V0 stands for a (1-8C) -alkylene radical, and the group of the formula tir or the - ? - for an unsaturated Group of the formula -CH N- or Heterocycle and which are a saturated heterocycle.

Z preferably denotes Z1, i.e., independently of one another, a radical of the formula -NR'11R'12 or -R'13R'14R'15 A-, preferably Z2, as defined below.

R11 and R12 are preferably R'11 or R'12, i.e. independently from each other hydrogen, linear or branched (1-6C) -alkyl, unbranched hydroxy- (2-3C) -alkyl, Benzyl, 2-cyanoethyl or 2-chloroethyl.

R13 and R14 are preferably R'13 and R'14, i.e. independently linear or branched (1-6C) -alkyl, unbranched hydroxy (2-3C) -alkyl, Benzyl, 2-cyanoethyl or 2-chlorobathyl, and preferably R''13 or R ″ 14, i.e., independently of one another, methyl or ethyl.

R15 preferably denotes R'15, i.e. methyl, ethyl, propyl or benzyl, and preferably R "15, i.e. methyl or ethyl.

R16 preferably denotes R'16 and preferably hydrogen, the radicals R'5 and R'6 or R'11 and R'12 together with the N atom attached to them being a morpholine, piperidine, pyrrolidine, piperazine or N-methylpiperazine ring or the radicals R'13, R'14 and R'15 together with the N atom bonded to them a pyridine, a γ- or β-picoline or a lutidine ring or a ring of the formula in which can form, R16a methyl or ethyl and W the direct bond, -CH2-, -O-, -S-, -SO2-, -SO-, -NH-, -4-R16a or 2 A- mean. Rx, independently of one another, preferably denotes R'x, ie a radical of the formula - (CH2) 2-3 - NR'5 - (CH2) 2-3 - NR'5 - C2Hs, - (CH2) 23 - N (R'7) 2-- (CH2) 2-3- + N (R'7) 2 - C2H5 2, - (CH2) 2-3 - NR'5 - C2H5, - (CH2) 23 - N (R'7) 2 - C2H5 A (3, -NHCO-CH2 - Z2, -CH2-CONH -V'-Z2, or R'x and R'5 together with the N atom bonded to them are a radical can form, V 'independently of one another an optionally substituted by OH (1-4C) -alkyene radical, Z' -N (CH3) 2, -N (CH3) 3 A-, -CONH-V'Z2, -SO2NH- V'-Z2, -V'-Ze, -NHNHCOCH2-Z2 or -CO-V1-Z2, R'7 methyl or ethyl, Z2 a radical -NR1,11R "12 or -NR" 13R "14R" 15 AO, R "11 and R" 12 are hydrogen, methyl, ethyl.

The bridge link B preferably has one of the following meanings of B1, ie from (b1) to (bg): Y one of the meanings of Q or where t = 0 or 1, Y preferably denotes Q1 or and preferably Q2 or R17 (1-4C) alkylene, R21 and R22 independently of one another an unsubstituted or substituted (1-6C) -alkyl or (2-6C) -alkenyl radical, R23 and R24 independently of one another hydrogen, an unsubstituted or substituted (1-6C) -Alkyl or (2-6C) -alkenyl radical, R25 is the direct bond or a bridge member.

The rest preferably denotes -NH- (CH2) 2-OH, -N (CH2-CH2-0H2) 29 -NH- (CH2) 2-3N (C2H5) 2, -NH- (CH2) 3N (CH3) 2 -NHCH2CH (CH3) -NH2 -NH (CH2) 3N (CH3) 3 AO, -NHNHCOCH2N (CH3) 3 13.

The remainder (bug) preferably means a remainder (b8a): The remainder (bg) preferably means a remainder (bga): wherein R'21 and R'22 independently of one another a (1-4C) -alkyl radical which is optionally substituted by phenyl or a (2-4C) -alkyl radical which is substituted by OH, CN or halogen, R'23 and R'24 independently of one another are hydrogen or an unsubstituted or a (1-4C) -alkyl radical which is substituted by OH, CN or halogen, R125 is the direct bond, -O-, -S- or -NR7-, a straight-chain or branched (1-10C) -alkylene radical, the may optionally be interrupted by -0-, -S- or -NR7- or a (2-1OC) -alkenylene radical, a phenylene or cyclohexylene radical or a group of the formula m and n independently of one another 0, 1, 2, 3, 4, 5 or 6, WO a radical -NHCONH-, -NHCO (CH2) nCONH-, or mean.

Of the groups (b1) to (b7), the radicals (b1) and (b7) are preferred, which is assigned the designation B 'here.

Group (b7) with the designation 8 ″ is particularly preferred.

Basic groups according to (bg) and bg) are detailed in the DE-OS 32 15 361 described. The preferences given there also apply here.

Of the basic groups (bg) and (bg) are the groups preferred.

Basic groups include protonatable, primary, secondary, and tertiary groups and to understand quaternary ammonium groups. Unless otherwise noted, If several substituents with the same name in the molecule have one of the other independent importance.

Compounds of the formula are preferred and in particular compounds of the formula The process for the preparation of the compounds of the formula (I) is characterized in that (i) 2 or 3 moles of a compound of the formula with 1 mole of a (503H) t X <N = N ß T II I II Compound of formula BY) d (III), in which Y denotes a radical which can be split off as an anion, is reacted in a manner known per se, or (ii) 1 mol of a diazo compound from a di- or triamino compound of the formula to 2 or 3 moles of a compound of the formula clutch.

Both methods can also be used to prepare asymmetric compounds by reacting with various compounds of the formulas (II) or (IV) in a mixture or in succession. The compounds of the formulas (II), (III), (IV) and (V) are widely known. If they are not known, they can be prepared by analogous methods. Compounds of formula (V) wherein or AO means, is prepared from the corresponding pyridone, in which T = - CH2NHCOCH2Cl, by reaction with HNR13R14 or NR13R14Rls in a manner known per se.

The compounds of the formula (I) in the form of the water-soluble acid addition salts or as quaternary ammonium salts are dyes; they are used for colors or printing on fibers, threads or textiles made from them, which are made of cellulose material, e.g. cotton, consist or contain it, according to methods known per se; Cotton is preferably dyed using 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 is compiled according to a method known per se.

The compounds of the formula (I) are particularly suitable (in the form their water-soluble acid addition salts or as quaternary ammonium salts) for coloring or printing paper, e.g. for the production of sized or unsized, wood-free or wood-containing paper in bulk like in the size press. However, they can also be used to dye paper by the dipping process. The inking and printing of paper is carried out using known methods.

The new dyes can also be used for coloring or printing of leather, especially of low-affinity leather types that are vegetable retanned were to be used according to methods known per se. The connections serve also for dyeing or printing bast fibers such as hemp, flax, sissal, jute, coconut or straw.

The colors and prints obtained (especially those on paper) show good fastness properties.

The compounds of the formula (I) can also be used in the form of coloring preparations can be used. Processing in stable, liquid, preferably aqueous, color preparations can be done in a generally known manner, advantageously by lots in suitable Solvents, optionally with the addition of an auxiliary, for example a stabilizer; for example can make such preparations as in the French U.S. Patent No. 1,572,030.

A favorable composition of such liquid preparations is, for example the following (parts mean parts by weight): 100 parts of a compound of the formula (I) as an acid addition salt or as a quaternar ammonium salt, 1-100, preferably 1-10 parts of an inorganic salt, 1-100 parts of an organic acid such as Formic, acetic, lactic, citric acid, 100-800 parts of water, 0-500 parts of a Dissolving agent (e.g. glycols such as diethylene glycol, triethylene glycol, hexylene glycol; Glycol ethers such as methyl cellosolve, methyl carbitol, butyl polyglycol; Urea, formamide, Dimethylformamide).

The compounds of the formula (I) can also be known per se Way to be processed into solid, preferably granulated color preparations, advantageous by granulating as described in French Patent No. 1,581,900.

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

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

The dyes of the formula (I) (as acid addition salt or quaternary Ammonium salt) have good solubility properties, in particular they are characterized by are characterized by good cold water solubility. Since the dyes are highly substantive, color the wastewater in the production of both sized and unsized paper practically not at all or only slightly. They don't blotch on paper when they are colored and are largely insensitive to fillers and pH fluctuations between 4 and 9. The colorations on paper are brilliant and are remarkable Lightfastness off; after prolonged exposure, the shade changes tone-on-tone. the Dyed papers are very good wetfast not only to water, but also to water Milk, fruit juices, sweetened mineral water, soap and saline solutions; also own they have good alcohol fastness and are easy to bleach.

The dyes have high substantivity, i.e. they practically draw quantitatively and show a good build-up ability; they can be in the pulp added directly, i.e. without previous dissolving, as a dry powder or granulate without a reduction in the brilliance or a reduction in the dye yield entry.

The sized paper does not show any color compared to the unsized paper Starch drop. The dyes according to the invention can also be used in soft water can be colored with full color yield.

Fibers that contain wood pulp are mixed with the dyes of the present invention dyed in good and level quality.

Furthermore, the dyes can be used for the production of coated Find paper use. Due to their tendency to pigmentation, it becomes a useful one Fillers, e.g. kaolin, colored with the compounds according to the invention and with this mass gave the paper a one-sided surface coating. The colored ones Papers can be bleached both oxidatively and reductively, which means they can be reused of scrap and waste paper is important.

In the following examples, the parts mean parts by weight or parts by volume; the temperatures are given in degrees Celsius.

Examples 1 5.8 parts of 2,4-bis (4'-amino-3'-sulphophenylamino) -6- (diethylaminopropylamino) -5-triazine (0.01 mol) are dissolved in 150 parts of water and 6 parts of 30% hydrochloric acid and at 0-5 by adding an approx.

25% sodium nitrite solution diazotized. The yellow-brown tetrazo solution 7.4 parts of 3-cyano-6-hydroxy-4-methyl-1- (3'-trimethylammonium) propylpyridone (2) methyl sulfate are now obtained added as an approx. 35% aqueous solution. By adding sodium acetate, the Slowly increase the pH to 5 and at the same time increase the temperature to 20-25 " left, a red dye suspension being formed. After the coupling reaction is complete the precipitated dye is suction filtered and the residue with a little water washed.

The dye of the formula is obtained Anion of the reaction medium The dye dissolves well in water, especially when a carboxylic acid such as acetic acid, lactic acid, formic acid, methoxy- or ethoxyacetic acid, glycolic acid is added, and colors paper in a red shade.

The dye has very good wet fastness properties (water, alcohol, milk, Urine, sodium chloride solution, soapy water, sulfuric acid fastness and an excellent one Lightfastness.

When dyeing in the pH range from 4 to 9, the nuance is practically experienced no change. The wastewater is practically colorless.

The following table shows the structure of other dyes listed as they are obtained according to the information in Example 1.

They correspond to the formula wherein the symbols have the meanings given in the table. Those listed in the description are suitable as anions.

Table 1 - No. DTM Nuance on paper 2 -NH (CH2) 3N (C2H5) 2 - Ae - (CH2) 3N (CH3) 2 yellow. Red 3 do. H do. orange 4 do. CN do. Red 5 do. N @ Ae -CH2CHNH2 yellow. Red CH3 6 do. eSAe do. do. 7 do. do.H3 - (CH2) 3N (CH3) 2 do. 8 do. do. -CH2CH2NH2 do. 9 Cl do. - (CH2) 3N (CH3) 2 orange 10 -NH CH2CHOH @ A (3 do. Yellow. Red 11 -NH0 do. do. do. 12 -NHCH2CHNH2 do. do. do. CH3 13 th. - NO do. do. 14 do. do. H3 -CH3 do. 15 do. do. - (CH2) 3-CH3 do. 16 do. do. - (CH2) 30CH3 do. 17 th. do. -CH2CH20H do. 1 rHCZH40H 18 th. do. b Ht ° q bluust. Red NH (CH2) 3-N (2H5) 2 19 th. do. -CH2CHNH2 yellow. Red CH3 20 -NH (CH2) 3N (C2H5) 2 03N too - (CH2) 2N (C2H5) 2 scarlet 21 do. do. A - (CH2) 3NHCH (CH3) 2 do. 22 th. do. -CH2) 3-NO Pn do. -CH2) 3-N0 23 th. do. -CH2) 3NHCH3 orange 24 th. do. H do. 25 -N N-CH2CH2NH2 do. - (CH2) 3N (CH3) 2 scarlet 26 -NH (CH2) 3NHCH3 do. do. do. 27 -NH (CH2) 3N (C2H5) 2 do. - (CH2) 3- (CH3) 3 do.

In the following Table II the structural structure of further dyes is given, as they can be obtained according to the information in Example 1. They correspond to the formula wherein the symbols have the meanings given in the columns.

The anions in the description come into question.

Table II E.g. DTM Nuance No. on paper 28 -NH (CH2) 3N (C2H5) 2 -d) N to - - (CH2) 3-N (CH3) 2 scarlet 29 CH3, -CN do. bluish ro CH3 H3 30 -NHCH2CHNH2 -NO - do. Scarlet fever 31 -NHCH2CH2OH do. - (CH2) 2N (C2H5) 2 do.

The dyes of the following general formula can be prepared in an analogous manner: E.g. RM Nuance No. on paper 32 H - (CH2) 3-N (CH3) 2 orange scarlet 33 CH3 do. do. 34 H - (CH2) 2N (C2H5) 2 do. 35 H -CH2CH2NH2 do. 36 CH3 do. do.

The dyes represented by the following general formula can be prepared in a similar manner Table IV E.g. BM Nuance No. on paper 37 -CO- - (CH2) N (CH3) 2 orange 38 do. -CH2CH2NH2 do. 39 do. - (CH2) 3-NX do. 40 -CO-CH = CH-CO- - (CH2) 3-N (CH3) 2 do. 41 -CO- (CH2) 2Co-do. do. 42 -COCH2H2CO- 2 A do. do. 43 -COCH2NH (CH2) 3-N N-CH2CO- do. do.

Example 44 (from Table 5) 5.8 parts of 2,4-bis (4'amino-3'-sulfophenylamino) -6- (diethylaminopropylamino) -5 triazine (0.01 mol) are dissolved in 150 parts of water and 6 parts of 30% hydrochloric acid and at 0-5. by adding an approx.

25% sodium nitrite solution diazotized. The yellow-brown tetrazo solution 2.87 parts of 6-hydroxy-4-methyl-1- (3'-dimethylamino) propylpyridonyl- (3) -pyridinium are obtained betaine base (0.01 mol) added. The pH is 1.5 to 2.0 at 0-5g. To One hour of stirring under these conditions ends the one-sided coupling. Now 3.6 parts of 3-cyano-6-hydroxy-4-methyl-1- (3'-trimethylammonium) propylpyridone (2) methyl sulfate are added (0.01 mol) was added as an approx. 35% aqueous solution.

By adding sodium acetate, the pH is slowly increased to 2.5 to 3.0 increased and the temperature allowed to rise to 20-25, leaving a red dye solution arises. After the coupling reaction, the Disazo dye through Sprinkle with soda precipitated at pH 9-9.5 and then separated by filtration.

The dye of the formula is obtained: The dye dissolves well in a dilute carboxylic acid such as acetic acid, lactic acid or methoxyacetic acid. The dye solution colors paper in a bluish-red shade. The dyeing has good wet fastness properties and good light fastness.

The wastewater is colorless.

Dyes of the general formula can be prepared in a similar way: Table V E.g. M1 M2 No. 45 - (CH2) 3-N (CH3) 2 as M1 46 do. - (CH2) 3N (CH3) 3 ND Application examples Color specification 70 parts of chemically bleached sulphite cellulose from coniferous wood and 30 parts of chemically bleached sulphite cellulose from birch wood are ground in 2000 parts of water in a hollander. 0.2 part of the dye from Example 1 (as an acid addition salt) is sprinkled over this mass.

After a mixing time of 20 minutes, it is made into paper. That on The absorbent paper obtained in this way is scarlet in color. The sewage is colorless.

Color regulation B 0.5 part of the dye solution according to Example 1 become 100 parts of bleached sulfite cellulose with 2000 parts of water in was ground by a Dutchman, poured. Mixing takes place after 15 minutes the gluing. Paper made from this material shows a scarlet color Nuance and has excellent wet fastness properties.

Dyeing instruction C An absorbent paper web made of unsized paper is drawn through a dye solution of the following composition at 40-50: 0.5 Parts of the dye from Example 1 (as acid addition salt), 0.5 parts of starch and 99.0 parts of water.

The excess dye solution is squeezed out through two rollers.

The dried paper web is colored scarlet.

Analogous to the dyeing instructions A to C can also be used with the dyes of the other examples in the form of their water-soluble salts or as a preparation, e.g. granulate preparation, can be colored.

Dyeing instructions D 100 parts of freshly tanned and neutralized chrome grain leather are in a liquor of 250 parts of water of 55 and 1 part of the example 1 prepared dye (as acid addition salt) tumbled in the barrel for 30 minutes and in the same bath with 2 parts of an anionic sulphonated fat liquor Oil base treated for a further 30 minutes. The leathers are in the usual Kind of dried and trimmed. You get leather of any color in scarlet tones.

Other low-affinity, vegetable retanned leathers can also be used be colored according to known methods. You can also use the dyes in an analogous manner of the rest of the examples.

Color specification E 2 parts of the dye from Example 1 (as acid addition salt) are dissolved in 4000 parts of softened water and heated to 40. You bring 100 Divide pre-wetted cotton fabric into the bath and heat it to boiling temperature in 30 minutes. The bath is kept at the boiling point for one hour. You take on that remove the fabric from the liquor, rinse with water and dry. The dye pulls practically quantitatively on the fiber, because the dye bath is almost colorless. You get a scarlet coloration of good lightfastness and good wetfastness. Analog can can also be colored with the dyes of the other examples.

Color regulation F (paper with a high content of wood, wood pulp) in one Hollander becomes 70 parts highly bleached wood pulp and 30 parts semi-bleached Sulphate pulp from softwood ground in 2000 parts of water. Scatters to this mass 0.30 parts of the dye from Example 1 (as an acid addition salt). After 20 minutes Mixing time is made from paper. The paper thus obtained is colored scarlet. The wastewater is practically colorless.

Claims (9)

Basic compounds, their preparation and use Patent claims 1. Compounds of the formula in which the azo group is preferably bonded in the 3- or 4-position and the sulfo group is preferably bonded in the ortho position to the azo group, and B is a di- or trivalent bridge member, X is hydrogen or alkyl (C1-4), R is hydrogen, --NH2, a (1-4C) -Alkyl, (5-6C) -cycloalkyl radical, which can be substituted by 1 to three (1-4C) -alkyl radicals, or a phenyl, benzyl or phenylethyl radical, the phenyl radicals of which by one or two methyls , Ethyl, methoxy or ethoxy can be substituted, d 2 or 3, t 0 or 1, T hydrogen, halogen, CN, -COOR4, -CONR5R6, -SO2 NR5Rf or mean, Ac means an optionally substituted acyl radical and preferably Acl, ie -CO-alkyl (C1-4), -CO-alkylene (C1,4) -halogen, -CO-alkylene- (C1-4) -CN, - CO-alkylene (C14) -OCH3, R. a -Co S02-alkyl (C1.4), -S02 -aryl, Ra hydrogen, methyl, halogen, methoxy, cyano, -CONH2, M hydrogen, -NRi1Rl2, (1-4C) -alkyl, hydroxy (2-4C) -alkyl, (1-4C) -alkoxy- (1-4C) -alkyl, (5-6C-cycloalkyl, phenyl- (1-3C) -alkyl, -R1-NH-R0, -V1-NR13R14 or -v -R13R14R15, A- an anion, R1 an alkylene or alkenylene radical optionally interrupted by one or two heteroatoms, a phenylene or cyclohexylene radical, Ro a radical of the formula q 0 or 1, R2 is a residue of the formula -CO- (CH2) 1-3-Z b) or hydrogen, R3 hydrogen, a (1-4C) -alkyl radical, -NR5R6 or -CONR5R6, R4 a (1-6C) -alkyl- or phenyl- (1- 3C) -alkyl radical, R5 and R6 independently of one another hydrogen or (1-40) -alkyl, R7 (1-4C) -alkyl, R8 hydrogen or (1-4C) -alkyl, Rg -5-, -0- or - N-R5, R10 an aliphatic, cycloaliphatic, aromatic or heterocyclic amine or hydrazine radical in which the N atom is bonded to the C atom of the triazinyl radical, and the aliphatic, cycloaliphatic, aromatic or heterocyclic amine or hydrazine radical protonatable and / or quaternary N atoms, Q halogen, OH, -NH2, (1-4C) -alkyl, (1-4C) -alkoxy, phenyl or Rlo, $ Z a radical -NR11R12 or -R13R14R15039 R11 and R12 independently of one another Hydrogen, unsubstituted (1-6C) -alkyl, (2-6C) -alkyl substituted by OH, CN or halogen, phenyl- (1-3C) -alkyl, whose phenyl radical has 1 to 3 substituents from the chlorine series, (1 -4C) -alkyl or (1-4C) -alkoxy substituted se in can, unsubstituted or substituted by 1 to 3 (1-4C) -alkyl groups (5-6C) -cycloalkyl, R13 and R14 independently of one another one of the meanings of R11 and R12 where in the radical -V1-NR13R14 one of the radicals R13 and R14 and preferably both radicals and in the radical -NRl3Rl4Rls AO both radicals R13 and R14 are different from hydrogen, R15 is a (1-4C) -alkyl radical which is optionally substituted by phenyl, R16 is hydrogen, halogen, (1-4C) -alkyl, (1- 4C) alkoxy or nitro, V a (2-6C) -alkylene radical which is optionally substituted by OH, which can be interrupted by -N (1-4C) alkyl, or a (2-6C) -alkenylene radical, V1 a (1- 6C) -alkylene or (2-6C) -alkenylene radical, where the radicals R5 and R6, or R11 and R12 or R13 and R14 together with the N atom bonded to them are a saturated heterocyclic ring and R13, R14 and R15 together with the nitrogen atom attached to it can form a pyridine ring, and the pyridine and the saturated heterocyclic ring can be formed by one, two or three (1-4C ) -Alkyl groups can be substituted, the number of basic groups in the molecule is> 3 and the compounds of the formula I must have at least two -SO3H groups. 2. Process for the preparation of the compounds of the formula (I) according to claim 1, characterized in that 1 mol of a diazo compound is obtained from a di- or triamino compound of the formula with 2 or 3 moles of a compound of the formula clutch. 3. Storage-stable, liquid dye preparations containing a compound of formula (I) according to claim 1. 4. Containing water-soluble, solid, granulated dye preparations a compound of the formula (I) according to claim 1 in the form of a water-soluble SXure addition salt or as a quaternary salt. 5. Use of the compounds of the formula (I) according to claim 1 for coloring or printing paper and leather. 6. Use of the compounds of the formula (I) according to claim 1 for coloring, padding or printing on natural or regenerated cellulose. 7. Use of the compounds of the formula (I) according to claim 1 for coloring, padding or printing of bast fibers such as hemp, flax, sissal, Jute, coconut or straw. 8. According to claim 5, dyed or printed leather or paper. 9. The gemwass claims 6 or 7 colored, padded or printed Material.