DE1190126B - Process for the production of basic dyes - Google Patents

Description

Process for the preparation of basic dyes It has been found that new valuable basic dyes are obtained by using naphtholactams of the general formula wherein R represents an alkyl, cycloalkyl, aryl or aralkyl radical and in which the aromatic rings and the alkyl or cycloalkyl radical are replaced by halogen, alkoxy, acyl, acylamino, dialkylamino and / or alkylarylamino groups, the aromatic rings can also be substituted by alkyl and / or aryl groups, with amines of the general formula where Ar stands for an aromatic radical and R2 and R3 mean an alkyl, cycloalkyl, aryl or aralkyl radical, the alkyl radicals can also be part of a saturated heterocyclic ring system and the aromatic rings as well as the alkyl and cycloalkyl radicals by halogen, Alkoxy, acyl, dialkylamino and / or alkylarylamino groups, the aromatic rings can also be substituted by alkyl and / or aryl groups, heated in the presence of dehydrating condensing agents.

Examples of naphtholactams of the formula I are: N-methyl-naphtholactam-1,8, N ethylnaphtholactam-1,8, N-n-propyl-naphtholactam-1,8, N-i-propyl-naphtholactam-1,8, N-n-butyl-naphtholactam-1,8, N-i-amyl-naphtholactam-1,8, N-cyclohexyl-naphtholactam - 1,8, N - benzyl - naphtholactam-1,8, N-2'-phenylethyl-naphtholactam-1,8, N - phenyl - naphtholactam-1,8 and N- (4'-methylphenyl) -naphtholactam-1,8. These are lactams z. B. obtainable by adding the corresponding carbamic acid chlorides in the presence Friedel-Crafts catalysts in inert solvents, e.g. B. in Di- or Trichlorobenzene, heated, expediently to temperatures between 130 and 180 ° C. Even the substitution products of the lactams produced in this way, such as N-methyl-4-bromo-naphtholactam-1,8, N-ethyl-4-bromo-naphtholactam-1,8, N-ethyl-4-chloro-naphtholactam-1,8, N-ethyl-2,4-dichloro-naphtholactam-1,8, N-Ethyl-4- (N ', N'-bisacetylamino) -naphtholactam-1,8, N-Ethyl-4-dimethylamino-naphtholactam-1,8, N-ethyl-4-acetylnaphtholactam-1,8, N- (4'-methoxyphenyl) -naphtholactam-1,8, N-methyl-2-ethoxy-naphtholactam-1,8 and N-ethyl-2-methoxy-naphtholactam-1,8, are suitable as starting materials for the method according to the invention.

Compounds of the formula II include N, N-dimethylaniline, N, N-diethylaniline, N-n-butyl-N-ß-chloroethylaniline, 2-ethoxy-N, N-dimethylaniline, 3-methyl-dimethylaniline, N-methyl-diphenylamine, N-ethyl-diphenylamine, N-methyl-4-ethoxy-diphenylamine, N-ethyl-4-ethoxy-diphenylamine, 1-dimethylamino-naphthalene and 1-diethylaminonaphthalene called.

Examples of suitable condensing agents are: the halides the acids of phosphorus, such as phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride and phosphorus trichloride, also sulfuryl and thionyl chloride as well as phosgene, tin (IV) chloride, Titanium (IV) chloride, zinc chloride, aluminum chloride, boron trifluoride and silicon (IV) chloride or mixtures thereof.

To carry out the method according to the invention, one can proceed as follows: that the lactam with the amine - optionally in a diluent - on heated to a temperature between 70 and 150 ° C and then the condensing agent is added.

It is advantageous to use the starting materials in the process according to the invention N-lower-alkyl-substituted naphtholactams-1,8 and carries out the reaction 70 to 150 ° C, preferably at 90 to 110 ° C, through.

You can also first heat the lactam with the condensing agent and then add the amine; are sufficient for this embodiment frequently lower temperatures, for example those from 30 to 100 ° C. 1m in general it is sufficient to use the amount of amine equimolar to the lactam, but it is also possible Apply an excess, the excess can be chosen so large that the Amine serves as a solvent. Also suitable as diluents are chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, nitrobenzene, chlorobenzene and the isomers Di- and trichlorobenzenes as well as phosphorus oxychloride and thionyl chloride.

The dyes obtainable according to the process correspond to the general formula in which Ri, R2, Ra and Ar have the meaning given above and in which the aromatic rings and the alkyl and cycloalkyl radicals are replaced by halogen, alkoxy, acyl, acylamino, dialkylamino and / or alkylarylamino groups, and the aromatic rings also can be substituted by alkyl and / or aryl groups and in which X is an anionic radical, for example the radical of hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid. The new dyes are particularly suitable for dyeing, printing and spin-dyeing materials which are wholly or predominantly, generally more than 85%; consist of polymerized acrylonitrile or vinylidenecyanide. It is noteworthy that, when dyeing mixtures of these materials with wool, they hardly dye the animal fibers. A particular advantage of the dyes produced according to the invention is their high yield, which enables very deep dyeings and prints to be produced. The dyeings and prints have excellent fastness properties, in particular light, decatur and wash fastness; they are characterized by uniform coloration and high brilliance. The new dyes are also suitable for dyeing and printing tannin cotton, cellulose esters, cellulose acetate and paper pulps and for producing inks or ballpoint pen pastes.

The parts given in the following examples are parts by weight.

Example 1 19.7 parts of N-ethyl-peri-naphtholactam and 27 parts of 4-ethoxy-N-methyl-diphenylamine are fused. At 50 ° C., 19 parts of phosphorus oxychloride are allowed to drip into the melt with stirring, the mixture is stirred for 24 hours at 50 to 55 ° C. and the dye paste obtained is introduced into 2000 parts of water. After the excess phosphorus oxychloride has decomposed, 0.5 to 1 part of activated charcoal is added to the solution, heated to 95 ° C. and filtered. The pH of the filtrate is adjusted to 3 to 4 by adding sodium acetate, soda or sodium hydroxide solution and then 50 to 100 parts of saturated sodium chloride solution are added dropwise, the resulting dye of the formula is excreted in crystalline form. The yield is very good. On polyacrylonitrile fabrics, the dye produces strong reddish blue, extremely lightfast dyeings and prints.

The N-ethyl-peri-naphtholactam used can be prepared as follows: A solution of 23.5 parts of N is added to a suspension of 26.5 parts of anhydrous aluminum chloride in 100 parts of 1,2-dichlorobenzene at 140 to 160 ° C. with stirring -Athyl-N-1-naphthyl-carbamic acid chloride in 50 parts of 1,2-dichlorobenzene are added dropwise and the mixture is then stirred at 160 ° C. for a further 30 minutes. After cooling, the mixture is poured onto 100 parts of ice, the aqueous layer is separated off and the organic layer is stirred with 60 parts of 20% strength sodium carbonate solution until the dichlorobenzene layer is acid-free. After the soda solution has been separated off, the dichlorobenzene is distilled off under reduced pressure. The remaining crude N-Ethylperi-naphtholactam can easily be purified by vacuum distillation or by recrystallization from n-hexane or cyclohexane with the addition of activated charcoal. It is obtained in this way in greenish-yellow fluorescent crystals with a melting point of 68 ° C. The boiling point is below 15 mm Hg at 202 to 206 ° C. The yield is almost quantitative. EXAMPLE 2 60 parts of anhydrous zinc chloride are added in portions to a melt of 57 parts of N-ethyl-perinaphtholactam and 51 parts of N, N-dimethylaniline with stirring at 70 to 80 ° C., then 30 parts of phosphorus trichloride are added dropwise, and the mixture is initially stirred to 10 to 15 minutes at 80'C and then diluted with 200 parts of dry benzene. After the reaction mixture has been heated to the boil for 12 hours, it is allowed to cool to about 50 ° C., poured into 2000 parts of water, and the emulsion formed is stirred. until the phosphorus trichloride is decomposed and separates the benzene layer. The aqueous dye solution is heated to 90 to 95 ° C. with 0.5 to 2 parts of activated charcoal and filtered. The resulting dye separates out of the filtrate upon addition of common salt. This one has the formula The product dyes fabrics made of polyacrylonitrile or acetate silk blue-violet.

Example 3 27.6 parts of x-monobromo-N-ethyl-peri-naphtholactam, 16.8 parts of phosphorus oxychloride and 16.5 parts of N, N-diethvlaniline are heated to 70.degree. 9 parts of tin (IV) chloride are added dropwise to the resulting melt with stirring over the course of about 5 minutes. It is important to ensure that this is the case. that the temperature does not rise above 150C. After the melt has been stirred for 45 minutes at 110.degree. C., it is allowed to run into 2000 parts of water. The excess condensing agent is decomposed; 0.2 to 2 parts of activated charcoal are then added to the obtained dye solution, the mixture is heated to the boil with stirring and filtered. Adding 50 to 100 parts of saturated sodium chloride solution dropwise to the cooled filtrate gives the dye of the formula in a very good yield in crystalline form. The dye gives brilliant results on polyacrylonitrile fabrics. very real dyeings and prints. The monobromo-N-ethyl-peri-naphtholactam used can be prepared as follows: A solution of 160 parts of bromine in a solution of 197 parts of N-ethyl-perinaphtholactam in 580 parts of 1,2-dichlorobenzene is added at 125 to 130.degree 300 parts of 1,2-dichlorobenzene are run in, the solution is stirred for a further 15 minutes at 130 ° C., allowed to cool to 60 to 70 ° C. and the solvent is distilled off under about 15 mm of mercury. It is also possible to use 1,2-dichlorobenzene The bromolactam remaining can easily be obtained in pure form by recrystallization from acetone; it melts at 116 ° C. The yield is almost quantitative. EXAMPLE 4 18.3 parts of N-methyl-peri-naphtholactam are mixed with 18.3 parts of phosphorus oxychloride 15 minutes to 80 ° C. 21.1 parts of Nn-butyl-N-, 1-chloroethylaniline are then allowed to run in with stirring at 80 ° to 90 ° C., the mixture is stirred for 1 hour at 80 ° C. and then diluted with 50 parts Chlorobenzene, which has previously been heated to 80 ° C. ind. After the mixture has been kept at 80 to 90 ° C. for a further 12 hours, the excess phosphorus oxychloride is destroyed by the dropwise addition of 20 parts of water. The chlorobenzene is then distilled off with steam and the remaining aqueous dye solution is filtered after adding 0.5 part of activated charcoal. Salting out gives the dye of the formula in good yield which colors polyacrylonitrile fibers blue-violet. The N-methyl-peri-naphtholactam used can be prepared according to the following procedure: 24 parts of 1-methylamino-naphthalene are heated with 400 parts of 1,2,4-trichlorobenzene. The solution obtained is treated with phosgene for 2 hours at 150 to 160 ° C. The excess phosgene is then removed by blowing in dry air. 40.6 parts of anhydrous aluminum chloride are introduced in portions into the carbamic acid chloride solution obtained in this way at 165 to 170 ° C. and the solution is stirred at this temperature for a further 20 minutes. The mixture is then cooled to about 50.degree. C. and the mixture is poured onto 1000 parts of ice. Working up is carried out analogously to the procedure described in Example 1 for N-ethylperi-naphtholactam. Very good yields of N-methylperinaphtholactam are obtained, which boil under 12 mm of mercury at 198 to 204 ° C. The product recrystallized from n =? Exane or cyclohexane melts at 77 to 78 ° C.

Example s 28.9 parts of N-phenyl-peri-naphtholactam with 23.6 Fused parts of N-ethyl-diphenylamine. At 90 to 100 ° C one leaves in this melt 20 parts of phosphorus oxychloride run in with stirring and the mixture is stirred for 8 hours at this temperature. Should the mass become too viscous. can them by adding be diluted by a further 10 to 20 parts of phosphorus oxychloride. After the specified time, the phosphorus oxychloride by pouring the melt into a Mixture of 500 to 1000 parts of ice and 100 parts of saturated aqueous sodium acetate solution decomposed. The blue dye separates out immediately. It is suitable for coloring of polyacrylonitrile in bulk.

The N-phenyl-peri-naphtholactam used can be prepared as follows 56 parts of N-phenyl-N-1-naphthyl-carbammic acid chloride are added in portions a 150 to 170 # C mixture of 70 parts of anhydrous aluminum chloride and 200 parts of 1,2-dichlorobenzene entered. The mixture is then 10 to 15 minutes stirred at 160 to 170 ° C and then cooled to 30 to 50 ° C. Then lets 500 parts of 15% hydrochloric acid are added dropwise over the course of about 30 minutes and the mixture is separated remove the dichlorobenzene layer and add 1 to 2 parts of activated charcoal. After about After stirring for 2 hours, the solution is filtered and the 1,2-dichlorobenzene is filtered in vacuo distilled off. The remaining crude N-Phenylperi -naphtholactam is purified by recrystallization from cyclohexane. The lactam forms greenish-yellow Crystals which melt at 110 ° C. The yield is good.

Example 6 3 parts of N-ethyl- (N ', N'-bis-acetyi) -amino-perinaphtholactam are introduced into a mixture of 3 parts of 4-methoxy-N-ethyl-diphenylamine and 6 parts of phosphoroxychloride. The mass is heated to 95 to 100 ° C. for 40 minutes and, after cooling, poured into 100 parts of water. The rigidly acidic dye solution obtained in this way is brought to a pH of about 4 by adding sodium acetate. Some of the dye is already precipitated in the process. The excretion is completed by dripping in saturated saline solution. The crude dye can be purified by recrystallization from 100 parts of 5 ° Joiger acetic acid. He corresponds to the formula and produces reddish blue dyeings and prints on polyacrylonitrile materials.

The N-ethyl- (N ', N'-bis-acetyl) -aminoperi-naphtholactam (melting point 170 ° C) can be obtained from N-ethyl-peri-naphtholactam by nitration with nitric acid in sulfuric acid solution, reduction of the mononitro derivative (melting point 162 ° C) up to 163 ° C) by means of iron to the amino derivative (melting point 196 ° C) and heating the amino compound with excess acetic anhydride. Example ? 6 parts of N-ethyl-dimethylamino-pearl-naphtholactam and 6 parts of 4-ethoxy-N-methyl-diphenylamine are heated to 80 ° C. with 40 parts of phosphorus oxychloride for 2 hours. After the mixture has cooled, most of the phosphorus oxychloride is distilled off in vacuo. The crude dye that remains is dissolved in 300 parts of water. The pH of the solution is adjusted to about 5 with sodium acetate, and the resulting dye of the formula is excreted by adding table salt. It dyes polyacrylonitrile fabric greenish blue.

The N-ethyl- (dimethylamino) -naphtholactam used can be obtained from ethyl-amino-naphtholactam (cf. Example 6) by methylation with dimethyl sulfate at 100 to 110 ° C. It can be recrystallized from cyclohexane and forms orange-colored crystals with a melting point of 112 to 113 ° C. Morpholine, N-phenyl-piperidine, N-cyclohexyl-N-methylaniline, N-benzyl-N-ethylaniline, N-methyl-diphenylamine, 1- Dimethylamino-naphthalene or I-diethylamino-naphthalene, if the procedure is otherwise unchanged, valuable blue-violet to blue dyes are also obtained.

If the anions customary in basic dyes other than C1 ° are present in the dye salts obtainable according to the process, there is no change in the coloring properties of the dyes. Example 8 59 parts of N-ethyl-peri-naphtholactam and 61.2 parts of phosphorus oxychloride are heated to 70 ° C. for 45 minutes. 67 parts of N, N-diethylaniline are then added dropwise to the constantly stirred melt, the mixture is stirred for 7 hours at 95 ° to 100 ° C. and then allowed to run into 1000 parts of water. The dye solution thus obtained is heated to 95 ° C. with 0.5 to 2 parts of charcoal and filtered. The dye obtained is deposited by adding 100 parts of common salt. This colors polyacrylonitrile materials in blue-violet tones.

In this example, if the N, N-diethylaniline is replaced by the equivalent amount of 2-methoxy-N, N-dimethylaniline, 3-chloro-N, N-dimethylaniline, 3-methyl-Nn-butyl-N-ß-chloroethylaniline, N -Phenvl-Example9 22.7 parts of the lactam of the formula and 18.3 parts of N-methyl-diphenylamine are heated to 95 to 100 ° C. with 40 to 50 parts of 1,2-dichlorobenzene and 75 parts of phosphorus oxychloride for 8 to 10 hours. The still warm mass is poured onto water and the dichlorobenzene is distilled off with steam. The dyestuff of the formula is separated from the aqueous solution obtained in this way on cooling and after addition of common salt the end. It is suitable for dyeing, printing and dyeing in the bulk of polyacrylonitrile in very real, purple tones. In an analogous manner, when using equivalent amounts of the following naphtholactams, real, violet dyes are also obtained: Example 10 19.7 parts of N - ethyl - perl - naphtholactam and 22.5 parts of the amine of the formula are heated to 75 to 80 ° C for 8 to 10 hours with 100 parts of 1,2-dichloroethane, 75 parts of phosphorus oxychloride and 26 parts of tin (IV) chloride. The mixture is then carefully decomposed by the dropwise addition of water, the dichloroethane is distilled off and the dyestuff which has separated out is recrystallized from dilute acetic acid. He corresponds to the formula and is suitable for dyeing in the mass of polyacrylonitrile in purple tones.

Claims (2)

Claims: 1. Process for the preparation of basic dyes, characterized in that naphtholactams of the general formula wherein R represents an alkyl, cycloalkyl, aryl or aralkyl radical and in which the aromatic rings and the alkyl or cycloalkyl radical are replaced by halogen, alkoxy, acyl, acylamino, dialkylamino and / or alkylarylamino groups, the aromatic rings can also be substituted by alkyl and / or aryl groups, with amines of the general formula where Ar stands for an aromatic radical and R2 and R3 mean an alkyl, cycloalkyl, aryl or aralkyl radical, the alkyl radicals can also jointly be part of a saturated heterocyclic ring system and the aromatic rings as well as the alkyl and cycloalkyl radicals by halogen, alkoxy , Acyl, dialkylamino and / or alkylarylamino groups, the aromatic rings can also be substituted by alkyl and / or aryl groups, heated in the presence of dehydrating condensing agents. 2. The method according to claim 1, characterized in that that N-lower-alkyl-substituted naphtholactams-1,8 are used as starting materials and the reaction at 70 to 150.degree. C., preferably at 90 to 110.degree. C., is carried out. at The announcement of the application is accompanied by a coloring table with explanations been.