DE1904112C3 - Fiber-reactive formazan dyes containing heavy metals, processes for their production and their use for dyeing or printing textile material - Google Patents

Description

N N

metal-containing formazan dyes of the formula Ia

N N

N-Y '

I R '

Z "

(I)

N N -F

wherein

Ri is hydrogen or halogen, one optionally substituted by halogen lower alkyl radical, an aryl radical, a carboxamide group, a lower carboxylic acid ester group or the Cyano group.and

R2 is the same as Ru or a sulfonic acid amide group, a lower alkylsulfonyl group or the nitro group, and

hydrogen

15th

A and B a phenyl radical, which is optionally replaced by halogen, lower alkyl, sulfamoyl, Lower alkylsulfonyl, which can be further substituted by nitro or sulfo, and which contains the substituents Xi or X2 in the o-position to the nitrogen bond,

R one optionally through the sulfo group and / or halogen and lower alkyl so groups further substituted phenyl radical,

Me copper or nickel,

Xi is the -COO group or an oxygen atom and

X _{2 is} an oxygen atom,

Z the SO ₃ H group,

m the numbers 2 to 4,

η the number 1 and

Y is a pyrimidyl radical of the formula

40

Me

N N

- (NHR '),

N Z,

mean, where the pyrimidyl radical is located in the B core.

2. Process for the preparation of fiber-reactive, heavy metal-containing formazan dyes according to Claim 1, characterized in that one

wherein the symbols have the meaning given in claim 1, with one of the substituents Y according to claim 1 corresponding pyrimidine compound which has more than one reactive fluorine atom has, implements.

3. Modification of the method according to claim 2, characterized in that the dyes general formula II

R-C

N-NH-AX ₁ H

N = NBX ₂ H

N-Y

R 'Z _n ,

wherein R, A, B, Xi, X ₂ , Y, Z, R ', m and η have the meaning given in claim 1, with a copper or nickel-introducing agent.

4. Use of the fiber-reactive, heavy metal-containing formazan dyes of the formula 1 according to Claim 1 for dyeing or printing textile material.

The present invention relates to new, valuable, fiber-reactive, heavy metal-containing formazan dyes, Process for the preparation of these dyes, their use for dyeing or printing organic Materials, especially textile material, and as an industrial product made using the new dyes colored or printed material.

It has been found that formazan dyes which correspond to the general formula I

55

bO

b5

A Me B

N N

N-

R '
Z "

due to pure color tones and good overall fastness of the dyeings or prints produced with it on organic

see materials, especially those made of cellulose or polyamide, distinguish themselves.
In this formula I mean:

A and B are a phenyl radical which can optionally be further substituted by halogen, lower alkyl, sulfamoyl, lower alkylsulfonyl, the nitro or the sulfo group, the o-position to the diazo nitrogen being occupied by the substituents Xi and X ₂ , respectively,

R one optionally through the sulfo group

and / or halogen and lower alkyl groups further substituted phenyl,

Me copper or nickel,

Xi is the - COO group or an oxygen atom

and

X2 is an oxygen atom,

Z the SO ₃ H group,

m the numbers 2 to 4,

π the number 1 and

Y is a pyrimidyl radical of the form!

—F

wherein

Ri is hydrogen or halogen, a lower one which is optionally substituted by halogen An alkyl radical, an aryl radical, in particular a phenyl radical, a carboxamide group, a lower carboxylic acid ester group or the cyano group, and

R2 the same as Ri or a sulfonic acid amide group, a lower alkylsulfonyl group or the nitro group, and

Mean hydrogen,

where the pyrimidyl radical is located in core B.

If Ri and / or R2 are halogen, it is about bromine, but especially about fluorine or chlorine; if it means a lower alkyl radical, it is preferably around the methyl group, it means a halogen-substituted lower alkyl radical, see above it is, for example, the monochloromethyl, lower difluromethyl or trifluoromethyl group; it means a carboxylic acid ester group, it is z. B. to the carboxylic acid methyl or Carboxylic acid ethyl ester group. If R2 is a lower alkylsulfonyl group, it is z. B. to the Methylsulfonyl group or ethylsulfonyl group.

The pyrimidyl radical of the above formula is derived, for example, from the following pyrimidines:

2,5-dichloro-4,6-difluoropyrimidine;

2,5-dibromo-4,6-difluoropyrimidine;

2,4-difluoropyrimidine;

2,4-difluoro-5-chloropyrimidine;

2,4-difluoro-5-cyanopyrimidine;

2,4-difluoro-5-methylpyrimidine;

2,4-difluoro-5-trifluoromethyl-pyrimidine;

2,4-difluoro-5-nitropyrimidine;

2,4-difluoro-5-phenylpyrimidine;

2,4-difluoro-5-sulfamic pyrimidine;

2,4-difluoro-5-carbamoyl-pyrimidine;

2,4-difluoro-5-methylsulfonyl-pyrimidine; 2,4-difluoro-5-ethylsulfonyi-pyrimidine; 2,4-difluoro-5-carboxylic acid methyl ester pyrunidine;

2,4-difluoro-6-chloro-pyrimidine; 2,4-difluoro-6-bromo-pyrimidine; 2,4-difluoro-6-methyl-pyrimidine; 2,4-difluoro-6-cyano-pyrimidine; 2,4-difluoro-6-phenyl-pyrimidine; 2,4-difluoro-6-trifluoromethyl-pyrimidine; 2,4-difluoro-6-carbamoyl-pyrimidine; 2,4-difluoro-6-carboxylic acid methyl ester pyrimidine;

2,4-difluoro-5,6-dichloropyrimidine; 2,4-difluoro-5-chloro-6-methyl-pyrimidine, 2,4-difluoro-5-chloro-6-phenyl-pyrimidine; 2,4-difluoro-5-chloro-6-difluoromethyl-

pyrimidine;
2,4-difluoro-5-chloro-6-trifluoromethyl-

pyrimidine;
2,4-difluoro-5-chloro-6-carboxylic acid methyl ester pyrimidine;

2,4-difluoro-5,6-dibromopyrimidine; 2,4-difluoro-5-bromo-6-methyl-pyrimidine; 2,4-difluoro-5-bromo-6-trifluoromethylpyrimidine;

2,4,5-trifluoro-6-methyl-pyrimidine; 2,4-difluo: -5-nitro-6-chloro-pyrimidine; 2,4-dif'uor-5-methyl-6-chloropyriinidine; 2,4,6-trifluoro-5-trifluoromethyl-pyrimidine; 2,4,6-trifluoropyrimidine; 2,4,6-trifluoro-5-chloro-pyrimidine; 2,4,6-trifluoro-5-bromo-pyrimidine; 2,4,6-trifluoro-5-nitro-pyrimidine; 2,4,6-trifluoro-5-cyano-pyrimidine; 2,4,6-trifluoro-5-methyl-pyrimidine; 2,4,6-trifluoro-5-chloromethyl-pyrimidine; 2,4,6-trifluoro-5-difluoro-methyl-pyrimidine; 2,4,6-trifluoro-5-carbamoyl-pyrimidine; 2,4,6-trifluro-5-carboxylic acid methyl ester

pyrimidine;
2,4,6-trifluoro-5-carboxylic acid ethyl ester

pyrimidine;
2,4,6-trifluoro-5-methylsulfonyl-

pyrimidine and
2,4,5,6-tetrafluoropyrimidine.

Preferred pyrimidines are 2,4,6-trifluoropyrimidine or 2,4,6-trifluoro-5-chloropyrimidine.

The new formazan dyes of the formula I according to the invention are obtained by various processes. One is that metal-containing formazan dyes of the formula Ia

Me B

w <in the symbols have the meaning given in formula I, with an initially defined Pyrimidine compound, which is more than a mobile

Has fluorine atom, to a fiber-creative formazan dye of formula I converts

The starting materials of the formula Ia used according to the invention are obtained according to known methods Methods, such as by coupling 1 mol of an o-hydroxy-aryldiazonium compound with an a-aryl-Λ-acrylacetate, for example with an Λ-Pher.yl-ixformylessigsäurealkylester, subsequent saponification of the carbalkoxy to the carboxyl group in the alkaline Agent and action of a second molecule of the same or a different o-carboxy or o-Hydroxyaryldiazonium compound, the starting components being chosen in such a way that the diazo component B a «; acylatable amino group or a substituent which can be converted into such a group contains. The diazo component B expediently contains an acylamino group. After metallization has taken place the acyl radical in the alkaline range is then split off with a metal donor.

The compounds mentioned at the outset are used as the compounds introducing the fiber-reactive radical Y Fluoropyrimidines, which are known and can be prepared by known methods.

The conditions for the reaction of the metal-containing formazan dyes of the formula la with the fluoropyrimidines are to be chosen so that neither as a result of an excessively high pH value of the reaction medium nor as a result too high temperature premature replacement of moving groups occurs. That's why you work with the aqueous solutions of the alkali salts of the metal-containing formazan dyes at the lowest possible temperatures and pH values, optionally in the presence of mineral acid deadening agents, such as alkali salts lower fatty acids, d. H. at pH values from about 2 - 7 and at temperatures from 0 to about 60 ° C, respectively according to the stability of the pyrimidine compound or mobility of the exchangeable substituents. the Pyrimidine compounds are used in at least an equimolecular amount in a fine dispersion, for example as a suspension or emulsion, if appropriate with the aid of inert, easily removable organic solvents such as lower ketones, for example Acetone. The pyrimidine compound is allowed to act until the amino group to be acylated the formula Ia can no longer be detected; is a detection reaction for primary amino groups for example the diazotization and subsequent coupling with sodium 2-naphthol-3,6-disulfonic acid.

The isolation and drying of the formazan dyes according to the invention must also be carried out with care happen, for example by salting out the alkali salts with sodium chloride in a weakly acidic solution, Filter off and dry at a moderately elevated temperature; preferably in a vacuum.

Another process for the production of new fiber-reactive formazan dyes containing heavy metals of the formula I consists in that dyes of the general formula II

Ν —NH-A — X ₁ H

N = NBX ₂ H

N-Y

(II)

wherein R, A, B, Xi. X ₂ . Y, Z, k ', m and η have the meaning given under formula I, with a copper or nickel-introducing agent.

It is advantageous to use those dyes of the formula II which, as group Y, are a 2,6-difluoropyrimidyl-4 radical or contain a 2,6-difluoroc-5-chloro-pyrimidyl-4 radical.

The metal-free dyes of the formula II are prepared, for example, while observing the first-mentioned Procedure indicated precautionary measures

ίο the mobility of critical substituents from components which contain the defined group - NR'-Y in the core B, or one leads into Dyes which have an acylatable amino group or a group which can be converted into such a group in the core B contain, after the protective group has been cleaved off, the pyrimidyl radical Y according to the definition a.

For the metallization of the metal-free dyes of the general formula II, the usual metal-donating dyes are used Agents used, for example mineral acid salts of nickel, preferably of copper. Appropriate one works in the presence of alkali salts of lower fatty acids or of polybasic oxygen acids of phosphorus as a mineral acid deadening agent, as well as at moderately high temperatures and pH values of about 1–7, in order to prevent a premature exchange of mobile substituents as much as possible. In the isolation and drying of the dyes are also those in the first method specified precautionary measures to be observed.

The starting materials of the formula II are obtained, for. B. such that one of an o-carboxyarylhydrazine and an aromatic aldehyde-derived hydrazone with an o-carboxy, o-hydroxy or o-acyloxy

j5 coupling aryldiazonium compound, whereby the Components are selected in such a way that the starting component with the core B is the acylatable amino group or contains a substituent which can be converted into an acylatable amino group and which is in a suitable stage of the synthesis converted into the free amino group by cleavage of the protective group and this reacts with fluoropyrimidine.

The new heavy metal-containing formazan dyes of the formula I represent dark powders in ^F orm of their alkali metal salts in water 5 highly soluble. They are suitable for dyeing or printing organic materials, in particular natural and regenerated cellulose fibers, in red-brown, violet, blue-violet, blue, navy blue, green to gray tones. The cellulose material is expediently impregnated or printed at a low temperature, for example at 20-5O ⁰ C, with the optionally thickened dye solution, and the dye is then fixed by treatment with acid-binding agents. Sodium carbonate, di- and trisodium phosphate, sodium hydroxide solution, and at temperatures above 50 ° C. also sodium bicarbonate are suitable as such. Although the treatment with these means already at room temperature or at slightly increased

bo temperature can take place, it is often (advantageous after a gentle intermediate drying of the impregnated or printed goods) with better success at elevated temperature, e.g. B. at 70-16O ⁰ C. Instead of an alkaline post-treatment

b5 one, especially with hot fixation, the acid-binding Agents, preferably in the form of alkali bicarbonates, including the impregnation liquors or printing pastes add and then develop the color

cause by brief heating or vapors at temperatures above 100 ⁰ C to 160 ° C. The addition of hydrotropic agents to the printing inks and impregnation liquors is advantageous in these processes, for example the addition of urea in amounts of 10-200 g per liter of colorant.

By treating them with acid-binding agents, the new reactive dyes are chemically attached to the Fiber bound, and in particular the cellulose stains are after soaping for the purpose of removing non-fixed dye excellent wet fastness.

Natural and synthetic polyamide fibers are appropriately dyed in an acidic bath or printed on neutral to slightly acidic printing inks. Thanks to this, there is a lot for the wool dyes and prints produced with it high fixation value of the newer. Reactive dyes an aftertreatment in an alkaline bath for the purpose of improvement the wet fastness properties are not required.

The fiber-reactive formazan dyes according to the invention are distinguished by their color strength, by their pure hues and, above all, by their high reactivity. It is surprising that, despite the high reactivity of the new dyes, the dyeing and printing preparations obtainable with them are very stable, and furthermore that the dyeings and prints produced therewith have good stability, in particular towards acid and alkali hydroxide hydrolysis. The strong dyeings produced with the dyes according to the invention are also characterized by very good lightfastness and rubfastness and excellent wetfastnesses, such as, for. B. good wash, alkali, milled and perspiration fastnesses. In addition, the colorations are uniform and show an unexpectedly high resistance to signs of boiling. A reactive dye according to the invention, finally, show a high fixation yield also at low temperatures (10-50 ⁰ C); Unfixed dye can be washed out very easily, which is one of the essential prerequisites for good wet fastness properties, and the dyeings are stable to the usual synthetic resin finishes.

Compared to the next comparable from DE-AS 11 52 774 known formazan dyes according to the invention have a higher formazan dyes Reactivity and better draw and fixation values on cotton.

BE-PS 6 44 495 relates to dyes which contain a halogenpyrimidylcarbonyl radical as a reactive radical, where the carbonyl group is bonded in the 5-position. In contrast, the contain Reactive radicals of the dyes according to the invention are not a carbonyl bridge member and are also in 2- or 4-position tied. The carbamide bridge in the dyes of this BE-PS is unstable, so it becomes in split the alkaline hot wash (low fastness properties on cotton).

The dyes of BE-PS 6 50 328 contain as a reactive radical a halotriazine radical, which has a N-alkylurea bridge is bound to the chromophore These dyes have an insufficient alkaline bond stability, which is e.g. B. a shift in nuances in the alkaline hot wash

BE-PS 6 14 405 relates exclusively to anthraquinone dyes. It does not describe any dye with a fluoropyrimidyl radical.

In NL-PS 67 10 087 formazan dyes with various reactive radicals are described. It is but not named a dye with a fluoropyrimidyl radical

Further details can be found in the following examples. The temperatures are Degrees Celsius.

example 1

SO ₃ H

SO ₃ H

64.8 g of the copper complex compound of N- (2-Hydroxy-5-aminophenyl-3-sulfonic acid) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-phenylformazans (Obtained by coupling equimolecular amounts of diazotized 2-amino-1-hydroxybenzene-4,6-disulfonic acid re and 4-acetylamino-2-amino-1-hydroxybenzene-6-sulfonic acid in the presence of copper salts with pheny ethyl formyl acetate by a method known per se and subsequent saponification of the acetylam group with dilute sodium hydroxide solution) are dissolved in 1200 ml of water at a pH of 6.0-6.5 16.9 g of 2,4,6-trifluoro-5-chloropyrimidine in 100 are added to this solution within one hour at 10-15 ° Acetone, simultaneously with an aqueous solution of sodium carbonate added dropwise so that the pH de Reaction mixture is always 6.0 - 6.5. As soon as the condensation is over, the dye becomes the obei given formula, precipitated by adding sodium chloride, filtered off with dilute sodium chloride Washed rid solution and dried carefully in a vacuum. It represents a dark powder that fell dissolves in water with a blue color.

Example 2

SO ₃ H

SO ₃ H

HO ₃ S

NH

64.3 g of the nickel complex compound of N- (2-hydroxy-5-aminophenyl-3-sulfonic acid) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-phenylformazans (Obtained by coupling equimolecular amounts of diazotized 2-amino-1-hydroxybenzene-4,6-disulfonic acid and 4-acetylamino-2-amino-1-hydroxybenzene-6-sulfonic acid in the presence of nickel salts with ethyl phenylformylacetate according to a method known per se and subsequent saponification of the acetylamino group with dilute sodium hydroxide solution), are dissolved in 1200 ml of water until neutral. For this solution are 20-25 ° within one hour 13.4 g of 2,4,6-trifluoropyrimidir in 100 g of acetone at the same time as an aqueous one Sodium carbonate solution is added dropwise in such a way that the reaction mixture remains constantly neutral. As soon as no free Amine is more detectable, the dye will through Addition of sodium chloride precipitated, filtered off and washed with dilute sodium chloride solution. Of the Dye of the above constitution is a dark powder after drying in vacuo, which turns into Dissolves water with a purple color.

Example 3

Cl F

SO ₃ HV /

NH- <N
O OI N <

A / \ / \ A ν

Ji I Cu T: 1 ^h

/ V \ / \ / V \
HO ₃ S NN SO ₃ H

N N

64.8 g of the copper complex compound of N- (2-hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-hydroxy- phenyI-3 ', 5'-disulfonic acid) -ms-phenylformazans (obtained by coupling equimolecular amounts diazotized 2-amino-1-hydroxybenzoM.ö-disulfonic acid and 6-acetyl aiiiiiiu-2-arriiriü-i-hydroxybenzo! -4-Su! - Fonsäure in the presence of copper salts by a known method with phenylformylacetic acid ethyl ester and subsequent saponification of the acetylamino group with dilute sodium hydroxide solution) are in 1200 ml Dissolved water at a pH of 6.0-6.5 is added dropwise to this solution over the course of an hour 15-20 ° 163 g of 2,4,6-trifluoro-5-chloropyrimidine simultaneously with an aqueous sodium carbonate solution in this way to ensure that the reaction always remains neutral. After the condensation has ended, the reaction product is precipitated by adding sodium chloride The dye is filtered off, washed with dilute sodium chloride solution and in vacuo at 40-45 ° dried After drying, the dye of the above constitution is a dark powder, which is dissolves in water with a blue color

HO ₁ S

at sp iel 4 SO ₁ H COO 0 i \ Cu Ii j N V
Il N ι!
N ν /
Q i

Cl F

NH- / '' 'N N <

67.6 g of the copper complex compound of N- (2-hydroxy-5-aminophenyl-3-sulfonic acid) -N '- (2'-carboxyphenyl-4'-sulfonic acid) -ms-2 "-sulfonic acid phenylformazane (obtained by coupling diazotized 4-Acetylamino-2-amino-1-hydroxybenzene-6-sulfonic acid with the hydrazone of benzaldehyde-2-sulfonic acid and phenylhydrazine-2-carboxylic acid-4-sulfonic acid according to a known method and subsequent coppering and saponification of the acetylamino group with dilute sodium hydroxide solution) are dissolved neutral in 1200 ml of water are added to this solution over 2 hours at 10 -. 15 ° 16.9 g of 2,4,6-trifluoro-5-chloropyrimidine at a pH value of 6.0 - 6.5 was added dropwise.

As soon as the starting dye is no longer detectable, the dye is deposited by adding sodium chloride, filtered off, washed with dilute sodium chloride solution and finally dried in vacuo. The dye of the above constitution dissolves in water with a blue color.

Example 5

Cl

SO ₃ H

SO ₃ H

67.6 g of the copper complex compound of N- (2-hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-carboxy-

phenyl-4'-sulfonic acid) -ms-2 "-sulfophenylformazans (obtained by coupling diazotized 6-acetylami- ■ no-2-amino-1-hydroxybenzene-4-sulfonic acid with the Hydrazone from benzaldehyde-2-sulfonic acid and phenylhydrazine-2-carboxylic acid-4-sulfonic acid according to per se known method, coppering and saponification of the acetylamino group with dilute sodium hydroxide solution) are dissolved in 1200 ml of neutral water to this solution are added within 2 hours at 10-15 ° 16.9 g of 2,4,6-trifluoro-5-chloropyrimidine and through

simultaneous dropwise addition of a dilute sodium carbonate solution becomes the pH of the reaction mixture held at 6.0 -6.5. The condensation product is separated out by adding sodium chloride, filtered off, washed with dilute sodium chloride solution and dried at 60-65 ° in vacuo. Of the Dye of the above constitution is a dark powder that dissolves in water with a blue color.

HO ₁ S

lie COO \, 1 S ρ 1 / el 6 C. SO ₁ H O 1 ' / \ Λ N I.
N \ / N
Il !!
N

N = <

SO, H

67.6 g of N- (2-hydroxy-5-aminophenyl-3-sulfonic acid) -N '(2'-carboxyphenyl-4'-sulfonic acid) -ms-2 "-sulfophenylformazan (obtained by coupling the diazonium compound from 4-acetylamino-2-amino-1-hydroxyben-

zol-6-sulfonic acid with the hydrazone from benzaldehyde-2-sulfonic acid and phenylhydrazine ^ -carboxylic acid ^ -sulfonic acid and subsequent saponification of the acetylamino group with dilute sodium hydroxide solution) are in 1200 ml of water dissolved at a pH of 6.0-6.5. This solution will be within one hour 30-35 ° 13.5 g of 2,4,6-trifluoropyrimidine in 100 g of acetone simultaneously with an aqueous solution of sodium carbonate added dropwise so that the reaction mixture remains constantly neutral. As soon as no more free amine can be detected is, he becomes dye by adding 100 ml of 1 molar copper sulfate solution at 20-25 ° in the corresponding copper complex compound transferred. The copper-containing dye is then added by adding precipitated from sodium chloride, filtered off, washed with dilute sodium chloride solution and in vacuo carefully dried. The dye of the above constitution obtained in this way is a dark powder, which is dissolves in water with a blue color.

By using equivalent amounts of those listed in the following table, columns II and IV Components, compliance with the reaction conditions given in column V and analogous procedure according to Example 6, in order to introduce the metal atom, mineral acid salts of the in column III If the metals listed are used, further formazan dyes are obtained which dye cotton of similarly good properties. The hue of these cotton dyes is in column Vl given in the table.

Tabel

Il

No. AminoformazylfarbstolT

III IV V VI

Metal pyrimidine compound reaction conditions hue

pH temp.

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-2 ", 4" -disulfonphenylformazan

the same

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-hydroxyphenyl-3', 5'-di- sulfonic acid) -ms-3 "-sulfophenylformazan

the same

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-2 "-chloro-5" -sulfubphenylformazan

the same

N - ^ - Hydroxy - ^ - aminophenyl-S-sulfonic acid) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-4 "-sulfophenylformazan

the same

Cu 2,4,6-trifluoropyrimidine

Cu 2,4,6-trifluoro-

5-chloro-pyrimidine

Cu desgl.

Cu 2,4,6-trifluoropyrimidine

Cu desgl.

Cu 2,4,6-trifluoro-

5-chloropyrimidine

Cu desgl.

Cu 2,4,6-trifluoropyrimidine

6.0-6.5 30-35 °

blue

6.0-6.5 10-15 ° blue

6.0-6.5 10-15 ° blue

5.0-5.5 30-35 ° blue

5.0-5.5 30-35 ° blue

6.0-6.5 10-15 ° blue

6.0-6.5 10-15 ° blue

6.0-6.5 40-45 °

blue

14th

-orisct / ung

No. aminoformazyl dye T.

III IV

Metal l'yrimidine compound

N- (2-Hydroxy-3-aminophenyl-5-sulphonic acid) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-phenylformazan

the same

the same

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-carboxyphenyl-4'-sulfonic acid) -ms-4 "-sulfonic acid-phenylformazan

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-carboxyphenyl4'-sulfonic acid) -ms-phenylformazan

N- (2 * Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-hydroxy-5'-chlorophenyl-3'-sulfonic acid) -ms-3 "-sulfophenylformazan

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-hydroxy-5'-chlorophenyl-3'-sulfonic acid) -ms-4 "-sulfophenylformazan

N- (2-Hydroxy-3-amino-5-methylsulibnylphenyl) -N '- (2'-hydroxypnenyl-3 \ 5'-disulfonic acid) -ms-2 ", 4" -disulfophenylformazan

the same

N- (2-Hydroxy-3-amino-5-ethylsulfonylphenyl) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-phenylformazan

the same

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid amide) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-4 "-sulfophenylformazan

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-hydroxy-5'-nitrophenyl-3'-sulfonic acid) -ms-4 "-sulfophenylformazan

N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid amide) -N '- (2'-hydroxyphenyl-3', 5'-disulfonic acid) -ms-4 "-sulfophenylformazan

N- (2-Hydroxy-5-aminophenyl-3-sulfonic acid) -N '- {2'-carboxypheny! -4'-sulfonic acid) -ms-2 "-chlor-5" -sulfophenylformazan

N- (2-Hydroxy-3-ainophenyl-5-sulfonic acid) -N '- {2'-carboxyphenyl-4'-sulfonic acid) -ms-2 "-chlor-5" -sulfophenylformazan

V VI

Reaction conditions color pH temp.

Cu 2,4-di-fluoro-6-chloropyrimidine

Cu 2,4-dinuor-5,6-dichloropyrimidine

Cu 2,4-difluoro-

5-cyanopyrimidine

Cu 2,4,6-Trinuor-

5-chloropyrimidine

Cu desgl.

Cu desgl.

Cu desgl.

Cu desgl.

Cu 2,4,6-trifluoropyrimidine

Cu desgl.

Cu 2,4,6-trifluoro-

5-chloropyrimidine

Cu 2,4,6-trifluoropyrimidine

Cu desgl.

Cu 2,4,6-trifluoro-

5-bromopyrimidine

Cu 2,4,6-trifluoro-

5-chloropyrimidine

Cu desgl.

5.0-5.5 30-35 ° blue

6.5-7.0 30-35 ° blue

6.5-7.0 30-35 ° blue

6.0-6.5 i5-2O ° blue

5.0-5.3 10-15 ° blue

5.0-5.5 10-15 ° blue

5.0-5.5 15-20 ° blue

5.0-5.5 15-20 ° blue

6.0-6.5 30-35 ° blue

6.0-6.5 30-35 ° blue

6.0-6.5 10-15 ° blue

6.0-6.5 30-35 ° blue

6.0-6.5 30-35 ° blue

6.0-6.5 10-15 ° blue

6.0-6.5 10-15 ° blue

6.0-6.5 10-15 ° blue

continuation

I II

Nr Aniinoformazylfarbs'ofl '

III IV V VI

Metal pyrimidine compound reaction conditions hue

pH temp.

25 N - ^ - Hydroxy-S-aminophenyU-sulfoic acid) -N '- (2'-carboxyphenyI-4'-sulfonic acid) -ms-4 "-methyl-3" -sulfophenyI-formazan

26 N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-carboxyphenyl-4'-sulfonic acid) -ms'-4 "-methyl-3" -sulfophenylphonmazane

27 N- (2-Hydroxy-3-aminophenyl-5-sulfonic acid) -N '- (2'-carboxyphenyl-4'-arntno) -ms-3 "-sulfop heny lformazan

28 N- (2-Hydroxy-4,6-disulfonaphthyJ) -N '- {2'-carboxypnenyl-4'-amino) -ms-2 "-sulfophenylformazan

Cu 2,4,6-trifluoro-6,0-6,5 10-15 ° blue

5-chloropyrimidine

Cu desgl.

Cu desgl.
Cu desgl.

6.0-6.5 10-15 ° blue

6.0-6.5 30-35 ° blue

6.0-6.5 30-35 ° blue

Example 7

SO ₃ H

SO ₃ H

HO ₃ S

26.9 g of 2-amino-1-hydroxybenzene-4,6-disulfonic acid are diazotized indirectly. The suspension of the diazonium compound is added dropwise with good stirring a suspension of 20.4 g of ethyl phenylformylacetate in 200 ml of water, 250 g of dioxane and 10.5 g of one lOn sodium hydroxide solution in the presence of such Amount of calc. Sodium carbonate added at 0-10 °, that after the introduction of the diazonium compound, the reaction mixture is weakly phenolphthalein alkaline reacts After the coupling is complete, it is reacted by adding cone. Hydrochloric acid to a pH of 7 adjusted, diluted, and heated to the boil. After adding so much 10 η sodium hydroxide solution that strong If an alkaline reaction is ensured until the end of the saponification, the reaction product 10 Maintained minutes at the reflux condenser at boiling temperature. The solution of the saponification product becomes then adjusted to a pH value of 7 with hydrochloric acid and treated with a copper sulfate solution (corresponding to 7 g of copper) are added and then at 0-10 ° with that obtained by diazotizing 38.7 g of 4- [2 ', 6'-difluoropyrimidyl- (4') -amino] -2-amino-1 -hydroxybenzene-6-sulfonic acid (produced by the condensation of 4-acetylamino-2-amino-1-hydroxybenzoI-6-sulfonic acid with 2,4,6-trifluoropyrimidine with prior saponification of the acetylamino group combined with 10% aqueous hydrochloric acid at 90 °) obtained neutral diazonium salt.

After heating to 40-45 °, the copper-containing Formazan complex of the above formula precipitated by adding sodium chloride, filtered off, with Washed sodium chloride solution and carefully dried in vacuo. It represents a dark powder which dissolves in water with a blue color.

Example 8

If cotton is obtained with a solution containing 20 g of the dye per 1000 ml of water, according to Example 13 of the table, contains 20 g of sodium carbonate and 50 g of sodium chloride, padded, rolled up, while 4 Stored for hours and then soaped at the boil for 10 minutes, you get a deep, pure, dark blue color, which is very light and wet fast after soaping.

30th

35

45

55

60

Example 9

If cotton is padded with a solution consisting of 20 g of the dye according to Example 12 of the table, 20 g of sodium carbonate, 200 g of urea and 1000 ml of water and then exposed to dry heat of 140 ° for 5 minutes, a deep, blue color, which is very light and wet fast after soaping.

Example 10

2 g of the dye obtained according to Example 19 of the table are dissolved in 5000 ml of water at 40 ° and then with 0.5 g of a condensation product of 25 moles of ethylene oxide and 1 mole of octadecyl alcohol or octadecylamine, 6 g of acetic acid and finally with 0.5 g of a polyquaternary ammonium compound, for example the condensation product of 11.5 g Ν, Ν ', Ν "- pentamethyl diethylenetriamine and 14.3 g ß, ß' dichlorodimethyl ether, added. One goes into the resulting dyebath with 100 g of wool, heated e; boil within 30 minutes and color for one hour at this temperature. Then wire rinsed with water at 60 °. One obtains without alkaline «

130 221/8

Post-treatment a uniform, blue dyeing with good fastness properties.

Example 11 With a printing paste consisting of:

30 g of the dye according to Example 16 of the table, 200 g of urea,
400 g water,

340 g of a 5% aqueous solution of sodium alginate and

30 g sodium bicarbonate

If you print cotton fabric, the printed goods are steamed for 30 seconds with saturated steam at a

Temperature of approx. 105 °, washes the goods first in cold water and then hot, rinsing for 15 minutes with a soap solution (5 g / l soap) at boiling temperature, washes again hot and cold and drying

A pure blue printed cotton fabric is obtained which has very good light and wet fastness having

If you use a rayon fabric instead of the cotton fabric and do not steam for 30 seconds

ίο the printed goods, but fixed for 1 minute at 110-150 ° and otherwise works analogously to the Details of Example 11, a printed one is obtained Cellulose tissue, which has the same valuable properties

Claims (1)

Patent claims: 1. Fiber-reactive, heavy metal-containing formazan dyes of the formula I X ₁ X, / \ / ~ \
A Me B