DE1419840C - Process for the production of reactive dyes - Google Patents

Description

The present invention relates to a method for the production of reactive dyes.

Many of the previously known ones, with the fiber, contain chemical groups as reactive groups Bonding dyestuffs one or more substituted amino groups, their substituent at least contains a residue that can easily be split off as an anion, for example halogen. These substituted Amino groups, advantageously halogenazinylamino groups, are usually directly linked to aromatic ones Remnants of the dye structure linked. To the er / iclimg This substitution is certain properties, for example to achieve certain particularly pure color tones undesirable.

If one tries to relocate the amino group containing reactive radicals to customary external groups, so one encounters the difficulty that extensive substituents have the required very good solubility in water and often raise the noun properties to an undesirable extent. This is for example in the case of substituted atninobenzoylamino groups as substituents of the dye structure Case. In addition, it is often not possible in phenylazo dyes to have all the desired substituents in the phenyl radical. z. B. acylamino, sulfonic acid and other groups to accommodate.

It has now been found that dyes which, in addition to at least one substituted amino group containing reactive radicals, also have one or two aryldisulfiinide groups —SO ₂ —NH — SC) ₂ - are very valuable reactive dyes, which are primarily due to their good water solubility and the property to give very pure cellulose dyeings are excellent. The disulfimide groups not only give the dyes they contain good water solubility, they also allow the accommodation of further substituents which make water soluble or which promote water solubility, in that such aryl radicals bound to the disulfimide group are introduced into or can be contained in the same. If only this external aryl radical contains the substituted amino group having reactive radicals, then the undesirable properties mentioned above do not occur.

Reactive dyes according to the invention are obtained by adding a disulfimide group-containing dye of the general formula I.

A— / SO, N —SO, - ϋ \ -

- (SOjX). _,

(I)

5 °

where A is the residue of an organic dye, B is an aryl residue containing at most two benzene rings or the residue of a monoazo dye, X is a hydrogen atom or the equivalent of a cation, Y is an aylable amino group and> 1 and /> are positive integers, where in at most 2 and /> and //; together should be at least 1. '· "With a compound containing at least two al> anion easily abspallbare radicals, condensed under conditions such that in the (" Condensationsprodukt such as anion lcitltl cleavable Resl is obtained at least. Mil or an encryption'^'s bond, It contains a residue capable of conducting conductive addition and at least one C ('-. Meliifachhiud.uiig contained therein condensed under such conditions that at least one addition-capable multiple bond is obtained in the condensation product.

Compounds which contain a residue that can easily be split off as an anion and furthermore either at least one or at least one C — C multiple bond capable of addition are primarily halides and sometimes anhydrides of mobile halogen or Aliphatic carboxylic acids capable of addition, containing C --- C double bonds, are examples of the halides or anhydrite of chloroacetic acid, bromoacetic acid, / i'-clilo and // - bromopropionic acid, propiolic acid, acrylic acid and methacrylic acid, tier <i- or // - chloro- odi -bromoacrylic acid, the «, / i'-dichloro- or -dibronic acid, tier", />'-or; -chloro- or bromocroloic acid, tier ", // -Dichlorocrolonic acid and if necessary chlorinated or brominated maleic or Fiiniai acid called. Preferred compounds with at least two radicals that can easily be split off as anions are the cyclic imide polyhalides, which are the reactive grouping

N == C

halogen

included several times. As such come first and foremost Halogenazine compounds of aromatic character ter into consideration which at least two tertiary ring N-Atomc and on these adjacent ring-C-atomsei contain at least two mobile halogen atoms of atomic numbers 17 to 35, so for example 2,4,6-trichloro-otler -tribromo-I ^ .S-triazine, 2-alkoxy-, 2-alkyl, 2-phenyl, 2-amino, 2-alkylamino, 2-phenylamino, 2-sulfophynylamino, 2-ureido or 2-guanidino-4,6-tlichlor- Otler -dibromo-1,3,5-triazine, 2,4- or 4,6-dichloro- or dihromopyrimidines, which are in the remaining positions further substituents, in particular further halogenamines or negative groups, such as nitro, acyl, cyano or even just alkyl or contain phenyl groups, and finally also tetrarneres Chlor- otler Bromcyan.

When reacting disulfimide dyes containing amino groups with the aforementioned polyvalent carboxylic acid halides! or carboxymide halides are to be chosen so that the reaction conditions are such that the premature exchange of mobile substituents occurs as a result of an excessively high pH of the reaction medium as a result of excessively high temperature. It is therefore advantageous to work with the aqueous solubilizing agents of the alkali metal salts which can be used according to the purpose at temperatures and pI values which are as constant as possible. As mineral acid deadening agents it is advantageous to use buffer salts, e.g. B. Alkali salts of lower fatty acids. The reaction temperature and animal pH who! The reaction conditions depend on the resistance of the acylation or azinylic compound or on the mobility of the residue to be split off as an anion. Temperatures from 0 to about (> () C and pII values of about 1 to K are possible. The acylic compounds are used in at least a small amount of the ocular ocular and, depending on the shell, in a fine dispersion! , for example as Sus Pensions ndri ΙίιηιΚχίιγμ !! cgcbenciilaUs iiiiki

I 419 840

With the aid of inert, easily removable organic ones Solvents such as lower ketones. The acylic agent or azinyl agent is allowed to act for so long until the amino group to be acylated can no longer be detected, for example by diazotization and coupling, if it is a primary amino group, which is preferably the case. the Isolation and drying of the dyes according to the invention must also be done with caution, for example by salting out the Alkatisalzc with sodium chloride in neutral to weakly acidic Solution and by drying at a moderately elevated temperature and preferably in a vacuum.

A modification of the original procedure consists in that, if necessary, dye intermediates which already contain chromophoric groups, the total of one or two disulfimide - "groups with a substituted amino group, whose Substituent at least one easily cleavable radical as an anion or at least one easily for addition contains capable C — C multiple bond, in the remainder B have, converted into the corresponding dye under such conditions that in this still at least one bonded to the substituent of an amino group and easily split off as an anion Remainder or at least one easily capable of addition C — C multiple bond is obtained.

The modified process is used in particular for the production of azo dyes according to the invention Consideration. The procedure is that a diazonium compound is used and an azo component, which may already contain chromophoric groups and which have a total of one or two disulfimide groups with a substituted amino group, the substituent of which is at least one easily split off as an anion Contains radical or at least one easily capable of addition C — C multiple bond, in radical B have, coupled to the corresponding azo dye under such conditions that in this still at least one bonded to the substituent of an amino group and easily split off as an anion Remainder or at least one easily capable of addition C — C multiple bond obtained is.

Azo groups, for example, can be present as chromophoric groups, resulting in dis- or Polyazo dyes.

According to the general formula I, at least one disulfimide group to be used as starting materials and in B an appropriately primary, but optionally also acylatable secondary amino group containing dyes can belong to any classes of dyes. However, it comes here in the first place Line those classes of dyes into consideration which are technically easily accessible and by good Stability and fastness properties are excellent. For this reason, A in the general formula means I especially the remainder of an anthraquinone dye or the remainder of a metal-free or heavy metal-containing one Phthalocyanine dye or those of a nitro dye, and especially those of a optionally containing heavy metal azo dyes, the so-called under let / tereni term I onn; i / yl dyes are included. When the dyes that can be used as starting materials only have to have a single I) isulfimidgi lip They / vvccks contain sufficient water-soluble wedge a StilfonsauiVunippc : A total of three to four acidic, salt-forming water-solubilizing agents are generally advantageous Groups available.

From the following description of various groups of dyestuffs or from the information on their preparation it can be seen which dyes are primarily used as starting materials in the process according to the invention be considered.

In the preferred azo dyes, disulfimide groups according to the definition can be present in the remainder of the diazo components or in that of the azo component or in both radicals. In preferred Dyes, B is an optionally further substituted benzene radical and in particular the radical a monoazo dye. In the latter case too, dyes with good water solubility are obtained and low substantivity, which results in good washability of the unfixed dye. Such dyes are suitable for the production of brown tones, especially in the form of metal complexes.

The azo dyes containing disulfimide and acylatable amino groups are obtained, for example by coupling diazonium compounds with azo components, at least one of which at least one aryl disulfimide group and in the aryl radical B one convertible into an acylatable amino group Substituents, e.g. B. contains a nitro or saponifiable acylamino group, and subsequent reduction the meaning of the nitro to primary amino groups or saponification of the acylamino group B of a residue of a monoazo dye can also contain acylatable amino groups from the outset contain. The diazo components chosen are advantageously those of the benzene series, and if appropriate also those the naphthalene series, preferably hydroxynaphthalenes and / or aminonaphthalenes as azo components and their sulfonic acids and carboxylic acids as well as 5-amino or 5-hydroxypyrazole compounds. Contain the diazo and azo components still metallisable groups are obtained therefrom Azo dyes are advantageous before the substitution according to the invention of the amino groups with heavy metal the atomic numbers 24 to 29, so for example with copper, chromium or cobalt importing agents treated. Preferred heavy metal containing azo dyes are above all the complex copper, cobalt and chromium compounds of o, o'-dihydroxyazo and o-hydroxy-o'-carboxyazo dyes. In the case Of the chromium and cobalt compounds, 1 atom of heavy metal should advantageously account for 2 moles of basic dye. In the case of chromium complexes, only one of the two azo dyes bound to the chromium has to be used contain at least one disulfide group with an acylatable amino group in B.

The diazo or azo components containing disulfimide groups are for their part known per se Process by condensation of 1 mole of a sulfonic acid halide with 1 mole of a sulfonic acid amide group Connection in the presence of a

(*> Mineral acid binding agent available. Components with symmetrical structure with respect to the disulfimide group can also be obtained by condensation of 2 moles of a compound containing sulfonic acid halide groups with 1 mole of ammonia or 1 mole of a

^{f <} 5 ammonia-releasing substance can be obtained. Aminophthaloeyanine dyes which can be used in accordance with the present invention and contain disulfiniidur groups are obtained, for example from optionally also sulphonic acid groups

Pen-containing and advantageously copper-containing phthalocyanine sulfonic acid halides by condensation with nitro groups or saponifiable acylamino groups containing arylsulfonic acid camides in the presence of an acid-binding agent and the following Reduction of the nitro or saponification of acylamino to amino groups. Further that can be used according to the invention Phthalocyanine dyes are obtained, for. B. by condensation of Phthalocyaninsulfonsäurehalogenidcn with organic, advantageously aromatic amino compounds, which already have at least one Disulfimidgruppc and a nitro or saponifiable Acylaminogruppc contain, whereupon in turn Reduced nitro groups or saponified the acylamino groups.

Nitro dyes which can be used according to the invention are, for. B. by condensation of aminodiarylaminosulfonic acids or similar p-phenylenediamine derivatives with reactive halogen-containing nitrodiaryldisulfimides, which still have a hydrolyzable acylamino group, and subsequent saponification this acylamino group available.

In a similar way one obtains z. B. according to the invention usable anthraquinone dyes Condensation of aminodisulfimide compounds containing nitro or saponifiable acylamino groups with anhraquinones having reactive substituents, for example with 1-amino-4-bromoanthraquinone-2-sulfonic acid or one halogenated or sulfated in the 6- and / or 7-position Derived from the same, whereupon the nitro groups are reduced to amino groups or the acylamino groups saponified.

The new dyes according to the invention correspond the general formula II

A- / SO ₂ - N-SO ₂

- (SO ₃ X), _,

(H)

wherein A is the residue of an organic dye, B is an aryl residue containing at most two benzene rings or the residue of a monoazo dye, X is a hydrogen atom or the equivalent of a cation, Z is a substituted amino group whose substitution is at least one residue that can be easily removed as an anion or at least one easily for addition contains capable C — C multiple bond, and m and ρ denote positive integers, where m should be at most 2 and ρ and m together should be at least 3.

The dyes obtainable according to the invention are readily soluble in water and are eminently suitable for Dyeing and printing of hydroxyl-containing fiber material, especially natural and regenerated Cellulose using agents that increase the pH. The ones with these new ones The pulp dyeings and prints obtained from dyes are very pure and, in particular, are excellent Wet fastness properties. The dyes are also suitable for dyeing and printing natural and synthetic polyamides such as wool, silk and synthetic polyamide fibers.

From what has been said above, it follows that among the dyes of the general formula II primarily the azo dyes and among these the at least one sulfonic acid group and only one single disulfimide group-containing mono- or disazo dyes are preferred. Preferred according to the invention Dyes also contain a radical B bonded to the disulfimide group Bcnzolrcsl. In particularly preferred cases, the radical B is the radical of a monoazo dye, in particular the remainder of a copper-containing o, o'-dihydroxymonoazo dye.

It should also be noted that dyes obtained by reacting amino compounds with tri- or

ίο Tetrahalopyrimidines may be made Are mixtures of isomers, with the pyrimidine radical probably predominantly in the 4-position is bound to the amino group.

Compared to the German patent specification 1 109 807, the German Auslegeschrift 1 017 303 and the Swiss patent 370 388 known next comparable reactive dyes, which reactive Amino groups bearing residues are bonded directly to the aromatic ring of the dye structure contain, the dyes obtainable according to the present process, which by reactive Residues of a substituted amino group via a phenyl disulfimide group on the aromatic ring of the dye structure contained bound, not only the advantage of a significantly better water solubility, but also significantly purer shades of the cotton dyes obtained with it:

In the following examples, parts are parts by weight; these are related to parts of volume like grams to the cubic centimeter. The temperatures are given in degrees.

Example I.

25.3 parts of 1-aminobenzene-2,5-disulfonic acid are dissolved neutrally in 3 (K) parts of water and diazotized with 25 parts of 30% strength hydrochloric acid and 6.9 parts of sodium nitrite at 0 ° to 2 ° while cooling with ice. The solution obtained is added to a solution, cooled to 0 ° to 5 °, of 57 parts of the sodium salt of 4-hydroxynaphthyl- (l) -3'-dichloropyrimidylaminophenyl- (r) -disulfimide in 4 (K) parts of water and coupling is carried out at pH Value from 6 to 7. After the coupling has ended, the dye of the formula

SO ₃ H

OH

= ^N YY \ Cl- P -, V ^ J Cl SO ₃ H T -NH - N = L SO ₂ —Ζ, j> NH
ι ^N I I.
SO ₂ Ϊ (X w-

precipitated by the addition of sodium chloride, filtered, washed with sodium chloride solution and dried at 40 to 50 in vacuo. It dissolves ^{easily ()} 5 in cold water with an orange-red color.

The preparation of the above-mentioned 4-hydroxynaphthy I - (1) - 3 '- dichloropyrimidylaminopheny 1 - (T) -disulfimide occurs through condensation of 1- [ρ-Το-

luenesulfonyloxy] - naphthalene - 4 - sulfonic acid amide with m-nitrobenzenesulfochloride, saponification of the toluenesulfonyloxy group, Reduction of the nitro compound and condensation of the amine obtained with 2,4,6-trichloropyrimidine.

If cotton is padded with a 1% g ^cn solution of this dye, which still contains 20 parts sodium carbonate and 200 parts urea per liter, at 50 ', the impregnated goods are dried, then heated to 140 to 160 "for 4 minutes and finally for 30 minutes Soaped at the boil for minutes, the result is a uniform, very washable, orange-red color.

According to this method, the diazotisables given in column II of the table below are obtained Amines and the azo components mentioned in column III dyes, the cotton in the colors listed in column V.

table

I. II III Acylic compound Acylation or
Azinylating agents IV ν No. Diazo component 1 -hydroxynaphthyl- (3) -
3'-aminophenyl- (l ') -
disulfimide 2,4,6-trichloro
pyrimidine PH value hue
on cotton 1 1-aminobenzene
2,4-disulfonic acid 1 -hydroxynaphthyl- (3) -
3'-amino-4'-sulfo-
phenyl (1 ') disulfimide / i-chlorocroton
acid chloride 7 to 8 orange 2 1-aminobenzene
2-sulfonic acid 2,4,6-trichloro
s-triazine 7 to 8 orange 3 1-aminobenzene-
2,5-disulfonic acid H _; CC CH ₁
OC N 5 to 6 yellow Q-SO ₂ NH ^Η2 ^ / i-chloropropion-
acid chloride 4th 2-amino-4'-chloro-
diphenyl
1,1 -disulfimide 1 -hydroxynaphthyl- (3) -
3'-aminophynyl- (l ') -
disulfimide 6 to 7 Red orange

Example 71.9 parts of the amino monoazo dye of the formula

HOjS

NH,

SO ₃ H

55

(obtained by coupling diazotised 2-amino-1-hydroxybenzene-4,6-disulfonic acid with 4-hydroxynaphthyl - (1) - 3 '- aminophenyl - (Γ) - disulfimide in alkaline medium and treatment of the aminomonoazo dye obtained with copper-releasing agents) are dissolved in 800 parts of water. To this solution are added at 40 to 50 '24 parts of tetrachloride

HO ₁ S

-Cu

-N = N

SO, NHSO,

pyrimidine and maintains the pH of the reaction solution by gradually adding dropwise sodium carbonate solution at 6 to 6.5. As soon as no amino monoazo dye is obtained by diazotizing and coupling a small sample is more detectable, the new dye becomes the formula

Cl

NH

SO ₃ H

SO, NHSO

deposited by adding sodium chloride, filtered off and dried in vacuo at 40 to 50 ". The dark powder dissolves in water with a red color.

Cotton is padded with a 2% aqueous solution of this dye at 20 °, dried and then treated with a 1% sodium hydroxide solution which still contains 30 "/ ₀ sodium chloride, then steamed for 5 minutes at 100 to 103", then rinsed and Soaped at the boil for 30 minutes, the result is a real bordo-red color. Dyes with similar properties are obtained if, in place of the above amino monoazo dye, corresponding parts of the aminoazo dyes listed in Table 2 below are used and these are reacted with corresponding parts of the acylating or azinylating agents listed.

table

AminouzofurbstofT

l-Amino-2-hydroxybenzene-3,5-disulfonic acid - »l-hydroxynaphthyl- (4) -3'-aminophynyl- (r) -disulfimide

l-Amino-2-hydroxybenzene-3,5-disulfonic acid - > 2-hydroxynaphthyl- (6) -4'-aminophenyl- (l ') -disulfimide

l-aminobenzene-3-sulfonic acid - ♦ I-amino-2-hydroxy-5-methylbenzene - »2-Hydroxynaphthyl- (6) -3-aminophenyl- (l '(- disulfimide the same

4-Amino-5-hydroxy-2-methoxyphenyl- (1) -3'-nitrophenyl- (1 ') -disulfimide - * 1-Amino-8-hydroxynaphthalene-2,4-disulfonic acid, reduced

4-Amino-5-hydroxy-2-methoxyphenyl- (1) -3'-nitro-4-sulfophenyl- (1 ') -disulfimide - ♦ 1-Phenylamino-8-hydroxynaphthalene-4-sulfonic acid, reduced

2-aminophenyl- (l) -3-acetylaminophenyl ') -disulfimide - ¹ * i-amino-S-hydroxynaphthalene-6-sulfonic acid, saponified

3-Amino-4-sulfophenyl- (1) -3'-acetylaminophenyl- (1 ') -disuirimide - ♦ 2-Hydroxynaphthah'n-6,8-disulfonic acid, saponified - »1-amino-3-methylbenzoI

Complex-bound
Heavy metal

Cu
Cu
Cr

Co
Cu

Cu

Acylation or A / inylicrungsmittcl

2,4,5,6-tetrachloropyrimidine

2,4-dichloro-6-amino-s-triazine

/ i'-chloroacrylic acid chloride

// - chloropropionic acid chloride

2,4,5,6-tetrachloropyrimidine

2,4,6-trichlorotriazine

2,4,6-trichloro-5-bromopyrimidine

2,4,5,6-tetrachloropyrimidine

Color on cotton

Red Red Teal

Blue blue

blue

Red yellow orange

Example 3

HO NH-CO

SOjH

50.8 parts of condensation product of the formula

NH ₂

SO ₁

NH SC) ₁

Cl-

NH

are warm as sodium sulphide in 5 (K) parts of Wusser dissolved, acidified with 25 parts of 30% strength hydrochloric acid and treated with 6.9 parts of sodium nitrite at 5 to K). When the diazotization is complete, a neutralized solution of 42.3 parts of 1-benzoylamino is added to the mixture - 8 - hydroxynaphthalene - 3,6 - disulfonic acid in 2 (X) parts of water added and the solution at 10 up to 20 "with sodium bicarbonate to a pH of 7 to 7.5. After the coupling is complete the new dye precipitated with sodium chloride, filtered off and dried in vacuo at 50 to 60 ".

It is a red powder that easily dissolves in water with a red color.

The diazo component used in this example is prepared as follows: 32.7 parts of the known methods by condensation of 2-nitroben / ol-l-sulfochloride and 3-nitrobenzenesulfamide and subsequent reduction obtainable 2,3'-diaminodiphenyl-1,1'-disilfimides are suspended in 2 (X) parts of water and by adding sodium hydroxide at a pH 6.5 brought into solution. 21, X parts of 2,4,5,6-tetrachloropyriinidine are added to the solution and stir it at 30 ", adding dropwise sodium carbonate solution to the pll-Werl / wipe 6.5

11th

and 7 is held. After the reaction has ended, dyes with similar properties are obtained,

the condensation product by adding Na- if one aminodiphenyldisulfimidverbindungen.

Trium chloride deposited, filtered off and cooked which is obtained by condensation of the in column 2

salt solution washed. the following table with diamines each

Is cotton ° / _o solution of this 5 1 mol of the mentioned compounds in column 3 with a 2

Dye, which still contains 5% urea and 1% sodium, diazotized and with the in the column 4

contains carbonate, padded at 50 ", then at 80" azo components mentioned in column 5

dried, then coupled for 5 to 10 minutes specified pH values,
Steamed at 100 to 110 'and soaped at the boil, so

you get a pure red color, which is excellent io is washable and lightfast.

Table 3

Diamino compound

Acylation resp. Azo components pH of the hue Azinylating agents coupling on cotton 2,4,6-trichloro 1 -Benzoylamino-8-hy- 7 to 8 Red pyrimidine droxynaphthalene 4,6-disulfonic acid 2,4-dichloro-6-amino- 1 -Carbethoxyamino- 7 to 8 Red s-triazine 8-hydroxynaphthalene 3,6-disulfonic acid 2,4,5,6-tetrachloro 1-hydroxynaphthalene 7 to 8 Red orange pyrimidine 4,7-disulfonic acid 2,4-dichloropyrimidine 1-hydroxynaphthalene 7 to 8 Red orange 6-carboxylic acid 3,6-disulfonic acid chloride 2,4,5,6-tetrachloro 1 -Benzoylamino-8-hy- 7 to 8 Red pyrimidine droxynaphthalene 3,6-disulfonic acid 2,4,6-trichloro 1 -hydroxynaphthalene- 6 to 7 Orange red s-triazine 4-sulfonic acid 2,4-dichloro-6-phenyl- 1 -hydroxynaphthalene- 7 to 8 Orange red amino-s-triazine 4,6-disulfonic acid 3 - (> chloroethylsulf- 2-acetylamino-5-hy- 7 to 8 orange amyl) -benzoyl- droxynaphthalene chloride 7-sulfonic acid // - chlorocrotonic acid 1-hydroxynaphthalene 7 to 8 orange chloride 3-sulfonic acid // - chloropropionic acid 2-benzoylamifto-5-hy- 7 to 8 orange chloride droxynaphthalene
7- ^ ii ι Ifon <ίπ 11 rf * 2,4,5,6-tetrachloro / oUIIUIIjUUI Lf
2-hydroxynaphthalene 7 to 8 orange pyrimidine 6-sulfonic acid the same 2-hydroxynaphthalene 7 to 8 orange 6,8-disulfonic acid the same 2-BenzoyIamino-5-hy- 7 to 8 orange droxynaphthalene 7-sulfonic acid

2,3'-Diaminodiphenyl-Ι, Γ-disulfimide

the same

3 2,4'-diaminodiphenyl

Ι, Γ-disulfimide

4 the same.

3,3'-diamino-4-sulfodipheny 1-1,1'-disulfimide

6 the same.

7 3,4-diamino-4-sulfo-

diphenyl-l, l'-disulfimide desgl.

9 the same.

10 the same.

11 the same.

12 3,3'-diamino-4-sulfo-

diphenyl-l, l'-disulfimide

13 the same.

Cotton or rayon is printed using one of the usual methods with the following printing inks: 30 parts of the dye obtained according to Example 3,

2 (K) parts of urea,

4 (K) parts of water,

350 parts of sodium alginate, 5% aqueous solution,

20TeJ Ie potassium carbonate. • ν ί ^; '- ^: KKK) TeUe

N.; ieli <tom; Tiroekiieh is for 10 to 15 minutes neutrally subdued or at 145 for 5 minutes

Fixed to 150 ", then rinsed well and during Soaped at the boil for 30 minutes. You get one

pure red print that is extremely washable is. The printing ink described above is durable.

Example 4

HO, S-

50.8 parts of the condensation product described in Example 3 from 2,3'-diaminodiphynyl-1,1'-disulfimide and tetrachloropyrimidine are diazotized in the usual way and at a pH of 6 to 7 in the presence of sodium bicarbonate with 35.0 parts of 1 - (2 ', 5' - disulfophenyl) - 3 - methyl - 5 - pyrazolone 10 to 20 ^ coupled. The dye is made by adding separated from potassium chloride, filtered off and carefully dried in vacuo. He is hiring

ίο yellow powder that turns yellow in water in water solves.

If cotton is dyed with this dye under the conditions described in Example 3, the result is a very pure greenish yellow color that is extremely washable and lightfast.

Dyes with similar properties are obtained

if one uses the diaminodiphenyldisulfimide compounds listed in the following table in column 2 condensed with 1 mol of the acylating or azinylating agents mentioned in column 3, the condensation products diazotized and the diazonium compounds obtained according to the information in this example with the azo components described in column 4 couples.

table

Diamino bond

2,3'-diaminodiphenyl-1,1'-disulfimide
the same

the same

3,3-diaminodiphenyl-1,1'-disulfimide-4-sulfonic acid

the same

3,4'-Diaminodiphenyl-1,1-disulfimide-4-sulfonic acid . ·

Acylicrungs- b7w. Azinylation Millcl

. 2,4,6-trichloro-s-triazine / i-chloroacrylic acid chloride

2,4,6-trichloropyrimidine

2,4-dichloro-6-aminos-triazine

2,4-dich! Or-6-methoxy-

s-triazine chloromaleic acid azo components

1 - (2-chloro-5'-sulfophenyl) -3-methyl-5-pyrazolone

1 -Naphthyl- (2 ') -3-methyl-5-pyrazolone-4', 8'-disulfone-
acid

1- (2 ', 5'-disulfophenyl) -3-methyl-5-pyrazolone

S-methyl-S-pyrazolone

1- (2 ', 5'-dichloro-4'-suIfophenyl) -3-methyl-5-pyrazolone

1 - (4'-sulfophenyl) -3-methyl-5-pyrazolone

Hue on cotton

yellow
yellow

yellow
yellow

yellow
yellow

Example 5

SO ₃ H NH ₂

SO ₃ H

NH

55

60

NH ₂

52.8 parts of the by condensation of 3,4'-diaminodiphenyl - 1,1 '- disulfimide - 4 - sulfonic acid and 4,6-dichloro-2-amino-s-triazine produced diazo component are diazotized as usual. The suspension of the Diazoniumvci bond turns into a suspension registered of 25.1 parts of 2-amino-8-hydroxynaphthalene-6-sulfonic acid in 2 (X) parts of water and the coupling mixture is adjusted to a pH of 4 to 5 at 10 to 20 ° with sodium acetate. After the coupling has ended, the dye is precipitated by adding sodium chloride and filtered off and carefully dried in vacuo.

It is a red powder that dissolves in water with a red color. ^N

If cotton is dyed with this dye under the conditions described in Example 3, this gives a washable red color.

Dyestuffs with similar properties are obtained if the in the following table in column 2 Listed diaminodiphenyl disulfimide compounds with 1 mol of the acylation mentioned in column 3 or azinylation agents are condensed, the condensation products are diazotized and the diazonium compounds obtained according to the information in this example with the azo components described in column 4 clutch.

15th i 41 y Ö4U 16 ! • 'arbton up
cotton orange Diaminuvcrbinduiip Table 5 Azo components No. 2,3'-diaminodiphenyl Ac-ylicrunps or
Azinylation millcl 2-aminonaphlhalin-5,7-di- orange t 1,1'-disulfimide 2,4,5,6-trachlor- sulfonic acid orange the same pyrimidine the same orange 2 the same 2,4,6-trichloropyrimidine the same. 3 2,3'-diamino-4-chloro 2,4,6-trichloro-s-triazine 2-aminonaphthalene-3,6-di- orange 4th diphenyl-1,1'-disulfimide / i-chlorocrotonic acid chloride sulfonic acid 3,4-diaminodiphynyl 2-aminonaphthalene-6-sulfone 5 1,1 -disulfimide-4-sulfone- 2,4,6-trichloro-5-bromo acid orange acid pyrimidine the same 2-aminonaphthalene-5-sulfone Red 6th / i-chloropropionic acid acid orange the same chloride 2-amino-8-hydroxynaphthalene
6-sulfonic acid 7th the same / i-chloroacrylic acid chloride 2-aminonaphthalene-7-sulfone 8th 2,4-dichloropyrimidyl acid c 6-carboxylic acid chloride

example

O NH

SO ₂ -NH-SO ₂

NH

20 parts of cyanuric chloride are dissolved in 100 parts of acetone by the condensation of 4-bromo-l-aminoanthra-

dissolved and the solution with rapid stirring to 40 quinone - 2 - sulfonic acid with 3,3 '- diaminodiphenyl

Poured 200 parts of ice water. The dye formed in this suspension l, i'-disulfimide-4-sulfonic acid

leaving a solution of 71.6 parts of the formula at 0 to 5

O NH

flow in 500 parts of water and at the same time ensures that the The pH of the mixture is 4 to 4.5. When the reaction has ended, the pH is adjusted to 7 and the new dye is precipitated by adding sodium chloride, then filtered and washed with saline washed. The dye, dried at 20 to 25 in a vacuum, is a blue powder. that dissolves in water with a blue loaf.

If cotton becomes a solution with 20 mil of the new 1 aibstoll untei addition of 15 parts Nalriiimcarbonat pio 1000 parts FIoIIc padded.

NH,

SO ₂ -NH-SO,

SO ₃ H

rolled up and left to stand for 2 hours at room temperature rinsed and soaped at the boil for 30 minutes, you get a lightfast and washfast Coloration of a pure blue shade.

Similar dyes are obtained using the anthiachinone dye mentioned in this example by corresponding parts of one of the anthraquinone colors listed in the following table

(15 substances and the cyanuric chloride by an equivalent Amount of an aeration b / w mentioned in column 3. Λ / inylieiiingsniittels ersel / l.

109 614 2nd ^r 7th

17th

i y Ö4U

table

18th

Anllir; ichinonf; irbsl (> rf

O NH,

1 ι "

1 I) - ^s

O Nile

SUN, 11

- SO, Nile - SO,

O Nile,

V-SO ₁ II

O NH

NH,

SO, - NH - SO, - ■

O NH,

SOjH

SO ₁ H

O NH

SO, - NH - SO, -

SO ₃ H

O NH

SO, - NIi SO,

O NH ₂

( j S (), H

O Nile /

O Nile,

Il I (( j «μι

SO, Nile SO,

Si) ₁ II

O Nile

SO, Nile SO, ^y

Ac) IiLTiHIgS- b / w.
A / iii) ÜLTiiiigsmitlL'l liirblon on
Diiiiinwollc 2,4,5,6-Tclra-
chlorpyriiniclii “Hiii 2,4,6-trichloro
pyrimitlin purple / * '- Chlorcrot () ii-
acid chloride blue 2-AmiiH) -4,6-di-
chloro-s-triazine blue SO ₁ H / i-C'hlorpropioii-
sulfur chloride blue 2,4, \ (> - Tclra-
chlorpyriinicliii purple

Example 7

57.6 parts of copper phthalocyanine are heated to 145 parts in 270 parts of chlorosulfonic acid for 3 hours. The mixture is then allowed to cool to 75 and 33.5 parts of thionyl chloride are inoculated into it over the course of one hour. It is stirred for a further 3 hours at 70 ° to 75 °, then allowed to cool to room temperature, then poured onto 1500 parts of ice. The resulting Suspen..ion is filtered and washed precipitate with eggs 500'TCiIcIi l "/ _o hydrochloric acid. The filter cake is then slurried in 500 parts water and 300 parts F.is and the suspension with dilute sodium hydroxide to a pH of 7. A solution of 40.4 parts of 3-nitrobenzenesulfainide in 400 parts of water, which has been adjusted with sodium hydroxide solution to a pH of 9. The temperature is increased to 60 to 65 'and the pH is maintained, is poured into this Addition of dilute sodium carbonate solution to 8 to 8.5. If this pH value remains constant, the reaction solution is allowed to cool to 40 "and 120 parts of sodium hydrosulfite are added in portions to reduce the nitro group Caustic soda to 8 holds. Now the mixture is acidified with hydrochloric acid, heated, the

Dye precipitated by adding sodium chloride, filtered off and 500 parts of weak hydrochloric acid Brine I () "/" washed. The filter cake is stirred one in 1000 parts of water and the pH is adjusted to 6 * 5 by adding sodium hydroxide solution. to 25 parts of 2,4,5,6-tetrachloropyrimidine and the temperature are added to this solution with stirring increased to 60 to 65. By adding

ίο the dilute sodium carbonate solution is kept pH of the mixture between 5 and 6.5. When no more primary amino groups can be detected the dye is salted out, filtered and dried at 60 in vacuo.

is If cotton is mixed with an aqueous solution of the Dye impregnated according to the information in Example 1 in the presence of sodium carbonate and urea, squeezed off and heated to 140 to 150 for 2 minutes, so obtained after soaking a pure blue color. The dyed material is very good moisture and lightfast.

If you replace the 2,4,5,6-tetrachloropyrimidine in this example by 18.5 parts of 2,4,6-trichloropyrimidine or 18.6 parts of 1,3,5-trichlorotriazine or 12.7 parts of i-chloropropionic acid chloride are obtained Dyes with similarly good properties.

Example 8

NO,

SO, - NH-SO, - <

HO ₁ S-

HO ₁ S-

NH

CO - CH
CH,

N / A'

67.3 parts of the aminoazo dye prepared by coupling 6-nitro-1-diazo-2-hydroxynaphthalene-4-sulfonic acid with 1-hydroxynaphthyl- (5) -3'-aminophenyl- (r) -disilfimide in the presence of sodium carbonate at 80 in 5 (K) parts of water. Sodium carbonate is added to the solution until its pH value is 10 to 11, and 44 parts of the I: I chromium complex of the monoazo dye from lI) iu / .o-2-hydroxyiiaphthulin-4-sulfonic acid and 2-hydroxynaphthalene are added. The mixture is stirred for 1 hour at 80 to 85 ", the pH being kept between 10 and II. It is then cooled to 20 to 30, the pH is adjusted to 6.5 to 7 with acetic acid and it is added within one hour with 1/2 parts of acrylic acid chloride Gradually adding sodium carbonate keeps the pH at 6.5 to 7. As soon as free amino groups can no longer be detected, the new dye is precipitated by adding sodium chloride, filtered off and in vacuo Dried at 40 to 45 ', it is a dark powder which dissolves in water with a gray color.

If cotton is padded with an aqueous solution of this dye which also contains 20 parts of sodium carbonate and 2 (1) parts of urea per KXK) parts of liquor at 50, the impregnated fabric is dried, then for 4 minutes to 140 to 160 heated and finally soaped at the boil for 30 minutes, the result is a uniform, washable, gray color.

NH

NO,

NH

OC ₂ H ₃

Nil - CO CH = C

40.2 parts of 3-nitro-4-chlorophynyl- (l) -4'-acetyl aminophenyl- (l ') -disulfimide and 30.8 parts of 4-amino-4'-ethoxy-1,1'-diphenylamino-2 sulfonic acid are dissolved neutral in 250 parts of water with sodium hydroxide solution, 14 parts of sodium acetate are added to the solution and the mixture is refluxed for several hours. The reaction mixture is made mimosa-alkaline with sodium hydroxide solution, a further 5 parts of sodium hydroxide are added and the mixture is heated until the acetylamino group has been saponified completely. It is adjusted to a pH of 6 to 6.5 with hydrochloric acid and 16.7 parts of chlorocrotonic acid chloride are added dropwise to it at a temperature of 20 to 30, a pH of 6 to 6 being achieved by adding soda solution , 5 is complied with. The dye is then precipitated by adding sodium chloride, filtered off and dried at 40 to 50 in vacuo. L ^; r represents a yellow powder that dissolves in water with a yellow color.

If cotton is mixed with a 2 "/" strength aqueous solution of this dye thickened by means of sodium alginate, which contains 2 (X) parts of urea and 20 parts of sodium carbonate per 1000 parts of liquor, impregnated, the goods after gentle drying steamed neutral for 5 to 10 minutes or for 5 minutes Heated to 130 to 150, soaped with hot, rinsed and dried, this gives a real yellow color Color of very good lightness.

MO., S

~ C

so } / '\ C. N - ι \ / N N N

Example K) SO, - NH- SO, - <

NH CO CU, CH, -Cl

26.9 parts of 2-amino-1-h) hydroxybenzene-4,6-disulfonic acid are diazotized indirectly using the usual method. The suspension of the diazonium bond is added dropwise, with thorough stirring, to a suspension of 20.4 parts of ethyl phenylformyl acetate in 2 (X) parts of water, 250 parts of dioxane and 10.5 parts by volume of a 10N sodium hydroxide solution in the presence such amounts of sodium carbonate at 0 to 15 "are given that after the entry of the diazonium compound the reaction mixture reacts weakly in a phenolphthalcine alkali. After the coupling is complete the reaction is adjusted to slightly brilliant alkaline by adding concentrated hydrochloric acid, diluted and / or heated to the boil. After adding so much caustic soda that it is strongly alkaline Reaction is ensured until the end of the saponification, the reaction mixture is 10 to 20 minutes kept at boiling temperature.

The solution of the saponification product is then made with glacial acetic acid and at 0 to 10 with a condensation product of 39% due to diazoticrene from 2,3'-diamino-l, l -diphynyldisiillimide and 1 mol / »- ('chloropropionic chloride obtained, neutrally placed dia / oniiiinsal / soliing united.

The coupling mixture is then mixed with a copper sulfate solution, corresponding to 7 parts of copper, offset. After briefly heating to 45, the copper-containing dye is made by adding sodium chloride precipitated, abfillricil. with sodium chloride solution washed and carefully dried in vacuo. It represents a dark powder that is dissolves in water with a blue color.

If cotton is impregnated with a 2% solution of this dye which contains 90 parts of urea per K) (K) parts of liquor, the goods are dried and then impregnated with a solution containing K) parts of K) parts of sodium hydroxide and 300 parts Contains sodium chloride, I minute at 100 to K) I
steamed, soaped at the boil, rinsed and dried, the result is a blue, washable color.

Dyes with similar properties are obtained if, instead of the condensation product, from 2.3'-Diamino-I.I '-diphenyldisulfimid and // - Chlorpiopionsätuechloiid equivalent amounts of the condensation products from 2,4-diamiiio-1, r-diplienyldisiilfimid and 2,4,6-tri- or 2,4.5.6-tertracliloipyrimidine or 2.4.6-trichloro-s-tria / in or 2.4-dichloro-6-amino-s-tiia / in used. :

SOjH

O - Cu - O - (.

C = C N = N

Example II > - SO ₁ NHSO,

/ N

SO ₁ H

34.3 parts of 4-hydroxy-3,3-diaminodiphenyl-lr-disulfimide are dissolved in 200 parts of water and tetrazotized with 50 parts of 30% strength hydrochloric acid and 13.8 parts of sodium nitrite at 0 to 5 ~. The yellow, Congo acidic tetrazo suspension is cooled to 0 to 5 in a solution of 38.4 parts of l-naphthyl- (2 ') - 3-methyl-5-pyrazolone-4'.8'-disulfonic acid (as alkali

salt present) in 100 parts of water, with
After the coupling has ended, the disazo dye has the formula

the pH of the coupling is kept at 4 to 5 by adding sodium acetate. After about The monoazodiazo dye has formed for 30 minutes and a suspension of 42 parts of 2-trichloropyrimidylamino-S-hydroxynaphthalene-V-sulfonic acid is added in 200 parts of water and at the same time increases the pH of the coupling to 8 to 9 by adding of sodium carbonate.

SO ₃ H

SO ₂ NHSO ₂

CH ₃

SO ₃ H

deposited by addition of sodium chloride, filtered off and washed with sodium chloride solution. The filter cake is dissolved in 2000 parts of water until neutral and 60 parts of crystallized copper sulfate in 400 parts of water are added. By adding 30 parts of crystalline Natriumacetal and a little acetic acid provides the solution to a pH value of 5. Then let mam FCEI a temperature of 4Ö ^C over 30 min J (JO parts 3% Wasserstöffsoperisxydiostmg zattöpfeS, The Dikapferkompfexfarbstoff is formed with the aid of Separated from sodium chloride, dried, washed with sodium chloride solution and dried. It is a brownish black powder which dissolves in water with a brown color.

The preparation of the used in this example Tetrazo component took place by condensation of 3-Nitro-4-chlorobenzene [ilfochtorid with 3-nitrobenzoI-sulfamide. Exchange of the balogenate for hydroxyl .by boiling «lit- sodium hydroxide solution for several hours or soda solution as well as reduction of the nitrate for Dianimo connection.

Zar production of wet-fast dyeings are used in a dye bath 2 Teife of the Bach example above ParbstofTs obtained dissolved in 40 parts of water.

One enters at 40 to 45 ^J with fOO parts of cotton and heated within 90 minutes to 90 with the poTtionwise addition vestt SOg sodium chloride per LiteT. After this time 2 g sodium carbonate per liter are added and for a further 60 minutes

Jarfft at this temperature. Then will

rinsed iittä 30! vfifltffen soaped at the boil. You get

A strong SefnS, washable water-boil-proof

brown coloring.

Man-obtained dyes with similar properties when in Kofomre 1 Table 7 below arfgefiihrteTi tetrazotized diamines önd with those indicated in column 2 and 3 clutch components in the order listed couples maxi and the heads as described in the example. The reactive component can already be bound at the two coupling components, but it can also be introduced later.

\ 096Um7

25th

- 1 »O

Table 7

26th

Dia minoverbincJ ung

4-IIydroxy-3,3'-diaminodiphenyl-1,1 '-disulfimide

the same

the same
the same

the same
the same

the same

4-hydroxy-3,4'-diaminodiphenyl-1,1 -disulfimide

the same

the same
the same

the same

the same

the same

1. A / o component

1-Naphthyl- (2 ') -3-methyl-5-pyr-azolone-4', 8'-disulfonic acid

1-naphthyl- (2> 3-methyl-5-pyrazolone-5 ', 7'-disulfonic acid

the same

1-naphthyl- (2> 3-methyl-5-pyrazolone-4 ', 8'-disulfonic acid

2-amino-6-hydroxynaphthalene-8-sulfonic acid

the same

the same

1-naphthyl- (2> 3-methyl-5-pyrazolone-4 ', 8'-disulfonic acid c

1-Naphthyl- (2 ') -3-methyl-S-pyrazolone-5', 7'-disilfonic acid

the same

1-Naphthyl- (2 ') -3-methyl-5-pyrazolone-4', 8'-disulfonic acid

the same

1-Naphthyl- (2 ') - -Vnicthyl-5-pyra / olone-5', 7'-disulfonic acid c

2-amino-6-hydroxynaphthalene-8-sulfonic acid

the same

2. A / okoniponcntc

2-Aniino-5-hydroxynaphthalene-7-sulfonic acid

the same

2-amino-8-hydroxynaphthalene 6-sulfonic acids

dcsul.

1-Naphthyl- (2) -3-methyl-5-pyra / olone-4 ', 8'-disilfonic acid

1-Naphthyl- (2 ') -3-methyl-5-pyr-azolone-5'.7'-disulfonic acid

the same

2-amino-5-hydroxynaphthalene 7-sulfonic acid

the same

the same

2-amino-8-hydroxynaphthalene 6-sulfonic acid

desgl. de, sgl.

1-Naphthyl- (2 ') - i-methyl-S-pyrazoli> n-4', 8'-disulfonic acid

I-naphthyl- (2 ') -3-methyl-5-pyra / olone-5', 7'-disulfonic acid

Acylicr b / w.
Λ / injlierunusmillcl

2.4.6-trichlorotriazine

2,4,5,6-tetrachloropyrimidine

dcsul.

desul.

the same

the same

2,4,6-trichlorotriazine

2,4,5,6-tetrachloropyriniidine

2,4,6-trichloropyriinidine

2,4,6-trichloro-s-triazine

2,4,5,6-tetrachloropyrimidine

// - chloropropionic acid chloride

2,4,5,6-trachloropyriniidine

2,4 /> - Trifhlor-s-triazin '

2,4,5,6- lelrachliirpyriinidin.; ·; - · :! '

Piirbum on cotton

Brown brown

Brown brown

Brown

Brown

Brown brown

Brown

Brown brown

Brown . Brown

Brown brown -

Claims (7)

Patent claims: 1. Process for the preparation of reactive dyes. ei a marked by, c! a (.i one uses a disulfimide group-containing dye of the general formula I A-ZSO ₂ - N. — SO, —B \ 1 χ υ I. (SO ₃ X) _11. , (D IO Λ the radical of an organic dye, B an aryl radical containing at most two benzene nuclei or the radical of a monoazo dye, X a hydrogen atom or the equivalent of a cation. Y is an acylatable amino group and in and /) are positive integers, where in should be at most 2 and / »and in together at least 3, condenses with a compound which contains at least two radicals which can be easily split off as anions under such conditions that im Condensation product still contains at least one such residue that can easily be split off as an anion, or with a compound which contains a residue that can easily be split off as an anion and at least one C - C multiple bond capable of addition is condensed under such conditions that in the condensation product at least a multiple bond capable of addition is obtained. 2. Modification of the method according to claim 1, characterized in that optionally Dye intermediates which already contain chromophoric groups and which have a total of one or two disulfimide groups with one substituted amino group, the substituent of which is at least one easily split off as an anion Contains a remainder or at least one C - C multiple bond capable of addition, im Have radical B, converted into the corresponding dye under such conditions that in this still at least one bonded to the substituent of an amino group and as an anion easily cleavable residue or at least one C - C multiple bond which is easily capable of addition is preserved. 3. The method according to claim 2, characterized in that there is a diazonium compound and an azo component, which may already contain chromophoric groups and which in total 45 50 including one or two disulfimide groups with a substituted amino group, the substituent of which contains at least one easily cleavable radical as an anion or at least one C - C multiple bond easily capable of addition in radical B, under such conditions couples to the corresponding azo dye that in this at least one radical bonded to the substituent of an amino group and easily cleavable as an anion or at least one C -C multiple bond capable of addition is still obtained. 4. Process according to Claims I to 3, characterized in that the starting materials is chosen so that the reactive dyes prepared therefrom according to the invention are complexed Contains heavy metal with atomic numbers 24 to 29. 5. Process according to claims 1 to 4, characterized in that the starting materials so selected that the reactive dyes obtained therefrom according to the invention at least one Sulfonic acid group and only a single disulfimicl group containing mono- or disazo dyes are. 6. The method according to claim 1, characterized in that there is an aminoanthraquinone dye of the general formula I given in claim 1 with a compound which either at least two can be split off as anions Remainders or one such and at least one C - C multiple bond easily capable of addition contains, condensed under such conditions that in the condensation product at least a residue that can easily be split off as an anion or at least one easily capable of addition C-C multiple bond is obtained. 7. The method according to claim 1, characterized in that there is an aminophthalocyanine dye of the general formula I given in claim 1 with a compound which either at least two easily split off as anions Contains radicals or one such and at least one C - C multiple bond easily capable of addition, among such Condensed conditions that in the condensation product at least one easily split off as an anion Remainder or at least one C — C multiple bond easily capable of addition is obtained is.