CA1145331A

CA1145331A - Anionic dyestuffs

Info

Publication number: CA1145331A
Application number: CA000357881A
Authority: CA
Inventors: Francois Benguerel
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1979-08-10
Filing date: 1980-08-08
Publication date: 1983-04-26
Also published as: CH643580A5; FR2465766A1; DE3028838A1; BE884619A; JPS5628244A; BR8005021A; GB2058815B; IT8024083A0; ES494137A0; ES8200712A1; GB2058815A

Abstract

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
Abstract of the Disclosure The present invention relates to compounds of formula I, I
in which A is the radical of a sulpho group containing diazo component of the aniline- or amino-naphthalene-series, K is a coupling component radical of the phenol series, of which the free hydroxy group may be etherified or acylated, R1 is hydrogen, alkoxy or optionally substituted alkyl, R2 is alkyl, -CONH2 or alkyl or hydroxyalkyl bound to -CO-, -COO- or

Description

-S~l Case 150-4353 IMPP~OVEMENTS IN OR RELATING TO ORGANIC C0~P0TJ~3S
The present invention relates to anionic disazo compounds, their preparation and use as anionic dye~
stuffs.
More particularly, the present invention provides compounds of formula I, A - N = N~N = N - K

in which A is the radical of a sulpho group containing diazo component of the aniline series or l- 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, Rl is hydrogen, Cl_4alkoxy or Cl_4alkyl option ally monosubstituted by halogen, R2 is Cl 4alkyl, -CO(Cl 6)alkyl, -COO(Cl_6)-alkyl, -CONH2, -CONH(Cl 6)alkyl, -CON(Cl_6-alkyl)2, -CONH (C2 6)hydroxyalkyl or -CON-(C2 6hydroxyalkyl)2 with the hydroxy group in other than the l-position, and Rlo is hydrogen or Cl ~alkyl and the molecule contains one single sulphonic acid group which is in the radical A, ,, ~

53~3~
15~-4~

and mixtures of such compounds, ~,7hich compounds are in free acid or salt form.
Any alkyl or alkoxy groups as Rl, preferably ; contain l or 2 carbon atoms, more preferably 1 carbon atom, any alkyl substituted by halogen is preferably monochloro(Cl 2)alkyl.
Rl is preferably Ri, where Rl is hydrogen, methyl, ethyl, methoxy or ethoxy. More preferably Rl is Rl, where Rl is hydrogen, methyl or methoxy. Most preferably Rl is Rl', where Rl' is hydrogen or methoxy, with hydrogen being especially preferred.
Any alkyl as R2 is preferably methyl or ethyl, especially methyl. Any Cl 6alkyl group in R2 which lS
bound to -CO-, -COO- or -CON~(H) preferably contains l 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-hydroxy-propyl.
R2 is preferably R2, where R2 is -CO(Cl 4)alkyl, -COO(Cl 4)alkyl or -CONH2. More preferably R2 is R2, where R2 is -CO(Cl 2)alkyl, -COO(Cl 2)alkyl or -CONH2.
Most preferably R2 is R2', where R2' is -COCH3, -COOCH3 or -CONH2, especially -COCH3.
Any alkyl as Rlo is preferably methyl or ethyl, especially methyl.
Rlo is preferably hydrogen, methyl or ethyl, more preferabl~ hydrogen or methyl, especially hydrogen.

- 2 -S~33~
15~-~353 A is preferably a radical of formula (a) or (b3, R3 ~ or (a) (b) in which R3 is hydrogen, halogen, Cl 4alkyl optionally monosubstituted by halogen; Cl 4alkoxy, mono-Cl 6alkylamino, di-Cl 6alkylamino, Cl 6alkyl-carbonylamino,Cl l2alk~xyca~onylalmin~ or N-Cl 4-alkyl-N-(Cl 6alkyl or Cl l~a~oxy)c ~ onyl-amino, ar,d R4 is hydrogen, halogen, Cl 4alkyl or Cl 4alkoxy.
K is preferably a radical of formula (c) or (d), 5a or ~ OR5b R6a R6b (c) (d) in ~7hich 10each of R5a and R5b is hydrogen, Cl_4alkyl, C2_4hYdrXY~
alkyl with the hydroxy group in other than the l-posi-tion; -COR8, -COOR8 or -S02 ~ Rg in which R8 is Cl_l2alkyl or phenyl-Cl 4alkyl, and Rg is hydrogen, halogen, Cl 4alkyl or Cl 4alkoxy, 15R6a is an aliphatic, cycloa.liphatic, carbocyclic aromatic or araliphatic radical; halogen, Cl_4alkXy, -NRllCO(Cl_6)alkyl or -NRllCOO-(Cl 6)alkyl, ~5~3~
; 150-43r~3 R7 is hydrogen, halogen, Cl 4alkyl, Cl 4alkG~y or -NRllCO(Cl 6)alkyl, ~7ith the proviso that R7 is other than -NRllCO~Cl_6)alkYl ~Ihen R6a is -NRllCO(Cl 6)alkyl;
R6b is hydrogen, cl_4alkyl, cl_4alkoxy, halogen~
-NRllCO(Cl 6)alkyl or -NRllCOO(Cl_6) Y
Rll is hydrogen or Cl_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 l 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. ~ny di-alkylamino group as R3 preferably contains methyl- and/
or ethyl groups, especially methyl groups. Any Cl 4-alkyl in N-a~yl~N-a~ylcarbonyl- or -N-alkoxycarbonyl-am~a as R3 is prefer-ably methyl. Any alkylcarbonylc~uno as R3 iS most preferc~bly aoetam~do;
- 25 any alko~c~rbonylanQno is preferably Cl 4aIkoxy-, m~st preferably Cl 2-a~.~ycar'~nylc~no, or C~ 12alkox~carhonylamino.
R3 is preferably R3, where R3 iS hydrogen, halogen, Cl_4alkyl, Cl 4alkoxy or acetamido. More preferably R3 is R3, where R3 is hydrogen, chlorine, Cl_2alkyl, Cl 2-alkoxy or acetamido. Most preferably R3 is R3', where R3' is hydrogen, chlorine, methyl, methoxy or acetamiao, especially hydrogen.
R4 is preferably R4, where R4 is hydrogen, halogen, Cl 2alkyl or Cl 2alkoxy. More preferably R4 is R4, where R4 is hydrogen, chlorine, methyl or methoxy. Most pre-ferably R4 is hydrogen. Preferably R4 is hydrogen, when R3, R3, R3 or R3' is acetamiao.
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).l~hen 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. ~hen 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 5-position ~nd the sulpho group is in the 2-position; or wherein ~5~3~
15~-4353 (iii) R3 and R4, independently, are methyl, methoYsy or chlorine and R3, R4 and the sulpho group are in the 2,4,5- or 2,4,6-positions.
I~hen the naphthalene radical of formula (b) is bound in the l-position,the sulpho group is preferably in the 4-, 5-, 6-, 7- or 8-position, especially in the 4- or 5-position. ~hen 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 (bl), where (bl) is 4- or 5-sulphonaphthyl-1 or 1-, 5- or 6-sulphonaphthyl-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 3-hydroxy-propyl. Any -COR8 group as R5a or R5b preferably contains R8a,where R8a is straight chain or branched Cl 4alkyl or phenyl-(Cl 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 R~3b is straight chain or branched Cl 12alkyl or phenyl-(Cl_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 -S0 ~ 9 group any halogen as Rg is most pre-, , . . .

15~ J~
ferably chlorine; any alkyl is preferably rnethyl or ethyl, especially methyl, and any alkoY.y is prefPrably methoxy or ethoxy.
R5a is preferably R5a, where R5a is hydrogen, methyl, ethyl, 2-hydroxyethyl, -COR8a, -COOR8b, phenyl-sulphonyl or tosyl. More preferably R5a is R5a, T,7here R5a is hydrogen, methyl, ethyl or -COOR8b (especially -COOR8b). Even more preferably R5~ is R5a, where R5a is hydrogen, methyl or ethyl. Most preferably R5a is R5Va , where R5Va is hydrogen or methyl, especially hydrogen.
R5b is preferably R5b, where R5b is hydrogen, straight chain Cl ~alkyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, -COR8a, -COOR8b, phenylsulphonyl or tosyl.
More preferably R5b is R5b, where R5b is hydrogen, straight chain Cl 4alkyl, -COR8a, -COOR8b (especially -COOR8b); phenylsulphonyl or tosyl. Even more prefer-ably R5b is R5b, where R5b is hydrogen or straight chain Cl 4alkyl. Most preferably R5b is R5ibV~ where R5ibV is me-- 20 thyl or ethyl, especially methyl.
Any alkyl as Rll in the groups R6a, R6b or R7 is preferably methyl or ethyl, especially methyl.
Rll is preferably hydrog~n or me~yl, especially hydro~n-Any aliphatic, cycloaliphatic, carbocyclic aro-25 mal:ic or araliphatic groups as R6a may contain con-ventional substituents, for example substituents selected from the group consisting of halogen (fluorine, chlorine or bromine~, Cl 4alkyl and Cl 4alkoxy; additionally, particularly any aliphatlc group may contain hydroxy--- 7 ~

. .

~ S~3~ 15~-~353 or cyano-groups.
Any aliphatic group as R6a i8 preferably an un-substituted straight chain or branched alkyl group con-taining 1-lO 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 substi-tuted phenyl- or phenyl-(Cl 4)alkyl-group in which the sub-stituents are selected from the group consisting ofhalogen, Cl 4alkyl and Cl_4alkoxy.
Any halogen as R6a is preferably chlorine; any alkoxy is preferably methoxy or ethoxy.
Any -NCOalkyl or NCOOalkyl groups as R6a pre-ferably contain Cl 4alkyl groups, especially Cl 2alkylgroups.
R6a is preferably R6a, where R6a is straight chain or branched Cl 6alkyl, cyclohexyl, phenyl, benzyl, chlorine, methoxy, ethoxy or acetamido. More preferably R6a is R6a, where R6a is straight chain or branched Cl 4alkyl, benzyl, chlorine, methoxy or ethoxy. Most preferably R6a i5 R6a, where R6a is straight chain or branched Cl 4alkyl or chlorine.
Any halogen as R7 is preferably chlorine; any 2S alkyl or alkoxy groups preferably contain l or 2 carbon atoms, especially l carhon atom. Any -NCOalkyl as R7 preferably contains Cl 4alkyl groups, more preferably Cl 2alkyl groups, and is most preferably acetamido.

/

. '~ .
~ .

~53~1 15~-4~53 R7 is preferably R7, where R7 is hydrogen, chlorlne, ; methyl, ethyl, methoxy, ethoxy or acetamido. More prefer-ably R7 is R7, where R7 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 l or 2 carbon atoms, especially 1 carbon atom. Any -NCOalkyl or ~NCOOalkyl groups as R6b preferably contain Cl 4alkyl, especially methyl.
R6b is preferably R6b, where R6b is hydrogen, chlor-ine, bromine, methyl, ethyl, methoxy, ethoxy or acetamido.

More preferably R6b is R6b~ where R6b is hydrogen, chlor-ine, methyl, methoxy or acetamido, especially hydrogen.
A is preferably a group (al), where (al) is a group f formula (a), wherein R3 is R3 and R4 is R4, or of for-mula (bl). More preferably A is a group (a2), where (a2) is a group of formula (a), wherein R3 is R3 and R4 is R4, or of formula (b1). Most preferably A is a group (a3), where (a3) is a group of formula (a), wherein R3 is R3', espe-cially hydrogen, and R4 is R4, especially hydrogen. In thegroups (al) to (a3) the substituents are in the above-given preferred positions.
K is preferably a group (cl), where (cl) is a group of formula (c), wherein R5a is R5a, R6a 6a 7 R7; or a group (dl), where (dl) is a group of formula (d), wherein R5b is R5b (especially RSb) and R6b is R6b- More preferably K is a group (c2), where (c2) is a group of . g _ 50-~353 formula (c), wherein R5a is R5a, R6a is R6a 7 7 - or a group (d2), where (d2) is a group of formula (dj, 5b is R5b and R6b is R6b- Even more prefer~bly K is a group (c3), where (C3) is a group of formula (c), wherein R5a is R5aV (especially hydrogen), R6a is R6' and R7 is hydrogen; or a group (d2). Still further more pre-ferably K is a group (d3), where (d3) is a group of for-mula (d), wherein R5b is R5b and R6b 6b preferably K is a group (d4), where (d4) is a group of for-mula (d), wherein R5b is ~5ibv (especially methyl) and R6b is hydrogen.
Preferred compounds of formula I are . (1) those wherei.n A is a group (al) or (b~
(2) those wherein A is a group (a2) or (bl);

(3) those wherein Rl is Ri, R2 is R2 and Rlo is hydrogen;

(4) those wherein K is a group (cl) or (dl);

(5) those wherein K is a group (C3) or (d2);

(6) those wherein K is a group (d2);

(7) those of formula Ia, ~1 : 2 ~ N K Ia , in which A2 is a group of formula (a2) R3 ~ (a2) and R4 SO~H
K2 is a group of formula (d3) -. :

~; ' ' ' ' ' ~ ~5~3~
1~0-43~3 OR5b (d~) t R6b

(8) those of (7), where.in A2 is a group (a3);

(9) those of (7), wherein K2 is a group (d4), and especially the group ~ OCH3;
(lO) those of (7), (8) or (9), wherein Rl is P~l', especially hydrogen, and R2 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, Rl A - N = N ~ N~I2 II

2Rlo 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, ~1 Al - N = N~ N - N - Kl Ib in which Al is a group of formula (a) or (b), Kl is a group of formula (c) or (d) and Rl, R2 and Rlo are as de~ined above, and mixtures thereof are obtained comprising ~S3~
150-~3~3 a) coupling the diazonium derivative of the compound o' formula IIa, ~R l A - N = N ~ NH2 IIa NR2 Rlo or a mixture thereof, with a phenol of formula IIIa or IIIb H
H ~ R7 IIIa or -~ H~ OH IIIb R6 R6b ~ S or a mixture thereof, : to obtain a compound of formula Ix, ~1 ;~ Al - N - N ~ N = N - KlX Ix 2 lO
: in which KlX i5 a group of formula tax~ or (bx), H

7 ~ax) or ~ OH (bx) R6a 6b 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 R5a or R5b is other than hydrogen.

., .

'',~' :
" ~' , ~ , ~ 3~ 150~4-~,53 The coupling reaction may be effected in a~cord-ance with known methods; suitably, coupling i5 effec.ed 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 IIa 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 alkylene-oxide. The reaction is suitably carried out in aqueousalkaline medium, the preferred pH being from 9 to 11. The reaction temperature is suitably from 30 to 90C, more preferably from 40 to 70C.
Acylation is suitably effected employing the corresponding acid chloride. The reaction mixture is pre-~erably aqueous which is made alkaline with soda, the preferred pH being vom 8 to 10. The reaction temperature is suitably between 30 an~ 90C`C, preferably between 60 and 70C.
The compounds of formula I may be isolated in accord-ance with known methods. In general owing to the process/
isolation conditions, the compounds of formula I may be ob-tained in salt form.
~Ihen the compounds of formula I are in the salt form, the catiGn of the sulpho group is not critical and may be any of those non chromophoric cations conventional in anionic dye-stu~f~. Examples of such cations are alkali metal cations and ~ 13 -~ 33~ 150-~35~

cations of the ammonium type including unsubstituted and substituted ammonium cations e.g., lithium, sodium, potassium, a~nonium, mono-, di-, tri- and tetra-methyl-ammonium, 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 he converted into the free acid form or into other salt forms in accordance with known methods.
The starting materia]s 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 deriva~ive of an amine A-NH2 in a weakly acid to neutral medium with the corresponding aniline of formula IV, ,~ .:
~H ~ NH2 IV
N 2Rlo or a derivative thereof reacted with w-methanesulphonic acid. Compounds of ~ormula IV and phenols of formula IIIa or IIIb 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 3~

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 con-ventional methods, for example by dissolving in suitable solvents e.g. water, optionally with the addition of con-ventional additives such as solubiliziny agents, for example urea, or by grinding or granulating. Such prepara-tions may be obtained in accordance with the procedure described in French Patents 1,572,030 or 1,581,900.
Further, the compounds of formula I and mixtures thereof, may be made up into preparations which are dis-persible in cold water. Such dispersions may be prepared, for example, by grinding the dye dry or wet in aqueous dispexsing medium in the presence of one or more con-2~ ventional 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 533~
15~-435~

formula I and mixtures thereof exhaust from a neutral dyebath. Furthermore, the compounds o~ 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 dyeinys obtained possess notable light-fastness. Furthermore, the compounds of formula I and their mixtures give dyeings which have notable general fastnesses, such as wet-fast-nesses, especially wash-, water-, milling- and sweat-fast-ness.
The compounds of formula I are suitab~e for com~ining with other anionic dyes which exhaust from a neutral dyebath, whereby tone-in-tone dyeinys having the above-mentioned advantageous properties are obtained. Further, such dyeings do not exhiblt cataly~ic fading.
The following Examples further serve to illustrate the invention. In the Examples, all parts are by weight and all 2~ degrees are in degrees Centigrade.

33~
150~43~3 Exam~le .. , 17.3 Parts sodium salt of l-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 5-10, the excess of nitrous acid is destroyed by adding a small ~uantity of amidosulphonic acid. The diazonium suspension obtained is added to a solution of 18.7 parts 3-amino-acetanilide in the hydrochloric acid salt form and 5 partscalcinated sodium carbonate in 150 parts water and 100 parts ice, at 0-5 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 60 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 5-10 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 g.5 parts phenol and 13 par~s 30%
caustic soda in 1~0 parts wa-~er at room temperature. After ~ 15~~4353 15 minutes the coupliny reaction is complete. The dyestuf is pecipitated by the addition of sodium chloride at p~ 9, and is isolated by filtering, washed with 5% sodium chloride solution and dried. The dyestuff which, ln the free acid form, corresponds to the formula N = ~ ~ = ~ OH

; is obtained in the sodium salt form and gives dyeings on natural or synthetic polyamides of reddish-yellow 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 follo~Js: The filtered and washed dyestuff of Exa~ple 1 in paste form is dissolved in water of 45-50 by adding of 10 parts 30% sodium hydroxide solution. To this solution 25 parts dime-thylsulphate 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 20 adding sodiu~ chloride. The dyestuff is isolated by filter- -ing, washed with 5% sodium chloride solution and dried. The disazo compound which~ in the free acid form, corresponds to the formula ., ' ' , ' ' 3~
150 4~5:~

~N = N~ N = N~oCH3 is obtained in the sodium salt form and gives dyeings on natura], or synthetic polyar,~ides of reddish yellow-shades.
The dyeings have yood light- and wet-fastnesses.
In analogy with the procedure described in Example 1 using a mixture of l-aminobenzene-3- and -4-sulphonic acid o (in the ratio of approximately 1:1) instead of l-amino-benzene-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 parti-cularly well soluble in water and therefore especially use-ful for dyeing of natural or synthetlc 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-ana isolation-steps, are obtained in the sodium salt form.
The dyestuffs correspond to the general formula A, R3 ~1 N = N ~ N = N ~ OR5 A

for Table l;

/

~S331 1~0-4353 to the general formula B, Rl OR5 N = N~N = N ~ B

for Table 2;
and to the general formula C, A - N = N~N = N~oR5 C
R

for Table 3 .
; 5 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-yellowr g is brownish-red; and h is brown.
The polyamide dyeings obtained have good light- and : wet-fastnesses.

3~
15~ 5 Table 1 / fonnula - Example positio . S03H R3 Rl R2 ¦ R5 ¦ I

3 4 H ~rCOCH~ a 4 4 H H do. CH3 a 3 H OCH3do. H c 6 3 E do.do. CH3 c 7 4 H do.do. do.
8 4 H do.do. C2H5 c 9 4 H H do. Tosyl a 11 3 H H do. CH3 a 12 2-NHCOCH3(4) H COCH3 H a 13 2 do. H do. CH3 a 14 2-~1HCOCil3(5) H do. do. a 3 X CH3do . do. a 16 3 H OCH3 do. C2H5 c 17 4 C~13(2) do. do. CH3 c 18 4 do. CH3 do. do. a 19 4 do. do. do. C2H5 a do. H do. CH3 b 21 2 3( ) OCH3 do. do. c 22 5 OCH3(2) H do. C2H5 b 23 2 Cl(4) H do. CH3 a 24 2 do. H do. Tosyl a Cl(2) H - do. CH3 a 26 3 H OCH3 do. COOCH3b 7 3 H do. do. CoocH2cH(cH3)2 b 28 3 X do. do. COOClOH21(n) b 29 4 CH3(2) do. do. C2H5 c 3o 4 Cl(2) do. do. CH3 c 31 2-~ICOCH3(4) do. do. do. c 32 3 H H 2-5 do. a 33 4 }1 H do. do. a 3~
~ 35 Table 1 continued Noxa~pIe 3__ R3 R~ R2 34 4 H OCH3 COC2H5C2~5 - c 3 H H do.do. a 36 3 TT H do.Tosyl a 37 5 Cl(2) H COOCH3CH3 a 38 5 do. CH3 do.do. a 39 2 3( ) OCH3 do.do. c 2 do. H do,do. a : 41 2 do. H do,C2H5 a 42 5 OCH3(Z) H do.CH3 b 43 4 H H do.CzH5 a 44 4 H H COOC2H5 CH3 a 3 H OC~3 CO~T2do. c 46 4 H do. do.do. c 47 4 H H do.Tosyl , 533~
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~ ~_ o ~ o o o ~ ~ x ~ o o o o o o o o o o o t~ c~ o o o ~ o o oco~ co~
o o ~ ~ o o o o o o o o o o o o o o o o o ~ ~ c~
o o X ~: W s X ~ :~ s ~C ~ s ~ ~ tc s ~ s s ~
r . _ _ _ .
~ . C~, _. o s o a) ~ 0~ o ~ C~ ~ co cn O ~ ~ ) ~ u~ ~9 r~ ~ O ~
. ~ r~ r~ r~ r~ r- ~-- r~ r~ r~ r~ co c3 c~ ~o r~ oo co ~ co ~ a~

:q o S33~
-150-43~3 Takle 3 / formula C

Exa~.ple A 1 R2 OR5 P~6 ¦ I

92 4-Sulfon~?hthyl-1 H COCH30~4) H c 93 do. H do.3( ) ~ c 94 5-Sulfonaphth~ l H do. do. H . c do. H COC2~35 do. H c 96 do. H CO~H2 do. ~ c 97 do. H COCH 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.3( ) Cl(5) b 103 5-Sulfonaphthyl-2 H do.OH(4~ H b 104 do. H do.OCH3(4) H b 105 1-Sulfonaphthyl-2 CH3 do.do. H c -Example 106 In analogy with the procedure described in ~.xam~les l and 2 using appropriate starting materials a dyestuff may be prepared which, in the free acid form, corresponds to the formula OCH3 ~ N = N ~ N = 21 ~OCH3 S03E~ OCH3 and is obtained in the sodium salt form. The dyestuff gives dyeings on natural or synthetic polyamides of scarlet-red c.hades.
The dyestuffs of Example l to 106 which are in the lo sodium salt form may, depending on the xeaction/

isolation conditions, be obtained in accordance with known 3~
15~~4353 methods in free aci~ 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 40 into a dyebath con-sisting of 4000 parts water, lO parts of anhydrous sodium sulphate and 2 parts of the dyestuff of Example 2.
The dye li~uor is heated over the course of 30 minutes to boiling tempera-ture and kept at this temperature for l 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 li~uor, 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 EY~a~ples l to 106 may be employed to dye nylon or wool in accordance with the method described above.

33~
150-~3~3 A~lication ~xa,ll~le B
,, Polyamide is printed with a printing paste con-taining:
30 parts dyestuff of Example 2 50 parts urea 50 parts solubilizing agent te.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 102 (saturated steam), rinsed cold, subsequently washed at 60 for 5 minutes with a dilute solution of a con-ventional detergent and rinsed again with cold water. A
reddish-yellow print having notable light- and wet-fast-nesses is obtained.
In analogous manner printing pastes may be made - 20 employing the dyestuffs of Examples 1 and 3 to 106 or mixtures o 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

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of formula I, 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 option-ally monosubstituted by halogen, R2 is C1-4alkyl, -CO(C1-6)alkyl, -COO(C1-6)-alkyl, -CONH2, -CONH(C1-6alkyl, -CON(C1-6-alkyl)2, -CONH(C2-6)hydroxyalkyl or -CON-(C2-6hydroxyalkyl)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 thereof, which compound is in free acid or salt form.

2. A compound according to Claim 1, in which R1 is R?, where R? is hydrogen, methyl, ethyl, methoxy or ethoxy.

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

4. A compound according to Claim 1 or Claim 3, in which R10 is hydrogen.

5. A compound according to Claim 1, in which A is a radical of formula (a) or (b), or (a) (b) wherein R3 is hydrogen, halogen, C1-4alkyl optionally monosubstituted by halogen; C1-4alkoxy, mono-C1-6alkylamino, di-C1-6alkylamino, C1-6alkylcar-bonylamino, C1-12alkoxyearbonylamino or N-C1-4-alkyl-N-(C1-6alkyl or C1-12alkoxy)carbonyl amino, and R4 is hydrogen, halogen, C1-4alkyl or C1-alkoxy.

6. A compound according to Claim 1, in which K is a radical of formula(e) or (d), or (c) (d) wherein each of R5a and R5b is hydrogen, C1-4alkyl, C2-4hydroxy-alkyl with the hydroxy group in other than the 1-posi-tion; -COR8, -COOR8 or , in which R8 is C1-12alkyl 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, C1-4alkoxy or -NR11CO(C1-6)alkyl, with the proviso that 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 Claim 5, in which A is a group of formula (a), wherein R3 is R?, where R? 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-sulpho-naphthyl-1 or 1-, 5- or 6-sulphonaphthyl-2.

8. A compound according to Claim 6, in which K is a group of formula (c), wherein R5a is R??, where R??
is hydrogen, methyl or ethyl; R6a is R?a, where R?a is straight chain or branched C1-4alkyl, benzyl, chlorine, methoxy or ethoxy, and R7 is R?, where R? is hydrogen, chlorine, methyl, methoxy or acetamido; or a group (d2), where (d2) is a group of formula (d), wherein R5b is R??, where R?? is hydrogen or straight chain C1-4alkyl, and R6b is R?b, where R?b is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy or acetamido.

9. A compound according to Claim 6, in which K is a group of formula (c), wherein R6 is straight chain or branched C1-4alkyl, benzyl, chlorine, methoxy or ethoxy.

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

11. A compound according to Claim 1, of formula Ia, Ia in which R? is hydrogen, methyl or methoxy, R? is -CO(C1-2)alkyl, -COO(C1-2)alkyl or -CONH2, A2 is a group of formula (a2), (a2) and K2 is a group of formula (d3), (d3), wherein R? is hydrogen, chlorine, C1-2alkyl, C1-2alkoxy or acetamido, R? is hydrogen, halogen, C1-2alkyl or C1-2alkoxy, R?? is hydrogen or straight chain C1-4alkyl, and R?b is hydrogen, chlorine, methyl, methoxy or acetamido.

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

13. A compound according to Claim 12, in which both R3 and R4 are hydrogen.

14. A compound according to Claim 11, in which K2 is a group of formula (d3), wherein R?? is methyl or ethyl and R?b is hydrogen.

15. A compound according to Claim 14, in which R?? is methyl.

16. A compound according to Claim 11, in which R? is hydrogen.

17. A compound according to Claim 16, in which K2 is and R? is -COCH3.

18. A compound according to Claim 1, of formula in free acid or salt form.

19. The compound according to Claim 18, in sodium salt form.

20. 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 II, II

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

21. A process for dyeing or printing substrates dyeable with anionic dyes comprising employing a compound or mixture according to Claim 1, as dyeing or printing agent.

22. A process according to Claim 21, in which the substrate consists of or comprises leather, natural or synthetic polyamides, polyurethanes or basic-modified poly-olefins.

23. A process according to Claim 22, in which the substrate is a textile consisting of or comprising natural or synthetic polyamides.