Compounds of formula (I) wherein all substituents have the meanings as defined in the Specification, their production and their use.
1. A compound of formula (I)
wherein
each A is independently —NH— or —O—,
B is
—[—(CH 2 ) 1-4 —O—(CH 2 ) 1-4 ] 4 C or
[—(CH 2 ) 1-3 —O—(CH 2 ) 1-3 —O—(CH 2 ) 1-3 ] 4 C or
[—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 ] 4 C or
[(—CH 2 ) 1-4 ] 2 N(CH 2 ) 1-4 N[(—CH 2 ) 1-4 ] 2
n′ and n″ are natural numbers and the sum of n′ and n″ is ≧2,
m is a natural number ≧0,
CC is a moiety of formula (a)
wherein
R 1 is H; C 1-4 alkyl; C 1-4 alkyl monosubstituted by hydroxy, halogen, cyano or C 1-4 alkoxy,
X 1 and X 2 independently of each other are halogen; an aliphatic, cycloahphatic, aromatic or heterocyclic amino group, said amino group comprising a protonatable nitrogen atom or a quaternary ammonium group, and being an aliphatic, cycloaliphatic, aromatic or heterocyclic mono(C 1-4 alkyl)-amino group, the C 1-4 alkyl-group being unsubstituted or monosubstituted by halogen, C 1-4 alkoxy, C 1-4 alkyl, phenyl or hydroxy; an aliphatic, cycloaliphatic, aromatic or heterocyclic di(C 1-4 alkyl)-amino group, the C 1-4 alkyl-groups being independently unsubstituted or monosubstituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, phenyl or hydroxy; a C 5-6 cycloalkylamino group, the cycloalkyl group being unsubstituted or substituted by one or two C 1-2 alkyl groups; a phenylamino group, the phenyl ring being unsubstituted or substituted by one or two groups selected from halogen, C 1-4 alkyl, C 1-4 alkoxy, hydroxy and phenoxy; or a 5- or 6-membered ring containing one or two hetero atoms, in addition to N, O or S, which heterocyclic ring is unsubstituted or substituted by one or two C 1-4 alkyl groups; or a group Z, where Z is independently selected from the group consisting of:
wherein
p is 0 or an integer 1, 2 or 3,
each R 9 is independently hydrogen; unsubstituted C 1-4 alkyl or C 1-4 alkyl monosubstituted by hydroxy, halogen, cyano or C 1-4 alkoxy,
each R 2 and R 3 is independently hydrogen; unsubstituted C 1-6 alkyl; C 2-6 alkyl monosubstituted by hydroxy, amino or cyano; phenyl or phenyl-C 1-4 alkyl, where the phenyl ring of the latter two groups is unsubstituted or substituted by one to three groups selected from chlorine, C 1-4 alkyl, C 1-4 alkoxy, unsubstituted C 5-6 cycloalkyl or C 5-6 cycloalkyl substituted by one to three C 1-4 alkyd groups or a pyridinium ring, or
R 2 and R 3 together with the nitrogen atom to which they are attached, form a 5- or 6-membered ring containing one to three hetero atoms (in addition to N, one or two further N, O or S), which heterocyclic ring is unsubstituted or substituted by one or two C 1-4 alkyl groups,
each R 4 and R 5 has independently one of significances of R 2 and R 3 , except hydrogen,
R 6 is C 1-4 alkyd or benzyl with the exception that R 6 is not benzyl when R 4 and R 5 have one of the cyclic significations of R 2 and R 3, or
R 4 , R 5 and R 6 together with the nitrogen atom to which they are attached, form a pyridinium ring which is unsubstituted or substituted by one or two methyl groups,
Q 1 is C 2-8 alkylene; C 3-6 alkylene substituted by one or two hydroxy groups; C 1-6 alkylene-1,3- or 1,4-phenylene, or —*NHCOCH 2 , where * denotes the atom bound to —NR 9 ,
Q 2 is C 2-8 alkylene; C 3-6 alkylene substituted by one or two hydroxy groups; C 1-6 alkylene-1,3- or -1,4-phenylene or 1,3- or 1,4-phenylene,
Q 3 is C 2-8 alkylene,
R 7 is hydrogen; unsubstituted C 1-6 alkyl or C 1-6 alkyl monosubstituted by hydroxy, cyano, chlorine or phenyl,
R 8 is unsubstituted C 1-6 alkyl or C 1-6 alkyl monosubstituted by hydroxy, cyano or chlorine, and An θ is a non-chromophoric anion,
Y is direct bond, —CO— or —CO—NH—*, wherein the asterisk signifies the bond to the benzene ring and
o is 0 or 1 or
CC is a moiety of formula (b)
wherein
D is a basic group —NR 1 -Q 4 -NR 2 R 3 or a cationic group —NR 1 -Q 4 -N + R 4 R 5 R 6 , in which R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as above and
Q 4 is C 2-6 alkylene, which may be interrupted by —O—, —S— or —N(R 1 )—; C 2-3 alkylene substituted by one or two hydroxy groups; or —*NHCOCH 2 —, where * denotes the atom bound to the —NR 1 -radical,
or CC is a moiety of formula (c 1 ) or (c 2 )
wherein
each R 10 independently of each other is H; C 1-4 alkyl; C 5-6 cycloalkyl; phenyl, benzyl or phenylethyl,
each R 10 ′ independently of each other is H; —OH or C 1-4 alkyl
each T 1 independently of each other is H; —CN; —COOR 15 ; CONR 16 R 17 ; SO 2 NR 16 R 17 ;
G is H; —R 11 NHR 12 or —R 11 NR 13 R 14 , wherein
R 11 is C 1-6 alkylene or C 2-6 alkenylene,
R 12 and R 13 independently of each other are H; unsubstituted C 1-6 alkyl; C 2-6 alkyl substituted by OH, CN or halogen; phenyl-C 1-3 alkyl, wherein the phenyl radical is optionally substituted from 1 to 3 times, by a substituent selected from the group consisting of; chlorine, C 1-4 alkyl or C 1-4 alkoxy; unsubstituted C 5-6 cycloalkyl and C 5-6 cycloalkyl substituted from 1 to 3 times by C 1-4 alkyl groups,
R 14 is any of the meanings of R 12 or R 13 or hydrogen,
R 15 is a C 1-6 alkyl radical or phenyl-C 1-3 alkyl radical,
R 16 and R 17 independently of each other are H or a C 1-4 alkyl radical,
R 18 independently of each other signifies H; a C 1-4 alkyl radical; —NR 16 R 17 —(CH 2 ) 2-4 —NR 16 R 17 or —CONR 16 R 17 ,
R 19 is a C 1-4 alkyl radical or a hydroxy-C 1-4 alkyl radical,
R 20 is —S— or —O—,
R 21 is hydrogen or a C 1-4 alkyl radical and
An − is a non-chromophoric anion,
with the provisos that
(i) the sum of n′, n″ and m is smaller as or equal to the valencies of B,
(ii) when the sum of n′ and n″=2 then m is ≧1,
(iii) when the sum of n′ and n″=3 and A=NH then m is ≧1
and their salts and mixtures thereof.
2. A compound according to claim 1 where A is —O—.
3. A compound according to claim 1 wherein CC is formulae (c 2 ) or (a 1 ):
where
R 10 is H; —CH 3 or —CH 2 CH 3 ,
T 1 is H; —CN; —CONH 2 ; —CONHCH 3 ;
R 10 ′ is H; —CH 3 or —OH,
G is H or —(CH 2 ) 2-4 NR 13 R 14 ,
where R 13 and R 14 are independently from each other H; —CH 3 or —CH 2 CH 3 ,
or
where
each R 1 is independently from each other H; —CH 3 , —CH 2 CH 3 or substituted C 1-4 alkyl,
X 1 and X 2 are independently from each other halogen or —NR 2 R 3 wherein R 2 and R 3 are independently from each other H; C 1-4 alkyl;
—C 2-4 alkylene-NH 2 — or —C 2-4 alkylene-OH—;
Y signifies a direct bond;
wherein the asterisk is the bond to the benzene ring and
o is 0 or 1.
4. Mixtures of compounds comprising at least one compound of formula (I) according to claim 1 .
5. Mixtures according to claim 4 comprising at least one compound according to formula (I) and at least one compound selected from the group consisting of:
wherein D1 is a radical
and B 1 , B 2 , D 2 , R 1 , R 2 , R t and M are indicated in Table I below;
TABLE I
R t
Position of
(position on
the azo {circle around (1)}
Ex.
R 1
M
R 2
ring B)
on ring B
B 1
B 2
D 2
3
H
H
4
OH
OH
H
4
″
″
H
H
4
OH
OH
D 1
5
″
″
H
H
4
NH 2
NH 2
H
6
″
″
H
H
4
NH 2
NH 2
D 1
7
″
″
H
H
4
NH 2
OH
H
8
″
H
H
H
3
OH
OH
4
9
″
H
H
H
3
OH
OH
D 1
10
″
H
H
H
3
NH 2
NH 2
H
11
″
H
H
H
3
NH 2
D 1
12
″
H
H
H
3
OH
NH 2
H
13
″
H
H
H
4
OH
OH
H
14
″
H
H
H
4
OH
OH
D 1
15
″
H
H
H
4
OH
NH 2
H
16
H
H
H
3
OH
OH
H
17
″
H
H
H
3
OH
OH
D 1
18
″
H
H
H
4
NH 2
NH 2
H
19
″
H
H
H
4
NH 2
NH 2
D 1
20
″
H
H
H
4
NH 2
OH
H
21
—(CH 2 ) 3 —N(C 2 H 5 ) 2
H
H
3
OH
OH
H
22
″
″
H
H
3
OH
OH
D 1
23
″
″
H
H
4
NH 2
NH 2
H
24
″
″
H
H
4
NH 2
OH
H
25
″
″
H
H
4
OH
OH
H
26
—CN
″
H
H
3
OH
OH
H
27
″
″
H
H
3
OH
OH
D 1
28
″
″
H
H
4
OH
OH
H
29
″
″
H
H
4
OH
NH 2
H
30
″
″
H
H
4
NH 2
NH 2
H
31
—CONH 2
″
H
H
3
OH
OH
H
32
″
″
H
H
3
OH
OH
D 1
33
″
″
H
H
4
NH 2
NH 2
H
34
H
″
H
H
3
OH
OH
H
35
H
″
H
H
3
OH
OH
D 1
36
H
″
H
H
4
NH 2
NH 2
H
37
H
″
H
H
4
NH 2
OH
H
38
—CN
—(CH 2 ) 3 N(C 2 H 5 ) 2
H
H
3
OH
OH
H
39
—CONH 2
″
H
H
4
OH
OH
H
40
H
″
H
H
4
NH 2
NH 2
H
41
—(CH 2 ) 3 —N(CH 3 ) 2
OH
H
5
OH
OH
H
42
″
H
OH
H
5
OH
OH
H
43
″
H
H
OH-(4)
3
OH
OH
H
44
H
—(CH 2 ) 3 —N(CH 3 ) 2
OH
H
5
OH
OH
H
45
H
″
H
OH-(4)
3
OH
OH
H
46
H
″
H
H
4
OH
OH
H
wherein R 1 , M and Me are indicated in Table 2
TABLE 2
Me
Ex.
R 1
M
Metal complex
47
—(CH 2 ) 3 —N(CH 3 ) 2
1:1-Cu
48
″
″
1:2-Cr
49
″
″
1:2-Co
50
″
″
1:2-Fe
51
″
H
1:1-Cu
52
″
H
1:2-Cr
53
″
H
1:2-Co
54
″
H
1.2-Fe
55
H
1:1-Cu
56
″
H
1:2-Fe
57
H
—(CH 2 ) 3 N(CH 3 ) 2
1:1-Cu
58
H
″
1:2-Cr
59
H
″
1:2-Co
60
H
″
1:2-Fe
wherein R 1 , M and Me are indicated in Table 3 below;
TABLE 3
Me
Ex.
R 1
M
Metal complex
61
H
1:1-Cu
62
″
H
1:2-Cr
63
″
H
1:2-Co
64
″
H
1:2-Fe
65
H
1:1-Cu
66
″
H
1:2-Fe
67
H
—(CH 2 ) 3 N(CH 3 ) 2
1:1-Cu
68
H
″
1:2-Cr
69
H
″
1:2-Co
70
H
″
1:2-Fe
wherein D 3 is hydrogen or a radical of formula
and B 1 , B 2 , R a , R b , R 6 , R 7 , R 8 , R 9 , M a , and M b are as Indicated in Table 4;
TABLE IV
Significances of Ma and Mb
M 1 is H
M 2 is —(CH 2 ) 3 N(CH 3 ) 2
M 7 is —(CH 2 ) 3 N ⊕ (CH 3 ) 3 A ⊖
M 3 is —(CH 2 ) 2 N(C 2 H 5 ) 2
M 10 is —(CH 2 ) 2 NH 2
Significances of Ra and Rb
R 1 is H
R 4 is CN
Position of
Position of
the azo {circle around (1)}
H
the azo {circle around (2)}
Ex.
Ra
Ma
R 6
R 8
on ring B
or D 3
R b
M b
R 7
R 9
on ring C
B 1
B 2
73
R 2
M 2
SO 3 H
H
3
H
—
—
—
H
—
OH
OH
74
R 2
M 2
″
H
4
H
—
—
—
H
—
OH
NH 2
75
R 2
M 2
″
H
4
H
—
—
—
H
—
NH 2
NH 2
76
R 2
M 2
″
H
3
D 3
R 2
M 2
SO 3 H
H
3′
NH 2
NH 2
77
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
NH 2
NH 2
78
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
NH 2
NH 2
79
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
NH 2
OH
80
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
OH
OH
81
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
3′
NH 2
NH 2
82
R 3
M 1
H
H
3
D 3
R 2
M 2
SO 3 H
H
4′
NH 2
NH 2
83
R 1
M 4
H
H
3
D 3
R 2
M 5
″
H
4′
OH
NH 2
84
R 4
M 4
H
H
3
D 3
R 2
M 6
″
H
4′
NH 2
NH 2
85
R 5
M 4
H
H
3
D 3
R 2
M 7
″
H
4′
NH 2
NH 2
86
R 2
M 2
SO 3 H
H
4
D 3
R 2
M 2
H
H
3′
OH
NH 2
87
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
3′
OH
OH
88
R 2
M 8
″
H
4
D 3
R 2
M 1
H
H
3′
OH
OH
89
R 2
M 8
″
H
4
D 3
R 2
M 2
H
H
3′
OH
NH 2
90
R 2
M 8
H
H
4
D 3
R 2
M 4
SO 3 H
H
3′
NH 2
NH 2
91
R 2
M 9
H
H
4
D 3
R 2
M 5
SO 3 H
H
3′
OH
NH 2
92
R 2
M 9
H
H
3
D 3
R 4
M 3
″
H
4′
OH
OH
93
R 2
M 8
H
H
3
D 3
R 5
M 4
″
H
4′
NH 2
NH 2
94
R 2
M 3
H
H
4
D 3
R 2
M 3
″
H
3′
NH 2
NH 2
95
R 2
M 2
H
CH 3
3
D 3
R 2
M 2
″
H
4′
OH
OH
96
R 2
M 3
H
Cl
3
D 3
R 2
M 3
″
H
4′
NH 2
NH 2
97
R 2
M 2
H
OCH 3
3
D 3
R 2
M 4
″
H
4′
NH 2
NH 2
98
R 2
M 7
SO 3 H
H
4
D 3
R 2
M 7
H
Cl
3′
OH
OH
99
R 2
M 8
″
H
4
D 3
R 2
M 2
H
CH 3
3′
OH
NH 2
100
R 2
M 6
″
H
4
D 3
R 2
M 2
H
OCH 3
3′
NH 2
NH 2
101
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
3′
OH
NH 2
102
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
4′
NH 2
NH 2
103
R 2
M 2
″
H
4
D 3
R 2
M 2
SO 3 H
H
4′
NH 2
NH 2
104
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
3′
NH 2
NH 2
105
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
4′
NH 2
OH
106
R 2
M 2
″
H
3
D 3
R 2
M 2
SO 3 H
H
4′
OH
NH 2
107
R 2
M 10
″
H
3
D 3
R 2
M 2
H
H
3′
OH
OH
wherein d4 is H or D4
and R a , R b , R 5 , R 6 , B 1 , B 2 , M a , and M b are as indicated in Table 5 below;
TABLE V
Position of
Position of
Ex.
the azo {circle around (3)}
the azo {circle around (4)}
Nr.
Ra
Ma
R 5
on ring D
d 4
R b
M b
R 6
on ring E
B 1
B 2
109
R 2
M 2
SO 3 H
1
H
—
—
—
—
OH
OH
110
R 2
M 2
″
1
H
—
—
—
—
NH 2
NH 2
111
R 2
M 2
″
2
H
—
—
—
—
OH
NH 2
112
R 2
M 2
″
2
H
—
—
—
—
NH 2
NH 2
113
R 2
M 2
″
1
D 4
R 2
M 2
H
1′
OH
NH 2
114
R 2
M 2
″
1
D 4
R 2
M 2
H
1′
NH 2
NH 2
115
R 2
M 2
″
1
D 4
R 2
M 2
SO 3 H
1′
OH
OH
116
R 2
M 2
″
1
D 4
R 2
M 2
H
2′
OH
OH
117
R 2
M 2
″
1
D 4
R 2
M 2
H
2′
NH 2
NH 2
118
R 2
M 2
″
1
D 4
R 2
M 2
SO 3 H
2′
OH
NH 2
119
R 2
M 2
″
2
D 4
R 2
M 2
″
2′
OH
OH
120
R 3
M 3
″
1
D 4
R 3
M 3
H
1′
OH
OH
121
R 2
M 4
″
1
D 4
R 2
M 4
H
2′
NH 2
NH 2
122
R 2
M 5
H
1
D 4
R 2
M 5
SO 3 H
2′
NH 2
OH
123
R 2
M 5
H
2
D 4
R 2
M 6
″
1′
OH
OH
124
R 3
M 7
H
2
D 4
R 3
M 7
″
1′
NH 2
OH
125
R 1
M 8
SO 3 H
2
D 4
R 1
M 8
″
1′
OH
OH
126
R 1
M 8
″
2
D 4
R 1
M 8
H
1′
NH 2
NH 2
127
R 2
M 9
″
1
D 4
R 2
M 9
H
2′
OH
NH 2
128
R 2
M 2
″
2
D 4
R 2
M 2
H
1′
OH
OH
129
R 2
M 2
H
2
D 4
R 2
M 2
SO 3 H
1′
OH
OH
130
R 2
M 2
SO 3 H
2
D 4
R 2
M 2
H
1′
NH 2
NH 2
131
R 2
M 2
H
2
D 4
R 2
M 2
SO 3 H
1′
NH 2
NH 2
132
R 2
M 2
SO 3 H
2
D 4
R 2
M 2
″
1′
NH 2
NH 2
133
R 2
M 2
″
1
D 4
R 2
M 2
″
1′
NH 2
NH 2
134
R 2
M 2
H
2
D 4
R 2
M 2
″
1′
OH
NH 2
135
R 2
M 2
SO 3 H
2
D 4
R 2
M 2
″
1′
OH
NH 2
136
R 2
M 2
″
1
D 4
R 2
M 2
″
1′
OH
NH 2
and a dye selected from the group consisting of: C.I. Basic Red; C.I. Basic Brown; C.I. Basic Blue; C.I. Basic Violet and combinations thereof.
6. Mixtures according claim 4 comprising from 2 to 98 parts (by weight) of at least one compound of formula (I) as component one and at least one compound selected from the group consisting of:
wherein D1 is a radical
and B 1 , B 2 , D 2 , R 1 , R 2 , R t and M are indicated in Table I below;
TABLE I
R t
Position of
(position on
the azo {circle around (1)}
Ex.
R 1
M
R 2
ring B)
on ring B
B 1
B 2
D 2
3
H
H
4
OH
OH
H
4
″
″
H
H
4
OH
OH
D 1
5
″
″
H
H
4
NH 2
NH 2
H
6
″
″
H
H
4
NH 2
NH 2
D 1
7
″
″
H
H
4
NH 2
OH
H
8
″
H
H
H
3
OH
OH
4
9
″
H
H
H
3
OH
OH
D 1
10
″
H
H
H
3
NH 2
NH 2
H
11
″
H
H
H
3
NH 2
D 1
12
″
H
H
H
3
OH
NH 2
H
13
″
H
H
H
4
OH
OH
H
14
″
H
H
H
4
OH
OH
D 1
15
″
H
H
H
4
OH
NH 2
H
16
H
H
H
3
OH
OH
H
17
″
H
H
H
3
OH
OH
D 1
18
″
H
H
H
4
NH 2
NH 2
H
19
″
H
H
H
4
NH 2
NH 2
D 1
20
″
H
H
H
4
NH 2
OH
H
21
—(CH 2 ) 3 —N(C 2 H 5 ) 2
H
H
3
OH
OH
H
22
″
″
H
H
3
OH
OH
D 1
23
″
″
H
H
4
NH 2
NH 2
H
24
″
″
H
H
4
NH 2
OH
H
25
″
″
H
H
4
OH
OH
H
26
—CN
″
H
H
3
OH
OH
H
27
″
″
H
H
3
OH
OH
D 1
28
″
″
H
H
4
OH
OH
H
29
″
″
H
H
4
OH
NH 2
H
30
″
″
H
H
4
NH 2
NH 2
H
31
—CONH 2
″
H
H
3
OH
OH
H
32
″
″
H
H
3
OH
OH
D 1
33
″
″
H
H
4
NH 2
NH 2
H
34
H
″
H
H
3
OH
OH
H
35
H
″
H
H
3
OH
OH
D 1
36
H
″
H
H
4
NH 2
NH 2
H
37
H
″
H
H
4
NH 2
OH
H
38
—CN
—(CH 2 ) 3 N(C 2 H 5 ) 2
H
H
3
OH
OH
H
39
—CONH 2
″
H
H
4
OH
OH
H
40
H
″
H
H
4
NH 2
NH 2
H
41
—(CH 2 ) 3 —N(CH 3 ) 2
OH
H
5
OH
OH
H
42
″
H
OH
H
5
OH
OH
H
43
″
H
H
OH-(4)
3
OH
OH
H
44
H
—(CH 2 ) 3 —N(CH 3 ) 2
OH
H
5
OH
OH
H
45
H
″
H
OH-(4)
3
OH
OH
H
46
H
″
H
H
4
OH
OH
H
wherein R 1 , M and Me are indicated in Table 2
TABLE 2
Me
Ex.
R 1
M
Metal complex
47
—(CH 2 ) 3 —N(CH 3 ) 2
1:1-Cu
48
″
″
1:2-Cr
49
″
″
1:2-Co
50
″
″
1:2-Fe
51
″
H
1:1-Cu
52
″
H
1:2-Cr
53
″
H
1:2-Co
54
″
H
1.2-Fe
55
H
1:1-Cu
56
″
H
1:2-Fe
57
H
—(CH 2 ) 3 N(CH 3 ) 2
1:1-Cu
58
H
″
1:2-Cr
59
H
″
1:2-Co
60
H
″
1:2-Fe
wherein R 1 , M and Me are Indicated in Table 3 below;
TABLE 3
Me
Ex.
R 1
M
Metal complex
61
H
1:1-Cu
62
″
H
1:2-Cr
63
″
H
1:2-Co
64
″
H
1:2-Fe
65
H
1:1-Cu
66
″
H
1:2-Fe
67
H
—(CH 2 ) 3 N(CH 3 ) 2
1:1-Cu
68
H
″
1:2-Cr
69
H
″
1:2-Co
70
H
″
1:2-Fe
wherein D 3 is hydrogen or a radical of formula
and B 1 , B 2 , R a , R b , R 6 , R 7 , R 8 , R 9 , M a , and M b are as indicated in Table 4;
TABLE IV
Significances of Ma and Mb
M 1 is H
M 2 is —(CH 2 ) 3 N(CH 3 ) 2
M 7 is —(CH 2 ) 3 N ⊕ (CH 3 ) 3 A ⊖
M 3 is —(CH 2 ) 2 N(C 2 H 5 ) 2
M 10 is —(CH 2 ) 2 NH 2
Significances of Ra and Rb
R 1 is H
R 4 is CN
Position of
Position of
the azo {circle around (1)}
H
the azo {circle around (2)}
Ex.
Ra
Ma
R 6
R 8
on ring B
or D 3
R b
M b
R 7
R 9
on ring C
B 1
B 2
73
R 2
M 2
SO 3 H
H
3
H
—
—
—
H
—
OH
OH
74
R 2
M 2
″
H
4
H
—
—
—
H
—
OH
NH 2
75
R 2
M 2
″
H
4
H
—
—
—
H
—
NH 2
NH 2
76
R 2
M 2
″
H
3
D 3
R 2
M 2
SO 3 H
H
3′
NH 2
NH 2
77
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
NH 2
NH 2
78
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
NH 2
NH 2
79
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
NH 2
OH
80
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
4′
OH
OH
81
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
3′
NH 2
NH 2
82
R 3
M 1
H
H
3
D 3
R 2
M 2
SO 3 H
H
4′
NH 2
NH 2
83
R 1
M 4
H
H
3
D 3
R 2
M 5
″
H
4′
OH
NH 2
84
R 4
M 4
H
H
3
D 3
R 2
M 6
″
H
4′
NH 2
NH 2
85
R 5
M 4
H
H
3
D 3
R 2
M 7
″
H
4′
NH 2
NH 2
86
R 2
M 2
SO 3 H
H
4
D 3
R 2
M 2
H
H
3′
OH
NH 2
87
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
3′
OH
OH
88
R 2
M 8
″
H
4
D 3
R 2
M 1
H
H
3′
OH
OH
89
R 2
M 8
″
H
4
D 3
R 2
M 2
H
H
3′
OH
NH 2
90
R 2
M 8
H
H
4
D 3
R 2
M 4
SO 3 H
H
3′
NH 2
NH 2
91
R 2
M 9
H
H
4
D 3
R 2
M 5
SO 3 H
H
3′
OH
NH 2
92
R 2
M 9
H
H
3
D 3
R 4
M 3
″
H
4′
OH
OH
93
R 2
M 8
H
H
3
D 3
R 5
M 4
″
H
4′
NH 2
NH 2
94
R 2
M 3
H
H
4
D 3
R 2
M 3
″
H
3′
NH 2
NH 2
95
R 2
M 2
H
CH 3
3
D 3
R 2
M 2
″
H
4′
OH
OH
96
R 2
M 3
H
Cl
3
D 3
R 2
M 3
″
H
4′
NH 2
NH 2
97
R 2
M 2
H
OCH 3
3
D 3
R 2
M 4
″
H
4′
NH 2
NH 2
98
R 2
M 7
SO 3 H
H
4
D 3
R 2
M 7
H
Cl
3′
OH
OH
99
R 2
M 8
″
H
4
D 3
R 2
M 2
H
CH 3
3′
OH
NH 2
100
R 2
M 6
″
H
4
D 3
R 2
M 2
H
OCH 3
3′
NH 2
NH 2
101
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
3′
OH
NH 2
102
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
4′
NH 2
NH 2
103
R 2
M 2
″
H
4
D 3
R 2
M 2
SO 3 H
H
4′
NH 2
NH 2
104
R 2
M 2
″
H
3
D 3
R 2
M 2
H
H
3′
NH 2
NH 2
105
R 2
M 2
″
H
4
D 3
R 2
M 2
H
H
4′
NH 2
OH
106
R 2
M 2
″
H
3
D 3
R 2
M 2
SO 3 H
H
4′
OH
NH 2
107
R 2
M 10
″
H
3
D 3
R 2
M 2
H
H
3′
OH
OH
wherein d4 is H or D4
and R a , R b , R 5 , R 6 , B 1 , B 2 , M a , and M b are as indicated in Table 5 below;
TABLE V
Position of
Position of
Ex.
the azo {circle around (3)}
the azo {circle around (4)}
Nr.
Ra
Ma
R 5
on ring D
d 4
R b
M b
R 6
on ring E
B 1
B 2
109
R 2
M 2
SO 3 H
1
H
—
—
—
—
OH
OH
110
R 2
M 2
″
1
H
—
—
—
—
NH 2
NH 2
111
R 2
M 2
″
2
H
—
—
—
—
OH
NH 2
112
R 2
M 2
″
2
H
—
—
—
—
NH 2
NH 2
113
R 2
M 2
″
1
D 4
R 2
M 2
H
1′
OH
NH 2
114
R 2
M 2
″
1
D 4
R 2
M 2
H
1′
NH 2
NH 2
115
R 2
M 2
″
1
D 4
R 2
M 2
SO 3 H
1′
OH
OH
116
R 2
M 2
″
1
D 4
R 2
M 2
H
2′
OH
OH
117
R 2
M 2
″
1
D 4
R 2
M 2
H
2′
NH 2
NH 2
118
R 2
M 2
″
1
D 4
R 2
M 2
SO 3 H
2′
OH
NH 2
119
R 2
M 2
″
2
D 4
R 2
M 2
″
2′
OH
OH
120
R 3
M 3
″
1
D 4
R 3
M 3
H
1′
OH
OH
121
R 2
M 4
″
1
D 4
R 2
M 4
H
2′
NH 2
NH 2
122
R 2
M 5
H
1
D 4
R 2
M 5
SO 3 H
2′
NH 2
OH
123
R 2
M 5
H
2
D 4
R 2
M 6
″
1′
OH
OH
124
R 3
M 7
H
2
D 4
R 3
M 7
″
1′
NH 2
OH
125
R 1
M 8
SO 3 H
2
D 4
R 1
M 8
″
1′
OH
OH
126
R 1
M 8
″
2
D 4
R 1
M 8
H
1′
NH 2
NH 2
127
R 2
M 9
″
1
D 4
R 2
M 9
H
2′
OH
NH 2
128
R 2
M 2
″
2
D 4
R 2
M 2
H
1′
OH
OH
129
R 2
M 2
H
2
D 4
R 2
M 2
SO 3 H
1′
OH
OH
130
R 2
M 2
SO 3 H
2
D 4
R 2
M 2
H
1′
NH 2
NH 2
131
R 2
M 2
H
2
D 4
R 2
M 2
SO 3 H
1′
NH 2
NH 2
132
R 2
M 2
SO 3 H
2
D 4
R 2
M 2
″
1′
NH 2
NH 2
133
R 2
M 2
″
1
D 4
R 2
M 2
″
1′
NH 2
NH 2
134
R 2
M 2
H
2
D 4
R 2
M 2
″
1′
OH
NH 2
135
R 2
M 2
SO 3 H
2
D 4
R 2
M 2
″
1′
OH
NH 2
136
R 2
M 2
″
1
D 4
R 2
M 2
″
1′
OH
NH 2
and a dye selected from the group consisting of: C.I. Basic Brown 23; C.I. Basic Red 12; C.I. Basic Blue 1; CA. Basic Red 14; C.I. Basic Violet 10; and C.I. Basic Blue 26; in an amount to have 100 parts in total as component two.
7. A process for dyeing or printing fiber material or dyeing or printing paper comprising the steps of:
providing a dye or printing paste comprising a compound according to claim 1 ;
providing a fiber material or paper; and
contacting said dye or printing paste with said fiber material or paper.
8. A material dyed or printed with compounds according to claim 1 .
9. An ink-jet ink comprising a compound according to claim 1 .
10. A process for the preparation of an ink-jet ink comprising the step of: adding a compound according to claim 1 to at least one other compound.
11. A process for the preparation of an azo compound of formula (I) according to claim 1 comprising: reacting the diazonium salt of a compound according to formula (II)
or mixtures of such diazonium salts with a suitable coupling component comprising moieties of formula CC or with a mixture of suitable coupling components comprising moieties of formula CC wherein B and the moiety CC have the meaning as defined in claim 1 .
12. A compound according to formula (II)
wherein
B is
—[—(CH 2 ) 1-4 —O—(CH 2 ) 1-4 ] 4 C or
[—(CH 2 ) 1-3 —O—CH 2 ) 1-3 —O—(CH 2 ) 1-3 ] 4 C or
[—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 ] 4 C or
[(—CH 2 ) 1-4 ] 2 N(CH 2 ) 1-4 N[(—CH 2 ) 1-4 ] 2
A is independently —NH— or —O—
m and n are natural numbers
with the provisos that
(i) the sum of n and m is smaller as or equal to the valencies of B,
(ii) when n=2 then m is ≧1,
(iii) when n=3 and A=NH then m is ≧1,
and their salts and/or mixtures thereof.
13. A compound according to claim 12 wherein A is —O—.
14. A material dyed or printed with at least one mixture according to claim 4 .
15. A material dyed or printed with at least one mixture according to claim 5 .
16. An ink-jet ink comprising a mixture according to claim 4 .
17. An ink-jet ink comprising a mixture according to claim 5 .
18. A compound of formula (Ia)
wherein
CC is a moiety of formula (a 1 ) or (c 2 ),
wherein
R 10 is H; —CH 3 or —CH 2 CH 3 ,
T 1 is H; —CN; —CONH 2 ; —CONHCH 3 ;
R 10 ′ is H; —CH 3 or —OH,
G is H or —(CH 2 ) 2-4 NR 13 R 14 ,
wherein R 13 and R 14 are independently from each other H; —CH 3 or —CH 2 CH 3 , or
wherein
each R 1 is independently from each other H; —CH 3 , —CH 2 CH 3 or substituted C 1-4 alkyl,
X 1 and X 2 are independently from each other halogen or —NR 2 R 3
wherein R 2 and R 3 are independently from each other H; C 1-4 alkyl;
—C 2-4 alkylene-NH 2 — or —C 2-4 alkylene-OH—,
Y is a direct bond;
wherein the asterisk is the bond to the benzene ring and
o is 0 or 1
n″ is 1, 2, 3 or 4, with the provisos that
when n″ is 1 then B″ is C(CH 2 OH) 3
when n″ is 2 then B″ is C(CH 2 OH) 2
when n″ is 3 then B″ is C(CH 2 OH)
when n″ is 4 then B″ is
C; [—(CH 2 ) 1-4 —O—(CH 2 ) 1-4 ] 4 C; [—(CH 2 ) 1-3 —O—(CH 2 ) 1-3 —O—(CH 2 ) 1-3 ] 4 C;
[—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 —O—(CH 2 ) 1-2 ] 4 C or [(—CH 2 ) 1-4 ] 2 N(CH 2 ) 1-4 N[(—CH 2 ) 1-4 ] 2 .
19. A mixture comprising:
at least one compound of formula (Ia) according to claim 18 wherein B″ is C(CH 2 OH) 3 and n″ is 1,
at least one compound wherein B″ is C(CH 2 OH) 2 and n″ is 2,
at least one compound of formula (Ia) wherein B″ is C(CH 2 OH) and n″ is 3,
and at least one compound of formula (Ia) wherein B″ is C and n″ is 4.
20. A mixture comprising at least one compound of formula (Ia) of claim 18 .
21. A process for dyeing or printing fiber material or dyeing or printing paper comprising the steps of:
providing a dye or printing paste comprising a compound according to claim 18 ;
providing a fiber material or paper; and
contacting said dye or printing paste with said fiber material or paper.
22. A material dyed or printed with at least one compound according to claim 18 .
23. A material dyed or printed with at least one mixture according to claim 20 .
24. An ink-jet ink comprising at least one compound according to claim 18 .
25. An ink-jet ink comprising at least one mixture according to claim 20 .
26. A process for the preparation of an ink-jet ink comprising the step of:
adding a compound according to claim 18 to at least one other compound.
27. A process for the preparation of an ink-jet ink comprising the step of:
adding a mixture according to claim 20 to at least one other compound.