Naphtholactam derivatives

The present invention relates to compounds of the formula I ##STR2## where A is a radical of the formula ##STR3## n is 2 or 3, R is hydrogen or unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl, R.sup.1 is hydrogen, chlorine, bromine, alkyl, alkoxy, NO.sub.2 or arylmercapto, R.sup.2 is hydrogen or chlorine, R.sup.3 is hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, acylamino, alkylsulfonylamino, arylsulfonylamino, alkylmercapto, arylmercapto, arylsulfonyl, alkylsulfonyl, unsubstituted or N-substituted sulfamide, alkanoyl or aroyl, R.sup.4 is hydrogen, chlorine, alkoxy, arylmercapto or alkylmercapto, or R.sup.3 and R.sup.4 together are a radical of the formula ##STR4## R.sup.5 is hydrogen, chlorine or alkoxy, B is hydrogen, methyl, methoxy or chlorine, X is cyano or unsubstituted or substituted carbamoyl, Y is hydrogen, hydroxyl, alkyl of 1 to 4 carbon atoms, chlorine, bromine, C.sub.1 to C.sub.4 alkoxycarbonyl or unsubstituted or N-substituted carbamoyl, or X and Y together are a radical of the formula ##STR5##
More particularly, R is alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of 3 to 8 carbon atoms, .beta.-chloroethyl, .beta.-cyanoethyl, alkoxycarbonylethyl, where alkoxy is of 1 to 4 carbon atoms, carbamoylethyl, N-monosubstituted or N,N-disubstituted alkylcarbamoylethyl, where alkyl is of 1 to 4 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenyl.
Specific examples of R are propyl, butyl, hexyl, .beta.-ethylhexyl, .beta.-hydroxyethyl or .beta.-hydroxypropyl, methoxyethyl, ethoxyethyl, methoxypropyl, ethoxypropyl, butoxypropyl, amyloxypropyl, methoxycarbonylethyl, ethoxycarbonylethyl or butoxycarbonylethyl and preferably methyl, ethyl or .beta.-cyanoethyl.
Examples of alkyl, alkoxy and arylmercapto groups R.sup.1 are methyl, ethyl, methoxy, ethoxy and phenylmercapto which is unsubstituted or substituted by chlorine, methyl, methoxy, phenyl, phenoxy or methoxycarbonyl.
Examples of R.sup.3 are the same radicals as those mentioned for R.sup.1, as well as naphthylmercapto, acylaminophenylmercapto, diacylaminophenylmercapto, acetylamino, propionylamino, benzoylamino which is unsubstituted by chlorine, methyl or methoxy, methylsulfonylamino, ethylsulfonylamino, phenylsulfonylamino, tolylsulfonylamino, methylmercapto, ethylmercapto, .beta.-hydroxyethylmercapto, .beta.-hydroxypropylmercapto, butylmercapto, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, tolylsulfonyl, chlorophenylsulfonyl, acetyl, chloroacetyl, propionyl, butyryl, benzoyl which is unsubstituted or substituted by methyl, methoxy, chlorine or bromine, sulfamoyl, N-methyl-, N-ethyl-, N-butyl-, N-phenyl-, N-chlorophenyl, N-methylphenyl-, N-methoxyphenyl-, N-trifluoromethylphenyl-, N-methyl-N-phenyl-, N,N-dimethyl-, N,N-diethyl-, N,N-dipropyl- and N,N-dibutyl-sulfamoyl, pyrrolidinosulfonyl, piperidinosulfonyl or morpholinosulfonyl. R.sup.3 may also be a radical of the formula NHCONH.sub.2, NHCONHCH.sub.3 or NHCONHC.sub.6 H.sub.5.
R.sup.4 may be hydrogen, chlorine, or one of the alkoxy, alkylmercapto and arylmercapto radicals mentioned for R.sup.1.
Examples of alkoxy radicals R.sup.5 are methoxy and ethoxy. Examples of N-substituted carbamoyl radicals Y are CONHCH.sub.3, CONHC.sub.2 H.sub.5, CONHC.sub.4 H.sub.9, CONHC.sub.2 H.sub.4 OH, CON(CH.sub.3).sub.2, CON(C.sub.3 H.sub.7).sub.2, CON(C.sub.4 H.sub.9).sub.2 and ##STR6##
The compounds of the formula I may be manufactured by reacting compounds of the formula II ##STR7## where X.sup.1 is oxygen or sulfur and A.sup..crclbar. is an anion, and alkyl is of 1 to 4 carbon atoms, with compounds of the formula A--H.sub.2.
If X.sup.1 is 0, a condensing agent must be present, whilst if X.sup.1 is S or the compounds containing the S-alkyl groups are used, this is not necessary.
Suitable condensing agents are phosphorus halides, eg. phosphorus pentachloride, phosphorus trichloride, phosphorus oxytribromide and especially phosphorus oxytrichloride.
The reaction may be carried out in an inert solvent, eg. a glycol diether or polyglycol diether, butyrolactone, toluene, chlorobenzene, dichlorobenzene, nitrobenzene or dioxane, or in an excess of the condensing agent.
If the reaction of the naphtholactam derivatives is carried out without a condensing agent, the above solvents may again be used; additional examples of suitable solvents are pyridine, glacial acetic acid, dimethylformamide or N-methylpyrrolidone.
The compounds of the formula ##STR8## where T is oxygen and R and Y have the stated meanings, or the R bound to the ring nitrogen and T together are a radical of the formula ##STR9## and B, the other R and Y have the stated meanings, may be manufactured by reacting compounds of the formula
Y--COCH.sub.2 COO--alkyl
with compounds of the formula ##STR10## Suitable reaction conditions are similar to those for the manufacture of, for example, 2-hydroxy-3-cyano-6-pyridones.
The reactions are known in principle. Details may be found in the Examples, in which parts and percentages are by weight.
The invention in particular relates to compounds of the formula I, where A is a radical of the formula ##STR11## n is 2 or 3, R is hydrogen, alkyl of 1 to 12 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of 3 to 8 carbon atoms, .beta.-chloroethyl, .beta.-cyanoethyl, alkoxycarbonylethyl, where alkoxy is of 1 to 4 carbon atoms, carbamoylethyl, N-mono- or N-di-alkylcarbamoylethyl, where alkyl is of 1 to 4 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenyl, R.sup.1 is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, nitro, phenylmercapto or phenylmercapto substituted by chlorine, methyl or methoxy, R.sup.2 is hydrogen or chlorine, R.sup.3 is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenoxy and nitro, alkanoylamino of 1 to 4 carbon atoms, benzoylamino, alkylsulfonylamino of 1 to 4 carbon atoms, phenylsulfonylamino, tolylsulfonylamino, alkylmercapto of 1 to 4 carbon atoms, phenylmercapto which is unsubstituted or substituted by chlorine, methyl or methoxy, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, tolylsulfonyl, sulfamoyl which is unsubstituted or is monosubstituted or disubstituted by alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of a total of 3 to 11 carbon atoms, .beta.-cyanoethyl, .beta.-chloroethyl, cyclohexyl, phenylalkyl (where alkyl is of 1 to 4 carbon atoms) or phenyl, sulfopiperidide, sulfopyrrolidide, sulfomorpholide, alkanoyl of 1 to 4 carbon atoms, chloroacetyl, .beta.-chloropropionyl, or benzoyl which is unsubstituted or substituted by chlorine, methyl or methoxy, R.sup.4 is hydrogen, chlorine, methoxy, ethoxy, alkylmercapto of 1 to 4 carbon atoms or phenylmercapto which is unsubstituted or substituted by chlorine, methyl or methoxy, R.sup.3 and R.sup.4 together are a radical of the formula ##STR12## R.sup.5 is hydrogen, chlorine, methoxy or ethoxy, B is hydrogen, methyl, methoxy or chlorine, X is cyano, carbamoyl or CONHR, Y is hydrogen, hydroxyl, alkyl of 1 to 4 carbon atoms, chlorine, bromine, alkoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms) or CONHR, or X and Y together are a radical of the formula ##STR13##
Dyes which are industrially particularly important are those of the formula I a ##STR14## where B.sup.1 is hydrogen, alkylsulfonyl of 1 to 4 carbon atoms, allylsulfonyl, propargylsulfonyl, alkanoyl of 2 to 8 carbon atoms, benzoyl, alkylmercapto of 1 to 4 atoms or phenylmercapto, A.sup.1 is a radical of the formula ##STR15## B.sup.2 is hydrogen or methyl, and R and X have the stated meanings.
Specific examples of radicals B.sup.1, in addition to those already mentioned, are methylsulfonyl, ethylsulfonyl, propylsulfonyl and butylsulfonyl, acetyl, propionyl, butyryl, hexanoyl, .beta.-ethylhexanoyl and methylmercapto, ethylmercapto, propylmercapto and butylmercapto.
X is preferably cyano.
Examples of preferred radicals R are methyl, ethyl, n-propyl and i-propyl, n-butyl and i-butyl, .omega.-hydroxyethyl and .omega.-hydroxypropyl, and .omega.-alkoxyethyl and .omega.-alkoxypropyl, where alkoxy is of 1 to 4 carbon atoms.
The compounds of the formula I may be used as dyes for textile material, especially made of polyesters, and for coloring plastics, eg. polystyrene, polycarbonate, polyolefins, polyesters, polyacrylonitrile and nylons, so as to retain their transparency.
The new dyes give brilliant hues ranging from orange to blue, which have excellent fastness to light, thermofixation and wet treatments. The fact that some of the dyes are of very high tinctorial strength should also be singled out.

EXAMPLE 1
180 parts of phosphorus oxychloride are added dropwise, at 80.degree. C, to a mixture of 1,500 parts of ethylene glycol dimethyl ether, 169 parts of naphtholactam and 170 parts of 1-ethyl-3-cyano-6-hydroxypyrid-2-one. After a short time, a red solution forms, from which red crystals begin to separate out. The mixture is stirred for 4 hours at 80.degree. C and 1,000 parts of methanol are added whilst the mixture is cooling. After it has cooled, the product is filtered off, washed with methanol and dried. 267 parts of a dye of the structure ##STR16## are obtained in the form of dark red crystals. When used to dye polyesters from an aqueous bath, the dye gives brilliant yellowish red hues having very good fastness properties.
Dyes with very similar hues are obtained if 1-ethyl-3-cyano-6-hydroxypyrid-2-one is replaced by the corresponding 1-propyl-, 1-butyl-, 1-(3-methoxypropyl)- or 1-(2-ethyl-hexyl)-compounds.
When 6-ethoxy-1,8-naphtholactam is condensed by a similar method with N-substituted 3-cyano-6-hydroxypyrid-2-ones, dyes which dye polyesters in neutral red hues are obtained; the dyeings are outstandingly fast.
EXAMPLE 2
276 parts of N-ethyl-4-bromonaphtholactam and 226 parts of 1-phenyl-3-cyano-4-methyl-6-hydroxypyrid-2-one are introduced into 1,000 parts of toluene and the mixture is stirred at 90.degree. C. 165 parts of phosphorus oxychloride are added dropwise in the course of an hour and the mixture is stirred for a further 2 hours at 90.degree. C. An equal volume of methanol is then added and the mixture is allowed to cool whilst stirring. After filtering off, washing with methanol and drying, 311 parts of a dye of the structure ##STR17## are obtained in the form of a dark crystal powder.
The dye may be used for mass-coloring polystyrene to give brilliant blue hues of good lightfastness and good heat stability.
Dyes having similar blue hues are obtained when N-ethyl-4-bromonaphtholactam is replaced by the corresponding N-butyl, N-methoxyethyl or N-cyclohexyl compounds.
EXAMPLE 3
The "naphthostyrol-imide chloride" obtained from 169 parts of naphtholactam by the method described in German Laid-Open Application DOS 1,445,624, and 209 parts of the benzimidazopyridone of the formula (B .dbd. H, Y .dbd. H) ##STR18## are introduced into 1,000 parts of nitrobenzene and the mixture is stirred at 85.degree. C until the elimination of hydrogen chloride has ceased. After the mixture has cooled, the suspended crystals are filtered off, washed with ethanol and dried. 301 parts of a dye of the structure ##STR19## are obtained in the form of dark crystals. When used to dye polyesters from an aqueous bath, the dye gives violet dyeings which are outstandingly fast. Dyes with similar tinctorial properties are obtained if benzimidazopyridones substituted in the benz-nucleus (B .dbd. --CH.sub.3, --OCH.sub.3, --Cl, Y .dbd. H) are employed as the starting material. The analogous dye with Y .dbd. CH.sub.3 and B .dbd. H is blue and may be used to color thermoplastics, giving fast blue hues.
EXAMPLE 4
385 parts of 2,4-bis-(phenylmercapto)-naphtholactam and 185 parts of 1-methyl-3-cyano-4-ethyl-6-hydroxypyrid-2-one are introduced into 1,000 parts of chlorobenzene and the mixture is stirred at 90.degree. C. 165 parts of phosphorus oxychloride are added dropwise and stirring is continued for 1 hour at 90.degree. C. 1,200 parts of methanol are now added to the reaction mixture, which is then left to stand for 24 hours. The product is then filtered off, washed with methanol and dried. 339 parts of a dye of the structure ##STR20## are obtained, which may be used for dyeing polyesters from an aqueous bath, and for mass-coloring polystyrene, giving pure reddish blue hues.
If 2,4-bis-(phenylmercapto)-naphtholactam is replaced by the corresponding 2,4-bis-(p-tolyl)- or 2,4-bis-(4-methoxyphenyl)- compounds, dyes giving neutral blue hues are obtained.
EXAMPLE 5
183 parts of naphtholactam-o-methyl ether and 250 parts of 1-(3-ethoxypropyl)-3-cyano-4,6-dihydroxypyrid-6-one are stirred into 1,200 parts of ethylene glycol and the mixture is heated to 125.degree. C. It is then stirred for 8 hours at 125.degree. - 130.degree. C and the methanol formed is distilled off through a descending condenser. After the reaction mixture has cooled, it is filtered and the product is washed with ethanol and dried. 281 parts of a dye of the structure ##STR21## are obtained in the form of reddish brown crystals. The dye may be used for dyeing polyesters in orange red hues exhibiting a high level of fastness.
EXAMPLE 6
A mixture of 600 parts of butyrolactone, 277 parts of 4-phenylmercaptonaphtholactam and 155 parts of 1-methyl-3-cyano-6-hydroxypyrid-2-one is stirred at 80.degree. C. 170 parts of phosphorus oxychloride are added dropwise and stirring is continued for 2 hours at 80.degree. C. 1,000 parts of methanol are then added to the reaction mixture and the product is filtered off and rinsed with methanol. After drying, 299 parts of a dye of the structure ##STR22## are obtained in the form of brown crystals. The dye may be used for dyeing polyesters from an aqueous bath, giving vivid violet hues; the dyeings have outstanding light fastness and fastness to thermofixation. Dyes of a similar hue are obtained if the phenylmercapto-naphtholactam is replaced by the corresponding 4-tolylmercapto-, 4-methoxyphenylmercapto-, 4-chlorophenylmercapto- or 4-carbomethoxyphenylmercapto-naphtholactam.
EXAMPLE 7
271 parts of 4,5-benzoylene-naphtholactam (prepared as described in CA 53, 9183 g) and 239 parts of benzimidazopyridone of the formula ##STR23## are introduced into 1,200 parts of butyrolactone and the mixture is stirred at 120.degree. C. 200 parts of phosphorus oxychloride are added dropwise and stirring is continued for 6 hours at 120.degree. C. The product is filtered off at 80.degree. C and is rinsed with warm ethanol. After drying, 399 parts of the dye of the structure ##STR24## are obtained in the form of red crystals. When worked into thermoplastics, the dye gives brilliant red hues having very good lightfastness.
EXAMPLE 8
328 parts of N-benzyl-4,5-dichloro-1,8-naphtholactam and 150 parts of 1-methyl-3-cyano-6-hydroxyoyrid-2-one are introduced into 1,200 parts of butyrolactone and the mixture is stirred at 90.degree. C. 190 parts of phosphorus oxychloride are then added dropwise whilst stirring and the mixture is kept at 90.degree. C for 12 hours. It is diluted with 800 parts of ethanol and the product is filtered off and washed with ethanol. After drying, 413 parts of the dye of the structure ##STR25## are obtained in the form of a dark crystal powder. The dye colors polystyrene in violet hues distinguished by very good lightfastness and heat stability. If 178 parts of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one are employed as the pyridone component, an analogous dye which may be used to color thermoplastics in blue hues is obtained.
EXAMPLE 9
307 parts of 3,4,5,6-tetrachloro-1,8-naphtholactam and 212 parts of 1-phenyl-3-cyano-6-hydroxypyrid-2-one are introduced into 1,500 parts of dehydrated nitrobenzene and the mixture is heated to 100.degree. C. 300 parts of phosphorus oxychloride are added dropwise in the course of one hour and stirring is continued for 16 hours at 100.degree. C. 500 parts of methanol are then added dropwise and the mixture is boiled for one hour under reflux. After filtering off, washing with methanol and drying, 443 parts of a dye of the structure ##STR26## are obtained in the form of a dark red crystal powder. When worked into thermoplastics, the dye gives red hues having excellent lightfastness.
If N-ethyl-3,4,5,6-tetrachloro-1,8-naphtholactam is used as the naphtholactam component, an analogous dye which colors thermoplastics in fast violet hues is obtained.
EXAMPLE 10
275 parts of the compound ##STR27## and 208 parts of 1-ethoxyethyl-3-cyano-6-hydroxypyrid-2-one are introduced into 2,000 parts of dichlorobenzene. The mixture is stirred at 90.degree. C and 250 parts of phosphorus oxychloride are added in the course of 2 hours. Stirring is continued for 12 hours at 90.degree. C and 1,000 parts of ethanol are then added carefully. The reaction mixture is boiled up briefly and is filtered warm. After washing the product with ethanol, and drying it, 398 parts of a dye of the structure ##STR28## are obtained in the form of dark crystals having a metallic gloss. When worked into polystyrene, the dye gives fast greenish blue colorations.
The further dyes shown in the Table were obtained by the processes of Examples 1 - 10.
TABLE 1__________________________________________________________________________Dyes ##STR29##Ex-ample R R.sup.3 Y Hue__________________________________________________________________________11 (CH.sub.2).sub.3 OC.sub.5 H.sub.11 Cl CH.sub.3 violet12 (CH.sub.2).sub.2 COOC.sub.3 H.sub.7 H CH.sub.3 reddish violet13 ##STR30## OC.sub.2 H.sub.5 CH.sub.3 violet14 CH.sub.2 C.sub.6 H.sub.5 NHCOC.sub.2 H.sub.5 CH.sub.3 violet15 CH.sub.3 SC.sub.6 H.sub.5 C.sub.2 H.sub.5 bluish violet16 CH.sub.2 CH.sub.2 OH H C.sub.4 H.sub.9 violet17 C.sub.6 H.sub.5 SC.sub.4 H.sub.9 C.sub.4 H.sub.9 bluish violet18 H CH.sub. 3 Br reddish violet19 CH.sub.3 H H yellowish red20 C.sub.2 H.sub.5 Br H red21 C.sub.2 H.sub.5 NO.sub.2 H reddish violet22 C.sub.2 H.sub.5 OCH.sub.3 H "23 " NHCONHCH.sub.3 H "24 " NHSO.sub.2 C.sub.2 H.sub.5 H "25 " SCH.sub.3 H bluish violet26 " SCH.sub.2 CHOHCH.sub.3 H "27 " SO.sub.2 CH.sub.3 H bluish red28 " SO.sub.2 C.sub.6 H.sub.4 CH.sub.3 (4) H "29 " COCH.sub.3 H red30 " COCH.sub.2 Cl H "31 " COC.sub.6 H.sub.5 H "32 " SO.sub.2 N(C.sub.4 H.sub.9).sub.2 H "33 C.sub.3 H.sub.7 (n) H H yellowish red34 " CH.sub.3 H "35 C.sub.3 H.sub.7 (iso) NHCOCH.sub.3 H reddish violet36 C.sub.4 H.sub.9 (n) NHSO.sub.2 C.sub.6 H.sub.4 CH.sub.3 (4) H "37 C.sub.4 H.sub.9 (n) SC.sub.2 H.sub.5 H bluish violet38 " COC.sub.6 H.sub.4 CH.sub.3 (4) H red39 Ch.sub.2 CH.sub.2 OCH.sub.3 H H yellowish red40 CH.sub.2 CH.sub.2 OCH.sub.3 SC.sub.6 H.sub.4 CH.sub.3 (4) H bluish violet41 (CH.sub.2).sub.3 OC.sub.2 H.sub.5 SO.sub.2 N(CH.sub.3).sub.2 H red42 (CH.sub.2).sub.3 OC.sub.4 H.sub.9 NHCOC.sub.6 H.sub.5 H reddish violet43 (CH.sub.2).sub.3 OC.sub.4 H.sub.9 NHCOC.sub.6 H.sub.4 OCH.sub.3 (4) H "44 CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 Br H red45 CH.sub.2 CH.sub.2 CN ##STR31## H bluish violet46 CH.sub.2 CH.sub.2 COOCH.sub.3 NHCOC.sub.6 H.sub.4 OCH.sub.3 (4) H reddish violet47 CH.sub.2 CH.sub.2 COOC.sub.4 H.sub.9 H H yellowish red48 CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.5 SO.sub.2 C.sub.2 H.sub.5 H bluish red49 CH.sub.2 CH.sub.2 CON(CH.sub.3).sub.2 SO.sub.2 C.sub.6 H.sub.4 Cl(4) H "50 CH.sub.2 CH.sub.2 CON(C.sub.4 H.sub.9).sub.2 H H yellowish red51 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 H H "52 " ##STR32## H red53 C.sub.6 H.sub.5 SCH.sub.2 CH.sub.2 OH H bluish violet54 " SC.sub.6 H.sub.4 OCH.sub.3 (4) H "55 " SC.sub.6 H.sub.4 Cl(4) H "56 " SO.sub.2 NHC.sub.4 H.sub.9 H red57 C.sub.6 H.sub.5 ##STR33## H "58 CH.sub.3 SC.sub.6 H.sub.5 OH bluish red59 C.sub.2 H.sub.5 COC.sub.2 H.sub.5 OH reddish brown60 " SO.sub.2 CH.sub.3 OH red61 " OC.sub.2 H.sub.5 OH reddish brown62 " NHSO.sub.2 CH.sub.3 OH "63 " SO.sub.2 N(C.sub.3 H.sub.7).sub.2 OH red64 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 COC.sub.6 H.sub.5 OH reddish brown65 (CH.sub.2).sub.3 OCH.sub.3 H OH orange66 (CH.sub.2).sub.3 OCH.sub.3 SC.sub.6 H.sub.4 OC.sub.6 H.sub.5 OH bluish red67 C.sub.3 H.sub.7 H OH orange68 " SO.sub.2 CH.sub.3 OH red69 " SO.sub.2 C.sub.6 H.sub.5 OH "70 CH.sub.3 H COOCH.sub.3 violet71 " NHCONHC.sub.6 H.sub.5 COOC.sub.2 H.sub.5 bluish violet72 " COC.sub.4 H.sub.9 COOC.sub.2 H.sub.5 violet73 " NHSO.sub.2 CH.sub.3 COOC.sub.2 H.sub.5 "74 " SO.sub.2 NHCH.sub.3 COOC.sub.4 H.sub.9 bluish violet75 " SO.sub.2 NHC.sub.6 H.sub.4 CH.sub.3 (2) COOC.sub.4 H.sub.9 "76 " SO.sub.2 N(C.sub.2 H.sub.5).sub.2 CONHC.sub.2 H.sub.5 "77 C.sub.2 H.sub.5 H CONHC.sub.2 H.sub.5 violet78 CH.sub.3 Cl CON(CH.sub.3).sub.2 "79 C.sub.4 H.sub.9 H CON(CH.sub.3).sub.2 "80 CH.sub.3 SC.sub.6 H.sub.5 CON(C.sub.2 H.sub.5).sub.2 blue81 " COC.sub.6 H.sub.5 CON(C.sub.3 H.sub.7).sub.2 violet__________________________________________________________________________
TABLE 2______________________________________Dyes ##STR34##Ex. R R.sup.3 Y Hue______________________________________82 CH.sub.3 H H violet83 CH.sub.3 SO.sub.2 CH.sub.3 H bluish violet84 CH.sub.3 SC.sub.6 H.sub.5 H blue85 CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 Cl H violet86 CH.sub.2 CH.sub.2 CN Br H "87 CH.sub.2 CH.sub.2 CON(CH.sub.3).sub.2 H H "88 CH.sub.2 C.sub.6 H.sub.5 SC.sub.6 H.sub.3 Cl.sub.2 (2,5) H blue89 C.sub.6 H.sub.5 SCH.sub.3 H "90 CH.sub.3 H OH violet91 CH.sub.3 H CH.sub.3 blue92 CH.sub.3 Br CH.sub.3 blue93 " SC.sub.6 H.sub.5 " green- ish blue94 " SO.sub.2 C.sub.6 H.sub.5 " blue95 C.sub.2 H.sub.5 SCH.sub.3 " tur- quoise96 " SO.sub.2 CH.sub.3 " blue97 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 COC.sub.6 H.sub.5 C.sub.2 H.sub.5 "98 CH.sub.2 CH.sub.2 COOCH.sub.3 H C.sub.2 H.sub.5 "99 " Br " "______________________________________
TABLE 3__________________________________________________________________________Dyes ##STR35##Ex. R R.sup.1 R.sup.3 Y Hue__________________________________________________________________________100 CH.sub.3 SC.sub.2 H.sub.5 SC.sub.2 H.sub.5 CH.sub.3 blue101 " SC.sub.6 H.sub.4 CH.sub.3 (4) SC.sub.6 H.sub.4 CH.sub.3 (4) CH.sub.3 "102 " Cl Cl C.sub.2 H.sub.5 reddish violet103 " Br NO.sub.2 " violet104 " SC.sub.6 H.sub.4 Cl(4) SC.sub.6 H.sub.4 Cl(4) " blue105 C.sub.2 H.sub.5 Br Br CH.sub.3 reddish violet106 " SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 " reddish blue107 CH.sub.3 Br Br H red108 " SCH.sub.3 SCH.sub.3 H bluish violet109 C.sub.2 H.sub.5 Br NO.sub.2 H bluish red110 C.sub.2 H.sub.5 SC.sub.4 H.sub.9 SC.sub.4 H.sub.9 H bluish violet111 " SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 H bluish violet112 " SC.sub.6 H.sub.4 CH.sub.3 (4) NO.sub.2 H "113 C.sub.3 H.sub.7 Cl Cl H red114 C.sub.4 H.sub.9 SCH.sub.2 CH.sub.2 OH SCH.sub.2 CH.sub.2 OH H bluish violet115 C.sub.4 H.sub.9 SC.sub.6 H.sub.4 OCH.sub.3 (4) SC.sub.6 H.sub.4 OCH.sub.3 (4) H "116 CH.sub.2 C.sub.6 H.sub.5 Cl Cl H red117 CH.sub.2 C.sub.6 H.sub.5 SC.sub.6 H.sub.4 Cl(4) SC.sub.6 H.sub.4 Cl(4) H bluish violet118 C.sub.6 H.sub.5 SC.sub.3 H.sub.7 SC.sub.3 H.sub.7 H "119 C.sub.6 H.sub.5 SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 H "120 " SC.sub.6 H.sub.3 Cl.sub.2 (2,5) SC.sub.6 H.sub.3 Cl.sub.2 (2,5) H "121 " C.sub.2 H.sub.5 H CH.sub.3 reddish violet122 " NO.sub.2 Br CH.sub.3 violet__________________________________________________________________________
TABLE 4______________________________________Dyes ##STR36##Ex. R R.sup.1 = R.sup.3 Y Hue______________________________________123 CH.sub.3 Cl CH.sub.3 bluish violet124 " SC.sub.6 H.sub.5 " tur- quoise125 CH.sub.2 CH.sub.2 CON(C.sub.2 H.sub.5).sub.2 Br " bluish violet126 C.sub.2 H.sub.5 Cl OH violet127 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Cl COOCH.sub.3 blue128 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 Br " "129 CH.sub.3 Cl H violet130 C.sub.2 H.sub.5 SC.sub.2 H.sub.5 H blue131 C.sub.2 H.sub.5 SC.sub.4 H.sub.9 H "132 C.sub.2 H.sub.5 SC.sub.6 H.sub.5 H "133 CH.sub.2 CH.sub.2 OH Br H violet134 (CH.sub.2).sub.3 OCH.sub.3 SCH.sub.3 H blue135 CH.sub.2 CH.sub.2 CN " H "136 CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7 SC.sub.6 H.sub.5 H "137 CH.sub.2 CH.sub.2 CONHCH.sub.3 Cl H violet138 CH.sub.2 CH.sub.2 CON(C.sub.3 H.sub.7).sub.2 Br H "139 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 SC.sub.3 H.sub.7 H blue______________________________________
TABLE 5__________________________________________________________________________Dyes ##STR37##Ex-ample R R.sup.3 R.sup.4 Y Hue__________________________________________________________________________140 H Cl Cl H red141 H SCH.sub.3 SCH.sub.3 H bluish violet142 CH.sub.3 Cl Cl H red143 C.sub.2 H.sub.5 Cl SC.sub.6 H.sub.5 H violet144 " Cl SC.sub.6 H.sub.4 OCH.sub.3 (4) H "145 " Cl SC.sub.6 H.sub.4 Cl(4) H "146 " SC.sub.2 H.sub.5 SC.sub.2 H.sub.5 H bluish violet147 " SC.sub.6 H.sub.5 H "148 CH.sub.2 CH.sub.2 OH Cl Cl H red149 CH.sub.3 Cl Cl CH.sub.3 reddish violet150 CH.sub.3 SCH.sub.2 CH.sub.2 OH SCH.sub.2 CH.sub.2 OH " blue151 CH.sub.3 Cl SC.sub.6 H.sub.5 " "152 CH.sub.3 H OCH.sub.3 CH.sub.3 reddish violet__________________________________________________________________________
EXAMPLE 153
160 parts of phosphorus oxychloride are added dropwise at 70.degree. C to a mixture of 800 parts of butyrolactone, 169 parts of naphtholactam and 188 parts of 1-ethyl-2-hydroxypyrid-6-one-3-carboxamide.
The mixture is stirred for 8 hours at 70.degree. C, 400 parts of methanol and 400 parts of water are added successively and the whole is allowed to cool. After filtering off, washing and drying the product, 276 parts of the dye ##STR38## are obtained.
If the condensation is carried out at 70.degree. C or with a substantial excess of phosphorus oxychloride, the reaction product contains substantial amounts of the dye described in Example 1. The dye of Example 153 is also obtained by hydrolyzing the dye 1, for example with 91% strength sulfuric acid at 85.degree. C (more concentrated sulfuric acid leads to sulfonation of the naphthalene ring). The dye has very similar tinctorial properties to those of the dye described in Example 1.
TABLE 6__________________________________________________________________________Dyes ##STR39##Ex-ample R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R Hue__________________________________________________________________________154 H H H H H CH.sub.3 yellowish red155 H H H H H (CH.sub.2).sub.3 OCH.sub.3 yellowish red156 H H Cl H H C.sub.4 H.sub.9 red157 H H Br H H C.sub.2 H.sub.5 red158 Br H Br H H C.sub.2 H.sub.5 red159 H Cl Cl Cl Cl C.sub.2 H.sub.5 red160 H H SC.sub.6 H.sub.5 H H C.sub.2 H.sub.5 violet161 H H SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 H C.sub.2 H.sub.5 violet162 H H COC.sub.6 H.sub.5 H H C.sub.2 H.sub.5 red163 H H COCH.sub.2 CH.sub.2 Cl H H CH.sub.3 red164 H H SO.sub.2 CH.sub.3 H H C.sub.2 H.sub.5 bluish red165 H H NO.sub.2 H H C.sub.2 H.sub.5 reddishviolet166 H H ##STR40## H H C.sub.2 H.sub.5 red167 H H SO.sub.2 N(CH.sub.3).sub.2 H H C.sub.2 H.sub.5 red168 SC.sub.6 H.sub.5 H SC.sub.6 H.sub.5 H H C.sub.2 H.sub.5 bluish violet169 ##STR41## H ##STR42## H H C.sub.2 H.sub.5 bluish violet170 H H SO.sub.2 N(C.sub.3 H.sub.7).sub.2 H H C.sub.2 H.sub.5 red171 H H ##STR43## H H C.sub.2 H.sub.5 red172 H H ##STR44## H H C.sub.2 H.sub.5 red173 H H SO.sub.2 NHC.sub.6 H.sub.5 H H C.sub.2 H.sub.5 red174 H H ##STR45## H H C.sub.2 H.sub.5 red__________________________________________________________________________
EXAMPLE 175
200 parts of phosphorus oxychloride are added dropwise, at 80.degree. C, to a mixture of 1,200 parts of ethylene glycol dimethyl ether, 247 parts of 4-methylsulfonyl-naphtholactam and 264 parts of N,N'-dipropyl-2-hydroxypyrid-6-one-3,4-dicarboximide. Dark crystals separate out from the solution. The mixture is boiled for 2 hours under reflux and 800 parts of methanol are added whilst it is cooling. After it has cooled, the product is filtered off, washed with methanol and dried. 401 parts of the dye having the structure ##STR46## are obtained in the form of dark crystals having a metallic gloss. The dye may be used to dye polyesters, from an aqueous bath, in brilliant neutral blue hues having good fastness properties.
TABLE 7__________________________________________________________________________ ##STR47##Example R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R Hue__________________________________________________________________________176 H H H H H ##STR48## violet177 H H H H H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 bluish violet178 Cl H Cl H H C.sub.4 H.sub.9 (iso) reddish blue179 Cl H Cl Cl Cl CH.sub.2 CH.sub.2 CN reddish blue180 H H Br H H (CH.sub.2).sub.3 OCH.sub.3 bluish violet181 H H Br H H ##STR49## bluish violet182 H H H H H C.sub.6 H.sub.5 reddish blue182 H H C.sub.2 H.sub.5 SO.sub.2 H H C.sub.2 H.sub.5 blue183 H H CH.sub.3 C.sub.6 H.sub.4 SO.sub.2 H H C.sub.4 H.sub.9 blue184 H H CH.sub.3 CO H H C.sub.5 H.sub.11 reddish blue185 H H ClCH.sub.2 CO H H C.sub.3 H.sub.7 (iso) reddish blue186 H H C.sub.2 H.sub.5 CO H H C.sub.2 H.sub.5 reddish blue187 H H ##STR50## H H C.sub.2 H.sub.5 reddish blue188 H H ##STR51## H H C.sub.2 H.sub.5 reddish blue189 H H ##STR52## H H C.sub.2 H.sub.5 reddish blue190 H H ##STR53## H H C.sub.2 H.sub.4 bluish violet192 H H ##STR54## H H C.sub.2 H.sub.5 bluish violet193 H H ##STR55## H H C.sub.2 H.sub.5 bluish violet194 H H ##STR56## H H C.sub.2 H.sub.5 bluish violet195 H H CH.sub.3 NHCONH H H C.sub.2 H.sub.5 bluish violet196 H H NO.sub.2 H H C.sub.3 H.sub.7 blue__________________________________________________________________________
EXAMPLE 197
169 parts of naphtholactam and 227 parts of ##STR57## are introduced into 1,200 parts of dimethyl glycol and the mixture is stirred at 70.degree. C. 165 parts of phosphorus oxychloride are added dropwise in the course of one hour and stirring is continued for 8 hours. After the mixture has cooled, it is filtered and the filter cake is dispersed in dilute ammonia. After again filtering off, and washing the product with water and drying it, 287 parts of the dye having the structure. ##STR58## are obtained; it may be used to dye polyesters, from an aqueous bath, in light-fast violet hues. Dyes with B .dbd. CH.sub.3 or OCH.sub.3, which have been prepared similarly, exhibit a hue somewhat shifted toward blue.
TABLE 8______________________________________ ##STR59##Ex. R R.sup.3 B Hue______________________________________198 H Br H vio- let199 H OCH.sub.3 H blu- ish vio- let200 H CH.sub.3 H vio- let201 H NO.sub.2 H blu- ish vio- let202 H SC.sub.6 H.sub.5 H blue203 H SC.sub.6 H.sub.4 CH.sub.3 (4') H blue204 H SC.sub.6 H.sub.4 OCH.sub.3 (4') H blue205 CH.sub.3 H H blue206 CH.sub.2 CH.sub.2 CN H H blue207 CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5 H H blue208 H C1 OCH.sub.3 blue209 H H C1 vio- let______________________________________
EXAMPLE 210
169 parts of naphtholactam and 309 parts of a compound having the structure. ##STR60## are introduced into 1,500 parts of ethylene glycol dimethyl ether, and 185 parts of phosphorus oxychloride are added at 75.degree. C. After boiling the mixture for 4 hours, 500 parts of ethanol are added dropwise and the batch is allowed to cool. 500 parts of water are then added dropwise and the product is filtered off and washed with dilute ammonia solution and with water. After drying, 344 parts of the dye having the structure ##STR61## are obtained. This dye may be used to dye polyesters from an aqueous bath, giving slightly greenish blue dyeings with good fastness properties. Dyes of the same hue are obtained if the butyl group is replaced by other alkyl radicals, including substituted or branched radicals. Dues with B = CH.sub.3 or OCH.sub.3 exhibit a hue shifted somewhat more toward green.
The following are further dyes which have been prepared in accordance with the methods of Examples 1 - 10: ##STR62##
EXAMPLE 219
169 parts of naphtholactam and 210 parts of N,N'-diethyl2-hydroxypyrid-6-one-3-carboxamide are introduced into 750 parts of butyrolactone and the mixture is stirred at 70.degree. C. 175 parts of phosphorus oxychloride are added dropwise, whereupon the reaction mixture assumes a deep red color. The mixture is stirred for a further 6 hours at 70.degree. C, after which 250 parts of methanol and 250 parts of water are successively added dropwise. After the mixture was cooled, the crystals are filtered off and washed with 50% strength methanol. After drying, 309 parts of the dye having the structure ##STR63## are obtained in the form of a red crystal powder. The dye may be used to dye polyester fibers and fabrics, from an aqueous bath, in brilliant red hues having very good fastness properties, especially excellent light fastness.
EXAMPLE 220
277 parts of 4-phenylmercaptonaphtholactam and 182 parts of N,N'-dimethyl-2-hydroxypyrid-6-one-3-carboxamide are introduced into 1,000 parts of dehydrated chlorobenzene. 180 parts of phosphorus oxychloride are added dropwise at 80.degree. C, whilst stirring, and the mixture is then kept for 4 hours at 80.degree. C. The heating bath is then temporarily removed and 1,000 parts of methanol are carefully added to the reaction mixture. The batch is then boiled for half an hour under reflux and is allowed to cool, and the product is filtered off.
After drying, 336 parts of the dye having the structure ##STR64## are obtained in the form of a dark crystal powder. The dye may be used to dye polyesters from an aqueous bath, giving light-fast violet hues.
The pyridone derivative is obtained as follows:
72 parts of sodium methylate are introduced into a mixture of 75 parts of ethyl formate and 120 parts of ethyl acetate at -10.degree. to 0.degree. C, whilst stirring. The mixture is left to stand overnight at room temperature, the colorless crystal slurry is then dissolved by pouring 750 parts by volume of absolute ethanol over it, and 130 parts of malonic acid bis-methylamide are introduced. The reaction mixture is now boiled for 8 hours under reflux, in the course of which it gradually solidfies to a crystal slurry. Excess 10% strength hydrochloric acid is then added and ethanol/water is distilled off until the internal temperature has reached 100.degree. C. On cooling, colorless crystals separate out from the clear solution; they are filtered off and dried. Yield: 123 parts of 1-methyl-2-hydroxypyrid6-one-3-carboxylic acid methylamide of melting point 206.degree. - 208.degree. C.
Analysis: C.sub.8 H.sub.10 N.sub.2 O.sub.3 (182) calculated C 52.8; H 5.5; N 15.4; O 26.4; found 52.8; 5.5; 15.5; 26.4.
TABLE 9__________________________________________________________________________ ##STR65##Example R.sup.3 A.sup.1 Hue__________________________________________________________________________221 H CH.sub.3 red222 H C.sub.3 H.sub.7 (n) red223 H C.sub.3 H.sub.7 (iso) red224 H C.sub.4 H.sub.9 (n) red225 H C.sub.4 H.sub.9 (sec) red226 H ##STR66## red227 H CH.sub.2 CH.sub.2 OH red228 H CH.sub.2 CH.sub.2 OCOCH.sub.3 red229 H CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5 red230 H CH.sub.2 CH.sub.2 CN red231 H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 red232 H CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 red233 H CH.sub.2 C.sub.6 H.sub.5 red234 H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 red235 H CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 red236 H ##STR67## red237 H CH.sub.2 CH(C.sub.6 H.sub.5)CH.sub.3 red238 H C.sub.6 H.sub.5 red239 H ##STR68## red240 H ##STR69## red241 H ##STR70## bluish red242 Cl C.sub.2 H.sub.5 red243 Br C.sub.2 H.sub.5 bluish red244 Br C.sub.3 H.sub.7 (iso) bluish red245 Br C.sub.4 H.sub.9 (n) bluish red246 CH.sub.3 CH.sub.3 red247 OC.sub.2 H.sub.5 CH.sub.3 bluish red248 COCH.sub.3 C.sub.2 H.sub.5 red249 COCH.sub.3 C.sub.3 H.sub.7 red250 COC.sub.2 H.sub.5 C.sub.2 H.sub.5 red251 COCH.sub.2 Cl C.sub.2 H.sub.5 red252 COCH.sub.2 CH.sub.2 Cl C.sub.2 H.sub.5 red253 COC.sub.6 H.sub.5 CH.sub.3 red254 COC.sub.6 H.sub.5 C.sub.3 H.sub.7 red255 COC.sub.6 H.sub.5 C.sub.4 H.sub.9 (sec) red256 ##STR71## CH.sub.3 red257 ##STR72## CH.sub.3 red258 ##STR73## CH.sub.3 red259 ##STR74## CH.sub.3 red260 ##STR75## CH.sub.3 red261 SO.sub.2 CH.sub.3 CH.sub.3 bluish red262 SO.sub.2 C.sub.2 H.sub.5 CH.sub.3 bluish red263 SO.sub.2 CH.sub.2 CHCH.sub.2 CH.sub.3 bluish red264 SO.sub.2 NHC.sub.2 H.sub.5 CH.sub.3 red265 SO.sub.2 NH(CH.sub.2).sub.3 OC.sub.2 H.sub.5 CH.sub.3 red266 ##STR76## CH.sub.3 red267 SO.sub.2 NH(CH.sub.2).sub.3 OC.sub.4 H.sub.9 C.sub.2 H.sub.5 red268 SO.sub.2 N(CH.sub.3).sub.2 C.sub.4 H.sub.9 (n) red269 ##STR77## CH.sub.3 red270 SO.sub.2 N(C.sub.4 H.sub.9).sub.2 C.sub.2 H.sub.5 red271 SO.sub.2 NHCl.sub.6 H.sub.5 C.sub.2 H.sub.5 red272 ##STR78## CH.sub.3 red273 ##STR79## C.sub.2 H.sub.5 red274 ##STR80## C.sub.3 H.sub.7 (iso) red275 SO.sub.2 NHCH.sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 red276 SO.sub.2 NH(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH CH.sub.3 red277 SO.sub.2 NH(CH.sub.2).sub.3 O(CH.sub.3).sub.2 OC.sub.6 H.sub.5 CH.sub.3 red278 ##STR81## C.sub.4 H.sub.9 red279 ##STR82## C.sub.4 H.sub.9 (tertiary) red280 ##STR83## C.sub.3 H.sub.7 (n) red281 ##STR84## C.sub.2 H.sub.5 red282 SC.sub.2 H.sub.5 CH.sub.3 violet283 SCH.sub.2 CH.sub.2 OH CH.sub.3 violet284 SC.sub.4 H.sub.9 C.sub.2 H.sub.5 violet285 SC.sub.6 H.sub.5 C.sub.2 H.sub.5 violet286 SC.sub.6 H.sub.5 C.sub.3 H.sub.7 (iso) violet287 ##STR85## CH.sub.3 violet288 ##STR86## CH.sub.3 violet289 ##STR87## CH.sub.3 violet290 ##STR88## CH.sub.3 violet291 ##STR89## CH.sub.3 violet292 ##STR90## C.sub.2 H.sub.5 violet293 ##STR91## CH.sub.3 violet294 ##STR92## CH.sub.3 violet295 SO.sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 bluish red296 ##STR93## C.sub.2 H.sub.5 bluish red297 NO.sub.2 CH.sub.3 bluish red298 NO.sub.2 C.sub.2 H.sub.5 bluish red299 NO.sub.2 C.sub.3 H.sub.7 bluish red300 NO.sub.2 C.sub.3 H.sub.7 (iso) bluish red301 NHCOCH.sub.3 C.sub.2 H.sub.5 reddish violet302 NHCOC.sub.2 H.sub.5 C.sub.2 H.sub.5 reddish violet303 NHCONH.sub.2 C.sub.2 H.sub.5 reddish violet304 NHCOC.sub.6 H.sub.5 C.sub.3 H.sub.7 reddish violet305 NHSO.sub.2 CH.sub.3 C.sub.2 H.sub. 5 reddish violet306 NHSO.sub.2 C.sub.4 H.sub.9 CH.sub.3 reddish violet307 ##STR94## C.sub.2 H.sub.5 reddish violet308 ##STR95## C.sub.2 H.sub.5 reddish violet__________________________________________________________________________
EXAMPLE 309
190 parts of phosphorus oxychloride are added in the course of one hour to a mixture of 1,200 parts of butyrolactone, 259 parts of N-benzyl-naphtholactam and 266 parts of N,N'-dibutyl-2-hydroxypyrid6-one-3-carboxamide at 100.degree. C and the batch is kept at this temperature for 2 hours. The heating is then discontinued and 800 parts of methanol are added dropwise at a rate such that the reaction mixture comes to the boil. In the course thereof, the dark melt turns to a crystal suspension, which is filtered after it has cooled. After washing the product with methanol and drying, 355 parts of the dye having the structure ##STR96## are obtained. When worked into thermoplastics, the dye gives violet hues having very good lightfastness. Tinctorially equivalent dyes are obtained with N-phenylnaphtholactam and N-phenylethylnaphtholactam.
TABLE 10__________________________________________________________________________Dyes ##STR97##Example R R.sup.3 A A.sup.1 Hue__________________________________________________________________________310 CH.sub.3 H H C.sub.2 H.sub.5 violet311 CH.sub.3 H CH.sub.3 CH.sub.3 blue312 C.sub.2 H.sub.5 Br H CH.sub.3 violet313 CH.sub.3 H C.sub.4 H.sub.9 CH.sub.3 blue314 H COC.sub.6 H.sub.5 CH.sub.3 CH.sub.3 reddish violet315 H H OH C.sub.2 H.sub.5 orange316 H SO.sub.2 CH.sub.3 OH C.sub.3 H.sub.7 yellowish red317 H SC.sub.6 H.sub.5 OH CH.sub.3 dull bluish red318 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 OH C.sub.2 H.sub.5 yellowish red319 CH.sub.2 CH.sub.2 CN H OH CH.sub.3 violet320 C.sub.4 H.sub.9 COC.sub.6 H.sub.5 OH C.sub.2 H.sub.5 violet321 C.sub.2 H.sub.5 SC.sub.6 H.sub.5 OH CH.sub.3 reddish blue322 CH.sub.2 C.sub.6 H.sub.5 H OH C.sub.4 H.sub.9 violet323 (CH.sub.2).sub.2 COOCH.sub.3 Cl H C.sub.2 H.sub.5 violet324 (CH.sub.2).sub.2 CON(CH.sub.3).sub.2 H H CH.sub.3 violet325 CH.sub.3 SC.sub.6 H.sub.5 H CH.sub.3 reddish blue326 (CH.sub.2).sub.3 OCH.sub.3 Br H CH.sub.3 violet__________________________________________________________________________
TABLE 11__________________________________________________________________________Dyes ##STR98##Example R.sup.1 R.sup.3 A A.sup.1 Hue__________________________________________________________________________327 Cl Cl H C.sub.2 H.sub.5 red328 Cl NO.sub.2 H C.sub.2 H.sub.5 red329 Br Br H C.sub.3 H.sub.7 bluish red330 Br NO.sub.2 H CH.sub.3 bluish red331 NO.sub.2 Br H C.sub.2 H.sub.5 red332 SCH.sub.3 SCH.sub.3 H C.sub.2 H.sub.5 bluish violet333 SCH.sub.2 CH.sub.2 OH SCH.sub.2 CH.sub.2 OH H CH.sub.3 bluish violet334 SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 H C.sub.2 H.sub.5 bluish violet335 ##STR99## ##STR100## H CH.sub.3 violet336 ##STR101## ##STR102## H C.sub.2 H.sub.5 bluish violet337 Br Br OH C.sub.2 H.sub.5 reddish orange338 SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 OH CH.sub.3 violet339 ##STR103## ##STR104## OH C.sub.2 H.sub.5 violet340 Cl Cl CH.sub.3 CH.sub.3 reddish violet341 SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 CH.sub.3 CH.sub.3 blue__________________________________________________________________________
TABLE 12__________________________________________________________________________Dyes ##STR105##Example R.sup.3 R.sup.4 A A.sup.1 Hue__________________________________________________________________________342 Cl Cl H C.sub.2 H.sub.5 red343 Cl Cl H C.sub.3 H.sub.7 (iso) red344 SC.sub.2 H.sub.5 SC.sub.2 H.sub.5 H CH.sub.3 bluish violet345 Cl SC.sub.6 H.sub.5 H C.sub.2 H.sub.5 reddish violet346 Cl SC.sub.6 H.sub.5 H C.sub.4 H.sub.9 reddish violet347 Cl ##STR106## H C.sub.2 H.sub.5 reddish violet348 Cl ##STR107## H C.sub.2 H.sub.5 reddish violet349 H OCH.sub.3 H CH.sub.3 red350 Cl Cl OH C.sub.2 H.sub.5 orange351 Cl ##STR108## OH C.sub.2 H.sub.5 red352 SC.sub.6 H.sub.5 SC.sub.6 H.sub.5 OH C.sub.2 H.sub.5 reddish violet353 Cl Cl CH.sub.3 CH.sub.3 reddish violet354 SCH.sub.3 SCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 blue355 ##STR109## ##STR110## CH.sub.3 CH.sub.3 blue__________________________________________________________________________
EXAMPLE 356
307 parts of 3,4,5,6-tetrachloronaphtholactam and 250 parts of N,N'-diisopropyl-2-hydroxypyrid-6-one are introduced into 1,300 parts of dehydrated nitrobenzene and the mixture is stirred at 90.degree. C. 195 parts of phosphorus oxychloride are added dropwise and stirring is continued for 4 hours at 99.degree. - 100.degree. C. The excess phosphorus oxychloride is then decomposed by adding 700 parts of ethanol and the mixture is boiled up briefly and allowed to cool. After filtering off, washing the product with ethanol and drying it, 411 parts of the dye having the structure ##STR111## are obtained. In polystyrene, this dye gives heat-stable and very light-fast brilliant red colorations. The dye with R .dbd. H and A .dbd. OH, prepared similarly, colors polystyrene reddish orange whilst the dye with R .dbd. --CH.sub.3 and A .dbd. H colors polystyrene violet.
EXAMPLE 357
271 parts of 4,5-benzoylenenaphtholactam (prepared as described in C.A. 53, 9183 g) and 300 parts of N,N'-bis-methoxypropyl-2-hydroxypyrid-6-one-3-carboxamide are introduced into 1,200 parts of dehydrated dichlorobenzene and the mixture is stirred at 100.degree. C. 200 parts of phosphorus oxychloride was added dropwise and stirring is continued for 4 hours at 110.degree. C. When the mixture has cooled, 800 parts of methanol are added and the product is filtered off and washed with methanol. After it has been dried, 443 parts of the dye of the formula ##STR112## are obtained. When worked into thermoplastics, the dye gives reddish violet colorations distinguished by very good lightfastness.
EXAMPLE 358
275 parts of the compound ##STR113## and 266 parts of N,N'-bis-isobutyl-2-hydroxypyrid-6-one-3-carboxamide are introduced into 1,500 parts of butyrolactone. The mixture is stirred at 90.degree. C and 200 parts of phosphorus oxychloride are added in the course of 2 hours. Stirring is continued for 10 hours at 90.degree. C and 1,000 parts of methanol are then added dropwise, whilst discontinuing the heating. After filtering off, washing the product with methanol and drying it, 336 parts of the dye having the structure ##STR114## are obtained. This dye, worked into polystyrene or other thermoplastics, gives light-fast greenish blue colorations.
EXAMPLE 359
250 parts of phosphorus oxychloride are added in the course of 2 hours to a mixture of 1,400 parts of ethylene glycol dimethyl ether, 169 parts of naphtholactam and 299 parts of the compound ##STR115## whilst stirring at 70.degree. C. The mixture is then stirred for a further 6 hours at 70.degree. C, after which 1,000 parts of methanol are added. When the mixture has cooled, it is filtered and the filter residue is dispersed in dilute ammonia. After again filtering off, washing the product with water and drying it, 297 parts of the dye ##STR116## are obtained. This dye may be used to dye polyester fibers and fabrics from an aqueous bath, giving strong brilliant violet dyeings distinguished by good lightfastness and fastness to thermofixation. Dyes with equivalent tinctorial properties are obtained by varying A.sup.1 from methyl to 2-ethylhexyl, the optimum affinity being found with a total of from 4 to 5 carbon atoms.
The condensation products may be prepared by, for example, the following method:
77 parts of sodium methylate are introduced into a mixture of 80 parts of ethyl formate and 140 parts of ethyl acetate whilst cooling at from -20.degree. to 0.degree. C. After being left to stand overnight, the colorless slurry of the sodium salt of formylethyl acetate is dissolved by adding 400 parts by volume of ethylene glycol monomethyl ether, and 189 parts of benzimidazolyl-2-aceto-N-methylamide are added to the solution. The mixture is boiled for 4 hours under reflux, 600 parts by volume of water are added and the batch is acidified with concentrated hydrochloric acid. The reaction mixture is boiled for 1/2 hour, sodium acetate is added until the mixture reacts neutral, and the product is filtered off. After washing the product with warm water and drying it, 208 parts of the compound of the formula ##STR117## are obtained. The melting point of a sample recrystallized from dimethylformamide is 321.degree. C (with decomposition).
Analysis: C.sub.13 H.sub.11 N.sub.3 O.sub.2 (241); calculated C 64.8 H 4.6 N 17.4 O 13.3; found 64.5 4.9 17.3 13.7.
TABLE 13__________________________________________________________________________Dyes ##STR118##Example R R.sup.3 A A.sup.1 Y Hue__________________________________________________________________________360 C.sub.2 H.sub.5 H H C.sub.4 H.sub.9 H blue361 H Br H C.sub.2 H.sub.5 H violet362 H SO.sub.2 CH.sub.3 H (CH.sub.2).sub.3 OC.sub.2 H.sub.5 H bluish violet363 H H H C.sub.3 H.sub.7 Cl violet364 H H H C.sub.3 H.sub.7 CH.sub.3 violet365 H Cl H (CH.sub.2).sub.3 OCH.sub.3 OCH.sub.3 bluish violet366 H NO.sub.2 H (CH.sub.2).sub.3 OCH.sub.3 H blue367 H SC.sub.6 H.sub.5 H C.sub.4 H.sub.9 H blue368 H SO.sub.2 N(C.sub.4 H.sub.9).sub.2 H CH.sub.3 H bluish violet369 H ##STR119## H C.sub.2 H.sub.5 H bluish violet370 H COC.sub.2 H.sub.5 H C.sub.4 H.sub.9 H bluish violet371 H H CH.sub.3 CH.sub.3 H blue372 H Br CH.sub.3 CH.sub.3 H blue373 H H OH C.sub.2 H.sub.5 H reddish violet374 CH.sub.3 H OH CH.sub.3 H bluish violet375 CH.sub.2 CH.sub.2 CN Br H CH.sub.3 H blue376 CH.sub.2 C.sub.6 H.sub.5 H H CH.sub.3 H blue377 H H H C.sub.3 H.sub.7 CON(CH.sub.3).sub.2 bluish violet378 H Cl H C.sub.2 H.sub.5 CON(C.sub.4 H.sub.9).sub.2 bluish violet379 H H H C.sub.2 H.sub.5 COOCH.sub. 3 bluish violet__________________________________________________________________________

Naphtholactam derivatives

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Entry
Brack et al., Chem. Abs. 83, 12204w (1975).
Schefczik, Chem. Abs. 84, 107077s (1976).