DE4414693A1 - Prepn. of anthra-quinone-imide(s), useful as vat dye or intermediate - Google Patents

Abstract

In the prepn. of anthraquinone-imide cpds. (I) by condensation of (a) anthraquinone cpds. contg. prim. amino gp(s). with halogenated aromatics or (b) halogenated anthraquinone cpds. with prim. aromatic amines in the presence of a Cu catalyst and acid-binding agent in an organic solvent, condensation is carried out in the presence of a phase transfer catalyst. Pref. (I) is of formula (IA), where R = phenyl, anthraquinone, benzanthrone, anthanthrone, pyranthrone, (iso)-dibenzanthrone, anthraquinoneacridone, flavanthrone, fluoranthene or dibenzpyrenequinone gp. or the residue of a condensation prod. of these aromatics, opt. with substits. usual for vat dyes; X = halogen, OH, NH2, 1-4C alkylamino, 1-4C alkanoylamino, benzoylamino (opt. substd. by halogen or 1-4C alkyl) or 1-4C alkyl; m = 0-4; and n = 1-4. The catalyst is a quat. ammonium salt, oligo- or polyethylene or -propylene glycol or its mono- or diether. The acid binding agent is an alkali metal phosphate; and the solvent is an alkyl benzoate.

Description

The prior invention relates to a new method for manufacturing position of anthraquinone imide compounds by condensation of anthraquinone ver containing at least one primary amino group halogenated aromatic or halogenated compounds Anthraquinone compounds with primary aromatic amines in Ge presence of a copper catalyst and an acid-binding agent in an organic solvent.

Anthraquinone imides are important precursors for vat color substances or are already known vat dyes that often for dyeing or printing cotton or cotton blended fabrics can be used.

The anthraquinone imides are known to be produced by condensation of one by at least one primary amino group substituted anthraquinones with a corresponding ha logenated aromatic reactants, the reaction gene usually mix a copper catalyst and an acid-binding Agents are added.

Naphthalene (BIOS Fi nal Report 987, pages 71 and 76 and 1493, page 32, DRP 696 425) and nitrobenzene (BIOS Final Report 987, page 63, FIAT Final Report 1313 II, pages 102 and 182, FR-A 654 536, CH-A 208 953, US-A 3 040 063) and also, as in the older one German patent application P 43 35 975.2 described benzoic acid alkyl esters, especially methyl benzoate. The Last but not least, alkyl benzoic acid esters are preferred to give because, unlike nitrobenzene, they do not protect the environment strain and do not pose a health hazard.

In particular, acid-binding agents are used for the condensation Alkali metal carbonates and phosphates proposed. When used The carbonates were satisfactory hold, however, the reaction becomes carbonated water of reaction released, which can lead to corrosion of the reactor. With Ver This occurs after the phosphates do not release water not part, but long response times were here required during which the starting materials decompose, so that often only get products with unsatisfactory color strength become.  

The invention was therefore based on the object of these defects help and an advantageous method for producing To provide anthrimides.

Accordingly, a method for producing anthraquinone has been developed imide compounds by condensation of at least one primary Anthraquinone compounds containing amino group with halogenated ten aromatics or of halogenated anthraquinone compounds primary aromatic amines in the presence of a copper catalyst tors and an acid-binding agent in an organic Solvent found, which is characterized in that the condensation in the presence of a phase transfer catalyst tors performs.

All known are suitable as phase transfer catalysts for this times for reactions in multiphase systems are used the connections, for example:

• - Ammonium salts of the formula R₄N⁺X⁻, in which the radicals R are the same or various alkyl groups (usually C₁-C₁₆) and / or Aryl groups (usually phenyl or benzyl) mean and the anions X⁻ preferably for anions of inorganic acids, such as chloride, bromide, iodide, hydrogen sulfate, methyl sulfate, Perchlorate and hydroxide, but also more organic for anions Acids such as benzoate are available;
• - Phosphonium salts of the formula R₄P⁺X⁻;
• - pyridinium salts of the formula R (C₅H₅N) ⁺X⁻;
• - Oligo- and polyethylene glycols and their mono- and di- (in usually C₁-C₁₆ alkyl or phenyl) ether;
• - Oligo- and polypropylene glycols and their mono- and di- (in usually C₁-C₁₆ alkyl or phenyl) ether;
• - Mixed oligo- and polymers of ethylene glycol and propylene glycol;
• - Crown ethers and cryptands.

The polyethylene glycols and especially those are preferred quaternary ammonium salts.

Examples include: tetra-n-butylammo nium chloride, bromide, iodide, hydrogen sulfate and hydroxide, Tetra-n-pentylammonium chloride and bromide, tetra-n-hexyl-ammo  nium chloride, bromide and hydrogen sulfate, trioctylpropylammo nium chloride and bromide, tricaprylmethylammonium chloride, cetyl trimethylammonium chloride, bromide and methyl sulfate, benzyl tri methylammonium chloride, bromide and hydroxide, benzyltriethyl ammonium chloride and bromide and benzyltributylammonium chloride and -bromide; Tetraphenylphosphonium chloride, benzyltriphenylphospho nium iodide, ethyl triphenylphosphonium bromide, tetra-n-butylphospho nium chloride and tri-n-butylhexadecylphosphonium bromide; Di-, Tri-, Tetra and polyethylene glycols (average molecular weights ins special from 200 to 400) and di-, tri-, tetra- and polyethylene glycol mono- and dimethyl, ethyl and butyl ether; Di-, Tri-, Tetra- and poly-1,2- and -1,3-propylene glycols (middle molecule lar weights in particular from 200 to 400) and di-, tri-, tetra- and poly-1,2- and 1,3-propylene mono- and dimethyl, ethyl and -butyl ether; 18-crown-6.

Very particularly preferred examples are polyethylene glycols Molar masses 400 and especially cetyltrimethylammonium salts, ins special cetyltrimethylammonium methyl sulfate.

Mixtures of the phases mentioned can of course also be used transfer catalysts are used.

As a rule, depending on the reaction temperature 0.1 to 50, preferably 1.5 to 40 wt .-% phase transfer kata analyzer, based on the halogenated starting compound puts.

The quantities used for the ammonium salts are in particular: specified lower quantity range and for the polyethylene glycols especially in the upper area.

Furthermore, lower reaction temperatures become more common as larger amounts of phase transfer catalyst and higher Temperatures require smaller amounts of phase transfer catalyst be.

In general, the reaction temperature is 150 to 250 ° C, be preferably 180 to 200 ° C.

The manufacturing method according to the invention can be used for this Reactions of known organic solvents such as nitrobenzene and alkyl benzoates are carried out. Of course Lich is the use of benzoin for the reasons mentioned above preferred acid alkyl esters.  

In general, it is used as the solvent according to the invention put alkyl benzoates on the nature of the alkyl radical not on, provided the esters are liquid under the reaction conditions are. C₁-C₆ alkyl esters such as Benzoic acid hexyl, n, iso and sec pentyl, n, iso and sec-butyl and n and isopropyl esters, preferably benzoic acid ethyl ester and particularly preferably methyl benzoate.

The amount of solvent is usually 1 to 15, before preferably 3 to 10 kg per kg of condensation product.

Acid-binding agents in the process according to the invention also all commonly used for this purpose Connections are used, e.g. B. Alkaline earth metal oxides and hydroxides such as magnesium oxide, calcium oxide and hydroxide, Alkali metal salts of weak organic acids such as sodium acetate, Alkali metal carbonates such as sodium and potassium carbonate, alkali tall borates such as sodium and potassium borate and in particular also Al potassium metal phosphates such as sodium and potassium dihydrogen phosphate, Disodium and dipotassium hydrogen phosphate and tripotassium and before all trisodium phosphate.

The particular advantage of the method according to the invention lies in that even those that do not cause corrosion of the reactor Acid-binding phosphates without problems while maintaining a short reak tion times of usually 6 to 12 hours can be used.

Generally 0.15 to 1 kg comes per kg of condensation product acid binding agent for use.

Suitable copper catalysts are copper compounds such as Copper (I) acetate, copper (I) bromide, copper (I) chloride, preferred Copper (I) oxide and particularly preferably copper powder.

As a rule, 5 to 150 g of kata are used per kg of condensation product lysator used.

In some cases, e.g. B. in the implementation of tetrabrompyr anthrone, the presence of an oxidizing agent is also recommended tels. Aromatic nitro compounds are particularly useful for this considered, e.g. B. o-, m- and p-nitrobenzoic acid, o-, m- and p-Nitrobenzoic acid methyl and ethyl esters, o-, m- and p-nitro chlorobenzene, o-, m- and p-nitrophenol as well as o-, m- and p-nitro benzenesulfonic acid and its sodium salts.  

Suitable amounts of oxidizing agent are generally 0.1 up to 0.3 kg per kg of condensation product.

The response times to complete sales are at The inventive method usually 1 to 40 h, in particular 3 to 20 h compared to reaction times of 6 to 60 h without closing set of phase transfer catalyst.

In terms of process engineering, the procedure is expediently such that presents the solvent, the starting materials, the copper catalyst, the acid-binding agents and the phase transfer catalyst and ge if necessary, the oxidizing agent and the mixture then heated with stirring to the desired temperature and until holds at the end of the reaction at this temperature.

Working up the reaction mixture on the products according to Ab cooling can be done in different ways. One possibility is steam distillation of the overall approach to removal and Solvent recovery by phase separation and filtration tion of the product from the aqueous suspension. Another possibility Lichity consists in the solvent, optionally in Va vacuum, distill off, slurry the residue in water, remove the residual solvent by steam distillation and recover and the product again from the aqueous Sus filter pension. Finally, the product can also be used di filter off directly from the reaction mixture, then in water slurry, a steam distillation for removal and return Undertake extraction of the adhering solvent and close filter again from the aqueous suspension.

The process according to the invention has particular importance provision of anthraquinone imide compounds of the general For mel I.

The radical R means in particular aromatic radicals such as they are common for vat dyes. In particular, for. B. Anthraquinone, benzanthrone, anthanthrone, pyranthrone, dibenz anthrone (violanthrone), isodibenzanthrone, anthraquinone acri don- (phthaloylacridone), flavanthrone, fluoranthene and di called benzopyrenchinone residues. Remnants of are also suitable  Condensation products of these aromatics, for example with amino dibenzanthron condensed halopyranthrone.

The radical R can carry customary substituents for vat dyes. These correspond essentially to the substituents X on the ant residues of hrachinone.

Suitable radicals X are, for. B. halogen, especially chlorine and bromine, Hydroxy, amino, C₁-C₄ alkylamino, especially methylamino and ethyl amino, C₁-C₄ alkanoylamino, especially acetylamino and propionyl amino, benzoylamino, substituted by halogen or C₁-C₄-alkyl Benzoylamino such as p-chlorobenzoylamino and p-methylbenzoylamino, and C₁-C₄ alkyl, especially methyl and ethyl.

The anthraquinone residues can tra up to 4 of these substituents gene, up to 2 substituents are preferred.

The variable n finally means integers from 1 to 4 and depends on the nature of the aromatic radical R.

The production of the anthraquinone imides can be done by condensate tion of a substituted by at least one primary amino group anthraquinones with a halogenated aromatic as well Condensation of a halogenated anthraquinone with a primary aromatic amine. Usually the first variant be preferred.

Examples of preferred amine components in addition to 2-amino anthraquinone, 2-amino-3-bromoanthraquinone, 2-amino-3-methylanthra quinone and 2-amino-3-hydroxyanthraquinone, especially 1-amino anthraquinone, 1, 4- and 1,5-diaminoanthraquinone, 1-amino-4-ben zoylaminoanthraquinone and 1-amino-5-benzoylaminoanthraquinone so like called aminoviolanthrone.

Preferred halogen components, i. H. usually chlorinated and / or brominated compounds are, for example, 1-chloroanthra quinone, 1,4- and 1,5-dichloroanthraquinone, 3-bromo and 3-chlorine benzanthrone, 3,9-dibromo and 3,9-dichlorobenzanthrone, bromodichlor anthraquinone acridone, bromoanthraquinone acridone, dibromo fluoranthen, Tetrabromopyranthron and dibromo violanthron.

The amine component, if desired also a mixture of various ner amine components, and the halogen component are preferred used in stoichiometric amounts; an excess of up to however, about 20% of one of the components is also possible.  

The method according to the invention for the production of anthraquinone imiden is characterized by a smooth reaction and complete implementations with significantly shorter reaction times. In particular, it also enables the use of phosphates as acid-binding agents with surprising compliance cheaper Response times.

example 1

A mixture of 223 g methyl benzoate, 26.7 g dibromofluor anthen, 50 g 1-amino-4-benzoylaminoanthraquinone, 3 g Copper (II) oxide, 32.6 g of anhydrous trisodium phosphate and 0.42 g Cetyltrimethylammonium methyl sulfate (cetyl mixture from C₁₂-C₁₅ alkyl) was stirred at 180-185 ° C until thin layer chromatographically no more 1-amino-4-benzoylaminoanthraquinone was to be demonstrated. The reaction was complete after 12 hours.

After distilling off most of the solvent and water steam distillation to its complete removal, filtering, Washing with hot water and drying were 71 g of the anthrimide of the formula

receive.

Carbazolation in sulfuric acid according to Example 7 US-A 2 219 707 gave the corresponding brown vat dye in good quality.

The reaction remained without the addition of the phase transfer catalyst stand at 80% conversion after 36 hours. After subsequent addition 0.3 g of CuO and 3 g of Na₃PO₄ the reaction was complete after 24 h.  

Example 2

The reaction was analogous to Example 1, but at 195 ° C and below 0.21 g of cetyltrimethylammonium methyl sulfate was added and was finished after 8 hours.

The reaction took no addition of the phase transfer catalyst 16 h.

Example 3

The reaction was analogous to Example 1, but at 195 ° C and below Use of 10.0 g of a medium Mo polyethylene glycol made molecular weight 400 as a phase transfer catalyst and  was over after 8 hours.

If the reaction was carried out at 200 ° C (180-185 ° C), it was ended after 6 h (12 h).

Example 4

The reaction was carried out analogously to Example 1, but using of 30.0 g of anhydrous sodium carbonate as an acid-binding agent made and was finished after 3 h.

The reaction took no addition of the phase transfer catalyst 6 h.

Example 5

The reaction was carried out analogously to Example 1, but using of 10.0 g of a medium molecular weight polyethylene glycol Important 400 as a phase transfer catalyst and 30.0 g of anhydrous Sodium carbonate as an acid-binding agent and was finished after 3 h.

Example 6

The reaction was carried out analogously to Example 1, but using  of 10.0 g of a medium molecular weight polyethylene glycol Important 400 as a phase transfer catalyst and 30.0 g of anhydrous Sodium carbonate as an acid-binding agent and was finished after 1 h.

The reaction took no addition of the phase transfer catalyst 4 h.  

Example 7

The reaction was analogous to Example 1, but at 195 ° C and below Use of 30.0 g of anhydrous sodium carbonate as the acid bin made the mean and was finished after 1 h.

The reaction took no addition of the phase transfer catalyst 2 h.

Example 8

The reaction was carried out analogously to Example 1 using 0.42 g Benzyltrimethylammoniumchlorid as phase transfer catalyst before taken and was finished after 12 h.

Example 9

A mixture of 184 g of methyl benzoate, 16.9 g of bromodichlor acridone, 14.1 g 1-amino-5-benzoylaminoanthraquinone, 0.35 g cup ground, 9.4 g of anhydrous sodium carbonate and 10.0 g of one Polyethylene glycol with an average molecular weight of 400 was used Stirred at 195 ° C.

After every 1 h, a total of four times through thin layer chromatography complete implementation of the present bromine dichloracridons checked and the following additives made:

• 1) 1.7 g bromodichloracridone and 0.35 g copper powder;
• 2) 1.7 g bromdichloracridone;
• 3) 0.85 g of bromdichloracridone;
• 4) 0.85 g of bromdichloracridone.

After stirring for another hour at 195 ° C was the Reaction ended.

After working up analogously to Example 1, 35 g of the anthrimide of the formula

receive.

Subsequent carbazolation in sulfuric acid provided the ent speaking highly lightfast brown vat dye in very good coloristic quality.

Without the addition of the phase transfer catalyst, the reaction was time to the first addition of bromdichloracridone already 6 h and a total of 12 h.

Example 10

The reaction was carried out analogously to Example 9, however the total amount of bromodichloracridone and copper powder directly to Be used at the start of the implementation. The reaction was complete after 4 hours.

The reaction took no addition of the phase transfer catalyst 12 h.

Example 11

The reaction was carried out analogously to Example 9, but using of 1.26 g of cetyltrimethylammonium methyl sulfate as phase transfer made catalyst and was finished in the same time.  

Example 12

The reaction was carried out analogously to Example 10, but using of 1.26 g of cetyltrimethylammonium methyl sulfate as phase transfer made catalyst and was finished in the same time.

Example 13

A mixture of 202 g methyl benzoate, 18 g bromoacridone, 16.8 g 1-amino-5-benzoylaminoanthraquinone, 0.4 g copper cut, 11.5 g of anhydrous sodium carbonate and 5.0 g of a polyethylene glycol with average molecular weight 400 was ge at 195 ° C. stirs. The reaction was complete after 5 hours.

After working up analogously to Example 1, 32 g of the anthrimide of the formula

receive.

Subsequent carbazolation in sulfuric acid gave the corresponding good brown vat dye.

The reaction took no addition of the phase transfer catalyst 12 h.

Example 14

The reaction was carried out analogously to Example 13, but using 0.42 g of cetyltrimethylammonium methyl sulfate as phase transfer made catalyst and was also finished after 5 h.

Claims (5)

1. A process for the preparation of anthraquinone imide compounds by condensation of at least one primary amino group-containing anthraquinone compounds with halogenated aromatics or of halogenated anthraquinone compounds with primary aromatic amines in the presence of a copper catalyst and an acid-binding agent in an organic solvent, characterized in that the condensation in the presence of a phase transfer catalyst. 2. The method according to claim 1, characterized in that one quaternary ammonium salts as phase transfer catalysts, Oligo or polyethylene or propylene glycols or their Mono- or Diether used. 3. The method according to claim 1 or 2, characterized in that an alkali metal phosphate is used as the acid-binding agent used. 4. The method according to claims 1 to 3, characterized in net that as an organic solvent a benzoic acid alkyl ester used. 5. Process according to claims 1 to 4, characterized in that it is used for the preparation of anthraquinone imide compounds of the general formula I. applies, in which the variables have the following meaning:
R is a phenyl residue, an anthraquinone, benzanthrone, anthanthrone, pyranthrone, dibenzanthrone, isodibenz anthrone, anthraquinone acridone, flavanthrone, fluoranthene, dibenzopyrenquinone residue or the residue of a condensation product of these aromatics, the said residues for cans, the said dyes can carry usual substituents;
X halogen, hydroxy, amino, C₁-C₄-alkylamino, C₁-C₄-alkanoyl amino, benzoylamino, the benzoyl radical of which may be substituted by halogen or C₁-C₄-alkyl, or C₁-C₄-alkyl;
m 0 to 4, where the radicals X for m 2 may be the same or different;
n 1 to 4.