GB2027734A

GB2027734A - Chromium complex dyestuffs

Info

Publication number: GB2027734A
Application number: GB7927462A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1978-08-12
Filing date: 1979-08-07
Publication date: 1980-02-27
Also published as: BR7905148A; DE2835493C2; GB2027734B; FR2433036A1; JPS5525493A; CH643581A5; FR2433036B1; DE2835493A1; NL7906018A; JPS6147174B2

Abstract

Chromium complex dyestuffs of the formula <IMAGE> wherein R and R1, independently denote hydrogen or an alkyl or aryl group provided that at least one of R and R1 is hydrogen or an alkyl group, Z is chlorine or a nitro group, and R2, R3, X1, X2, X3 and Me<+> have the meaning indicated in the description, and their use for dyeing and printing the most diverse substances, but above all for dyeing nitrogen-containing materials, such as silk, leather and, in particular, wool, and also synthetic fibres of polyamides or polyurethanes. The resulting dyeings have good fastness properties.

Description

SPECIFICATION Chromium complex dyestuffs The present invention relates to new chromium complex dyestuffs of the formula

wherein R and R1 represent a hydrogen atom or an alkyl or aryl group, with the proviso that at least one of the radicals R1 or R represents hydrogen or alkyl; Z is a chlorine atom or the nitro group.

R2 and R3 represent an alkyl, aryl, carboxylic acid, carboxylic acid ester, carboxamide or cyano group; the radicals Xr, X2 and X3 are hydrogen, halogen, nitro, alkyl, alkoxy, arylsulphone, alkylsulphone or optionally substituted sulphonamide; and Me+ is a cation.

The alkyl, aryl and alkoxy radicals can optionally contain further substituents.

Preferred alkyl groups are those with C1-C12, in particular those with 1--4 C atoms, which can optionally be further substituted, for example by cyano, halogen, in particular chlorine, phenyl, hydroxyl or C1-C4-alkoxy.

Preferred aryl radicals are, in particular, optionally substituted phenyl radicals with substituents such as halogen, in particular CI and Br, NO2, C 1-C4-alkyl, C1-C4-alkoxy or cyano.

The sulphonamide groups and carboxamide groups can be monosubstituted or disubstituted by optionally substituted alkyl, in particular C1-C4-alkyl, or optionally substituted phenyl, possible substituents being those indicated above. Preferred carboxylic acid ester groups are carboxylic acid C1-C4-alkyl ester groups.

The new chromium complex dyestuffs are prepared by a process in which dyestuffs of the formula

are converted into the 1:1 chromium complex in a manner which is in itself known by reaction with an agent which donates chromium, and this complex is then reacted with the non-metallised dyestuff of the formula (III) or (II) to give the 1:2 Cr complex.

Preferably, the 1:1 Cr complex of the dyestuff of the formula (II) is prepared and the dyestuff of the formula (III) is added onto this.

The monoazo dyestuffs of the formula (II) are obtained in a known manner by coupling diazotised it-amino-1 -hydroxy-4-sulpho-6-nitro- or 6-chloro-benzene to a pyrazolone of the formula (IV)

and those of the formula (III) are obtained by coupling a diazotised aminophenol of the formula (V) to a pyrazolone of the formula (VI)

wherein R, R3, R2 and R, have the meaning indicated.

Examples of suitable pyrazolones of the formulae (IV) and (VI) are 3-methyl-5-pyrazolone, 3-ethyl5-pyrazolone, 3-butyl-5-pyrazolone, 3-phenyl-5-pyrazolone, 5-pyrazolone-3-carboxylic acid, 5pyrazolone-3-carboxamide, 5-pyrazolone-3-carboxylic acid ethyl ester, 3-cyano-5-pyrazolone, 1phenyl-3-methyl-5-pyrazolone, 1-(2'-, 3'- or 4'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2',5'- or 3'4'-dichlorophenyl)-3-methyl-5-pyrazolone, 1-(2'-, 5'-dibromophenyl)-3-methyl-5-pyrazolone, 1 (2',4',6'-trich lorophenyl)-3-methyl-5-pyrazolone, 1 (4'-bromophenyl)-3-methyl-5-pyrazolone, 1 -(2'- chloro-6'-methylphenyl)-3-methyl-5-pyrazolone, 1 -(4'-methyl-phenyl)-3-methyl-5-pyrazolone, 1 -(2'- ethylphenyl)-3-methyl-5-pyrazolone, 1 -(4'-methoxyphenyl)-3-methyl-5-pyrazolone, 1 -(2'-, 3'- or 4'- nitrophenyl)-3-methyl-5-pyrazolone, 1 -phenyl-3-aminocarbonyl-5-pyrazolone, 1-phenyl-3-cyano-5- pyrazolone, 1-phenyl-3-carboxy-5-pyrazolone, 1,3-diphenyl-5-pyrazolone, 1-phenyl-3methoxycarbonyl-5-pyrazolone and 1 -(3'-sulphodimethylamide-phenyl)-3-methyl-5-pyrazolone.

Examples of possible diazo components of the formula (V) are: 2-amino-1 -hydroxy-benzene, 4- or 5-chloro-2-a mino-hydroxy-benzene, 4- or 5-nitro-2-a mino-hydroxy-benzene, 4- or 5-methyl-2-aminohydroxy-benzene, 4-methoxy-2-amino-hydrnxy-benzene, 4,6-dichloro-2-a mino-hydroxy-benzene, 4,6- dinitro-2-amino-hydroxy-benzene, 4-chloro-5-nitro-2-amino-hydroxy-benzene, 6-chloro-4-nitro-2amino-hydroxy-benzene, 4-ch loro-6-n itro-2-a m ino-hydroxy-benzene, 6-nitro-4-methyl-2-amino- hydroxy-benzene, 2-amino-l -hydroxy-4- or 5-(methyl sulphone)-benzene, 2-amino-I -hydroxy-4- or 5 (phenyl sulphone)-benzene, 2-amino-l -hydroxy-4- or 5-sulphonamido-benzene, 2-amino-l -hydroxy-4- or 5-sulphomethylamido-benzene, 2-amino-l -hydroxy-4- or 5-sulphodimethylamino-benzene and 2 amino-1 -hydroxy-4- or 5-sulphanilido-benzene.

The dyestuffs of the formula (II) or (III) are converted into the 1:1 chromium complex by customary methods which are in themselves known, for example by reacting the metal-free dyestuff with a salt of 3-valent chromium, such as chromium formate, chromium sulphate or chromium fluoride, in an acid medium at the boiling point or if appropriate at temperatures which exceed 1 000C. It is also possible to produce trivalent chromium in the reaction mixture from chromium-VI compounds if a reducing agent, such as, for example, glucose, is simultaneously added. The metallisation can also be carried out in the presence of organic solvents. The reaction is preferably carried out in organic solvents, such as alcohols or ketones, and as far as possible with exclusion of water.

The reaction of the 1:1 chromium complex of the dyestuff of the formula (II) or (III) with the metalfree dyestuff of the formula (III) or (II) is appropriately carried out in an alkaline to weakly acid medium in an open or closed vessel at normal or elevated temperature, for example at temperatures between 500C and 1200C.

The reaction can be carried out in organic solvents, for example alcohols or ketones, or in aqueous solution, in which case additions of solvents, such as, for example, of alcohols or dimethylformamide, can promote the reaction if appropriate. In general, it is advisable to react as far as possible equivalent amounts of the chromium-containing 1:1 complex and the metal-free dyestuff with one another, the molecular ratio between the metal-free dyestuff and the 1:1 complex appropriately being at least 0.85:1 and at most 1:0.85; as a rule, an excess of metal-containing dyestuff is less disadvantageous than an excess of metal-free dyestuff. In general, the closer this ratio is to 1 the more advantageous is the result.

Instead of single dyestuffs of the formula (II) or (III), it is also possible to employ mixtures of appropriate dyestuffs. Interesting shades are frequently obtained in this manner.

The new, chromium-containing mixed complexes obtainable by the above processes are advantageously isolated in the form of their salts, in particular alkali metal salts, and above all sodium salts, or ammonium salts or salts of organic amines with a positively charged nitrogen atom, and are suitable for dyeing and printing the most diverse substances, but above all for dyeing nitrogencontaining materials, such as silk, leather and, in particular, wool, and for synthetic fibres of polyamides or polyurethanes. They are suitable, above all, for dyeing from a weakly alkaline bath, a neutral bath or a weakly acidbath, for example a bath containing acetic acid. The dyeings ths obtained areuniform and have good fastness to light, washing, milling, decatising and carbonising.

In the examples which follow, unless otherwise indicated, parts denote parts by weight and percentages denote percentages by weight, and the temperatures are given in degrees Celsius.

EXAMPLE 1 0.1 mol of the 1:1 Cr complex dyestuff prepared by coupling diazotised 6-nitro-2-aminophenol-4sulphonic acid to 1 -phenyl-3-methyl-5-pyrazolone and then chroming the coupling product is stirred in 1.2 1 of water with 0.1 mol of the monoazo dyestuff prepared by coupling diazotised 5-nitro-2aminophenol to 3-methyl-5-pyrazolone. The resulting suspension is heated to 90-950C and adjusted to pH 8-8.5 by means of dilute sodium hydroxide solution. The suspension is stirred until no further starting dyestuffs can be detected, 260 g of sodium chloride are then introduced, the pH is adjusted to 5 with a little acetic acid and the chromium mixed complex dyestuff which has precipitated is filtered off at 650C.After drying, a dark brown powder is obtained which dissolves in water giving a red-coloured solution and dyes wool and polyamide, from a weakly acid bath, in red shades with good fastness to light and good fastness to wet processing.

EXAMPLE 2 0.1 mol of the 1:1 Cr complex dyestuff prepared by diazotising 6-nitro-2-aminophenol-4sulphonic acid, coupling the diazotisation product to 3-methyl-5-pyrazolone and chroming the coupling product is stirred in 1 litre of water together with 0.1 mol of the dyestuff prepared by diazotising 5-nitro2-aminophenol and coupling the dlazotisation product to 3-methyl-5-pyrazolone, and the mixture is warmed to 80--850C and adjusted to pH 9 with dilute sodium hydroxide solution. The mixture is stirred at this pH until no further starting components can be detected, 200 g of potassium chloride are introduced, the pH is adjusted to 6.5 with dilute acetic acid and the precipitate is filtered off at 500 C.

When dried, the dyestuff is a dark brown powder which dissolves in water and dyes wool and polyamide, from a weakly acid bath, in clear red shades. In the acid form, the dyestuff corresponds to the formula

If the monoazo dyestuffs I and II listed in the tables are used, chromium mixed complex dyestuffs which have similar properties and dye wool and polyamide in orange to bluish-tinged red colour shades are obtained analogously.

Ex ample Azo dyestuff I Azo dyestuff li No. OK OH 3 M0);CH3 HO3S K CH3 OH CI Ij 054 H XTrICHa H3 N X t KO3 02Nt H 5 02Nto N=N ;;!$C54a N rN S 1)rcI K Ho N 6 QzN N=N CH3 02NB Q 054 OZN L\/ NoN?7CH3 CM N:N HO t Nsn 54 7 H035 cI CM 0l4 OSLFI N=N C543 -b "'" 8 Ozt F OiN' oas 54

Ex ample Azo dyestuff I Azo dyestuff 1. No. 0 og 0214 > [ ,N=NT7W,CH3 e N::l4tjfCH3 9 HO 4,N O2FJR HO N Y N 02NN I 10 t O] 3 HB' HogS NDz H ai oH 11 OaNtN n > 3 Cr43 HQ3S H OK 054 OaN CI cHa 1:N11CHa 12 N HONN HO3S t H OH OH 02N NtN t,,/cnj N=N CK3 rj(CH3 13 H I( II II II woas t soZNH2 H 0 OK N: CHA ca 14 O1Ni9=9 C3 it 11M a25 2N Cl43 f arc3 HO NP4 Y FIO N 1 5 HODS < 3 SQ Cl43

Ex ample Azo dyestuft I Azo dyestuff II No. N--N CM II b o 17 O2N1 HONCH3 S 9~14 '4a H%S CH3 ~ caN 1N:N11CM 18 '4ONN hLOS CM3CMS 19 N=No irNo)(lN Ho35 sOacb3 0 ~ 20 OZN > [RN=N OaN 9 NHC3'hlJ/NVU!:: So3M OH OH NrN /CH3 21 503H N CM3 CH3 22 =N ga3 J 02NA N =N B C"S sO3M Ci

Ex ample No. No. 014 Cii Ir II WN=N Cii N=N 23 S03 < 3 cl N soaK CI cii CM N -NCKa 0 N CH3 o N - - - a 24 140 6 HO ,N 24 SOaK OH CK3 0i4N-N CM3 25 02N > 6 =N g;Cw3 Rj,N^ W3 So3H cr3 n o 0" oFt NtOtrlN cHa 26 we E ;;N so3K CM OZN N-N3 27 yO 3 H3CE iiO So354 Oi H 28 Iss U ceN n > 3 t =Ng COOT 28 Zo oF4 02f4 uo 9SN SO3K p" M N CN 028 N UC3 tN CW3 "' 29 50314 t

Ex ample No. Azo dyestuff I Azo dyestuff II OF AN N ] CH3 S < 30 5 K 2 C'3 M:Cii3 O2NN =NCLK 31 5 Q3 H 6 02N""Hb ozCls 32 SO3M K t e o oz N 02.4t-S uCH3 tNN % > 3 33 ScaM H 14 0aN 34 N=N IOI soa K (msi 3 35 \ N i i T 5oa" H CM 36 CaN HON3 X i pN

Ex ample No. Azo dyestuff I Azo dyestuff II OH OH C'";" cH N=NCW3 a SN CK: N'N c N=N CH3 :C' 39 N N0 N C i N 39 Ho oN c IY 503H 0', CM 40 C'1 i)r MN0 CW3 503K SoaNK 503H 502b4Hz H U OH OR 41 C N o)#IM3 N > WtN02 SOCH 6 a --I 42 C t HoRN'" SO3FT t kH3 OK 43 f N =N LC443 N rv=N CHJ 'CH3 0', OK cl 4NS C443 g CH3 44 503H 9 i40 , Sq3H tOz H

Ex ample No. Azo dyestuff I Azo dyestuff II Clss 3 > N= C3 HO N 45 503K oz Cs K C( N=s > 3 s-v3 46 sCK 47 CI N :Ha OzN3w SO3H '4 Ct'3 K N ow 48 Cl ss N- Z M > X ~ ~ CI ow CZ ZOH CI CI C3 9W JiS. CH3 50 Soa14 29 NA H L CI sown S E

Ex ample No. Azo dyestuff I Azo dyestuff II OK Ib""" PH 5= -Nil CCCII 54 ";:'" I N ... CIJNNr71cH3 55 3Y OrE N N1 N ~ ow Csi1 Cl ssN=N MCH3 ss ffi 3H OK OK oH oH oatINCCCCIi 57 S03w H OH oH Cts Ht o 58 SO3|4 ,1K N 2 H U

Ex ample No. Azo dyestuff I Azo dyestuff II Oil OK D.LNILYN:NCHNSN II cw3 II :, ozC sl\N.II 59 SojH HoN oC /N 4 1 60 SO3R 02N > ;( t CH2CH2C2C93

Claims

1. A chromium complex dyestuff of the general formula

in which R and R1 independently denote a hydrogen atom or an alkyl or aryl group, with the proviso that at least one of the radicals R1 or R denotes a hydrogen atom or an alkyl group; Z denotes a chlorine atom or a nitro group, R2 and R3 denote an alkyl, aryl, carboxylic acid, carboxylic acid ester, carboxamide or cyano group; X1,X2 and X3 independently denote a hydrogen or halogen atom or a nitro, alkyl, alkoxy, arylsulphone, alkylsulphone or optionally substituted sulphonamide group; and Me+ denotes a cation.

2. A dyestuff according to Claim X, rn which one of R and R1 denotes a hydrogen atom and the other of R and R, denotes a phenyl radical which is optionally substituted by halogen or C1 to C4 alkyl.

3. A dyestuff according to Claim 2, in which R denotes the hydrogen atom and R1 denotes the phenyl radical which is optionally substituted by halogen or C1 to C4 alkyl.

4. A dyestuff according to any of the foregoing claims in which Z denotes a nitro group.

5. A dyestuff according to any of the foregoing claims in which X2 denotes a nitro group or an optionally substituted sulphonamide group.

6. A dyestuff according to any of Claims 1 to 4 in which X1 denotes a nitro group, X2 denotes a hydrogen atom and X3 denotes a chlorine atom or a methyl group.

7. A dyestuff according to any of the foregoing claims in which B) and R, denote a methyl or carboxamide group.

8. A dyestuff according to Claim 1 as hereinbefore specifically identified.

9. A process for the production of a dyestuff as claimed in Claim 1, in which a dyestuff of the formula

is reacted with an agent which donates chromium, and the resulting chromium complex is reacted with the other one of dyestuffs of formula (il) or (III) to give the 1:2 chromium complex.

10. A process for the production of a dyestuff as claimed in Claim 1 when carried out substantially as described in any one of the Examples.

1 A dyestuff as claimed in Claim 1 when produced by the process of Claim 9 or 10.

12. A process for dyeing or printing a natural nitrogen-containing material or a synthetic fibre of a polyamide or polyurethane comprising treatment with a dyestuff as claimed in any of Claims 1 to 8 and 11.

13. A process according to Claim 12 in which the material is silk, leather or wool.

14. A natural nitrogen-containing material or a synthetic fibre of a polyamide or polyurethane when dyed or printed by the process of Claim 12 or 13.