GB2053261A

GB2053261A - Organic compounds

Info

Publication number: GB2053261A
Application number: GB8020474A
Authority: GB
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1979-06-26
Filing date: 1980-06-23
Publication date: 1981-02-04
Also published as: DE3022927A1; WO1981000111A1; FR2459821A1; JPS568460A; FR2459821B1; IT8049047A0; GB2053261B

Abstract

Mono-azo reactants for fibers, having the formula: (FORMULA) wherein the different meanings of the symbols R<u1>u to R<u6>u, Hal, m and n are given in claim 1, with the conditions that: a) n can not be zero and must be zero when R<u2>u is -NHCOOR<u10>u; b) the group -NHR<u5>u and the azo group are in ortho position one with respect to the other and are in the positions 1 and 2 and respectively 2 and 1 of the naphtalen ring, and c) when n equals 1, m equals 1 and the azo group is in position 1 of the naphtalen ring, then either R<u6>u in the position 8 of the ring is not a group OH or the sulphonic group is in a position other than position 4 of the ring, comprising at least two sulphonics groups per molecule, the mixture and the salts thereof. The compounds are obtained by coupling of the corresponding starting products and prior or subsequent condensation with the triazinic compound. They are used as dyes for the coloration or impression of substrates comprising nitrogen-containing groups or OH groups, such as for example natural or regenerated cellulose or natural or synthetic polyamides, particularly wool. Easily combinable, they are appropriate as elements for the trichromatic process, for example with coloring anthraquinonic acids.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to fibre-reactive monoazo compounds, their preparation and use as dyestuffs.

More particularly the present invention provides compounds of formula l,

in which R, is C1-4alkyl Hal is halogen R2isSO3H,

SO201-4 alkyl, -SO2NR8Rg or-NHCOOR10, the triazinyl group is bound to the 4-or 5-position with the proviso that when R2 is -N HCOOR1o it is bound to the 4-position, R3 is hydrogen, C1--4 alkyl or C1-4 alkoxy, R4 is hydrogen or 01-4 alkyl, R5 is hydrogen; C1 4 alkyl; cyclohexyl optionally substituted by up to three 01-4 alkyl groups; phenyl optionally substituted by up to two sub stituents selected from the group consisting of halogen, 01-4 alkyl and C1--4 alkoxy, Ra is hydrogen or hydroxy, with the proviso that R6 is other than hydroxy when R2 is -NHCOOR,o R, is hydrogen, C1-4 alkyl or C1-4 alkoxy, each of Ra and R9, independently, is hydrogen, 01-4 or C2-4 hydroxyalkyl in which the hydroxy group is in the p-, y- or 6-position; cyclohexyl; or phenyl optionally substituted by up to two substituents selected from the group consisting of halogen, C1-4 alkyl, 01-4 alkoxy, sulpho and carboxy with the proviso that when one of Ra and Ra is cyc lohexyl or optionally substituted phenyl the other has a significance other than cyclohexyl or optionally substituted phenyl, R10 is C1~6 alkyl, mis 1 or2 n is0 or 1 p is O or 1 with the provisos: a) that n is only 0 and must be 0 when R2 is -NHCOOR10, b) that the -NHR5 and the azo groups are ortho to each other in the 1- and 2-or 2- and 1-position of the naphthalene ring; and c) that when n is 1 and m is 1 and the azo group is in the 1-position of the naphthalene ring then, either, Ra is other than hydroxy in the 8-position or, the sulpho group is in other than the 4-position of the naphthalene ring, and the molecule contains at least two sulpho groups, and mixtures of such compounds, which compounds are in free acid or salt form.

By halogen is meant fluorine, chlorine or bromine.

On the triazinyl group the preferred halogens are fluorine and chlorine, especially chlorine and any halogen on a phenyl ring is preferably chlorine or bromine, especially chlorine.

Any alkyl groups or moieties in the molecule are straight chain or branched.

R1 is preferably C1 3 alkyl, especially methyl.

Any alkyl or alkoxy groups as R3, preferably contain 1 or2 carbon atoms, more preferably 1 carbon atom.

R3 is preferably R3,, where R3, is hydrogen, methyl, ethyl, methoxy or ethoxy. More preferably R3 is R3", where Ra" is hydrogen, methyl or methoxy, especially hydrogen.

Any alkyl as R4 is preferably methyl. R4 is preferably hydrogen or methyl, especially hydrogen.

Any alkyl as Era is preferably methyl or ethyl. Any substituted cyclohexyl as R3 is preferably substituted by up to three methyl groups. Preferred substituted phenyl groups as R5 are those which are substituted by up to two substituents selected from the group consisting of chlorine, methyl, ethyl, methoxy and ethoxy, especially from the group consisting of chlorine, methyl and methoxy.

Rs is preferably R5', where Rsl is hydrogen, methyl, ethyl, cyclohexyl, phenyl optionally mono substituted by chlorine, methyl or methoxy. More preferably R5 is R5", where R5,, is hydrogen, methyl or phenyl, especially hydrogen.

Any alkyl or alkoxy as R7 preferably contain 1 or 2 carbon atoms, especially 1 carbon atom.

R7 is preferably R,', where R7, is hydrogen, methyl or methoxy. More preferably R7 is R,", where R7,, is hydrogen or methyl, especially hydrogen.

Any alkyl as Ra and/or Era is preferably methyl or ethyl. Any hydroxy alkyl as Ra and/or Ra preferably contains 2 or3 carbon atoms, with 2-hydroxyethyl being most preferred. Any substituted phenyl as Ra or Era is preferably substituted by up to two substituents selected from chlorine, 01-2 alkyl, C1-2 alkoxy, sulpho and carboxy, especially from the group consisting of methyl and sulpho.

Ra is preferably R8, where R8' is hydrogen, methyl, ethyl or 2-or 3-hydroxy C2-3, alkyl; more preferably Ra is R8", where R8" is methyl, ethyl or 2-hydroxyethyl.

R9is preferably R9', where R9' is methyl, ethyl, 2- or 3-hydroxy 02-3 alkyl, cyclohexyl or phenyl optionally substituted by up to two substituents selected from the group consisting of chlorine, C1-2 alkyl, C,-2 alkoxy, sulpho and carboxy; more preferably Era is R9", where R9" is methyl, ethyl, 2-hydroxyethyl or phenyl optionally substituted by up to two substituents selected from the group consisting of methyl and sulpho.

R10 is preferably C,~4 alkyl, more preferably methyl or ethyl.

R3 as-SO2C,~4 alkyl is preferably-SO2C1-2 alkyl.

R2 is preferably R2a or Rab, where R24 is -SO3H,

-SO2CH3, -SO2C2Hs or-SO3NR8,R9' and R3b is -NHCOOC1-4alkyl. More preferably R3a is R2a', where R2a' is -SO3H,

-SO,CH, -SO2C2Hs or-SO3NR8"R9,,. Most preferably R2a is R2a", where R3a" is-SO3H or

with -SO3H being especially preferred. R2b is preferably R2b', where R2b' is-NHCOOCH3 or-NHCOOC2H5.

Preferably the compounds of formula I contain 2 sulpho groups. When R6 is hydroxy m is preferably 1.

In the naphthalene ring the substituents are preferably as follows:- a) whennisl with the NHR5 group in the 1-position and when R6 is hydrogen and when m is 1, the sulpho group is in the 4-position and when m is 2 the sulpho groups are in the 3,6-, 3,8-,or4,6-, preferably, the 3,6- or4,6positions; with the -NHR5 group in the 2-position and when R6 is hydrogen and when m is 1 the sulpho group is in the 5-, or7-position and when m is 2 the sulpho groups are in the 3,6- or 5,7-positions; with the-NHRs group in the 2-position and R6 is hydroxy (preferably in the 8-position) and m is preferably 1 and the sulpho group is in the 6-position.

b) when n is0 and m is 2 with the azo group in the 1-position the sulpho groups are in the 3,6-, 3,8-, 4,6-or 4,8-positions; with the azo group in the 2-position the sulpho groups are in the 3,6-, 4,8-, 5,7- or 6,8-positions.

The MHR5 group is preferably in the 2-position of the naphthalene ring.

Preferred compounds of formula I are (i) those in which n is 1, R3 is R3a, Hal is fluorine or chlorine and the compound contains 2 sulpho groups; (ii) those of (i) in which R3 is R3" and R4 is hyd rogen or methyl; (iii) those of (i) or (ii) in which R5 is R5'; (iv) those of formula la

in which m is as defined above with the proviso that m is 1 when R6 is hydroxy; (v) those of (iv) in which R3" is hydrogen; (vi) those of (iv) or (v) in which R2a' is R3a", espe cially-SO3H; and (vii) those of(iv), (v) or (vi) in which R1 is C1-3 alkyl, especially methyl.

(viii) those of formula Ib

in which Hal' is fluorine or chlorine; (ix) those of (viii) in which R2b is R2b'.

(x) those of (viii) or (ix) in which R3" and R4 are both hydrogen, Hal' is chlorine and R1 is C1-3 alkyl, especially methyl.

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

in which R2, is R2 as defined above with the exception ofthe group-NHCOOR10, X is -NO2 or NR4Z1 and is in the 4-or 5-position Z1 is a protecting group or is a radical of formula (a) or (b)

our a mixture thereof, with the compound of formula Ill

our a mixture thereof, and when Z1 is (a) condensing the product with a compound R1OH andwhen X is nitro reducing the same or Z1 is a protecting group, splitting off such group and reacting the -NH3 or-NHR4 group either with cyanuric halide followed by reacting the product with a compound R1OH or with a compound of formula (c)

to obtain a compound of formula I in which n is 1, or b) reacting the compound offormula W

or a mixture thereof, either, with cyanuric halide followed by reacting with a compound R1OH, or, with a compound of formula (c), to obtain a compound of formula I in which n isO.

In processes a) and b) it is preferred to employ the compound of formula(c) rather than reacting with cyanuric halide and then with a compound R1OH.

The condensation reactions with cyanuric halide and R1OH or with the compound offormula (c) are carried out in accordance with known methods. The compound of formula IV is obtained by coupling the diazonium derivative of the compound of formula V

with a compound of formula VI

The coupling reaction is carried out in accordance with known methods, suitable in acid medium, preferably in a medium having a pH in the range of from 2.0to4.5.

The compounds of formula I may be isolated in accordance with known methods. it will be appreciated that, depending on the reaction and isolation conditions, the compounds of formula I may be obtained in the salt form whereby the neutralizing cation may be any of those non-chromophoric cations conventional for the salt form of reactive dyestuffs. Preferred cations are lithium, sodium and potassium, especially sodium.

The starting materials of formulae 11, III, V and VI are either known or may be prepared in accordance with known methods for available starting materials.

The compounds of formula I and mixtures thereof are useful as reactive dyestuffs for dyeing or printing hydroxy group-containing or nitrogen-containing organic substrates. Preferred substrates are leather and textile materials consisting of or comprising natural or regenerated cellulose such as cotton, viscose and spun rayon, natural or synthetic polyamides such as wool, silk or/and nylon. The most preferred substrates are those textile substrates consisting of or containing wool.

The compounds offormula I, in dyebaths or with printing pastes may be employed in accordance with the conventional dyeing and printing methods for reactive dyes. For polyamide substrates it is preferred to employ exhaust dyeing methods.

The dyeings and prints obtained have notable wet-fastness (wash-, water-, sweat- and millingfastness) and light-fastness. Further the compounds of formula I are useful as combination dyes especially for use with other sulpho-group containing reactive dyestuffs, preferably with anthraquinone reactive dyestuffs. Such combinations are two or three component mixtures so that the dyestuffs of the present invention may be employed to obtain the much sought after tertiary mixtures for use in dyeing processes.

The preferred anthraquinone dyestuffs for such combinations are those offormulaVll

in which R1 is C1~4 alkyl especially, in the salt form, the cation of which may be any of those mentioned above for the salt form of the dyestuffs of formula I.

The compounds of formula VII may be prepared by condensing a compound of formula VIII

with a compound of formula IX

Preferred two and three component mixtures are those containing the salt form of the compound of formula Ic

as orange component and the salt form of the compound of formula Vlla

as blue component, and/or the salt form of the compound of formula Id

as red component.

The amount of each component in the two and three component (tertiary) mixtures is not critical 1 and will depend on the dye-shade required. The dye ings made with the combinations are level, espe cially on wool where the degree of patchiness is much less than expected. In addition the combina tion dyeings have good light-fastness and do not exhibit catalytic fading, the wet-fastnesses thereof are also notable.

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

5Example 1 23 Parts 4 - acetylamino - 2 - aminobenzenesulphonic acid are dissolved at pH 8 in 80 parts water with 33 parts 20% sodium carbonate solution and are reacted with 6.9 parts sodium nitrite in 25 parts water. This solution is added dropwise within 60 minutes at 0 to 50 to 25 parts 30% hydrochloric acid.

After a further 60 minutes the pH is adjusted to 3 with 6.6 parts sodium acetate. A solution of 22.3 parts 2 - aminonaphthalene - 5 - sulphonic acid in 100 parts water and 10 parts 30% sodium hydroxide solution is added dropwise for 45 minutes at 0 to 5 to the diazonium solution. During coupling the pH is maintained at2.8-3.2 bythe addition of 12 parts sodium acetate. After 2 hours the pH is adjusted to 8.5 with 14 parts 30% sodium hydroxide solution and the whole is heated for a short time to 800. 33 Parts sodium chloride are added to the clear solution and the product is filtered off at 40".

The paste obtained is stirred in 300 parts water and 63 parts 30% sodium hydroxide solution for 75 minutes at 900 to split off the acetyl group. The pH is adjusted to 9 with 53 parts 30% hydrochloric acid, then 36 parts sodium chloride are added at 700 and the aminoazo die is filtered off at room temperature.

The dye paste is dissolved in 600 parts water at pH 6.8 and is reacted with 18 parts 2,4- dichloro - 6 methoxy - 1,3,5 - triazine at room temperature. The pH is maintained at 6.7 by the addition of 13 parts sodium bicarbonate. Stirring is effected for 60 minutes at 30-40". The product which is filtered off and dried in vacuo is in the free acid form, of formula

The product which is in the sodium salt form dyes polyamides, especially wool, in orange shades; the dyeings have good wet- and light4astnesses.

Example 2 23 Parts 4- acetylamino -2 - aminobenzenesulphonic acid are diazotized as described in Example 1.

Coupling is effected by the dropwise addition of the diazonium solution at Oto 50 over a period of 35 minutes to a suspension of 23.9 parts 7 - amino - 1 hydroxynaphthalene - 3 - sulphonic acid in 140 parts water, the pH being kept at 3.3-3.5 by the addition of 31 parts sodium acetate. After 60 minutes the temperature is allowed to rise to 200, the whole is stirred for 60 minutes at room temperature and then filtration is effected also at room temperature.

The paste obtained is stirred in 120 parts water, 80 parts ethanol and 80 parts 30% hydrochloric acid for 14 hours at90 to splitoffthe acetyl group. The product is filtered off at room temperature and is sus pended in 1000 parts water at pH 7 and 18 parts 2,4 dichloro - 6 - methoxy - 1,3,5 -triazine are added over 15 minutes, the pH being kept at 6.8 by the addition of 32 parts sodium bicarbonate. Stirring at room temperature is effected overnight, the product is filtered off and dried in vacuo. The product, in the free acid form, formula of formula

is obtained in the sodium salt form and dyes polyamide, especially wool in red shades; the dyeings have good wet- and light-fastnesses.

Example 3 23 Parts 5 - acetylamino - 2 - aminobenzenesulphonic acid are dissolved in 200 parts water with the addition of 42 parts 20% sodium carbonate solution at pH 7 and are reacted with 6.9 parts sodium nitrite in 25 parts water. The solution is added dropwise over 30 minutes at 0-5 to a mixture of 80 parts ice and 28 parts 30% hydrochloric acid. After 15 minutes further stirred the reaction is complete and a white suspension of the diazo compound is obtained. 34.3 parts 2 - (2,'6' - dimethylphenyl) amino - 8 - hydroxy - naphthalene - 6 - sulphonic acid are dissolved in 180 parts water with the addition of 8 parts 30% sodium hydroxide solution at room temperature and precipitated in finely divided form by the dropwise addition of 8.5 parts 30% hydrochloric acid.The diazo solution is, over the period of 30 minutes added thereto whilst the pH is kept at 2.0 to 3.0 by the addition of 30% sodium hydroxide solution. Coupling is complete once the dropwise addition is finished, the dye is isolated by the addition of 30% sodium hydroxide solution until pH 7 is reached followed by filtration.

The acetylamino group is hydrolysed by stirring the paste in 500 parts water with 100 parts 30% sodium hydroxide solution for 45 minutes at 95". The product is salted out by the addition of 140 parts sodium chloride and is filtered at 600.

The paste is dissolved at pH 6 in 1200 parts water.

18 parts 2,4 - dichloro -6 - methoxy - 1,3,5 -triazine are added within 15 minutes at room temperature whilst the pH is kept at 5.5-6.0 by adding 30 parts 20% sodium carbonate solution. The precipitated dye is filtered and dried in vacuo. The dye, in the free acid from, is of formula

is obtained in the sodium salt form. The dye gives bordeaux-red dyeings on po lyamide, especially wool, which dyeings have notable wet- and lightfastnesses.

Example 4 40.6 Parts 1 - amino - 2 -p -toluene - sulphonyl - 4 (2' - chloro - 4' - methoxy - 1,3,5 - triazinyl) aminobenzene are reacted with 25 parts 30% hydrochloric acid in 600 parts water/acetone mixture fol lowed by diazotization with 7 parts sodium nitrite in 50 parts water. The reaction mixture is diluted with 900 parts water, stirred for 1 hour at 0-5 and the excess nitrous acid is decomposed with aminosulphonic acid.

The diazo suspension is added dropwise to a solution of 30.3 parts 2 - aminonaphthalene - 3,6 - disulphonic acid in 600 parts water at 0-5 whilst the pH is kept at 4.0-4.5 by adding 75 parts sodium acetate.

The suspension is diluted with 600 parts acetone and the temperature is allowed to rise to 20 , the pH is adjusted to 8 and the product is filtered off. The product, in the free acid form is of formula

is obtained in the sodium salt form and dyes polyamides especially wool in scarlet-red shades.

The dyeings have good light- and wet-fastnesses.

In the following Table further dies, which may be prepared in analogy with the procedure of Examples 1 to 4, are given. The compounds correspond to the general formula

In Table 1 the symbol K denote the following naphthalene groups (K1) to (Kls)

The dyeings on wool have the shades indicated in the last column of Table 1, whereby a=orange, b=scarlet-red, c=red and d=bordeaux red.

Table 1

Ex. K R2 Hal R, position shade on No. of-NH-Z wool 5 K, SO,H CI CH, 1 4 a i 6 K1 do. CI C2H5 5 a 7 K, do. F CH, 5 a 8 K, do. CI do. 4 c 9 1 K5 do. CI 02H3 5 c 10 K, do. Cl -CH(CH3)2 5 a 11 K5 do. Cl do 5 c 12 K10 do. Cl do. 5 d 13 K10 do. Cl C2Hs 4 d 14 Kl 2 SO2s%R Cl CH3 4 b 15 ~ Ka do. CI do. 5 b 16 K2 do. CI do. 4 b 17 K3 do. F do. 5 b 18 K3 do. Cl 02H5 5 b 19 K4 do. CI CH3 5 a 20 K4 SO3H Cl do. 5 a 21 K2 do. - CI do. 5 a 22 K5 2 3 Cl do. 5 c 23 K5 -s 02 < Cl CH3 5 c so a 3 011 3 24 K4 SO2 e CH3 Cl do. 5 a do.

25 K, do. Cl do. 5 b 26 K2 do. Cl do. 4 b 27 K3 do. Cl do. 5 b 28 K4 do. F do. 5 b 29 Ks do. CI do. 5 c 30 Ks do. Cl CH(CH3)2 5 c 31 K10 do. - CI CH3 5 d 32 Ks SO3H Cl do. 5 b 33 Ks do. Cl do. 4 c 34 K,S02S03H Cl do. 5 c 35 Kro do. Cl do. 5 d 36 Ks do. CI do. 4 c 37 Ks SO3H CI do. 4 c 38 Ks do. F do. 5 c 39 K do. Cl 02H5 5 b 40 K12 do. Cl CH3 5 a 41 K.2 S02fft0113 F do. 5 b 42 Kl do. Cl do. 5 b 3 43 K13 -so24 Cl CH3 5 b 44 K12 do. Cl do. 4 b 45 Kr4 do. Cl do. 5 b 46 K.2 -SO2CH3 Cl do. 4 b 47 K12 do. CI do. 5 b 48 Ka3 do. Cl O2H5 5 b Table No. 1 continued

Ex. K RP Hal R, position shade on No. of-NH-Z wool 49 K,, -SO,C,H, CI CH, 5 b 50 K12 2t 3 Cl do. b 51 K2 do. Cl 52 K13 -SO2CH4H9 Cl 53 K14 SO2CH3 Cl do. 4 b 54 K15 -5024 55 K13 -SO2N(CH2)2 Cl 56 K12 -SO2NHCH3 Cl 57 K12 -S02N(C2H5)2 Cl 58 K12 -S02N(CH,CH20H)2 CI 59 K13 -5o2Ne Cl 60 K13 < 3 Cl do. 5 b 61 K13 -S 2E4 Cl do. 5 b 62 K13 -So2l*Cffi3 Cl CH3 4 b Ca3 63 Kt ~5o2stso34 Cl 02H5 5 b SO?H 64 Ks do. Cl CH3 5 c 65 K4 do. So3g Cl do. 5 b 66 K1 50311 Cl 02H5 5 13 -so2cH3 Example 67 30.3 Parts 2 - aminonaphthalene - 6,8 - disulphonic acid are stirred in 180 parts water, 100 parts ice and 14 parts 30% hydrochloric acid and are diazotized within 30 minutes at 0-5" by the addition of 6.9 parts sodium nitrite in 25 parts water. After stirring for a further 15 minutes the reaction is complete.

18.4 Parts 1 - aminobenzene - 3 - carbamic acid ethylesterare stirred in 150 parts water. The diazo suspension is added within 30 minutes to the solution whilst the pH is kept between 4 and 4.5 by adding 20 parts 30% sodium-hydroxide solution. The dissolved dye is precipitated by the addition of 85 parts sodium chloride and is then filtered. The paste obtained is condensed with 2,4 - dichloro - 6 methoxy - 1,3,5 - triazine analogously to the method described in Example 3. After condensation is complete, 100 parts sodium chloride are added and the precipitated dye is filtered. The product, in the free acid form offormula

is obtained in the sodium salt form. The dye gives golden-yellow dyeings on polyamides such as wool which dyeings have good light- and wet4astnesses.

In analogy with the procedure described in Exam ple 67, the dyes of Table 2 which correspond to the general formula

may be prepared.

In the Table the dye shade on wool is given in the last column whereby e=yeliow and f=goldenyellow.

Table2

Ex. amine containing Rlo R1 shade on No. D wool 68 2 - aminonaphthalene -6,8 - disulfonic acid 02H5 -CH(CH3)2 f 69 do. CH3 CH3 f 70 do. C2H5 02H5 f 71 2- aminonaphthalene - 4,8 disulfonic acid do. CH3 f 72 do. do. -CH2CH2Cf13 f 73 do. C4H6(n) CH3 f 74 2- aminonaphthalene - 5,7 disulfonic acid CH3 do. f 75 2 - aminonaphthalene - 5,7 disulfonic acid O2H5 do. f 76 do. do. -CH(CH3)2 f 77 1 3.6- -aminonaphthalene-3,6- disulfonic acid do. CH3 e 78 1 - aminonaphthalene - 4,6 disulfonic acid do. do. e 79 1 - aminonaphthalene - 4,8 disulfonic acid do. do. e In analogy with the procedure described in Example 1 or 2 using appropriate starting materials the Syes of Examples 80 and 81 are obtained.

Example 80 The dye, in the free acid form offormula

is obtained in the sodium salt form and dyes wool in orange shades.

Example 81 The dye, in the free acid form of formula

is obtained in the sodium salt form and dyes wool in red shades.

Example 82 49.4 Parts pure 1 - amino -4 - (4' - aminophenylamino) - anthraquinone - 2,3' - disulphonic acid are dissolved at 40 in 300 parts water at pH 7. Subsequently, 18.1 parts 2,4- dichloro - 6 - methoxy - 1,3,5- -triazine are sprinkled in at 40" within 45 minutes; the pH is simultaneously kept between 7.5 and 8.5 by the addition of 20% soda solution. Afterthe reaction is com plete the dye is salted out with 10 parts sodium chloride, the suspension is stirred for 30 minutes and then filtered. The dye which is dried is vacuo at 40 and, in the free acid form is of formula

is obtained in the sodium salt form; the product gives brilliant blue dyeings and prints of good fastness on wool.

When 2,4 - dichloro - 6 - ethoxy - 1,3,5 - triazine is used in place of the 6-methoxy compound, the corresponding dyestuff is obtained which gives blue dyeings on polyamide having good light- and wetfastnesses.

Other salt forms of the dyes of Examples 1 to 82 may be.obtained in accordance with known methods.

Dyeing Example A 1 Part ofthe dye of Example 1 or2 is dissolved in 250 parts demineralized water.5 parts unchlorinated wool cable yarn are added to the dyebath and the temperature is adjusted to 40". 5 parts calcinated Glauber's salt, 1.5 parts glacial acetic acid and 1 part conventional levelling agent are added to the bath; the batch is heated to the boil within 90 minutes and keptatthe boil for 60 minutes. During dyeing evapo rated water is replaced every 15 minutes. The dyed substrate is washed in running hot water, then in running cold water (each for c. 3 minutes) and dried at approximately 70 . An orange (resp. red, Example 2) dyeing having good light- and wet-fastness is obtained.Synthetic polyamide may be dyed in simi lar manner. Similarly, the dyes of Examples 3 to 82 may be employed to dye wool in accordance with the method described above.

Dyeing Example B A dye mixture consisting of 0.94 parts dye of Example 1,0.22 parts dye of Example 2,0.84 parts dye of Example 82 are dissolved in 250 parts demineralised water and 5 parts wool gaberdine are added thereto. The dyebath is heated to 40 and 5 parts calcinated Glauber's salt, 2 parts acetic acid and 1 part conventional levelling agent are added to the bath.

The bath is brought to the boil over 90 minutes and kept at the boil for 60 minutes (evaporated water is replaced every 15 minutes). The dyeing is rinsed in hot- and then cold-running water and dried at approximately 70 . An olive dyeing having good light-fastnesses and general good fastnesses is obtained.

Claims

1. A compound of formula I

in which R1 is C1-4 alkyl Hal is halogen R3isSO3H,

-SO,CI-4 alkyl, -SO2NR8Rg or-NHCOOR,0, the triazinyl group is bound to the 4-or 5-position with the proviso that when R2 is-NHCOOR,0 it is bound to the 4-position, R3 is hydrogen, C1-4 alkyl or C1-4 alkoxy, R4 is hydrogen or C1-4 alkyl, R5 is hydrogen;C,~4 alkyl; cyclohexyl optionally substituted by up to three C1-4 alkyl groups; phenyl optionally substituted by up to two sub stituents selected from the group consisting of halogen, C1-4 alkyl and C14 alkoxy, R6 is hydrogen or hydroxy, with the proviso that R6 is other than hydroxy when R2 is-NHCOOR10, R7 is hydrogen, C, 4 alkyl or C1-4 alkoxy, each of R6 and R9, independently, is hydrogen, C1--4 alkyl or 02-4 hydroxyalkyl in which the hydroxy group is in the p-, y- or 6-position; cyclohexyl; or phenyl optionally substituted by up to two sub stituents selected from the group consisting of halogen, C,~4 alkyl, C,~4 alkoxy, sulpho and car boxy with the proviso that when one of R6 and R9 is cyclohexyl or optionally substituted phenyl the other has a significance other than cyc lohexyl or optionally substituted phenyl, Rio is C1-6 alkyl, mis 1 or2 n is 0 or 1 pisOor1 with the provisos: a) that n is only 0 and must be 0 when R3 is -NHCOOR10, b) that the -NHRs and the azo groups are ortho to each other in the 1- and 2-or 2- and 1-position ofthe naphthalene ring; and c) that when n is 1 and m is 1 and the azo group is in the 1-position of the naphthalene ring then, either, R6 is other than hydroxy in the 8-position or, the sulpho group is in other than the 4-position of the naphthalene ring, and the molecule contains at least two sulpho groups, and mixtures of such compounds, which compounds are in free acid or salt form.

2. A compound according to Claim 1, in which R3 is R3,, where R3, is hydrogen, methyl, ethyl, methoxy or ethoxy.

3. A compound according to Claim 1 or Claim 2, in which R4 is hydrogen or methyl.

4. A compound according to any one of Claims 1 to 3, in which R5 is R5,, where R5' is hydrogen, methyl, ethyl, cyclohexyl, phenyl optionally mono substituted by chlorine, methyl or methoxy.

5. A compound according to any one of the preceding claims, in which R3 is R2a or R3b, where R3, is SO3H,

-SO2CH3,-SO2C2Hs or-SO2NR6'Rg' in which R7, is hydrogen, methyl or methoxy R6, is hydrogen, methyl, ethyl or 2- or3-hydroxy C2-3 alkyl; R9-is methyl, ethyl, 2- or3-hydroxy C2-3 alkyl, cyclohexyl or phenyl optionally substituted by up to two substituents selected from the group consisting of chlorine, C,-2 alkyl, C1-2 alkoxy, sulpho and carboxy; and R2b is -NHCOOC1-4 alkyl.

6. A compound according to any one of the preceding claims, in which R1 is C,~3 alkyl.

7. A compound according to any one of the preceding claims, in which Hal is fluorine or chlorine.

8. A compound according to Claim 1, in which n is 1, R2 is R3a, as defined in Claim 5, and the compound contains 2 sulpho groups.

9. A compound according to Claim 8, in which R3 is R3", where R3" is hydrogen, methyl or methoxy.

10. A compound according to Claim 8 or Claim 9, in which R5 is Rs, as defined in Claim 4.

11. Acompound according to Claim 8 of formula la,

in which R5" is hydrogen, methyl or phenyl, R2a' is -SO3H,

-SO,C H,, -SO,C,H, or-SO3NR3"R9", in which R7" is hydrogen or methyl, R8" is methyl, ethyl or2-hydroxyethyl, R9,, is methyl, ethyl, 2-hydroxyethyl or phenyl optionally substituted by up to two substituents selected from the group consisting of methyl and sulpho, m is as defined in Claim 1 with the proviso that m is 1 when R6 is hydroxy.

12. A compound according to Claim 11, in which R5,, is hydrogen.

13. Acompound according to Claim 11 or Claim 12, in which R3a is sulpho.

14. A compound according to any one of the preceding claims.

15. Acompound according to Claim 14, in which Rl is methyl.

16. Acompound according to Claim 1 offormula Ib,

in which R2b is as defined in Claim 5, R3" is hydrogen, methyl or methoxy and Hal' is fluorine or chlorine.

17. Acompound according to Claim 16, in which R3b is R2b', where R2b' is -NHCOOCH3 or -N HCOOC2Hs.

18. A compound according to Claim 16 or Claim 17, in which R3" and R4 are both hydrogen, Hal' is chlorine and R, is Ci~3 alkyl.

19. A compound according to any one of Claims 16 to 18, in which Rt is methyl.

20. A lithium, sodium or potassium salt of a compound according to any one of the preceding claims.

21. A compound offormula

in free acid or salt form.

22. The sodium, lithium or potassium salt of the compound of Claim 21.

23. Acompound offormula

in free acid or salt form.

24. The sodium, lithium or potassium salt of the compound of Claim 23.

25. A compound according to Claim 1, in which R3 is SO3H, R3 is hydrogen, m is 1, and the sulpho group is in the 5-or 6-position, R6 is hydrogen or hydroxy in the 8-position, R5 is hydrogen, n is 1, and the -NH2 group is in the 2-position, R4 is hydrogen and Hal is chlorine.

26. A mixture comprising a compound of formula I according to any one ofthe preceding claims or a mixture of such compounds, and a compound of formula VII,

in which R, is C1-, alkyl which compounds are in salt form.

27. A mixture according to Claim 26, containing (a) the salt form of a compound offormula Ic,

together with (b) the salt form ofthe compound of formula Vlla

and/or (c) the salt form ofthe compound offormula Id,

28. A process for the production of a compound of formula I in which n is 1, comprising coupling the diazonium derivative of the compound of formula II,

in which R3, is R3 as defined above with the exception of the group-NHCOOR10, X -NO3 or NR4Z, and is in the 4-or 5-position, Zi is a protecting group or is a radical of formula (a) or (b)

ora mixture thereof, with a compound of formula Ill

our a mixture thereof, and when Z, is (a) condensing the product with a compound R,OH and when X is nitro reducing the same orZ, is a protecting group, splitting offsuch group and reacting the -NH2 or-NHR4 group either with cyanuric halide followed by reacting the product with a compound R1OH or with a compound of formula (c)

29. A process forthe production of a compound of formula I, in which n is 0, comprising reacting the compound offormula IV

our a mixture thereof, either, with cyanuric halide followed by reacting with a compound R,OH, or, with a compound of formula (c) as given in Claim 28.

30. A process according to Claim 29, substantially as hereinbefore described with reference to any one of Examples 1 to 66, 80 and 81.

31. A compound of formula I, as defined in Claim 1, whenever obtained by a process according to Claim 28 or Claim 30.

32. A process according to Claim 29, substantially as hereinbefore described with reference to any one of Examples 67 to 79.

33. A compound of formula I, as defined in Claim 1, whenever obtained by a process according to Claim 29 or Claim 32.

34. A process for dyeing or printing hydroxy group- or nitrogen-containing organic substrates comprising employing a compound according to any one of Claims 1 to 27,31 and 33, as dyeing agent.

35. A process according to claim 34, in which the substrate comprises leather or a texture material consisting of or comprising natural or regenerated cellulose or natural or synthetic polyamides.

36. A process according to Claim 35, in which the substrate consists of or comprises wool.

37. A process for dyeing or printing hydroxy group- or nitrogen-containing organic substrates substantially as hereinbefore described with reference to Dyeing Example A or B.

38. Dyed or printed substrates whenever obtained by a process according to any one of Claims 34 to 37.