JPH0526830B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to basic sulfo-containing polyazo compounds. Structure, operation, and effects of the invention According to the present invention, a metal-free form of 1:1
or in 1:2 metal complex form and in free acid or addition salt form, compounds of the formula are provided: [Here, R is C _1-4 alkyl or phenyl; T is hydrogen; -CH;

[Formula] or -CONH ₂ ; B is -A-NH-R ₂ ; hydrogen; C _1-4 alkyl unsubstituted or substituted by C _1-4 alkoxy; C _2- substituted by hydroxy ₄ alkyl; phenyl (C _1-3 alkyl): -A ₁ -N(R ₇ ) ₂
or _-A2 - _N ( _R8 ) _2R9A ; where _R3 is hydrogen or _C1-4 alkyl; A is _C2-6 alkylene, phenylene or cyclohexylene; _A1 is C _2-6 alkylene; A ₂ is C _1-6 alkylene; R ₂ is

[Formula], where q is 0 or 1; R ₁₂ is

[Formula] or -CO(CH ₂ ) _a -Z, a is an integer from 1 to 3, and R ₁₄ is an aliphatic, alicyclic, aromatic or heterocyclic group in which the N atom is bonded to the triazinyl ring. is a cyclic amine group; R ₁₃ has the meaning of R ₁₄ or halogen, OH
or _-NH2 and Z is -N( _R7 ) ₂ or -N( _R8 ) _2R9A ; _{each R7} is independently substituted with hydrogen; _C1-4 alkyl; -OH C _2-4 alkyl; phenyl (C _1-3 alkyl) (the phenyl ring is unsubstituted or substituted with 1 to 3 groups selected from halogen, C _1-4 alkyl and C _1-4 alkoxy) ) or unsubstituted or one or three
C _5-6 cycloalkyl substituted with a C _1-4 alkyl group; or both R ₇ contain 1 to 3 heteroatoms together with the N atom to which they are attached.
- forms a saturated ring (hereinafter referred to as "the cyclic meaning of R ₇ "); each R ₈ independently has one of the acyclic meanings of R ₇ , excluding hydrogen, and R ₉ is unsubstituted. or C _1-4 alkyl substituted by phenyl; or both R ₈ , R ₉ and the N to which they are attached
The atoms are taken together to form a pyridinium group (bonded by an N atom) which is unsubstituted or substituted with one or two C _1-4 alkyl groups; one R ₆₀ is OH and the other R ₆₀ is -NH ₂ ; R ₆₁ is hydrogen, C _1-4 alkoxy or OH; R ₆₃ is hydrogen, halogen, nitro, C _1-4 alkyl,
C _1-4 alkoxy or OH; R ₆₄ is −CONH−Y ₂ −Z;−Y ₂ −Z;NH−CO−Y ₂
-Z or _-SO2 -NH- _Y2 -D; _Y2 is _C1-6 alkylene; and A is a non-chromogenic anion, provided that (i) a cation or a protonatable basic group; is at least 1 greater than the number of sulfo groups present.
(ii) R ₆₄ is 3 on the phenyl ring to which it is attached;
- or -4- position (positions as indicated). ] When B is -A-NH- _R2 , it is preferable that B does not contain a sulfone. In this specification, halogen refers to fluorine, chlorine,
It means bromine or iodine, preferably chlorine. If the sign appears more than once in the expression,
Unless otherwise specified, their meanings are assumed to be independent of each other. Alkyl or alkylene present may be straight chain or branched unless otherwise specified. Unless otherwise specified, the alkyl group of the alkoxy group is a straight chain or branched chain. Sulfo groups present can be in free acid or salt form. In the salt form, _-SO3 is a cation M (M is a non-chromogenic cation such as Na,
K 2 or NH ₄ ) or by protonated basic non-cationic groups or by cationic groups in the molecule. Unless otherwise indicated, the preferred meaning of a variable applies to the variable wherever it appears in the specification. Preferably, the aliphatic amine group is a mono(C _1-4 alkyl)- or di(C _1-4 alkyl)amino group. Each alkyl group can be independently substituted with 1 to 3 substituents independently selected from halogen, phenyl, hydroxy or C _5-6 cycloalkyl, but may be unsubstituted or phenyl or hydroxy. Preferably, it is monosubstituted by (the hydroxy is in a position other than the 2-position). The cycloaliphatic amine groups present are preferably C _5-6 cycloalkylamines, the cycloalkyl groups of which may be substituted by one or two C _1-2 alkyl groups. The aromatic amine present is preferably aniline, the phenyl ring of aniline being unsubstituted or substituted with one selected from C _1-4 alkyl, C _1-4 alkoxy, halogen, hydroxy and phenoxy.
Substituted with ~3 substituents. Heterocyclic amines present (or 5- or 6
-membered heterocycle) is preferably a pyridine, triazine, pyridazine, pyrimidine, or pyrazine group or a formula: group (if unsaturated) or morpholine, pyrrolidine, piperidine, piperazine group (if saturated)
It is. Each group may be substituted by 1 to 3 C _1-4 alkyl groups; where R is preferably R'(R' is methyl, ethyl or unsubstituted phenyl). More preferably R is R''(R'' is methyl or unsubstituted phenyl). T is preferably T'(T' is hydrogen, CH,

[Formula] or CONH ₂ (R′ ₃ is hydrogen or methyl)]. More preferably, T is
T″ [T″ is −CN or

[Formula]]. B is preferably B'[B' is -A'-NH-R' ₂ , hydrogen, -CH ₃ , -C ₂ H ₅ , -
C ₂ H ₄ OH, benzyl, −(CH ₂ ) _1-3 N(R′ ₇ ) ₂ or −(CH ₂ ) _2-3 N (R′ ₈ ) ₂ R′ ₉ A (signs are shown below). Define)〕. More preferably, B is B''[B'' is -A''-NH-R'' ₂ , hydrogen, -CH ₃ , -
C ₂ H ₅ , benzyl, −(CH ₂ ) _b N (R″ ₇ ) ₂ , −(CH ₂ ) _b N (R″ ₈ ) ₂ R″ ₉ A (symbols are defined below. b is 2 or 3)].Most preferably B is B (B is _-CH3 , -
C ₂ H ₅ , benzyl, −(CH ₂ ) _2-3 −N(R″ ₇ ) ₂ , −
(CH ₂ ) _2-3 −N (R″ ₈ ) ₂ R″ ₉ A or −A″−
NH- _R2 ). A is preferably A'(A' is C _2-4 alkylene or unsubstituted phenylene). More preferably, A is A″ (A″ is 1,2-ethylene,
1,3-propylene or unsubstituted meta- or paraphenylene). R ₂ is preferably R′ ₂ [R′ ₂ is of the formula: (symbol R ₁₂ 'defined below)]. More preferably R ₂ is R″ ₂ [R″ ₂ is hydrogen or (R″ ₁₂ is defined below). Most preferably R ₂ is R ₂ (R ₂ is ). R ₇ is preferably R′ ₇ (R′ ₇ is hydrogen, straight chain or branched C _1-4 alkyl, unbranched hydroxy C _2-3 alkyl or benzyl, and both R ' ₇ together with the N atom to which they are attached form an unsubstituted pyrrolidine, piperidine, morpholine, piperazine, or N-methylpiperazine group). More preferably R ₇ is R″ ₇ (R″ ₇ is hydrogen, methyl, ethyl or 2-hydroxyethyl or both R″ ₇ together with the N atom to which they are attached are unsubstituted morpholine, piperidine ,
piperazine or N-methylpiperazine group). R ₈ is preferably R′ ₈ (R′ ₈ is
R′ ₇ is one of the meanings of R′ 7), R ₉ is R′ ₉ (R′ ₉ is methyl, ethyl, propyl or benzyl) or R′ ₈ and R′ ₉ are Together with the N atom, a pyridinium ring is formed which is unsubstituted or substituted by one or two methyl groups. More preferably, R ₈ is R″ ₈ (R″ ₈ is one of the meanings of R″ ₇ excluding hydrogen) and R ₉ is R″ ₉ (R″ ₉ is −CH ₃ , -C ₂ H ₅ or benzyl), or R″ ₈ and R″ ₉ together with the N atom to which they are attached represent a pyridinium ring which is unsubstituted or substituted by one or two methyl groups. R ₁₂ is preferably R′ ₁₂ (R′ ₁₂ is

or -CO(CH ₂ ) _1-2 Z', where R' ₁₃ , R' ₁₄ and Z' are as defined above). More preferably R ₁₂ is R″ ₁₂ [R″ ₁₂ is −COCH ₂ −Z″ or

(R″ ₁₃ , R″ ₁₄ and Z″ are defined below)]. Most preferably R ₁₂ is R ₁₂ [R ₁₂ is

[Formula] (R ₁₃ and R ₁₄ are defined below)]. R ₁₃ is preferably R' ₁₃ [R' ₁₃ is chloro, -
OH, _-NH2 ,

【formula】

[Formula] Mono C _1-4 alkylamino, di- (C _1-2 ) alkylamino, monohydroxy (C _2-4 )
alkylamino, bis[hydroxy(C _2-4 )alkyl]amino or

[Formula] {where R ₂₁ is −CH ₂ CONH−Y ₁ −Z; −Y ₁ −Z;

【formula】

【formula】

【formula】

[expression] or

[Formula] or

[Formula] is an expression

[Formula] or

is a group of [Formula] (where Y ₁ is -N(R ₇ )- or

A C _1-6 alkylene group which may be interrupted by [Formula],
Z is -N( _R7 ) ₂ or _-N ( _R8 ) _2R9A ,
R ₂₄ is the group -N(R' ₇ ) ₂ or -N(R' ₈ ) ₂ R' ₉ A , R ₅ is hydrogen or C _1-4 alkyl, R' ₅ is hydrogen, methyl or ethyl )}]. R ₁₃ is more preferably R″ ₁₃ [R″ ₁₃ is

[Formula] {where R″ ₅ is hydrogen or methyl, and _R′21 is −(CH ₂ ) _2-3 −N(R″ ₇ )−(CH ₂ ) _2-3 −N(R ″ ₇ ）
R′ ₆ , −(CH ₂ ) _2-3 −N (R″ ₈ ) ₂ −(CH ₂ ) _2-3 −
(R″ ₈ ) ₂ R′ ₆ A, −(CH ₂ ) _2-3 −N(R″ ₇ ) −C ₂ H ₅ , −(CH ₂ ) _2-3 −N (R″ ₈ ) ₂ −C _{2H5 ,}

[Formula] −CH ₂ −CONH− Y′ ₂ −Z″ or −Y′ ₂ −Z″, or

【ceremony

[expression] or

[Formula] (R' ₆ is methyl or ethyl and Y' ₂ is C _1-4 alkylene)]. Most preferably R ₂₁
is R″ ₂₁ {R″ ₂₁ is −(CH ₂ ) _2-3 −Z″ or

[Formula] (R' ₂₄ is -N(CH ₃ ) ₂ or N (CH ₃ ) ₃ A)}. Most preferably R ₁₃ is R ₁₃ (R ₁₃ is

[Formula]). Z is preferably Z'(Z' is -N( _R'7 ) ₂ or - _{( R'8} ) _2R'9A ). More preferably, Z is Z″ (Z″ is −N
(R″ ₇ ) ₂ or −N (R″ ₈ ) ₂ R″ ₉ A). R ₁₄ is preferably R′ ₁₄ (R′ ₁₄ is

[Formula]). More preferably, R ₁₄ is R″ ₁₄ (R″ ₁₄ is −N(R″ 5 )R′ ₂₁ ). Most preferably, R ₁₄ is R ₁₄ (R ″ 14 is −N(R″ ₅ )R′ ₂₁ ).

[Formula]). R ₆₁ is preferably R' ₆₁ (R' ₆₁ is hydrogen, methoxy or hydroxy). R ₆₃ is preferably R' ₆₃ (R' ₆₃ is hydrogen, methoxy, ethoxy, OH, methyl, ethyl or chloro). More preferably R ₆₃ is R″ ₆₃ (R″ ₆₃ is hydrogen, -OH or methoxy). Preferred compounds of formula 1 are metal-free, 1:
1 or 1:2 in metal complex form and in free acid or acid addition salt form: [Here, R′ ₆₄ is

[Formula] −CONH−Y′ ₂ −Z′, −Y′ ₂ −Z′, −SO ₂ NHY′ ₂ −Z′ or −NHCOY′ ₂ −Z′; other symbols are the same as above. ; However, (i) the number of cationic or protonatable basic groups is at least one more than the number of sulfo groups present; (ii) R′ ₆₄ is the 3-
or in the 4-position (the position is as indicated). Further preferred compounds of the formula are compounds of the formula "in metal-free, 1:1 or 1:2 metal complex form: [Here, the symbols are as described above; provided that (i) the number of cations or protonatable basic groups is at least 1 greater than the number of sulfo groups present;
(ii) the amino group on ring E is in the 3- or 4-position (positions as indicated); (iii) the azo group on ring G is in the 3- or 4-position (The location is as indicated)]. The most preferred compounds of formula are compounds of formula: [Here, T″, R′ ₆₁ , R ₆₀ , R″ ₆₃ , B, R ₁₃ and
R″ ₁₄ is the same as above, provided that (i) the number of cationic or protonatable basic groups is at least one greater than the number of sulfo groups present; (ii) the amino group on ring E is 3- or in the 4-position (positions as indicated); (iii) the azo group on ring G is in the 3- or 4-position (positions as indicated). Preferred. Metallizable groups are _-NH2 , -OH or -O ( _C1-4 alkyl) in the ortho position to the azobridge on the phenyl or naphthyl group.Metallation of such groups is as follows: It can be expressed as: or

[Formula] [where each A ₅ is independently -O- or -NH-;
Me _a is a 1:1 or 1:2 metal complexing metal; both R ₆₆ and R ₆₇ are in the ortho position to each other;
together form an aromatic ring system (e.g.
along with the two carbon atoms to which they are bonded

[Formula] forming a group)]. Preferred compounds of formula in metallized form are compounds of formula a to c: [wherein Ya is -O- or -NH-; Me is copper, chromium, cobalt, nickel or iron, manganese or zinc in the case of a 1:1 metal complex (in which case Me is preferably copper) ), or Me is chromium, cobalt, in the case of a 1:2 metal complex,
iron or nickel (in which case Me is preferably iron); the other symbols are as above; provided that (i) in compounds of formulas a, b and c:
R′ ₆₄ is in the 3- or 4-position, the naphthylazo group on ring G is in the 3- or 4-position, and the number of cationic and protonatable basic groups is greater than the number of sulfo groups present; (ii) in compounds of formula b, -O-Me-O- is ortho to the naphthylazo group; (iii) in compounds of formula b and c, when Ya is -NH-, R ₆₀ is OH; Yes, Ya-
When O-, R ₆₀ is NH ₂ ]. The metal-free form of a compound of the formula diazotized formula: A compound with the formula: By reacting in an acid medium with a compound of the formula: The compound of formula is then diazotized to form a compound of formula: by reacting a compound of formula in an alkaline medium or by reacting a diazotized compound of formula with a compound of formula in an acid medium to form a compound of formula: can be prepared by forming a compound of formula and then reacting the compound of formula with a diazotized compound of formula in an alkaline medium. The SO ₃ H group can be converted into a salt form by known methods. Coupling to form a compound of the formula can be carried out by known methods. Advantageously, coupling is carried out in an aqueous (acidic, neutral or alkaline) medium at -10 DEG C. and room temperature, if necessary in the presence of a coupling promoter such as pyridine or urea. Alternatively, coupling can be carried out in a mixture of solvents, such as a mixture of water and an organic solvent. Metallization of compounds of the formula can be carried out by known methods. The azo compound of the formula in 1:1 metal complex form is a compound of the formula in metal-free form containing copper, cobalt,
It can be prepared by metallization with metals selected from iron, nickel, manganese, chromium and zinc. Azo compounds of the formula in 1:2 metal complex form can be prepared by metallizing the metal-free form of the compounds of the formula with metals selected from chromium, nickel, cobalt and iron. The metallization is preferably carried out in an aqueous medium or in a mixture of water and a water-miscible organic solvent, such as acetone, lower alkyl alcohols, dimethylformamide, formamide, glycols or acetic acid, at a pH of 1.0 to 8.0, preferably 2 to 7. It's advantageous. The metallization step can be carried out at a temperature between room temperature and the boiling point of the reaction medium. Alternatively, metallization can be carried out in an all-organic medium (eg dimethylformamide). Advantageously, for example, the cobaltation can be carried out in the presence of inorganic nitrites, such as lithium, sodium, ammonium or potassium nitrite, in a ratio of 2 to 6 moles of nitrite per gram atom of cobalt. Suitable cobalt-generating compounds are, for example, cobalt() or cobalt() sulfates, acetates,
Formate or chloride. Copper-generating compounds are, for example, copper sulfate (), copper formate (), copper acetate () and copper chloride (). Nickel-generating compounds are Ni() or Ni()
Compounds such as nickel formate, nickel acetate and nickel sulfate. Preferred manganese generating compounds are Mn() compounds and iron generating compounds are Fe() or Fe
() is a compound. Examples of these and zinc-generating compounds are formates, acetates and sulphates of manganese, iron and zinc. Preferred chromium generating compounds are Cr() and Cr
() are formates, acetates and sulfates. In the compounds of formula 1, the anion A can be any non-chromogenic anion such as those commonly used in basic dye chemistry. Suitable anions include chlorine, bromine, sulfuric acid, bisulfuric acid, methyl sulfuric acid, aminosulfonic acid, perchloric acid, benzenesulfonic acid, oxalic acid, maleic acid, acetic acid, propionic acid, lactic acid, succinic acid, tartaric acid, malic acid, Methanesulfonic acid and benzoic acid anions and complex anions such as zinc chloride double salts and adducts of boric acid, citric acid, glycolic acid, diglycolic acid and adipic acid or orthoboric acid with polyalcohols in which at least one cis diol group is present. Examples include the anion. These anions can be removed by ion exchange resins or by reaction with acids or salts (e.g. via hydroxides or bicarbonates or by
(by number) can be exchanged with each other. The azo compounds of formula 1 are suitably formed into solid or liquid formulations, for example by granulation or by dissolving in suitable solvents. The compounds of formula 1 are suitable for dyeing, padding or printing fibres, yarns or textile materials, in particular natural or regenerated cellulosic materials such as cotton or synthetic polyamides or synthetic polyesters modified with acid groups. Such polyamides are covered by Belgian Patent No. 706104 and such synthetic polyesters are covered by US Pat. No. 3,379,723.
listed in the number. The azo compounds of formula 1 can also be applied to stem fibers such as hemp, flax, sisal, juute, coir or straw. Azo compounds of the formula are also used for dyeing, padding or printing fibers, yarns or textile products made therefrom consisting of or containing homopolymers or mixed polymers of acrylonitrile or 1,1-dicyanoethylene. The fiber material is dyed, printed or padded using known methods. Acid-modified polyamide has a boiling point of ~60℃ in aqueous, neutral or acidic media or under pressure
It is particularly advantageous to dye at temperatures above 100°C. Textile materials can also be dyed with compounds of the formula in organic solvents, for example according to the instructions given in DE 24 37 549. Cellulose materials are mainly dyed by the exhaust method, i.e. from long or short baths at room temperature to the boiling point, optionally under pressure, with bath ratios of from 1:1 to
The ratio is 1:100, preferably 1:20 to 1:50. When dyeing is carried out from short baths, the liquid ratio is 1:5 to 1:15.
It is. The PH of the dyebath is 3-10 (short and long dyebath). Preferably, staining is carried out in the presence of electrolytes. Printing can be carried out by impregnating a printing paste produced by a known method. The dyes of the formula are also suitable for dyeing or printing paper, for example for the production of bulk dyed sized and unsized paper. Similarly, dyes can be used to dye paper by dipping. The paper is dyed by known methods. The dyes of the formula are also suitable for dyeing or printing leather by known methods. Dyeings with good fastness can be obtained both on paper and on leather. Dyed leather with dyes of the formula has good sunlight fastness, good diffusion properties with PVC, good water-wash- and sweat-fastness, good dry-cleaning fastness, good water-drop fastness and good It has excellent hard water fastness. Dyeing of paper with dyes of this type produces a substantially clear waste liquid that is of environmental importance. This dye has good dyeing properties, does not run once applied to paper, and is not sensitive to pH. The dyeings obtained with the dyes of the formula have good light fastness and only become lighter in tone on prolonged exposure to light. The dyestuffs of the formula have good wet fastness not only to water but also to milk, soapy water, sodium chloride solution, fruit juice and sweetened mineral water. moreover,
The dyeings obtained with the dyes of the formula have good alcohol fastness and are therefore fast to alcoholic beverages. Furthermore, the dyes of the formula have good shade stability. The dyes of the formula can be converted into dyeing preparations. The preparation into stable liquid or solid dyeing preparations is carried out in a generally known manner, advantageously by grinding or granulation or in a suitable solvent, optionally with the addition of auxiliaries such as stabilizers or dissolution media such as urea. This can be done by dissolving. Such preparations are covered by e.g. French patents.
1572030 and 1581900 or by the method described in German Published Patent Application No. 2001748 and
No. 2001816. Preferably, a liquid formulation of a compound of formula consists of 10 to 30% by weight of a compound of formula and up to 30% by weight of a solubilizing agent such as urea, lactic acid or acetic acid and the balance water. Solid formulations contain 20-80% dye,
20-80% solubilizer such as urea or Na ₂ SO ₄
and 2 to 5% water. EXAMPLES In the examples below, all parts and percentages are by weight and temperatures are in °C, unless otherwise indicated. Example 1 Formula 1a in hydrochloric acid medium in 600 parts of water: 22.2 parts (0.05 mol) of the compound of 3.45 parts (0.05 mol)
diazotized with sodium nitrite at 0-5°. To this solution was added dropwise a solution of 15.9 parts (0.05 mol) of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 150 parts of water and 3 parts of sodium carbonate. The pH of the solution was 1.5.
The pH was brought to 2.3 by adding 10 parts of sodium acetate over 12 hours. The resulting dye has formula 1b: It was a compound of 22 parts (0.05 mol) of 2,4-bis(diethylaminopropylamino)-6-(3'-aminophenylamino)-5-triazine in hydrochloric acid medium are mixed with 3.45 parts (0.05 mol) of nitrous oxide in aqueous medium. Diazotized with sodium nitrate at 0-5° and then added to the compound of formula 354b in acid medium. The pH was brought to 8.5-9 by adding 45 parts of 30% NaOH aqueous solution. After the cup ring is finished,
Formula 1c: of dye was obtained. This compound 1c dyed paper and leather in a black tone. Example 2 22 parts (0.05 mol) of 2,4-bis(diethylaminopropylamino)-6-(3'-aminophenylamino)-3-triazine in hydrochloric acid medium are mixed with 3.45 parts (0.05 mol) in aqueous medium. ) diazotized with sodium nitrite at 0-5°. This is then converted into 1-amino-8-hydroxynaphthalene-
3,6-disulfonic acid and then 22.2 parts of the compound of formula 1a (from Example 1) in an alkaline medium to form formula 2a: of the compound was produced. It is an isomeric form of compound 1c and dyes paper and leather in black tones. Both dyes 1c and 2a had good fastness properties. Examples 3 to 38 From suitable starting materials in a similar manner to Example 1 or Example 2, the formula: Compounds [where the codes are shown in Table 1] can be formed. In these examples, the sign
A _28-42 and T _2-5 are as follows. A ₂₈ −(CH ₂ ) ₃ −NHCH ₂ CH ₂ OH A ₃₁ −(CH ₂ ) ₃ − N(CH ₃ ) ₃ Cl A ₃₂ −(CH ₂ ) ₃ −N(C ₂ H ₅ ) ₂ A ₃₃ −(CH ₂ ) ₃ N(CH ₃ ) ₂ A ₃₄ − ( _{CH2 ) 2NH2} A ₄₀ −NHCOCH ₂ −N (CH ₃ ) ₃ Cl A ₄₁ −CONH(CH ₂ ) ₃ N(CH ₃ ) ₂ A ₄₂ −SO ₂ NH(CH ₂ ) ₂ N(C ₂ H ₅ ) ₂ T ₂ − CN T ₃ −CONH ₂

【table】

[Table] Examples 39-41 By metallizing suitable compounds, the following metal compounds can be formed: Example 39: 1:1 copper complex of Example 20 Example 40: 1:1 copper complex of Example 22 Example 41: 1:1 copper complex of Example 24 Examples 3, 4, 9-19, 21-25, 28, 30-32 and
Compounds 35-41 are black, Examples 5-8, 20,
Compounds 26, 27, 29, 33 and 34 were greenish black. Application Example A 70 parts of chemically bleached sulfite pulp obtained from pine wood and chemically bleached sulfite pulp obtained from birch wood were placed in a beater and ground in 2000 parts of water. Formula from example 1
0.12 parts of 1c dye was sprinkled into this pulp.
Paper was made from this pulp after 20 minutes of mixing. The absorbent paper thus obtained was dyed in a black tone. The wastewater was virtually colorless. Application Example B 0.5 part of the dye of formula 1c from Example 1 was added to 100 parts of chemically bleached sulphite pulp which had been ground in a beater with 200 parts of water. After thorough mixing for 15 minutes, sizing was performed. Paper made from this material was black in color and had good sunlight and wet fastness. Application Example C A paper without absorption length sizing was passed through a dye solution having the following composition at 40-50°C: 0.5 parts of the dye of Example 1 0.5 parts of starch 99.0 parts of water 2 parts of excess dye solution It was squeezed out using two rolls. The dried lengths of paper were dyed a black tone. Application example D: 100 parts of freshly tanned neutralized chrome leather.
It was stirred for 30 minutes in a vessel containing a dye bath consisting of 250 parts of water at 550 DEG C. and 0.5 parts of the dyestuff of Example 1, and then treated for 30 minutes in the same bath with 2 parts of an anionic fat based on sulfonated whale oil. The leather was then dried and treated in a conventional manner to obtain leather uniformly dyed in black tone. Other low affinity vegetable tanned leathers can be similarly dyed by known methods. Application Example E 2 parts of the dyestuff from Example 1 were dissolved in 4000 parts of deionized water at 40°C. 100 parts of pre-moistened cotton textile substrate were added and the temperature of the bath was raised to boiling point over 30 minutes and held at boiling point for 1 hour. After rinsing and drying, a black dyeing with good light and wet fastness properties was obtained.
Virtually all of the dye was exhausted and the wastewater was nearly colorless. In any of Application Examples A to C, the dyes of other Examples 2 to 41 can be used in place of the compound of Example 1. The dyes so used can be in the form of solid or liquid preparations. λmax. (nm), measurement example in 1% acetic acid/water λmax. Example λmax. 31 627 10 624 32 630 11 626 33 560 12 624 34 582 13 625 35 638 14 625 36 621 15 625 37 624 16 627 38 626 17 626 18 627 23 626

Claims (1)

Claims: 1. Compounds of the formula in metal-free form, in 1:1 or 1:2 metal complex form and in free acid or addition salt form. [Here, R is C _1-4 alkyl or phenyl; T is hydrogen; -CH; [Formula] or -CONH ₂ ; B is -A-NH-R ₂ ; hydrogen; unsubstituted or _C1-4 alkyl substituted by _C1-4 alkoxy; _C2-4 alkyl substituted by hydroxy; phenyl ( _C1-3 alkyl); _-A1 -N( _R7 ) ₂
or _-A2 - _N ( _R8 ) _2R9A ; where _R3 is hydrogen or _C1-4 alkyl; A is _C2-6 alkylene, phenylene or cyclohexylene; _A1 is C _2-6 alkylene; A ₂ is C _1-6 alkylene; R ₂ is [formula], where q is 0 or 1; R ₁₂ is [formula] or −CO ( _CH2 ) _a -Z, a is an integer from 1 to 3, and _R14 is an aliphatic, cycloaliphatic, aromatic or heterocyclic amine group in which the N atom is bonded to the triazinyl ring; R ₁₃ has the meaning of R ₁₄ or halogen, OH
or _-NH2 and Z is -N( _R7 ) ₂ or -N( _R8 ) _2R9A ; _{each R7} is independently substituted with hydrogen; _C1-4 alkyl; -OH C _2-4 alkyl; phenyl (C _1-3 alkyl) (the phenyl ring is unsubstituted or substituted with 1 to 3 groups selected from halogen, C _1-4 alkyl and C _1-4 alkoxy) ) or unsubstituted or one or three
C _5-6 cycloalkyl substituted with a C _1-4 alkyl group; or both R ₇ contain 1 to 3 heteroatoms together with the N atom to which they are attached.
- forms a saturated ring (hereinafter referred to as "the cyclic meaning of R ₇ "); each R ₈ independently has one of the acyclic meanings of R ₇ , excluding hydrogen, and R ₉ is unsubstituted. or C _1-4 alkyl substituted by phenyl; or both R ₈ , R ₉ and the N to which they are attached
The atoms are taken together to form a pyridinium group (bonded by an N atom) which is unsubstituted or substituted with one or two C _1-4 alkyl groups; one R ₆₀ is OH and the other R ₆₀ is -NH ₂ ; R ₆₁ is hydrogen, C _1-4 alkoxy or OH; R ₆₃ is hydrogen, halogen, nitro, C _1-4 alkyl,
C _1-4 alkoxy or OH; R ₆₄ is −CONH−Y ₂ −Z; −Y ₂ −Z; −NH−CO−
Y ₂ -Z or -SO ₂ -NH-Y ₂ -Z; Y ₂ is C _1-6 alkylene; and A is a non-chromogenic anion, provided that (i) a cation or a protonatable base; The number of functional groups is at least 1 greater than the number of sulfo groups present.
(ii) R ₆₄ is 3 on the phenyl ring to which it is attached;
- or -4- position (positions as indicated). 2. Compounds according to claim 1, which are metal-free, in the form of 1:1 or 1:2 metal complexes, or in the form of free acids or acid addition salts, having the formula ". [Here, _R''63 is hydrogen, OH or methoxy, _R60 is the same as the provisions of claim 1, R'' is the same as the provisions of claim 3, T″ is −CN or [Formula] (R′ ₃ is hydrogen or methyl), B″ is −A″−NH−R″ ₂ , hydrogen, −CH ₃ , −C ₂ H ₅ , benzyl, −(CH ₂ ) _b N(R″ ₇ ) ₂ or −(CH ₂ ) _b N
(R″ ₈ ) ₂ R″ ₉ , b is 2 or 3, A″ is 1,2-ethylene, 1,3-propylene or unsubstituted meta- or paraphenylene, R″ ₇ is hydrogen, methyl , ethylene or 2-hydroxyethyl or both R″ ₇ together with the N atom to which they are attached unsubstituted morpholine, piperidine,
may form a piperazine or N-methylpiperazine group, R″ ₈ is one of the meanings of R″ ₇ excluding hydrogen, and R″ ₉ is _-CH3 , _-C2H5 or benzyl _. or R″ ₈ and R″ ₉ may be unsubstituted or form one or two methyl groups with the N atom to which they are attached, R″ ₂ teeth (where q is 0 or 1),
R″ ₁₂ is −COCH ₂ −Z″ or [formula], and Z″ is −N(R″ ₇ ) ₂ or −N (R″ ₈ ) ₂ R″ ₉ A
, R″ ₁₃ is [Formula], R″ ₁₄ is [Formula], R″ ₅ is hydrogen or methyl, and R′ ₂₁ is −(CH ₂ ) _2-3 −N(R″ ₇ )-( _CH2 ) _2-3 -N(R″ ₇ )
R′ ₆ , −(CH ₂ ) _2-3 −N (R″ ₈ ) ₂ −(CH ₂ ) _2-3 −N
(R″ ₈ ) ₂ R′ ₆ A , −(CH ₂ ) _2-3 −N(R″ ₇ ) −C ₂ H ₅ , −(CH ₂ ) _2-3 −N (R″ ₈ ) ₂ −C ₂ H ₅ , [Formula] −CH ₂ −CONH− Y ₂ −Z″ or −Y′ ₂ −Z″, or [Formula] is [Formula] or [Formula], and R′ ₆ is methyl or ethyl, Y′ ₂ is C _1-4 alkylene, and R ₂₄ is −N(R′ ₇ ) ₂ or −N
(R′ ₈ ) ₂ R′ ₉ A and R′ ₇ is hydrogen, straight-chain or branched C _1-4 alkyl, unbranched hydroxy
C _2-3 alkyl or benzyl, or both R′ ₇ together with the N atom to which they are attached form an unsubstituted pyrrolidine, piperidine, morpholine, piperazine, or N-methylpiperazine group;
R′ ₈ is one of the meanings of R′ ₇ except for hydrogen, and R′ ₉
is methyl, ethyl, propyl or benzyl, or R' ₈ and R' ₉ together with the N atom to which they are attached are unsubstituted or one or two methyl groups. However, (i) the number of cationic or protonatable basic groups is at least 1 more than the number of sulfo groups present;
(ii) the amino group on ring E is in the 3- or 4-position (positions as indicated); (iii) the azo group on ring G is in the 3- or 4-position (The location is as indicated). ] 3 Formula in metal-free form, in 1:1 or 1:2 metal complex form and in free acid or addition salt form [Here, R is C _1-4 alkyl or phenyl; T is hydrogen; -CH; [Formula] or -CONH ₂ ; B is -A-NH-R ₂ ; hydrogen; unsubstituted or _C1-4 alkyl substituted by _C1-4 alkoxy; _C2-4 alkyl substituted by hydroxy; phenyl ( _C1-3 alkyl); _-A1 -N( _R7 ) ₂
or _-A2 - _N ( _R8 ) _2R9A ; where _R3 is hydrogen or _C1-4 alkyl; A is _C2-6 alkylene, phenylene or cyclohexylene; _A1 is C _2-6 alkylene; A ₂ is C _1-6 alkylene; R ₂ is [formula], where q is 0 or 1; R ₁₂ is [formula] or -CO( _CH2 ) _a -Z, a is an integer from 1 to 3, and _R14 is an aliphatic, cycloaliphatic, aromatic or heterocyclic amine group in which the N atom is bonded to the triazinyl ring; R ₁₃ has the meaning of R ₁₄ or halogen, OH
or _-NH2 and Z is -N( _R7 ) ₂ or -N( _R8 ) _2R9A ; _{each R7} is independently substituted with hydrogen; _C1-4 alkyl; -OH C _2-4 alkyl; phenyl (C _1-3 alkyl) (the phenyl ring is unsubstituted or substituted with 1 to 3 groups selected from halogen, C _1-4 alkyl and C _1-4 alkoxy) ) or unsubstituted or one or three
C _5-6 cycloalkyl substituted with a C _1-4 alkyl group; or both R ₇ contain 1 to 3 heteroatoms together with the N atom to which they are attached.
- forms a saturated ring (hereinafter referred to as "the cyclic meaning of R ₇ "); each R ₈ independently has one of the acyclic meanings of R ₇ , excluding hydrogen, and R ₉ is unsubstituted. or C _1-4 alkyl substituted by phenyl; or both R ₈ , R ₉ and the N to which they are attached
The atoms are taken together to form a pyridinium group (bonded by an N atom) which is unsubstituted or substituted with one or two C _1-4 alkyl groups; one R ₆₀ is OH and the other R ₆₀ is -NH ₂ ; R ₆₁ is hydrogen, C _1-4 alkoxy or OH; R ₆₃ is hydrogen, halogen, nitro, C _1-4 alkyl,
C _1-4 alkoxy or OH; R ₆₄ is −CONH−Y ₂ −Z; −Y ₂ −Z; −NH−CO−
Y ₂ -Z or -SO ₂ -NH-Y ₂ -Z; Y ₂ is C _1-6 alkylene; and A is a non-chromogenic anion, provided that (i) a cation or a protonatable base; The number of functional groups is at least 1 greater than the number of sulfo groups present.
(ii) R ₆₄ is 3 on the phenyl ring to which it is attached;
- or -4- position (positions as indicated). ] In producing the compound of (1) diazotized formula: A compound with the formula: By reacting in an acid medium with a compound of the formula: The compound of formula is then diazotized to form a compound of formula: (2) reacting a diazotized compound of formula in an alkaline medium with a compound of formula in an acidic medium, or (2) reacting a diazotized compound of formula in an acid medium with a compound of formula: A process comprising forming a compound of formula and then reacting the compound of formula with a diazotized compound of formula in an alkaline medium and optionally metallizing the product obtained. 4 Formula in metal-free form, in 1:1 or 1:2 metal complex form and in free acid or addition salt form [Here, R is C _1-4 alkyl or phenyl; T is hydrogen; -CH; [Formula] or -CONH ₂ ; B is -A-NH-R ₂ ; hydrogen; unsubstituted or _C1-4 alkyl substituted by _C1-4 alkoxy; _C2-4 alkyl substituted by hydroxy; phenyl ( _C1-3 alkyl); _-A1 -N( _R7 ) ₂
or _-A2 - _N ( _R8 ) _2R9A ; where _R3 is hydrogen or _C1-4 alkyl; A is _C2-6 alkylene, phenylene or cyclohexylene; _A1 is C _2-6 alkylene; A ₂ is C _1-6 alkylene; R ₂ is [formula], where q is 0 or 1; R ₁₂ is [formula] or -CO( _CH2 ) _a -Z, a is an integer from 1 to 3, and _R14 is an aliphatic, cycloaliphatic, aromatic or heterocyclic amine group in which the N atom is bonded to the triazinyl ring; R ₁₃ has the meaning of R ₁₄ or halogen, OH
or _-NH2 and Z is -N( _R7 ) ₂ or -N( _R8 ) _2R9A ; _{each R7} is independently substituted with hydrogen; _C1-4 alkyl; -OH C _2-4 alkyl; phenyl (C _1-3 alkyl) (the phenyl ring is unsubstituted or substituted with 1 to 3 groups selected from halogen, C _1-4 alkyl and C _1-4 alkoxy) ) or unsubstituted or one or three
C _5-6 cycloalkyl substituted with a C _1-4 alkyl group; or both R ₇ contain 1 to 3 heteroatoms together with the N atom to which they are attached.
- forms a saturated ring (hereinafter referred to as "the cyclic meaning of R ₇ "); each R ₈ independently has one of the acyclic meanings of R ₇ , excluding hydrogen, and R ₉ is unsubstituted. or C _1-4 alkyl substituted by phenyl; or both R ₈ , R ₉ and the N to which they are attached
The atoms are taken together to form a pyridinium group (bonded by an N atom) which is unsubstituted or substituted with one or two C _1-4 alkyl groups; one R ₆₀ is OH and the other R ₆₀ is -NH ₂ ; R ₆₁ is hydrogen, C _1-4 alkoxy or OH; R ₆₃ is hydrogen, halogen, nitro, C _1-4 alkyl,
C _1-4 alkoxy or OH; R ₆₄ is −CONH−Y ₂ −Z; −Y ₂ −Z; −NH−CO−
Y ₂ -Z or -SO ₂ -NH-Y ₂ -Z; Y ₂ is C _1-6 alkylene; and A is a non-chromogenic anion, provided that (i) a cation or a protonatable base The number of functional groups is at least 1 greater than the number of sulfo groups present.
(ii) R ₆₄ is 3 on the phenyl ring to which it is attached;
- or -4- position (positions as indicated). ] A method for dyeing a substrate, comprising applying a compound of the following to the substrate. 5. The method according to claim 4, wherein the base material is a fibrous material, paper or leather.