CS216836B2 - Method of preparation of reactive dyes - Google Patents

Description

The invention relates to a process for the preparation of reactive dyes, in particular reactive disazo dyes containing a 2,5-disulfo-1,4-phenylene group.

Dyes containing a cellulose-reactive group and a 2,5-disulfo-1,4-phenylene group are known, for example, from British Patent Specification No. 1,093,354. Various reactive dyes containing a disulfo-1,3-phenylene group are also known from DE. DAS No. 1085,629. A new class of reactive dyes has now been found

2,5-diisulfo-1,4-phenylene group exhibiting surprisingly good properties, for example, they often combine high dyeing strength, good incorporation and good light fastness, in an unexpected extent with respect to dyes very related structure.

The reactive dyes of the general formula are prepared by the process according to the invention

Q — N (R) —E1 — N = N — D — N = N — E2 where is

A cellulose-reactive group selected from fluortriazinyl, cMortriazinyl or bromotriazinyl, chloropyrimidinyl or fluoropyrimidinyl, fluorisophthalonitrile, fluorocyanopyridine, chlorophthalazine or chloroquinazoline,

R is hydrogen, methyl, or. ethyl,

Ei sulfo-1,4-naphthylene or sulfo-1,4-phenylene optionally substituted with up to two of methyl, methoxy, ethoxy, NHCONHz, dichlorotriazinylamino, benzoylamino or acetylamino,

D 2 _! A 5-disulfo-1,4-phenylene group; and

E is 1-N-phenylamionaphthylamino having a phenyl ring optionally substituted by a chlorine atom, methyl, methoxy or dichlorotriabinylamino, wherein the naphthyl ring is substituted with 1 to 2 sulfocycles and optionally hydroxyl.

Examples of cellulose-reactive Q groups are, for example, 1,3-dicyanobenzene groups, such as 2,4-dicyano-3,5-difluoro-6-chlorophenyl, 2,4-dicyano-3,5-difluoro-6. -nitrophenyl, 2,4-dicyano-3,5,6-trichlorophenyl, 2,4-dicyano-3,5,6-trichlorophenyl, 2,4,6-tricyano-3,5-trichlorophenyl, 2,4,6 -tricyan-3,5-yl, 2,4-dichloroquinazoline-6-sulfonyl, 2,4-dichloroquinazoline-7216836

-sultonyl, 2,4,6-trichloroquinazoline-7-sulfoinyl, 2,4,6-trichloroquinazoline-8-sulfonyl, 2,4,7-trichloroquinazoline-6-sulfonyl, 2,4,8-trichloroquinazoline-6- sulfonyl, 2,4-dichloroquinazoline-6-carbonyl, l, 4-dichloro-6 rftalazin ^l-carbonyl, 2,4-dichloropyrimidine-5-carbonyl, activated 4,6-dihalopyridine-2-yl and 2,6-dihalopyridine -4-yl groups such as 3,4,5,6-tetrafluoro-pyridin-2-yl, 2,3,5,6-tetrafluoropyridin-4-yl, 2,5,6-trifluoro-3-cyanopyridine -4-yl,

2,5.6-trichloro-3-cyanopyridin-4-yl, 2,6-difluoro-3-cyano-5-chloropyridin-4-yl, 2,6-difluoro-3,5-dichloropyridin-4-yl, and, in particular, the triazinyl group and the pyrimidinyl group.

Particularly preferred pyrimidinyl groups are pyrimidin-2-yl or pyrimidin-4-yl groups having a cellulose-reactive atom or group, in particular a chlorine or fluorine atom, in at least one of the remaining positions 2, 4 and 6. At position 5, be various substituents, such as a chlorine atom or a cyano group, which are normally not reactive with cellulose as such, but promote the reactivity of the substituents at other positions of the pyrimidine core.

Specific cases of such pyrimidinyl groups include:

2,6-dichloropyrimidin-4-yl,

4,6-dichloropyrimidin-2-yl,

2.5.6-Trichloropyrimidin-4-yl

4.5.6- trichloropyrimidin-2-yl,

5-chloro-2-methylsulfonyl-6-methylpyrimidin-4-yl,

2,6-dichloro-5-cyanopyrimidin-4-yl,

4,6-dichloro-5-cyanopyrimidin-2-yl,

2,6-difluoro-5-chloropyrimidin-4-yl,

4,6-difluoro-5-chloropyrimidin-2-yl,

2,6-Difluoro-5-cyanopyrimidin-4-yl,

4,6-Difluoro-5-cyanopyrimidin-2-yl.

Examples of particularly preferred triazinyl groups include triazin-2-yl groups having cellulose-reactive atoms or groups in one or both of the 4 and 6 positions. In this case, various cellulose-reactive atoms or groups are preferred, but preferably reactive atoms or groups such as fluorine, bromine or especially chlorine.

Triazinyl groups having only one reactive atom or one reactive group on the nucleus at the 4 or 6 position may have a cellulose-non-reactive substituent at the 4 or 6 position.

Examples of such non-reactive substituents are alkylthio or arylthio, alkoxy or aryloxy and optionally substituted amino.

Preferred forms of such groups include lower alkoxy groups, i.e., C 1 -C 4 alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, and lower alkoxy lower alkoxy such as beta-methoxyethoxy, beta-ethoxy phenoxy and sulfophenoxy; an amino group further mentioned as suitable; lower alkylamino, such as methylamino, ethylamino, butylamino, di [lower alkyl) amino, e.g. dimethylamino, diethylamino, methylethylamino, dibutylamino, and the latter two types, in which the alkyl moieties are particularly substituted by hydroxyl, sulfonyl, cyano, such as beta-hydroxyethylamino, di (betahydroxyethyl) amino, beta-cyanoethylamino, di- (beta-cyanoethyl) amino, beta-sulfoethylamino, beta-hydroxypropylamino, (beta-hydroxybutyl-ethylamino) and (beta-hydroxyamino, methylaminoethyl) amino, such as, for example, cyclohexylamino, cyclic amino groups such as morpholino or piperazino, naphthylamino substituted with one, two or three sulfo groups of SO 2 H and optionally phenylamino.

A particularly preferred form of optionally substituted phenylamino is the groups of formula (2),

(II) where is

G is hydrogen, methyl, ethyl, ω-sulfomethyl, beta-carboxy, beta-hydroxy or beta-cyanoethyl and

Z and X are independently hydrogen, carboxyl, sulfo of SCbH, methyl, ethyl, methoxy, ethoxy, chloro, bromo, cyano, nitro, NHCOGH3, and beta-sulfatoethylsulfonyl.

Specific examples of such groups include anilino, o-sulfoanilino, m-sulfoanilino and p-sulfoanilino, o -carboxyanilino, n-carboxyanilino and p-carboxyanilino, 4-sulfo-2-carboxyanilino and

5-sulfo-2-carboxyanilino, 4-sulfo-o-tolylamino and 5-sulfo-o-tolylamino, 2,4-disulfoanilino, 2,5,5-disulfounilino and 3,5-disulfoanilino,

2,4-dicarboxyanilino, 4-sulfo-2-methoxyanilino and 5-sulfo-2-methoxyanilino, N-methyl-o-sulfoanilino, N-methyl-m-sulfoanilino and N-methyl-p-sulfoanilino, Ν-ω- sulfomethylani216836 linogroup, N- (beta-hydroxyethyl) -3-sulfoaniline-clamp.

Optionally, the cellulose reactive group Q may be in the form of the formula

Ht — Dm — Q ‘where is

Ht sym-triazine core containing a cellulose-reactive atom or group,

Dm diamine residue joining the proportion of Ht and Q ‘by two amino groups and

Q ‘a cellulose reactive group having the meaning given in the case of the symbol Q.

In particular, it is generally preferred that the cellulose-reactive atom or group in the moiety Ήί be a fluorine, bromine or especially chlorine atom and that Q ‘is the symtriazine residue defined above for the symbol Q.

The cellulose-reactive group Q may also take the form of a formula

--Hť — Dm — Q ‘where

D m and Q ‘are as defined above, and wherein H is a sym-triazine nucleus free of cellulose reactive atoms or groups, such as a 2,4-sym-triazinyl group having an optionally substituted amino group at the 6-position.

In the case where Q is a symtriazine nucleus containing a halogen atom and a non-reactive substituent, the non-reactive substituent may be a colored amine residue, for example azoads, anthraquinone series or phthalocyanine series, in particular residue 1, but without Q, so dye as a whole it comprises two radicals of the general formula 1 without the group Q, linked by a halogen-sym-triazine group or two such groups bonded via two halogen-sym-triazine groups and the above-mentioned group Dm. In such dyes, the halogen atom may be a fluorine or bromine atom, but is generally preferably a chlorine atom.

Examples of diamines of the formula DmH2 wherein Dm is as defined above and which may provide a residue Dm include heterocyclic diamines such as piperazine, aliphatic diamines such as alkylenediamines, hydroxyalkylenediamines or sulfatoalkylenediamines, especially diamines with 2 to 6 carbon atoms such as ethylenediamine,

1,2-propylenediamine and 1,3-propylenediamine,

1,6-diaminohexane, beta-hydroxyethylaminoethylamine,

2-hydroxy-1,3-diaminopropane,

2-sulfato-1,3-diaminopropane, other alpha-diaminoaliphatic and ω-diaminoaliphatic compounds such as triethylenetetramine, di- (beta-aminoethyl ether), naphthylenediamine sulfonic acids such as e.g.

2,6-diaminonaphthalene-4,8-disulfonic acid, 1,5-diaminonaphthalene-3,7-disulfonic acid ^: and diamine derivatives of monocyclic and dicyclic benzene series compounds such as phenylenediamines and their monosulfonic and disulfonic acids such as for example m-phenylenediamine and p-phenylenediamine,

1,3-phenylenediamine-5-sulfonic acid p

1,3-phenylenediamine-4,6-disulfonic acid,

1,4-Phenylenediamine-2-sulfonic acid a

1,4-phenylenediamine-2,5-disulfonic acid, diamines of formula 3,

where p and q are always 0 or 1,

E is a direct bond or a group selected from the group consisting of SO2, oxygen, CH2, CH2, C2H2, C2H4, NH, NHCONH, such as

4,4'-diaminostilbene-2,2'-clisulfonic acid, benzidine-2-sulfonic acid and benzidine-2,2'-disulfonic acid, 3,3'-diaminodiphenyl urea, 4,4'-diaminodiphenyl urea, 4,4 ' -diaminodiphenylurea-2,2'-disulfonic acid,

4,4‘-diamihodiphenylureaBina-3,3‘-disulfonic acid,

4,4‘-diaminodiphenylamine-2-sulfonic acid,

4,4‘-diaminodiphenylmethane,

4,4‘-diaminodiphenylmethane-2,2‘-disulfonic acid,

4,4‘-diaminodiphenyl ether,

4,4‘-diaminodiphenylsulfone,

4,4‘-diaminodiphenylethane-2,2‘-disulfonic acid, and N-lower alkyl and N, N‘-di (lower alkyl) derivatives of the above diamines, such as:

4-Thethylaminoaniline-3-sulfonic acid, 4-ethylaminoaniline-3-sulfonic acid, N, N‘-dlmethyl-4,4‘-diammodiphenylamine-2-sulfonic acid.

Examples of the Ei symbol group include:

1.4- phenylene,

2-ureido-1,4-phenylene,

2-acetylamino-1,4-phenylene,

2-methyl-1,4-phenylene,

2-methyl-5-methoxy-1,4-phenylene,

2,5-dimethyl-1,4-phenylene,

3-methyl-1,4-phenylene,

2,5-drmethoxy-1,4-phenylene,

2-methoxy-1,4-phenylene,

3-methoxy-1,4-phenylene,

6-sulfo-1,4-naphthylene,

7-Sulfo-1,4-naphthylene,

8-sulfo-1,4-naphthylene,

2-dlhortriazinylamino-1,4-phenylene, it being assumed that in these examples the azo group is attached at the 1-position of the E 1 group.

Examples of the E2 symbol group are:

1-hydroxy-8-N-phenylamino-5-sulfonaphth-2-yl,

2-hydroxy-5-N-phenylamino-3-sulfonaphth-2-yl,

4-N-phenylamino-6-sulfonaphth-1-yl,

4-N-phenylamino-7-sulfonaphth-1-yl,

4-N-phenylamino-5-sulfonaphth-1-yl,

4-N-phenylamino-5,7-disulfonaphth-1-yl, 1-hydroxy-8-N-phenylamino-3-sulfonaphth-2-yl, 1-hydroxy-8-N-phenylamino-3,5-disulfonaphthalen- 2-yl, 1-hydroxy-8-N-phenylamino-3,6-disulfonaphth-2-yl, 1-hydroxy-N-SCmethylphenylamino-seculfenes-2-yl, 1-hydroxy-8-N-2 ' methyl-phenylamino-3,6-disulfonaphth-2-yl, 1-hydroxy-8-N-3'-methylphenylamino-3,5-disulfonaphth-2-yl, 1-hydroxy-8-N-4'-methoxyphenylamino- 3,6-disulfonaphth-2-yl, 1-hydroxy-8-N-3'-methoxyphenylamino-3,5-disulfonaphth-2-yl, 1-hydroxy-5-N-4'-methylphenylamino-3-sulfonaphthyl- 2-yl, 1-hydroxy-5-N-3'-methylphenylamino-3-sulfonaphth-2-yl, 1-hydroxy-8-N-phenylaniino-5-sulfonaphth-2-yl, 1-hydroxy-8-N -phenylamino-3-sulfonaphth-2-yl, 1-hydroxy-8-N-3'-2 ", 4" -dichloro-sym-triazin-6 "-ylaminophenylamino-3,6-disulfonaphth-2-yl, 1 -hydroxy-8-N-4 ', 2 ", 4" -dichloro-sym-triazin-6 "-ylaminophenylamino-3,6-disulfonate-2-yl, 1-hydroxy-8-N-4', 2 ", 4" -dichloro-sym-triazin-6 "-ylaminophenylamino-3,5-disulfonaphth-2-yl and,

4-N-4 ‘, 2“, 4 ich -dichlo-t-sym-triazin-6--ylaminophenylamino-5-sulfonaphth-1-yl

4-N-4'-methylphenylamino-5-sulfonaphth-1-yl,

4-N-2‘-methylphenylamino-7-sulfonaphth-1-yl,

4-N-3‘-methylphenylamino-6-sulfonaphth-1-yl;

4-N-4‘-methylphenylamino-5,7-disulfonaphth-1-yl,

4-N-4‘-methoxyphenylamino-5-sulfonaphth-1-yl.

From the above examples for the group

E2 clearly shows that this group may have substituents such as dichlorotriazinylamino that are reactive with cellulose. Therefore, in such cases, the dyes of Formula 1 may contain a second cellulose-reactive group in addition to the Q group.

A preferred class of dyes of the formula are dyes having one or more of the following characteristics:

a] Q represents a triazinyl or pyrimidine group,

b] R represents an ethyl or methyl group and in particular a hydrogen atom,

c] E 1 represents a group of the general formula

where it means

Y is hydrogen, methyl, or methoxy; and

X is hydrogen, methyl, methoxy, amino NH2, NHCOCH3, NHICONH2, wherein X is ortho to the azo group, or is

(C1) E2 represents a group of the formula

or a group of formulas

If the reactive group Q has the general formula

Ht — Dm — Q ‘where

Ht, Dm and Q ‘are as defined above, the compound of formula Qhal used in the above reaction has the general formula:

hal — Ht — Dm — Q ‘

him 2

This compound can be prepared by reacting a diamine of the formula

DmH2 with one mole of carbylsulfate or with a compound of formula wherein ring A is unsubstituted or has up to two substituents selected from the group consisting of amino, substituted amino, or especially methyl, methoxy or chloro, and NH is attached at the 1 or 4 position of the naphthalene core.

A particularly preferred group E2 is that of formula

wherein ring A has the above substituents and one of B ¹ and B ² is a sulfo group of SO 3 H and the other is hydrogen.

The process according to the invention is generally carried out in an aqueous medium, whereby the presence of an acid scavenger such as carbonate, bicarbonate or sodium hydroxide is desirable at a temperature appropriate to the reactivity of the compound of formula Qhal, generally at a temperature of D to 100 ° C.

Specific examples of the compounds of formula Qhal are apparent from the specific disclosure of the examples given for symbol Q. It is generally preferred that the halogen is chlorine. For example, the compound of formula Qhal is beta-chloropropionyl chloride, cyanuric chloride, methoxydichlorosymetriazine, 2,4,5, 8-tetrachloropyrimidine, etc., but in some cases hal may be another more suitable halogen such as fluorine, when fluorine is a cellulose-reactive substituent contained in the Q group, for example, the compound of formula Qhal may be 2,4,6-trifluoro-5-chloropyrimidine to introduce a difluoro-5-chloropyrimidinyl group.

Qhal as defined above and with one mole of the symtriazine compound of the general formula hal hal kdeυ where Y represents a cellulose-reactive group.

Preferably, Ht is chloro-sym-triazinyl, Y is chloro; for example, the aforementioned symtriazine compound is cyanuric chloride.

The dye base of formula 6

H. N (R) —E1 —N = N — D — N = N — E2 (6) wherein each symbol is as defined above, is obtained by monoacetylation of an amine of formula 5

by diazotization and coupling with the 1-N-phenylaminonaphthalene coupling component of the formula

E2H and hydrolysis to remove the acetyl group.

As such, the amines of formula 5 can be obtained by coupling the diazonium salt of 4216836

acetylaminoaniline-2,5-disulfonic acid with a paracopulative amine of formula

HEiNJRJH under conventional conditions for coupling in an acidic aqueous medium and removal of the acetyl group by hydrolysis, typically using a hot, aqueous alkali.

If the paracoplating amine of general formula

HEiN (R) H has a hydrolytically labile group such as an acetylamino or ureido group, it will also be hydrolyzed to convert, for example, to an amino group. The dyes in which the group E 1 has hydrolytically labile substieuents are obtained in a modified manner. For example, they can be prepared by coupling a paracopulation amine of the formula

HEiNJR1H with a diazonyl salt of 4-aminoaniline-2,5-disulfonic acid, although this generally results in a lower yield than from acetylaminodiazonium salts.

As examples of para-coupling amines of general formula

HEiNJRJH are mentioned for example:

aniline,

3-acetylaminoaniline,

3-ureidoaniline,

3-methylaniline,

2-methylaniline,

2i, 5-dimethylaniline,

2-methoxy-5-methylaniline,

2-methoxyaniline,

3-methoxyaniline,

3-acetylamino-6-methoxyaniline,

N-methylaniline,

N-ethylaniline,

3-methyl-N-ethylaniline, 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-8-sulfonic acid, 1-naphthylamine-6,8-disulfonic acid, 3-aminoaniline.

In cases where E1 in the amine of formula (5) is a substituted amino group in addition to the group of formula HN1 (R) -, this group may also react with Qhal or carbyl sulfate simultaneously with the N: H '(R) - group. This provides an intermediate for the process of the invention which leads to a compound of formula 1 in which E 1 is a cellulose-reactive group substituted by a cellulose reactive group, for example a dichlorotriazinylamino group, in addition to a group of the formula

However, Q-N (R1-Dye base of formula 6) can be conveniently obtained by a smaller number of diazotization steps of the 1,4-phenylenediamine-2,5-disulfonic acid amino group, coupling with the 1-N-phenylaminonaphthalene coupling component of formula E2H, diazotation of the second Or, 4-acetylaminoaniline-2,5-disulfonic acid can be diazotized and coupled to E2H, and the acetyl group can be removed by hydrolysis if the coupling is diazotized with 1,4-phenylenediamine. The phenylenediamino-2,5-disulfonic acid with E 2 H is unacceptably slow in each case The second diazotization and coupling with the compound HEiN (R) H is carried out as described above.

The dyes prepared as described above can be isolated by any method known in the art, for example by spray drying or precipitation and filtration.

The dyes of the invention contain sulfonic acid groups which carry water solubility and can be isolated with such free acid groups. In general, however, it is preferable to isolate them in the form of salts, especially alkali metal salts, especially sodium salts.

The dyes prepared by the process of the invention can be used to color a wide range of hydroxyl or ammonium containing textile materials, such as wool, silk, synthetic polyamides and natural or regenerated cellulose, such as cotton or viscose materials, by known methods for dyeing such water-soluble reactive dye materials, for example in the case of cellulosic materials, is preferably applied in conjunction with treatment with acid binding agents such as sodium hydroxide, carbonate, phosphate, silicate, or bicarbonate, which may be applied to textile materials prior to dye application , during or after the dye has been applied.

The dyes prepared by the process of the invention are valuable reactive dyes for cellulosic materials. In their use, dyes with good fastness to washing and to light are obtained. As a rule, they are characterized by great strength and ability to create rich shades.

The invention is illustrated by the following examples in which all parts are by weight and the weight / volume percentages are grams / 100 millimeters.

Example 1

To a solution of 14.3 parts of disodium 4-amino-4'-N-methylamino-2,5-disulphol, 1'-azobenzene in 2) 50 parts of water at 0-5 ° C was added 16.7 min. 2N aqueous sodium nitrite solution was added followed by concentrated hydrochloric acid to adjust the pH to 1. The mixture was stirred for half an hour at 0-5 ° C and then the excess nitrous acid was destroyed by the addition of sulfamic acid.

The above diazonium mixture is added to a neutral solution of 27.1 parts of disodium 1-N-phenylamino-8-naphthol-3,6-disulfonic acid in 200 parts of water together with 2N aqueous sodium carbonate solution to maintain the pH at 6.5- 7 and the mixture was stirred at 0-10 ° C for two hours. Sodium chloride (20% w / v) was added, the mixture was filtered, and the residue on the filter was then dried.

A neutral solution of the 8.31 mine tetrasodium salt of the N-methylaminodisazo compound so obtained in 800 parts of water is added to a stirred mixture of 1.75 parts of cyanuric chloride, 20 parts of acetone and 40 parts of ice and water, maintaining the pH at 6.5-7 by adding. 2N aqueous sodium carbonate solution and stirred at 0-10 ° C for three hours. Sodium chloride (10 ° / o w / v), the mixture was filtered and the residue on the filter is processed to a paste by adding about ^1, 66 parts of a mixture of 1 part dinatriummonohydrogenfosfátu and two parts potassium dihydrogen phosphate and then dried.

The dye thus obtained contains 1 atom of hydrolysable chlorine for each azo group present. When applied to cellulosic textile materials together with an acid binding agent, strong black tones are obtained.

Example 2

A diazonium salt was prepared from 31.2 parts of 4-aminoaniline-2,5-disulfonic acid disodium salt and added to a neutral solution of 44.3 parts of N-phenylamino-8-naphthol-3,6-disulfonic acid disodium salt in 300 parts. water together with a 3N aqueous sodium carbonate solution to adjust the pH to 6.5 to 7, and the coupling mixture is stirred at 0 to 5 ° až for 5 hours.

A portion of the above solution of 1-N-phenylamino-7-4'-amino-2 ', 5'-disulfophenylazo-8-naphthol-3,6-disulfonic acid (= 0.05 gmol) was diazotized at 0 to 0. 5 ° C by adding concentrated hydrochloric acid to adjust the pH to 2 and then adding 5N aqueous sodium nitrite solution to generate excess nitrous acid. The mixture was stirred for half an hour, then excess nitrous acid was then removed by addition of sulfamic acid.

Dissolve 6.9 parts of 2-methoxy-5-methylaniline in 40 parts of water by adding 10 parts of concentrated hydrochloric acid, cool the solution to 0-5 ° C and adjust its pH to 5 to 5 with a 3N aqueous sodium carbonate solution. 5.5.

The above diazonium mixture is added to said solution together with a 3N aqueous sodium carbonate solution to adjust the pH to 5 to 5.5 and the mixture is stirred for 6 hours to complete the coupling. A solution of 11.1 parts of cyanuric chloride in 75 parts of acetone together with 3N aqueous sodium carbonate solution is then added to the above aminodisazo compound thus prepared to adjust the pH of the mixture to 6 to 6.5 and stirred at 0 to 5 °. C for two hours. 21 parts of liquid ammonia (specific gravity 0.88) were added to the mixture and the mixture was stirred at 3 ° C for three hours. Sodium chloride (15% w / v) was added, the mixture was filtered, and the residue on the filter was then dried.

The following table gives additional examples of novel dyes prepared according to the invention as described in Example 2. The diazotized 4-aminoaniline-2,5-disulfonic acid is coupled to phenylaminonaphthalene to give the amino monoazo compound shown in column II. This aminomonoazo compound is diazotized and coupled to the β-coupling amine in column III. The aminodisazo compound thus obtained is condensed with the heterocyclic compound shown in column IV. If the amine is present in the salt V, it is reacted sequentially with the heterocyclic compound of column IV and then with the reaction product of the compounds of column II and III.

Color shades obtained on cellulosic textile materials are shown in column VI.

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Claims (1)

SUBJECT Process for preparing reactive dyes of the general formula (1), Q — N (R) —E1 — N = N — D — N = N — E2 (1) where is A cellulose-reactive group selected from the group consisting of fluorotriazinyl, chlorotriazinyl or triazolinyl, chlorpyrimidinyl or fluoropyrimidimyl, fluorisophthalonitrile, fluorocyanopyrldine, chlorophthalazine R is hydrogen, methyl or ethyl, Ei sulfo-1,4-naphthylene or sulfo-1,4-phenylene, optionally substituted with up to two groups selected from methyl, methoxy, ethoxy, NHGONHa, dichlorotriazinylamino, benzoylamino or acetylamino, the invention D 2,5-disulfo-1,4-phenylene; and E2 1-N-phenylamino-naphthylamino with ph. optionally substituted by a chlorine atom, methyl, methoxy, or dichlorotriazinylamino, wherein the naphthyl ring is substituted with 1 to 2 sulfo groups and optionally a hydroxyl group by reacting a compound of the formula Qhal wherein Q is as defined above and hal represents a halogen atom with a dye base of formula 6, H - N (R 1 - E ₁ - N = N - D - N - N - E ₂ (6) wherein D, E _1, E ₂ and R are as defined above.