Azo compounds having at least one 6-hydroxypyrid-2-one coupling component radical metal complexes thereof and intermediates therefor

• US 4,673,735 A
• Filed: 04/09/1984
• Issued: 06/16/1987
• Est. Priority Date: 04/15/1982
• Status: Expired due to Term

• Current Assignee: Clariant Finance (Bvi) Limited
• Original Assignee: Sandoz Inc. (Novartis Ag)
• Inventors: Moser, Helmut, Wald, Roland, Pedrazzi, Reinhard, Greve, Manfred
• Primary Examiner(s): Higel, Floyd D.
• Application Number:
  US06/598,236
• Time in Patent Office: 1,163 Days
• Field of Search: 260/153, 260/187, 534/797, 534/603, 534/604, 534/605, 534/613, 534/606, 544/181, 544/198, 546/2, 546/193
• US Class Current: 534/606
• CPC Class Codes: C07D 213/20 Quaternary compounds thereof
• CPC Class Codes: C07D 213/74 Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
• CPC Class Codes: C07D 213/77 Hydrazine radicals
• CPC Class Codes: C07D 231/26 1-Phenyl-3-methyl-5- pyrazolones, unsubstituted or substituted on the phenyl ring
• CPC Class Codes: C07D 251/44 with halogen atoms attached to the two other ring carbon atoms
• CPC Class Codes: C07D 251/50 with a halogen atom attached to the third ring carbon atom
• CPC Class Codes: C07D 251/70 Other substituted melamines
• CPC Class Codes: C07D 401/14 containing three or more hetero rings
• CPC Class Codes: C09B 35/461 D being derived from diaminobenzene
• CPC Class Codes: C09B 44/02 containing ammonium groups not directly attached to an azo group
• CPC Class Codes: C09B 45/24 Disazo or polyazo compounds
• CPC Class Codes: D06P 1/41 using basic dyes

Abstract

A compound of formula I ##STR1## in metal-free; 1:1 or 1:2 metal complex form and, when an acid group is present, in free acid or acid addition salt form, in which R₁ is hydrogen or --N═N--D where D is a diazo component and R, T and B are organic radicals defined in the text.

Claims

1. A metal-free compound of the formula ##STR275## or a 1:

1 or 1;

2 metal complex thereof, or an acid addition salt of a metal-free compound of said formula or a 1;

1 or 1;

2 metal complex thereof,

wherein

B is hydrogen;

C_1-4 alkyl;

C_1-4 alkyl monosubstituted by C_1-4 alkoxy;

C_2-4 alkyl substituted by hydroxy;

C_5-6 cycloalkyl;

C_5-6 cycloalkyl substituted by 1 to 3 C_1-4 alkyl groups;

phenyl(C_1-3 alkyl);

phenyl(C_1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from C_1-4 alkyl, C_1-4 alkoxy and halo;

--A--NH--R₂ ;

--A₄ '"'"'--N(R₇)₂ ;

--A₄ --N.sup.⊕

(R₈)₂ R₉ A.sup.⊖

or --N(R₇)₂,

wherein

A is linear or branched C_2-8 alkylene;

linear or branched C_2-8 alkylene interrupted by 1 or 2 hetero atoms;

linear or branched C_2-8 alkenylene;

linear or branched C_2-8 alkenylene interrupted by 1 or 2 hetero atoms;

phenylene or cyclohexylene,

A₄ is linear or branched C_2-8 alkylene or linear or branched C_2-8 alkenylene,

A₄ '"'"' is linear or branched C_1-8 alkylene or linear or branched C_2-8 alkenylene, and

R₂ is ##STR276## wherein R₁₁ is hydrogen, halo, nitro, C_1-4 alkyl or C_1-4 alkoxy, and

R₁₂ is --CO--(CH₂)_a --Z or ##STR277## wherein Z is --N(R₇)₂ or --N.sup.⊕

(R₈)₂ R₉ A.sup.⊖

, and a is 1, 2 or 3,

R is hydrogen;

C_1-4 alkyl;

C_5-6 cycloalkyl;

C_5-6 cycloalkyl substituted by 1 or 2 C_1-4 alkyl groups;

phenyl;

phenyl substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy;

benzyl;

phenylethyl;

or benzyl or phenylethyl the phenyl group of which is substituted by 1 or 2 substituents selected from methyl, ethyl, methoxy and ethoxy,

R₁ is hydrogen or --N═

N--D,

wherein D is a diazo component radical, with the proviso that R₁ must be ##STR278## when B is other than --A--NH--R₂, wherein

A₁ is a tetrazo component radical,

R₁₇ is hydrogen, --N═

N--K₁, --N═

N--A₁₀ --N═

N--K₁, ##STR279## wherein A₁₀ is a tetrazo component radical or a coupling/diazo component radical,

K₁ is a diazo component radical or a coupling component radical,

R₂₀ is --(NR₅)_q --Q₁ --N(R₇)₂, --(NR₅)_q --Q₂ --N.sup.⊕

(R₈)₂ R₉ A.sup.⊖

or ##STR280## wherein Q₁ is linear or branched C_2-6 alkylene, --CH₂ C*O-- or --CH₂ --CON*H--, wherein the * denotes the atom attached to the --(NR₅)_q -- radical, and

Q₂ is linear or branched C_2-6 alkylene, --CH₂ C*O--, --CH₂ CON*H-- or --CH₂ CONHC*O--, wherein the * denotes the atom attached to the --(NR₅)_q -- radical,

X_o is a bridging radical,

R₁₉ is hydrogen;

hydroxy;

amino;

(C_1-4 alkyl)carbonylamino;

benzoylamino;

phenylamino;

or benzoylamino or phenylamino the phenyl group of which is substituted by 1 or 2 substituents selected from halo, nitro, amino, C_1-4 alkyl and C_1-4 alkoxy, with the proviso that R₁₉ must be hydrogen when R₁₇ is other than --N═

N--K₁ and --N═

N--A₁₀ --N═

N--K₁, and

R₆₀ is hydroxy or amino, and

R_60a is hydrogen, hydroxy or amino, with the proviso that R_60a is hydrogen or amino when R₆₀ is hydroxy and is hydroxy when R₆₀ is amino, and

T is hydrogen, cyano, --COOR₄, --CO--N(R₅)₂, --SO₂ --N(R₅)₂, ##STR281## wherein each R₃ is independently hydrogen, C_1-4 alkyl, --N(R₅)₂ or --CO--N(R₅)₂,

R₄ is C_1-6 alkyl or phenyl(C_1-3 alkyl),

R₆ is C_1-4 alkyl, and

X_a is --O--, --NR₅ -- or --S--,

wherein

each R₅ is independently hydrogen or C_1-4 alkyl or, when two R₅ '"'"'s are attached to a nitrogen atom, both R₅ '"'"'s taken together and with the nitrogen atom may form a saturated ring containing 1 to 3 hetero atoms,

each R₇ is independently hydrogen;

C_1-6 alkyl;

C_2-6 alkyl monosubstituted by halo, hydroxy or cyano;

phenyl(C_1-3 alkyl);

phenyl(C_1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from halo, C_1-4 alkyl and C_1-4 alkoxy;

C_5-6 cycloalkyl or C_5-6 cycloalkyl substituted by 1 or 3 C_1-4 alkyl groups, or both R₇ '"'"'s taken together and with the nitrogen atom to which they are attached form a 5- or 6-membered saturated ring containing 1 to 3 hetero atoms,

each R₈ is independently C_1-6 alkyl;

C_2-6 alkyl monosubstituted by halo, hydroxy or cyano;

phenyl(C_1-3 alkyl);

phenyl(C_1-3 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from halo, C_1-4 alkyl and C_1-4 alkoxy;

C_5-6 cycloalkyl or C_5-6 cycloalkyl substituted by 1 or 3 C_1-4 alkyl groups,

each R₉ is independently C_1-4 alkyl or C_1-4 alkyl substituted by phenyl or both R₈ '"'"'s and R₉ taken together and with the nitrogen atom to which they are attached are pyridinium;

pyridinium substituted by 1 or 2 C_1-4 alkyl groups;

or a 5- or 6-membered saturated ring containing 1 to 3 hetero atoms,

each R₁₃ is independently amino;

an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group the nitrogen atom of which is attached to the 1,3,5-triazine ring;

halo;

hydroxy;

C_1-4 alkoxy;

phenyl or ##STR282## wherein A₂ is linear or branched C_2-6 alkylene or --N*HCOCH₂ --,

wherein the * denotes the atom attached to the --NR₅ -- radical, and R, R₁, R₅ and T are as defined above,

each R₁₄ is independently an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group the nitrogen atom of which is attached to the 1,3,5-triazine ring,

each n is independently 0, 1 or 2,

each q is independently 0 or 1, and

each A.sup.⊖

is independently a non-chromophoric anion,

with the provisos that (i) when the compound of Formula I is a monoazo compound free of sulfo groups, it contains at least one water-solubilizing basic or cationic group, (ii) when the compound of Formula I is free of sulfo groups and is other than a monoazo compound, it contains at least two water-solubilizing groups, and (iii) when the compound of Formula I contains one or more sulfo groups, the total number of basic and cationic groups exceeds the number of sulfo groups by at least one.

2. A compound according to claim 1 having the formula ##STR283## wherein A.sup.⊖

is a non-chromophoric anion.

3. A metal-free compound, 1:

1 or 1;

2 metal complex or acid addition salt according to claim 1 wherein T is hydrogen, cyano, --CO--N(R₅ '"'"')₂ or ##STR284## wherein each R₃ '"'"' is independently hydrogen, methyl, ethyl, amino or dimethylamino, and

each R₅ '"'"' is independently hydrogen, methyl or ethyl.

4. A metal-free compound, 1:

1 or 1;

2 metal complex or acid addition salt according to claim 1

wherein

B is hydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_a --N(R₇ '"'"')₂, --(CH₂)_b --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

or --A'"'"'--NH--R₂ '"'"',

wherein

A'"'"' is linear or branched C_2-8 alkylene or phenylene,

R₂ '"'"' is ##STR285## wherein R₁₁ '"'"' is hydrogen, chloro, nitro, methyl or methoxy,

R₁₂ '"'"' is --CO--(CH₂)_t --Z'"'"' or ##STR286## wherein R₁₃ '"'"' is chloro, hydroxy, amino, N,N-di-(C_2-4 hydroxyalkyl)amino, --NR₅ '"'"'R₂₁, ##STR287## wherein R₁₁ '"'"' is as defined above, R₁₄ '"'"' is --NR₅ '"'"'R₂₁, ##STR288## Z'"'"' is --N(R₇ '"'"')₂ or --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

, wherein R₇ '"'"', R₈ '"'"' and R₉ '"'"' are as defined below, and

t is 1 or 2, and

q is 0 or 1,

each R₇ '"'"' is independently hydrogen, C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl or

--N(R₇ '"'"')₂ is pyrrolidino, piperidino, morpholino, piperazino or N'"'"'-methylpiperazino,

each R₈ '"'"' is independently C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl, and

R₉ '"'"' is methyl, ethyl, propyl or benzyl or

--N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"' is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR289## wherein Z_o is a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕

(R₆)₂ --A.sup.⊖

, and

R₉ '"'"' is as defined above,

a is 1, 2 or 3, and

b is 2 or 3,

wherein

R₅ '"'"' is hydrogen, methyl or ethyl, and

R₂₁ is C_1-12 alkyl;

C_2-12 alkyl substituted by hydroxy;

C_3-12 alkyl interrupted by 1 to 3 radicals selected from --NR₇ -- and --N.sup.⊕

(R₈)₂ --A.sup.⊖

;

--NHCO--CH₂ --Z;

--CH₂ --CONH--Y₁ --Z;

--Y₁ --Z;

##STR290## wherein R₂₃ is halo, hydroxy, nitro, C_1-4 alkyl or C_1-4 alkoxy,

R₂₄ is --N(R₇ '"'"')₂, --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

, --CO--Y₂ --Z'"'"', --NHCO--Y₂ --Z'"'"', --CONH--Y₂ --Z'"'"'--SO₂ NH--Y₂ --Z'"'"', --Y₂ --Z'"'"' or --NHNHCO--CH₂ --Z'"'"',

wherein

Y₂ is linear or branched C_1-8 alkylene, and

R₇ '"'"', R₈ '"'"', R₉ '"'"' and Z'"'"' are as defined above,

each Y₁ is independently linear or branched C_1-8 alkylene or linear or branched C_3-8 alkenylene,

Z'"'"' is as defined above, and

R₇, R₈ and Z are as defined in claim 1,

wherein

each R_5a is independently hydrogen or C_1-4 alkyl,

each R₆ is independently C_1-4 alkyl, and

each A.sup.⊖

is independently a non-chromophoric anion.

5. A metal-free compound, 1:

1 or 1;

2 metal complex or acid addition salt according to claim 1 wherein R is methyl, ethyl, phenyl, benzyl or cyclohexyl.

6. A metal-free compound according to claim 1 having the formula ##STR291## or a 1:

1 or 1;

2 metal complex thereof, or an acid addition salt of a metal-free compound of said formula

or a 1;

1 or 1;

2 metal complex thereof,

wherein A₁ '"'"' is ##STR292## wherein R₅₁ is hydrogen, halo, C_1-4 alkyl or C_1-4 alkoxy,

R₅₂ is hydrogen, hydroxy, halo, cyano, --CONH₂, (C_1-4 alkyl)carbonylamino, --NHCONH₂, carboxy, sulfo, C_1-4 alkyl or C_1-4 alkoxy,

each R₅₃ is independently hydrogen, halo, cyano, C_1-4 alkyl, C_1-4 alkoxy, carboxy, sulfo or hydroxy, and

Y_o is a direct bond, --(CH₂)_a --, --O--, --S--, --SO₂ --, --NHCO--, --NHCONH--, --NHCO--(CH₂)_b --CONH--, --CONH--(CH₂)_b --NHCO--, --O--(CH₂)_b --O--, --N═

N-- or --CH═

CH--CO--CH═

CH--,

B₁ '"'"' is hydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_b --N(R₇ ")₂ or --(CH₂)_b --N.sup.⊕

(R₈ ")₂ R₉ "A.sup.⊖

,

wherein

each R₇ " is independently hydrogen, methyl, ethyl or 2-hydroxyethyl or

--N(R₇ ")₂ is morpholino, piperidino, piperazino or N'"'"'-methylpiperazino,

each R₈ " is independently methyl, ethyl or 2-hydroxyethyl, and R₉ " is methyl, ethyl or benzyl or

--N.sup.⊕

(R₈ ")₂ R₉ " is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR293## wherein R₉ '"'"' and Z_o are as defined below, R'"'"' is methyl, ethyl, phenyl, benzyl or cyclohexyl,

R_17a is --N═

N--K₁ '"'"', --N═

N--A₁ '"'"'--N═

N--K₁ '"'"' or ##STR294## wherein K₁ '"'"' is ##STR295## wherein K_b is ##STR296## wherein each R₂₈ is independently hydrogen, halo, C_1-4 alkyl or C_1-4 alkoxy,

R₂₉ is --(CH₂)_m --Z, ##STR297## wherein R₄₆ is hydrogen, --NHCO--(CH₂)_b --Z, --SO₂ NH--(CH₂)_b --Z, --CO--Y₁ --Z or ##STR298## each R₄₇ is independently hydrogen, halo, C_1-4 alkyl, C_1-4 alkoxy, nitro or cyano, and

R₄₈ is C_1-4 alkoxy,

R₃₂ is C_1-4 alkyl or phenyl,

each R₃₃ is independently hydrogen, C_1-4 alkyl, --(CH₂)_b --OCH₃, 2-hydroxyethyl, --(CH₂)_b --N(CH₃)₂ or --(CH₂)_b --N.sup.⊕

(CH₃)₃ A.sup.⊖

,

R₃₄ is amino or hydroxy,

R₃₅ is C_1-4 alkyl, --COOR₆, --CO--N(R_5a)₂ or --CONH--Y₁ --Z,

R₃₆ is hydrogen, ##STR299## wherein R₄₉ is hydrogen, --CONH--Y₁ --Z, --SO₂ NH--Y₁ --Z, --NHCO--(CH₂)_b --Z or ##STR300## and each R₅₀ is independently hydrogen, halo, C_1-4 alkoxy, C_1-4 alkyl, nitro or amino,

R₃₇ is hydrogen, --NHCO--(CH₂)_a --Z, --SO₂ NH--Y₁ --Z, --CONH--Y₁ --Z, --CONHNH₂, --NH--Y₁ --Z, --CH₂ --Z, --NHNHCO--CH₂ --Z, nitrophenylcarbamoyl or ##STR301## R₃₈ is C_1-4 alkyl, benzyl or 2-cyanoethyl, R₃₉ is C_1-4 alkyl or --(CH₂)_m --Z,

each R₄₀ is independently hydrogen, C_1-4 alkyl or C_1-4 alkoxy,

R₆₃ is hydrogen, chloro, nitro, C_1-4 alkyl, C_1-4 alkoxy or hydroxy,

R₆₄ is hydrogen, dimethylamino, trimethylammonium A.sup.⊖

, diethylamino, triethylammonium A.sup.⊖

, --CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂ --Z, --NHCO--Y₂ --Z, --SO₂ NH--Y₂ --Z, --NHNHCO--CH₂ --Z or ##STR302## R'"'"' is as defined above, and B'"'"' and T'"'"' are as defined below,

X_o '"'"' is --NH--, --NHCONH--, --NHCO--CH═

CH--CONH--, --NHCO--(CH₂)_b --CONH--, ##STR303## , and

A₁ '"'"' is as defined above, and

T'"'"' is hydrogen, cyano, --CO--N(R₅ '"'"')₂ or ##STR304## wherein each R₃ '"'"' is independently hydrogen, methyl, ethyl, amino or dimethylamino, and

each R₅ '"'"' is independently hydrogen, methyl or ethyl,

wherein

B'"'"' is hydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_a --N(R₇ '"'"')₂, --(CH₂)_b --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

or --A'"'"'--NH--R₂ '"'"',

wherein

A'"'"' is linear or branched C_2-8 alkylene or phenylene,

R₂ '"'"' is ##STR305## wherein R₁₁ '"'"' is hydrogen, chloro, nitro, methyl or methoxy,

R₁₂ '"'"' is --CO--(CH₂)_t --Z'"'"' or ##STR306## wherein is chloro, hydroxy, amino, N,N-di-(C_2-4 -hydroxyalkyl)amino, --NR₅ '"'"'R₂₁, ##STR307## wherein R₁₁ '"'"' is as defined above, R₁₄ '"'"' is --NR₅ '"'"'R₂₁, ##STR308## Z'"'"' is --N(R₇ '"'"')₂ or --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

, wherein R₇ '"'"', R₈ '"'"' and R₉ '"'"' are as defined below, and

t is 1 or 2,

each R₇ '"'"' is independently hydrogen, C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl or

--N(R₇ '"'"')₂ is pyrrolidino, piperidino, morpholino, piperazino or N'"'"'-methylpiperazino,

each R₈ '"'"' is independently C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl, and

R₉ '"'"' is methyl, ethyl, propyl or benzyl or

--N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"' is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR309## wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕

(R₆)₂ --A.sup.⊖

, and

R₉ '"'"' is as defined above,

wherein

R₅ '"'"' is hydrogen, methyl or ethyl, and

R₂₁ is C_1-12 alkyl;

C_2-12 alkyl substituted by hydroxy;

C_3-12 alkyl interrupted by 1 to 3 radicals selected from --NR₇ -- and --N.sup.⊕

(R₈)₂ --A.sup.⊖

;

--NHCO--CH₂ --Z;

--CH₂ --CONH--Y₁ --Z;

--Y₁ --Z;

##STR310## wherein R₂₃ is halo, hydroxy, nitro, C_1-4 alkyl or C_1-4 alkoxy,

R₂₄ is --N(R₇ '"'"')₂, --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

, --CO--Y₂ --Z'"'"', --NHCO--Y₂ --Z'"'"', --CONH--Y₂ --Z'"'"' --SO₂ NH--Y₂ --Z'"'"', --Y₂ --Z'"'"' or --NHNHCO--CH₂ --Z'"'"',

wherein R₇ '"'"', R₈ '"'"' and R₉ '"'"' are as defined above,

wherein

each R_5a is independently hydrogen or C_1-4 alkyl,

each R₆ is independently C_1-4 alkyl,

each R₇, R₈, R₁₃, R₁₄ and Z is independently as defined in claim 1,

each R₁₃ '"'"', R₁₄ '"'"' and Z'"'"' is independently as defined above,

each Y₁ is independently linear or branched C_1-8 alkylene or linear or branched C_3-8 alkenylene,

each Y₂ is independently linear or branched C_1-8 alkylene,

each a is independently 1, 2 or 3,

each b is independently 2 or 3,

each m is independently 1, 2, 3, 4, 5 or 6,

each q is independently 0 or 1, and

each A.sup.⊖

is independently a non-chromophoric anion.

7. A metal-free compound according to claim 1 having the formula ##STR311## or a 1:

1 or 1;

2 metal complex thereof, or an acid addition salt of a metal-free compound of said formula or a 1;

1 or 1;

2 metal complex thereof,

wherein

A" is 1,2-ethylene, 1,3-propylene, 1,3-phenylene or 1,4-phenylene,

R" is methyl or phenyl,

R₁ "'"'"' is hydrogen or --N═

N--D",

wherein

D" is ##STR312## wherein K_a " is ##STR313## R₁₇ '"'"' is hydrogen, ##STR314## --N═

N--K₁ '"'"', --N═

N--A₁ '"'"'--N═

N--K₁ '"'"' or ##STR315## wherein R₂₀ '"'"' is --NR₅ '"'"'--Q₁ --N(R₇ '"'"')₂, --NR₅ '"'"'--Q₂ --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

or ##STR316## R₂ " is ##STR317## wherein R₁₂ " is --CO--CH₂ --Z" or ##STR318## wherein R₁₃ " is --NR₅ "R₂₁ ", ##STR319## R₁₄ " is --NR₅ "R₂₁ '"'"', ##STR320## and Z" is --N(R₇ ")₂ or --N.sup.⊕

(R₈ ")₂ R₉ "A.sup.⊖

, and

R" is cyano or ##STR321## wherein R₃ " is hydrogen or methyl,

wherein

each A₁ '"'"' is independently ##STR322## wherein R₅₁ is hydrogen, halo, C_1-4 alkyl or C_1-4 alkoxy,

R₅₂ is hydrogen, hydroxy, halo, cyano, --CONH₂, (C_1-4 alkyl)carbonylamino, --NHCONH₂, carboxy, sulfo, C_1-4 alkyl or C_1-4 alkoxy,

each R₅₃ is independently hydrogen, halo, cyano, C_1-4 alkyl, C_1-4 alkoxy, carboxy, sulfo or hydroxy, and

Yo is a direct bond, --(CH₂)_a --, --O--, --S--, --SO₂ --, --NHCO--, --NHCONH--, --NHCO--(CH₂)_b --CONH--, --CONH--(CH₂)_b --NHCO--, --O--(CH₂)_b --O--, --N═

N-- or --CH═

CH--CO--CH═

CH--,

wherein

B'"'"' is hydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_a --N(R₇ '"'"')₂, --(CH₂)_b --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

or --A'"'"'--NH--R₂ '"'"',

wherein A'"'"' is linear or branched C_2-8 alkylene or phenylene,

R₂ '"'"' is ##STR323## wherein R₁₁ '"'"' is hydrogen, chloro, nitro, methyl or methoxy,

R₁₂ '"'"' is --CO--(CH₂)_t --Z'"'"' or ##STR324## wherein R₁₃ '"'"' is chloro, hydroxy, amino, N,N-di-(C_2-4 -hydroxyalkyl)amino, --NR₅ '"'"'R₂₁, ##STR325## wherein R₁₁ '"'"' is as defined above, R₁₄ '"'"' is --NR₅ '"'"'R₂₁, ##STR326## Z'"'"' is --N(R₇ '"'"')₂ or --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

, wherein R₇ '"'"', R₈ '"'"' and R₉ '"'"' are as defined below, and

t is 1 or 2,

wherein K₁ '"'"' is ##STR327## wherein K_b is ##STR328## wherein R₂₉ is --(CH₂)_m --Z, ##STR329## wherein R₄₆ is hydrogen, --NHCO--(CH₂)_b --Z, --SO₂ NH--(CH₂)_b --Z, --CO--Y₁ --Z or ##STR330## each R₄₇ is independently hydrogen, halo, C_1-4 alkyl, C_1-4 alkoxy, nitro or cyano, and

R₄₈ is C_1-4 alkoxy,

R₃₂ is C_1-4 alkyl or phenyl,

each R₃₃ is independently hydrogen, C_1-4 alkyl, --(CH₂)_b --OCH₃, 2-hydroxyethyl, --(CH₂)_b --N(CH₃)₂ or --(CH₂)_b --N.sup.⊕

(CH₃)₃ A.sup.⊖

,

R₃₄ is amino or hydroxy,

R₃₅ is C_1-4 alkyl, --COOR₆, --CO--N(R_5a)₂ or --CONH--Y₁ --Z,

R₃₆ is hydrogen, ##STR331## wherein R₄₉ is hydrogen, --CONH--Y₁ --Z, --SO₂ NH--Y₁ --Z, --NHCO--(CH₂)_b --Z or ##STR332## and each R₅₀ is independently hydrogen, halo, C_1-4 alkoxy, C_1-4 alkyl, nitro or amino,

R₃₇ is hydrogen, --NHCO--(CH₂)_a --Z, --SO₂ NH--Y₁ --Z, --CONH--Y₁ --Z, --CONHNH₂, --NH--Y₁ --Z, --CH₂ --Z, --NHNHCO--CH₂ --Z, nitrophenylcarbamoyl or ##STR333## R₃₈ is C_1-4 alkyl, benzyl or 2-cyanoethyl, R₃₉ is C_1-4 alkyl or --(CH₂)_m --Z,

each R₄₀ is independently hydrogen, C_1-4 alkyl or C_1-4 alkoxy,

R₆₃ is hydrogen, chloro, nitro, C_1-4 alkyl, C_1-4 alkoxy or hydroxy,

R₆₄ is hydrogen, dimethylamino, trimethylammonium A.sup.⊖

, diethylamino, triethylammonium A.sup.⊖

, --CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂ --Z, --NHCO--Y₂ --Z, --SO₂ NH--Y₂ --Z, --NHNHCO--CH₂ --Z or ##STR334## and B'"'"' is as defined above,

K_b '"'"' is ##STR335## wherein B'"'"' is as defined above, each R'"'"' is independently methyl, ethyl, phenyl, benzyl or cyclohexyl,

each R_5a is independently hydrogen or C_1-4 alkyl,

each R₅ '"'"' is independently hydrogen, methyl or ethyl,

each R₅ " is independently hydrogen or methyl,

each R₆ is independently C_1-4 alkyl,

each R₇ '"'"' is independently hydrogen, C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl or

--N(R₇ '"'"')₂ is pyrrolidino, piperidino, morpholino, piperazino or N'"'"'-methylpiperazino,

each R₇ " is independently hydrogen, methyl, ethyl or 2-hydroxyethyl or

--N(R₇ ")₂ is morpholino, piperidino, piperazino or N'"'"'-methylpiperazino,

each R₈ '"'"' is independently C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl, and

each R₉ '"'"' is independently methyl, ethyl, propyl or benzyl or --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"' is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR336## wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕

(R₆)₂ --A.sup.⊖

, wherein R₆ is as defined above, and

R'"'"'₉ is as defined above,

each R₈ " is independently methyl, ethyl or 2-hydroxyethyl, and

each R₉ " is independently methyl, ethyl or benzyl or --N.sup.⊕

(R₈ ")₂ R₉ " is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR337## wherein R₉ '"'"' and Zo are as defined above, each R₁₃ '"'"' and R₁₄ '"'"' is independently as defined above,

R₂₁ is C_1-12 alkyl;

C_2-12 alkyl substituted by hydroxy;

C_3-12 alkyl interrupted by 1 to 3 radicals selected from --NR₇ -- and --N.sup.⊕

(R₈)₂ --A.sup.⊖

;

--NHCO--CH₂ --Z;

--CH₂ --CONH--Y₁ --Z;

--Y₁ --Z;

##STR338## wherein R₂₃ is halo, hydroxy, nitro, C_1-4 alkyl or C_1-4 alkoxy,

R₂₄ is --N(R₇ '"'"')₂, --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

, --CO--Y₂ --Z'"'"', --NHCO--Y₂ --Z'"'"', --CONH--Y₂ --Z'"'"'--SO₂ NH--Y₂ --Z'"'"', --Y₂ --Z'"'"' or --NHNHCO--CH₂ --Z'"'"',

wherein R₇ '"'"', R₈ '"'"' and R₉ '"'"' are as defined above, and

R_5a and R₆ are as defined above,

R₂₁ '"'"' is --(CH₂)_b --N(R₇ ")--(CH₂)_b --NR₇ "R₆ '"'"', --(CH₂)_b --N.sup.⊕

(R₈ ")₂ --(CH₂)_b 13 N.sup.⊕

(R₈ ")₂ R₆ '"'"'2A.sup.⊖

, --(CH₂)_b --N(R₇ ")--C₂ H₅, --(CH₂)_b --N.sup.⊖

(R₈ ")₂ --C₂ H₅ A.sup.⊖

, --NHCO--CH₂ --Z", --CH₂ --CONH--Y₂ '"'"''"'"'Z", ##STR339## wherein R₆ '"'"' is methyl or ethyl,

Y₂ '"'"' is linear or branched C_1-4 alkylene, and

R₇ ", R₈ ", R₂₄ and Z" are as defined above,

each R₂₆ is independently hydrogen, halo, nitro, amino, C_1-4 alkyl, C_1-4 alkoxy, cyano, trifluoromethyl, phenyl, anilino, benzoyl, carbamoyl, phenoxy, halophenoxy, dihalophenoxy, C_1-4 alkylsulfonyl, phenylsulfonyl, C_1-4 alkylsulfonylamino or N,N-di(C_1-4 alkyl)sulfamoyl,

each R₂₈ is independently hydrogen, halo, C_1-4 alkyl or C_1-4 alkoxy,

R₂₉ '"'"' is --(CH₂)_m'"'"' Z'"'"', ##STR340## wherein R₄₆ '"'"' is hydrogen, --NHCO--(CH₂)_b --Z'"'"', --SO₂ NH--(CH₂)_b --Z'"'"' or ##STR341## wherein R₁₃ '"'"' and R₁₄ " are as defined above, each R₄₇ '"'"' is independently hydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy, nitro or cyano, and

R₄₈ '"'"' is methoxy or ethoxy, and

each R₃₃ '"'"' is independently hydrogen, 2-hydroxyethyl, 3-methoxypropyl, --(CH₂)_b --N(CH₃)₂ or --(CH₂)_b --N.sup.⊕

(CH₃)₃ A.sup.⊖

,

R₃₄ is hydroxy or amino,

R₃₆ '"'"' is hydrogen, ##STR342## wherein R₄₉ '"'"' is hydrogen, --CONH--(CH₂)_m '"'"'--Z'"'"', --NHCO--(CH₂)_b --Z'"'"' or ##STR343## wherein R₁₃ '"'"' and R₁₄ '"'"' are as defined above, and each R₅₀ '"'"' is independently hydrogen, chloro, methyl or methoxy,

R₃₇ '"'"' is ##STR344## wherein R₁₃ " and R₁₄ " are as defined above, R₃₈ '"'"' is methyl, ethyl, 2-cyanoethyl or benzyl,

R₃₉ '"'"' is methyl, ethyl or --(CH₂)_m '"'"'--Z,

R₄₀ is independently hydrogen, C_1-4 alkyl or C_1-4 alkoxy,

each T'"'"' is independently hydrogen, cyano, --CO--N(R₅ '"'"')₂ or ##STR345## wherein each R₃ '"'"' is independently hydrogen, methyl, ethyl, amino or dimethylamino, and

R₅ '"'"' is as defined above,

X'"'"' is --NH--CO--NH--, ##STR346## wherein R_42a is hydrogen, chloro, methyl or methoxy,

each R₄₃ is independently linear or branched C_1-4 alkylene,

each R₄₄ is independently hydrogen or C_1-4 alkyl,

R₄₅ is halo, 2-hydroxyethylamino, N,N-di-(2-hydroxyethyl)amino, amino, hydroxy, --NH--(CH₂)_b --N(C₂ H₅)₂, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino, piperidino, methoxy or ethoxy,

R_45a is chloro, 2-hydroxyethylamino, methoxy, ethoxy, hydroxy, amino, N,N-di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino or piperidino, and

g is 1, 2, 3 or 4,

X_o '"'"' is --NH--, --NHCONH--, --NHCO--CH═

CH--CONH--, --NHCO--(CH₂)_b --CONH--, ##STR347## wherein R₁₃ '"'"' is as defined above, each Y₁ is independently linear or branched C_1-8 alkylene or linear or branched C_3-8 alkenylene,

each Y₂ is independently linear or branched C_1-8 alkylene,

each Z'"'"' is independently as defined above,

each Q₁, Q₂, R₇, R₈, R₁₃, R₁₄ and Z is independently as defined in claim 1,

each a is independently 1, 2 or 3,

each b is independently 2 or 3,

each m is independently 1, 2, 3, 4, 5 or 6,

each m'"'"' is independently 2, 3 or 4,

each n is independently 0, 1 or 2,

each q is independently 0 or 1, and

each A.sup.⊖

is independently a non-chromophoric anion,

with the proviso that when R₁ "'"'"' is hydrogen, the compound is in metal-free form.

8. A metal-free compound according to claim 1 having the formula ##STR348## or a 1:

1 or 1;

2 metal complex thereof, or an acid addition salt of a metal-free compound of said formula or an acid addition salt thereof,

wherein

A" is 1,2-ethylene, 1,3-propylene, 1,3-phenylene or 1,4-phenylene,

R₁^iv is hydrogen or --N═

N--D"'"'"',

wherein

D"'"'"' is ##STR349## wherein R₂₆ '"'"' is hydrogen, nitro, chloro, methyl, methoxy or chlorophenoxy,

each R_26a is independently nitro, chloro, methyl or methoxy,

each R_27a is independently hydrogen, chloro, methyl or methoxy, and

R_27b is hydrogen, methyl or methoxy,

R₂ " is ##STR350## wherein R₁₂ " is --CO--CH₂ --Z" or ##STR351## wherein R₁₃ " is --NR₅ "R₂₁ '"'"', ##STR352## R₁₄ " is --NR₅ "R₂₁ '"'"', ##STR353## and Z" is --N(R₇ ")₂ or --N.sup.⊕

(R₈ ")₂ R₉ "A.sup.⊖

, and

T" is cyano or ##STR354## wherein R₃ " is hydrogen or methyl, wherein

A₁ '"'"' is ##STR355## wherein R₅₁ is hydrogen, halo, C_1-4 alkyl or C_1-4 alkoxy,

R₅₂ is hydrogen, hydroxy, halo, cyano, --CONH₂, (C_1-4 alkyl)carbonylamino, --NHCONH₂, carboxy, sulfo, C_1-4 alkyl or C_1-4 alkoxy,

each R₅₃ is independently hydrogen, halo, cyano, C_1-4 alkyl, C_1-4 alkoxy, carboxy, sulfo or hydroxy, and

Yo is a direct bond, --(CH₂)_a --, --O--, --S--, --SO₂ --, --NHCO--, --NHCONH--, --NHCO--(CH₂)_b --CONH--, --CONH--(CH₂)_b --NHCO--, --O--(CH₂)_b --O--, --N═

N-- or --CH═

CH--CO--CH═

CH--,

K_a " is ##STR356## wherein K_b '"'"' is ##STR357## X", when both R_27a '"'"'s and R_27b are hydrogen, is a direct bond, --S--, --O--, --CH═

CH--, --NH--, --NHCO--, ##STR358## or --CONH--(CH₂)₂ --NHCO--, wherein

R_42a is hydrogen, chloro, methyl or methoxy,

R₄₃ is linear or branched C_1-4 alkylene,

R_45a is chloro, 2-hydroxyethylamino, methoxy, ethoxy, hydroxy, amino, N,N-di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino or piperidino, and

g is 1, 2, 3 or 4, and

wherein

B'"'"' is hydrogen, methyl, ethyl, hydroxyethyl, cyclohexyl, benzyl, --(CH₂)_a --N(R₇ '"'"')₂, --(CH₂)_b --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

or --A'"'"'--NH--R₂ '"'"',

wherein

A'"'"' is linear or branched C_2-8 alkylene or phenylene,

R₂ '"'"' is ##STR359## wherein R₁₁ '"'"' is hydrogen, chloro, nitro, methyl or methoxy, and

R₁₂ '"'"' is --CO--(CH₂)_t --Z'"'"' or ##STR360## wherein R₁₃ '"'"' is chloro, hydroxy, amino, N,N-di-(C_2-4 -hydroxyalkyl)amino, --NR₅ '"'"'R₂₁, ##STR361## wherein R₁₁ '"'"' is as defined above, R₁₄ '"'"' is --NR₅ '"'"'R₂₁, ##STR362## and Z'"'"' is --N(R₇ '"'"')₂ or --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

,

R'"'"' is methyl, ethyl, phenyl, benzyl or cyclohexyl, R₂₁ '"'"' is --(CH₂)_b --N(R₇ ")--(CH₂)_b --NR₇ "R₆ '"'"', --(CH₂)_b --N.sup.⊕

(R₈ ")₂ --(CH₂)_b --N(R₈ ")₂ R₆ '"'"'2A.sup.⊖

, --(CH₂)_b --N(R₇ ")--C₂ H₅, --(CH₂)_b --N.sup.⊕

(R₈ ")₂ --C₂ H₅ A.sup.⊖

, --NHCO--CH₂ --Z", --CH₂ --CONH--Y₂ '"'"'--Z", ##STR363## wherein R₆ '"'"' is methyl or ethyl,

R₂₄ is --N(R₇ '"'"')₂, --N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"'A.sup.⊖

, --CO--Y₂ --Z'"'"', --NHCO--Y₂ --Z'"'"', --CONH--Y₂ --Z'"'"'--SO₂ NH--Y₂ --Z'"'"', --Y₂ --Z'"'"' or --NHNHCO--CH₂ --Z'"'"',

wherein Z'"'"' is as defined above,

Y₂ '"'"' is linear or branched C_1-4 alkylene, and

Z" is as defined above,

each R₂₈ is independently hydrogen, halo, C_1-4 alkyl or C_1-4 alkoxy,

R₂₉ '"'"' is --(CH₂)_m'"'"' --Z'"'"', ##STR364## wherein R₄₆ '"'"' is hydrogen, --NHCO--(CH₂)_b --Z'"'"', --SO₂ NH--(CH₂)_b --Z'"'"' or ##STR365## wherein R₁₃ ", R₁₄ " and Z'"'"' are as defined above, each R₄₇ '"'"' is independently hydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy, nitro or cyano, and

R₄₈ '"'"' is methoxy or ethoxy, and

each R₃₃ '"'"' is independently hydrogen, 2-hydroxyethyl, 3-methoxypropyl, --(CH₂)_b --N(CH₃)₂ or --(CH₂)_b --N.sup.⊕

(CH₃)₃ A.sup.⊖

,

R₃₄ is hydroxy or amino,

R₃₆ '"'"' is hydrogen, ##STR366## wherein R₄₉ '"'"' is hydrogen, --CONH--(CH₂)_m'"'"' --Z'"'"', --NHCO--(CH₂)_b --Z'"'"' or ##STR367## wherein R₁₃ '"'"', R₁₄ '"'"' and Z'"'"' are as defined above, and each R₅₀ '"'"' is independently hydrogen, chloro, methyl or methoxy,

R₃₇ '"'"' is ##STR368## wherein R₁₃ " and R₁₄ " are as defined above, R₃₈ '"'"' is methyl, ethyl, 2-cyanoethyl or benzyl,

R₃₉ '"'"' is methyl, ethyl or --(CH₂)_m'"'"' --Z,

R₄₀ is independently hydrogen, C_1-4 alkyl or C_1-4 alkoxy, and

each T'"'"' is independently hydrogen, cyano, --CO--N(R₅ '"'"')₂ or ##STR369## wherein each R₃ '"'"' is independently hydrogen, methyl, ethyl, amino or dimethylamino,

wherein

each R₇ '"'"' is independently hydrogen, C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl or

--N(R₇ '"'"')₂ is pyrrolidino, piperidino, morpholino, piperazino or N'"'"'-methylpiperazino,

each R₇ " is independently hydrogen, methyl, ethyl or 2-hydroxyethyl or

--N(R₇ ")₂ is morpholino, piperidino, piperazino or N'"'"'-methylpiperazino,

each R₈ '"'"' is independently C_1-6 alkyl, n-hydroxy(C_2-3 alkyl), benzyl or 2-cyanoethyl, and

each R₉ '"'"' is independently methyl, ethyl, propyl or benzyl or

--N.sup.⊕

(R₈ '"'"')₂ R₉ '"'"' is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR370## wherein Zo is a direct bond, --CH₂ --, --O--, --S--, --SO--, --SO₂ --, --NH--, --NR₆ -- or --N.sup.⊕

(R₆)₂ --A.sup.⊖

, and

R₉ '"'"' is as defined above,

each R₈ " is independently methyl, ethyl or 2-hydroxyethyl, and each R₉ " is independently methyl, ethyl or benzyl or

--N.sup.⊕

(R₈ ")₂ R₉ " is pyridinium, pyridinium substituted by 1 or 2 methyl groups or ##STR371## wherein R₉ '"'"' and Zo are as defined above, each R₁₃ '"'"' and R₁₄ '"'"' is independently as defined above,

R₂₁ is C_1-12 alkyl;

C_2-12 alkyl substituted by hydroxy;

C_3-12 alkyl interrupted by 1 to 3 radicals selected from --NR₇ -- and --N.sup.⊕

(R₈)₂ --A.sup.⊖

;

--NHCO--CH₂ --Z;

--CH₂ --CONH--Y₁ --Z;

--Y₁ --Z;

##STR372## wherein R₂₃ is halo, hydroxy, nitro, C_1-4 alkyl or C_1-4 alkoxy, and

R₂₄ and Z'"'"' are as defined above,

wherein

each R₅ '"'"' is independently hydrogen, methyl or ethyl,

each R₅ " is independently hydrogen or methyl,

each R_5a is independently hydrogen or C_1-4 alkyl,

each R₆ is independently C_1-4 alkyl,

each Y₁ is independently linear or branched C_1-8 alkylene or linear or branched C_3-8 alkenylene,

each Y₂ is independently linear or branched C_1-8 alkylene,

R₇, R₈, R₁₇, R₁₉ and Z as defined in claim 18,

each a is independently 1, 2 or 3,

each b is independently 2 or 3,

each m'"'"' is independently 2, 3 or 4,

each n is independently 0, 1 or 2,

each q is independently 0 or 1,

each t is independently 1 or 2, and

each A.sup.⊖

is independently a non-chromophoric anion,

with the proviso that when R₁^iv is hydrogen, the compound is in metal-free form.

9. A metal-free compound according to claim 1 having the formula ##STR373## or a 1:

1 or 1;

2 metal complex thereof, or an acid addition salt of a metal-free compound of said formula or a 1;

1 or 1;

2 metal complex thereof,

wherein

one R₆₀ is hydroxy and the other is amino,

R₆₁ is hydrogen, C_1-4 alkoxy or hydroxy,

R₆₂ is hydrogen, chloro, nitro, C_1-4 alkyl, C_1-4 alkoxy or hydroxy,

R₆₃ is hydrogen, chloro, nitro, C_1-4 alkyl, C_1-4 alkoxy or hydroxy,

R₆₄ is hydrogen, dimethylamino, trimethylammonium A.sup.⊖

, diethylamino, triethylammonium A.sup.⊖

, --CO--Y₂ --Z, --CONH--Y₂ --Z, --Y₂ --Z, --NHCO--Y₂ --Z, --SO₂ NH--Y₂ --Z, --NHNHCO--CH₂ --Z or ##STR374## wherein Y₂ is linear or branched C_1-8 alkylene, each M is independently hydrogen or a non-chromophoric cation, and

B, R, R₁₃, R₁₄, T, Z and A.sup.⊖

are as defined in claim 1,

with the provisos tht (i) the total number of cationic and protonatable basic groups exceeds the number of sulfo groups by at least one, and (ii) R₆₄ is in the 3- or 4-position of the ring to which it is attached.

10. The compound according to claim 1 having the formula ##STR375##

11. The compound according to claim 1 having the formula ##STR376##

12. The compound according to claim 1 having the formula ##STR377##

13. The compound according to claim 1 having the formula ##STR378##