DE1275711B - 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. CL:

C09b

German class: 22 b-3/03

Number: 1275 711

File number: P 12 75 711.8-43 (D 38370)

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:

C-E

C ⁷
R ₂

C-

Il

(D

R,

wherein E is the remainder of the 1,4-, 1,5- or 1,8-diaminoanthrahydroquinonyl disulfuric acid ester according to the general formula

SO ₁ H

HN

NH

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:

Dr. Walter Oppliger,

Dr. Max Aaberli, Basel (Switzerland)

Claimed priority:

Switzerland of March 24, 1961 (3521)

Compound of the general formula

(H)

Cl

SO, H

Il

y /

(III)

each of the radicals Ri is an amino group or one

- NH-alkyl-, -N (AIlCyI) ₂ -, - NH-cyclohexyl-,

- NH-aryl-, - O-alkyl-, - O-aryl radical or the piperidine or morpholine radical and each of the radicals Rz is an amino group, an - NH-alkyl-, - N (alkyl> 2-, —NH-cyclohexyl- , —NH-aryl, —O-alkyl, —O-aryl, the —CbHs, piperidine or morpholine radical, where both the R1 radicals and the R2 radicals can be identical or different radicals and are covered by the term “Alkyl” is to be understood as meaning low molecular weight alkyl radicals with 1 to 6 carbon atoms.

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 process according to the invention is characterized in that 2 moles of one and the same in which R3 is a chlorine atom or an amino group or an - NH-alkyl-, - N (alkyl) ₂ -, - NH-cyclohexyl-, - NH-aryl-, - O-alkyl, —O-aryl or the piperidine or morpholine radical and R4 is a chlorine atom or an amino group, an —NH-alkyl-, —N (alkyl> 2-, —NH-cyclohexyl-, —NH-aryl-, - O-alkyl, - O-aryl radical, denotes the - QHs, piperidine or morpholine radical, with 1 mol of the compound

Η —Ε —Η

(IV)

where E has the above meaning, in an aqueous medium and in the presence of a mineral acid-binding agent Means to implement.

Reaction products of the above formula I which contain 2 or 4 chlorine atoms in the triazine nucleus

809 597/423

hold, are then with a compound of the general formula

H-Ri

(V)

where Ri is an amino group or an —NH-alkyl, - N (alkyl) ₂ , —NH-cyclohexyl, —NH-aryl, —O-alkyl, —O-aryl radical or the piperidine or morpholine radical, implemented, this type of procedure is often of practical advantage. The diamines on which the leuco-sulfuric acid ester salts according to the general formula II are based are:

1,4-diaminoanthraquinone,
1,5-diaminoanthraquinone,
1,8-diaminoanthraquinone.

Compounds of the formula III suitable for implementation are 2,4,6-trichlorotriazine and its by the radical Ri defined above mono- and disubstituted derivatives and 2,4-dichloro-6-phenyltriazine and its derivatives monosubstituted by the radical Ri defined above.

Links underlying the rest of Ri are for example the following amines: methyl, ethyl, n-propyl, isopropyl, η-butyl, n-amyl, n-hexyl, Cyclohexyl-, 1,3-dimethyl-butyl, dimethyl-. Diethyl, Dibutyl, diamyl, dihexylamine, piperidine, morpholine, aniline, monochloraniline, nitroaniline, and the following alcohols, namely methyl, ethyl, n-propyl, isopropyl, η-butyl, 2-ethyln-butyl, n-hexyl alcohol, phenol and 4-chlorophenol.

To accelerate the reaction according to the invention, it is advantageous to use the compounds of general formula III to be completely or partially dissolved in an inert solvent. As special suitable solvents have z. B. benzene. Monochlorobenzene, toluene, acetone. Methyl ethyl ketone and dioxane proved.

Sodium hydroxide, for example, is suitable as a mineral acid-binding agent. Potassium hydroxide. Sodium and potassium carbonate. The mineral acid binding agent can be added to the reaction mixture to be added as the hydrochloric acid is formed, the pH value with Advantage is held to less than 7. The gradual conversions customary in technology are present 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

38 parts (0.2 mol) of cyanuric chloride are dissolved in 150 parts of acetone, the resulting solution Poured onto 400 parts of ice with stirring and poured into the suspension thus obtained with stirring at 0 to 5 ° C 44 parts (0.1 mol) of the sodium salt of the leuco-sulfuric acid ester of 1,5-diaminoanthraquinone entered. At the same time, by adding a 10% sodium carbonate solution dropwise, the pH value is between 3 and 4 held. After about 2 hours of stirring at 0 to 5 C, the reaction is complete, whereupon the reaction product formed is separated off and dried.

74 parts of the leuco-sulfuric acid ester salt thus obtained are dissolved in 600 parts of water and brought to reaction with 40 parts (0.43 mol) of aniline and the temperature for 6 hours kept at 30 to 40 ° C. and for a further 6 hours at 85 to 90 ° C. This gives one real, yellowing dye.

A very similarly yellow-colored leuco-sulfuric acid ester salt is obtained if in the above example instead of the leuco-sulfuric acid ester salt of 1,5-diaminoanthraquinone, the leuco-sulfuric acid ester salt of 1.8-diaminoanthraquinone is used.

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

example Leucosulfuric acid ester salt
according to formula II
0.1 mole Triazine derivative according to formula III
0.2 mole hue
cotton Ί 1,4-diaminoanthraquinone 2-chloro-4,6-dibutylaminotriazine Red 3 the same 2- (chloro-4,6-dimethoxytriazine Red 4th the same 2-chloro-4-methoxy-6-piperidinotriazine Red 5 the same 2-chloro-4-amino-6-anilinotriazine Red 6th the same 2-chloro-4-phenyl-6-morpholinotriazine Red '7 the same 2-chloro-4,6-dianilinotriazine Red 8th the same 2-chloro-4,6-diaminotriazine Red 9 1,5-diaminoanthraquinone 2-chloro-4,6-diaminotriazine orange 10 the same 2-chloro-4,6-di (2,3-dimethyl) butylaminotriazine yellow 11 the same 2-chloro-4-ethylamino-6-anilinotriazine yellow 12th the same 2-chloro-4,6-dimethoxytriazine yellow 13th the same 2-chloro-4-phenoxy-6-anilinotriazine yellow 14th the same 2-chloro-4-butoxy-6-anilinotriazine yellow

continuation

example Leucosulfuric acid ester salt
according to formula II
0.1 mole Triazine derivative according to formula III
0.2 moles hue
cotton 15th 1,5-diaminoanthraquinone 2-chloro-4,6-dicyclohexylaminotriazine yellow 16 the same 2-chloro-4- (2-ethyl) -butoxy-6-anilinotriazine yellow 17th the same 2-chloro-4,6-diisopropylaminotriazine yellow 18th the same 2-chloro-4,6-di-diethylaminotriazine yellow 19th 1,8-diaminoanthraquinone 2-chloro-4,6-diaminotriazine orange 20th the same 2-chloro-4,6-dimethylaminotriazine yellow 21 the same 2-chloro-4-phenyl-6-anilinotriazine yellow 22nd the same 2-chloro-4,6-dianilinotriazine yellow

Claims (2)

Patent claims: 1. Water-soluble leuco-sulfuric acid ester salts of vat dyes of the anthraquinone series, their free acid of the following general formula C- E-C .N _x C ⁷
R ₂ correspond, where E is the remainder of the 1,4-, 1,5- or 1, S-diaminoanthraquinonyl disulfuric acid ester according to the general formula -HN NH- 40 45 SO ₃ H each of the radicals Ri is an amino group or - NH-alkyl-. - N (alkyl)., -. -NH-cyclohexyl-, - N H-aryl, - O-alkyl, - O-aryl radical or the piperidine or morpholine radical and each of the radicals Ro is an amino group, one - NH-alkyl-, - N (alkyl)> -, - NH-cyclohexyk - NH-aryl, - O-alkyl, - O-aryl radical. the - ChHo, piperidine or morpholine residue denotes, where both the radicals Ri and the radicals R2 are each identical or different Can be radicals and the term “alkyl” is to be understood as meaning low molecular weight alkyl radicals having 1 to 6 carbon atoms. 2. Process for the preparation of water-soluble leuco-sulfuric acid ester salts of vat dyes the anthraquinone series. their free acids of the following general formula C-E-C I I N N C ^x
R ₂ R, correspond, where E is the remainder of the 1,4-, 1,5- or 1,8-diaminoanthrahydroquinonyl disulfuric acid ester according to the general formula HN NH- SO, H each of the radicals Ri is an amino group or an —NH-alkyl, —N (alkyl> ₂ , —NH-cyclohexyl, —NH-aryl, —O-alkyl, —O-aryl radical or the piperidine or morpholine radical and each of the radicals R2 is an amino group, an - NH-alkyl, - N (alkyl) ₂ -, - NH-cyclohexyl, - NH-aryl, - O-alkyl, - O-aryl radical, the —C « Hö, piperidine or morpholine radical, both the radicals Ri and the radicals R2 can each be the same or different radicals and the term "alkyl" is to be understood as meaning low molecular weight alkyl radicals having 1 to 6 carbon atoms, characterized in that one and 2 moles of one and the same compound of the general formula Il V ^ 1 R ₄ wherein Rg is a chlorine atom or an amino group or a - NH-alkyl, -N (AIlCyI) ₂ -, -NH-cyclohexyl, - NH-aryl, - O-alkyl, - O-aryl radical or the piperidine or Morpholine radical and R4 is a chlorine atom or an amino group, an —NH-alkyl, - N (alkyl} ₂ -, -NH-cyclohexyl, —NH-aryl, —O-alkyl, —O-aryl radical, —CeHs -, piperidine or morpholine radical means with 1 mole of the compound Η —Ε —Η where E has the above meaning, in an aqueous medium and in the presence of a mineral acid brings binding agent to the reaction and the reaction product obtained, if it still Has 2 or 4 chlorine substituents on the triazine nuclei, then with a compound the general formula HR ₁ wherein Ri is an amino group or an - NH-alkyl-, - N (alkyl) 2-, - NH-cyclohexyl-, - NH-aryl-, -O-alkyl-, - O-aryl radical or means the piperidine or morpholine radical, converts. When the registration is announced, there is a coloring table with explanations and a priority document has been laid out.