DE1275710B - 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 ^ M PATENT OFFICE Int. Cl .:

C09b

EDITORIAL

German class: 22 b -3/03

Number: 1 275 710

File number: P 12 75 710.7-43 (D 38369)

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 general formula

SO ₃ H

I / ^N \

O NH-C

C-

R ₁

Water-soluble leuco-sulfuric acid ester salts
of vat dyes of the anthraquinone series
and methods of making 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:

SO ₃ H

wherein each of the radicals χ denotes a hydrogen or chlorine atom or a - NH-aroyl radical, each of the radicals y represents a hydrogen or chlorine atom, Ri is an -NH ₂ -, - NH-alkyl-, - N (alkyl> s-,

- NH-cyclohexyl-, - NH-aryl-, - O-alkyl-,

- O-aryl, the piperidine or the morpholine radical and R ₂ a - NH ₂ -, - NH-alkyl-, - N (AIlCyI) ₈ -,

- NH-cyclohexyl-, --NH-aryl-, - O-alkyl-,

- O-aryl radical, —CgHs-, the piperidine or the 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 on the carbon atoms of the anthracene nucleus are bound and that under the term "alkyl" consistently 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 general formula I above.

The inventive method is characterized in that 1 mol of a compound of general formula

Dr. Walter Oppliger,

Dr. Max Aaberli, Basel (Switzerland)

Claimed priority:

Switzerland of March 24, 1961 (3518)

- NH-aryl-, - O-alkyl-, - O-aryl-, the piperidine or the morpholine radical and R4 is a chlorine atom or an -NH ₂ -, --NH-alkyl-, - N (alkyl) a-,

- NH-cyclohexyl-, -NH-aryl-, -O-alkyl-,

- O-aryl radical, the CeHs - piperidine or the Morpholine radical means with 1 mole of a compound which in the form of the free acid of the following general Formula corresponds to:

SO ₃ H

Cl-C

C-R,

R ₄

wherein Ra is a chlorine atom or an —NH ₂ -, - NH-alkyl-, - N (alkyl} ₂ -, —NH-cyclohexyl-, SO ₃ H

Π wherein each of the radicals χ and y has the above meaning

has and where at least 6 hydrogen atoms are bonded directly to the carbon atoms of the anthracene nucleus are, in an aqueous medium and in the presence of a mineral acid binding agent to react. Reaction products according to formula I which still contain 1 or 2 chlorine atoms in the triazine nucleus are

"" 809 597/422

then with compounds of the general formula

H-Ri

wherein Ri is an -NH ₂ -, - NH-alkyl-, -N (alkyl) 2-, - NH-cyclohexyl-, - NH-aryl-, - O-alkyl-, - O-aryl-, the piperidine or means the morpholine radical, implemented, 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- and -8-chloranthra-

quinones,
l-amino-4-, -5- and -8-benzoylaminoanthra-

quinones,
l-amino-4-, -5- and -8- (chlorobenzoylamino) -

anthraquinones and
1-amino-4-, -5- and -8- (4'-phenylbenzoylamino) anthraquinone.

Compounds of the formula II which are suitable for implementation are 2,4,6-trichlorotriazine and its through a radical Ri monosubstituted or by two radicals disubstituted derivatives in which Ri has the above Has meaning, as well as the 2,4-dichloro-6-phenyltriazine and its monosubstituted by the radical Ri Derivatives. The compounds on which the remainder Ri is based are, for example, the following amines: Methyl, ethyl, n-propyl, isopropyl, n-butyl, n-amyl, n-hexyl, cyclohexyl, 1,3-dimethylbutyl, Dimethyl, diethyl, dibutyl, diamyl, dihexylamine, Piperidine, morpholine, aniline, monochloroaniline, nitroaniline, and the following alcohols: Methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethyl-n-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 proven.

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 gradual 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

190 parts (1.03 mol) of cyanuric chloride are dissolved in 600 parts by volume of acetone and the solution is poured onto 1200 parts of ice with stirring. With vigorous stirring, 429 parts (1 mole) of sodium salt of Leukoschwefelsäureesters of the 1-aminoanthraquinone at most 5 ⁰ C was added with simultaneous addition of a solution of 40 parts of sodium hydroxide in 120 parts of water so that the pH of the reaction solution 3 to 5 amounts to. The reaction has ended after about 20 minutes. The pH is adjusted to 8.5 and the reaction mixture is evaporated to dryness in vacuo.

58 parts (0.1 mole) of the thus obtained Leukoschwefelsäjireestersalzes are dissolved in 250 parts of water, admixed with 50 parts of a concentrated aqueous ammonia solution, for one hour at 30 to 40 ⁰ C and for a further hour at 80 to 90 ⁰ C stirred. The reaction product is deposited by salting out and dried.

The leuco-sulfuric acid ester salt thus obtained is a yellow powder that is easily soluble in water Dyeing by known processes gives excellent reddish yellow shades on cotton Lightfastness.

Exactly the same dye is obtained when 43 parts (0.1 mol) of the sodium salt of the leuco-sulfuric acid ester of 1-aminoanthraquinone with 22 parts (1.5 mol) of 2,4-diamino-6-chlorotriazine- (1,3,5) during 4 hours at 80 to 90 ⁰ C are brought to implementation.

In accordance with the information in Example 1, those listed in the table below can also be used Run examples.

Leucosulfuric acid ester salt Triazine derivative according to formula II hue example according to formula III 2,4-di-isopropylamino-6-chlorotriazine cotton 2 1-aminoanthraquinone 2,4-di- (l ', 3'-dimethylbutylamino) - yellow 3 the same 6-chlorotriazine yellow 2,4-Di- (n) -butylamino-6-chlorotriazine 4th the same 2,4-Di- (di- (n) -butylamino) -6-chlorotriazine yellow 5 the same 2,4-dicyclohexylamino-6-chlorotriazine yellow 6th the same 2-amino-4-morpholino-6-chlorotriazine yellow 7th the same 2,4-dianilino-6-chlorotriazine yellow 8th the same 2,4-di-4'-chloroanilino-6-chlorotriazine yellow 9 the same 2-methoxy-4-piperidino-6-chlorotriazine yellow 10 the same 2-butoxy-4-anilino-6-chlorotriazine yellow 11 the same yellow

continuation

Leucosulfuric acid ester salt Triazine derivative according to formula II hue example according to formula III 2- (2-ethyl-butoxy) -4-piperidino- cotton 12th 1-aminoanthraquinone 2-phenoxy-4-piperidino-6-chlor1; riazine yellow 13th the same 2-phenyl-4-anilmo-6-chlorotriazine yellow 14th the same 2,4-diethylamino-6-chlorotriazine yellow 15th 1-amino-4-chloroanthraquinone 2,4-dianilino-6-chlorotriazine yellow 16 1 - Amino-5-chloroanthraquinone 2,4-dimethoxy-6-chlorotriazine yellow 17th 1-amino-6-chloroanthraquinone 2,4-dimethoxy-6-chlorotriazine yellow 18th l-amino-7-chloroanthraquinone 2,4-dimethoxy-6-chlorotriazine yellow 19th Mixture of l-amino-6-chloro and yellow 1 - Amino-7-chloroanthraquinone 2-amino-4-anilino-6-chlorotriazine 20th 1 - Amino-8-chloroanthraquinone 2,4-diamino-6-chlorotriazine yellow 21 1-aniino-4-benzoylaminoanthraquinone 2,4-dimethoxy-6-chlorotriazine Red 22nd l-amino-4-benzoylaminoanthraquinone 2,4-dimethoxy-6-chlorotriazine Red 23 l-amino-4- (4'-phenyl) -benzoylamino-
α ti til r ρ ph ι η CiTt 2,4-diamino-6-chlorotriazine Red 24 ΛΙχ till tX \ slllll * ~ JIl
l-amino-5-benzoylaminoanthraquinone 2,4-di (dimethylamino) -6-chlorotriazine yellow 25th l-amino-5-benzoylaminoanthraquinone 2,4-dianilino-6-chlorotriazine yellow 26th l-amino-5-benzoylaminoanthraquinone 2,4-dianilino-6-chlorotriazine yellow 27 1-amino-8-benzoylaminoanthraquinone yellow

Claims (2)

Patent claims: 1. Water-soluble leuco-sulfuric acid ester salts of vat dyes of the anthraquinone series, their free acids of the general formula O NH-C R ₂ χ Ο χ
SO ₃ H correspond, in which each of the radicals χ is a water substance or chlorine atom or an —NH-aroyl radical means, each of the radicals y represents a hydrogen or chlorine atom, Ri a —NH2-, - NH-alkyl-, - N (AIkJd) ₂ -, - NH-cyclohexyl-, - NH-aryl-, - O-alkyl-, - O-aryl-, the piperidine- or morpholine residue and R2 a - NH2-, - NH-alkyl-, - N (AIkJrI) ₂ -, - NH-cyclohexyl-, - NH-aryl-, - O-alkyl-, - O-aryl-, - C ₆ H ₅ -, the piperidine or the morpholine radical, both the χ radicals and the y radicals can be identical or different radicals , with the condition that at least 6 hydrogen atoms are bonded directly to the carbon atoms of the anthracene nucleus and that the term "alkyl" consistently refers to low molecular weight alkyl radicals with 1 to 6 carbon atoms. 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 general formula SO ₃ H in which each of the radicals χ represents a hydrogen or chlorine atom or an —NH-aroyl radical means, each of the radicals y represents a hydrogen or chlorine atom, Ri a —NH2-, - NH-Alkyl-, - N (AlkylV, - NH-Cyclohexyl-, - NH-aryl-, - O-alkyl-, - O-aryl-, the piperidine or the morpholine radical and R _{2 is} an -NH ₂ -, --NH-alkyl-, - N (alkyl) ₂ -, -NH- Cyclohexyl-, - NH - aryl-, - O - alkyl-, - O-aryl, —CeHs, the piperidine or the 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 C atoms of the anthracene nucleus are bound and that under the term "alkyl" throughout Low molecular weight alkyl radicals with 1 to 6 carbon atoms are to be understood, characterized in that one mole of a compound of the general formula Λ, wherein R3 is a chlorine atom or an —NH2-, - NH-alkyl-, - N (AIkVl) ₂ -, - NH-cyclohexyl-, - NH-aryl-, - O-alkyl-, - O-aryl-, the piperidine or the morpholine radical and R4 is a chlorine atom or a - NH ₂ -, - NH-alkyl-, - N (alkyl) ₂ -, - NH - cyclohexyl, - NH - aryl, - O-alkyl, - O-aryl radical, _{denotes the C 6} H ₅ piperidine or the morpholine radical, with 1 mol of a compound which is in the form of the free acid of the general formula IO corresponds to, wherein each of the radicals χ and y has the above meaning and wherein at least 6 hydrogen atoms are bound directly to the carbon atoms of the anthracene nucleus, in an aqueous medium and in the presence of a mineral acid-binding agent Bring means to the reaction, and the reaction product obtained, if there is still one or has two chlorine substituents on the triazine nucleus, then with a compound of the general formula H-Ri wherein Ri is - NH ₂ -, - NH-alkyl-, - N (alkyl) a-, - NH-cyclohexyl-, - NH-aryl-, - O-alkyl-, - O-aryl-, the piperidine or means the morpholine residue. Considered publications:
U.S. Patent No. 1,867,125. When the registration is announced, there is a coloring table with explanations and a priority document has been laid out.