DE1275712B - Water-soluble leuco-sulfuric acid ester salts of Kuepen dyes of the anthraquinone series and process for the preparation thereof - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C09b

German class: 22 b - 3/03

Number: 1275 712

File number: P 12 75 712.9-43 (D 38371)

Filing date: March 15, 1962

Opening day: August 22, 1968

The invention relates to new water-soluble leuco-sulfuric acid ester salts of vat dyes of the anthraquinone series, the free acids of which correspond to the following general formula:

wherein each of the radicals χ represents a hydrogen or chlorine atom or a - NH ■ aroyl radical, each of the radicals y represents a hydrogen or chlorine atom, one of the radicals ζ represents the NH · aroyl radical and the two remaining radicals ζ represent hydrogen, while the radical R represents the - NH2 group, an - NH · alkyl, N (alkyl) *, -NH -cyclohexyl, -NH-aryl, - O · alkyl, - O · aryl radical, the - ChH ₅ -, piperidine or Morpholine radical means, where both the radicals χ and the radicals y can each be identical or different radicals, with the condition that at least 6 hydrogen atoms are bonded directly to the 'carbon atoms of each individual anthracene nucleus and that under the term "alkyl" low molecular weight Alkyl radicals with 1 to 6 carbon atoms are to be understood.

The invention also relates to a process for the preparation of these new water-soluble leuco sulfuric acid ester salts of vat dyes of the anthraquinone series, the free acids of which correspond to the above general formula (I).

The process according to the invention is characterized in that it is carried out in any order a compound of the general formula

Water-soluble leuco-sulfuric acid ester salts
of vat dyes of the anthraquinone series
und'Verfahren for the production of the same

Applicant:

Durand & Huguenin A..G., Basel (Switzerland)

Representative:

Dr. W. Muller-Bore

and Dipl.-Ing. H. Gralfs, patent attorneys,

8000 Munich 22, Robert-Koch-Str. 1

Named as inventor:

Dr. Walter Oppliger,

Dr. Max Aaberli, Basel (Switzerland)

Claimed priority:

Switzerland of March 24, 1961 (3519)

hexyl-, -NH-aryl-, -Ο-alkyl-, - O-aryl radical, the —CbH5, piperidine or morpholine radical means with 1 mole of a compound which, in the form of its free acid, of the following general Formula corresponds to:

SO ₃ H
χ Ο NH ^

Cl-C

/ ^N \

C-Cl

il

(II)

ι in which each of the radicals χ and y has the above meaning

with the condition that at least

¹ 50 6 hydrogen atoms directly on the carbon atoms of the

wherein Ri is a chlorine atom, the - NHo group, anthracene nucleus are bonded, and with 1 mol a - NH · alkyl-, - N (alkyl) i-, - NH · cyclo- a compound which in the form of its free

809 597/424

Acids corresponds to the following general formula: SO ₃ H

ζ Ο NH ₂

(IV)

SO ₃ H

wherein each of the radicals ζ has the above meaning with the proviso that at least 6 hydrogen atoms are bound directly to the carbon atoms of the anthracene nucleus, in aqueous medium and in Brings the presence of a mineral acid binding agent to the reaction.

Reaction products of the above formula I which still contain 1 chlorine atom in the triazine nucleus are then with compounds of the general formula

HR ₂

(V)

where R2 is the - NH2 group, an - NH alkyl, - N (alkyl) 2-, -NH-cycloalkyl-, -NH-aryl-, - O alkyl, - O aryl radical, the piperidine or morpholine radical means, and this type of procedure is often of practical advantage. The leuco-sulfuric acid ester salts used according to the general formula III are based, for example, on the following 1-aminoanthraquinones:

1-aminoanthraquinone,
l-amino-4-, -5-, -6-, -7- or

-S-chloranthraquinones,
l-amino-4-, -5- or -8-benzoylamino-

anthraquinones,
l-amino-4-, -5- or -8-chlorobenzoylamino-

anthraquinones and
l-amino-4-, -5- or -8- (4'-phenylbenzoyl-

amino) anthraquinones.

The 1-aminoanthraquinones on which the formula IV is based are for example:

l-amino-4-, -5- or -8-benzoylamino-

anthraquinones,
l-amino-4-, -5- or -8-chlorobenzoylamino-

anthraquinones and
l-amino-4-, -5- or -8- (4'-phenylbenzoyl-

amino) anthraquinones.

Compounds of the formula II suitable for implementation are, for example, 2,4,6-trichlorotriazine and its derivatives monosubstituted by the radical Ri defined above, as well as 2-phenyl-4,6-dichlorotriazine.

The compounds on which the radical R is based are, for example, the following amines: methyl, ethyl, n-propyl, isopropyl, η-butyl, n-amyl, n-hexyl, Cyclohexyl, 1,3-dimethylbutyl, dimethyl, diethyl, Dipropyl, dibutyl, diamyl, dihexylamine, piperidine, morpholine, aniline, monochloroaniline, nitroaniline, also the following alcohols: methyl, ethyl, n-propyl, isopropyl, η-butyl, 2-ethyl, η-butyl, n-hexyl alcohol and phenol.

To accelerate the reaction according to the invention, it is advantageous to use the compounds of the general Formula II to be completely or partially dissolved in an inert solvent. As particularly suitable Solvents have z. B. benzene, monochlorobenzene, toluene, acetone, methyl ethyl ketone and dioxane proved.

Suitable mineral acid binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium and potassium carbonate. The mineral acid binding agent can be added to the reaction mixture at the rate at which the hydrochloric acid is formed, the pH being advantageously kept at less than 7. The stepwise conversions customary in industry are preferably in the temperature ranges from 0 to 5, 30 to 40 and 70 to 90 ^° C.

The salts of lithium, sodium, potassium, Ammonium and triethanolamine in question.

The leuco-sulfuric acid ester salts of vat dyes of the anthraquinone series which can be prepared according to the invention represent yellow, easily soluble in water powder, which is according to the for this dye class usual application methods on textiles deliver very real dyeings or prints.

The parts given in the examples are parts by weight.

example 1

56 parts (0.3 mol) of cyanuric chloride are dissolved in 200 parts of acetone, the resulting solution is poured onto 600 parts of ice with stirring and 160 parts (0.3 mol) of the sodium salt ^{are added to the suspension thus obtained with stirring at 0 to 5 ° C.} Leucosulfuric acid ester of l-amino-5-benzoylammoanthraquinone entered. At the same time, a 10% sodium carbonate solution is added dropwise to keep the pH between 5 and 6. After about 20 minutes of stirring at 0 to 5 ° C, the reaction is complete. 160 parts (0.3 mol) of the sodium salt of the leuco-sulfuric acid ester of l-amino-4-benzoylaminoanthraquinone are now added, the temperature is increased to 30 to 40 ° C. and the pH is between 5 and 6 by adding 10% sodium carbonate solution dropwise held. After about 2 hours stirring at 30 to 4O ⁰ C the reaction is complete. After the acetone has been distilled off from the reaction mass in vacuo, the reaction product is separated off by salting out and dried.

If the leuco-sulfuric acid ester salts are used in reverse order to the exact same product.

118 parts (0.1 mole) of the thus obtained Leukoschwefelsäureestersalzes are dissolved in 500 parts of water and with 20 parts (0.21 mole) of aniline (100 ° / ₀ excess) for 3 hours at 90 ⁰ C with stirring at a pH of about 4 reacted, whereupon the dye formed is separated off and dried.

The leuco-sulfuric acid ester salt obtained in this way is a yellow powder which easily dissolves in water and delivers very real, orange dyes on cotton.

If the appropriate amount of ammonia solution is used instead of aniline, in this way a similar, orange-colored dye with very good fastness properties is obtained.

Example 2

18 parts (0.1 mol) of 2,4-dichloro-6-methoxytriazine are dissolved in 50 parts of acetone, the resulting solution is poured onto 200 parts of ice with stirring, and 46 parts ^{are added to the suspension thus obtained with stirring at 30 to 40 ° C.} (0.1 mol) sodium salt of the leuco-sulfuric acid ester of l-amino-5-chloroanthraquinone and kept the pH between 5 and 6 by adding dropwise a 10% sodium carbonate solution. After 30minutigem stirring at 30 to 4O ⁰ C the reaction is complete, after which 53 parts (0.1 mole) sodium salt of Leukoschwefelsäureesters of l-amino-5-benzoylaminoanthrachinons added at 90 ⁰ C and as much of a 10% sodium carbonate solution, that the pH value between 5

and 6 is held. After stirring for 5 hours at 9O ⁰ C, the reaction is complete. After the acetone has been distilled off, the reaction product is separated off in vacuo by salting out with potassium chloride.

The leuco-sulfuric acid ester salt obtained in this way is a yellow powder which easily dissolves in water and gives very real, yellow dyeings on cotton.

Instead of 18 parts of 2,4-dichloro-6-methoxytriazine, 22 parts of 2,4-dichloro-6-diethylaminotriazine are used applied, a similar yellow coloring dye is obtained.

According to the information in Examples 1 and 2, those in the table below can also be found execute the examples mentioned.

example Leucosulfuric acid ester salt
according to formula III Triazine derivative according to formula II Leucosulfuric acid ester salt
according to formula IV hue
cotton 3 1 - aminoanthraquinone 2,4-dichloro-6-amino- l-amino-4-benzoylamino- orange triazine anthraquinone 4th the same 2,4-dichloro 1 - amino-5-benzoylamino- yellow 6- (2,3-dimethyl) -butyl- anthraquinone aminotriazine 5 the same 2,4-dichloro the same yellow 6-anilinotriazine 6th the same 2,4-dichloro-6-cyclohexyl- the same yellow aminotriazine 7th the same 2,4-dichloro l-amino-4-benzoylamino- orange 6-butoxytriazine anthraquinone 8th the same 2,4-dichloro-6- (2'-ethyl- l-amino-5-benzoylamino- yellow butoxy) triazine anthraquinone 9 the same 2,4-dichloro l-amino-8-benzoylamino- yellow 6-methylaminotriazine anthraquinone 10 l-amino-4-chloro 2,4-dichloro l-amino-5-benzoylamino- yellow anthraquinone 6-morpholinotriazine anthraquinone 11 l-amino-5-chloro 2,4-dichloro l-amino-4-benzoylamino- orange anthraquinone 6-dimethylaminotriazine anthraquinone 12th the same 2,4-dichloro l-amino-5-benzoylamino- yellow 6-anilinotriazine anthraquinone 13th l-amino-6-chloro the same the same yellow anthraquinone 14th l-amino-7-chloro 2,4-dichloro 1-amino-4-benzoylamino- orange anthraquinone 6-methoxytriazine anthraquinone 15th the same 2,4-dichloro l-amino-5-benzoylamino- yellow 6-anilinotriazine anthraquinone 16 Mixture of 1-amino the same the same yellow 6-chloro and 1-amino 7-chloroanthraquinone 17th l-amino-8-chloro 2,4-dichloro 1 - amino-4-benzoylamino- orange anthraquinone 6-anilinotriazine anthraquinone 18th the same 2,4-dichloro l-amino-8-benzoylamino- yellow 6-methylaniinotriazine anthraquinone 19th . l-amino-4-benzoyl- 2,4-dichloro 1-amino-4-benzoylamino- Red aminoanthraquinone 6-piperidinotriazine anthraquinone 20th the same 2,4-dichloro the same Red 6-anilinotriazine 21 l-amino-5-benzoyl- the same 1-amino-5-benzoylamino- yellow aminoanthraquinone anthraquinone

continuation

r
example Leucosulfuric acid ester salt
according to formula III Triazine derivative according to formula II Leucosulfuric acid ester salt
according to formula IV hue
Cotton' 22nd l-amino-5-benzoyl- 2,4-dichloro l-amino-5-benzoylamino- yellow aminoanthraquinone 6-phenoxytriazine anthraquinone 23 l-amino-8-benzoyl- 2,4-dichloro l-amino-8-benzoylamino- yellow anthraquinone 6-anilinotriazine anthraquinone 24 l-amino-4- (4'-phenyl- 2,4-dichloro l-amino-4- (4'-phenyl- Red benzoylamino) - 6-phenyltriazine benzoylamino) - anthraquinone anthraquinone

Claims (2)

Patent claims: 1. Water-soluble leuco-sulfuric acid ester salts of vat dyes of the anthraquinone series, their free acids of the following general formula SO ₃ H _XT SO ₃ H I / ^N \ I O NH-C C-HN O ζ Il C.
R. SO ₃ H correspond, in which each of the radicals χ is a hydrogen or chlorine atom or a - NH · aroyl radical, each of the y radicals is a hydrogen or chlorine atom, one of the ζ radicals is the - NH · aroyl radical and the two remaining radicals ζ represent hydrogen, while the radical R represents the —NH2 group, a - NH · alkyl-, - N (alkyl}> -, -NH cyclohexyl-, -NH-aryl-, O · alkyl-, - O · aryl radical, the - CeHq, piperidine or Morpholine radical means, where both the χ radicals and the y radicals are each identical or different May be radicals, with the condition that at least 6 hydrogen atoms are directly attached to the Carbon atoms of each individual anthracene nucleus are bound and that under the term "alkyl" Low molecular weight alkyl radicals with 1 to 6 atoms are to be understood. 2. Process for the preparation of water-soluble leuco-sulfuric acid ester salts of vat dyes of the anthraquinone series, their free acids of the following general formula SO ₃ H _XT SO ₃ H I / ^Ν \ I χ O NH-C C-HN O ζ Λ. SO ₃ H SO ₃ H correspond, in which each of the radicals χ is a water Substance or chlorine atom or - NH ■ aroyl radical, each of the radicals y is a hydrogen or chlorine atom, one of the radicals ζ represents the - NH · aroyl radical and the other two radicals ζ hydrogen, while the radical R represents the - NH ₂ group , an -NH-alkyl-, - N (alkyl) 2-, -NH-cyclohexyl-, -NH-aryl-, O-alkyl-, - O ■ aryl radical, the - CeHs, piperidine or morpholine radical, where Both the radicals χ and the radicals y can be identical or different radicals, with the proviso that at least 6 hydrogen atoms are bonded directly to the carbon atoms of each individual anthracene nucleus and that under the term "alkyl" low molecular weight alkyl radicals with 1 to 6 Atoms are to be understood, characterized in that a compound of the general formula is used in any order Cl-C / ^N \ C-Cl where Ri is a chlorine atom or the - NH> group, a - NH ■ alkyl, - N (alkyl) ₂ -, - NH · cyclohexyl, - NH · aryl, - O · alkyl, - O · aryl radical, denotes the - CoHö, piperidine or morpholine radical, with 1 mol of a compound which, in the form of its free acid, of the general formula SO ₃ H O χ SO ₃ H corresponds, in which each of the radicals χ and y has the above meanings, with the proviso that at least 6 hydrogen atoms are bonded directly to the carbon atoms of the anthracene nucleus, and with 1 mole of a compound which is in the form their free acid of the general formula SO ₃ H
ζ Ο NH ₂ corresponds, in which each of the radicals ζ has the above meaning, with the proviso that at least 10 6 hydrogen atoms are bound directly to the carbon atoms of the anthracene nucleus, in aqueous Brings medium and in the presence of a mineral acid binding agent to react, and the reaction product obtained, provided it still has a chlorine substituent on the triazine nucleus, then with a compound of the general formula HR ₂ where R2 is the NH2 group, a - NH alkyl, - N (alkyl) ₂ -, - NH cycloalkyl, - NH aryl, - O · alkyl, - O · aryl radical, the piperidine or Morpholine radical means converts. Considered publications:
U.S. Patent Nos. 2,716,645, 2,508,814. When the registration is announced, there is a coloring table with explanations and a priority document has been laid out. ,