DE2113298B2 - REACTIVE DYES AND THEIR USE FOR INKING AND PRINTING FIBER MATERIALS CONTAINING HYDROXYL OR AMIDE GROUPS - Google Patents

Description

MI,

in which Q and P are hydrogen or a sulfonic acid group, but cannot at the same time have the same meaning and D is a benzene or naphalin nucleus, which is also represented by A = COOH. —SO ₃ H. '- (Ί. Br. -NO _2. -CH _3. -OCH ₃ or OC ₂ H ₅ and which can be substituted via a group - N (Rl to a carbon atom of the benzene or naphthalene nucleus bonded contains one of the reactive groups which are characterized in more detail in the description and which contain at least one removable substituent bonded to a carbon atom of a C = N bond of a 5- or 6-membered aromatic-heterocyclic ring, i the number 1 or 2 and R for hydrogen or C ₁ -C
stands.

2. 1-form reactive dyes!

CH, SO.H (Al ,, C-O 'ζ , NH
SO-H D- ■ N = -N-CH
j C N-
Il H
O

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

A '

CH ₃
C = O

X-HN-

= N-CH

CN-- II H.
O

SO ₃ H

/ NH ₂

SO ₃ H

where A 'represents a hydrogen atom, a Carhoi acid or sulfonic acid group and X represents a reactive group which has at least one removable substituents on a C-Au in a —C = N bond of a 5- or fig-membered aromatic heterocyclic compound Contains ring bound.

The subject of the present krlindimg are new ones Reactive dyes of the general I formula

(H,

(Ai ₁ , <■ '

η \ N (

SO ₁ II

C N

NH ₁ lh

where Q and P are hydrogen or a sulfoic acid group, but cannot have the same meaning at the same time. D represents a benzene or naphthalene compound, possibly replaced by A - -COOH. SO ₃ H. -Cl. --Br. - NO ₂ . -CH ,.

- OCH, or OCH ₅ can be substituted 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 characterized in more detail in the description and which have at least one removable substituent on a C atom one

- C = N bond; mg of a 5- or 6-membered aromatic-heterocyclic Ring bound contains,; i the

vs number 1 or 2 and R is hydrogen or C ₁ -C ₄ -Alk ν1.

Suitable reactive groups which have at least one removable substituent on a 5- or 6-membered aromatic-heterocyclic ring bonded to a carbon atom of a —C— = N bond those with a monoazine, diazine or triazine ring. such as a pyridine, pyrimidine, pyridazine, pyrazine. Thiazine, oxazine, sym.-triazine, ch'noline-phthalazine. Cinnoline, quinazoline or quinoxaline ring or a thiazole, thiadiazole, isothiazole Benzthiazole or benzoxazole ring.

Among the reactive substituents on the heterocycle, halogen (CI, Br or F), ammonium including hydrazinium, sulfonium, sulfonyl, azido (N ₃ ), rhodanido, thio, thioether, oxyether, sulfonic acid and sulfonic acid should be mentioned. Mono- or dihalogen-sym, for example, may be mentioned in detail. triazinyircst. z. B.

2,4-dichlorotriazinyl-6-,

2-amino-4-chlorotriaziazinyl-6-. 2-AIlCyUImInO ^ -ChIOrIrIaZiIIyI-O-, 2-ethylamino- or 2-propyl-amino-4-chloro-tri ■ azinyl-6-,

2-Di - / <- oxäthy! Amino-4-chlorotria7.inyl-6-uiid the corresponding sulfuric acid half-2-diethylamino-4-chlorotriazine-6-, 2-morpholino or 2-piperidino-4-chlorotriazinyl-6-.

2-cyclohexyl-ai: rino-4-chlorotriazine-6-.

2-arylamino and subst. Arvlamino-4-chlorotri azinvl-6-, like

2- Plicny lamino-4-chlonna / m \ I-6-.

2-Id-. m- t) dcr p-t'arbo \> - dJci Sullophcin hammo-4-ehlori.riaym \ I-6-,

2-alkoxy-4-chiortria / in \ 1-6. how 2-Methoxy- odei Athox \ -4-i: hkirina / in \! - iv.

2- (I ¹ HcIiN isulfoinlmethow i-4-chioriria / m \! - <> -.

2- \ ry! O \ y- and subst. Aryloxy-4-chlonria / iny 1-6-. how

2-phenoxy-4-chlorine / in \ 1-6.

2-lp-Su) fopheml | -ox> -4-chlorlria / in \ l-6-. _μ ,

2- {o-. m- or p-Melhyl- or Meihow phein lio \\ - 4-chlortria / .in \ l-6-.

2-alkylcapio- nder 2-ar \ lmercap'o- or 2- | subst. Ar \ l) -merc ₁ ipto-4-chloitria / in;% l- (i-. Wie

2- |.; - H_ \ drox_ \ äth \ li-mereapto-4-cli] or-iri- ι ^

a / in \ l-6-,

2- I'henylmei'capto ^ -ehlorlria / iii} 1-6-.

2- (4 -Melhyl-phenyl-mercapto 4-ehlorui-ίΐ7Ϊη_ν1-6-.

2- (2'.4'-Dinitro | -phenylmercapto-4-chlorortria / invl-6-.

2-meth \ l-4-chloro-tria / in \ l- (v.

2- PhenyM-ch'ior-triazinvl-e-.

Mono-. Di- or trihalo-pyrimidinyl resie.

like; s

2,4-dichloroprimidinyl-6-.

2.4.5-trichloropyrimidinyl-6-.

2.4-dichloro-5-nitro- or -5-methyI- or -5-carboxymethyl- or -5-earboxy- or -5-cyano- or -5-vin \ l- or -5-sulfo- or -5-mono-. -di or -triehlomethyl- or -5-carhoalkoxy-pyrimidinyl-6-,

2.6-dichloropyrimidine-4-carbonyl-.

2,4-dichloropyriniidin-5-carbonyl-.

2-chloro-4-meth \ lpyrimidine-5-carbon \ 1-. _iS

2-methyl-4-chloropyrimidine-5-carbon \ I-.

Z-Methylthio ^ -lluopyrimidine-f-caibonyl-.

6-methyl-2,4-dichloropyrimidine-5-carbony! -.

2.4.6-trichloropy: rimidine-5-carbonyl-.

2.4-DichloΓpyrirnidin-5-sulfonyl-. ^ ₀

2-chloroquinoxaline-3-carbonyl-.

2- or 3-monochloroquinoxaline-6-carbonyl-.

2- or S-monochloro-quinoxaline-o-sulfonyl-, 2.3-dichloroquinoxaline-6-carbonyl-,

l ^ -Dichlorphthalazin-o-sulfonyl- or -carbonyl-,

2- or 3- or 4- (4 ', 5-dichloropyridazon-fi'-yM) -phenylsulfonyl- or -carbonyl, /i-(4'.5'- dichloropyridazen-6'-yl-l ') -älhylcarbonyl-,

N-methyl-N- (2,4-dichlorotria7.inyl-6) -carbam \ l-. N-methyl-N- (2-methylamino-4-chlorotriazinyl-6) -carbamyl-,

N-methyl-N- (2-dimethylamino-4-chlorlriazinyI-6) -carbamyl-,

N-methyl- or N-ethyl-N- (2,4-dichlorotriazinyl-6) -aminoacetyl-,

N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacctyl-,

N-Methyl-N- (2,3-dichloroquinoxaline-6-carbonyl) -atninoacelyi

as well as the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic radicals, including for example

2-fluoro-4-pyrimidinyl-.
2.6-Diiliior-4-pyrimidinevl-.

_s0 2. (il) itluoro-5-chloro-4-p \ rimidiny 1-, 2-1 luo! -ri.f) -dichlor-4-p \ rimidin \ I-.

2.fi-Dilluor-5-mclhyl-4-py rimidiny! -.

2.5-DiiUior-6-meth) l-4-pyrimidine \ 1-, 2-1 luoro-methyl-d-chloro- ¹ , -pyriniidii:> I.

2-1 ■ kior-5-nilro-6-chli> r-4-pyrimidine \ l.

5-bromo-2-ti uor-4-py rimidiny l-2-fluoro-3-cyano-4-p \ rimidiny 1, 2.5.6-1 rill uor-4-py ri midi nyl, 5-chloro-6-chloromethyl-2-nuor-4-p \ rimidiny 2.6-Dill uor-5-bromo-pyri midi nyl.

l-fluoro-5-bromo-6-metlv, l-4-p \ rimidiny 1.

2-Fluoro-5-bromo-6-chloromelhyl-4-pyrimiJin \ l.

2.6-Difluoro-5-chloromethyl-4-pyrimidine \ l.

2.6 Difluor-5-nitro-4-p \ rimidiny 1.

2-fluoro-6-methyl-4-pyrimidiny 1,2-fluoro-5-chloro-6-methyl-4-pyrimidinyl.

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

2-fluoro-S-chloro ^ -py rimidiny 1.

2-fluoro-6-chloro-4-py rimidiny 1.

6-Trifluoromethyl-5-chloro-2-fluorine-4-p \ riniidiiiN 6-trifluoromethyl-2-fluoro-4-pyrimidine \ l.

2-fluoro-5-nitro-4-pyrimidinyl.

2-fluoro-5-trifluoromethyl-4-p_ \ rimidinyl.

2-fluoro-5-phenyl- or -5-methylsulfonyl-4-pyrimidinyl,

2-fluoro-5-carbonamido-4-pyrimidinyl.

2-Fkior-5-carbomethoxy-4-pyrimidinyl.

2-Fk] or-5-bromo-6-lrifluoromethyl-4-p> rimidiny 2-fluoro-6-carbonamido-4-pyrimidine \ l, 2-fluoro-6-carbomethoxy-4-pyrimidiny], 2-fluorine-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidine \ l.

2-fluoro-5-sulfonainido-4pyriinidinvl.

2-FIuOr-S-ChIOr-O-CaTbOmCtIiOXy ^ -Py rimidi nyl.

2,6-difluoro-5-trifluoromethyl-4-pyrimidiny 1; triazine radicals containing sulfonyl groups. how 2,4-bis (phenylsi'lfonyl) -lriazinyl-6-, 2- (3'-Carbc \ vphenyl) -sulfonyl-4-chlorotriazinyl-6-,

2- (3'-sulfophenyl) -sulfonyl-4-clilortriazinyl-6-, 2,4-bis (3'-carboxy-phenylsulfonyI-1 ') -triazinyl-6;

pyrimidine rings containing sulfonyl groups, such as 2-carboxymethylsulfonyI-pyrimidinyl-4, 2-methylsulfonyI-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-ethyl-pyl · imidillyl-4.

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

2,6-bis-methylsulfonyl-pyrimidinyl-4.

2,6-bis-methylsulfonyl-5-chloro-pyrimidinyl-4.

2.4-bis-methylsulfonyl-pyrimidine-5-sulfonyl.

2-methylsulfonyl-pyrimidinyl-4, 2-plienylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl-pyrimidinyl-4, 2-phenylsulfonyl-pyrimidinyl-4.

2-trichloromethylsulfonyl-6-methyl-pyrimidinyl-4,

2-methylsulfonyl-5-chloro-6-methyl-p \ rimidinyl-4,

2-methylsilinyl-lfonyl-5-bromo-6-mct! Iy l-p \ rimidinyl-4,

2-Methyisulfonyl-5-chloi-6-alhvl-pyrimidinvl-4.

2-methylsulfonyl-5-chloro-6-chloromcth \ l-p \ rimidinyl-4,

2-methylsulfonyl-4-chloro-6-methylpimidine-5-sulfonyl.

2- \ leih \ lsulfony! -5-nilni-6-nieliiyl-p \ rimidnn! 4 2.5.6-Tris-niethylsulfonyl-pyrimidine \ 1-4.
2-Meth \ lsulfonyl-5,6-dimethyl-p> iimidiine 1-4.
2-. ^: \ ihylsulfon \ l-5-chloro-6-methyl-p \ rimidiii> 1-4.
2-Melh \! Sulfonyl-6-chloro-pyrimidinyl-4.
2.6-Bis-methyl-sulfoiiyl-5-chloro-p \ rimidm> l-4.
2-meth> isulfonyI-6-carboxy-pynmidine \ 1-4
2-methylsulfonyl-5-sulfo-pyi; midine> 1-4.
2-Vlethv lsulfi> nyI-6-carbonu-lhi) xy-p \ rimidiin 1-4. 2-methylsulfonyl-5-carboxy-pyrimidine \ 1-4.
2-Metb \ lsulfonyl-5-cyano-6-methoxy-p \ rimidin \! - 4. "

2-Mclh \ lsulfonyl-5-chloi-pyrimidins 1-4.
2-sulfoethylsulfonyl-6-methyl-pyrimidine \ 1-4.
2-Moth \ lsulfonvl-5-bromo-pyrimidine \. 1-4.
2-Phen \ lsulfonyl-5-chloro-p \ rimidinyl-4.
2-Ca rhoxy met hy lsulfony lo-chloro ^ -met In 1-p \ rimidinyl-4.

2-Meth \ lsulfonyI-6-chloropyrimidine-4- and -5-carbonyl.

2.6-bis (methylsulfon \ ll-pyrimidin-4- or
-5-carbonyl ·.

2-Ath \ l-sulfonyl-6-chloropyr <midin-5-carbon \ I-.
2.4-bis- (Mcthy lsulfony 1) -pyrimidine-5-sulfone>'-.
2-Met hy lsulfony l-4-chloro-6-mclhylpy rim id in-5-sulfone \ I- or carbonyl-;
triaxial rings containing ammonium groups. how
2-Ti "imethylammonium-4-phcnyIiimino- or
-4- (o-, m- or p-sulfophynyl) -aminolriazmvl-6-. 2-1 ll-Diniethyl-liydrazinium) -4-phenylamino-
or -4- (o-, m- or p-sulfophcnv l) -aminolria / m \ l-6-.

2-12-1 sopropylidcn-1.1-dimethyl) -hydra / inium-4-phcnylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-,

2-N-aminopyrrolidinium- or 2-N - / \ mino-pipcridinium-4-phenyl-amino- or -4- (o-, m- or p-sulfophenyl) -aminolriazinyl-6-,
furthermore 4-Phcny / amino or 4- (sulfophenylaniino | - tria / ynyl-6 radicals, which in 2-Slellimg via a nitrogen bond the 1,4-bis-aza-bicvclo-f 2,2,2} octane or contain the 1,2-bis-aza-bicyclo-f 0.3,3 J-octane bonded quaternary.2-pyridinium-4-phciivlamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl -6- and corresponding 2-oniumtriazinyl-6 radicals, which are in the 4-position by alkylamino, such as methylamino, ethylamino or / f-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy or aroxy, such as Phenoxy or sulfophenoxy groups are substituted;

2-ChIoTbCnZIhIaZoI-S- or -6-carbonyl- or -5- or -6-sulfonyl-,

2-arylsulfonyl- or -alkylsulfonylbenzthiazole-5- or -o-caYbonyl- or -5- or -6-sulfonyl-, such as 2-methylsulfonyl- or 2-ethylsulfonyl-benzothiazole-5-orr -6-sulfonyl- or -carbonyl-. 2-Phcnylsulfonyl-Benzthiazol-5- or -6-sulfonyl- or -carbonyl- and the corresponding in addition Benzene ring sulfo groups containing 2-sulfonylbenzthia / ol-5- or -6-carbonyl- or sulfonyl derivatives,

2-chlorobenzene / oxazole -5- or -6-carbonyl- or -sulfonyl-, 2-Chlorobenzimidaz.ol-5- or -6-carbon \ iodcr -sulfonyl-, 2-chloro-1-methylbenzimida / ol-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-4-methylthia / ol- (1.3) -5-carbonyl- or -4- or ^ -sul- \ -1) \ _ \ d read 4- ('hliT- or 4-Niliochint Ίπι - "-».; !! ■ bon \ I

In the Kalimcii del new I aihslolfe be \ iüen speak the formulas

ι \ ι. CO

I) \ \ (H
C.
o Il

SO ₁ I! Nile

SO ₁ II where Ιλ Λ and the aivjcuebene BcücuHihl I

CH ₁

^Λ CO

HN ■ "NNCH ^{S ()} . ' ⁿ

X CN NH-I

Uli

¹ SO ₁ H

wherein Λ 'represents a carboxylic acid or sulfoiic acid group sees and X stands for a reactive group which at least one of the above-mentioned reactive aspallbaren substituents on a C -. \ tom a C N 'bond of one of the previously mentioned 5- or d-membered aromatic-helerocyclic ring contains bound.

Halogenamines (chlorine, bromine or fluorine) are particularly mentioned as residues that can be removed. ammonium including hydrazinium. Sulfonium. Sulfonyl. Azido- (N,). Rhodanido. Thio. Thioether. Oxyether. the sulfinic and sulfonic acid groups.

The new dyes are obtained when one the diazo compound of a \ min of the formula

(A) ,,
I) NII,

where I). A and η have the abovementioned meaning, with at least 1 mol of a coupling component of the formula

CH,

CO
CH ₂

CN
O Il

SO ₁ H ■ NH, 1 '

(IVl

where in Q and P the;: n given meanings are united The coupling erloigi in the weakly acidic, neutral n in weakly alkaline medium.

SO ₃ H

One can make the connections according to the invention also produce in such a way that one in a dye of the formula

CH.,
CO

I) ₁ N -N- -CH

CN - ^; ■ NH, (V)

I! η / ■ = ;;

° Q P

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

One can proceed in such a way that one enters a Dye of the formula

NS

/ - NH, (V P

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

D ₂ - N · - = - ■ N - CH, O C. H N - -CH N R. C-- H : j C)

NH
R.

by condensation with an at least bifunctional reactive component X-Y '. where X the _ _,? has the abovementioned meaning and Y 'denotes an anionically removable group into a radical

-N-X

I.

in which R and X have the meaning given, converted. ss

The remainders D are, for example:

Phenylenes 1.3) or - (1.4).

2-sulfo-phenylene- (1.3) or - (1.4).

2-carboxy-phenylene- (1.4). f, o

2- or 3-carboxy-phenyl-6-methylene-4-sulfophenylene-U.3).

5-methoxy-2-sulfophynylene- (1.4).

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

2-chloro-phenylene- (1.4). <, <,

6-sulfonaphthylene- (1.4).

4.H-Disuir) -: i :: phvM-T! - (2.ft) - or - (2.5i. 14.4!

Suitable Acetessiuaiylide are for example acelacetic acid-4-amino-3,5-disulfoanilid. Acetic acid 4-amino-2.5-disulfoanilide.

As amines

IA) ,,
D NlI ₂

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

NHX

X-NH

SC) ₃ H
A-NH ₂

SO ₃ H

/ -NH ₂

SO ₃ H

NH-X

HN
X

HN-

S.
χ

NH ₁

SO ₃ H

SO, H

-NH,

X-NH CH,
S (), H

SO ₃ H

X-HN

HO ₃ S

X HN

NH,

SO ₃ H

HN,

Si) ₁ H

(VIl)

(VIII)

(IX)

(Xl

(XI)

(XII)

(XlII)

(XlV)

(XVi

709 519/481

X UN

COOIl

-NU,

(XVI)

in which X has the meaning given above.

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

(Al ₁ ,

I.

Z-D -NH,

represents wherein Z is a group -NH (R or convertible into such a group radical, in particular a nitro group and D, the above-mentioned _loading; has importance, then the group converts, if necessary, Z in the group -NH (R) around Suitable. Amines are for example:

S-Nilro ^ -amino-benzene-sulfonic acid. 4-nitro-l-aminobenzene,: ^t

4 - ^^ 0-2- ^ 10 ^ 1 ^ 11111110 ^ 1 ^ 01, o-nitro ^ -amino-naphthalene ^ .S-disulphonic acid. S-nitro ^ -amino-1-carboxy-bcnzol. l-Amino ^ -nitro-naphlhalin-o- or 7-sulfonic acid-4. - ■

5-nitro-2-amino-1-melhoxy-benzene-sulfonic acid-3.

The implementation of the color bodies of the formula VI with active components X-Y '. wherein X aiiL.gebene, _(meaning and Y 'represents an anionically removable substituent, in a known per se.

Suitable reactive components for this are X - Y ' for example those belonging to the aforementioned reactive groups X are based, d. H. in general the halides, in particular the chlorides of the above Acyl components X. The following are excerpts from the large number of compounds available mentioned:

Trihalogen-sym.-triazines, such as

Cyanuric chloride and cyanuric bromide.

Dihalogen-monoamino- and -mono-substituted-amino-sym.-triazines, how

2,6-dichloro-4-aminotriazine. ₄ ,

2,6-dichloro-4-methylaminotriazine.

2,6-dichloro-4-ethylaminolriazine.

2.6-dichloro-4-oxethylaminotriazine.

2,6-dichloro-4-phenylaminotriazine.

2.6-dichloro-4- (o-. M- or p-sulfophenvll-amino- ^ triazine,

2.6-dichloro-4- (2.5'-. -2'.4'- or -.V.5'-disulfophenyO-aminotriazine.

Dihalo-alkoxy- and -aryloxy-sym. -triazines, w ic

2,6-dichloro-4-methoxytriazine. _s

2.6-dichloro-4-ethoxytriazine.

2,6-dichloro-4-phenoxy triazine.

2.6-dichloro-4- (o-, m- or p-sulfophenyl | -ox \ - triazine.

Dihalo-alkylmercapto- and -arvlmercapto- ₍ , sv m.-triazine, like

2.6-dichloro-4-ethylmercapto-triazine.

2,6-dichloro-4-phenyl mercapto-triazine.

2.6-dichloro-4- (p-methylphcnvl) mercaptotriazine:

Tetrahalopyrimidines. how ,,

Teirachlor-. Tetrabromo- or tetrafluoroprimi din.

2.4.6-1 rich tor-, -Trihmin- or -Trilluor-pyrimidine.

Pihaloprimidine. like 2.4-dichloro-. -Dibromo- or -Ditluor-pv riniidin: 2.4.6-trichloro-5-nitro- or -5-methyl- or -5-carbomcthi '\\ - or -f.-carboäthox) - or -5-carbo. \\ meih \ l- or -5-mono-. -di or -trichloniiethvl- or -5-caiboxy- or 5-sulfo- or -5-c \ ano- or -S-vinyl-pyrimidine. 2.4-bil] uor-ft-melhylpyimidine. 2.6-dilluur-4-methyl-5-clilor-pyritnidine. 2,4-Dinuor-pyrimidine-5-ethyl sulfone. 2.6-dif1uor-4-chloropyrimidine, 2.4.6-tri-fluorine-5-chloro-pyrimidine, 2.6-difluoro-4-meth> l-5'bromopyrimidine. 2,4-difluoro-5,6-dichloro- or -dibromopyrimidine. 4,6-difluoro-4,5-dichloro- or -dibromo-pv rimidine. 2.6-Diiluoro-4-bromopyrimidine, 2.4.6-trifluor-5-bromopyrimidine. 2.4.6-Trifluoro-5-chloromethylpyryridine. 2.4.6-trifluoro-5-nitropy rimidine. 2.4.6-trifluoro-5-cyanopyrimidine. 2.4.6-Trifluoropyriniidin-5-carboxylic acid alkyl ester or -S-carboxamides. 2.6-Difluoro-5-methyl-4-chloropyrimidine. 2,6-difluoro-5-chloropyrimidine. 2.4.6-trifluoro-5-methylpyimidine. 2.4.5-triίluoro-6-methylpyrinlidine. 2,4-difluoro-S-nitro-o-chloropyrimidine. 2,4-difluoro-5-cyano-pyrimidine, 2,4-difluoro-5-methyl-pyrimidine. 6-Trif ^ uormethyl-5-cnίor-2.4-dir ^ uor-ρyrimidine. 6- Phcnyl-2,4-difluoropyrimidine. 6-Trifluormet hy 1-2.4-difluorpyimidine. 6-6-trifluoromethyl-2.4-difluoropyrimidine. 5-Trilluorniethyl-2,4,6-trifluoropvimidine. 2.4-Difluoro-5-nitro-pyrimidine, 2.4-Difluoro-5-trifluorometh \ l-pyrimidiii. 2.4-Difluoro-5-methylsulfonyI-pyrimidine. 2,4-difluoro-5-phenyl-pyrimidine. P ^ -Difluoro-S-carbonamido-pyrimidine. 2.4-Difluoro-5-carbomethoxypyrimidine. 2.4-difluoro-o-trifluoromethyl-pyrimidine. 2.4-D: fluoro-5-bromo-6-trifluoromelhyl-pyrimidine. 2,4-difluoro-6-carbonamido-pyrimidine. 2,4-Difluoro-6-carbonamido-pyrimidine. 2,4-difluoro-6-carbomethoxy-primidine. 2,4-difluoro-6-phenyl-pyrimidine. 2,4-di-fluoro-6-cyano-pyrimidine. 2.4.6-Trifluoro-5-methylsulfonyl-pyrimidine. 2.4-di f ^ uor-5-sulfonamido-pyrimidine. 2.4-Difluoro-5-chloro-6-carbomethoxy-ρyriITlidine. f-Trifluoromethyl ^^ - difluoropyrimidine. 2,4-dichloropyrimidine-5-carboxylic acid chloride. 2.4.6-Trichloropyrimidine-5-carboxylic acid chloride. 2-methyl-4-chloropyrimidine-5-carboxylic acid chloride.

2-chloro-4-methylpyrimidine-5-carboxylic acid chloride.

2,6-dichloropyrimidine-4-carboxylic acid chloride: pyrimidine reactive components with cleavable Sulfonyl groups. such as 2-carboxymethyl sulfonyl-4-chloropyr.midine. 2 ■ methylsulfonyl-4-chloro-6-methylpyrimide! N. 2,4-bis-methylsulfonyl-6-methylpyrimidine. 2.4-bis-phenylsulfonyl-5-chloro-6-methylpyr-

imidine.

■ - - 4. & -! 'Ns-methykiulfonyipyririiiiiiii.

2.6-Bis-met hy Is iilfoin 1-4.5-dich lurid p \ rimidin. 2,4-Bis-methylsulfonylpyimidin-5-sLi Ho nsä Ii rcchlorid.

2-methyl-sulfonyl-4-chlo rp \ riniidin. 2-phenylsulfonyl-4-chloropynmidine. 2.4-bis-trichloromethylsuironyl-6-melh \ lpyrimidine.

2.4-bis-methyl-sulfonyl-> chloro-6-melhyrimidine.

2.4-bis-methylsulfonyI-5-bromo-6-melh \ lp \ rimidin,

2-methylsulfonyl-4,5-dicli Io r-6-meth \ lp \ riniidin. 2-methylsulfonyl-4,5-dichloro-6-chloromethanol rim id in,

2-methylsulfonyl-4-chk> r-6-melhyIpyrimidine-5-sulfonic acid chloride.

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

2.4,5,6-tetramelhvlsulfonyl-pyrimidine. 2-Mcthy! Sulfonvl-4-chloro-5,6-dimcth \ lpyrimidine. 2-ethylsulfonyl-4,5-dichloro-6-methylpyrimidine. 2-methylisulfonyl-4,6-dichloropyrimidine. 2.4.6-tri.smethylsulfonyl-5-chloropyrimidine, 2-methylsulfonyI-4-chloro-f) -carboxypyrimidine. 2-methylsulfonyl-4-chloropyrimidine-5-sulfonic acid.

2-methylsulfonyl-4-dilor-6-carbomethox \ - pyrimidine.

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

2-MethyIsulphonyl-4-chloro-5-cyano-6-mctho. \ Ypyrimidine,

2-methylsulfonyl-4,5-dichloropyrimidine. 4-methylsulfonyl-o-chloropyrimidine. 2-sulfoethylsulfonyl-4-chloro-6-meth \ l-p \ iimidine.

2-methylsulfonyl-4-chloro-5-bromopyrimidine. 2-methylsulfonyl-4-chloro-5-bromo-6-mcth \ lpyrimidine,

2.4-bis-methylsulfonyl-5-chloropyrimidine. 2-Phenylsulfonyl-4,5-dichloropyrimidine. 2-phenyl-sulfonyl-4,5-dichloro-6-methylpyrimidine.

2-Carboxy-melhyisulfonyl-4,5-dichloro-6-methylpyrimidine.

2- (2'- or 3'- or 4'-Carbo. \ Y-phenyl sulfonyl) -4.5-dichloro-6-methylpyrimidine. 2.4-bis- (2'- or 3'- or 4'-carboxyphynylsulfonyl) -5-chloro-6-methylpyrimidine: 2-MethyIsulfonyl-6-chloroprimidin-4- or -S-carboxylic acid chloride.

2-AtHyIsUIfOrIyI-O-ChIOrPyTJmIdIn ^ - or -5-carboxylic acid chloride.

2,6-bis (methylsulfony!) - pyrimidine-4-carboxylic acid chloride,

2-methylsulfonyl-6-methyl-4-chloro- or ^ -bromopyrimidine-S-carboxylic acid chloride or -bromide,

2.6-bis (methylsulfonyI) -4-chloropyrimidine-5-carboxylic acid chloride:

further reactive components of the heterocyclic series with reactive sulfonyl substituents are for example
3,6-bis-pnenylsulfonylpyridazine. 3-methylsulfonyl-6-chloropyridazine. i.fi-bis-trichloromethylsulfonylpyridazine. 3.6-bis-methylsulfonyl-4-methyl-pyrida / !! i. 5Tif

2.4-bis-methylsulfony! -1.3,5-triazine.

2,4-bis-methylsulfonyl-6- (3'-sulfophenylamino) -1.3.5-triazine,

2,4-bis-methylsulfonyl-6-N-methylanilino-

1.3.5-triazine,

2,4-Bismelhylsulfonyl-6-trichlorälho \ y-

1.3.5-iri.azin.

2.4.6-Tris-phenylsulfonyI-1,3,5-tiia / in.

2,4-bis-methylsulfonylquinazoline,

2.4 • Bis-trichloromethylsulfonylquinoline.

2,4-bis-carboxy-methylsulfonylehinoline,

2,6-bis- (methylsulfonyl) -pyridine-4-carboxylic acid chloride and 1-M'-chlorocarbonylphenyl or

2-chlorocarbon ethyl) -4,5-bis-methyl-sulfone \ l-

P) ridazone- (6);

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

Further heterocyclic reactive components with mobile halogen are inter alia. 2- or 3-monochloro quinoxaline-o-carboxylic acid chloride or -6-sulfonic acid c chloride. 2- or S-mono-bromoquinoxaline-o-uirbon acid bromide or -6-sulfonic acid bromide. 2,3-dichloroquinoxaline-o-carboxylic acid chloride or -6-sulfonic acid c chloride. 2,3-Dibromoquinoxaline-6-carboxylic acid bromic or -6-sulfonic acid bromide, I 4-dichlorophthalazine 6-carboxylic acid chloride or -6-sulfonic acid chloride so like the corresponding bromine compounds. 2,4-Dichloroquinazein-6- or -T-carboxylic acid chloride as well as the corresponding bromine compounds. 2- or 3 or 4- (4 ', 5'-dichloropyridazon-6'-yl-r) -phenylsulfone acid chloride or carboxylic acid chloride and the corresponding bromine compounds, ^ - (4,5'-dichloropyridazon-o'-yl-1 'I-ethyl carboxylic acid chloride. 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding bromine compounds. N-methyl-N- (2.4-dichlorotriazinyl-6) -carbamic acid chloride, N-methyl-N- (2-chloro- 4 - methylamino - triazinyl - 6) - carbamic acid chloride. N - methyl - N - (2 - chloro - 4 - dimethylaniino - triazinyl-6) carbamic acid chloride. N-methyl- or N-ethyl-N- (2,4-dichlorotriazinyl-6) -amino-acetyl chloride. N-Mcthyk N-ethyl or N-hydroxyethyl-N- (2,3-dichloroquinoxaline-6-sulfonyl or 6-carbonyl) -aminoacetyl chlorides and the corresponding bromine derivatives, also 2-chlorobenzothiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds. 2-arylsulfonyl- or 2-alkylsulfonyl-benzothiazole-5- or -o-carboxylic acid chloride or -5- or -6-sulfonic acid chloride. like 2-methylsulfonyl- or 2-ethylsulfonyl- or 2-PhenyIsulfonyl-benzothiazole-5- or -6-sulfonic acid chloride or -5- or -o-carboxylic acid chloride and the corresponding 2-sulfonyl-benzothiazole derivatives containing sulfonic acid groups in the fused-on benzene ring 3,5-bis-methylsulfonyl-isolhiazole-4-carboxylic acid chloride. 2-chlorobenzoxazole-5- or -o-carboxylic acid chloride or -sulfonic acid chloride as well as the corresponding bromine derivatives. 2-chlorobenzimidazole-5- or -6-carboxylic acid chloride or -sulfonic acid chloride and the corresponding bromine derivatives. 2-chloro-1-methyl-benzimidazole-5- or -6-carbon-> acid chloride or sulfonic acid chloride and the corresponding Birom derivatives. 2-chloro-4-methylthiazole- (1.3) -5-carboxylic acid chloride or -4- or -5-sulfonic acid chloride. 2-chlorothiazole-4- or -5-sulfonic acid chloride and the corresponding bromine derivatives.

The new dyes are suitable for dyeing and printing.-HydrowI- or Amidgrti-r-v ^ ri _enihaitcndcr? Mai-enaiicu. v.; c Tcxii'fa.serri-Fadeu ufnt

Woven fabrics made of wool. Silk, synthetic l'ohamid- and Polvurelhanl'asei η and for real colors and printing wm naliver or regenerated cellulose, the treatment of cellulosic filaments expediently in the presence of acid-binding agents

lel and, if necessary, by exposure to heat the methods known for reactive dyes he follows.

The inventive dye of the formula

NH;

CO CH ₃
N CH CO Nile

SO ₃ H
■ NH

SO ₃ H SO, H

shows compared with the dye known from British Patent 8 52 120. Example 7 which can be compared the surprising advantage that it dyes cotton more deeply after the exhaustion process from a long liquor. The dyes according to the invention of the formula

Cl

Cl - <:

NH

Cl

CH,

■ C. O SO ₃ H -N N - C H , Nl C. N · ' SO, H O H

SO., I

Cl

NH

CH ₃ O SO ₃ H c- H v-NH C- N- ■ SO ₁ H - N --- NC ^- - H O

/ peculiar to the dye known from Example 97 of BE-PS 5 78 742 which can be compared the surprising advantage of delivering deeper colors on cotton after the exhaust process.

In the following examples, parts represent parts by weight. The temperature data are degrees Celsius.

example 1

22 parts of 2-amino-5-nitro-bcn / ol-sulfonic acid-1 are indirectly diazoticrl. The suspension of the diazo compound is allowed to add to a solution of 35 parts of 4-amino-3,5-disulfoacctacetic anilide and 28 parts Biuirbiin ::! i-- · '· ^ Share water running in The K'.ipr »- ίιιημ success; r;: -. ch. -

25 parts of Na ₂ S 3H ₂ O are dissolved in 300 parts of Wassc and by adding conc. Hydrochloric acid precipitated to pH 1. the addition takes place under the liquid surface. The mixture is then heated to 50-60 ° C. and the nitro compound obtained in accordance with paragraph 1 is added. After the reduction is complete, the precipitated sulfur is filtered off and the dye is salted out and filtered off from the filtrate by adding 20% by volume of sodium chloride.

The paste is dissolved in 800 parts of water and heated to 45 mils to 28 parts of 2,3-dichloro quinoxaline-o-carboxylic acid chloride added. Through Zi A drop of 10 "little soda solution will adjust the pH-Wc: / wipe ft and 7 bnlien N; j <" h for several hours Üuhren? Sf STc "Condensation bcc" '' ct M ^ n clear! U.N

- uhc ι J c I ai ^ dem i ilir.ii den 1 .ub-i. · ;: iiüi i> ν. :, i- -inltpuKcr. dt ^ light mn gelhci I aihe in Wi- ^ cr Iu -.- men- ",, Nainumchlo.; α ab. N.ich the suction. iuiiiv i r. I ii; ίι the free acid corresponding ilIii de! laib -Iockiien and grinding one receives a ^ egg- 1-aib- ^ inii of the lminel

( 1

(1

ι. \

Il

S (> 11

(11

(O

N N (H

t N
11

SO. H

According to one of the following examples some achieves: mil on cellulose-based materials a clear, griny (ielb \ on good iditunci Washing chiheil.

/ ui "Production of the coupling component 4-Amiij <i -. \ 5-disii! f (> -; ice! e.s> ii.'s; iiire.i!) i) id is the following!) - ßen proceed:

540 I eile 1.4-I) iamino-ben / ol-2. (Vdisiilfonsäui e werden with 120 Yokimenieilen conc. Caustic soda d / 1.5) neutralized in 2000 parts of water. Then you do 17h drip in yolum parts of diketene, whereby one through cooling ensures that the temperature does not rise above 40 C. 2700 parts by volume are obtained clear solution that is used directly for the clutch can be. By adding 25% by volume of table salt the connection can be deposited.

Coloring examples
Printing regulations

If you print cotton nettle with a printing paste containing 20 u of the dye in kilograms. KiOg urea. 300 ml of water. 500 g alginate thickener (60 g sodium alginate kg thickener and Contains 10 g of soda, and which was made up to 1 kg with water, dries. 1 minute at 103 C "steams with rinsing with hot water and soaking at the boil, a clear, greenish-yellow print of good wet- and lightfastness.

Blocking regulation

30 parts of the dye shown in Example I are dissolved in 1000 parts of water. With this A BaumwoUgcwebe is fouladed and pressed until a weight loss of 90% is reached. the Cotton that is still moist is placed in a bath at 70 ° C. for 30 minutes. which in 1000 parts Water contains 300 parts of calcined sodium sulfate and K) parts of calcined sodium carbonate uelösl. treated. The coloring is then completed in the usual way. A clear greenish yellow is obtained Coloring with excellent wet and light smudges.

lärbe \ regulation

In a staining beaker with a content of 3 (K) ml, which is in A heatable water bath is located, UiS ml of water at 20 25 C are presented. 0.3 g of des of the dye obtained according to Example I with 2 ml of cold water and add 30 ml of hot water (70 ι to: the dye dissolves in the process. The dye solution is added to the initially charged water and 10 g Cotton yarn kept in motion in this dye liquor. You increase within 10 minutes the temperature of the dye liquor to 70 80. add 10 g of anhydrous sodium sulfate and color for 30 minutes Further. Then 4 g of anhydrous are added to the dye liquor Sodium carbonate is added and the dye is stained for 60 minutes at 7 (1 SO. The dyed material is then removed the dye liquor removes the adhering FIoUc Wring or press and rinse the material first with cold water and then with hot Water until the rinsing fiotle no longer blisters will. The colored material is then in 200 ml of a liquor containing 0.2 g of sodium alkyl sulfate contains, soaped for 20 minutes at boiling temperature, Rinsed again and at 60 70 in a drying cabinet dried. A greenish yellow coloration of excellent washing and light smudges is obtained. One discolored according to the procedure given in Example I, however, using the The diazo and reactive components listed in the table below are also valuable Reactive dyes. The different reactivity of the reactive components during acylation is taken into account by an appropriate choice of the temperature, as it is known from the literature.

Example diazo component

Keaklivrarhsloffe

I arblon

1 ■. '\ Mino-4-nitrobenzene-2-sulfonsuuri.'

the same

the same
desi.-!

2.4.6-Trifluoro-5-chloro-pynmidin green. yellow

Tetrachloropyrimidine green. yellow

^ -Dichlorphthalazine-ft-carbon-acid-green. yellow

chloride

2-methylsulfonvi-benzothiazole-5- or green. yellow

6-carboxylic acid chloride

2.5-bis-methylsulfonyl-isothiazole green. yellow

4-carboxylic acid chloride

17th

L /

IN

Dl.i. ·, ik.πι;

1-Ληιιηο-4-ηιΐΓι> 1χ · ηΛ> Ι-2- · .ιιίΙ'.ιη *:! - .. ι S. the same y the same 10 the same 11th the same 12th the same 13th 1-aniino-2-carbo. \ Y-4-nit! o-ben / ol 14th the same 15th the same

l-amino-i-nitro-naphthalene-o- or

7-sulfonic acid the same. The same. The same. 2-amino-6-nitro-naphthai in-4.S-di.su lfon- the same. acid like l-amine-2-methoxy-4-nitro-ben / ol-

5-sulfonic acid like.

■ vanurchioi \ d gi us !, ι jn-,

2- \ nii! Ni-4. (I-dicliliii-tna / in giuiist (i _L -1 h

2 - \ mino-phen \ M.fi-dichlorina / in green. (iclh

VMcihylNuIfonyl-i ^ -dichloMi-meihyl- griiiiM. c iclb

p \ π midi η 2.4.6-Trchloro-primidin-5-carboxylic acid green, (iclh

L'hlorid 3- | 4 .5-Dichloropynda / on-6'-yl-1 i -progrünst. GeIn

pionyl chloride

2.3-dichlorochmoxaline-O-carboxylic acid green. yellow

chloride

2.4.6-Trifluoro-f-chloro-pyrimidine green. yellow

2-methylsulfonyl-4,5-dichloro-6-meth \ 1- gi inst. yellow

pyrimidine

2.3-DjchJorchino. \ Alin-6-carboxylic acid- ( Iclb

clilorid

1-amino-4-nitrobenzene like.

2.4.6-trifluoro-5-chloropyrimidine CJeIb yellow Cyanuric chloride yellow yellow Tetrachloropyrimidine yellow the same yellow yellow Cyanuric chloride yellow the same greenest. 2,3-dich iorquinoxaline-6-carboxylic acid greenest. chloride Cyanuric chloride greenest.

2- (4'-sulfophenylamino) -4.6-dichlorotriazine green. yellow

Sodium nitrite solution. The yellow B c i s ρ i e I 26 40 diazotization obtained is added to an ice-cold, 28 parts of sodium hy-

drug carbonate containing solution of 35 parts

A 4-amino-3,5-disulfo-acetic acid anilide neutralized with sodium carbonate is added. After been solution of 26.8 parts of M-diamino-benzolO.S-digter coupling is the excess with hydrochloric acid sulfonic acid to an aqueous suspension of 18.5 parts of sodium hydrogen carbonate and destroyed the color Cyanuric chloride and stir the mixture at a 45 substance isolated by salting out and filtering. The color temperature from 0 5, whereby one becomes fabric paste by dropping in with a mixture of 5 parts of Dieiner dilute sodium hydroxide solution, the pH sodium pliosphate and 5 parts of monosodium phosphate keeps weakly angry. When the condensate is finished, mixed and in a vacuum at low tempesation acidified with 30 parts of 3 () "iger hydrochloric acid, dried at temperature. The dye, of the following formula and diazotized with 24.5 parts by volume of a 30 "oigen 50 corresponds.

Cl

N ^ N Cl

N Ή

SO ₁ H

C. H, C) H NS j
C. ■ -N -
1 y - N N- C. I i C. O

SO, H

gives clarity according to a l-'urheverialiren called animal greenish tinged iirbiingen \ on under light uiul Naßechtheii

li ¹ · ■: man in example. "Oilas 4 \ ηιιινι-.ν" -disulfoie · η. iiire.ii \ ^i:, 'dureh the opponent .Menge • ie -i \ nuin 1- ^\; - li-.:i!!i> .ii eiessiü ^ a ii rear \ lids, so he-SO, H

you can also find a valuable reactive dye, which dyes cotton in greenish tones.

Example 27

/ u obtained according to the information in Example 32 Solution of the didilortria / infarstoffs uiht mm

2) 13 298

50 "file frequent ammonia / u and holds the solution 2 stools at 35. Then the formed monochlorine dye becomes salted out. isolated and dried. A dye, cotton, is obtained colors in clear, greenish yellow tones. Replace one Ammonia by equivalent amounts of AtIn lamb. Ethanol or diethanolamine. this is how you get colored foil with similar characteristics.

Example 2K

The neutral solution of 33.7 g of 4- (2'.6-difluoro-5 - chloro - pyrimidinyl - (4Ί - amino) - anilisulfonic acid (2 | I calculated as the free acid) in 2O ml of water becomes after dissolving 7.2 i: sodium nitrile in a

Mixture of 30 ml of concentrated hydrochloric acid (ι / 1.1 X | and entered 200 g of ice. It is stirred for 1 hour at 0 (before excess nitrite with amidosilfonic acid / is destroyed. A neutral solution of 35.2 g of 4-Aee! -Acetvl-aminoaniline-disulfonic acid-12.6) is then added (Calculated as free acid in 150 ml of water tiiul another 100 g of ice and IaBi add about 110 ml of 10% sodium hydroxide solution at 0 C within 1 hour 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

τ i

N Λ F.

Cl

(TL

CO

N-N-CH (O NH - ■■■

S C), Na

V-NH ₂

SO ₁ Na

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

Claims (1)

Claims
Reactive dyes dei i \> i :: w .}. ViTv \ cndimgdci I aibsinfledct Xiisprüchci / to 1 aibcn and printing nuirowl- or ami. Jruppenhalliger Kisermalerialien - ■ N CH, N ι ΛI ₁ , C. H η \ CH C. !! O SO.