DE1129249B - Process for the preparation of anthraquinone dyes - Google Patents

Description

GERMAN

PATENT OFFICE

B 56256 IVc / 22b

REGISTRATION DATE: 15 J Λ N U A R 1960

NOTICE THE REGISTRATION AND ISSUE OF

EDITORIAL: MAY 10, 1962

It has been found that valuable anthraquinone dyes of high purity can be obtained in a simple manner obtained when 1,4-diammoanthraquinone-2,3-dicarboximide with 5- or 6-membered cyclic Esters of carbonic acid or sulphurous acid, which are derived from optionally substituted 1,2-dihydroxyethanes or 1,3-dihydroxypropanes are converted.

Esters of carbonic acid or sulphurous acid - also known as carbonates or sulphites for short - that derive from optionally substituted 1,2-dihydroxyethanes or 1,3-dihydroxypropanes as substituents, for example halogen atoms, such as chlorine or bromine atoms, alkyl radicals, such as low molecular weight saturated or unsaturated alkyl radicals, alkoxyl groups, such as low molecular weight alkoxyl groups, or aromatic radicals, such as aryl radicals with up to two benzene rings, carry. In detail are the following compounds are mentioned: ethylene sulfite, ethylene carbonate, propylene carbonate (1,2), 3-chloropropylene carbonate - (1,2), 3 - methoxypropylene carbonate (1,2), vinyl ethylene carbonate, butylene carbonate (2,3), phenylethylene carbonate, 5,5 - dimethyl -1,3 - dioxanone - (2), 5-methyl- 5 -n-propyl-1,3-dioxanone- (2), 5,5 - dimethyl- -l, 3-dioxathione- (2) and 4-n-propyl 5,5-dimethyll, 3-dioxanone- (2).

Appropriately, one goes in the new process per M oil 1 ^ -Diaminoanthraquinone ^^ - dicarboximide of 2 to 10 moles, preferably 3 to 5 moles, of the esters mentioned of carbonic acid or sulfurous acid and works in a polar solvent, e.g. B. in N, N-dimethylformamide, acetamide or N-methylpyrrolidone, and in the presence, preferably from 0.05 to 1 mol, of a strongly alkaline agent, for example an alkali metal hydroxide, carbonate or alcoholate, e.g. B. from sodium or potassium. The reaction is generally carried out at temperatures between 80 and 18O ⁰ C, preferably between 100 and 16O ⁰ C, and requires no more generally as 1 to 4 hours. With ethylene carbonate, the reaction has ended after just one hour. However, prolonged heating is not harmful.

The method according to the invention can also be used in other than the above-mentioned polar solvents, for example in the esters of carbonic acid mentioned as reaction participants or the sulphurous acid itself or in the usual organic solvents such as nitrobenzene or o-dichlorobenzene, carried out in the presence or absence of the aforementioned strongly alkaline agents will.

As a rule, the implementation takes place in a simple manufacturing process of anthraquinone dyes

Applicant:

Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Willy Braun, Heidelberg, Manfred Ruske and Dr. Karl Maier,

Ludwigshafen / Rhein, have been named as inventors

Way under normal pressure, so that one can generally dispense with the use of increased or reduced pressure. When using esters of sulphurous acid as starting materials, it is expedient to remove the sulfur dioxide formed during the reaction with the aid of a gas or air stream passed through the reaction mixture. From the literature, for example, German Patent Specification 939 044, it is known that 1,4-diaminoanthraquinone - 2,3 - dicarboxylic acid - (2 - hydroxyethyl) imide obtained when 2-hydroxyethylamine at 19O ⁰ C and under elevated pressure Leave to act on 1,4-diaminoanthraquinone-2,3-dicarboximide for 4 hours. The blue dye obtained in this way, however, is contaminated by red-colored by-products as a result of the high reaction temperature required for its formation. According to the new process, however, the same dye is obtained in greater yield and higher purity if 1,4-diaminoanthraquinone-2,3-dicarboximide is used in a polar solvent at ordinary pressure with ethylene carbonate in the presence of a strongly alkaline agent at 100 to 130 ⁰ C converts within an hour. The dye obtained in a known manner is surpassed by the dye produced by the new process by the clarity of its blue colorations on fabrics made of polyethylene terephthalate and by its greater thermal stability.

209 579/230

3 4

The dyes obtainable according to the invention, example 3

z. B. the condensation products of 1,4-diamino

anftrachinon-2,3 - dicarboximide with propylene In a mixture of 125 parts of nitrobenzene,

carbonate (l, 2) or 3-Methoxypropylencarbonat- (l, 2), 31 parts of M-diaminoanthraquinone ^ -dicarboxylic acid-Vinyläthylencarbonat, Butylencarbonat- (2,3), phenyl 5 imide and 3 parts of sodium carbonate in 14O ⁰ C ethylene carbonate, 5,5 - dimethyl -1,3 - dioxanone - (2), 35.2 parts of ethylene carbonate registered. Thereafter heated 5-methyl-5n-propyl-l, 3-dioxanone (2) and 5,5-di- one within one hour at 160 ⁰ C and stirred for methyl-l, 3-dioxathion- (2), excel the 1,4-di- the mixture for 3 hours at this temperature, aminoanthraquinone - 2,3 - dicarboxylic acid - (2 - hydroxy- After cooling to 3O ⁰ C the reaction ethyl) imide and the other in the German patent io well suctioned off, washed with nitrobenzene, methanol and water font 939 044 mentioned dyes and dried. You get about Brülanz and its better drawability. You are 33.8 parts of dye (= 95.5% of theory). The also from the German Patent 945 112 dye contains about 61.1% carbon, 4.1% known dyes in the thermal resistance hydrogen, 11.7% nitrogen and 22.9% oxygen speed, especially in the sublimation and thermofixing 15 and corresponds in its dyeing properties of authenticity (20 seconds währendem heating to the dye obtained in example 1. 190 ⁰ C) superior. They are as disperse dyes ^. . .

in general for dyeing and printing hydro- is ei s ρ 1 e 1 4

phobic fiber well suited. Particularly strong 18.6 parts 1,4-diaminoanthraquinone-2,3-dicarbon-

However, dyeings and prints are obtained on gel acidimide and 1.8 parts of sodium carbonate are formed in such as foils, films and textiles, e.g. As fibers, 75 parts of N-methylpyrrolidone for approximately 10 minutes threads heated flakes, woven and knitted fabrics from linear long at 15O ⁰ C and then at 100 ⁰ C abge polyesters such as polyethylene terephthalate or cools on. At this temperature one carries in the mixture based on terephthalic acid and p-dimethylol a propylene carbonate 31.2 parts (1.2) heated within cyclohexane, in the deep blue to turquoise 25 from one hour to 12O ⁰ C and holds the mixture tones of excellent fastness to light, wet and thermo for 2 hours at 120 ⁰ C. Then the mixture is cooled to 20 dyed to be fixierechtheit. 25 ° C, sucks off the reaction material and washes it

The parts and proportions given in the examples with water. The condensation product is obtained decent units are weight units. of l ^ diammoanthraquinone ^ -dicarboximide

30 and propylene carbonate- (1,2) at about 80% strength

Example 1 Yield in the form of a dark blue powder from

Melting point 263 to 265 ⁰ C. The new dye Entin a heated to 100 ° C mixture of 12.4 parts holds about 62.4% carbon, 4.1% hydrogen, 1,4-diaminoanthraquinone - 2,3 - dicarboximide, 11 , 5% nitrogen and 21.9% oxygen and dyes 0.8 parts of sodium hydroxide (finely ground) and 35 polyester fabrics based on ethylene glycol and 51 parts of N-methylpyrrolidone, 16 parts of terephthalic acid in turquoise shades of very good ethylene carbonate are heated Mixture within light, wet and thermosetting fastness. one hour at 120 ⁰ C. and held there for about 5 minutes Beisoiel 5

long at this temperature. Then one cools the ^

The reaction mixture is reduced to 50 ° C., stirred with 40 22.8 parts of vinyl ethylene carbonate (obtainable from 100 parts of methanol, the separated material is filtered off with suction using the process in US Pat. No. 2,511,942) at 20 to 25 ° C. and washed with a little methanol are in a ^{heated to 70 0} C mixture from and then with water and dry it. 12.4 parts of l ^ -diaminoanthraquinone ^ S-dicarboxylic about 12.9 parts (92% of theory) of pure 1,4-diimide, 50 parts of N-methylpyrrolidone and 1.2 parts of aminoanthraquinone - 2,3 - dicarboxylic acid - are obtained (2 - Hydroxy sodium carbonate added. The ethyl) imide is then heated to a melting point of 286 to 287 ° C. The Umsetzungsgut within one hour at 12O ⁰ C dye contains about 12.1% nitrogen and colors and holds it for about 45 minutes at this temperature. Polyethylene terephthalate fibers in grünstichigblauen Thereafter, it is diluted at 20 ⁰ C with 100 parts of tones. The hue is purer than that of a methanol and separates the dye in the manner indicated in Example 1 with that of Example 8 of German Patent 50. This gives 13.5 parts of the dyestuff produced in writing 939 044, obtained condensation product of 1,4-diaminoanthra comparative dyeing. quinone-2,3-dicarboximide and vinylethylene car

bonat from melting point 238 to 239 ⁰ C. The new

Example 2 Dyestuff dyes textile material made of polyethylene terephthalate

55 in particularly strong and brilliant turquoise blue

6.2 parts of M-diammoanthraquinone - ^ - dicarbon- tones and corresponds to the empirical formula C ₂₀ H ₁₅ N ₃ O ₅ . acid imide, 1.1 parts of sodium carbonate and 23 parts. 1
Ν, Ν-dimethylformamide are brought together to 100 ° C

heated and stirred with 8.2 parts of ethylene carbonate. Calculated ... C 63.6, H 3.98, N 11.1, O 21.2%;

Now the temperature is raised within a 60 ... found C 63.09, H 4.35, N 10.99, O 21.2% · hour to 12O ⁰ C. The mixture is then at

Cooled to 25 ° C and the reaction product cooled down Example 6

soaks, washed with water and dried. The yield of 1 ^ -Diaminoanthraquinone ^ jS-dicarboxylic acid- In a molten mixture of 30 parts (2-hydroxyethyl) -imide is about 92 to 93% ⁶ S acetamide, 2.6 parts 1 ^ -Diaminoanthracbinon ^ S -dider theory. In its dyeing properties corresponds carboxylic acid imide and 1.1 parts of sodium carbonate, the dye carries speaks to the Example 1, produced a 8.2 parts of ethylene carbonate at 100 ⁰ C. Well dye. heated within one hour to 120 ⁰ C,

holds for about 20 minutes at this temperature, example 10 cools the melt to 100 ^° C. and stirs it with it

90 parts of hot water. Then in Example 7, 9.4 parts of 5,5-dimethyl-deposited reaction material are filtered off with suction at 40 ° C. and 1,3-dioxathione- (2) is washed in place of 5,5-dimethyl-1,3-dies with hot water. The dye is obtained from oxanone in 5 and heated with a simultaneous yield of 96% of theory. In terms of the passage of nitrogen through the reaction mixture, its properties correspond to those obtained according to Example 1 to 160 ° C. within one hour and then stir the dye. . For 4 hours at 16O ⁰ C, we obtain 6.4 parts

The same dye is obtained if one is without dye. This dye is identical to that of Example 7

Sodium carbonate works and the melt in place of the connection produced is identical. He shows you

of about 20 minutes at 12O ⁰ C for 2 hours nitrogen content of about 10.2%.

at 160 ⁰ C stirs. The sulfite used is due to the conversion of

Example 7 · 2,2-Dimethylpropanediol- (1,3) obtainable with thionyl chloride.

In a ^{heated to 150 0} C mixture of 25 parts of Example 11 N-methylpyrrolidone, 6.2 parts of 1,4-diaminoanthra-

quinone-2,3-dicarboximide and 0.6 parts of sodium in 40 parts of melted ethylene carbonate transmits carbonatwerden 10Teile5,5-dimethyl-l, 3-dioxanone (2) is at 8O ⁰ C 6.2 parts of 1,4-Diaminoanthrachinoneingetragen . The mixture is then heated internally 2,3-dicarboximide and 1.1 parts of sodium carbonate to 160 ^° C. for half an hour and it is maintained for 3 to 20 minutes. The melt is then heated at 160 ° to 165 ° C. for 4 hours. The Umsetzungsgut 3 hours at 140 to 15O ⁰ C, then cooled to 6O ⁰ C., is as indicated in Example 1, worked up. This dilutes the melt with 90 parts of water, sucks the 1,4-diaminoanthraquinone obtained in good yield from the reaction material and washes it with warm 2,3-dicarboxylic acid- (2,2-dimethyl-3-hydroxypropyl) imide water. Is thus obtained in approximately the Beiweist a melting point 239-243 ⁰ C to 6.5 parts. The 25 game 1 described dye, new dye dyes polyester fibers based on. Terephthalic acid and p-dimethylolcyclohexane in strong- Example 12-term greenish blue shades of good fastness- 4.1 parts l ^ -Diaminoanthraquinone ^^ - dicarbon properties. acid imide, 18 parts of N-methylpyrrolidone and 0.4 parts

Dasverwendete5,5'-dimethyl-l, 3-dioxanone (2), 30 of sodium carbonate at 140 ⁰ C with 6.2 parts

in the usual way by reacting 2,2-dimethyl-5-methyl-5-n-propyl-1,3-dioxanone- (2) [obtainable by

propanediol- (l, 3) are produced with phosgene. Conversion of 2-methyl-2-n-propylpropanediol- (l, 3)

-ίο KÜt phosgene] and then stirred within

Example 8 _{heated to 160 ° C. for one hour, the mixture}

In a mixture of 6.2 parts of 1,4-diaminoanthra-35 now for 4 to 5 hours at this temperature and quinone-2,3-dicarboximide, 1.3 parts finely worked up the reaction material in the usual way. It ground sodium hydroxide and 25 parts of N-methyl are 6.4 parts of l ^ -Diaminoanthraquinone ^ S-dipyrrolidone at 14O ⁰ C 10.8 parts of ethylene sulfite carboxylic acid (2-methyl-2-n-propyl-3-hydroxypropyl) -registered. The mixture is stirred for 2 hours in an imide with a melting point of 198 to 201 ^° C., which is obtained. The at this temperature, then 0.3 parts of sodium are 40 new dye contains about 9.2% nitrogen and hydroxide added and stirred then for another 3 hours colored fabrics based on ethylene glycol and stirred at 14O ⁰ C. During the entire duration of the Terephthalic acid in blue tones of very good light, implementation leads a weak stream of nitrogen, wet and thermoset fastness. through the conversion mixture. The implementation good _. .

is, as indicated in Example 1, worked up. Man 45 example

thus 5.2 parts of the described in Example 1 is used in Example 4 instead of propylene

Dye. carbonate 30 parts of phenylethylene carbonate and stir

Example 9 6 hours at 120 to 22O ⁰ C, one obtains

27.2 parts of the condensation product of 1,4-di-

9.3 parts of 1,4-diaminoanthraquinone-2,3-dicarbon- 50 aminoanthraquinone ^^ - dicarboximide with phesimide and 1 part of sodium carbonate become nyläthylencarbonat in the form of a dark blue together in 37 parts of N-methylpyrrolidone to 100 ⁰ C powder from the melting point 243 to 244 ° C. The new heated and at this temperature with 7.8 parts of dye dyes fibers made of polyethylene terephthalate 3-methoxypropylene carbonate- (1,2) (obtainable by in very clear turquoise-blue tones. Reaction of 3-methoxypropylene oxide with carbon

dioxide). The mixture is then heated to Example 14

120 ⁰ C and holds it for 2 hours at this tempe- 100 parts 1,4-diaminoanthraquinone-2,3-dicarbon-

rature. Then there is a further 2.6 parts of 3-methoxy acid imide and 9.8 parts of finely powdered Natriumpropylencarbonat- (l, 2) and stir again 2 hours carbonate in 784 parts of N, N-Dimethylformlang at 12O ⁰ C and continue for 30 ^{Heated at 140 °} C. for about 2 minutes at 60 amide. 140 ⁰ C. are the condensation product of 1,4-diamino Then in the cooled to 100 ⁰ C mixture of anthraquinone-2,3-dicarboximide with 3-methoxy within 5 minutes, 75.8 parts of a technical propylene carbonate (l, 2), as in Example 1, an-butylene carbonate mixture is entered, which is not added, separated off. The yield is 7 parts. Fähr 55 to 60% of Butylencarbonat- (1,2) and the new dye contains about 10.2% nitrogen, 65 about 40 to 45% Butylencarbonat- (2,3) has a melting point of 205-206 ⁰ C. and consists [obtainable by converting a technical dye textile material made of polyethylene terephthalate in deep mixtures of butylene oxide (1,2) and butylene oxide (2,3) blue shades with excellent fastness properties. with carbon dioxide]. Now you heat the conversion

mixture within 30 minutes at 120 ° C, holding it for 4 to 5 hours at 120 to 13O ⁰ C and allowed to slowly thereafter to 15 to 2O ⁰ C to cool. The deposited reaction material is filtered off with suction and washed successively with a little Ν, Ν-dimethylformamide, methanol 5 and water. About 103 parts of dye with a melting point of 233 to 236 ^° C. are obtained, which dyes fabric made of polyalkylene terephthalate in extremely lightfast, thermoset-fast and sublimation-fast turquoise-blue shades. The new dye is about 40 to 50% of ^a us 1,4-diaminoanthraquinone-2,3-dicarboxylic acid * (l-methyl-2-hydroxypropyl l) imide and about 50 to 60% of a mixture of 1, 4 - diaminoanthraquinone - 2,3 - dicarboxylic acid - (2 - hydroxybutyl-1) -imide and 1,4-diaminoanthraquinone-2,3 - dicarboxylic acid - (1 - hydroxymethylpropyl -1) -imide and is characterized by a very good drawability Textile made from linear polyesters.

Claims (1)

PATENT CLAIM: Process for the preparation of anthraquinone dyes, characterized in that i, 4 - diaminoanthraquinone - 2,3 - dicarboximide with 5- or 6-membered cyclic esters of carbonic acid or sulfurous acid, which are derived from optionally substituted 1,2-dihydroxyethanes or 1,3 -Dihydroxypropanes derive, converts. Considered publications:
German patent specifications No. 939 044, 945 112. When the application was announced, two coloring tables with explanations were laid out. © 209 579/230 5.62