Disperse Azo Dyes, a Process for the Preparation Thereof and the Use Thereof

Abstract

The present invention relates to azo dyes of formula

##STR00001##

wherein R.sub.1 denotes hydrogen or C.sub.1-C.sub.12alkyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.12alkoxy groups, C.sub.1-C.sub.12alkylcarbonyl groups, C.sub.7-C.sub.25arylcarbonyl groups, hydroxyl groups, amino groups, cyano groups or halogen atoms and which may be interrupted one or more times by the radical O, S, NR.sub.4, COO or OOC, R.sub.4 is hydrogen or C.sub.1-C.sub.12alkyl; X is hydrogen or halogen; and R.sub.2 and R.sub.3 are each independently of the other hydrogen; C.sub.1-C.sub.12alkyl which is unsubstituted or substituted by cyano, carboxy, hydroxy, C.sub.1-C.sub.6alkoxy or C.sub.2-C.sub.8alkoxyalkoxy; or are C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by cyano, carboxy, hydroxy, C.sub.1-C.sub.6alkoxy or C.sub.2-C.sub.8alkoxyalkoxy,
to mixtures containing said dyes and to the use thereof in dyeing or printing semi-synthetic and especially synthetic hydrophobic fibre materials, more especially textile materials.

Claims

1. An azo dye of formula ##STR00009## wherein R.sub.1 denotes hydrogen or C.sub.1-C.sub.12 alkyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.12 alkoxy groups, C.sub.1-C.sub.12 alkylcarbonyl groups, C.sub.7-C.sub.25 arylcarbonyl groups, hydroxyl groups, amino groups, cyano groups or halogen atoms and which may be interrupted one or more times by the radical O, S, NR.sub.4, COO or OOC, R.sub.4 is hydrogen or C.sub.1-C.sub.12 alkyl; X is hydrogen or halogen; and R.sub.2 and R.sub.3 are each independently of the other hydrogen; C.sub.1-C.sub.12 alkyl which is unsubstituted or substituted by cyano, carboxy, hydroxy, C.sub.1-C.sub.6 alkoxy or C.sub.2-C.sub.8 alkoxyalkoxy; or are C.sub.7-C.sub.25 aralkyl which is unsubstituted or substituted by cyano, carboxy, hydroxy, C.sub.1-C.sub.6 alkoxy or C.sub.2-C.sub.8 alkoxyalkoxy.

2. An azo dye of formula (1) according to claim 1, wherein X denotes hydrogen or bromo.

3. An azo dye of formula (1) according to claim 1, wherein R.sub.1 denotes methyl, ethyl, n-propyl, i-propyl or n-butyl.

4. An azo dye of formula (1) according to claim 1, wherein R.sub.2 and R.sub.3 represent 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-ethoxyethyl, 3-ethoxypropyl or 4-ethoxybutyl.

5. A dichromatic or trichromatic dye mixture comprising at least one azo dye of formula (1) according to claim 1 and at least one further disperse dye.

6. A process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials, in which process a dye of formula (1) according to claim 1 is applied to the said materials or incorporated into them.

7. (canceled)

8. A semi-synthetic or especially synthetic hydrophobic fibre material dyed or printed by the process according to claim 6.

9. A semi-synthetic or especially synthetic textile material dyed or printed by the process according to claim 6.

Description

I. PREPARATION EXAMPLES

I.1 Dyestuff of Formula (101)

[0043] ##STR00004##

[0044] 5.0 g of the dye of formula (101a)

##STR00005##

which was prepared as described in U.S. Pat. No. 3,980,634 are dissolved under stirring at RT (room temperature) in 60 ml of pyridine. 0.073 g finely powdered NaCN and 0.27 g finely powdered CuCN are given to 50 ml pyridine and suspended under vigorous stirring. The reaction mixture is stirred over night and then diluted with 80 ml pyridine. The precipitate is filtered off and washed with water.

[0045] According to HPLC analysis, the crude product essentially consists of a mixture of three different dyestuffs namely the educt of formula (101a), the dyestuff of formula (101) and the dicyano compound of formula (101 b) which are separated by conventional chromatographic methods.

##STR00006##

[0046] The dyestuff of formula (101) is characterized by the following properties:

[0047] m.p. (melting point)=217-226 C.

[0048] .sub.max=527 nm (.sub.max=wavelength of the absorption maximum, measured in DMF)

TABLE-US-00001 Elemental Analysis: in theorie found C 52.3% 52.4% H 4.9% 4.9% N 18.8% 18.6%

[0049] .sup.1H-NMR (CDCl.sub.3, 250 MHz): =11.49 (1H, NH), 8.08 (s, 1H), 7.05 (1H, NH), 3.69-3.82 (m, 6H), 3.61 (t, J=6.1, 2H), 3.45-3.50 (m, 2H), 3.44 (s, 3H), 3.33 (s, 3H), 2.83 (s, 3H), 1.91-2.00 (m, 4H), 1.31 (t, J=7.2, 3H)

I.2 Dyestuff of Formula (102)

[0050] ##STR00007##

[0051] The dye of formula (102) is prepared either by conventional coupling reaction of the relevant diazonium salt with the respective coupling component or according to the method described in Example 1.1 from the respective monobromo compound.

[0052] m.p. (melting point)=231-237 C.

[0053] .sub.max=527 nm (.sub.max=wavelength of the absorption maximum, measured in DMF)

TABLE-US-00002 Elemental Analysis: in theorie found C 60.22% 59.90% H 5.83% 6.0% N 21.61% 21.20%

[0054] .sup.1H-NMR (CDCl.sub.3, 250 MHz): =11.35 (1H, NH), 8.22 (s, 1H), 8.105 (s, 1H), 6.96 (1H, NH), 3.69-3.83 (m, 6H), 3.61 (t, J=5.45, 2H), 3.45-3.50 (m, 2H), 3.44 (s, 3H), 3.32 (s, 3H), 2.74 (s, 3H), 1.93-2.04 (m, 4H), 1.30 (t, J=7.2, 3H) The dyes of formulae (103)-(207) listed in the following Table 1 can be prepared in analogy to the method described above.

TABLE-US-00003 TABLE 1 Dyestuffs of formula (1) (1) [00008] Dye R.sub.1 X R.sub.2 R.sub.3 103 ethyl Cl 3-methoxypropyl 3-methoxypropyl 104 ethyl H 2-methoxyethyl 2-methoxyethyl 105 ethyl Br 2-methoxyethyl 2-methoxyethyl 106 ethyl Cl 2-methoxyethyl 2-methoxyethyl 107 ethyl H 4-methoxybutyl 4-methoxybutyl 108 ethyl Br 4-methoxybutyl 4-methoxybutyl 109 ethyl Cl 4-methoxybutyl 4-methoxybutyl 110 ethyl H 2-ethoxyethyl 2-ethoxyethyl 111 ethyl Br 2-ethoxyethyl 2-ethoxyethyl 112 ethyl Cl 2-ethoxyethyl 2-ethoxyethyl 113 ethyl H 3-ethoxypropyl 3-ethoxypropyl 114 ethyl Br 3-ethoxypropyl 3-ethoxypropyl 115 ethyl Cl 3-ethoxypropyl 3-ethoxypropyl 116 methyl H 3-methoxypropyl 3-methoxypropyl 117 methyl Br 3-methoxypropyl 3-methoxypropyl 118 methyl Cl 3-methoxypropyl 3-methoxypropyl 119 methyl H 2-methoxyethyl 2-methoxyethyl 120 methyl Br 2-methoxyethyl 2-methoxyethyl 121 methyl Cl 2-methoxyethyl 2-methoxyethyl 122 methyl H 4-methoxybutyl 4-methoxybutyl 123 methyl Br 4-methoxybutyl 4-methoxybutyl 124 methyl Cl 4-methoxybutyl 4-methoxybutyl 125 methyl H 2-ethoxyethyl 2-ethoxyethyl 126 methyl Br 2-ethoxyethyl 2-ethoxyethyl 127 methyl Cl 2-ethoxyethyl 2-ethoxyethyl 128 methyl H 3-ethoxypropyl 3-ethoxypropyl 129 methyl Br 3-ethoxypropyl 3-ethoxypropyl 130 methyl Cl 3-ethoxypropyl 3-ethoxypropyl 131 n-propyl H 3-methoxypropyl 3-methoxypropyl 132 n-propyl Br 3-methoxypropyl 3-methoxypropyl 133 n-propyl Cl 3-methoxypropyl 3-methoxypropyl 134 n-propyl H 2-methoxyethyl 2-methoxyethyl 135 n-propyl Br 2-methoxyethyl 2-methoxyethyl 136 n-propyl Cl 2-methoxyethyl 2-methoxyethyl 137 n-propyl H 4-methoxybutyl 4-methoxybutyl 138 n-propyl Br 4-methoxybutyl 4-methoxybutyl 139 n-propyl Cl 4-methoxybutyl 4-methoxybutyl 140 n-propyl H 2-ethoxyethyl 2-ethoxyethyl 141 n-propyl Br 2-ethoxyethyl 2-ethoxyethyl 142 n-propyl Cl 2-ethoxyethyl 2-ethoxyethyl 143 n-propyl H 3-ethoxypropyl 3-ethoxypropyl 144 n-propyl Br 3-ethoxypropyl 3-ethoxypropyl 145 n-propyl Cl 3-ethoxypropyl 3-ethoxypropyl 146 n-butyl H 3-methoxypropyl 3-methoxypropyl 147 n-butyl Br 3-methoxypropyl 3-methoxypropyl 148 n-butyl Cl 3-methoxypropyl 3-methoxypropyl 149 n-butyl H 2-methoxyethyl 2-methoxyethyl 150 n-butyl Br 2-methoxyethyl 2-methoxyethyl 151 n-butyl Cl 2-methoxyethyl 2-methoxyethyl 152 n-butyl H 4-methoxybutyl 4-methoxybutyl 153 n-butyl Br 4-methoxybutyl 4-methoxybutyl 154 n-butyl Cl 4-methoxybutyl 4-methoxybutyl 155 n-butyl H 2-ethoxyethyl 2-ethoxyethyl 156 n-butyl Br 2-ethoxyethyl 2-ethoxyethyl 157 n-butyl Cl 2-ethoxyethyl 2-ethoxyethyl 158 n-butyl H 3-ethoxypropyl 3-ethoxypropyl 159 n-butyl Br 3-ethoxypropyl 3-ethoxypropyl 160 n-butyl Cl 3-ethoxypropyl 3-ethoxypropyl 161 H H 3-methoxypropyl 3-methoxypropyl 162 H Br 3-methoxypropyl 3-methoxypropyl 163 H Cl 3-methoxypropyl 3-methoxypropyl 164 H H 2-methoxyethyl 2-methoxyethyl 165 H Br 2-methoxyethyl 2-methoxyethyl 166 H Cl 2-methoxyethyl 2-methoxyethyl 167 H H 4-methoxybutyl 4-methoxybutyl 168 H Br 4-methoxybutyl 4-methoxybutyl 169 H Cl 4-methoxybutyl 4-methoxybutyl 170 H H 2-ethoxyethyl 2-ethoxyethyl 171 H Br 2-ethoxyethyl 2-ethoxyethyl 172 H Cl 2-ethoxyethyl 2-ethoxyethyl 173 H H 3-ethoxypropyl 3-ethoxypropyl 174 H Br 3-ethoxypropyl 3-ethoxypropyl 175 H Cl 3-ethoxypropyl 3-ethoxypropyl 176 ethyl Cl 3-methoxypropyl 2-methoxyethyl 177 ethyl H 2-methoxyethyl 3-methoxypropyl 178 ethyl Br 3-methoxypropyl 2-methoxyethyl 179 ethyl Cl 2-methoxyethyl 3-methoxypropyl 180 ethyl H 4-methoxybutyl 2-methoxyethyl 181 ethyl Br 4-methoxybutyl 2-methoxyethyl 182 ethyl Cl 4-methoxybutyl 2-methoxyethyl 183 ethyl H 2-ethoxyethyl 2-methoxyethyl 184 ethyl Br 2-ethoxyethyl 2-methoxyethyl 185 ethyl Cl 2-ethoxyethyl 2-methoxyethyl 186 ethyl H 3-ethoxypropyl 2-methoxyethyl 187 ethyl Br 3-ethoxypropyl 2-methoxyethyl 188 ethyl Cl 3-ethoxypropyl 2-methoxyethyl 189 ethyl Cl H 3-methoxypropyl 190 ethyl H H 2-methoxyethyl 191 ethyl Br 2-methoxyethyl H 192 ethyl Cl 2-methoxyethyl H 193 ethyl H H 4-methoxybutyl 194 ethyl Br 4-methoxybutyl H 195 ethyl Cl 4-methoxybutyl H 196 ethyl H H 2-ethoxyethyl 197 ethyl Br H H 198 ethyl Cl 2-ethoxyethyl H 199 ethyl H H 3-ethoxypropyl 200 ethyl Br 3-ethoxypropyl H 201 ethyl Cl H 3-ethoxypropyl 202 ethyl Br n-butyl n-butyl 203 ethyl H n-butyl n-butyl 204 ethyl Br n-pentyl n-pentyl 205 ethyl H n-pentyl n-pentyl 206 ethyl Br benzyl Benzyl 207 ethyl H benzyl benzyl

II. APPLICATION EXAMPLES

II.1: Dyeing of Polyester

[0055] 15 parts by weight of the dye of formula (101) prepared in Example 1.1 is milled together with 4.4 parts of a commercially available dispersing agent in a total of 100 parts of aqueous dispersion. Using that formulation, a 1% dyeing (based on the dye and the substrate) is produced on woven polyester by high temperature exhaust process at 135 C.

[0056] Test results: the light fastness of the dyeing is excellent as well as the results in the AATCC 61 and ISO 105 tests. The build-up and wash fastness properties of the dye are very good.

II.2: Dyeing of Polyester

[0057] Example II.1 is repeated by using the dye of formula (102) instead of the dye of formula (101). Test results: the light fastness of the dyeing is excellent as well as the results in the AATCC 61 and ISO 105 tests.