GB2058815A

GB2058815A - Anionic disazo dyestuffs

Info

Publication number: GB2058815A
Application number: GB8025714A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1979-08-10
Filing date: 1980-08-06
Publication date: 1981-04-15
Also published as: DE3028838A1; FR2465766A1; JPS5628244A; ES494137A0; BE884619A; ES8200712A1; IT8024083A0; CH643580A5; CA1145331A; BR8005021A; GB2058815B

Abstract

The present invention relates to compounds of formula I, <IMAGE> in which A is the radical of a sulpho group containing diazo component of the aniline- or amino- naphtalene-series, K is a coupling component radical of the phenol series, of which the free hydroxy group may be etherified or acrylated, R1 is hydrogen, alkoxy or optionally substituted alkyl, R2 is alkyl, alkyl, -CONH2 or alkyl or hydroxyalkyl bound to -CO-, -COO- or <IMAGE> and R10 is hydrogen or C1-4 alkyl, and mixtures thereof, which compounds are in free acid or salt form and are useful for dyeing or printing anionic dyeable substrates.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to anionic disazo compounds, their preparation and use as anionic dyestuffs.

More particularly, the present invention provides compounds of formula I,

in which A is the radical of a sulpho group containing diazo component of the aniline series or 1- or 2 aminonaphthalene series, K is a coupling component radical of the phenol series, the free hydroxy group of which may be etherified or acylated, R, is hydrogen, C1-4alkoxy or C1-4alkyl optionally monosubstituted by halogen, Rz is C1-4alkyl, -CO(C1-6)alkyl, -COO(C1-6)alkyl, -CONH2, -CONH(C1-6)alkyl, -CON(C1-6alkyl)2, -COHN(C2-6)hydroxyalkyl or -CON(C26hydrnxya Ikyl)2 with the hydroxy group in other than the 1-position and R10 is hydrogen or C1-4alkyl and the molecule contains one single sulphonic acid group which is in the radical A, and mixtures of such compounds, which compounds are in free acid or salt form.

Any alkyl or alkoxy groups as R1, preferably contain 1 or 2 carbon atoms, more preferably 1 carbon atom; any alkyl substituted by halogen is preferably monochloro(C1-2)alkyl.

R, is preferably R1', where R; is hydrogen; methyl, ethyl, methoxy or ethoxy. More preferably R, is R1", where R', is hydrogen, methyl or methoxy. Most preferably R, is R1"', where R1"' is hydrogen or methoxy, with hydrogen being especially preferred.

Any alkyl as R2 is preferably methyl or ethyl, especially methyl. Any C1-6alkyl group in R2 which is bound to -CO-, -COO- or

preferably contains 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and is most preferably methyl. Any C2-6hydroxyalkyl group is preferably 2-hydroxyethyl or 2- or 3-hydroxypropyl.

R2 is preferably R2', where R2' is -CO(C1-4)alkyl, -COO(C1-4)alkyl or -CONH2. More preferably R2 is R2", where R2" is -CO(C1-2)alkyl, -COO(C1-2)alkyl or -CONH2. Most preferably R2 is R2"', where R2"' is -COCH3,-COOCH3 or -CONH2, especially -COCH3.

Any alkyl as R10 is preferably methyl or ethyl, especially methyl.

R10 is preferably hydrogen, methyl or ethyl, more preferably hydrogen or methyl, especially hydrogen.

A is preferably a radical of formula (a) or (b),

in which R3 is hydrogen, halogen, C1-4alkyl optionally monosubstituted by halogen; C1-4alkoxy, monoC1-6alkylamino, di-C1-6alkylamino, C1-6alkylcarbonylamino, C1-12alkoxycarbonylamino or N-C1~4alkyl-N-(C1~6alkyl or C1-12alkoxy)carbonyl-amino, and R4 is hydrogen, halogen, C1-4alkyl or C1-4alkoxy.

K is preferably a radical of formula (c) or (d),

in which each of R5a and R5b is hydrogen, C1-4alkyl, C2-4hydroxyalkyl with the hydroxy group in other than the 1position; -COR8, -COOR8 or

in which R8 is C,~,2alkyl or phenyl-C1-4alkyl, and R9 is hydrogen, halogen, C1alkyl or C14alkoxy, R6a is an aliphatic, cycloaliphatic, carbocyclic aromatic or araliphatic radical; halogen, C1-4alkoxy, -NR11CO(C1-6)alkyl or -NR11COO(C1-6)alkyl, R7 is hydrogen, halogen, C1-4alkyl, C1-4alkoxy or -NR11CO(C1-6)alkyl, with the proviso that R7 is other than -NR11CO(C1-6)alkyl when R6a is -NR11CO(C1-6)alkyl; R6b is hydrogen, C1-4alkyl, C1-4alkoxy, halogen, -NR11CO(C1-6)alkyl or -NR11COO(C1-6)alkyl, and R,1 is hydrogen or C1-4alkyl.

By halogen is meant fluorine, chlorine or bromine. Any halogen on a phenyl ring is preferably chlorine or bromine, especially chlorine; any alkyl substituted by halogen is preferably substituted by fluorine, chlorine or bromine, especially by chlorine.

Any unsubstituted or substituted alkyl groups as R3 preferably contain 1 or 2 carbon atoms, especially 1 carbon atom; R3 is preferably unsubstituted alkyl. Any alkyl as R4 is preferably methyl or ethyl, especially methyl. Any alkoxy as R3 or R4 is preferably methoxy or ethoxy, especially methoxy.

Any mono-alkylamino group as R3 preferably contains a methyl- or ethyl-, especially a methyl group. Any dialkylamino group as R3 preferably contains methyl- and/or ethyl groups, especially methyl groups. Any C1-4alkyl in N-alkyl-N-alkylcarbonyl- or -N-alkoxycarbonyl-amino as R3 is preferably methyl.

Any alkylcarbonylamino as R3 is most preferably acetamido; any alkoxycarbonylamino is preferably C1-4alkoxy-, most preferably C1-2alkoxycarbonylamino, or C8-12alkoxycarbonylamino.

R3 is preferably R3', where R3' is hydrogen, halogen, C1-4alkyl, C1-4alkoxy or acetamido. More preferably R3 is R3", where R3" is hydrogen, chlorine, C1-2alkyl, C1-2alkoxy or acetamido. Most preferably R3 is R3"', where R3", is hydrogen, chlorine, methyl, methoxy or acetamido, especially hydrogen.

R4 is preferably R4', where R4' is hydrogen, halogen, C1-2alkyl or C1-2alkoxy. More preferably R4 is R4", where R4" is hydrogen, chlorine, methyl or methoxy. Most preferably R4 is hydrogen. Preferably R4 is hydrogen, when R3, R3', R3" or R3"' is acetamido.

When both R3 and R4 are hydrogen the sulpho group is preferably in the 3- or 4-position (with the azo group in the 1- position). When one of R3 and R4 is hydrogen and the other is other than hydrogen the preferred positions are 2,4; 2,5; 2,6 or 3,4, especially 2,4 or 2,5. When both R3 and R4 are other than hydrogen the three substituents are preferably in the 2,3,5-; 2,4,5- or 2,4,6-positions and most preferably in the 2,4,5- or 2,4,6-positions.

Especially preferred is the radical of formula (a), wherein (i) both R3 and R4 are hydrogen and the sulpho group is in the 3- or 4-position; or wherein (ii) one of R3 and R4 is hydrogen and the other is chlorine, methyl or methoxy, the positions for R3 or R4 and the sulpho group are 2,4 or 2,5; or wherein R4 is hydrogen and R3 is acetamido in the 4- or 5position and the sulpho group is in the 2-position; or wherein (iii) R3 and R4, independently, are methyl, methoxy or chlorine and R3, R4 and the sulpho group are in the 2,4,5- or 2,4,6-positions.

When the naphthalene radical of formula (b) is bound in the 1-position, the sulpho group is preferably in the 4-, 5-, 6-, 7- or 8-position, especially in the 4- or 5-position. When the naphthalene radical is bound in the 2-position, the sulpho group is preferably in the 1-, 5-, 6-, 7- or 8-position, especially in the 1-, 5- or 6-position.

The radical (b) is preferably (b,), where (b), is 4- or 5-sulphonaphthyl-1 or 1-, 5- or 6sulphonaphthyl-2.

Any unsubstituted or substituted alkyl as R5a or R5b is preferably straight chain; any unsubstituted alkyl is preferably methyl or ethyl; any substituted alkyl is preferably 2-hydroxyethyl or 2- or 3hydroxypropyl. Any -COR8 group as R5a or R5b preferably contains R8a", where R8a' is straight chain or branched C1-4alkyl or phenyl-(C1-3)alkyl; more preferably it contains R8a", where R8a" is methyl, ethyl or benzyl. Any -COOR8 group as R5a or R5b preferably contains R8b', where R8b' is straight chain or branched C1-12alkyl or phenyl-(C1-3)alkyl; more preferably it contains R8b", where R8b" is straight chain or branched C8-12alkyl or benzyl; most preferably it contains R8b"', where R8b"' is C8-12alkyl. In the

group any halogen as R9 is most preferably chlorine; any alkyl is preferably methyl or ethyl, especially methyl, and any alkoxy is preferably methoxy or ethoxy.

R5a is preferably R5a', where R5a' is hydrogen, methyl, ethyl, 2-hydroxyethyl, -COR8a", -COO8b', phenylsulphonyl or tosyl. More preferably R5a is R'sa, where R5a" is hydrogen, methyl, ethyl or COOR'8'b (especially-COOR8b"'). Even more preferably R5a is R5a"', where R5a"' is hydrogen, methyl or ethyl. Most preferably R5a is R5aiv, where R5aiv is hydrogen or methyl, especially hydrogen.

R5b is preferably R5b', where R5b' is hydrogen, straight chain C1-4alkyl, 2-hydroxyethyl, 2- or 3hydroxypropyl, -COR8a', -COOR8b', phenylsulphonyl or tosyl. More preferably R5b is R5b", where R5b" is hydrogen, straight chain C1-4alkyl, -COR8a", -COOR8b" (especially -COOR8b"'); phenylsulphonyl or tosyl.

Even more preferably R5b is R5b"', where R5b"' is hydrogen or straight chain C1-4alkyl. Most preferably R5b is R, where R5biv is methyl or ethyl, especially methyl.

Any alkyl as R11 in the groups R6a, R6b or R7 is preferably methyl or ethyl, especially methyl.

R11 is preferably hydrogen or methyl, especially hydrogen.

Any aliphatic, cycloaliphatic, carbocyclic aromatic or araliphatic groups as R6a may contain conventional substituents, for example substituents selected from the group consisting of halogen (fluorine, chlorine or bromine), C1-4alkyl and C1-4alkoxy; additionally, particularly any aliphatic group may contain hydroxy or cyano-groups.

Any aliphatic group as R6a is preferably an unsubstituted straight chain or branched alkyl group containing 1-10 carbon atoms, more preferably 1-6 and especially 1-4 carbon atoms. Any cycloaliphatic group preferably contains 5-7 carbon atoms, especially 6 carbon atoms. Any carbocyclic aromatic or araliphatic group as R6a is preferably an unsubstituted or substituted phenyl- or phenyl-(C1-4)alkyl-group in which the substituents are selected from the group consisting of halogen, C1-4alkyl and C1-4alkoxy.

Any halogen as R6a is preferably chlorine; any alkoxy is preferably methoxy or ethoxy.

Any -NCOalkyl or -NCOOalkyl groups as R6a preferably contain C1-4alkyl groups, especially C1-2alkyl groups.

R6a is preferably R6a', where R6a' is straight chain or branched C1-6alkyl, cyclohexyl, phenyl, benzyl, chlorine, methoxy, ethoxy or acetamido. More preferably R8a is R6a", where R6a" is straight chain or branched C1-4alkyl, benzyl, chlorine, methoxy or ethoxy. Most preferably R6a is R6a"', where R6a"', is straight chain or branched C1-4alkyl or chlorine.

Any halogen as R7 is preferably chlorine; any alkyl or alkoxy groups preferably contain 1 or 2 carbon atoms, especially 1 carbon atom. Any -NCOalkyl as R7 preferably contains C1-4alkyl groups, more preferably C1-2alkyl groups, and is most preferably acetamido.

R7 is preferably R7,, where R; is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or acetamido.

More preferably R7 is R7", where Rt7 is hydrogen, chlorine, methyl, methoxy or acetamido, especially hydrogen.

Any halogen as R6b is preferably chlorine or bromine; any alkyl or alkoxy groups as R6b preferably contain 1 or 2 carbon atoms, especially 1 carbon atom. Any -NCOalkyl or -NCOOalkyl groups as R6b preferably contain C1-4alkyl, especially methyl.

R6b is preferably R6b', where R6,b is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy or acetamido. More preferably R6b is R'6b, where R'6b is hydrogen, chlorine, methyl, methoxy or acetamido, especially hydrogen.

A is preferably a group (a,), where (a1) is a group of formula (a), wherein R3 is R3' and R4 is R4', or of formula (b,). More preferably A is a group (a2), where la2) Is a group of formula (a), wherein R3 is R'3 and R4 is R4, or of formula (b,). Most preferably A is a group (a3), where (a3) is a group of formula (a), wherein R3 is R"3, especially hydrogen, and R4 is R4", especially hydrogen. In the groups (a1) to (a3) the substituents are in the above-given preferred positions.

K is preferably a group (c), where (c1) is a group of formula (c), wherein R5a is R6a', R6a is B0,a and R7 is R7'; o or a group (d), where (d1) is a group of formula (d), wherein Rsb is B5,b (especially R5b") and R6b is R6b. More preferably K is a group (c2), where (c2) is a group of formula (c), wherein R5a is R5a"', R6a is R6a" and R7 is R'7; or a group (d2), where (d2) is a group of formula (d), wherein Rsb is R5b"' and R6b is R6b. Even more preferably K is a group (C3), where (c3) is a group of formula (c), wherein Rsa is R5aiv (especially hydrogen), R6a is R6a"' and R7 is hydrogen; or a group (d2).Still further more preferably K is a group (d3), where (d3) is a group of formula (d), wherein Rsb is R5b"' and Rob is R'6b, and most preferably K is a group (d4), where (dd) is a group of formula (d), wherein Rob is R5biv (especially methyl) and Rob is hydrogen.

Preferred compounds of formula I are (1) those wherein A is a group (a1) or (b,); (2) those wherein A is a group (a2) or (b,); (3) those wherein R, is R1', R2 is R2 and R10 is hydrogen; (4) those wherein K is a group (c,) or (d,); (5) those wherein K is a group (c3) or (d2); (6) those wherein K is a group (d2); (7) those of formula la,

in which A2 is a group of formula (a2)

and K2 is a group of formula (d3),

(8) those of(7), wherein A2 is a group (a3); (9) those of (7), wherein K2 is a group (d4), and especially the group

(10) those of (7), (8) or (9), wherein R', is R1"', especially hydrogen, and R'2 is R2"', especially -COCH3.

The present invention further provides a process for the production of compounds of formula I comprising coupling the diazonium derivative of the compound of formula II,

or a mixture thereof, with a coupling component of the phenol series, and optionally etherifying or acylating the hydroxy group.

Thus, compounds of formula Ib,

in which A, is a group of formula (a) or (b), K, is a group of formula (c) or (d) and R,, R2 and Rro are as defined above, and mixtures thereof are obtained comprising a) coupling the diazonium derivative of the compound of formula lla,

or a mixture thereof, with a phenol of formula Illa or llib

or a mixture thereof, to obtain a compound of formula Ix,

in which Kix is a group of formula (ax) or (bx)

or a mixture thereof, or b) etherifying or acylating a compound of formula Ix or a mixture thereof, to obtain a compound of formula Ib wherein B51 or Rsb is other than hydrogen.

The coupling reaction may be effected in accordance with known methods; suitably, coupling is effected in alkaline medium at the pH range of 9 to 13, the preferred pH being from 10 to 12.

Diazotization of a compound of formula II or Ila to produce the starting materials thereof may also be carried out in conventional manner.

The etherification or acylation may be effected in known manner. Suitably, the etherification is carried out employing the corresponding dialkylsulphate or alkyleneoxide. The reaction is suitably carried out in aqueous alkaline medium, the preferred pH being from 9 to 11. The reaction temperature is suitably from 30 to 900C, more preferably from 40 to 700 C.

Acylation is suitably effected employing the corresponding acid chloride. The reaction mixture is preferably aqueous which is made alkaline with soda, the preferred pH being vom 8 to 10. The reaction temperature is suitably between 30 and 900 C, preferably between 60 and 700 C.

The compounds of formula I may be isolated in accordance with known methods. In general owing to the process/isolation conditions, the compounds of formula I may be obtained in salt form.

When the compounds of formula I are in the salt form, the cation of the sulpho group is not critical and may be any of those non-chromophoric cations conventional in anionic dyestuffs. Examples of such cations are alkali metal cations and cations of the ammonium type including unsubstituted and substituted ammonium cations e.g., lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra methylammonium, triethylammonium and mono-, di- and tri-ethanol-ammonium. The preferred cations are the alkali metal cations including ammonium, with sodium being the most preferred.

The compounds of formula I which are in the salt form may be converted into the free acid form or into other salt forms in accordance with known methods.

The starting materials of formula II are either known or may be prepared in accordance with known methods from available starting materials. Thus, the compounds of formula II are obtained by coupling the diazonium derivative of an amine A-NH2 in a weakly acid to neutral medium with the corresponding aniline of formula IV,

or a derivative thereof reacted with Gs-methanesulphonic acid. Compounds of formula IV and phenols of formula Illa or Illb are either known or may be prepared in accordance with known methods from available starting materials.

The compounds of formula I and mixtures thereof are useful for dyeing or printing anionic dyeable substrates. Suitable substrates include leather, natural or synthetic polyamides, polyurethanes and basic-modified polyolefins. Especially suitable are textile substrates consisting of or comprising natural and synthetic polyamides, such as wool and silk, and particularly nylon. The dyestuffs may advantageously be used for carpet printing.

The compounds of formula I and mixtures thereof, may be employed as such or may be used in the form of liquid or solid preparations. The preparation of stable liquid, for example concentrated aqueous preparations, or solid preparations may be carried out in accordance with conventional methods, for example by dissolving in suitable soivents e.g. water, optionally with the addition of conventional additives such as solubilizing agents, for example urea, or by grinding or granulating. Such preparations may be obtained in accordance with the procedure described in French Patents 1,572,030 or 1,581900 Further, the compounds of formula I and mixtures thereof, may be made up into preparations which are dispersible in cold water.Such dispersions may be prepared, for example, by grinding the dye dry or wet in aqueous dispersing medium in the presence of one or more conventional anionic dispersing agents and optionally in the presence of other conventional additives, optionally with subsequent spray-drying. The preparations so obtained are finely dispersed in cold water.

Dyeing and printing may be carried out in accordance with known methods, for example pad dyeing or exhaust dyeing, especially the latter since the compounds of formula I and mixtures thereof exhaust from a neutral dyebath. Furthermore, the compounds of formula I and mixtures thereof are also useful for use in the "space-dyeing" process.

The compounds of formula I and mixtures thereof are well soluble in water, build-up well, migrate well and give even dyeings, especially on stripy nylon. The dyeings obtained possess notable lightfastness. Furthermore, the compounds of formula I and their mixtures give dyeings which have notable general fastnesses, such as wet-fastnesses, especially wash-, water-, milling- and sweat-fastness.

The compounds of formula I are suitable for combining with other anionic dyes which exhaust from a neutral dyebath, whereby tone-in-tone dyeings having the above-mentioned advantageous properties are obtained. Further, such dyeings do not exhibit catalytic fading.

The following Examples further serve to illustrate the invention. In the Examples, all parts are by weight and all degrees are in degrees Centigrade.

EXAMPLE 1 17.3 Parts sodium salt of 1 -aminobenzene-3-sulphonic acid are dissolved in 80 parts water and are then mixed with 6.9 parts sodium nitrite. This solution is slowly added with stirring to a mixture of 50 parts ice and 28 parts 30% hydrochloric acid. After 1 hour at 510 , the excess of nitrous acid is destroyed by adding a small quantity of amidosulphonic acid. The diazonium suspension obtained is added to a solution of 1 8.7 parts 3-aminoacetanilide in the hydrochloric acid salt form and 5 parts calcinated sodium carbonate in 1 50 parts water and 100 parts ice, at O5 while stirring, the pH being maintained at 6-7 by the addition of calcinated sodium carbonate. After stirring for 1 hour, the monoazo compound is salted out by the addition of sodium chloride. The precipitated dyestuff is isolated by filtering and washed with 5% sodium chloride solution.

The paste obtained is dissolved in 170 parts water of 600 and is then mixed with 6.9 parts sodium nitrite. This solution is slowly added dropwise to a mixture of 60 parts ice and 28 parts hydrochloric acid, the temperature being kept at 510 by the addition of ice. After 2 hours the excess of nitrous acid is destroyed by the addition of amidosulphonic acid. The diazonium suspension is slowly added to a solution of 9.5 parts phenol and 13 parts 30% caustic soda in 140 parts water at room temperature.

After 1 5 minutes the coupling reaction is complete. The dyestuff is precipitated by the addition of sodium chloride at pH 9, and is isolated by filtering, washed with 5% sodium chloride solution and dried.

The dyestuff which, in the free acid form, corresponds to the formula

is obtained in the sodium salt form and gives dyeings on natural or synthetic polyamides of reddishyellow shades which have good light- and wet-fastnesses.

EXAMPLE 2 The etherification of the hydroxy group of the disazo dyestuff obtained by the method of Example 1 is carried out as follows: The filtered and washed dyestuff of Example 1 in paste form is dissolved in water of 4550 by adding of 10 parts 30% sodium hydroxide solution. To this solution 25 parts dimethylsulphate are added while stirring vigorously, the pH being kept at 10.5-11.0 by the addition of 30% sodium hydroxide solution. After 4 hours the etherification is complete. Precipitation of the dyestuff is completed by adding sodium chloride. The dyestuff is isolated by filtering, washed with 5% sodium chloride solution and dried.The disazo compound which, in the free acid form, corresponds to the formula

is obtained in the sodium salt form and gives dyeings on natural or synthetic polyamides of reddish yellow-shades. The dyeings have good light- and wet-fastnesses.

In analogy with the procedure described in Example 1 using a mixture of 1-aminobenzene-3- and 4-sulphonic acid (in the ratio of approximately 1:1) instead of 1 -aminobenzene-3-sulphonic acid, the mixture of corresponding dyestuffs is obtained which can be etherified according to the method described in Example 2. This mixture of dyes (containing hydroxy groups or methoxy groups) is particularly well soluble in water and therefore especially useful for dyeing of natural or synthetic polyamides, giving dyeings of reddish-yellow shades which have good light-and-wet-fastnesses.

In the following tables further dyestuffs are given which are prepared in analogy with the procedure described in Example 1 or 2. These dyestuffs, owing to the reaction- and isolation-steps, are obtained in the sodium salt form. The dyestuffs correspond to the general formula A,

for Table 1; to the general formula B,

for Table 2; and to the general formula C,

for Table 3.

The symbol I in the last column of the tables denotes the dye shade on natural or synthetic polyamides, especially on nylon, where a is reddish-yellow: b is orange; c is scarlet-red; d is red; e is yellowish-red; f is brownish-yellow; g is brownish-red; and h is brown.

The polyamide dyeings obtained have good light- and wet-fastnesses.

TABLE 1 / formula A

Example position No. SO3H R3 R1 R2 R5 l 3 4 H H COCH3 H a 4 4 H H do. CH3 a 5 3 H OCH4 do. H c 6 3 H do. do. CH3 c 7 4 H do. do. do. c 8 4 H do. do. C2H5 c 9 4 H H do. Tosyl a 10 3 H H CONH2 H a 11 3 H H do. CH3 a 12 2 -NHCOCH2(4) H COCH3 H a 13 2 do. H do. CH3 a 14 2 -NHCOCH3(5) H do. do. a 15 3 H CHs do. do. a 16 3 H OCH3 do. C2H5 c 17 4 CH3(2) do. do. CH2 c 18 4 do. CH3 do. do. a 19 4 do. do. do. C2H5 a 20 5 do. H do. CH3 b 21 2 CH3(4) OCH3 do. do. c 22 5 OCH3(2) H db. C2H5 23 2 Cl(4) H do. CH3 a 24 2 do. H do. Tosyl a 25 5 CI(2) H do. CH3 a 26 3 H OCH3 do. COOCH3 b 27 3 H do. do. COOCH2CH(CH3)2 b 28 3 H do. do. COOC10H21(n) b 29 4 CH3(2) do. do. C2Hs c 30 4 Cl(2) do. do. OH3. c 31 2 -NHCOCH3(4) do. do. do. c TABLE 1 continued

Example position No. SO3H R3 R2 R2 R5 32 3 H H COC2Hs do. a 33 -4 H H do. do. a 34 4 H OCH3 COC2H5 C2H5 c 35 3 H H do. do. a 36 3 H H do. Tosyl a 37 5 Cl(2) H COOCH3 CH3 a 38 5 do. CH3 do. do. a 38 2 CH3(4) OCH2 do. do. c 40 2 do. H do. do. a 41 2 do. - H do. C2H5 a 42 5 OCH3(2) H do. CH3 b 43 4 H H do. C2H5 a 44 4 H H COOC2Hs CH3 a 45 3 H OCH3 CONH2 do. c 46 4 H do. do. do. c 47 4 H H do. Tosyl a TABLE 2 / formula B

Example position No. SO3H R3 R4 R1 OR5 R6 R7 l 48 4 H H H OH(2) Cl(5) H a 49 4 H H H OCH3(2) do. H a 50 3 H H H OH(2) do. H a 51 3 H H H OCH3(2) do. H a 52 3 H H OCH3 OH(2) do. H g 53 3 H H do. OCH3(2) do. H e 54 3 H H CH3 OH(2) C(CH3)3(5) H b 55 3 H H OCH3 do. do. CH3(3) d 56 3 H H do. OC2H5(2) CH3(5) H d 57 4 H H do. OCH3(2) CH(CH3)2(5) H d 58 4 H H CH3 OH(2) CH3(5) H b 59 3 H H OCH3 OCH3(4) -NHCOCH3(3) H b 60 3 H H do. OC2H5(4) do. H c 61 3 H H CH3 do. -NHCOCH3(2) H d 62 4 H H OCH3 OCH3(4) do. H d 63 5 CH3(2) H H do. CH3(2) H b 64 6 do. CH3(4) OCH3 OC2H5(4) H H C TABLE 2 continued

Example 'CI P CI cn o No. SOsH B1 B4 B1 OR,, B,, B? I 65 2 Cl(S) CH1(4) OH3 OCH3(4) H H a 66 4 pI(2) Cl (5) OCH3 do. H H c 67 4 do. do. H do. H H a z I I I I :E: I b 69 3 H H H OCH1(4) -NHCOCH1(3) H a i3oS s; 6i3 71 3 H H H OH(2) OH1 (5) NHCOCI:l3(3) I CC I I I o o I I xX o do. do. X 73 3 H H H OC3H,,(4) -NHCOCH3(2) H b 74 4 H H 00K1 OCH3(4) do. H d 75 3 H H do. OCH3(2) -NHCOCH3(5) H 76 3 H H do. 00000K3 (4) -NKCOCH3(2) H d OH3 77 3 K H do,. OCOOCH2C (4) do. H d e O o o 8 ct O O 79 3 H H do. 002H,, (2) -NHCOCK3 (5) H g 60 3 H fdd d d d O O În N GO O CQ &commat; E t O o s eo CD o sa z so ED s0 s0 (D b N N b rv N b s rv s so UJ TABLE 2 continued

Example position No. SO3H R3 R4 R1 OR5 R6 R7 l 81 3 H H OCH3 OCH3(4) Cl(2) H c 82 3 H H do. OH(2) C(CH3)3(5) H g 83 3 H H do. OCH3(4) CH3(2) H b 84 4 Cl(2) H do. OH(2) C(CH3)3(5) H g 85 4 do. H do. OCH3(4) do. H c 86 3 H H do. OH(2) CH3(5) -NHCOCH3(3) h 87 4 Cl(2) H do. OCH3(4) -NHCOCH3(2) H d 88 3 H H do. do. OCH3(2) H c 89 4 OCH3(2) CH3(5) do. OH(4) H H c 90 4 do. do. do. OCH3(4) H H c 91 3 H H do. do. -NHCOCH3(2) H c TABLE 3 / formula C

Example No. A R1 R2 OR5 R6 92 4-Sulfonaphthyl-1 H COCK1 OH(4) H c 93 do. H do. OCH3(4) H c 94 5-Sulfonaphthyl-1 H do. do. H c 95 do. H -COC2H, do. H c 96 do. H CONH2 do. H c 97 do. H COCH3 OH(2) Cl(5) c 98 6-Sulfonaphthyl-2 H do. OH (4) H b 99 do. H do. OCH3(4) H b 100 do. CH3 do. do. H c 101 do. OCH3 do. do. H d 102 do. H do. OCH3(2) Cl(5) b 103 5 Sulfonaphthyl-2 H do. OH(4) H b 104 do. H do. OCH3(4) H b 105 14ulfonaphthyl-2 CH3 do. do. K C EXAMPLE 106 In analogy with the procedure described in Examples 1 and 2 using appropriate starting materials a dyestuff may be prepared which, in the free acid form, corresponds to the formula

and is obtained in the sodium salt form. The dyestuff gives dyeings on natural or synthetic polyamides of scarlet-red shades.

The dyestuffs of Example 1 to 106 which are in the sodium salt form may, depending on the reaction/isolation conditions, be obtained in accordance with known methods in free acid form or in other salt forms, for example those salt forms indicated in the description hereinbefore.

Application Example A 100 Parts of pre-wetted synthetic polyamide, for example nylon 66, are entered at 40O into a dyebath consisting of 4000 parts water, 10 parts of anhydrous sodium sulphate and 2 parts of the dyestuff of Example 2.

The dye liquor is heated over the course of 30 minutes to boiling temperature and kept at this temperature for 1 hour. 4 Parts of glacial acetic acid are then added thereto and dyeing is completed with heating for a further 30 minutes at boiling temperature. During dyeing, the water that evaporates is continuously replaced. The reddish-yellow dyed nylon cloth is then removed from the liquor, rinsed with water and dried. Wool may also be dyed by the same process.

Similarly, the dyes of Examples 1 and 3 to 106, or mixtures of two or more of the dyestuffs of Examples 1 to 106 may be employed to dye nylon or wool in accordance with the method described above.

Application Example B Polyamide is printed with a printing paste containing: 30 parts dyestuff of Example 2 50 parts urea 50 parts solubilizing agent (e.g. thiodiethylene glycol) 290 parts water 500 parts suitable thickening agent (e.g. based on carob bean gum) 20 parts acid donating agent (e.g. ammonium tartrate) 60 parts thiourea.

The printed textile goods are steamed for 40 minutes at 1020 (saturated steam), rinsed cold, subsequently washed at 600 for 5 minutes with a dilute solution of a conventional detergent and rinsed again with cold water. A reddish-yellow print having notable light- and wet-fastnesses is obtained.

In analogous manner printing pastes may be made employing the dyestuffs of Examples 1 and 3 to 106 or mixtures of two or more of the dyestuffs of Examples 1 to 106. Such pastes may be employed for printing in accordance with the above given procedure.

Claims

1. A compound of formula I,

in which A is the radical of a sulpho group containing diazo component of the aniline series or 1- or 2 aminonaphthalene series, K is a coupling component radical of the phenol series, the free hydroxy group of which may be etherified or acylated, R1 is hydrogen, C1-4alkoxy or C1-4alkyl optionally monosubstituted by halogen, R2 is C1-4alkyl, -CO(C1-6)alkyl, -COO(C1-6)alkyl, -CONH, -CONH(C1-6)alkyl, -CON(C1-6alkyl)2, -CONH(C2-6)hydroxyalkyl or -CON(C2-6hydroxyalkyl)2 with the hydroxy group in other than the 1-position and RX0 is hydrogen or C14alkyl and the molecule contains one single sulphonic acid group which is in the radical A, and mixtures thereof, which compound is in free acid or salt form.

2. A compound according to Claim 1, in which R, is RI, where B1, is hydrogen, methyl, ethyl, methoxy or ethoxy.

3. A compound according to Claim 1 or Claim 2, in which R2 is R2', where R2' is -CO(C1-4)alkyl, -COO(C1-4)alkyl or -CONH2.

4. A compound according to any one of Claims 1 to 3, in which R10 is hydrogen.

5. A compound according to any one of the preceding claims, in which A is a radical of formula (a) or(b),

wherein R3 is hydrogen, halogen, C1-4alkyl optionally monosubstituted by halogen; C1-4alkoxy, mono C1-6alkylamino, di-C1-6alkylamino, C1-6alkylcarbonylamino, C1-12alkoxycarbonylamino or N C1-4alkyl-N-(C1-6 or C1-12alkoxy)carbonyl-amino, and R4 is hydrogen, halogen, C1-4alkyl or C1-4alkoxy.

6. A compound according to any one of the preceding claims, in which K is a radical of formula (c) or(d),

wherein each of R,, and R5b is hydrogen, C1-4alkyl, C2-4hydroxyalkyl with the hydroxy group in other than the 1position; -COR8, -COOR8 or

in which R8 is C,~,2alkyl or phenyl-C1-4alkyl, and R9 is hydrogen, halogen, C1-4alkyl or C1-4alkoxy, R6a is an aliphatic; cycloaliphatic, carbocyclic aromatic or araliphatic radical; halogen, C1-4alkoxy, -NR11CO(C1-6)alkyl or -NR11COO(C1-6)alkyl, R7 is hydrogen, halogen, C1-4alkyl, C14a1l:oxy or-NR11CO(C1-6)alkyl, with the proviso that R, is other than -NR11CO(C1-6)alkyl when R6a is -NR11CO(C1-6)alkyl; R6b is hydrogen, C1-4alkyl, C1-4alkoxy, halogen, -NR11CO(C1-6)alkyl or -NR11COO(C1-6)alkyl, and R11 is hydrogen or C1-4alkyl.

7. A compound according to any one of the preceding claims, in which A is a group of formula (a), wherein R3 is R3, where R3 is hydrogen, halogen, C1-4alkyl, C1-4alkoxy or acetamido, and R4 is R4, where R4' is hydrogen, halogen, C1-2alkyl or C1-2alkoxy; or a group (b1), where (b1)is 4- or 5-sulphonaphthyl-1 or 1-, 5- or 6-sulphonaphthyl-2.

8. A compound according to any one of the preceding claims, in which K is a group of formula (c), wherein R5a is R5a"', where R5a"', is hydrogen, methyl or ethyl; R6a is R6a", where R6a" is straight chain or branched C1-4alkyl, benzyl, chlorine, methoxy or ethoxy, and R7 is R'7, where R7" is hydrogen, chlorine, methyl, methoxy or acetamido; or a group (d2), where (d2) is a group of formula (d), wherein R5b is R5b"', where R5b"' is hydrogen or straight chain C1-4alkyl, and R6b is R6b', where R6b' is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy or acetamido.

9. A compound according to Claim 8, in which K is a group (d2).

10. A compound according to Claim 1 of formula la,

in which R1" i is hydrogen, methyl or methoxy, R2" is -CO(C1-2)alkyl, -COO(C1-2)alkyl or -CONH.

A2 is a group of formula (a2),

and K2 is a group of formula (d3),

wherein R'3 is hydrogen, chlorine, C1-2alkyl, C12alI:oxy or acetamido, R4 is as defined in Claim 7, R'5b is as defined in Claim 8 and R'6b is hydrogen, chlorine, methyl, methoxy or acetamido.

11. A compound according to Claim 10, in which A2 is a group of formula (a2), wherein R'3 is hydrogen, chlorine, methyl, methoxy or acetamido and R4 is hydrogen, chlorine, methyl or methoxy.

12. A compound according to Claim 11, in which both R'3 and R4 are hydrogen.

13. A compound according to any one of Claims 10 to 12, in which K2 is a group of formula (d3), wherein B'8'h' is methyl or ethyl and R6b" @ is hydrogen.

14. A compound according to Claim 13, in which R"' is methyl.

15. A compound according to Claim 11, in which in the group of formula (a2) the substituents are in the positions: (i) when both R3 and R4 are hydrogen the sulpho group is in the 3- or 4-position; (ii) when one of R3 and R4 is hydrogen and the other is chlorine, methyl or methoxy, R3 or R4 and the sulpho group are in the 2,4- or 2,5-positions; when R4 is hydrogen and R3 is acetamido in the 4- or 5-position the sulpho group is in the 2 position; (iii) when R3 and R4, independently, are methyl, methoxy or chlorine, R3, R4 and the sulpho group are in the 2,4,5- or 2,4,6-positions.

16. A compound according to any one of Claims 10 to 15, in which R', is hydrogen or methoxy and R2 is 0CH3, -COOCH3 or --CONH,.

17. A compound according to any one of the Claims 10 to 16, in which R', is hydrogen.

18. A compound according to any one of the preceding claims, in which K is

and R2 is COCH3.

19. The compound of formula

in free acid or salt form.

20. The compound according to Claim 19, in sodium salt form.

21. A compound according to any one of Examples 1 or 3 to 106.

22. A process for the production of a compound of formula I, as defined in Claim 1, or a mixture thereof, comprising coupling the diazonium derivative of the compound of formula il,

23. A process for the production of a compound of formula 1, as defined in Claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 106.

24. A compound of formula I, whenever obtained by a process according to Claim 22 or Claim 23.

25. A process for dyeing or printing anionic dyeable substrates comprising employing a compound or mixture according to any one of Claims 1 to 21 or 24, as dyeing or printing agent.

26. A process according to Claim 25, in which the substrate consists of or comprises leather, natural or synthetic polyamides, polyurethanes or basic-modified polyolefins.

27. A process according to Claim 26, in which the substrate is a textile consisting of or comprising natural or synthetic polyamides.

28. A process for dyeing or printing anionic dyeable substrates, substantially as hereinbefore described with reference to Application Example A or B.

29. Dyed or printed substrates, whenever obtained by a process according to any one of Claims 25 to 28.