DE2507908A1 - Monoazo pigments contg 3,4-dihydro 4-oxo quinazoline gps - for colouring paints, resins, plastics, fibres, etc - Google Patents

Abstract

Pigments of formula: (in which K is the gp. of a coupling component; X is -NH-, -CONH-, -CHCO- or a direct bond; Y is -NH- or a direct bond; rings A and B may contain 1-3 other substits.), are used for the colouring of printing inks, plastics, paper, paints, etc. in yellow to bluish-red shades. (I) have excellent fastness, esp. to plasticisers, solvents, over-painting, light and weather, very high colour strength and enormous covering power.

Description

New pigment dyes The invention relates to azo pigments of the formula I. in which K is the remainder of a coupling component, X is -NH, -CONH-, -NHCO- or a direct bond, Y is -NE- or a direct bond, and rings A and B can also carry 1-3 substituents.

In particular, the invention relates to dyes of the formula II in which X -NH- and Y a direct bond, X an airect bond and Y -NH, K the remainder of a coupling component and R¹, R², R5 and R4 hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, cyano, Nitro, Ci to C4-alkoxycarbonyl, trifluoromethyl, methylsulfonyl or optionally N-substituted carbamoyl or sulfamoyl.

N-substituted carbamoyl radicals are e.g. N-methyl-, N-phenyl-, N- (chlorine, Bromine, methyl, methoxy, ethoxy or carbomethoxy) phenyl or N-ifaphthylcarbamoyl. The corresponding sulfamoyl radicals are equally suitable.

Particularly suitable coupling components are those with enolic Structure, for example pyrazolone-5, acetoacetic acid arylide, barbituric acid, aminobarbituric acid, 2,6-dihydroxypyridine, 2,4-diamino-5-hydroxypyrimidine, 2,4-dihydroxyquinoline and homophthalimide derivatives.

Preferred coupling components are those of the pyridine and pyrimidine series, for example: 4-methyl-5-cyano-2,6-dihydroxypyridine, 4-methyl-2,6-dihydroxypyridinecarboxylic acid 5-amide, 2,6-dihydroxy-4-aminopyridinecarboxylic acid-5-amide, 1,4-dimethyl-3-cyano-hydroxypyridone-2,6, 1- (B-methoxy-ethyl) -4-methyl-3-cyano-hydroxypyridone-2,6, 3-cyano-hydroxypyridone-S, 6, Barbituric acid, 2-aminobarbituric acid, 2,4-diiminobarbituric acid and those in the DT-OS 2 022 817 described connections.

Also to be mentioned are: 1-phenyl-3-methylpyrazolone-5, 1- (4'-chlorophenyl) -pyrazolone-5-carboxylic acid-3-amide, 1-phenyl-pyrazolon-5-carboxylic acid-3-anilide, 1 - (3 '-cyanophenyl) -3-methyl-pyrazolon-5, 1- (3'-nitrophenyl) -pyrazolon-5-carboxylic acid-3-anilide, 1- (4'-nitrophenyl) -3-methyl-pyrazolon-5, 1- (2'-methylphenyl ) -pyrazolon-5-carboxylic acid-3-amide, 1- (2 ', 5'-dichlorophenyl) -3-cyanpyrazolon-5, 1,3-dimethyl-pyrazolone-5, 1- (ß-cyanoethyl) -pyrazolone-5-carboxylic acid-3-amide, 1- (ß-hydroxyethyl) -3-methyl-pyrazolone-5, Acetoacetic anilide, acetoacetic acid-2,5-dimethoxy-4-chloranilide, acetoacetic acid-2-methyl-4-chloranilide, Acetoacetic acid-2,4-dichloroanilide, acetoacetic acid-2-nitro-4-methoxyanilide, acetoacetic acid-2-methoxy-5-nitroanilide, Acetoacetic acid-2,5-dichloroanilide, acetoacetic acid-2-nitro-4-methylanilide, acetoacetic acid-2-methoxyanilide, Acetoacetic acid-2-nitro-4-chloroanilide, acetoacetic acid-2,4-dinitroanilide, acetoacetic acid-2,4-dimethoxy-5-chloroanilide, Acetoacetic acid-2-methoxy-4-chloro-5-methylanilide, acetoacetic acid-2,5-dichloro-4-benzoylamino-anilide, Acetoacetic acid-2-methyl-3-chloroanilide and 5-aceto-acetylamino-benzimidazolone.

Also suitable are: 2,4-dihydroxyquinoline, 1-methyl-hydroxyquinolone-2,4, 1-phenyl-3-methyl-5-aminopyrazole, 1- (4'-acetylaminophenyl) -3-methoxy-5-aminopyrazole, 1 - (41 -Benzoylaminophenyl) -3-ynetbyl-5-aminopyrazole and homophthalimide.

To prepare the dyes of the formula I, a diazo compound of amines of the formula III can be used in which A, B, X and Y have the meanings given, react with a coupling component of the formula IV K - g IV.

Diazotization and coupling are carried out as usual. the The dyes produced in this way often do not fall directly into the for the respective Intended use optimal form, but they can by the usual measures such as crushing, salt grinding or recrystallization in accordance with the respective purpose adapted shape are brought.

The new pigments are yellow to bluish red and some have excellent fastness properties, of which the plasticizer, solvent, overmolding, Light and weather fastness are to be emphasized.

Some of them are characterized by a very high color strength and by an enormous opacity.

The new pigments can be used for dope coloring, for example of Viscose for the production of colored printing pastes, for the production of colored Varnishes, for coloring phenoplasts or aminoplasts, thermoplastics such as polystyrene, Polyolefin or PVC, from rubber or silicone resins, for coloring laminated papers or plates and for textile printing.

The dyes of Fornel II a are of particular technical importance in which R5 is hydrogen, chlorine, bromine or nitro, R6 is hydrogen or chlorine, R7 is hydrogen, methyl, methoxy, ethoxy, chlorine, bromine, methoxycarbonyl, isopropoxycarbonyl or nitro, R8 is hydrogen, methyl, methoxy, ethoxy or chlorine and a coupling component of pyridine -, pyrimidine, pyrazolone, benzimidazolone, dihydroxyquinoline or homophthalimide series.

Amines of the formula III are for example: In the following examples, unless otherwise stated, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius.

Example 1 14 parts of 3,4-dihydro-4-oxoquinazoline-2-carboxylic acid N- (4'-aminophenyl) amide are introduced into a mixture of 110 parts of propionic acid and 110 parts of formic acid and added at 0-5 oC diazotized by 15 parts of nitrosylsulfuric acid (45 96). The mixture is stirred for 4 hours at 5 ° C., then treated with a solution of 7.5 g of 3-cyano-2,6-dihydroxy-4-methyl-pyridine in 100 parts of dimethylformamide, and 70 parts of pyridine are slowly added. The mixture is stirred for a further 6 hours at room temperature, then for 2 hours at 80 ° C., filtered off with suction at 60-70 ° C., washed thoroughly with water and methanol and dried at 80 ° C. 20 parts of a light red powder of the formula are obtained Example 2 32.4 parts of 3,4-dihydro-4-oxoquinazoline-2-carboxylic acid N- (4'-amino-2'-methoxy-5'-methyl-phenyl) -amide are dissolved in 600 parts of dimethylformamide at 100.degree solved. It is then cooled to 0 ° C., 60 parts of conc. Sulfuric acid is added and 30 parts by volume of 23,96 aqueous sodium nitrite solution are slowly added. The mixture is stirred for 4 hours at 5 ° C., a solution of 17.4 parts of 3-methyl-1-phenyl-pyrazolone-5 in 300 parts of dimethylformamide and then 100 parts of pyridine are slowly added dropwise. After stirring for 6 hours at room temperature, the mixture is heated to 100 ° C. for 1 hour, filtered off with suction at 80 ° C., washed with water and methanol and dried at 80 ° C.

39 parts of a brilliant red powder of the formula are obtained Example 3 29.4 parts of 3,4-dihydro-4-oxoquinazoline-2-carboxylic acid N- (3'-amino 4'-methyl-phenyl) -amide are dissolved in 100 parts by volume of concentrated sulfuric acid at 20 ° C. and at 0 ° C. diazotized with 30 parts of nitrosylsulfuric acid. The mixture is stirred at 5 ° C. for 3 hours, the excess nitrite is removed by adding urea, the mixture is poured onto 600 parts of ice and 300 parts of water, a solution of 18 parts of N-phenylacetanilide in 400 parts of dilute sodium hydroxide solution is added and the pH is adjusted with dilute sodium hydroxide solution -Value from 5 - 6 a. The mixture is stirred for 6 hours, filtered off with suction, washed thoroughly with warm water and stirred with methanol. After drying, 44 parts of a brilliant yellow powder of the formula are obtained Example 4 62.9 parts of 4-amino-N- (6-chloroquinazolon-4-yl-2) -benzamide (diazo component 105) are diazotized in hydrochloric acid in the usual way.

33 parts of dihydroxy-3-cyano-4-methylpyridine are added and the pH of the reaction mixture with 10 pointer sodium acetate solution to 5 a and stirs for an hour. The dye is suctioned off, with water and finally washed with methanol. The moist filter material is in 850 parts of dimethylformamide Stirred for 2 hours at 110 ° C., filtered off with suction at 60 ° C., washed with methanol and dried.

87 parts of a powder of the formula are obtained If one proceeds in a manner analogous to the above examples, further Bzo pigments are obtained if the diazo components of the formula III identified by the number in the table are reacted with the coupling components EH listed. The last column of the table shows the color shades of the paint coatings produced with the pigments: For example, diazo component, coupling component KH color shade H, C 5 2 h CN red H0 N OH 6 3 "red 7 4" red 8 6 "violet-red 9 7" violet-red 10 8 "violet-red 11 9" violet-red 12 10 "orange-red 13 13" orange-red 14 14 "orange-red 15 17" orange-red 16 18 "yellow 17 19 1I yellow 18 22 "yellow 19 23" yellow 20 25 "yellow 21 27" violet 22 28 "orange-red 23 30" orange-red 24 31 "orange-red 25 35" yellow 26 36 "orange-red 27 37" yellow e.g. diazo component coupling component KU color HC 28 39 H3C H0 LIVING 29 41 "yellow 30 42 red 31 43" yellow 32 44 "orange-red 33 46 11 red 34 47 red red 35 48 red 36 50" yellow 37 52 1I violet-red 38 53 "orange-red 39 54 yellow 40 55" red 41 56 "orange-red 42 58 "yellow 43 59" violet-red 44 60 "violet-red 45 61" dark red 46 63 "orange-red 47 64" orange-red 48 65 "yellow 49 66" yellow 50 67 "violet-red e.g. diazo component coupling component KH color 51 oH; $ i <CoN 68 H3C CPT orange-red Red 52 69 "xiiiuiixix 53 70 "violet-red 54 71" violet-red 55 72 "violet-red 56 73" yellow 57 75 "yellow 58 76" orange-red 59 78 n yellow 60 79 1 orange-red 61 81 "violet-red 62 82" violet-red 63 83 "dark red 64 85" yellow 65 86 tt yellow 66 87 "orange-red 67 89" yellow 68 90 1 orange-red 69 91 "dark red 70 93" violet 71 95 "violet e.g. diazo component coupling component KH color 72 96 H3C yellow 31 CN X OH 73 97 "yellow 74 98 tI orange 75 99 n yellow 76 100 "yellow 77 102 "yellow 78 105 "yellow 79 106 n yellow 80 109 "yellow 81 120 "yellow H, C elNB, 82 2 W -NH2 orange HO OH 83 5 "orange 84 6 "red 85 7 "red 86 8 "red 87 9 .. red 88 10 "orange 89 12 n orange 90 16 n orange 91 19 "yellow 92 22 "yellow E.g. diazo component coupling component KH color Ts n 93 2i 3 OH JH3 - violet red C-NH2 Ho 'N OH 94 37 "yellow 95 46" red 96 47 "red 97 52" red 98 59 "red 99 60" red 100 61 "red 101 62" red 102 67 "red 103 69" red 104 70 "red 105 72" red 106 81 "red 107 82" red 108 83 "red 109 91" red 110 93 "red @ 11 95" red 112 96 "reddish yellow 113 97" yellow 114 98 "orange 115 100" yellow e.g. diazo component coupling component KH color 116 1 HO OH yellow OH 117 2 n orange 118 6 n red 119 7 "red 120 9" orange 121 12 n yellow 122 13 "yellow 123 22" yellow 124 26 "yellow 125 27" red 126 29 n yellow 127 35 n yellow 128 46 "orange-red 129 47 n orange-red 130 52 "red 131 53" yellow 132 59 "red 133 60" red 134 62 1I orange-red 135 69 "red e.g. diazo component coupling component KH color 136 81 HO OH e orange red OH 137 82 "orange red 138 85 .. red 139 96 "yellow 140 97 I1 yellow 141 99 "yellow 142 109 110 "yellow OH 143 1 g orange 2 144 2 .. orange 145 5 n orange 146 6 "red 147 7 "red 148 9 "red 149 15 .. yellow 150 23 .. yellow 151 27 n purple red 152 28 "yellow 153 46 II red 154 48 ri red 155 54 yellow 156 60 "red E.g. diazo component coupling component KH color 157 69 H0 ~~~~~ OH red III NtE NH2 158 81 "red 159 82 "red 110 NH2 160 1 4 reddish yellow NH2 161 2 II orange 162 6 "purple red 163 7 II purple red 164 9 "purple red 165 10 "reddish yellow 166 18 "yellow 167 22 "yellow 168 30 "yellow 169 38 "yellow 170 40 .. purple red 171 48. purple red 172 54 II yellow 173 55 reddish yellow 174 80 1 yellow 175 96 .. yellow 176 97 "yellow 177 99., Yellow 178 110 lt yellow 179 122 "yellow E.g. diazo component coupling component KH color 180 | e OH orange * ff OH 181 2 "orange 182 6 lt red 183 7 II red 184 8" red 185 9 lt red 186 18 "yellow 187 27 lt violet-red 188 10" orange 189 4o "red 190 54 tl yellow 191 59" red 192 60 "red 193 69 "red 194 81" red e.g. diazo component coupling component KH color gs 195 OH orange 196 2 lt orange red 197 6 tl purple red 198 7 lt purple red 199 9 "violet red 200 18 II yellow 201 29 tl yellow 202 46 tt purple red 203 54 e tt yellow 204 1 to N 4 orange OH 205 2 tl orange 206 6 II red 207 7 l1 red 208 8 tt yellowish red 209 9 11 yellowish red 210 10 "orange 211 16 II orange 212 18 lt yellow 213 22 lt yellow 214 27 n red 215 28 II orange E.g. diazo component coupling component KH color 216 36 3 to too orange OH 217 46 II red 218 47 II yellowish red 219 48 II yellowish red 220 52 II red 221 54 "yellow 222 59 II red 223 60 lt red 224 62 II red 225 69 II red 226 70 n red 227 81 II red 228 82 II red 229 91 "red 230 95 II red 231 96 EIC - according to yellow 232 6 «N 4 - Cl yellowish red H 233 7 n yellowish red 234 8 lt yellowish red 235 18 lt yellow 236 22 lt yellow 237 27 n red E.g. diazo component coupling component KH color 238 28 113C <Cl reddish yellow OH 239 46 .. yellowish red 240 52 n red 241 54 n yellow 242 59 lt yellowish red 243 62 n yellowish red 244 69 .. yellowish red 245 81 .. yellowish red 246 98 11 Cl reddish yellow 247 orange 011 orange 248 2 lt orange 249 6 II yellowish red 250 7 n yellowish red 251 8 tl yellowish red 252 10 n orange 253 12 lt orange 254 18 lt yellow 255 23., Yellow 256 27 lt red 257 46 n red 258 53 lt yellow 259 59 II red 260 60 II red E.g. diazo component coupling component KH color RC 261> 4 orange 011 Cl 262 6 lt yellowish red 263 7 n yellowish red 264 8 lt yellowish red 265 18 lt yellow 266 22 "yellow 267 25 lt yellow 268 46 lt yellowish red 269 48 lt orange 270 52 lt red 271 54 lt yellow 272 59 n yellowish red 273 69 lt yellowish red 274 106 lt yellow 275 2 H3C N NO2 orange OH 276 7 lt red 277 8 n red 278 10 n orange 279 19 lt yellow 280 27 II purple red E.g. diazo component coupling component KH color 11 C 281 31 3 \% ° 2 orange OH 282 46 II red-violet 283 54 lt yellow 284 58 lt yellow 285 59 tl red-violet 286 82 lt red 287 97 II yellow CONH2 288 2 QN 4 yellowish red OH 289 6 lt purple red 290 7 lt purple red 291 23 lt reddish yellow 292 47 lt red 293 52 lt purple 294 105 lt orange 0 0 II II 295 1 CH3-C-CH2-C-NH <yellow 296 2 lt yellow 297 5 n yellow 298 10 lt yellow 299 11 "yellow 300 12 lt yellow 301 14 n yellow 302 19 lt yellow E.g. diazo component coupling component KH color 0 0 303 cH, -e-CH2 3 to II yellow C113-C-C112-C-NH-C11 304 2 lt yellow 305 7 II yellow 306 16 lt yellow 307 .53 "yellow 308 54 lt yellow 3 ° 9 56 lt yellow 310 68 lt yellow 311 80 lt yellow 312 90 II yellow 313 100 lt yellow 314 104 II yellow OC113 315 1 CH3-C-CH2-C-NH yellow 316 10 lt yellow 317 18 n yellow 318 28 lt yellow 319 53 II yellow 320 54 lt yellow E.g. diazo component coupling component KH color 321 1 CH3-C-CH2-NH 0 OCH3 yellow CH3-1-CH2- yellow OCH3 322 3 lt yellow 323 13 w yellow 324 14 lt yellow 325 16 lt yellow 326 28 lt yellow 327 44 n yellow 328 53 lt yellow 329 54 »yellow 330 16 n yellow 0 0 C = O II III 331 1 CH3-C-CH2-3-2 HC = o yellow 332 2 n yellow 333 8 n yellow 334 10 lt yellow 335 12 n yellow 336 19 n yellow 337 28 II yellow 338 36 lt yellow 339 47 lt yellow 340 53 lt yellow E.g. diazo component coupling component KH color 0 0 II 55 CH -C-CH2-C-4 gC = O 341 55 CR-C-CH-C-N1 'yellow 342 68 lt yellow 343 79 n yellow 344 84 II yellow 345 90 II yellow 346 96 lt yellow 347 97 n yellow 348 105 II yellow 349 113 11oÄ31C%; CN HC yellow-yellow HO t CN 350 1 t bluish red 351 2 II bluish red 352 3 lt purple 353 4 lt bluish red 354 5 II bluish red 355 10 II red 356 12 lt bluish red 357 18 lt red 358 19 lt red 359 22 II red 360 30 lt red E.g. diazo component coupling component KU color H, C 1 CN A CN 361 53 11% ¼ %% CN bluish red 362 55 n bluish red 363 96 II bluish red 364 97 "red 365 106" red 366 108 "bluish red

Claims (4)

Claims 1. Pigment dyes of the formula in which K denotes the remainder of a coupling component 'X denotes -NH, -CONH-, -NHCO- or a direct bond, Y denotes -NE- or a direct bond, and rings A and B can also carry 1-3 substituents. 2. Dyes according to claim 1 of the formula in which R5 is hydrogen, chlorine, bromine or nitro, R6 is hydrogen or chlorine, R7 is hydrogen, methyl, methoxy, ethoxy, chlorine, bromine, methoxycarbonyl, isopropoxycarbonyl or nitro, hydrogen, methyl, methoxy, ethoxy or chlorine and K¹ is a coupling component of the pyridine , Pyrimidine, pyrazolone, benzimidazolone, dihydroxyquinoline or homophthalimide series mean. . Process for the preparation of dyes according to Claim 1, characterized in that a diazo compound of amines of the formula III in which A, 3, X and Y have the meanings given, where K - H is reacted with a coupling component of the formula IV, K here also has the meanings given. 4. Use of the dyestuffs according to Claim 1 for dyeing printing inks, Plastics, paper or paints.