JPS59217762A - Basic sulfo-containing polyazo compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Industrial applications The present invention relates to basic sulfo-containing polyazo compounds.

Structure, operation, and effect of the invention According to the present invention, a metal-free form of 1:1 or 1
: Compounds of formula (1) in bimetallic complex form and in free acid or addition salt form are provided: In the following margins (31) (33) (32) [wherein R is hydrogen; C1-4 alkyl; unsubstituted % A or C5-4 cycloalkyl polysubstituted with one or two Cl-4 alkyl groups; phenyl, benzyl or phenyl-ethyl (the phenyl groups of the three substituents are unsubstituted or (R5) substituted with one or two groups selected from methyl, ethyl, methoxy and ethoxy)
2: -80,N(R5)2$6; B is -A-NH-R2; hydrogen; Polysubstituted C2-4 alkyl; (3
4) C5-6 cycloalkyl unsubstituted or polysubstituted with 1 to 3 01-4 alkyl groups; phenyl C
4-6 alkyl (this phenyl group is unsubstituted or polysubstituted with 1 to 3 groups selected from C1-4 alkyl, C1-4 alkoxy and halogen) $ -AI-N (R7 )2 $ -A2-5R8)
2R2A0m9 is -N(Ra)2; Here, X is -0-, -N(R5) or -8-; R3
is hydrogen, C1-4 alkyl, -N(R5)2 or -C
ON(R5)2; R4 is C1-6 alkyl or phenyl-〇,-3 alkyl; R5 is hydrogen or C4-4 alkyl) S or two R5 are bonded to the nitrogen atom; If present, both 85
together with the N atom to which they are attached may form a saturated ring containing 1 to 3 heteroatoms; R6 is C4-. Alkyl; C2-8 alkylene optionally interrupted by up to 2 heteroatoms; C2-8 alkenylene, phenylene optionally interrupted by up to 2 heteroatoms or cyclohexylene; A is C2-8 alkylene or C2-8 alkenylene; A2 is q-8 alkylene or C2-8 alkenylene; where q is ot or 1; R is hydrogen, is O)f, NO2, OH, C, -4
is a full 1-kyl or Cl-4 alkoxy, or hydrogen, where a is an integer from 1 to 3 and 1, "14 is an aliphatic, alicyclic, in which the N atom is bonded to the triazinyl ring, is an aromatic or heterocyclic atronic group; RIM has the meaning of "14" or halodane, OH.

-NH2, C1, alkoxy, phenyl or where A is linear or branched C2-6 alkylene or Izu-CO-CH2- (N is attached to the -NR group); z Bar N(R,)2t *Bar N(R8)2R, Ao
"t' h D s where each B7 is independently hydrogen, Cl-4 alkyl, halogen,
C2-6 alkyl substituted with -OH or 10N group,
phenyl(C4-,)alkyl (the phenyl ring is unsubstituted or substituted with 1 to 3 groups selected from halogen, C1-4 alkyl and C1-4 alkoxy); or unsubstituted or C5- substituted with 1 or 3 Cl-4 alkyl groups.
6cycloalkyl; or both R7 together with the N atom to which they are attached form a 5- or 6-membered saturated term containing 1 to 3 heteroatoms, hereinafter referred to as "cyclic meaning of R7"); each R8 is independently, excluding hydrogen, R
C4- having one of the acyclic meanings of 7 and R2 being unsubstituted or polysubstituted by phenyl. Alkyl or both R8, R, and the N atoms to which they are bonded are unsubstituted or have one or two C4-4
5-1 or 6 containing pyridinium groups substituted with alkyl groups or 1 to 3 heteroatoms that are unsubstituted or polysubstituted by 1 or 2 01-4 alkyl groups - forms a saturated member; one R6o is OH and the other R6o is -NH2;
R6 is hydrogen, C4-4 alkoxy or OH;
R62 water, halodan, nitro, C1-4 alkyl,
C1-4 alkoxy or OH; R65 is R6□
The meaning of R62 is rich regardless of;■ −N(R7)2 Ni N(R8)2R? Aθ$ −CO
Y2-Z Knee C0NH-Y -Z: -YZ:
NH-Co-Y2-Z;2 -802-NH-Y2-Z or -NHNHCOCH2
-Z: Y2 is C1-8 alkylene; and Ao is a non-chromogenic anion. However, (1) The number of cations or protonatable basic groups is smaller than the number of sulfo groups present. is also at least one more; GD R64 has at least one more 3-
or in the 4-position (location is as indicated)
.

When B is -A-NH-R2, B preferably does not contain sulfo. ] As used herein, halodane means fluorine, chlorine, bromine or iodine, preferably chlorine.

When symbols appear more than once in a formula, their meanings are assumed to be independent of each other unless otherwise specified.

The alkyl, alkylene or alkenylene present is
Unless otherwise specified, it is a straight or branched chain. Unless otherwise specified, the alkyl group of the alkoxy group is a straight chain or a branched chain.

Sulfo groups present can be in free acid or salt form. In the salt form, -SO, is the cation yP (yP is a non-chromogenic cation, e.g. N1°, ni0m9 is NH4"
is balanced by basic non-cationic groups that are protonated or by cationic groups in the molecule.

In the absence of a proverb, the preferred meaning of a variable applies to the variable wherever it appears in the specification.

Preferably, the aliphatic amine group is a mono(Cl-4 alkyl)-matahadi(CI-4 alkyl) amine group, each alkyl group independently being halodane, phenyl, hydroxy or C5-6 cycloalkyl. Selected 1
It can be polysubstituted with up to 3 substituents, but it is preferably unsubstituted or monosubstituted with phenyl or hydroxy (hydroxy is 2
position).

The cycloaliphatic amine group present is preferably a C5-6 cycloalkyladenone, the cycloalkyl group of this amine optionally being polysubstituted by one or two 01-2 alkyl groups. The aromatic amine present is preferably aniline, in which the phenyl ring of the aniline is unsubstituted and C4-
4 alkyl% Cl-4 Substituted with 1 to 3 substituents selected from alkoxy, noherone, hydroxy, and phenoxy.

The heterocyclic ring/(or 5-1 or 6-membered heterocycle) present is preferably pyridine, triazine, pyridazine,
Pyrimidine, or pyrazine group or group of formula (if unsaturated) or morpholine, pyrrolidine,
piperidine, piperazine group (if saturated), each group optionally polysubstituted by 1 to 3 R6 groups; where R is preferably R' (a/ is methyl, ethyl ,
unsubstituted phenyl, unsubstituted benzyl or unsubstituted cyclohexyl). More preferably, R is R'' (R
“ stands for methyl or unsubstituted phenyl.

or C0N(RI5)2 (R' and R'i are defined below)].

More preferably, T is T"[T# is CN or elemental, -CH,, -C2H5, -C2H40H, unsubstituted cyclohexyl, benzyl, "CH2)1-IN("7)2
, (CH2)2-4N("8)2" 9 people (symbols are defined below)], more preferably B is B"[B" is -A"-NH-R", Hydrogen, -CuI2. −
C, R5, benzyl, -(OH2)bN(R)2, -
(C) I2), helmet (a%) 2R (signs are defined below, b is 2 or 3)].

Most preferably B is BJF (B# is CHs,
C2H,, benzyl, -(CH2)2-5-NCR5)
2, -(CH2)2-4-1 (1%), Big
, RI or Mu"-Nm-possible).

Human is preferably A' (A/ is C2-8 alkylene or 9 is unsubstituted phenylene), more preferably human is Mu' (A is 1,2-ethylene, 1,3-propylene). or unsubstituted meta t or noyaraphenylene), R2 is preferably RI2 [the symbol is a group of formula (
The symbols R1'I and R1□' are defined below)], more preferably R2 is a bow [I is hydrogen or R3 is preferably B/ (RI3 is hydrogen, methyl, ethyl, -NH2 or -N(CH,)2).

More preferably R5 is (R% Id hydrogen or methyl).

R5 is preferably RI5 (RI5 is hydrogen, methyl or ethyl). Preferably RI5 is hydrogen or methyl.

R6 is preferably RI6 (R- is methyl or ethyl).

R7 is preferably R/ (RI7 is hydrogen, straight chain or branched C7-6 alkyl, unbranched hydroxy C2-3 alkyl, benzyl, 2-chloroethyl, 2-
cyanoethyl or both B/, together with the N atom to which they are attached, are unsubstituted pyrrolidine, piperidine,
morpholine, piperazine, or N-methylpiperazine group). More preferably, R7 is R5 (
R1, is hydrogen, methyl, ethyl or 2-hydroxyethyl or both R1, together with the N atom to which they are attached, form an unsubstituted morpholine, piperidine, piperazine or N-methylpiperazine group).

R8 is preferably RI8 (RI8 has one of the meanings of R/, excluding hydrogen) and R2 is R6 (RI
9 is methyl, ethyl, zoro2 or benzyl)
or RI8 and R1, they are bonded R'9 is -0-1 direct bond, -CH2-1-NH-1-old R6
, to form a pyridinium ring substituted by .

More preferably, R8 is RIB (R18 is one of the meanings of RI7 excluding hydrogen), R1 is R1° (RI is -CH, -C2H5 or benzyl), Alternatively, RI8 and 马 together with the N atom to which they are attached form a pyridinium ring which is unsubstituted or substituted by one or two methyl groups or the group β.

R11 is preferably RI5. (“11 is hydrogen, chloro, nitro, methyl or methoxy).

More preferably, R11 is Rτ (R11 is hydrogen, methyl, or chloro).

R12 is preferably R1□ ("12 is or hydrogen). More preferably R12 is Rτ2 (R'3,
Rτ4 and 7.1 are defined below)]. most preferred (
H/# and R'N, 4 are defined below)].

R is preferably R1, ("15 is chloro, 5 monoC alkylamino, di(C,-2)alkyl-4amino, monohydroxy(C2-4)alkylamino,
bis[hydroxy(02-4)alkylcoamino or -N-R21 (R2, is unsubstituted C1-12 alkyl: R'5 -C2-12 alkyl substituted by -OH: -N(
R,)-■ C5~,2 alkyl pv interrupted by 1 to 3 groups selected from e and -N(R8)2A: -NHCO
CH2-Z: (47) (Yl is C1-8 alkylene or C5-8 alkenylene group, 2 is -N(R,)2t or -W(R8)2
R, Ae, R25 is halogen, -OR, -No2
, C4-4 alkyl or C4-4 alkoxy,
R24 is a group -N(R'7)21 *if: -N(R'
8) 2yt', Aet Taha group -co-Y2-z', -N
HCO-Y2-Z', -CONH-Y2-Zl, -So
, NH-Y2-Z', -y2-z' or -NHNHC
OCH2-Z' (Y2 is C1-8 alkylene))].

R15 is preferably Rτ5 [R%5 is -N-R'
2°R'5 (R'2. is -(CH2)2-5-N(kari)-(CH2)2-, -N
(R',)RQ, -(CHz)2-s-N(R%)2-
("2)z, 5-ff("a)2R2Ae, -(CH
2) 2-5-N(R',)-C2I(5,-(CH2)
2-4S-Stomach (Rs2-C2I (5%-NHcocH2
-zz, -CH2-coNH-yI2-zI, y'
2-zs, (R'6 is methyl or ethyl, Y
'2 is (C,-4)alkylene)]. Most preferably (48) R21 is R12, Teal (R'21 is -NHCOCH2
-Z#.

-CONH(CI(2)2.Z', -NI(CO(C
H2) 2-, -Zl.

-Co(CH2)2-, -Zl or 502NH(CH
2) 2-5zlte).

Most preferably R15 is R7ff5 (BIB
/, 5 is -N- possible.

R (R14 is preferably R', 4 ("14 is -N-"
21R'5). More preferably, R14 is R14 (
Rτ4 is -N(R%)Rrust). Most preferably,
R14 is to R (Sho is -N-R%)
.

R'5 R6, is preferably (R2, is hydrogen, methyl or methoxy).

R6□ is preferably R'62 (R'62 is hydrogen,
rilolo, nitro, methyl, methoxy or OH)
, more preferably RII62 (RI62 is hydrogen,
chloro is also methyl).

R63 is preferably R'63 C''65 is hydrogen, nitro, methoxy, ethoxy, OH1 methyl, ethyl or chloro).More preferably R6 is '65 (RI63 is hydrogen, OH or methoxy)
.

Preferred compounds of formula 1 are metal-free, 1:1 or 1:2 metal complexes and free acid or acid addition salt forms of formula I
' compound N(R'8)2R', Ao, C0NH-Y', -
Z'l-CO-Y4-Z'.

-y'-z' , -5o2NHYI2- z'
, -NHCOY/, -Z/.

NI ('NCOCH2-2'); other symbols are the same as above; however, 1) the number of cationic or protonatable basic groups is at least one more than the number of sulfo groups present; ; If) R'64 is in the 3- or 4-position of the phenyl ring to which it is attached (position as indicated)
.

More preferred compounds of formula (1) are metal-free, 1:
It is a compound of formula ■1 in the form of a 1 or 1:2 metal complex: The following margins (51) (52) [Here, the symbols are the same as above; (1) Cation or proton The number of basic groups that can be converted into sulfo groups is at least one more than the number of sulfo groups present; ); (iii) the azo group on 3Jc is in the 3- or 4-position (positions are as indicated)].

The most preferred compound of formula 1 is a compound of formula ■': below margin (55) [where TI#* R'62 + R6o+ R〃63 r f
r R''13 and R#, 4 are the same as above, provided that the number of neutral thion or protonatable basic groups is at least one more than the number of sulfo groups present; (11) Ring E The amine group above may be in the 3- or 4-position (
The azo group on GID G is in the 3- or 4-position (the positions are as indicated)].

A preferred metallizable group is -NH21-OH in the ortho position to the azo bridge on the benzo or phenyl group.
or -o (c, -4 alkyl).

The metallization of such groups can be expressed as follows: (56) [where each A5 is independently 10- or -NH-;
a is a 1:1 or 1:2 metal complexing metal; R66 and R67 are also ortho to each other with sb, -
Preferred compounds of formula (i) which together form an aromatic ring system (e.g. in metalized form together with the two carbon atoms to which they are attached are compounds of formula (i) a' to c') : (57) ...- Next (59) [Here, Y8 is 10- or →■-; Me is steel, 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, iron or nickel in the case of a 1:2 metal complex (in which case Me is preferably iron); other codes are Same as above; However, (1) In the compounds of formula 1 [a'Ilb' and ■c', R'64 is at the 3- or 4-position J), the naphthylazo group on 'JG is 3 - or 4-position, and the number of cationic and protonatable basic groups is greater than the number of sulfo groups present; (11) In the compound -0-Me-0-
is ortho to the naphthylazo group; (in compounds of formula 11b' and c',
When Ya is -NH-, R6o is OH; when Ya is 10-, R60 is NH2].

(60) A metal-free form of the compound of formula (1) is obtained by reacting a compound of formula (1): with a compound of formula Iv: in an acidic medium to form a compound of formula V:; A compound of formula ■ is reacted with a diazotized compound of formula ■ in an alkaline medium, or a diazotized compound of formula ■ is reacted with a compound of formula ■ in an acidic medium to form a compound of formula ■: and then a diazotized compound of formula ■ is reacted in an acidic medium to form a compound of formula ■: It can be prepared by reacting the compound (2) with the diazotized compound (2) in an alkaline medium.

The 5o3H group can be converted into polysalt form by known methods.

Coupling to form compound 2 can be carried out by known methods. Advantageously, the caragling is carried out in an aqueous (acidic, neutral or alkaline) medium at a temperature of from 0 DEG C. to room temperature, if necessary in the presence of force, a pulling promoter such as pyridine or urea. Alternatively, the coupling can be carried out in a mixture of solvents, such as a mixture of water and an organic solvent. .

Metallization of the compound of formula 1 can be carried out by known methods.

The azo compound of formula (1) in the form of a 1:1 metal complex can be obtained by metallizing the compound of formula (1) in metal-free form with a metal selected from copper, copper, iron, nickel, manganese, chromium and zinc. It can be prepared in various ways.

Azo compounds of the formula ■ in the form of 1:2 metal complexes are prepared by metallization of the compounds of the formula ■ in the metal-free form with metals selected from chromium, nickel, co-metallic acid and iron. I can do it.

The margin metallization is carried out in an aqueous medium or in a mixture of water and a water-miscible organic solvent, such as acetone, lower alkyl alcohol, dimethylformamide, formamide, glycol or acetic acid, from 1.0 to 8.0, preferably from 2 to 7. It is advantageous to do this at -. 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 include, for example, cobalt(II)
or copal) (III) sulfate, acetate, formate or chloride.

Examples of copper-generating compounds include sulfuric acid steel (■) and copper formate (II).
, acetate steel (II) and chloride steel (II).

The nickel generating compound is N1(II) or N1(2)
Compounds such as nickel formate, nickel acetate and nickel sulfate.

The preferred manganese-generating compound is the Mll(II) compound, and the iron-generating compound is F.(I[) or Fa(I
II) 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(II) and Cr(
(to) formates, acetates and sulfates.

In the compounds of formula 1, the anion 80 can be any non-chromogenic anion such as those commonly used in basic dye chemistry. As appropriate anions, chlorine,
Bromine, sulfuric acid, bisulfuric acid, methyl sulfuric acid, aminosulfonic acid,
perchloric acid, benzenesulfonic acid, oxalic acid, maleic acid, acetic acid, noropionic acid, lactic acid, co-phosphoric acid, tartaric acid, malic acid, methanesulfonic acid, and benzoic acid anions and complex anions such as zinc chloride double salt and boric acid, Mention may be made of the anions of citric acid, glycolic acid, diglycolic acid and adducts of adipic acid or orthoboric acid with polyalcohols in which at least one cis diol group is present. These anions can be removed by ion exchange resins or by reaction with acids or salts (e.g. via hydroxides or bicarbonates or as described in DE 2,001,74
8 or 2.001,816).

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 fibers, yarns or textile materials, in particular natural or regenerated ululose materials such as cotton or synthetic polyamides or synthetic polyesters modified with acid groups. Such polyamides are described in Belgian Patent No. 706,104 and such synthetic polyesters are described in US Pat. No. 3.3.
No. 79,723.

The azo compounds of formula 1 can also be applied to stem fibers such as hemp, flax, sisal, jute, coir or straw.

The azo compound of formula 1 is acrylonitrile or 1.1-
It is also used for dyeing, printing or printing fibers, yarns or textile products made from homopolymer mixed polymers of dicyanoethylene or containing the same.

The textile material is dyed, printed or pad dyed by known methods. It is particularly advantageous to dye the acid-modified polyamides in an aqueous, neutral or acidic medium at temperatures from 60 DEG C. to the boiling point or above 100 DEG C. under pressure.

Textile materials can also be dyed with compounds of the formula 1 in organic additives, for example according to the instructions described in DE 2,437,549.

Cellulose materials are primarily dyed by the exhaust method, ie from long or short baths at room temperature to the boiling point, optionally under pressure, with bath ratios of 1:1 to 1:100. Preferably it is 1:20 to 1:50. If dyeing is carried out from short baths, the liquor ratio is 1:5 to 1:15. -l of dye bath 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 formula 1 are also suitable for dyeing or printing paper, for example for the production of bulk-dyed paper with and without sizing. Similarly, dyes can be used to dye paper by dipping. The paper is dyed by known methods.

The dyes of formula 1 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 dyestuffs of formula 1 has good sunlight fastness, good diffusion properties with PVC, good water-wash- and sweat-fastness, good dry-cleaning fastness, good water-drop fastness and Has good hard water fastness.

Dyeing of paper with the dye of Formula 1 produces a substantially clear waste liquid which is of environmental importance. The dye of formula 1 has good dyeing properties, does not run off once applied to paper (67) and is not sensitive to -. The dyeings obtained with the dyes of formula 1 have good light fastness and only fade in intensity in their shade on prolonged exposure to light. The dyestuffs of formula 1 have good wet fastness not only to water but also to milk, soapy water, sodium chloride solution, fruit juices and sweetened mineral water. Furthermore, the dyeings obtained with the dyes of formula 1 have good alcohol fastness and are therefore fast to alcoholic beverages. Furthermore, the dyes of formula 1 have good shade stability.

Dyes of formula 1 can be converted into dyeing formulations. The preparation into stable liquid or solid dyeing preparations is carried out in a generally known manner, advantageously by grinding or granulation, optionally with the addition of auxiliaries such as stabilizers or dissolution medium, for example urea, or by suitable methods. This can be done by dissolving it in a solvent. Such preparations can be prepared, for example, by the methods described in French patents 1,572,030 and 1,581,900 or in German published patents 68, 2,001,748 and 2,001,816. It can be obtained by the number.

A liquid formulation of a compound of formula 1 contains 10-30% by weight of a compound of formula 1.
and up to 30 parts by weight of a solubilizing agent such as urea, lactic acid or acetic acid and the balance water. The solid formulation contains 20-80% dye, 20-80% solubilizer such as urea or Na25o4 and 2-5% dye.
Preferably, the water consists of water.

EXAMPLES In the following examples, all parts and units are by weight and temperatures are in degrees Celsius, unless otherwise indicated.

Margin Example 1 Compound 22 of formula 1: in 600 parts of water in hydrochloric acid medium,
2 parts (0.05 mol) were diazotized with 3.45 parts (0.05 mol) of sodium nitrite at 0-50. Add 150 parts of water and 3 parts of sodium carbonate to this solution.
A solution of 9 parts (0.05 mol) of 1-ano-8-hydroxynaltalene-3,6-disulfonic acid was added dropwise. - of the solution was 1.5. By adding 10 parts of sodium acetate over 12 hours, pi(
was set to 2.3. The dye obtained was the compound 21b: The following is a blank.

22 parts (0.05 mol) of 2.4-bls in hydrochloric acid medium
(diethylaminoprobylamino)-6-(3'-a is nophenylamino)-5-) lyazine with 3.45 parts (0.05 mol) of sodium nitrite in an aqueous medium.
Diazotized at 5° and then added to the compound of formula 354b in acid medium.

The voice was brought to 8.5-9 by adding 45 parts of 30% NaOH aqueous solution. After the coupling is completed, Equation 1
c: Below margin (71) Katasaki Q.

The dye (72) was obtained. This compound IC dyed paper and leather in a black tone.

Example 2 22 parts (0.05 mol) of 2,4-bis(
diethylaminoprobylamino)-6-(3'-aminophenylamino)-3-) riazine in an aqueous medium.
, 45 parts (0,05 mol) of sodium nitrite 0-5
Diazotized at °C. This was then added to 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in acid medium and then 22.2 parts of <1m compound (Example 1
) in an alkaline medium to produce a compound of formula 2a:

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 25 Compounds of the formula: [wherein the codes are given in Table 1] were prepared from appropriate starting materials in a similar manner to Example 1 or Example 2. can be formed. In these examples, the symbols A35-42 and T2. T4 and T5 are as follows.

Below margin (75) Person 5B -(CH2)3N(0His)2A34-(
CH2)2NU2 (77) (76) A4. -〇〇NH(CH2)3N(CH3)2A42-
8O2NH(CH2)2N(C2H5)2.2-CN (78) Examples 26-28 The following metallized compounds can be formed by metallizing appropriate compounds: Example 26: 1:1 of Example 20 Copper lead body example 27 parts Example 22 1=1 copper complex copper lead 28 2 Example 24 1=1 copper complex copper lead 3, 4. The compounds of 9 to 19 and 21 to 28 are black, and the compounds of Examples 5 to 8 and 20 The compound was greenish-black in color.

Application example A 70 parts of chemically bleached sulfite pulp obtained from pine wood and chemically bleached sulfite pulp obtained from campa wood were put into a beating machine and
000 parts of water. Dye of formula 1c from example 10
．． 12 parts were sprinkled into this pulp. After mixing for 20 minutes, paper was made from this 9 loops. The absorbent paper thus obtained was dyed in a black tone. The wastewater was virtually colorless.

Application Example B 0.5 part of the dyestuff of the formula 1c from Example 1 was added to 100 parts of chemically bleached sulfite powder 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 and 99.0 parts of starch. The water-excess dye solution was squeezed out into two rolls.

The dried lengths of paper are then dyed black.

Application example: 100 parts of freshly tanned and neutralized chrome leather, 550 parts
Stirred for 30 minutes in a dyebath consisting of 250 parts of water and 0.5 parts of the dyestuff of Example 1 at °C, 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 almost colorless.

In any of Application Examples A to C, instead of the compound of Example 1, the dyes of other Examples 2 to 28 can be used. The dyes so used can be in the form of solid or liquid preparations.

Below margin λmax, (nm), measured in 1 thiacetic acid/water 621 2 625 3 632 4 640 5 588 6 580 7 556 8 606 10 624 11 626 12 624 13 625 14 625 15 625 16 627 17 626 18 627 23 626 24 625 25 629 (O B) Procedural amendment (voluntary) June 2-7, 1980 Manabu Shiga, Commissioner of the Patent Office 1, Indication of the case 1982 Patent Application No. 90295 2, Name of the invention Basic Sulfo-Containing Polyazo Compound 3, Relationship with the Amended Person's Case Name of Patent Applicant: Sandoz Akchendaselschaft 4, Address of Agent: 8-1-5, Toranomon-chome, Minato-ku, Tokyo 105
Target of amendment (1) "Claims" column of the specification (2) To "Detailed description of the invention" column e of the specification (,,,5Q fi
=-27.

length makishio (83) 6. Contents of amendment (1) Amend the claims as shown in the attached sheet.

(2)H) Page 45 of the specification, line 3, [R5 is R3
"Theal (R5'' is hydrogen") is replaced with "R3 is H, //
(B, // is hydrogen").

(b) Page 47 of the specification, 3rd line from the bottom, “→JH2-1
Insert "r OCH,," after ".

(c) The formula on page 48 of the specification, 4th line from the bottom, center is corrected as follows.

(2) The formula on page 48 of the specification, second line from the bottom, on the left, is amended as follows.

(E) The formula on page 49, line 122 of the specification is corrected as follows.

e ■ 1r-(CH2),, -N(m'8)2-(CH,,)
2-5-N(R"8)2R'62Ae," (f) Formula (1') on page 53 of the specification, (g) Specification 1, page 55
In the formula on page, correct it to.

7. List of appended documents amended claims 1 copy 2. Claim 1: of the formula ■ in metal-free form, 1:1 or 1:2 metal complex form, and free acid or addition salt form Compound.

Space below □ (3) Nikon (1) (where, R is hydrogen: C1-4 alkyl; C5-6 cyclo unsubstituted or substituted by one or two Cl-4 alkyl groups alkyl; phenyl, benzyl or phenyl-ethyl (the phenyl group of the three substituents is unsubstituted or substituted with one or two groups selected from methyl, ethyl, thoxy and ethoxy); ; -COOR4: -CON(Rs)2; -802N
(R5)2: t volume 6; B is -A-■-R2; hydrogen; unsubstituted or C
C1-4alkyl substituted by alkoxy, C2-4alkyl polysubstituted by hydroxy;
C5-6 cycloalkyl, unsubstituted or substituted by 1 to 3 C1-4 alkyl groups; phenyl C4-3 alkyl (this phenyl group is unsubstituted or C alkyl% Cl-47-4 and 1 to 3 selected from halogeno, where X8 is -0-1-N(R5) or -8-; R3
is hydrogen, C1-4 alkyl, -N(R5) 2 or -
C0N(R5)2; R4 is C1-a alkyl or phenyl-CI-5 alkyl; R5 is hydrogen or C1-4 alkyl; or two R5 are present bonded to the nitrogen atom If both R
5 may together with the N atom to which they are attached form a saturated ring containing 1 to 3 heteroatoms; R6 is C1-4 alkyl; A is up to 2 heteroatoms; C2-8 alkylene optionally interrupted by C2-8 alkylene; C2-8 alkenylene, phenylene or cyclohexylene optionally interrupted by up to 2 heteroatoms; A is C2-8 alkylene or C2- 8 alkenylene; A is C alkylene or C2-8 alkenylene 2
1-8; q is O or 1; R11 is hydrogen, halogeno, NO2, OH% C1-4 alkyl or C1-. Alkoxy, -Co(CH2
)a-Z, or hydrogen, where 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 attached to the triazinyl ring. R1, has the meaning of R44 or ノ・口RN,OH
, -NH2,C,-, alkoxy, phenyl or
T where A is a straight chain or branched C2-6 alkylene or tetrastone -CO-CH2- (N is bonded to the -NR5 group); ■ z bar N(R,)2' * fc bar N(R8)2R,
A'' Teh Re: where each R2 is independently substituted with hydrogen, Cl-6 alkyl, ノ10r-0)1 or -CN group, 902-6furkyl, phenyl(C1-,)alkyl( This phenyl ring is unsubstituted or substituted with 1 to 3 groups selected from halo, C1-4 alkyl and C1-4 alkoxy) or unsubstituted or one or C5- substituted with 3 01-4 alkyl groups
or both R2 together with the N atom to which they are attached form a 5-1 or 6-membered saturated ring containing 1 to 3 heteroatoms; each 88 independently has one of the non-cyclic meanings of R7, excluding hydrogen, and R9 is C1-4 alkyl, which is unsubstituted or polysubstituted by phenyl, or Both R8, R7 and the N atoms to which they are attached are unsubstituted or one or two C5-4
A 5- or 6-membered saturated pyridinium group substituted with an alkyl group or containing 1 to 3 heteroatoms that are unsubstituted or substituted with 1 or 2 C1-47yl groups forming a ring; one R6o is OH and the other R6o is -NH2;
R61 is hydrogen, C4-4 alkoxy or OH, R62 is hydrogen, halodane, nitro, C1-4 alkyl,
C1-4 alkoxy or OH; R63 is R62
has the meaning of R62 regardless of; R64 is hydrogen; ■ N(R7)2: -N(R8)2R9Aθ: -CO
Y2-Z knee C0NH-Y -Z: -Y2Z;
N1(-Co-Y2-Z 280□-NH-Y2-
Z or -NHNHCOCH2-Z with Te; Y2 is C
1-8 alkylene; and Ae is a non-chromogenic anion, provided that (1) the number of cationic or zolotonizable basic groups is at least one greater than the number of sulfo groups present; (11) R64 is 3 on the phenyl ring to which it is attached
- or -4- position (positions as indicated). 2. The compound according to claim 1, wherein R is R', that is, methyl, ethyl, unsubstituted phenyl, unsubstituted hensyl or unsubstituted cyclohexyl.

3. The compound according to claim 1, wherein R is R'/ie methyl or unsubstituted phenyl.

4. T is 1, that is hydrogen, CN.

or C0N(R'5) 2 (R'5 is hydrogen, methyl,
ethyl, -Nf(2 or N(CH3)2, R'5
is hydrogen, methyl or ethyl).

Claim 4(8) Compounds described in Section.

6, B is B', i.e. - to -Nu-R'2, hydrogen, -a
■,, -C2H5, -C2H40H, unsubstituted cyclohexyl, benzyl, -(CH2)1-, N(R',)2
, -(CH2)2-sN("a)2"9A0 (A
' is C2-8 alkylene or unsubstituted phenylene,
R'7 is hydrogen, straight chain or branched C4-6 alkyl, unbranched hydroxy C2-, alkyl, benzyl,
2-chloroethyl, 2-cyanoethyl, or both R'7 together with the N atom to which they are attached are unsubstituted -
loridine, piperidine, morpholine, piperazine, or N-methylbiperacin group, R'8 is one of the meanings of R'7 excluding hydrogen, and W is methyl, ethyl,
propyl or benol, or R'8 and R
'9 together with the N atom to which they are attached may form a pyridinium ring which is unsubstituted or substituted by K (which is one or two methyl groups or groups (9) -8-) , B10 is a group of the formula, (where q is as defined in claim 1), and R1 is hydrogen, chloro, nitro, methyl or methoxy; , R', 3 is chloro, -OH, -NH
2. Lucylamino, di(C,-z)alkylamino, monohydroxy(C2-4)alkylamino, bis[
hkc5 Here, R2 is unsubstituted C1-12 alkyl; C s-127 roxy truncated by -■; -NHCOCH2-
Z nee Y, -N N-Yl-Z: V- group (Y is C1-8 alkylene or C3-8
and R24 is a group -N(R', )2 or -N(R'
8) 2R580 or group -co-y2-z', -NHC
O-Y2-Z'.

-CONH-Y2-Z', -8o2NH-Y2-Z',
-Y2-Z' or -NHNHCOCH2-Z' (Y
2 is C4-8 alkylenethi))) A compound according to any one of claims 1 to 5.

7. B is B"i.e. '-NH-R', hydrogen, -
CH3, -C2H5, benzyl, -(CH2), N(*
', )2, (12) ■ -(CH2), N (sing) 2 "9 (b is 2 or 3, A// is 1,2-ethylene, ■, 3-propylene or unsubstituted Meta or phenylene,
abbreviations are hydrogen, methyl, ethyl or 2-hydroxyethyl or both π'7 may together with the N atom to which they are attached form an unsubstituted morpholine, piperidine, biperanone or N-methylpiperazine group. , Shizu is one of the meanings of shout except for hydrogen, and Yagura is -CH3,
-C2H5 or benzyl, or 1.5 and R// together with the N atom to which they are attached are unsubstituted or one or two methyl groups or a group as defined in claim 6 <, &'2 may form a pyridinium ring substituted by β (where q is the same as defined in claim 1), and kl is hydrogen , methyl or chloro, ¥2 is C0CH2Z" or (13) K'5 ¥4 is -N-R'2. and R'21 is Q -(CH2)2.-N (omitted)- (CH2)2-, -N(
shout) R'6, -(CH2)2-3-N(ge'8)2-(
CH2)2-3-N('8)2R'6 A, R' are methyl or ethyl, R2 is the same as defined in claim 1, υ, Y'2 is (C4-4 ) alkylene) according to claim 6.

W' or A/LNH-R'''2 (A'', R'7
, ring and ring are the same as the provisions of claim 7, ■ ("24 is -N(CH3)2, N(CH,), Ao,
-CONH(CH2) 2-, Z'', -NHCO(C
H2) 2. -Z", -Co(CH2)2-5-Z//
Or 5O2NH(CH2)2-52! ! The compound according to claim 6 or 7, wherein γ is the same as defined in claim 7.

9, R6□ is R'62, i.e., hydrogen, chloro, nitro, methyl, methoxy, or OH, R61 is R'61, i.e., hydrogen, methoxy, or methyl, and R63 is 1?63, i.e., thihydrogen, nitro, methoxy, Ethoxy, OH1 methyl,
9. A compound according to any one of claims 1 to 8, which is ethyl or chloro.

10, R64 is R'64, that is, C0NH-Y'-Z',-CO-Y'2-Z'
, -Y'2-Z'.

-5O2NN('Y12-2', -NHCOY'2-2
', NHNI (COCH2-2', cocote R'7
, R'8, R/, and 2 are the same as the provisions of claim 6, and Y'2 is the same as the provisions of claim 7. Claims 1 to 9 A compound according to any of the paragraphs.

11, metal-free, in l:1 or 1:2 metal complex form, or in free acid or acid addition salt form, having the formula 1';
A compound according to claim 1.

Margin below (19) [Here, R' is the same as the provisions of claim 2, and T' is the same as the provisions of claim 4.]
, B' are the same as the provisions of claim 6, and R
6o is the same as the provision of claim 1, and
is the same as the provisions of claim 10), R'6
1, B'62 and R2 are the same as the provisions of claim 9.

provided that i) the number of cationic or protonatable basic groups is at least one greater than the number of sulfo groups present: +i) B'64 is in the 3- or 4-position of the phenyl ring to which it is attached; (The location is as indicated)].

12. A compound according to claim 1, which is metal-free, in the form of a 1:1 or 1:2 metal complex, or in the form of a free acid or acid addition salt, and has the formula (1).

The following margins (20) (21) [Here, "H" is hydrogen, chloro, or methyl; "H" is hydrogen, OH, or methoxy; , l is the same as the provisions of claim 3, τ' is the same as the provisions of claim 5, and 臘R〃 and h14 are the same as the provisions of claim 7. The same applies to the provisions of Section 3.

However, (1) the number of cationic or protonatable basic groups is at least one more than the number of sulfo groups present: (1i) the amino group on ring E is in the 3- or 4-position (the position (as indicated); (uD The azo group on ring G is in the 3- or 4-position (position as indicated)].

13. 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, and have the following formula:

Margin below (22) -414-(23) [Here, τ' is the same as the provisions of claim 5, R'62 is the same as the provisions of claim 12, R6o is the same as defined in claim 1, and B', R'τ3 and R'τ4 are defined as defined in claim 8.

However, (1) the number of cationic or protonatable basic groups is at least one more than the number of sulfo groups present: (+*) the amino group on ring z is in the 3- or 4-position (
location is as indicated); G11) fIIG
The azo group above is in the 3- or 4-position (positions are as indicated).

14. Compounds according to claim 1 having the following formulas 11a to Ilo in the form of 1:1 or 1:2 metal complex salts, or in the form of free acid or acid addition salts.

Margin below - 1
-(24), ; cut (25) [Here, R' is the same as the provisions of claim 2, τ is the same as the provisions of claim 4, υ,
B' is the same as the provisions of claim 6, and "6
2. Same as the provisions of claim 9, R6o
is the same as the provision of claim 1, and -B'6
5 is the same as the provisions of claim 9, and “64
is the same as the provisions of claim 10, Y is -0- or -NH-, and M. is steel, chromium, cobalt, nickel or iron, manganese or Zinc or M
s is chromium, cobalt, iron or nickel in the case of a 1:2 metal complex.

However, in the compounds of formulas na, nb and ■C (1),
``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; 01) In the compound 2nb, -0-
M.-0- is ortho to the phthylazo group; OiD In compounds of formula I[b and Ilc, Y
, L is -NI(-, R6o is OH, Y,
is -0-, R2O is NF2].

15. In producing the compound defined in claim 1, the diazotized compound is reacted with the compound of the formula (■) in an acid medium to form the compound of the formula (2): The compound of formula V is then reacted with a diazo compound of formula ■ in an alkaline medium and the resulting product is optionally metalized, or 2) the diazotized compound of formula ■ is reacted with a compound of formula ■ in an acid medium. reacting in an alkaline medium to form a compound of formula ■: and then reacting the compound of formula ■ with a diazotized compound of formula ■ in an alkaline medium and optionally metalizing the resulting product. Method.

16. A method for dyeing a substrate, comprising applying to the substrate a compound of formula I as defined in claim 1.

Claims (1)

[Scope of Claims] 1. Formula 1 in metal-containing complex form, l:1 or l:2 metal complex form, and free acid or addition salt form (wherein R is hydrogen; C1, alkyl; substituted C5-6 cycloalkyl, unsubstituted or polysubstituted with one or two C4-4 alkyl groups; phenyl, benzyl or phenyl-ethyl (the phenyl group of these three 1g substituents is at risk of being substituted) or substituted with one or two groups selected from methyl, ethyl, methoxy and ethoxy); -COOR4N(R5)2N802N(R5
) 2: R block; The following margin B is -A-NH-R2: Water; 02-4 alkyl;
C5-6 cycloalkyl substituted with at most or polysubstituted by 1 to 3 C4-4 alkyl groups; phenyl C
-A1-N(R7 )2; -A2-N(R8)
2R9Aθ or -N(R7)2; where X, L are 10-1-N(R5) or -8-); R
3 is hydrogen, C1-4 alkyl, -N(R5)2t or -
CON(R5)2; R4 is C1-6 alkyl or phenyl-CI-3 alkyl; R5 is hydrogen or Cl-4 alkyl; or two R5 are bonded to a nitrogen atom; If present, both R5
may form saturated salts containing 1 to 3 heteroatoms together with the N atom to which they are attached; R6 is C1-4 argyl; C2-8 alkylene optionally interrupted by atoms; C2-8 alkenylene, phenylene or cyclohexylene optionally interrupted by up to 2 heteroatoms; A is C2-8 A2 is C1-8 alkylene or C2-8 alkenylene; Where, q is 0 or l; R11 is hydrogen, halodane, NO□, OH , C, -4 alkyl or C4-4 alkoxy, and the following blank space is -Co (CH2-containing -2, or hydrogen), where a is an integer of 1 to 3, and R14 is JL - is an aliphatic, cycloaliphatic, aromatic or heterocyclic amine group attached to the ring; R15 has the meaning of R14 or halogen, OH,
-MH2, C4-4 alkoxy, phenyl or where A3 is linear or branched C2-6 alkylene or -CO-CH2- (F:j is bonded to the -NR5 group); ;Z! ”;i, -N(R,)2t *ij knee'W(R
6) 2R, A0 teri; Here, each R7 is independently hydrogen, 1-6 alkyl, halodane-O
C2-6 alkyl substituted with H or -CN group, phenyl (C1-3) alkyl (this phenyl ring is substituted with Hiko or halogen, C4-4 alkyl and C
(substituted with 1 to 3 groups selected from 4-4 alkoxy) or unsubstituted or 1 or 3 groups selected from 4-4 alkoxy
C5-6 cycloalkyl substituted with C1-4 alkyl groups; or both R7 together with the N atoms to which they are attached contain 1 to 3 heteroatoms;
- or a 6-membered orocyclic ring (hereinafter referred to as "the cyclic meaning of R7"); each R8 independently has one of the acyclic meanings of R7, excluding hydrogen, and R9 is unsubstituted. or C1-4 alkyl substituted by phenyl, or both R8, R2 and the N atoms to which they are bonded may be substituted or at least one or two 17)
Pyridinium group substituted with C1-4 alkyl group or unsubstituted or with 1 or 2 C1
forming a 5- or 6-negative saturated ring containing 1 to 3 heteroatoms substituted by -4 alkyl groups; one R6o is OH and the other R6o is -NH2;
R61 is hydrogen, C4-4 alkoxy or OH;
R62 is water, halodane, nitro, Cl-4 alkyl, C1-4 alkoxy or OH; R63 is R6
has the meaning of R62 regardless of 2; R64 is hydrogen; -N(R7)2; -W(R6)2R, Ao; -co
y2-z ;-CONH-Y2-Z: -y2z; N
H-Co-Y2-Z 5o2-NH-Y2-Z t or -NHNHCOCH2-Z text; Hereinafter, the margin Y2 is C1-8 alkylene 9; and Ae is a non-chromogenic anion, however, The number of basic groups that can be cationized or protonated is at least one more than the number of sulfo groups present; (11) R64 is 3 on the phenyl ring to which it is bonded.
- or -4- position (positions are as indicated). ] 2. R is R', i.e. methyl, ethyl, non-ff conversion 7
The compound according to claim 1, which is xyl, unsubstituted benzyl A or unsubstituted cyclohexyl. 3. The compound according to claim 1, wherein R is R'EII, methyl or unsubstituted phenyl. 4. T is hydrogen, CN. or C0N(bi,)2 (bi is hydrogen, methyl, ethyl, -NH2 or N(CH,)2, and bi is hydrogen, methyl or ethyl). 3
A compound according to any of the paragraphs. or methyl) according to claim 4. 6. B is W, i.e. -A'→m-*2, hydrogen, -CH3
, -C2H5, -C2H40H% unsubstituted cyclohexyl, be'''% -(0H2)1-3N(R7)2, -
(CI(2)zJ(oboro)2R480 (A' is C,
8 fullkylene or unsubstituted phenylene, p, w, are hydrogen, straight chain or branched C4-6 alkyl, unbranched hydroxy C2-3 alkyl, benzine, 2-chloroethyl, 2-cyanoethyl or both pi, together with the N atom to which they are attached, are unsubstituted pyrrolidine, piperidine, morpholine, piperazine, or N-methylbiperazine groups, and R'8, excluding hydrogen, is one of the meanings of B/, , ThD, R' are methyl, ethyl, propyl or benzyl, and R'B and R/, together with the N atom to which they are attached, are unsubstituted or one or two methyl groups. or a group -8-), and R'2 is of the formula, (ζ, where q is the same as defined in claim 1). ), R4, is hydrogen, chloro, nitro, methyl or methoxy, R'14 or hydrogen, W4. is chloro, -OH% -NH
2, alkylamino, di(C,-,)alkylamino, monohydroxy(C2-4)alkylamino, bis[
Hydroxy (C2-4) alkyl co-amino or cy, where R21 is unsubstituted Cl-42 alkyl A: C2-12 alkyl polysubstituted with -OH: -N(R7)-
(11) (Y is C1-8 alkylene or c, -8
-OR, -No□, C4-4 full + l or c, -4A-NHCO-Y, -Z/, -CONH-Y2-'21
, -802NH-Y, -Z', (12) -y2-z' or -NHNHCOCH, -Z'
(y2 is C7-, alkylene))) A compound according to any one of claims 1 to 5. 7. B is Bl, i.e. -hLNH-W, hydrogen, -CH
,, -C2H5, Hensyl, -(CH2)bN (R%)
2, -(CH2)b冑幌)2R4 (b is 2 or 3
#2-ethylene, 1.3-7'ropylene mata is IL with unsubstituted meta- or para-phenylene
R♂ is hydrogen, methyl, ethyl or 2-hydroxyethyl or both camellias may together with the N atom to which they are attached form an unsubstituted morpholine, piperidine, piperazine or N-methylpiperazine group; 18
is one of the meanings of 4 excluding hydrogen, 1) % is 10H,,
-C2H5 or benzyl], or 4 and B1
1. together with the N atom to which they are bonded form a pyridinium ring which is unsubstituted or polysubstituted by one or two methyl groups or the group β defined in claim 6; 4 may be a group with the following margins (where q is the same as defined in claim 1), ``11 is hydrogen, methyl or chloro, and 2 is C0CI (2z# or -Wcy,)
2BI9aetel, R',, tj knee N-R'2. Te s j), 5 Kyo-(CH2) 2- s -N(4')-(CH2)2
-, -N (omitted) to R, -(CH2)2-is-冑(R%
)2-(CH2)2-5-冑(R', )2R', A
o ・-(CH2) 2-5- N(R'7) -C
2R5・-CCH2)2-5-alarm)2-C2H5・-
NHCOCH2-Z', cH2Lccm-y-widey'2
-z", r1 generation) Bl is methyl or ethyl, R2 is the same as defined in claim 1), Y'2 is (C1-4)
7. The compound according to claim 6, which is alkylene. 8, B is f i.e. CH,, C2H5, benzyl, -(
CH2)2-, -N(force)2, -(CH2)2-5-'
*R', )24g or A4NH-v7 (A
”, 4, parrot, and time are the same as the provisions of claim 7, bird is 100 (φΣNH sumo, and t12 is 1 Φ e (”!4 is −N(CH ,)2,N(OH,)llAx-
CONH(CH2)2-,z',-NHCO(CH2
)2-, -Z'. -Co(CH2), -5-Z# or 802Ni((C
H2) 2-, Z'), zI is the same as defined in claim 7) The compound according to claim 6 or 7. 9, R6□ is -2, i.e. hydrogen, chloro, nitro, methi,
methoxy or OH, R6 is "Sl, hydrogen,"
methoxy or methyl, RAS is R13, i.e. hydrogen,
9. A compound according to any of claims 1 to 8 which is nitro, methoxy, ethoxy, OH1methyl, ethyl or chloro. No, R64 is "44" or the following margin (16) R'14 CONH-Y'2-Z' * -Co-Y', -Z'
, -Y'2-Z'h-80□NHY'2-Z' ,
-Nucoy'2-z', NHNI(cocn2-
z', where R/ 1,6, Bl, and 2 are the same as the provisions of claim 6, and Y'2 is the same as the provisions of claim 7. A compound according to any one of claims 1 to 9. 11. Compounds according to claim 1, which are metal-free and have the formula I' in l:1 or l:2 metal complex form, or in free acid or acid addition salt form. The following margins [Here, R' is the same as the provisions of claim 2, and f is the same as the provisions of claim 4.
B/ is the same as the provisions of claim 6, and R2
O is the same as the provisions of claim 1, and “44
is the same as the provisions of claim 10, and R'6
1, R'! 2 and "43" are the same as defined in claim 9. However, 1) the number of cationic or protonatable basic groups is at least one more than the number of sulfo groups present; i+) R '64 is in the 3- or 4-position of the phenyl ring to which it is attached (positions are as indicated)]. 12. Metal-free, 1:1 or 1:2 metal complex form. , or in free acid or acid addition salt form, the compound according to claim 1, having the formula 1. The following margins (19) ε (20) [where duck 2 is hydrogen, chloro or methyl] Yes, 4
3 is hydrogen, OH or methoxy, R2O is the same as the provisions of claim 1, R# is the same as the provisions of claim 3, and D is the same as the provisions of claim 3. V, V, and R14 are the same as the provisions of claim 7. However, (1) the number of cationic or protonatable basic groups is at least one more than the number of sulfo groups present; (ii) the amino group on ff1E is in the 3- or 4-position; 611) The azo group on ring G is in the 3- or 4-position (positions are as indicated). 13. A compound according to claim 1, having the following formula 11-, free of metal, in 1:1t or 1:2 metal complex form, or in free acid or acid addition salt form. The following margins (23) (24) [here, T// is the same as the provisions of claim 5 J), R116□ is the same as the provisions of claim 12, R6o are the same as the provisions of claim 1, h, B///, H#I, and Hal
1 and 4 are the same as the provisions of claim 8. However, the number of neutral thion or protonatable basic groups is at least one more than the number of sulfo groups present; (If) the amine group on mE is
The azo group on GiDma is in the 3- or 4-position (the positions are as indicated)]. 14. A compound according to claim 1 having the following formula [a = t] in the form of a 1:1 or 1:2 metal complex salt or in the form of a free acid or acid addition salt. Below margin (25) -
ri0wa-1
--) (26,) (27) [Here, R' is the same as the provisions of claim 2, J, and 'r' is the same as the provisions of claim 4. J), B/ are the same as the provisions of claim 6.
), R'62 is the same as the provisions of claim 9 J), R60 is the same as the provisions of claim 1), R'65 is the same as the provisions of claim 9 R'64 is the same as the provisions of Claim 10, Ya is 10- or -NH-, and Me is copper in the case of a 1:1 metal complex. , chromium, cobalt, nickel or iron, manganese or zinc, or M
e is chromium, cobalt, iron or nickel in the case of a 1:2 metal complex. However, (1) In the compounds of formula IIs'Ilb' and 11c/, R'64 is Ft at the 3- or 4-position, 3mI
The naphthylazo group on 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; (11) In the compound of 2nb', -0 -Me-0-
is ortho to the naph(28) tylazo group; in the compounds of Cl1D2nb and IIc', Ya
When Yl is ÷, R6G is OH), and when Yl is ÷, R6o is NH2]. 15. In order to produce the compound defined in claim 1, 1) the diazotized compound of 2I: is reacted with the compound of the formula ■: in an acid medium to produce the compound of the formula ■: 2) reacting the compound of formula (1) with the diazo compound of formula (2) in an alkaline medium and optionally metallizing the resulting product; or 2) reacting the diazotized compound of formula (2) with the diazo compound of (2) in an acidic medium to form 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. A method comprising: 16. A method for dyeing a substrate, which comprises applying to the substrate a compound of formula (1) defined in claim 1. Margin below