DE2113298C3 - Reactive dyes and their use for dyeing and printing hydroxyl- or amide-containing fiber materials - Google Patents

Description

(A) ₁ ,

CH ₃

C = O

D-N = N-CH

SO ₃ H

wherein D has the meaning given in claim I. 3. Reactive dyes of the formula

A '

where A 'represents a hydrogen atom. a carboxylic acid or sulfonic acid group and X a Represents reactive group, soft at least one removable, paltable η substituent on a ('atom of a C - N bond of a five or five-membered triune aromatic-heterocyclic Contains ring housing.

The present invention relates to no Reactive dyes of the general formula

in which Q and P are hydrogen or a sulfonic acid group, but cannot have the same meaning at the same time, and D is a benzene or naphthalene nucleus, which is optionally replaced by A = -COOH, -SO ₃ H, -Cl, -Br, -NO ₂ , -CH ₃ , -OCH ₃ or -OC ₂ H ₅ and which, via a group —N (R) to a carbon atom of the benzene or naphthalene nucleus, contains one of the reactive groups which are identified in more detail in the description and which contain at least one contains removable substituents bound to a carbon atom of a —C = N bond of a 5- or 6-membered aromatic-heterocyclic ring, /? the number is 1 or 2 and R is hydrogen or QQ-alkyl.

2. reactive dyes of the formula

CH ₃

(A) _n
DN = N-CH

C-N-

Il ^H
ο

SO ₃ H

wherein Q and P are hydrogen or a sulfonic acid group mean, but not at the same time can have the same * meaning, D a benzene odei

,, Naphthalenefn, which is optionally durel · A = —COOH, -SO ₃ H, -Cl, -Br ₅ -NO ₂ , -CH ₃

OCH ₃ or —OC ₂ H ₅ may be substituted unc

which via a group -N (R) to a carbon atom de: benzene or naphthalene nucleus bound a dei

, o contains reactive groups that are closer to in the description

"are marked and which contains at least one cleavable substituent attached to a carbon atom: _C = N bond of a 5- or ö-membered aromatic-heterocyclic ring, η the

Number 1 or 2 and R stands for hydrogen or Q-Ct-alkyl.

Suitable reactive groups which have at least one removable substituent on a 5- or 6-member ring aromatic-heterocyclic ring to a carbon atom

contain a —C = N bond bound, sine those with a monoazine, diazine or triazine ring, such as a pyridine, pyrimidine, pyridazine-pyrazine, Thiazine, oxazine, sym.-triazine, quinoline-phthalazine, cinnoline, quinazoline or quinoxaline ring or a thiazole, thiadiazole, isothiazole-benzothiazole or benzoxazole ring.

Among the reactive substituents on the heterocycle, halogen (CI, Br or F) and ammonium should be mentioned including hydrazinium, sulfonium, sulfonyl, azi-

do- (N ₃ ), rhodanide thio, thioether, oxyether, sulfinic acid and sulfonic acid. Mono- or dihalogen-sym, for example, should be mentioned in detail. triazinyl radical, e.g. B.

2,4-dichlorotriazinyl-6-,

2-Amino-4-chlorotriaziazinyI-6-,

2-alkylamino-4-chlorotriazinyl-6-,

2-ethylamino- or 2-propyl-amino-4-chloro-triazinyI-6-,

2- / i-oxethylamine-4-chlorotriazinyl-6-,

2-di- / y-oxethylamino-4-chlorotriazinyl-6-

and the corresponding sulfuric acid half esters 2-diethylamino-4-chlorotriazinyl-6-,

2-morpholino- or 2-piperid'ino-4-chlorotri-

azyl-6-.

2-Cyclohexyl-amino-4-chlorine / in \ l- (i-.

2-arylaniino and subst. Arylammo-4-chiirln-.i / ynyl-6-. how

? .phen> lamino-4-chlürtria / in \ l-0-.

ί (ο- m- or p-Carbi> -., \ - or Suliuphcrr.li

; "mino-4-c: -. lorlriazinyl-6-.

) -Alkox> -4-chlorotriazine> 1-6-. v, ic

i.Methox) - or Athoxy-4-criiortria / in \! - 6-.

i- (PhenyLsulfonylmethox>) -4-Lh! ortriaxin \ 1-Ci-.

i-Arvloxv- and subst. Aryloxy-4-chloriri-

azinyl-6-. how
2.phenoxy-4 -'-- chloro-riazine \ l-6-.

2- (p-Su! Fo'phenyl) -oxy-4-thlorotriazine 1-6.

?. (o- m- or p-methyl- or Meihmy phenyl i-

o ^ hloririazinyl-o-

20th

Ikvl-mercapto- or 2-An! Mercapto- <»Dci i-lsubst. Ar (l) mercapto-4-chlorotriazinyl-6-. ail-9_I ^ hydroxyethyl) -mercapto-4-chl () r-ir! -

azinyi-6-,.

• j.phenylmercapto- ^ chlorotnazinyl-o-.

i ^ '- Me'.hyl-phenylhmercapto ^ -chlorotri-

azinyl-6- · ,,

^/ 7 ^? '4'-DiniEro> -pheny] mercapiü-4-chJ (> nr) -

azinyl-6-. · ·,

^ Methvl - ^ - chlor-tnaziny! ^ -.

i.phenyl ^ chloro-triazinyl-o-.

Mono-.' Di- or trihalogenpyimidiny 1 radicals.

like · -j- ι *

-> ^ dichloropyrimidinyl-ö-.

i ^ .S-Trichloropyrimidinyl-o-.
^ Dichloro-S-nitro- or -5-meth \ 1- or -5-carboxymethyl- or -5-carboxy- or -5-c> ano- or -5-vinyl- 'or -5-sulfo- or - 5-mono-. -di or -trichloromethyl- or -5-carboalkoxy-pyrimidi-

1 6-dichloropyriraidin-4-carbony i-.

T ^ dichloropyrimidine-S-carbonyl-.

TlchloM-methylpyrimidino-carbonyl-.

i-methyl- ^ chloropyrimidine-S-carbonyl-.

i-methylthio ^ -fluoropyrimidine-S-carbonyl-.

ö-methyl ^^ - dichloropyrimidino-carbonyl-.

"> 4.6-trichloropyrimidine-5-carbony 1-,

T ^ dichloropyrimidine-S-sulfonyl-.

i-chloroquinoxaline-S-carbonyl-.

2- or 3-monochloroquinoxaline-6-carbon \ l-.

"i. or 3-monochloro-quinoxaline-6-sulfone \ l-.

^ -Dichlorquinoxaline-o-carbonyl-.

vj-dichloroquinoxaline-o-sulfonyl-.

^ Dichlorophthalazine-o-sulfonyl- or -carbonyl-.

ι- or 3- or 4- (4 ', 5'-dichloropyridazon-6 ->! -;> ■ phenylsulfonyl- or -carbonyl. (j - ^'. S'-dichloropyridazon-o'-yl-'i Väihyl - _s

arbonyl-. . . ,. ,

N-methyl-N- (2,4-dichlorotnazinyl-6: -: arDam :. _! -.

N-methyl-N- (2-methylamino-4-chlorine azine> l-6tcarbamyl-,

N-methyl-N- (2-dimethyiamino-4-ch! Cnn- ₅ <

azinyl-oy-carbamyl-,

N-methyl- or N-ethyl-N-i2.4-dich] onn-

azinyl-6) -aminoacetyi-.

N-methyl-N- (2.3-dichloroquinoxaline-6-iulphone> ri-

arninoacetyl-. ^:

M-Meihy] -N- (2.3-dichlurchinoxa! In-6-ca: Nn> ι \ - aminoaceiyl

as well as the corresponding bromine υηα Muor-

Derivatives of the above-mentioned Mo ^ .r-wv ^ a'.iv heierocvclisch ^ n

wise

2-fluoro-4-py rimidiny I-.

2.6-Difluoro-4-pyrimidine> i-.

under 2.f> -DiHuor-5-i; hl (> r-4-p \ rimidiny I-, 2-fluoro-5,6-dichloro-4-pyrimidinyI-,

2 /> - Dif] uor-5-melhyl-4-py rimidiny I-, 2.j-Difluoro-6-methyl-4-pyrimidinyl-, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl.

2-Fli! Or-5-nitro-6-chloro-4-pyrimidinyl, S-bromo-Z-fluoro ^ -pyrimidinyl.

2-Flu (jr-5-cyano-4-pyrimidinyl.

2.5.6-Trifluoro-4-pyrimidinyl.

- ■) -Chlor-6-Chlormethyl-2-Nuor-4-pyrimidiny 2.6-Dinuor-5-bromo-pynmidinyl, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2 - ^ -! Uor-S-bromo-6-chloromethyl-4-pyrimidinyl.

2.6-Dinuor-5-ch] ormethyl-4-pyrimidinyl.

2.6-Difluoro-5-nitro-4-py rimidiny 1.

2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-net:, yl-4-pyrimidinyl.

2- F luor-S-chlor-o-methyM-py rimidiny 1, 2- fluorine-5-chloro-4-pyrimidiny 1.

2-F] uor-6-chloro-4-pyrimidinyl,

6-Trifluoromethyl-5-chloro-2-fluoro-4-pyrimidine \ l.

6-Trifluormethy 1-2-MuOr ^ -PyTJmJdInVl.

2fluoro-5-nitro-4-pyrimidinyl, 2-F] uoro-5-trifluoromethyl-4-pyrimidinyl.

2-F! Uor-5-phenyi- or -5-methylsulfonyl-4-p \ rimidinyl,

2-fluoro-5-carbonamido-4-pyrimidinyl, 2-Fuor-5-carbomethoxy-4-pyrimidinyl,

2-Fluoro-5-bromo-6-trifluoromeihyi-4-pyrimidine \ l.

2-fluor-6-carbonamido-4-pyrimidinyl.

2-fluoro-6-carbomethoxy-4-pyrimidinyl.

2-fluoro-6-phenyl-4-pyrimidinyl.

2-fluoro-6-cyano-4-pyrimidinyl,

2.6-Difluoro-5-methylsulfonyl-4-pyrimidinyl.

2-fluoro-5-sulfonamido-4-pyrimidinyK

2-fluoro-5-chloΓ-6-caΓbomethΰxy-4-pyπmidin ^ l.

2.6-Difluoro-5-trifluoromethyl-4-pyrimidinyl:

triazine radicals containing sulfonyl groups. such as 2.4-bis-i-phenylsulfonyl) -triazinyl-6-.

2-i3-Carboxyphenyi) -sulfonyl-4-chlorotriazinyl-6-,
2- (3 '-' sulfophenyl) sulfonyl-4-chlorotriazinyl-6-.

2.4-bis- (3'-carboxy-phenylsulfonyl-1) -triazinyl-6:

pyrimidine rings containing sulfonyl groups. how

2-carboxy-methyl-methyl-pyrmlidinyl-4.

2- ^ ethylsulfonyl-6-methyl-pyrimidinyi-4-.

2-methylsulfonyl-6-ethyl-pyrimidinyl-4.

2-phenylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4.

2,6-bis-methylsulfonyl-pyπmidinyl-4.

2,6-bis-methyl-sulfonyl-5-chloro-pyrimidinyl-4.

2,4-bis-methylsulfonyl-pyrilTlidine-5-sulfonyl.

2-methylsulfonyl-pyrimidiny 1-4.

2-PhCnVlSuIfOnVl-PyTImIdIn) I ^.

2-MeIhVlSuIfOnVlPyHmIdJnVl ^.

2-phenylsulfonyl-pyrimidinyl-4.

Z-trichloromethylsulfonyl-o-methy 1-pyrimidinyl-4.
2-meth>li.ulfone> l-5-chloro-6-methyl-pyr- ■ rnidinyl-4.

2-meth> isulforn l-5-bromo-6-meth> l-py r-; rnidm \! - 4.

Z.-MeihyKulfv.'iiyl - ^ - chlor-fi-äihxl-pNriniKliuvl-

: -Meth> lMilfonyi-5- ^ hliM-e> -chl. -rmciliy lp> ι irniiiin \ i-4.
; -Meih> Kulfoi -,>! - 4-chiiT- (i-meih \ lpM-i! IiiJ! N-

I-Methylsuironyl-S-nitro ^ -methyl-pyrimid.nvM. 2 5 o-Tris-methylsulfonyl-pyrimidinylA "" -Methylsulfonyl-S ^ -dimethyl-pynmidinyl ^ I-Ethylsulfonyl-S-chlor-o-methyl-pynmidinyl- * 2-methylsulfonyl-6-chloro-pynmidinyl-4

_,, -. · .Ii "..ir, 1 ς, .m, -» r_nuriminir

_N. Oxide of 4-chloro- or 4-nitroquinoline-5-carbonyl.

the preferred colors of the new color lofle Formulas

2-methylsulfonyl-6-carboxy-pyrimidinyl-4,

2-methylsulfonyl-5-.sulfo-pyrimidinyl-4,

2-Methyulfonyl-6-carboromethoxy-pyrimidinyl-4.

2-methylsulfonyl-5-caΓboxy-pyrimidinyl-4,

2-methylsulfonyl-5-cyano-6-methoxy-pyrimidinyl-4,

2-methylsulfonyl-5-chloro-pyrimidinyl-4,

2-sulfoethylsulfonyl-6-methyl-pyrimidinyl-4,

2-methylsulfonyl-5-bromo-pyrimidinyl-4,

^ -Phcnylsulfonyl-S-chlor-pyrirnidinyM,

2-carboxymethylsulfonyl-5-chloro-6-methylpyrimidinyl-4,
2-methylsulfonyl-6-chloropyrimidine-4- and -5-carbonyl,
2,6-bis (methylsulfonyl) pyrimidine-4- or -5-carbonyl-.
2-ethyl-sulfonyl-6-chloropyrimidine-5-carbonyl-,

2,4-bis (methylsulfonyl) pyrimidine-5-sulfonyl-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl- or carbonyl-;
triazine rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyi-6-. 2- (1,1-Dimethyl-hydraziniumM-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminolriazinyl-6-,

2- (2-Isopropylidene-l, l-dimethyl) -hydrazinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminot. iazinyl-6-,
2-N-aminopyrrolidinium- or 2-N-aminopiperidinium-4-phenyl-amino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, also 4-phenylamino- or 4- (sulfophenylamino ) -triazinyl-6 radicals, which in the 2-position via a nitrogen bond are 1,4-bis-aza-bicyclo-f2,2,2} -octane or 1,2-bis-aza-bicyclo -F 0, Contains 3,3 J-octane quaternary bonded, 2-pyridinium-4-phenylamino- or -4- (o-, n>. Or p-sulfophenyl) -amino-triazinyl-6- and corresponding 2-oniumtriazinyl-6 radicals, which are substituted in the 4-position by alkylamino, such as methylamino, ethylamino or / 5-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy or aroxy, such as phenoxy or sulfophenoxy groups;
2-chlorobenzothiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl-,

2-Arylsulfonyl- or -AlkylsulfonylDenzthiazol-5- or -6-carbonyl- or -5- or -6-sulfonyl-, such as 2-methylsulfonyl- or 2-ethylsulfonyl-benzthiazole-5- or -6-sulfonyl- or -carbonyl-, 2-phenylsulfonyl-benzthiazole-5- or -6-sulfonyl- or -carbonyl- and the corresponding sulfo groups in the fused-on benzene ring 2-sulfonylbenzthiazole-5- or -6-carbonyl- or -sulfonyl derivatives,

2-chlorobenzoxazole-S- or -6-carbonyl- or -sulfonyl-, 2-Ch! Q! Benz! Midazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-l-methylbenzimidazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-4-methylthiazole- (l, 3) -5-carbonyl- or -4- or -5-sul-

SO ₃ H

NH,

SO ₃ H

where D. A and / have the meaning given. CH ₃

25th

30th

35

40

45

50 A 'stands for a carboxylic acid or sulfonic acid group and X is a reactive group which has at least one of the above-mentioned removable substituents on a carbon atom _C = N bond of one of the 5 "or o-membered aromatic-heterocyclic compounds mentioned earlier Rinnes aebundcn contains.

A? S cleavable residues are specially named Halogen atoms (chlorine, bromine or fluorine ^ ammonium including hydrazinium, sulfonium, sulfonyl. Azido (N rhodanido, thio, thioether, oxyalher. The Sulfinic acid and sulfonic acid group ^

The new dyes are obtained by using the diazo compound of an amine of the formula

(A) _n
D-NH ₂

in which D A and η have the abovementioned meaning, with at least 1 mol of a coupling component the formula

55

(lO

wherein Q and P have the meaning given, vei agree The coupling takes place in a weakly acidic, net tral or weakly alkaline medium.

13 298

You can also prepare the compounds of the invention in such a way that one in a dye formula

(V)

where D represents the remainder of a diazo component free of reactive groups and Q and P have the abovementioned meaning, _{introduces a reactive group X into remainder D 1} by conventional methods, for example by condensation or acylation.

The procedure here is to use a dye of the formula

HN-D ₂ -N

in which R, Q, P and D _{2 have} the meaning given above, the grouping

NH
R.

by condensation with an at least bifunctional Reactive component X-Y '. wherein X has the abovementioned meaning and Y 'is anionic Removable group means into a remainder

-NX
I.
R.

in which R and X have the meanings given, converted.
The radicals D ₂ are, for example:

Phenylenes 1,3) or - (1,4).

2-sulfophynyl- (1.3) or - (1.4).

2-carboxy-phenylcn- (1,4).

2- or 3-carboxy-phenylene-6-methyloxy-4-sulfophynylene- (1,3).

5-methoxy-2-sulfophynyl- (1 A ).

2-methyl-5-sulfophenylene- (1.3).

2-chloro-phenylene- (1,4).

6-sulfonaphthylene- (1.4).

4.8-disulfonaphthylene- (2.6) - or - (2.5). (4.4Ί.

^Ί S-nisulfo-phcnyicn-0.4).

Suitable acetoacetic arylides are, for example, acetoacetic acid ^ -amino ^ .S-disulfoanilide. Acetoacetic acid-4-amino-2.5-disulfoaniid.

As amines

■ AL
D-NH ₂

For example, compounds of the type of the formula VIl to XVI come into consideration:

(VII)

NH-X

SO ₃ H

> -NH ₂

SO ₃ H

SO ₃ H

SO ₃ H

X-HN-f / -NH ₂

SO ₁ H

HO, S

J ■ /

HN,

X HN

(VIII)

(IX)

(Xl

(XI)

(XII)

(XIIIl

(XIVi

(XVi

SO ₁ H

COOH

ιο

X-HN

in which X has the meaning given above.

If one wishes to obtain color bodies of the formula VI, then suitable amines are coupled

(A) _n

ZD-NH ₂

wherein Z is a group -NH (R), or can be converted into such a group radical, in particular a nitro group, and D represents the above-mentioned loading, ₅ has importance, then the group converts, if necessary, Z in the group -NH (R) in order. Suitable amines are, for example:

5-nitro-2-aminobenzene-sulfonic acid, 4-nitro-1-aminobenzene, - °

4-nitro-2-chloro-1-amino-benzene, 6-nitro-2-amino-naphthalene-4,8-disulformic acid, 5-nitro-2-amino-l-carboxy-benzene, l-amino ^ -nitro-naphthalene-6- or 7-sulfonic acid-4, S-Nitro ^ -amino-1-methoxy-benzene-sulfonic acid-3.

The reaction of the color bodies of the formula VI with reactive components X-Y ', where X is the specified The meaning and Y 'represents a substituent which can be removed anionically is carried out in a manner known per se.

Suitable reactive components for this are X — Y ' for example those on which the aforementioned reactive groups X are based, d. H. generally the Halides, especially the chlorides of the acyl components mentioned X. From the large number of the for The available connections are mentioned here in excerpts:

Trihalogen-sym.-triazines, such as

Cyanuric chloride and cyanuric bromide, dihalo-monoamino- and -mono-substituted-amino-sym.-triazines, how

2,6-dichloro-4-aminotriazine,

2,6-dichloro-4-methylaminotriazine, 2,6-dichloro-4-ethylaminotriazine, 2,6-dichloro-4-oxethylaminotriazine.

2,6-dichloro-4-phenylaminotriazine, 2,6-dichloro-4- (o-, m- or p-sulfophenyl) -amino- _so

triazine,

2,6-dichloro-4- (2 ', 5'-. -2', 4'- or -3 ', 5'-disulfophynyl) aminotriazine,

Dihalo-alkoxy- and -aryloxy-syni.-triazines, such as

2,6-dichloro-4-methoxytriazine, 2,6-dichloro-4-ethoxytriazine,

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

2,6-dichloro-4- (o-, m- or p-sulfophenyl) -oxy-

Iriazin,

Dihalogen-alkylmcreapto- and -arylniercaplo-

sym.-triazine, like

2 / v dichloro-4-ethylmercapto-tria / in, 2,6-diehlor-4-phcnylmercapto-iriazine.

i.fvDichloM-ip-mctliylphcnyll-meri.-aploina / in: TetrahaloiiciipyrimidiiK ·. how

lcliiiLhlor-. Tut la brom- or Ί ciralUioi - p \ riini din.

2. -Ι, ίι- Ί IiIIiIIiILIi ¹ Ii-In liniiiliiKv like

45

(K) 2,4,6-trichloro-, -tribromo- or -trifluoropyrimi-

Dihalopyrimidines, such as 2,4-dichloro-, -dibromo- or -difluoropyrimidine; 2,4,6-Trichior-S-HiIrO- or -5-methyl- or -S-carbomethoxy- or -5-carboethoxy- or -5-carboxymethyl- or -5-mono-, -di- or -trichloromethyl- or -5-carboxy- or 5-sulfo- or -5-cyano- or -5-vinyl-pyrimidine, 2,4-difluoro-6-methylpyrimidine, 2,6-difluoro-4-methyl-5-chloro-pyrimidine, 2,4-difluoro-pyrimidine-5-ethylsulfone, 2,6-difluoro-4-chloropyrimidine, 2,4,6-trifluoro-5-chloro-pyrimidine,

2,6-difluoro-4-methyl-5-bromopyrimidine,

2,4-difluoro-5,6-dichloro- or -dibromopyrimidine,

4,6-DiHuOM ₁ S ^ iChIOr- or -dibromo-pyrimidine,

2,6- difluoro-4-brompy ri midi n,

2,4,6-trifluor-5-bromopynmidine,

2,4,6-trifluoro-S-chloromethylpyrimidine,

2,4,6-trifluoro-5-nitropyrimidine,

2,4,6-trifluoro-5-cyanopyrimidine,

2,4,6-Trifluoropyrimidine-5-carboxylic acid alkyl ester

or -5-carboxamides, 2,6-difluoro-5-methyl-4-chloropyrimidine,

2,6-difluoro-5-chloropyrimidine,

2,4,6-trifluoro-5-methylpyrimidine,

2,4,5-trifluoro-6-methylpyrimidine,

^ -Difluoro-S-nitro-o-chloropyrimidine,

2,4-difluoro-5-cyanopyrimidine,

2,4-difluoro-5-methylpyrimidine,

6-trifluoromethyl] -5-chloro-2,4-difluoropyrimidine,

6-phenyl-2,4-difluoropyrimidine,

o-trifluoromethyl ^ -difluoropyrimidine,

6-6-trifluoromethyl-2,4-difluoropyrimidine,

5-trifluoromethyl-2,4,6-trifluoropyrimidine.

2,4-difluoro-5-nitro-pyrimidine,

^ -Difluoro-S-trifluoromethyl-pyrimidine,

2,4-difluor-5-methylsullbnyl-pyrimidine.

W-difluoro-S-phenyl-pyrimidine,

2,4-difluoro-5-carbonamido-pyrimidine,

2,4-difluoro-5-carbomethoxypyrimidine,

2,4-difluoro-6-trifluoromethyl-pyrimidine,

2,4-dif ^ uor-5-bromo-6-trifluoromethyl-pyπmidin,

2,4-difluoro-6-carbonamido-pyrimidine,

2,4-difluoro-6-carbonamido-pyrimidine,

2,4-difluoro-6-carbomethoxypyrimidine,

2,4-difluoro-6-phenyl-pyrimidine,

2,4-di-fluoro-6-cyano-pyrimidine,

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

2,4-difluoro-5-sulfonamido-pyrimidine.

2,4-Difluoro-5-chloro-6-carbomethyl-oxy-pyrimidine.

S-trifluoromethyl - ^ - difluoropyrimidine,

2,4-dichloropyrimidine-5-carbonsäιlrccllloι ■ iιl.

2,4,6-Tπchlorρyrimidin-5-caι · boIlsäιιreclllorid.

2-methyl-4-chloropyr! Midin-5-carboxylic acid

chloride, 2-chloro-4-octllylpyrimidine-5-carbonsäιιι · e-

chloride, 2,6-dichloropyrimidine-4-carboxylic acid chloride;

Pyrimidine reactive components with rinsing

barcn sulfonyl groups, such as

2-Carbo \ ymc (hylsulfonyl-4-chloropyrimidi! I.

- ■ Mclhylsuironyl ^ -chlor-n-methylpyrimidine.

-. 'i-Bis-methylsiiironyl-ft-metliylp'yrimiilin.

".-I-Bis-phenylsulfonyl-.S-elilor-ft-melliylp.M - imiilin.

2.4.f) - 'rris-inclh \ lsulfninln \ iimiilin.

2,6-bis-methylsulfonyl-4,5-dichloridpyriniidine, 2,4-bis-methylsulfonylpyrimidine-5-sulfonic acid chloride,

I-methyl-sulfonyM-chloropyrimidine, l-phenylsulfonyM-chloropyrimidine, 2,4-bis-trichloromethylsulfonyl-6-methylp \ rimidine,

2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine,

2,4-bis-methylsulfonyl-5-bromo-6-methylpyrimidine,

l-methylsulfonyl ^ S-dichloro-o-methylpyrimidine, 2-methylsulfonyl-4,5-dichloro-6-chloromethylpyrimidine,

I-MethylsulfonyM-chlor-o-methylpyrimidine-5-sulfonic acid chloride,

l-MethylsulfonyW-chlor-S-nitro-o-methylpyrimidine,

2,4,5,6-tetramethylsulfonyl-pyrimidine, 2-methylsulfonyl-4-chloro-5,6-dimethylpyrimidine, 2-EthyIsulfonyl-4,5-dichloro-6-methylpyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 2,4,6-trismethylsulfonyl-5-chloropyrimidine, 2-methylsulfonyl-4-chloro-6-carboxypyrimidine, 2-methylsulfonyl-4-chloropyrimidine-5-sulfonic acid,

2-methylsulfonyl-4-chloro-6-carbomethoxypyrimidine,

2-methylsulfonyl-4-chloropyrimidine-5-carboxylic acid,

2- ^ ϊethylsulfonyl-4-chloro-5-cyano-6-methoxypyrimidine,

2-methylsulfonyl-4,5-dichloropyrimidine, 4-methylsulfonyl-6-chloropyrimidine, 2-sulfoethylsulfonyl-4-chloro-6-methyl-pyrimidine,

2-methylsulfonyi-4-ch! Or-5-bromopyrimidine, 2-methylsulfonyl-4-chloro-5-bromo-6-methylpyrimidine,

2,4-bis-methylsulfonyl-5-chloropyrimidine.

2-phenylsulfonyl-4,5-dichloropyrimidine, 2-phenyl-sulfonyl-4,5-dichloro-6-methylpyrimidine,

2-carboxymethylsulfonyl-4,5-dichloro-6-methylpyrimidine,

2- (2'- or 3'- or 4'-carboxy-phenylsulfonyl | - 4,5-dichloro-6-methylpyrimidine, 2,4-bis- (2'- or 3'- or 4'-carboxyphynylsulfonyl) -5-chloro-6-methylpyrimidine; 2-MethyIsulfonyI-6-chloro pyrimidine or -S-carboxylic acid chloride,

2-ethylsulfonyl-fi-chlorpyrimi <liii-4 or ^> .; nboxylic acid chloride,

2,6-bis- (methylsijir <myl) -pyriniidin-4 - <.:; Irboxylic acid chloride,

2-methylsulfonyl - () - methyl-4 chloro or -4-bromopyrimi (lin-5-carbons; i () re (.: Hlori (l odci -bromide,

2,6-bis- (methylsulfonyl) -4 dilorpymide m '> cn boric acid chloride;

further Rcaktivkompomiile.ii <lei Ικ · ι <· ιο <γι Ii see row mil reactive SIIIIOIIyIMIIi-MiIiIi-Ii (I-Ii are for example

V> -Uis-phenyIsijl! Onyl [> yiiila / iii VMelfiylsulforiyl ■ (■> ι hloi pyi iiI; i / im

or ίΠ (-ιΙινΙ'.ιιΙΙι> η · _ν Ιρνιι <|, ι / ιη

l ('inyi 4 ιιι'-ιΙγ, Ι pyinl, i / iii 2. ^ / i- I ris rn <-thyl'.uli' > riyl [>', ii / m

2,4-bis-methylsulfonyl-1,3,5-triazine,

2,4-bis-methyl-sulfonyl-6- (3'-sulfophenylamino) -1,3,5-triazine,

2,4-bis-methyl-sulfonyl-6-N-methylanilino-1,3,5-triazine,

2,4-bismethylsulfonyl-6-lriehlorathoxy-

1,3,5-triazine,

2,4,6-tris-phenylsulfonyl-1,3,5-triazine,

2,4-bis-methylsulfonylquinazoline,
2,4-bis-trichloromethyl-sulfonylquinoline,

2,4-bis-carboxy-methylsulfonylquinoline,

2,6-bis- (methylsulfonyl) -pyridine-4-carboxylic acid chloride and l- (4'-chlorocarbonylphenyl or

2'-chlorocarbonylethyl) -4,5-bis-methyl-sulfonylpyridazon- (6);

2,4-bis-methylsulfonyl-6-phenoxy-1,3,3-triazine.

Further heterocyclic reactive components with mobile halogen are inter alia. 2- or 3-monochloroquinoxaline-o-carboxylic acid chloride or -6-sulfonic acid chloride, 2- or S-mono-bromoquinoxaline-o-carboxylic acid bromide or -6-sulfonic acid bromide, 2,3-dichloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-dibromoquinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 1,4-dichlorophthalazine-6-carboxylic acid chloride or -6-sulfonic acid chloride and the corresponding bromine compounds, 2,4-dichloroquinazein-6- or -7-carboxylic acid chloride and the corresponding bromine compounds, 2- or 3- or 4- (4 ', 5'-dichloropyridazon-6'-yl-1') -phenylsulfonic acid chloride or carboxylic acid chloride and the corresponding bromine compounds, /? - (4 ', 5'-dichloropyridazon-6'-yI-r) ethyl carboxylic acid chloride, 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding bromine compounds, N-methyl-N- (2,4-dichlorotriazinyl-ol-carbamic acid chloride.N-methyl-N-il-chloro-4 - methylamino - triazinyl - 6) - carbamic acid chloride, N - methyl - N - (2 - chloro - 4 - dimethylamino - triazinyI-6) carbamic acid chloride. N-methyl- or N - ethyl - N - (2,4 - dichlorotriazinyl - 6) - amino - acctyl chloride, N-methyl-, N-ethyl- or N-hydroxyethyl-N- (2,3-dichloroquinoxaline-6-sulfonyl- or -6-carbonyl) -aminoacctylchloride and the corresponding Bromderivalc, also 2-chlorobenzothiazole-5- or

,, s -rVarboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds. 2-arylsulfonyl- or 2-alkylsulfonyl-benzothiazole-5- or -fi-carboxylic acid chloride or -5- or -6-sulfonic acid chloride. like 2-methylsulfonyl- or 2-ÄlhyI-

• 0 sulfonyl- or 2-phenylsulfonyl-benzothiazol-5- or • 6-stii (acid chloride or -5- or -6-carboxylic acid chloride as well as the corresponding in the ankondcnsicrlcn 2-sulfonylben / thia / ol derivatives containing licii / ol ring sulfonic acid groups 3,5-bis-methylsulfonyl-iso

.... ihia / oie-carboxylic acid chloride, 2 - ('chlorobenzoxazole-5. odei • ft-carboxylic acid chloride or sulfonic acid chlorine: as well as the corresponding bromodic derivatives. 2-chlorobenzene / iiiiid;: / ol-'S- or -6-carboxylic acid chloride or sulfone siiiM'echlorid and the corresponding bromine derivatives

fi'i '?. ( hloi-1 ■ inelhyl-bcii / imida / ol-5- or -6-carbon ', äiiiei hloi id or sulfonic acid chloride as well as the ent', pni lieiideii broniderivate, 2-i'hloi -4 nielhylihia / ol (I ( ) '' ■ ! .Arhoiic acid chloride or -4- or -5-sulfone ■, aiiici hloi id. 2 ( hlorthia / ol-4- or - ^ - siilfonsiiiire

>. ·. ililoiid and the corresponding Hrdiiidcrivatc

The new I arbslolTc are suitable / around brains around HediiK ken of hydroxyl or ΛηικΙΐΜΐιρροη ₍ · ι, ι echoing materials, like I exlilia'-er 11 I, iik-ii um

each made of wool, silk, synthetic polyamide ind Polyurethane fibers and for washable dyeing and printing of native or regenerated zinc, where the treatment of cellulose materials: usually in the presence of acid-binding agents

tel and optionally by the action of heat according to the process that has become known for reactive dyes he follows.

The dye of the formula according to the invention

Cl

Cl

-N:

CO-CH ₃ SO ₃ H SO ₃ H > - N = - CH - CO - NH - < (^ Cnh ₂ \ SO ₃ H -NH- -Λ \ J

shows compared to the next comparable color known from British Patent 8 52 120, Example 7 fabric has the surprising advantage that it is deeper colored cotton after the exhaust process from a long liquor The dyes according to the invention of the formula

Cl

show the closest comparable dye known from Example 97 of BE-PS 5 78 742 the surprising advantage of delivering deeper colors on cotton after the stripping process.

In the following examples, parts are parts by weight. The tcmpcralurangabcn are Cclsiusgradc.

H c i s ρ i c 1 1

22 parts of 2-amino-5-nitro-bcnz.ol-siilfonsäuic-l willow indirectly diazolicrt. The suspension of the diazo compound is added to a solution of 35 parts 4-Amino-3,5-disu1foacclcssigsäurcanilid and 28 parts of Biearbonal in 150 parts of water. The coupling happens quickly.

25 parts of Na ₂ S · 3H ₂ O are in 300 parts of Was;

_S5 dissolved and by adding conc. Hydrochloric acid adjusted to pH, the addition being made under the liquid surface. The mixture is then heated to 50-60 "C and the nitro compound obtained in accordance with paragraph I is added; after the reduction is complete, is eliminated from!

do sulfur filtered off and from the filtrate the dye Salted out by adding 20% by volume of sodium chloride and filtered off.

The paste is dissolved in 800 parts of water and, after heating to 45 ", with 28 parts of 2,3-dichloro

ds quinoxaline-6-carboxylic acid chloride added. Through / The pH-W is kept between 6 and 7 by dropping 10% soda solution. After several hours The condensation is complete by stirring. One clarifies ii

separates the dye from the filtrate with K)% by volume Sodium chloride. After suction. Drying and grinding gives a yellow dye powder, which is easily soluble in water with a yellow color. In the form of the free acid corresponds to the dye the formula

Cl

Cl

N-
H SO ₃ H CH ₃ SO ₃ H -f y- N = N I.
C = O SO ₃ H C-
Il
ο 1 —CH
I.
CN-? Ii
0

One of the staining examples listed below is used to achieve this on cellulosic materials a clear, greenish yellow with good light and wash resistance.

For the production of the coupling component 4-amino-3,5-disulfo-acetic acetic acid; * urcanilid is done as follows:

540 parts 1,4-diamino-benzene-2,6-disulfonic acid will be with 120 parts by volume conc. Caustic soda (J = 1.5) made neutral in 2000 parts of water. 176 parts by volume of diketene are then added dropwise, with one passing through Cooling ensures that the temperature does not rise above 40 C. You get 2700 parts by volume of a clear solution that can be used directly for coupling. By adding 25% by volume of table salt the connection can be deposited.

Dye examples
Pressure regulations

If you print cotton nettle with a printing paste containing 20 g of the dye per kilogram. 100 g urea, 300 ml water, 500 g alginate thickener (60 g sodium alginate / kg thickener) and Contains 10 g of soda, and which was precipitated to 1 kg with water, dries, steams for 1 minute at 103 "C, with rinsing with hot water and soaking at the boil, this gives a clear, greenish-yellow print of good wet- and lightfastness.

Blocking regulation

30 parts of the dye shown in Example 1 are dissolved in 1000 parts of water. With this Solution, a cotton fabric is fouladed and pressed until a weight loss of 90% is reached. the cotton is still damp at 70 "C for 30 minutes in a bath, which is in 1000 parts Water contains 300 parts of calcined sodium sulfate and 10 parts of calcined sodium carbonate in solution.

treated. Subsequently, the staining becomes more usual Way finished. A clear greenish-tinged coloration with excellent wet and light fastness properties is obtained.

20th

Staining instructions

In one color! ; cher of 3 (0 ml content, which is in a heated water bath, 168 ml

Water from 20-25 ^! C submitted. 0.3 g of the dye obtained according to Example 1 is made into a paste with 2 ml of cold water and 30 ml of hot water (70) are added; the dye dissolves in the process. The dye solution is added to the initially charged water and 10 g

, ο Cotton yarn in this dye liquor constantly in motion held. The temperature of the dye liquor is increased to 70-80 ° within 10 minutes and 10 g are used add anhydrous sodium sulfate and continue staining for 30 minutes. Then add 4 g of water-

Ts free sodium carbonate and stains for 60 minutes 70-80 °. The colored material is then removed the dye liquor, removes the adhering liquor by wringing out or pressing and rinses the material first with cold water and then with hot

Water until the wash liquor is no longer bled. The dyed material is dissolved in 200 ml of a liquor containing 0.2 g of sodium alkyl sulfate, for 20 minutes, soaped at the boil, rinsed again and ^r at 60-70 in a dry

cupboard dried. A greenish yellow coloration with excellent washfastness and lightfastness is obtained. One discolored according to the procedure given in Example 1, but using the in the following table listed diazo and

Reactive components, valuable reactive dyes are also obtained. The different reactivity the reactive components in the acylation is taken into account by making an appropriate choice the temperature, as it is known from the literature.

Example diazo component

Reactive dyes

l-amino-4-nitrobenzene-2-sulfonic acid

the same

the same

the same

2,4,6-trifluoro-5-chloro-pyrimidine

Tetrachloropyrimidine

l ^ -Dichlorphthalazin-o-carbon-acid-

chloride

2-methylsulfonyl-benzothiazole-5- or

6-carboxylic acid chloride

2,5-bis-methylsulfonyl-isothiazole-

4-carboxylic acid chloride

hue

greenest. yellow
greenest. yellow
greenest. yellow

greenest. yellow
reassuring yellow

l-'ortscl / Linu

Example diazo component

7 1 -Amino ^ -nitrobeiuene ^ -sulfonic acid

8 the same.

9 the same.

10 the same.

11 the same.

12 the same.

13 1 -Amino ^ -carboxy ^ -nitro-benzene

14 the same

15 the same.

16 l-amino-4-nitro-naphthalene-6- or 7-sulfonic acid

17 the same.

18 the same.

19 the same.

20 2-Amino-6-nitro-naphihalin-4,8-disulfonic acid

21 the same.

22 1 -Amino ^ -methoxy ^ -nitro-benzene-5-sulfonic acid

23 the same

24 l-amino-4-nitrobenzo!

25 the same.

Example 26

A solution of 26.8 parts of 1,4-diamino-benzene-2,5-disulfonic acid, neutralized with sodium carbonate, is added to an aqueous suspension of 18.5 parts Cyanuric chloride and the mixture is stirred at a temperature of 0-5 °, being added dropwise a dilute sodium hydroxide solution keeps the pH slightly acidic. After the condensation has ended it is acidified with 30 parts of 30% strength hydrochloric acid and diazotized with 24.5 parts by volume of a 30% strength l <e: iK! i \ f; i.-bsloife

Cyanuric chloride

2-amino-4,6-dichloro-iriazine

2-Amino-phenyl-4,6-dichlorotriazine

I-methylsulfonyl- ^ S-dichloro-o-methylpyrimidine

2,4,6-trichloropyrimidine-5-carboxylic acid chloride

3- (4 ', 5'-dichloropyridazon-6'-yl-r) propionyl chloride

chloride

2,4,6-trifluoro-5-chloro-pyrimidine

2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine

2,3-dichloroquinoxaline-6-carboxylic acid chloride

2,4,6-trifluoro-5-chloropyrimidine

Cyanuric chloride

Tetrachloropyrimidine

the same

Cyanuric chloride

the same

Cow clay

greenest. Yellow green. Yellow green. Yellow green. yellow

greenrt. Yellow green. Yellow green. yellow

greenest. Yellow green. yellow

yellow

Yellow yellow yellow yellow

Yellow green. yellow

greenest. yellow

greenest. Yellow green. yellow

chloride

Cyanuric chloride green. yellow

2- (4'-sulfophenylamino) -4,6-dichlorotriazine green. yellow

Sodium nitrite solution. The yellow diazotization obtained is added to an ice-cold 28 parts of sodium hydrogen carbonate containing solution of 35 parts of 4-amino-3,5-disuifo-acetacetic anilide. After finished Coupling, the excess sodium hydrogen carbonate is destroyed with hydrochloric acid and the color 45 isolated by salting out and filtering. The dye paste is made with a mixture of 5 parts of disodium phosphate and 5 parts of monosodium phosphate mixed and dried in vacuo at low temperature. The dye, of the following formula 50 corresponds,

gives clear, greenish yellow colorations of good light and color after one of the dyeing processes mentioned Wet fastness.

In Example 26, the 4-amino-3,5-disulfoacetic acid arylide is replaced by the appropriate amount (Ifs ^ Amino- ^. S-disulfivacetessigsaurearylids. thus obtained a valuable reactive dye in cotton is also dyed in greenish-yellow tones.

'' 5 B c i s ρ i c 1 27

The dichlorotriazine dye solution obtained according to the instructions in Example 32 is added

50 parts of 10% ammonia are added and the solution is kept at 35 "for 2 hours. The monochlorotriazine dye formed is then salted out, isolated and dried. A dye is obtained which dyes cotton in clear, greenish yellow shades. Replace one Ammonia by equivalent amounts of ethylumin, ethanol or diethanolamine, one obtains dyes with similar characteristics.

Example 28

The neutral solution of 33.7 g of 4- (2 ', 6'-Dilluor-5' - chloro - pyrimidinyl - (4 ') - amino) - anilinesulfonic acid- (2) (calculated as free acid) in 200 ml of water after dissolving 7.2 g of sodium nitrite in a

Added mixture of 30 ml of concentrated hydrochloric acid (d = 1.18) and 200 g of ice. The mixture is stirred for 1 hour at 0 C before excess nitrite is destroyed with sulfamic acid. Then a neutral solution of 35.2 g of 4-acet-acetyl-aminoaniline-disulphonic acid (2.6) (calculated as the free acid) in 150 ml of water and a further 100 g of ice is added and allowed to about 10% over the course of 1 hour Drip in ml of 10% sodium hydroxide solution at OC until the pH value 7 is reached. The clutch is then ended.

The mixture is warmed to room temperature and the precipitation of the dye is completed by adding 100 g Sodium chloride and sucks off after 1 hour. The dye of the formula ## STR3 ## dried at 50 ° C. in vacuo

SO, well

SO ₃ Na

NH,

SO ₃ Na

represents a yellow powder and is identical to the product described in Example 2.

Claims (1)

Patent claims:
Reactive dyes of the formula 4. Use of the dyes of Claims I: for dyeing and printing hydroxyl or amide group containing fasting materials. SOjH