DE1243303B - Process for the production of pigments of the dioxazine series - Google Patents

Description

Process for the preparation of dioxazine series pigments The present The invention relates to a process for the production of pigments of the dioxazine series.

It has been found that pigments of the dioxazine series are obtained by that a stirrable mixture consisting essentially of water-soluble ammonium, Alkali or alkaline earth salt of sulfuric acid or hydrochloric acid and from optionally further substituted 2,5-bis- (2'-alkoxyphenylamino-, 2'-cycloalkoxyphenylamino-, 2'-aralkoxyphenylamino- or 2'-aryloxyphenyfamino) -1,4-benzoquinone Temperatures of at least 100'C heated.

As alkoxy groups in the 2'-position of the 2- and 5-position phenylamino groups contain the benzoquinone compounds which can be used as starting materials, for example the methoxy, ethoxy, propoxy, isopropoxy, n-, sec. or terL-butoxy or P-hydroxyethoxy group, as cycloalkoxy the cyclohexyloxy group, as aralkoxy the benzyloxy group and as aryloxy z. B. the phenoxy or a ring-substituted phenoxy group, such as a Halogen, alkyl or alkoxyphenoxy group.

The phenyl nuclei of the 2- and 5-position phenylamino groups can also contain other inert ring substituents customary in dioxazine dyes, e.g. B. aliphatic, cycloaliphatic, araliphatic or aromatic groups, halogen, Ether, carboxylic acid ester, sulfonic acid aryl ester, carboxylic acid and sulfonic acid amide, Acylamino, acyl, nitro, cyano or trifluoromethyl groups.

As substituents in the 3- and 6-positions those which can be used as starting materials Benzoquinone compounds are, for example, halogens, in particular Chlorine or optionally substituted alkyl or aryl groups or acyloxy or Acylamino groups.

Suitable according to the invention usable water-soluble ammonium, alkali or alkaline earth salts of sulfuric acid or hydrochloric acid are, for. B. ammonium chloride, Ammonium sulfate, sodium chloride, sodium sulfate, sodium hydrogen sulfate, potassium chloride, Potassium sulfate, potassium hydrogen sulfate or calcium chloride.

For the purpose of lowering the reaction temperature and for better heat transfer one adds preferably smaller amounts of high-boiling point to the benzoquinone salt mixture organic solvent added so that it is still a solid up at room temperature has a dough-like consistency.

Suitable solvents are water-immiscible solvents, z. B. optionally halogenated and / or nitrated aliphatic or aromatic Hydrocarbons, such as higher-boiling petroleum fractions, toluene, xylenes, diphenyl, Naphthalene, tetralin, chlorobenzene, di- and trichlorobenzenes and chloronaphthalene, Nitrobenzene, aromatic ethers such as diphenyl ether, aryl polycarboxylic acid esters, e.g. B. phthalic acid esters, such as dibutyl or dioctyl phthalate and miscible with water organic solvents, e.g. B. aliphatic and aromatic hydroxyl compounds, such as alkylene glycols and polyalkylene glycols and their monoethers, for example Ethylene glycol or ethylene glycol or diethylene glycol monomethyl or ethyl ether, also phenols, or organic acid anhydrides, such as succinic anhydride or phthalic anhydride.

To accelerate the reaction, it is often advantageous to add the reaction mixture add acidic condensing agents in small amounts, e.g. B. organic carbon or sulfonic acids, such as di- and trichloroacetic acid, lauric, myristic, succinic, Benzoic or phthalic acid or methane, ethanoic, benzene, toluene or xylene sulfonic acid, inorganic acids such as sulfuric acid, polyphosphoric acids or boric acid, acidic Metal chlorides, such as aluminum, zinc or iron (III) chloride, and also organic ones Acid chlorides, such as lauroyl, myristyl chloride, optionally ring-substituted Benzoyl chloride, or benzene or toluenesulphonic acid chloride or chlorides of organic Ortho acids such as benzotrichloride.

The mixture is heated, consisting on the one hand of a 2.5 bis - (2 '- alkoxyphenylamino-, 2' - cycloalkoxyphenylamino -, 2'-aralkoxyphenylamino- or 2'-aryloxyphenylamino) -1,4-benzoquinone and on the other hand of one or more water-soluble ammonium, alkali or alkaline earth salts of sulfuric acid or the Hydrochloric acid, to a temperature of 100 to 350 ° C, advantageously to 150 to 260 ° C. The weight ratio of the salts to the benzoquinone compounds is here advantageous 5: 1 to 1: 1. After cooling down, an alkaline treatment of the resulting product is often useful.

According to the process according to the invention, the dioxazine pigments fall in high levels Yields and can be refined by customary methods, for. B. with salts and / or organic solvents are ground.

Compared to the processes known from German Auslegeschriften 1 054 960, 1088 636, in which the dioxazine ring closure of 1,4-benzoquinone derivatives to the corresponding dioxazine compounds by heating the 1,4-benzoquinone derivatives on their own, whereby under extremely stormy, not controllable Reaction inconsistent reaction products in the form of lumps that can hardly be processed into pigments, or advantageously in inert high-boiling organic solvents such as dichlorobenzene or nitrobenzene at temperatures of 130 to 250 ° C, preferably in the presence of the dioxazine ring formation acidic condensing agents, the solvent-free or low-solvent process according to the invention has the advantage that the flammable, often poisonous solvents and the acidic condensing agents are completely or largely by the easy-to-use, harmless inert, easy control of the reac tion enabling, inorganic salts can be replaced and the purchase of expensive equipment can be dispensed with. Furthermore, the pigments in the process according to the invention are obtained without difficulty in good yield and high purity directly in a usable mixture together with the auxiliary material necessary for its refinement, so that in most cases both the ring closure and the refinement operation in one and the same apparatus, e.g. . B. in a heatable kneader, which saves time and effort.

Further details can be found in the following examples. Unless expressly stated otherwise, parts therein mean parts by weight. The temperatures are given in degrees Celsius. Parts by weight are related to Parts by volume such as grams to cubic centimeters. Example 1 30 parts of 3,6-dichloro-2,5-bis (2 ', 5'-diethoxy-4'-acetylaminophenylamino) -1,4-benzoquinone are intimately mixed with 60 parts of anhydrous sodium sulfate and with stirring heated to 240 to 260 ° C. for 30 minutes. After extraction with hot diluted Sodium hydroxide solution gives 23.5 parts of analytically pure 2,6-diacetylamino-3,7-diethoxy-9,10-dichlorotriphendioxazine.

Example 2 30 parts of 3,6-dichloro-2,5-bis (2 ', 5'-diethoxy-4'-benzoylaminophenylamino) -1,4-benzoquinone are intimately mixed with 60 parts of anhydrous calcium chloride and stirring heated to 250 to 260 ° C. for 15 minutes. After cooling, the whole reaction mass in the presence of 4 parts of a petroleum fraction boiling at 180 to 240 ° in one Vibrating mill ground for 11/2 hours. After extraction first diluted with hot Hydrochloric acid, then with hot, dilute sodium hydroxide solution, 20.5 parts of the strong color are obtained bluish purple 2,6-dibenzoylamino-3,7-diethoxy-9,10-dichlorotriphendioxazines.

If in this example the 3,6-dichloro-2,5-bis (2 ', 5'-diethoxy-4'-benzoylaminophenylamino) -1,4-benzoquinone by 30 parts of 3,6-dichloro-2,5-bis- (2 ', 5'-dimethoxy 4'-p-chlorobenzoylaminophenylamino) -1,4-benzoquinone or by 30 parts of 3,6-dichloro-2,5-bis (2 ', 5'-diethoxy-4'-p-methylbenzoylaminophenylamino) -1,4-benzoquinone replaced and the procedure described above is obtained with an equally good yield the blue 2,6-bis (4'-chlorobenzoylamino) -3,7-dimethoxy-9,10-dichlorotriphendioxazine or the blue 2,6-bis (4'-methylbenzoylamino) -3,7-diethoxy-9,10-dichlorotriphendioxazine.

Example 3 20 parts of 3,6-dichloro-2,5-bis (2 ', 5'-diethoxy-4'-acetylaminophenylamino) -1,4-benzoquinone with 60 parts of anhydrous sodium sulfate and 6 parts of diethylene glycol monomethyl ether heated to 190-200 ° for 15 minutes with stirring. After cooling down, the solid Reaction mass extracted with hot dilute sodium hydroxide solution. Receives after drying 14.4 parts of 2,6-diacetylamino-3,7-diethoxy-9,10-dichlorotriphendioxazine.

Example 4 20 parts of 3,6-dichloro-2,5-bis- (2'-phenoxy-5'-benzoylphenylamino-1,4-benzoquinone are with 60 parts of anhydrous sodium sulfate and 4 parts of ethylene glycol monophenyl ether intimately mixed and in a heatable kneader for 20 minutes at 210 to 220 ° heated. The cooled reaction mass is first with a hot aqueous, then extracted with an alcoholic sodium hydroxide solution and finally with water washed neutral. After drying, 9.6 parts of 3,7-dibenzoyl-9,10-dichlorotriphendioxazine are obtained as brown crystals with a green reflex.

Instead of sodium sulfate and ethylene glycol monophenyl ether can one also sodium chloride and 1-chloronaphthalene or 4 parts of a 200 to 250 ° boiling Use petroleum fraction. 3,7-Dibenzoyl-9,10-dichlorotriphendioxazine is also obtained with similar yields if, instead of 3,6 - dichloro-2,5-bis - (2'-phenoxy- 5'-benzoylphenylamino) -1,4-benzoquinone, 20 parts 3,6-dichloro-2,5-bis- (2'-p-chlorophenoxy-5'-benzoylphenylamino) -1,4-benzoquinone or 3,6-dichloro-2,5-bis (2'-o-methylphenoxy-5'-benzoylphenylamino) -1,4-benzoquinone or 3,6-dichloro-2,5-bis (2 '- o -ethylphenoxy-5' -benzoylphenylamino -) - 1,4-benzoquinone and otherwise proceed in the same way as described above.

Example s 20 parts of 3,6-dichloro-2,5-bis- (2'-methoxy-4'-benzoylamino-5'-methyphenylamino) -1,4-benzoquinone will with 60 parts of anhydrous sodium sulfate, 4 parts of 1-chloronaphthalene and 10 parts of benzoic acid are intimately mixed and stirred for 15 minutes Heated from 220 to 225 °. The result is a green, easily stirrable dough, which when cooled stiffens. The reaction mass is then ground in a vibrating mill, with hotter extracted dilute sodium hydroxide solution, the suspension filtered off, the residue with Water and alcohol washed and dried. 10 parts of strongly reddish tint are obtained violet 2,6-dibenzoylamino-3,7-dimethyl-9,10-dichlorotriphendioxazine.

Benzene sulfonic acid can also be used in place of benzoic acid and 1-chloronaphthalene or succinic acid together with 1-chloronaphthalene or benzoic acid use alone. Example 6 30 parts 3,6-dichloro-2,5-bis - (2 ', 5' -dimethoxy-4'-o -chlorobenzoylaminophenylamino) -1,4-benzoquinone are with 90 parts of sodium sulfate, 10 parts of a petroleum fraction boiling at 200 to 250 ° and 5 parts of o-chlorobenzoyl chloride intimately mixed and with stirring for 1 hour heated to 180 to 190 °. After cooling, the reaction mass is placed in a vibrating mill ground for 2 hours. After extracting the resulting powder, first with hot dilute hydrochloric acid, then with hot dilute sodium hydroxide solution, are obtained after drying, 20 parts of a strong, pure violet pigment, namely 2,6-bis (2'-chlorobenzoylamino) -3,7-dimethoxy-9,10-dichlorotriphendioxazine.

Claims (4)

Claims: 1. Process for the production of pigments of the dioxazine series, characterized in that there is a stirrable mixture which essentially consists of water-soluble ammonium, alkali or alkaline earth salt of sulfuric acid or hydrochloric acid and from optionally further substituted 2,5-bis- (2'-alkoxyphenylamino-, 2'-cycloalkoxyphenylamino-, 2'-aralkoxyphenylamino or 2'-aryloxyphenylamino) -1,4-benzoquinone Temperatures of at least 100 ° C heated. 2. The method according to claim 1, characterized characterized in that the stirrable mixture even smaller amounts of high-boiling organic Contains solvent. 3. The method according to claims 1 and 2, characterized in that that the stirrable mixture still contains small amounts of acidic condensing agents. 4. Process according to claims 1 to 3, characterized in that the weight ratio the water-soluble ammonium, alkali or alkaline earth salts of sulfuric acid or Hydrochloric acid to the 2,5-bis (2'-alkoxyphenylamino-, 2'-cycloalkoxyphenylamino-, 2'aralkoxyphenylamino- or 2'-aryloxyphenylamino) -1,4-benzoquinones in the stirrable mixtures approximately 5: 1 to 1: 1. Publications considered: German Auslegeschriften No. 1054 960, 1088 636.