CS216835B2 - Method of preparation of reactive dyes - Google Patents

Abstract

Reactive dyes of the formula Q-N(R)-E1-N=N-D-N=N-E2 (1> wherein Q is a cellulose reactive group, R is H or a C1-4 alkyl group optionally substituted by OH, CN, SO3H or OSO3H, E1 is an optionally substituted, 1,4-phenylene or 1,4-naphthylene group, D is a 2,5-disulpho-1,4-phenylene group, and E2 is an optionally substituted 1-N-phenylaminonaphthyl group. The dyes are valuable reactive dyes for cellulose showing good resistance to washing and light. They have good strength and build-up.

Description

The invention relates to a process for the preparation of reactive dyes of the formula I

Q — N (R) —Е, —N — N — D — N = N — E ₂ (1) where is

A cellulose-reactive group selected from the group consisting of fluorotriazine-lev, ch 1 ortho azin or 1 triazine, chloropyrimidinyl or fluoropyrimidine left, fluoride of t and I on it г left, fluorocyanopyridine, chlorothalaminic or chloroquinazoline,

R is hydrogen, methyl or ethyl,

E _{: 1} sulfo-1,4-naphthylene or sulfo-1,4-phenylene optionally substituted with up to two of methyl, methoxy, ethoxy, NHCONH2, dichlorotriazinylamino, benzoylamino or acetylamino,

D 2,5-disulfo-1,4-phenyl a

E 2 1-N-phenylamino-naphthylamino with a phenyl ring optionally substituted by chlorine, methyl, methoxy or dichlorotriazinylamino, wherein the naphthyl ring is substituted with 1 to 2 sulfo groups and optionally hydroxyl.

Examples of cellulose-reactive Q groups are, for example, 1,3-dicyanobenzene groups such as

2 ₅ 4-Dicyano-3,5-difluoro-o-chlorophenyl,

2,4-dicyano-3,5-difluoro-6-nitrophenyl,

2,4-dicyano-3,5,6-trifluorophenyl, 2,4-dicyclo-3,5,6-ЬсЬкнТепук ™,

2.4.6-Tricyan-3,5-difluorophenyl,

2.4.6-Tricyan-3,5-dichlorophenyl,

2,4-dichloroquinazoline-6-sulfonyl,

2,4-dichloroquinazoline-7-sulfenyl,

2.4.6- trichloroquinazoline-7-sulfonyl,

2.4.6- trichloroquinazoline-8-sulfonyl,

2.4.7- trichlorzinazole-6-sulfonic acid,

2.4.8- trichlorzinazole-6-sulfonyl,

2,4-Dichlorinazoline-6-carbonyl,

1,4-dichlorophthalazine-6-carbonyl,

2,4-dichloropyrimidine-5-carboxylic acid, activated 4,6-dihalopyridin-2-yl; and

2,6-dihalopyridin-4-yl groups such as

2.4.5.6-Tetra-4-fluoro-1H-2-yl

2.3 ₅ 5.6-Tetiafluoropyricim-4-yl,

2.5.6-Trifluoro-3-cyanopyridin-4-yl

2.5.6- trichloro-cyanopyricnib4-yl,

2,6-diCiuo 3Ayan-β-chloropyrimidin-4-ylyl,

2,6-difluoro-3,5-dichloro-pyridin-4-yl, and in particular the triazinyl group and the pyrimidinyl group.

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

Specific cases of such pyrimidipyl groups are as follows:

2,6-dlchioryyrimidin-4-yl,

4.6-dicOlorpyrimldip-2-yi,

2.5.6- trichloropyrimidin-4-yl,

4.5.6- trichlo ^! rpyrimidip-2-2-yl, 5-chloro-2-methylsulfopyl-6-methylpyrimidin-4-yl;

2,6-Dichloro-5-pyridylpyrimidip-4-yl;

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

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

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

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

4,6-Difluoro-5-yyanopyrimidin-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, a variety of cellulose-reactive atoms or groups are possible but preferably reactive atoms or groups such as fluorine, bromine or especially chlorine.

Triazipyl 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 include alkylthio or arylthio groups, alkoxy or aryloxy groups, and optionally substituted amino groups.

Preferred forms of such groups include lower aiУoxyskupipy, thus -alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, ^l botoxys Kupina and lower alkoxy lower -alkoxy, such as beta-methoxyethoxyskuyina, beta- ethoxyoxyethoxysУuyipa, phenoxy and suifofepoxysyl; furthermore ammonium is suitable; lower alkylamino, such as methylamiposkopipa, ethylamino, butylamino, di [lower alkylamino, for example dimethylamino, dlethylamino-amino, methylethylamino, dibutylamino or yyerazino-group; naphthylamino which the alkyl moieties are particularly substituted by a hydroxyl group, a cyano group or a sulfone of the formula SO3H, such as, for example, beta-hydroxyethylamino, di (beta-hydroxyethyl) amino, beta-acyapoethylamino amino, di- (beta-cyanoethyl) amino, beta-sulfoethylamino hydroxypropylamino, (beta-hydroxybutyl) ethylamino and (beta-hydroxyethyl) methylamino, cycloalkylamino such as cyclohexylamino; cyclic ampho groups, such as, for example, morpholipo group or piperazo group; naphthylamino substituted with one, two or three sulfo groups of the formula SO 3 H and optionally substituted phenylamino.

Particularly preferred forms of optionally substituted phenylamino groups include those of formula (2),

where it means

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

Z and X and P independently of one another are hydrogen, carboxyl, sulfo of SO3H, methyl, ethyl, methoxy, ethoxy, chlorine, bromine, cyapo, nitro, NHCOCH3 and beta-sulfatoethilsulfonyl.

Specific examples of such groups include apilipo, o-sulfoanilino, m-solfoanilino and p-solfoanilino, o -carboxyanilino, m-carboxyapilino, and p-carboxytniiino,

4-sulfo-2-carboxyapilipo a

P-sulfo-4-carboxianilinogroup,

4-sulfo-o-tolylamino group;

5-sulfo-o-toiylamlnoskuyina,

2.4- dlsuifoanШnoskopina,

2.5- dlsulfoapliinoskopina a

3,5- disulfoaul·l-no · skuyma

2,4-dicarboxyaniiinosine,

4-sulfo-2-methoxyamino a

5-sulfo-2-methoxyanimino,

N-methyl-o-sulfoamlmosyupine,

N-methyl-m-sulfoanilino a

N-methyl-p-sulfoanilino,

Ν-ω-sulfomethylanilino,

N- (beta-hydroxyethyl) -3-sulfoanilino.

Optionally, the cellulose-reactive group Q may be in the form of the general formula "Ht" Dm "Q" where

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

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

Q is a cellulose reactive group having the meaning given for Q.

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

Cellulose reactive. the Q group may also take the form of a 'H' 'Dm' Q 'where

Dm and Q 'have the above meaning and where they mean

This is a sym-triazine core, free from 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 azoadium, anthraquinone or phthalocyanine line, but especially a 1, but without Q, so that the dye as a whole it comprises two radicals of the general formula 1 without Q, linked by a halo-sym-triazine group or two such groups linked via two halo-sym-triazine groups, and the aforementioned group Dm. In such dyes, the halogen atom may be a fluorine or bromine atom, but is generally preferably a chlorine atom.

As examples of diamines of general formula

DMH2 where

Dm has the meaning given above, which may provide the remainder of Dm, as follows:

heterocyclic diamines, such as piperazine, aliphatic diamines, such as alkylenediamines, hydroxyalkylenediamines, or sulfatoalkylenediamines, but especially C 2 -C 6 diamines, such as ethylenediamine,

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

1,6-diaminohexane, beta-hydroxyethylamino-ethylamine,

2-hydroxy-1,3-diaminopropane,

2-sulfato-1,3-dlaminopropane, other alpha-diaminoaliphatic and ω-diaminoaliphatic compounds such as triethylenetetramine, di- (beta-aminoethyl) ether, naphthylenedlaminosulfonic acids such as 2,6-diamino-naphthalene-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 m-phenylenediamine and p-phenylenediamine,

1,3-Phenylenediamine-5-sulfonic acid a

1,3-phenylenediamine n-4,6-; isulfonic acid,

1,4-Phenylenediamyl-2-sulfonic acid a

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

where p and q are always 0 or 1

E a direct bond or a group selected from the group consisting of SO2, an oxygen atom, a methylene group CH2, a group of formula S2H2, C2H4, NH, NHCONH, such as

4,4'-diaminostilbeyt2,2'-disulfoyic acid, benzidine-2-sulfonic acid and beyzidium-2,2'-disulfonic acid, 3,3'-diaminodienyl urea, 4,4'-diaminodiphenylurea, 4,4'-diaminodiphenylurea 2,4,2 ' -disulfonic acid,

4,4´-diamiУodiSenylurea3,3´-disulfonic acid

4,4´-diaminodiSenylam-2-sulfonic acid,

4,4’tdiaminodiphenylmethay,

4,4'-diaminodifeyylmethay-2,2'-disulfoyic acid,

4,4´-diaminodifeyylether,

4,4´-diaminodiphenylsulfone,

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

4-methylaminoaniline-3-sulfonic acid,

4-ethylaminoaniline-3-sulfonic acid, N, N'-dimethyl-4,4'-diaminodiphenylamine-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-dimethoxy-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-dichlorotriazinylamino-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, 1-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-disulfonaphthyl- 2-yl, 1-hydroxy-8-N-phenylamino-3,6-disulfonaphth-2-yl, 1-hydroxy-8-N-3'-methylphenylamino-3,6-disulfo-2-yl, 1-hydroxy -8-N-2-methylphenylamino-3,6-disulphonaphth-2-yl, l-hydroxy-8-N-2 ', ^{5-dimethylamino-3,6-disulphonaphth-2-yl,} l-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-sulfonaphth-2-yl, 1-hydroxy-5-N-3'-methylphenylamino-3 -sulfonaphth-2-yl, 1-hydroxy-8-N-phenylamino-5-sulfonaphth-2-yl, 1-hydroxy-8-N-phenylamino-3-sulfonaphth-2-yl, 1-hydroxy-3-N 3'-2 ', 4' dichloro-s-triazin-6 "-ylaminofenylamino-3,6-disulphonaphth-2-yl, ^{l-hydroxy-8-N-4,} 2 ', 4' -dichloro- sym-triazin-6 "-ylaminophenylamino-3,6-disulfonaphth-2-yl, 1-hydroxy-8-4,2", 4 "-dichloro-sym-triazin-6" - y laminophenylamino-5-disulfonaphth-2-yl,

4-N-4 ', 2 ", 4" -dichloro-sym-triazine-6 "-ylaminophenylamino-5-sulfonaphth-1-yl,

^{4-N-4--methylfenylamino} 5-sulphonaphth-1-yl,

4-N-2'-methylphenylamino-7-sulfonaphthyl-

-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 group E2, it can be seen that this group may have substituents such as dichlorotriazinylamino group that are cellulose reactive. 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 formula 1 are dyes having one or more of the following characteristics:

a) Q represents a triazinyl or pyrimidinyl 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

X

where it means

Y is hydrogen, methyl, or methoxy; and

X is hydrogen, methyl, methoxy, amino NH2, NHCOCH3 or NHCONH2 wherein X is ortho to k azo or is a formula

It is treated with an acid and an alkali metal nitrite at a temperature of 0-5 ° C.

The amines of formula 4 themselves can be prepared by reacting an amine of formula 5

d) Ez means. group formula

or a group of formula

wherein ring Λ is unsubstituted or has up to two substituents selected from the group consisting of amino, substituted amino, or especially methyl, methoxy or chloro, and the NH group is attached at the 1 or 4 position of the naphthalene ring.

A particularly preferred group Ez is that of formula

where circle

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

According to the process of the invention, the dyes of formula 1 are prepared by coupling the diazonium salt of an amine of formula 4

GL-N (R) -E ₁ -N = N

with 1-N-phenylaminonaphthalene coupling component E 1 H, wherein Q, R, Et and E 2 are as defined above.

The reaction is generally carried out in an aqueous medium at a temperature of 0 to 20 ° C, generally with a pH setting of 6 to 8.

The diazonium salt of the amine of formula (4) may be prepared in a manner known per se, for example by reaction of the amine in aqueous medium.

with a compound of formula

Qhal where hal represents a halogen atom and

Q with a cellulose reactive group as defined above.

This reaction 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, typically at 0 to 109 ^° C.

Specific examples of the compounds of formula Qhal are apparent from the specific examples given above for 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, etc., but in some cases hal may be another more suitable halogen, such as fluorine if fluorine is with cellulose reactive substituent contained in the group Q, for example a compound of the formula · Qhal may be 2.4, ^and frifluor- ϋ-5-chloropyrimidine to introduce difluoro-5-chlorpyrimidinylové groups.

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 ‘

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

DmH2 with one mole of carbyla sulfate or with a compound of the formula

This is as defined above and with one mole of the symtriazine compound of the general formula halphal

where it means

Y is a cellulose-reactive group.

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

As such, the amines of formula 5 can be obtained by coupling the diazonium salt from 4-acetylammoaniline-2,5-disulfonic acid with the paracopulatory 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. Dyes in which the group E 1 has hydrolytically labile substituents are obtained in a modified manner. For example. may be prepared by coupling a paracopulatory amine of the general formula

HeiN (R) H with a diazonium salt of 4-ammoaniline-2,5-disulfonic acid, although this yields ¹ generally lower yield than from acetylaminodiazonium salts.

As examples of para-coupling amines of general formula

HeiNJRJH are mentioned for example:

aniline,

3-acetylaminoaniline,

3-ureidoamlin,

3-methylaniline, 2-methyl-2,5-dimethylaniline, 2-methoxy-5-methylaniline,

2-methoxyaniline,

3-methoxyaniline,

3-acetylamino-6-methoxyaniline,

N-methylaniline,

N-ethylaniline,

3-methyl-N-e1: hylanline, 1-naphthylamine-b-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-8-sulfonic acid,

3-aminoaniline.

In cases where. Ei in amine! of formula 5 represents a substituted amino group next to the group of formula

HN (R) -, this group can also react with Qhal or carbyl sulfate simultaneously with NH (R 1 -).

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

Q — N (R (-

In a particular case where Q is a halentriazinyl group having a colored amine residue and azoadium as a non-reactive substituent, this residue may be formed in parallel to the process. by. · The invention for coupling to E 2 H. To achieve this, in an amine of formula 4 in which Q is a triazinyl group with a substituent having a diazotable amino group, the amino group is tetrazotized and coupled with two moles of the coupling component. This method is particularly useful when the same coupling component is used for a substituent on the Q group to form the Ez group in Formula 1.

The dyes prepared by the methods described above can be isolated by any method known per se, for example by spray drying or precipitation and by filtration.

The dyes according to 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 according to the invention can be used to color a wide range of textile materials containing hydroxyl or amino groups 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 materials reactive dyes, for example in the case of a bed of lodged materials, are preferably applied in conjunction with the treatment with acid binding agents such as hydroxide, carbonate, phosphate, sodium silicate or bicarbonate 211635 which can be applied to the textile materials before, 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 following examples illustrate the invention in which all parts are by weight and percentages by weight / volume are grams / 100 milliliters.

Example 1

To a solution of 71 parts of 4-acetylamine-2,5-disulfoaniline disodium salt in 800 parts of water at 0-5 ° C was added 13.8 parts of sodium nitrite, followed by 36 ° Tw hydrochloric acid to adjust the pH of the mixture to 1,8. The diazotization mixture was stirred for half an hour at 0-5 ° C, then excess nitrous acid was removed by addition of sulfamic acid.

To the above diazonium mixture was added a solution of 30.6 parts of 2.5 - (4-hydroxyethoxy) aniline in 150 parts of water and 20 parts of 36 "Tw hydrochloric acid along with sodium acetate crystals to adjust the alkalinity to Congo red, The residue on the filter is suspended in 300 parts of water, 24 parts of sodium hydroxide pellets are added and the mixture is allowed to stir at 85-90 ° C for 5 hours.

The solution was neutralized to pH 5 by addition of hydrochloric acid, cooled to room temperature and the precipitate was filtered off.

A solution of 5.9 parts of 4,4'-diamino-4'-dimetlioxy-4'-disulfo-11'-azobenzene disodium salt thus obtained in 100 parts of water is added to a stirred suspension of 2.32 parts of cyanuric chloride, 10 parts of acetone and 20 parts of ice. The mixture is stirred for half an hour at 0-5 ° C, then the pH is raised to

6.5 to 7 by addition of 2N aqueous sodium carbonate solution. 0.86 parts of sodium nitrite is added, then 36 ° Tw hydrochloric acid is added to adjust the pH to 1.8, the mixture is stirred for half an hour at 0 to 5 ° C, then excess nitrous acid is removed by addition of sulfamic acid. . The above diazonium mixture was added with stirring to a solution of 5.7 parts of 1'-N-phenylaminomethyl-8-naphthyl-3,6-diisulfonic acid disodium salt in 100 parts of water, the pH being maintained at 6.5 to 7 by addition of sodium carbonate. The coupling mixture is stirred for two hours at 0-10 ° C and 3 parts of a buffer mixture consisting of 2 parts of potassium dihydrogen phosphate and 1 part of disodium monohydrogen phosphate are added, followed by the addition of 10% (w / v) sodium chloride. The mixture is filtered and the residue on the filter is dried.

The dye thus obtained contains 0.9 atoms of hydrolysed chlorine for each azo group contained. When applied to cellulosic textile materials together with treatment with an acid-binding agent, the dye is excellent in fiber bonding to give strong black shades with good wash and light fastness.

Example 2

The 4A (cis-amino-2,2'-diaminopheniline) diazotized, coupled to m-toluidine, and the resulting monoazo compound was hydrolyzed as described in Example 1.

To the solution so obtained of 10.7 parts of the disodium salt of ^{4,4-diamino-2-methyl-2'.5'-disuifo-l,} l'-azobenzene in 800 parts of water was added a solution of 6.2 parts of 5-cyano -2,4,6-Crichloropyrimidine in 30 parts of acetone and the mixture was stirred at 20 ° C for one hour and then the pH was raised to 5 by addition of 2N aqueous sodium carbonate solution. The solution is filtered and 1.75 parts of sodium nitrite are added to the filtrate at 0-10 ° C with stirring, then 36 ° Tw hydrochloric acid is added to adjust the pH to 1.8. The diazotization is allowed to proceed for half an hour at a temperature of - 0 to 10 ° C, then excess nitrous acid is removed by - 75g ® by addition of sulfamic acid.

The diazonium mixture was added with stirring to a solution of 11.5 parts of 1-N-phenylamino-8-naphtholc 3,6-disulfonic acid disodium salt in 200 parts of water, maintaining the pH at 6.5-7 by the addition of sodium carbonate. The mixture was stirred for three hours at 0-10 ° C, 10% (w / v) sodium choride was added, the mixture was filtered and the residue on the filter was then dried.

The dye obtained contains 0.9 atoms of hydrolysable chlorine for each azo group present. When applied to textile cellulosic materials together with the treatment with an acid-binding agent, strong black and wash-resistant blacks are obtained.

Example 3

The suspension of 2.32 parts of cyanuric chloride in 10 parts of acetone and 20 parts of ice used according to Example 1 is replaced with a neutral solution of 4.7 parts of sodium 3-suifocNc2'c4 ^, cdichlorosyme-triazine-6-amine in 120 parts of water and condensation of this sodium. salts with 4,4'-diammo-2, (E) -dimethoxyc2 ', 5'-disulio-1,1'-azoc benzene are carried out at a temperature of 40 to 45 degrees Celsius. The amine mono-mono compound thus obtained is cooled to 0 to 10 ° C, diazotized and coupled to a nylamino-aminophenol-3,6-disulfonic acid, generally as described in Examples 1-2.

Example 4

Neutral solution 4.65 parts. 4,4'-diammo-1'-diphenyl-2,2'-cis-sulfonated salts. of acid in 75 parts of water is added. to a stirred suspension of 4.64 parts of cyanuric chloride, 20 parts of acetone and 20 parts of ice, and the reaction mixture is stirred at 0-5 ° C for one hour while maintaining a pH of 6.5-7 by adding 2N aqueous sodium carbonate solution.

The bis-dichloro-sym-triazinylamino compound solution thus obtained is added to a solution of 5.3 parts of 4,4'-diamino-2-methyl-2 ', 5'-disulfo-1,1'-azobenzene disodium salt (prepared as described in the Example). 2) in 200 parts of water and the reaction mixture is heated at 35-40 ° C for one hour to complete the reaction. The reaction mixture was cooled to 0-5 ° C, diazotized and coupled to 1-N-phenylamino-8-hydroxynaphthalene-3,6-disulfonic acid as described in the previous examples.

Add 3 parts of a buffer mixture consisting of two parts of potassium dihydrogen phosphate and one part of disodium monohydrogen phosphate, then add 15% (w / v) sodium choride, filter the mixture and dry the residue on the filter.

The dye thus prepared contains 1.35 parts of hydrolysable chlorine for each azo group contained. When applied to cellulosic textile materials together with the treatment with an acid-binding agent, black shades are obtained with good laundering and light-fastness.

Example 5

5.9 parts of 4,4'-diamino - 2,5-dimethoxy-2 ^', 5'-disulfo-l, r-azobenzene is condensed with an equimolar amount of cyanuric chloride and the resulting dichloro-s-triazinylaminoazosloučenina was diazotised as described in of Example 1.

The diazonium salt thus obtained is added with stirring to a solution of 4.4 parts of 1-N-phenylaminonaphthalene-8-sulfonic acid sodium salt in 100 parts of water at 0-10 ° C, maintaining the pH of the mixture at 5 by the addition of sodium carbonate. The mixture is stirred at 0-10 ° C for two hours, then 3 parts of a buffer mixture consisting of two parts of potassium dihydrogen phosphate and one part of disodium monohydrogen phosphate are added, followed by 10% w / v sodium chloride. The mixture is filtered and the residue on the filter is then dried.

The dye thus obtained contains 0.9 atoms of hydrolysable chlorine for each azo group contained. When applied to cellulosic textile materials together with an acid binding agent, excellent incorporation into the fiber is achieved and a navy blue, wash-resistant and light-resistant shade is obtained.

Example 6

4,4'-Diamino-2,5-dimethoxy-2 ', 5'-disulfo-Ι, Γ-azobenzene was prepared and condensed with an equimolar proportion of cyanuric chloride as described in Example 1.

To a solution of 6.24 parts of the compound thus obtained in 150 parts of water was added a solution of 3.8 parts of methylamine in 15 parts of acetone, and the solution was stirred at 40-45 ° C for two hours at pH maintained at 7 by addition of 2N-aqueous solution. sodium carbonate. The solution is cooled to 0-5 ° C, 6.9 parts of sodium nitrite are added, and then the pH of the mixture is adjusted to 36 ° Tw with hydrochloric acid.

The diazotization is carried out to completion for one hour at 0 to 10 ° C, after which the excess nitrous acid is removed by the sulfamic acid.

The diazonine salt is added to a solution of 4.6 parts of 1-N-phenylamino-8-naphthol-4-disulfonic acid disodium salt in 100 parts of water, maintaining the pH at 6.5 to 7 by the addition of sodium carbonate. The mixture is stirred at 0-10 ° C for two hours, 10% (w / v) sodium chloride is added, the mixture is filtered and the residue on the filter is then dried.

The dye thus obtained contains 0.5 atoms of hydrolysable chlorine per azo group contained. When applied to cellulosic textile materials together with treatment with an acid-binding agent, strong black dyes are obtained with good washing and light fastness.

The following table provides additional examples of dyes prepared by the process of the invention. Proceed as described in the previous examples by preparing the diaminomonoazo compound shown in the column

II, by condensation of the diaminoazo compound with the equimolar proportion of the heterocyclic compound shown in column 111, diazotizing the amino monoazo compound thus obtained and coupling it with the equimolar portion of the coupling component shown in column 1V. If ammonia or amine is mentioned in column V, it is reacted with the reaction product of the substances of columns 11 and 111 prior to coupling as described in Example 6. The color shades are given in column V1 of the table.

Example Diaminoinone Compounds Heterocyclic Compound Coupling Ammoniacamine Hue

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Example Diaminomonoazo Compound Heterocyclic Compound Coupling Ammoniacamine Hue

25. 4-Amino-4'-N-methylamino-cyanuric chloride 1-N-phenylaminonaphthalene - nautical

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41. 4-Amino-4'-N-ethylamino-cyanuric chloride 1-N-phenylaminonaphthalene - nautical

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Example Diaminomonoazo Compound Heterocyclic Compound Coupling Ammoniacamine Hue

55. 4,4´-diamino-2-methyl-bis-1,4-, 4´-dichloro-sym-1-N-phenylamino-8-naphthol- - black

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56. 4,4´-diamino-2-methyl-bis-1,4-´, 4´-dichloro-syni-1-N-phenylamino-8-naphthol-ammonia black

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68. 4,4´-diamino-2-methyl-cyanuric chloride 1,37-methylphenylamino-8-naphthol-ammonia black

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69. ^{4,4-diamino-2-methyl-2,4-dichloro-6-methoxy-l,} 3'-methylphenylamino-8-naphtol - Black

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83. 4,4´-Diamino-2-methyl-5- 2,4-dichloro-6-methoxy-1-N-phenylamino-8-naphthol- - black

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94. 1-N-phenylamino-8-naphthol-4-sulfo-2-aminotoluene 4,4´-diamino-2-methyl-5-cyanuric chloride black

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124. 1,4'-Diamino-2-methyl-cyanuric chloride 1,4-methoxyphenylamino-8- black ammonia

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Example Diaminomonoazo compoundseye Heterocyclic Compound 'Coupling Component Ammoniacamine Hue

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Example Diaminomonoazo Compound Heterocyclic Compound Coupling Ammoniacamine Hue

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Example Diaminomonoazo Compound Heterocyclic Compound Coupling Ammoniacamine Hue

155. 4,4'-Diamino-2-methyl-5-cyanuric chloride 1-N-4'-methylphenylamino-2-naphthylamine-5,7-nautical

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Example 162

To a solution of 31.2 parts of 4-aminoaniline-2,5-disulfonic acid disodium salt in 400 parts of water was added concentrated hydrochloric acid to adjust the pH to 1.5 and the mixture was allowed to stir at 0-5 ° C. 52 parts of 2N aqueous sodium nitrite solution are added over 5 minutes, stirring is continued for another quarter of an hour and excess nitrous acid is removed by addition of sulfamic acid.

A suspension of 21 parts of m-ureidoaniline hydrochloride, 8 parts of thiourea and 1 part of cetylpyridinium bromide in 200 parts of water is added along with 5 parts of sodium acetate and the mixture is stirred for 24 hours at 0 to 10 degrees Celsius. Anhydrous soda was added to adjust the pH to 7, then sodium chloride (20% w / w, v / v) was added and the mixture was filtered, then the filter residue was squeezed anhydrous.

A solution of 2.32 parts of cyanuric chloride in 20 parts of acetone was added to a solution of 5.98 parts of the diaminomonoazo disodium salt thus obtained in 250 parts of water at 0-5 ° C and stirred for one hour. Add 6.25 parts of 2N aqueous sodium nitrite solution and adjust the pH to 1.8.

The mixture was stirred for half an hour and excess nitrous acid was then removed by the sulfamic acid addition. The above diazonium mixture is added to a stirred neutral solution of 5.48 parts of disodium N-phenylamino-8-naphthol-3,6-disulfonic acid disodium salt in 100 parts of water together with anhydrous sodium to maintain the pH at 7 and the coupling mixture is stirred at pH 7 and at 0 to 10 ° C for 3 hours. Sodium chloride (10% w / v) was added and the mixture was filtered. The filter residue is made into a paste with 1 part of a mixture containing 2 parts of potassium dihydrogen phosphate and 1 part of disodium monohydrogen 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, excellent incorporation is obtained and black shades are obtained with good light fastness and good wash fastness.

Using the method described in Example 162, the following diaminoazo dyes listed in column II are obtained by reaction with the heterocyclic compound listed in column III and optionally reaction with ammonia or amine listed in column V followed by diazotization and coupling with the coupling component listed in column IV. The shades of color obtained are shown in column VI.

Example Diaminomonoazo Compound Heterocyclic Compound Coupling Component Ammonia Amm

163. 4,4´fdlaminof2fureido-2 ´, 5´f куапигсЫо ^ l-N-eenylamino-8-naphthof - anlim black fdisulfo-l, Γ-azobenzene -3,6-i ^ ^ isulfonic acid 'X

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EXAMPLE Diammomoooazo Compound Heterocyclic Compound Coupling Component Amornacamine Decant

176. 4,4´-Diamino-2-acetylamino-cyanuric chloride 1,4-methylphenylamino-8- amomac black

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Example 179

To a solution of 12.48 parts of the disodium salt of 4-2 ', ^{4'-dichloro-s-triazin-6'-ylamine-4'-amino-2,5-dimethoxy-2, 5,} -disulfo-l, r- of azobenzene, prepared as described in Example 1, in 300 parts of water, a solution of 9.52 parts of 4,4'-diamino-2,5-dimethoxy-2 ', 5'-disullo-1'-azobenzene disodium salt is added in 250 parts of water are added and the reaction mixture is heated at 40 to 45 ° C for three hours while maintaining the pH at 7 by addition of 2N aqueous sodium carbonate solution.

The solution was cooled to 0-5 ° C, 2.76 parts sodium nitrite was added, and 36% hydrochloric acid was added to adjust the pH of the mixture to 1.8. The tetrazotizing mixture is stirred at 0-10 ° C for one hour with an excess of nitrous acid present, after which the excess nitrous acid is removed by addition of sulfamic acid.

The mixture is added with stirring to a neutral solution of 18 parts of 1 N-phenylamino-8-naphthol-3,6-disulfonic acid (i.e. 2 moles) in 700 parts of water at a temperature of 0-10 ° C, maintaining a pH of 6.5-7. by adding 2N aqueous sodium carbonate solution. The coupling mixture was stirred at 0-10 ° C for three hours, sodium chloride (18% w / v) was added and the mixture was filtered. The filter residue is then dried.

Claims (1)

Process for the preparation of reactive dyes of the general formula 1, Q - N (R) - E 1 - N = N - D - N = N - E 2 (1) where is A cellulose-reactive group selected from fluorotriazinyl, chlorotriazinyl 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, NHCONH 2, dichlorotriazinylamino, benzoylamino or acetylamino, D 2,5-disulfo-1,4-phenylene a The dye thus obtained contains 0.25 hydrolysable chlorine atoms for each azo group contained. Applying the dye to the cellulosic textile materials together with the treatment with the acid scavenger results in strong black shades having good light fastness and good wash fastness. Example 180 12.48 parts of 4-2 ', 4'-dichloro-sym-triazin-6 ^, -ylamino-4 ^, -amino-2,5-dimethoxy-2', 5'-disullo-1H-azobenzene disodium salt and 9 52 parts of the disodium salt of 4,4'-diamino-2,5-dimethoxy-2 ', ^5' - ^ j ^ i ^ i ^ L ^ ulco-K-azobenzene used in Example 179, substituting an equimolar amount of the disodium salt 4-2 ', 4'-dichloro-s-triazin-6'-ylamine-4'-amino-2-methyl-2', 5'-disulfo-Ι, Γ-azobenzene ^{4,4-diamino-2} -methyl-1'-azobenzene. The dye thus obtained is the same as the product of Example 159. Example 181 4,4'-diamino-2-methyl-2 ^', 5'-disulfo - r-azobenzene in Example 179 was replaced with an equimolar amount of the disodium salt of 4,4'-diamino-2-methyl-5-methoxy- ^{2, 5,} -disulfo-Ι, Γ-azobenzene. The dye thus obtained is the same as the product of Example 160, OF THE INVENTION A compound having a phenyl ring optionally substituted with a chlorine atom, methyl, methoxy or dichlorotriazinylamino, wherein the naphthyl ring is substituted with 1 to 2 sulfo groups and optionally a hydroxyl group, characterized in that the diazonium salt of the amine of formula 4 is coupled with ₃ h Q.-N (R 1 -E, -N = N 2 -, - NH ₂ ^{SO 4)} with 1-N-enylamino-naphthalenate coupling component E 2 H, wherein Q, R 1, E 1 and E 2 are as defined above.