Claims
- 1. A complex of the formula ##STR33## or a salt thereof each cation of which is independently a non-chromophoric cation,
- wherein
- each of R.sub.1c and R.sub.3c is independently --SO.sub.2 Zc, wherein Zc id hydroxy, phenyl or --NHR.sub.10c,
- wherein R.sub.10c is hydrogen, methyl, ethyl, cyclohexyl or 2- or 3-hydroxy-(C.sub.2-- 3 alkyl), and
- each of R.sub.2c and R.sub.4c is independently hydrogen, chloro, nitro, methyl, acetamido or --COXc, wherein Xc is hydroxy, --OR.sub.9c or amino,
- wherein R.sub.9c is methyl or ethyl, with the provisos that (1) each of R.sub.1c -R.sub.4c is in the 4- or 6-position of the ring to which it is attached and (2) when one of Rings A and B has an --SO.sub.2 NHR.sub.10c group in its 4-position, the other of Rings A and B has a sulfo or --SO.sub.2 NHR.sub.10c group, or a mixture of such complexes, salts or both.
- 2. A complex according to claim 1, or a salt thereof each cation of which is independently a non-chromophoric cation.
- 3. A complex according to claim 2, or a salt thereof each cation of which is independently lithium, sodium, potassium, ammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, triethylammonium, ethanolammonium, diethanolammonium or triethanolammonium.
- 4. A complex according to claim 2, or a salt thereof each cation of which is independently a non-chromophoric cation,
- wherein each of R.sub.2c and R.sub.4c is independently hydrogen, chloro or methyl.
- 5. A complex according to claim 4, or a salt thereof each cation of which is independently a non-chromophoric cation, wherein each of R.sub.1c and R.sub.3c is independently --SO.sub.2 Z.sub.d,
- wherein Zd is hydroxy or amino.
- 6. A complex according to claim 5, or a salt thereof each cation of which is independently a non-chromophoric cation, wherein each of R.sub.1c and R.sub.3c is sulfo, and
- each of R.sub.2c and R.sub.4c is independently hydrogen or chloro.
- 7. A complex according to claim 6, or a salt thereof each cation of which is the same non-chromophoric cation.
- 8. A complex according to claim 7, or a salt thereof each cation of which is lithium, sodium, potassium or ammonium, the cations being the same.
- 9. A complex according to claim 8, or a sodium salt thereof.
- 10. The complex according to claim 6 having the formula ##STR34## or a salt thereof each cation of which is independently a non-chromophoric cation.
- 11. The complex according to claim 10 in sodium salt form.
- 12. The complex according to claim 6 having the formula ##STR35## or a salt thereof each cation of which is independently a non-chromophoric cation.
- 13. The complex according to claim 12 in sodium salt form.
- 14. The complex according to claim 6 having the formula ##STR36## or a salt thereof each cation of which is independently a non-chromophoric cation.
- 15. The complex according to claim 14 in sodium salt form.
- 16. The complex according to claim 5 having the formula ##STR37## or a salt thereof each cation of which is independently a non-chromophoric cation.
- 17. A mixture of complexes according to claim 1 consisting of
- (A) the complex of the formula ##STR38## or a salt thereof each cation of which is independently a non-chromophoric cation,
- (B) the complex of the formula ##STR39## or a salt thereof each cation of which is independently a non-chromophoric cation, and
- (C) the complex of the formula ##STR40## or a salt thereof each cation of which is independently a non-chromophoric cation.
- 18. A mixture according to claim 17 wherein the ratio of (A) to (B) to (C) is approximately 2 : 1 : 1.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 3223022 |
Jun 1982 |
DEX |
|
Parent Case Info
This application is a continuation of application Ser. No. 06/683,602, filed Dec. 19, 1984 and now abandoned, which is a continuation-in-part of application Ser. No. 06/503,268, filed June 10, 1983 and now abandoned.
This invention relates to metallized disazo compounds, processes for their preparation and their use for dyeing or printing hydroxy group- or nitrogen-containing organic substrates employing conventional dyeing or printing methods; furthermore, this invention relates to a process for dyeing or printing textile material comprising cellulose fibres with the metallized disazo compounds and after-treating the dyed or printed substrate with a suitable fixing agent.
The invention provides compounds which, in free acid form, correspond to formula I ##STR2## in which
each of R.sub.1 and R.sub.2, independently, is hydrogen, halogen, nitro, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, --NHCOR.sub.8, --COX or --SO.sub.2 Z, R.sub.8 is C.sub.1-4 alkyl or phenyl,
each X, independently, is OH;--OR.sub.9 ; C.sub.1-4 alkyl; phenyl; phenyl substituted by 1 or 2 substituents selected from halogen, nitro, C.sub.1-4 alkyl and C.sub.1 14 4alkoxy; cyclohexyl; cyclohexyl substituted by 1 to 3 C.sub.1-4 alkyl groups; or is --NR.sub.10 R.sub.11,
each Z, independently, is --CH.sub.2 CH.sub.2 OSO.sub.3 H or --CH.dbd.CH.sub.2 or has one of the significances of X with the exception of C.sub.1-4 alkyl,
R.sub.9 is C.sub.1-4 alkyl; phenyl or phenyl (C.sub.1-4 alkyl), wherein the phenyl ring may be substituted by 1 or 2 substituents selected from halogen, nitro, C.sub.1-4 alkyl and C.sub.1-4 alkoxy,
R.sub.10 is hydrogen, C.sub.1-4 alkyl, C.sub.2-4 alkyl substituted by 1 or 2 substituents selected from-OH, C.sub.1-4 alkoxy, halogen and cyano; phenyl; phenyl substituted by 1 or 2 substituents selected from halogen, nitro, C.sub.1-4 alkyl and C.sub.1- 4 alkoxy; cyclohexyl; or cyclohexyl substituted by 1 to 3 C.sub.1-4 alkyl groups,
R.sub.11 is hydrogen, C.sub.1-4 alkyl; C.sub.2-4 alkyl substituted by 1 or 2 substituents selected from-OH, C.sub.1-4 alkoxy, halogen and cyano; cyclohexyl; or cyclohexyl substituted by 1 to 3 C.sub.1-4 alkyl groups; or
R.sub.10 and R.sub.11, together with the nitrogen atom to which they are bound, form a saturated 5- or 6-membered hetero ring which optionally contains a further hetero atom,
each of R.sub.3 and R.sub.4, independently, has one of the significances of R.sub.1 and R.sub.2 provided that either at least one and at most three of R.sub.1 to R.sub.4 are a group --SO.sub.2 Z, or, if no group --SO.sub.2 Z is present, at least two of R.sub.1 to R.sub.4 are a group --COX wherein X is --OH,
each R.sub.5, independently, is hydrogen, C.sub.1-4 alkyl; or C.sub.1-4 alkyl monosubstituted by --OH, chlorine or cyano,
each R.sub.7, independently, is hydrogen or halogen, and R.sub.6 is halogen, --OH, C.sub.1-4 alkoxy, phenoxy, --NH.sub.2, --NHOH, an aliphatic, aromatic or cycloaliphatic amine radical or a saturated heterocyclic amine radical in which the nitrogen atom is part of the heterocycle which optionally contains further hetero atoms, and mixtures of compounds of formula I, which compounds are in free acid or salt form, with the proviso that
a) when (1) both terminal phenyl groups contain a sulpho group in the 4-position and all other radicals of these phenyl groups are hydrogen, (2) each R.sub.5 is hydrogen, (3) each naphthyl ring is bound to the amino group in the 6- and 6'-positions, respectively, (4) each sulpho group on the naphthyl rings is in the 3- and 3'-positions, respectively, and all the conditions (1) to (4) occur simultaneously, R.sub.6 is other than --NHC.sub.6 H.sub.5, --NHCH.sub.2 CH.sub.2 OH or --NH.sub.2;
b) when (1) each R.sub.5 is hydrogen, (2) each naphthyl ring is bound to the amino group in the 6- and 6'-positions, respectively, (3) each sulpho group on the naphthyl rings is in the 3- and 3'-positions, respectively, (4) one of the two terminal phenyl groups contains a group --SO.sub.2 Z, wherein Z is --NR.sub.10 R.sub.11, in the 4-position, and all the conditions (1) to (4) occur simultaneously, either
c) when (1) both terminal phenyl groups contain a sulpho group in the 4-position and all other radicals of these phenyl groups are hydrogen, (2) each R.sub.5 is hydrogen, (3) each naphthyl ring is bound to the amino group in the 7- and 7'-positions, respectively, (4) each sulpho group on the naphthyl rings is in the 3- and 3'-positions, respectively, and all the conditions (1) to (4) occur simultaneously, R.sub.6 is other than 3-amino-4-chlorophenylamino.
Any halogen as an alkyl substituent is fluorine, chlorine or bromine, preferably chlorine or bromine. Any halogen as a phenyl substituent is chlorine or bromine, especially chlorine.
Any halogen as R.sub.6 is fluorine, chlorine or bromine, especially chlorine.
In any hydroxy- or alkoxy-substituted alkyl group as defined for R.sub.5, R.sub.10 and R.sub.11 which are linked to nitrogen atoms or for R.sub.6 as an amino group containing such a group, the hydroxy or alkoxy group is bound to a carbon atom other than to the C.sub.1 -atom; furthermore, in any alkyl group substituted by two hydroxy groups as defined for R.sub.10 and R.sub.11 or for R.sub.6 as an amino group containing such a group, the hydroxy groups are bound to different carbon atoms.
Any alkyl as R.sub.1 to R.sub.4, independently, is preferably methyl or ethyl, more preferably methyl; any alkoxy, independently, is preferably methoxy or ethoxy, more preferably methoxy.
Any alkyl as R.sub.8 is preferably methyl or ethyl, more preferably methyl.
R.sub.8 is preferably R.sub.8a, where R.sub.8a is methyl, ethyl or phenyl. More preferably, it is R.sub.8b, where R.sub.8b is methyl or phenyl. Most preferably, R.sub.8 is methyl.
Any alkyl as R.sub.9 is preferably methyl or ethyl. Any phenylalkyl group as R.sub.9 preferably contains a C.sub.1-2 alkyl group. In any substituted phenyl- or phenylalkyl-group the phenyl ring is preferably monosubstituted by chlorine, nitro, methyl or methoxy.
R.sub.9 is preferably R.sub.9a, where R.sub.9a is methyl, ethyl, phenyl or phenyl (C.sub.1-2 alkyl), wherein the phenyl ring may be monosubstituted by chlorine, nitro, methyl or methoxy. More preferably, it is R.sub.9b, where R.sub.9b is methyl, ethyl, phenyl or benzyl. Most preferably, it is R.sub.9c, where R.sub.9c is methyl or ethyl.
Any alkyl as X, independently, is preferably methyl or ethyl. Any substituted phenyl as X and Z, independently, is preferably monosubstituted by chlorine, methyl or methoxy.
Any alkyl as R.sub.10 and R.sub.11, independently, is preferably methyl or ethyl. Any substituted alkyl, independently, is preferably C.sub.2-3 alkyl, which is preferably monosubstituted by hydroxy, methoxy, chlorine or cyano; more preferably, it is monosubstituted by hydroxy.
Any substituted phenyl as R.sub.10 is preferably substituted by 1 or 2 substituents selected from chlorine, nitro, methyl and methoxy; more preferably, it is monosubstituted by chlorine or methyl.
Any alkyl substituted cyclohexyl as R.sub.10 and R.sub.11, independently, is preferably substituted by up to 3 methyl groups.
R.sub.10 and R.sub.11, together with the nitrogen atom to which they are bound, preferably form a morpholine-, piperidine-, piperazine- or pyrrolidine-ring, which preferably is unsubstituted; more preferably, they form an unsubstituted morpholine- or piperazine-ring, especially a piperazine ring.
R.sub.10 is preferably R.sub.10a, where R.sub.10a is hydrogen, methyl, ethyl; C.sub.2-3 alkyl monosubstituted by hydroxy, methoxy, chlorine or cyano; phenyl; phenyl substituted by 1 or 2 substituents selected from chlorine, nitro, methyl and methoxy; cyclohexyl or cyclohexyl substituted by 1 to 3 methyl groups or, together with R.sub.11 and the nitrogen atom to which R.sub.10a and R.sub.11 are bound, forms a piperidine-, piperazine- or morpholine-ring. More preferably, it is R.sub.10b, where R.sub.10b is hydrogen, methyl, ethyl, monohydroxysubstituted C.sub.2-3 alkyl; phenyl; phenyl monosubstituted by chlorine or methyl: cyclohexyl or, together with R.sub.11 and the nitrogen atom to which R.sub.10b and R.sub.11 are bound, forms a piperazine ring. Even more preferably, it is R.sub.10c, where R.sub.10c is hydrogen, methyl, ethyl, monohydroxy substituted C.sub.2-3 alkyl or cyclohexyl. Most preferably R.sub.10 is hydrogen.
R.sub.11 is preferably R.sub.11a, where R.sub.11a is hydrogen, methyl; ethyl; C.sub.2-3 alkyl monosubstituted by hydroxy, methoxy, chlorine or cyano; cyclohexyl or, together with R.sub.10 and the nitrogen atom to which R.sub.10 and R.sub.11a are bound, forms a piperidine-, piperazine- or morpholine-ring. More preferably, it is R.sub.11b, where R.sub.11b is hydrogen, methyl, ethyl, monohydroxy substituted C.sub.2-3 alkyl, cyclohexyl or, together with R.sub.10 and the nitrogen atom to which R.sub.10 and R.sub.11b are bound, forms a piperazine ring. Most preferably, R.sub.11 is hydrogen.
X is preferably Xa, where Xa is --OH;--OR.sub.9a ; methyl, ethyl, phenyl; phenyl monosubstituted by chlorine, methyl or methoxy; or --NR.sub.10b R.sub.11b. More preferably, it is Xb, where Xb is --OH, --OR.sub.9b, methyl, ethyl, phenyl or --NHR.sub.10c. More preferably, it is Xc, where Xc is --OH, --OR.sub.9c or --NH.sub.2. Most preferably, X is OH.
Z is preferably Za, where Za is --OH; --OR.sub.9c ; phenyl; phenyl monosubstituted by chlorine, methyl or methoxy; --NR.sub.10a R.sub.11a ; --CH.sub.2 CH.sub.2 OSO.sub.3 H or --CH.dbd.CH.sub.2. More preferably, it is Zb, where Zb is --OH, phenyl, --NR.sub.10b R.sub.11b, --CH.sub.2 CH.sub.2OSO.sub.3 H or --CH.dbd.CH.sub.2. More preferably, it is Zc, where Zc is --OH, phenyl or --NHR.sub.10c . More preferably, it is Zd, where Zd is --OH or --NH.sub.2. Most preferably, Z is --OH.
Each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is preferably R.sub.1a, R.sub.2a, R.sub.3a and R.sub.4a, where each of R.sub.1a -R.sub.4a, independently, is hydrogen, chlorine, nitro, methyl, ethyl, methoxy, ethoxy, --NHCOR.sub.8a, --COXa or --SO.sub.2 Za, with the proviso that 1 to 3 of R.sub.1a -R.sub.4a are --SO.sub.2 Za or at least two of R.sub.1a -R.sub.4a are --COOH. More preferably, each of them, independently, is R.sub.1b, R.sub.2b, R.sub.3b and R.sub.4b, where each of R.sub.1b -R.sub.4b is hydrogen, chlorine, nitro, methyl, methoxy, --NHCOR.sub.8b, --COXb or --SO.sub.2 Zb, with the proviso that 1 or 2 of R.sub.1b -R.sub.4b are --SO.sub.2 Zb or at least two of R.sub.1b -R.sub.4b are --COOH. More preferably, each of R.sub.1 and R.sub.3, independently, is R.sub.1c and R.sub.3c, where each of R.sub.1c and R.sub.3c is --SO.sub.2 Zc; and each of R.sub.2 and R.sub.4, independently, is R.sub.2c and R.sub.4c, where each of R.sub.2c and R.sub.4c is hydrogen, chlorine, nitro, methyl, --NHCOCH.sub.3 or --COXc. More preferably, each of R.sub.1 and R.sub.3, independently, is R.sub.1d and R.sub.3d, where each of R.sub.1d and R.sub.3d is --SO.sub.2 Zd; and each of R.sub.2 and R.sub.4, independently, is R.sub.2d and R.sub.4d, where each R.sub.2d and R.sub.4d is hydrogen, chlorine or methyl. Most preferably, each of R.sub.1 and R.sub.3 is --SO.sub.3 H; and each of R.sub.2 and R.sub.4, independently, is hydrogen or chlorine.
Preferably, each R.sub.7, independently, is R.sub.7a, where R.sub.7a is hydrogen or chlorine; most preferably, R.sub.7 is hydrogen.
Any alkyl as R.sub.5 is preferably methyl or ethyl; any substituted alkyl is preferably monohydroxy substituted C.sub.2-3 alkyl.
Each R.sub.5 is preferably R.sub.5a, where each R.sub.5a, independently, is hydrogen, methyl, ethyl or monohydroxy substituted C.sub.2-3 alkyl. Most preferably, R.sub.5 is hydrogen.
Any alkoxy as R.sub.6 is preferably methoxy.
When R.sub.6 is an aliphatic amino group it is preferably a monoalkyl-or dialkyl-amino group in which the alkyl group contains 1 to 4 carbon atoms and is straight chain or branched and is optionally substituted by halogen, --NH.sub.2, carboxy, sulpho or one or two hydroxy groups.
Any cycloaliphatic amine radical as R.sub.6 is preferably a C.sub.5-6 cycloalkylamino group, especially a cyclohexylamino group.
Any aromatic amine radical is preferably phenylamino in which the phenyl ring is optionally substituted by 1 or 2 substituents selected from halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, --NHCOC.sub.1-4 alkyl, sulpho, carboxy and --SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H; more preferably, it is monosubstituted by --NHCOC.sub.1-4 alkyl, sulpho or --SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H.
Any heterocyclic amine radical as R.sub.6 is preferably morpholine, piperidine, piperazine or pyrrolidine which are further unsubstituted.
R.sub.6 is preferably either R.sub.6a, where R.sub.6a is chlorine, --OH, --NH.sub.2, methoxy, mono-C.sub.1-4 alkylamino, monohydroxy-C.sub.3-4 alkylamino, monoamino-C.sub.2-4 alkylamino; dihydroxy-C.sub.2-4 alkylamino, bis(monohydroxy-C.sub.2-4 alkyl)amino; phenylamino in which the phenyl ring is optionally substituted by 1 or 2 substituents selected from chlorine, methyl, methoxy, acetamido, sulpho, carboxy and --SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H; or morpholino; or R.sub.6ax, where R.sub.6ax is --OH, methoxy, mono-C.sub.1-4 alkylamino, dihydroxy-C.sub.3-4 alkylamino, bis(monohydroxy-C.sub.2-4 alkyl)amino, monoamino-C.sub.2-4 alkylamino; phenylamino in which the phenyl ring is substituted by 1 or 2 substituents selected from chlorine, methyl, methoxy, acetamido, sulpho, carboxy and --SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H; or morpholino. More preferably, R.sub.6 is either R.sub.6b where R.sub.6b is chlorine, mono-Chd 1-2alkylamiono, monohydroxy-C.sub.2-3 alkylamino, dihydroxy-C.sub.3-4 alkylamino, bis(monohydroxy-C.sub.2-3 alkyl)amino; phenylamino in which the phenyl ring is monosubstituted by acetamido or sulpho; or morpholino; or R.sub.6bx, where R.sub.6bx is mono-C.sub.1-2 alkylamino, dihydroxy-C.sub.3-4 alkylamino, bis(monohydroxy-C.sub.2-3 alkyl)amino, phenylamino in which the phenyl ring is monosubstituted by acetamido or sulpho; or morpholino. More preferably, R.sub.6 is either R.sub.6c, where R.sub.6c is chlorine, 2-hydroxyethylamino, bis(2-hydroxyethyl)amino or sulphophenylamino; or is R.sub.6cx, where R.sub.6cx is bis(2-hydroxyethyl)amino or sulphophenylamino. Most preferably, R.sub.6 is chlorine. In the compounds of formula I the naphthyl radicals are bound to the --NR.sub.5 -groups preferably in the 6,6'- or 7,7'-positions, more preferably in the 6,6'-positions. The sulpho group of the naphthyl radicals is preferably bound to the 3- and 3'-positions, respectively.
Preferred compounds correspond, in the free acid form, to formula Ia, ##STR3## in which either each R.sub.1 is sulpho in the 4-position, each R.sub.2 is hydrogen and R.sub.6 is R.sub.6ax, more preferably R.sub.6bx, most preferably R.sub.6cx ; or R.sub.1 and R.sub.2 are in the 4,6-positions and each of R.sub.1 and R.sub.2 is R.sub.1a and R.sub.2a (where R.sub.1a and R.sub.2a are independently of each other), with the exception that when one of R.sub.1a and R.sub.2a is sulpho in the 4-position, the other is different from hydrogen, and R.sub.6 is R.sub.6a, provided that one of R.sub.1a and R.sub.2a is --COOH or --SO.sub.2 a, and the other is different from --SO.sub.2 Z.sub.1 ; more preferably, each of R.sub.1 and R.sub.2 is R.sub.1b and R.sub.2b in the 4,6-positions (where R.sub.1b and R.sub.2b are independently of each other), with the exception that when one of R.sub.1b and R.sub.2b is sulpho in the 4-position, the other is different from hydrogen, and R.sub.6 is R.sub.6b, provided that one of the radicals R.sub.1b and R.sub.2b is --COOH or --SO.sub.2 Zb, and the other is different from --SO.sub.2 Zb; more preferably, each R.sub.1 is R.sub.1c and each R.sub.2 is R.sub.2c and R.sub.1c and R.sub.2c are in the 4,6-positions, provided that when R.sub.1c is sulpho in the 4-position, R.sub.2c is other than hydrogen, and R.sub.6 is R.sub.6c ; most preferably, each R.sub.1 is R.sub.1d, especially sulpho, and each R.sub.2 is R.sub.2d, especially hydrogen or chlorine, and R.sub.1d and R.sub.2d are in the 4,6-positions, provided that when R.sub.1d is sulpho in the 4-position, R.sub.2d is other than hydrogen, and R.sub.6 is R.sub.6c, especially chlorine.
Also preferred are compounds which, in free acid form, correspond to formula Ib, ##STR4## in which on each phenyl ring R.sub.1b and R.sub.2b , and R.sub.3b and R4b, respectively, are in the 4,6-positions provided that either at least one and at most three, preferably at most two of R.sub.1b to R.sub.4b are a group --SO.sub.2 Zb or, if no group --SO.sub.2 Zb is present, at least two of R.sub.1b to R.sub.4b, are --COOH. Further preferred are compounds of formula Ib, wherein
(1) R.sub.6a is R.sub.6b ;
(2) each of R.sub.1b and R.sub.3b, independently, is R.sub.1c and R.sub.3c and each of R.sub.2b and R.sub.4b, independently, is R.sub.2c and R.sub.4c, and the radicals R.sub.1c and R.sub.2c and the radicals R.sub.3c and R.sub.4c are in the 4,6-positions;
(3) those of (2) wherein R.sub.6a is R.sub.6b ;
(4) each of R.sub.1b and R.sub.3b, independently, is R.sub.1d and R.sub.3d and each of R.sub.2b and R.sub.4b, independently, is R.sub.2d and R.sub.4d and the radicals R.sub.1d and R.sub.2d and the radicals R.sub.3d and R.sub.4d are in the 4,6-positions;
(5) those of (4) wherein each of R.sub.1d and R.sub.3d is sulpho and each of R.sub.2d and R.sub.4d, independently, is hydrogen or chlorine;
(6) those of (4) or (5), wherein R.sub.6a is R.sub.6c ;
(7) those of (6), wherein R.sub.6a is chlorine.
When the compounds of formula I, Ia or Ib are in the salt form, the cation of the sulpho and/or carboxy groups is not critical and may be any of those non-chromophoric cations conventional in the field of anionic direct dyestuffs. Generally, in a compound of formula I, Ia or Ib the cations of the sulpho and/or carboxy groups may be the same or different, e.g. the compound may be in a mixed salt form;, preferably, the cations are the same. Examples of such cations are alkali metal cations and unsubstituted or substituted ammonium cations e.g. lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, triethylammonium and mono-, di- and tri-ethanolammonium.
The preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.
The present invention further provides a process for the preparation of compounds of formula I comprising reacting the following components:
diazotized amino compounds of formulae IIa and IIb, ##STR5## wherein R.sub.1 to R.sub.4 and R.sub.7 are as defined above and each W, independently, is hydrogen, hydroxy or methoxy,
coupling components of formula III, ##STR6## wherein R.sub.5 is as defined above;
a triazine compound of formula IV, ##STR7## wherein Hal is halogen;
optionally a base or a compound of formula V,
a copper-donating compound to obtain a 1:1 copper complex;
which components must be present in the corresponding stoichiometric molar ratio to obtain a compound of formula I -by coupling and condensing in any desired order and coppering the resulting monoazo compounds before or after the condensation reactions.
It is preferred to carry out coppering as a final step comprising reacting a compound of formula VI, ##STR8## in which R.sub.1 to R.sub.7 and W are as defined above, with a copper donating compound which is employed in such an amount to provide at least one equivalent of copper per equivalent of monoazo compound to be metallized.
In the case where different compounds of formulae IIa and IIb and/or different compounds of formula III are employed and the coupling reactions are carried out other than by two separate processes, namely, by a one step mixed coupling, a mixture of compounds of formula I is obtained consisting of those compounds having two different chromophores and those having identical chromophores.
The 1:1 metallization is carried out in accordance with known methods. Suitably, the corresponding hydroxy group-containing compounds (W.dbd.--OH) are used as starting materials, and coppering is preferably effected at a temperature range of 20.degree.-50.degree. C. in a weakly acid reaction medium using the conventional copper(II) salts. Likewise, oxidative coppering (W.dbd.H), preferably at 40.degree.-70.degree. C. and at pH 4-7 in the presence of copper(II) salts or using copper powder in the presence of hydrogen peroxide or other conventional oxidizing agents; or demethylation coppering (W.dbd.--OCH.sub.3), preferably at pH 4-6 and at elevated to boiling temperature in the presence of copper(II) salts, are carried out.
Diazotization and coupling reactions may be effected in conventional manner. The replacement of the halogen atoms in a compound of formula IV by separate condensation steps may be effected in conventional manner.
The compounds of formula I may be isolated in accordance with known methods, for example by conventional salting out with a small amount of an alkali metal salt, filtering and drying in vacuo.
The starting materials of formulae IIa, IIb, III and V are either known or may be prepared in accordance with known methods from available starting materials.
The compounds of formula I and mixtures thereof which are preferably in salt form are useful for dyeing or printing hydroxy group- or nitrogen-containing organic substrates. Preferred substrates are paper, leather and textiles containing or consisting of cellulose fibres, such as cotton.
The compounds according to the invention show high affinity for the substrate and therefore are good direct dyes. Dyeing and printing may be carried out in accordance with known methods. Dyeing of natural or regenerated cellulose such as cotton is preferably carried out according to the conventional exhaust dyeing method using temperatures from 50.degree. to 100.degree. C. Continuous dyeing methods are also suitable and thus processes such as cold pad-batch, pad-steam, pad-roll or pad-dry may be applied.
The compounds of formula I give deep dyeings and show high exhaustion yields. The dyestuffs are also suitable for dyeing in combination with analogous dyes showing similar dyeing properties. Dyeings and prints on the above mentioned substrates exhibit good wet fastnesses (such as fastness to water, washing or sweat) and good light fastness. Furthermore, they show good fastness to peroxide, perborate and chlorinated water. The fastness to dry cleaning is also good.
The wet fastness properties of the dyeings and printings on textile material containing or consisting of cellulose fibres, especially on cotton, made with the compounds of formula I or a mixture thereof may be notably improved by a special resin after-treatment with cationic auxiliaries. Particularly, this treatment gives improved wash-fastness properties allowing repeated washing at high temperatures.
Suitable for applying to the dyed or printed substrate is a fixing agent comprising a precondensate of either
Details concerning the fixing agent as a combination of A), C) and D) and its use are described in British Published Patent Application No. 2 070 006, of which the whole subject matter disclosed on pages 1 to 6 is hereby incorporated by reference. Details concerning the combination B), C) and D) are described in British Published Patent Application No. 2 084 597, of which the entire subject matter disclosed on pages 1 to 5 and 7 is hereby incorporated by reference.
The following examples further serve to illustrate the subjects of the invention. In the examples all parts and percentages are by weight or volume and all temperatures are in degrees Centigrade.
US Referenced Citations (5)
Foreign Referenced Citations (13)
| Number |
Date |
Country |
| 0011873 |
Jun 1980 |
EPX |
| 436179 |
Oct 1926 |
DE2 |
| 1002898 |
Feb 1957 |
DEX |
| 2360725 |
Jun 1974 |
DEX |
| 1519130 |
Mar 1968 |
FRX |
| 39-23971 |
Oct 1964 |
JPX |
| 58-96656 |
Jun 1983 |
JPX |
| 523572 |
May 1984 |
ESX |
| 1454210 |
Nov 1976 |
GBX |
| 2007250 |
May 1979 |
GBX |
| 2007698 |
May 1979 |
GBX |
| 2114992 |
Sep 1983 |
GBX |
| 2122634 |
Jan 1984 |
GBX |
Non-Patent Literature Citations (2)
| Entry |
| Venkataraman, "The Chemistry of Synthetic Dyes", vol. I, pp. 523, 547 (1952). |
| Colour Index, 3rd Ed., vol. 4, pp. 2132, 4274, 5102 (1971). |
Continuations (1)
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Number |
Date |
Country |
| Parent |
683602 |
Dec 1984 |
|
Continuation in Parts (1)
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Number |
Date |
Country |
| Parent |
503268 |
Jun 1983 |
|
Patent Grant
5006644
