FR2459821A1 - NOVEL MONOAZOIC COMPOUNDS USED AS REAGENT DYES AND THEIR PREPARATION - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS THE NEW MONOAZOIC COMPOUNDS OF FORMULA: (CF DRAWING IN BOPI) IN WHICH M MEANS 1 OR 2, N MEANS 0 OR 1, HAL REPRESENTS HALOGEN, R MEANS AN ALKYL GROUP, R REPRESENTS A SULFO GROUP , ALKYLSULFONYL OR ALCOXYCARBONYLAMINO OR A PHENYLSULFONYL OR SULFAMOYL GROUP WHICH IS POSSIBLE SUBSTITUTED, R REPRESENTS HYDROGEN OR AN ALKYL OR ALCOXY GROUP, R MEANS HYDROYL REPRESENT OR A SUBSTITUTE GROUP, R MEANS HYDROYL REPRESENT OR A SUBSTITUTE GROUP, R SIGNIFICANT HYDROYPE REPRESENT OR A GROUP, R SIGNIFICANT HYDROYPE REDROUGENE OR A SUBSTITUTE GROUP, R SIGNIFICANT HYDROYPE REDROGENE OR A SUBSTITUTE GROUP. MEANS HYDROGEN OR A HYDROXY GROUP, AND THEIR PREPARATION. THESE COMPOUNDS MAY BE USED AS COLORS FOR DYING OR PRINTING ORGANIC SUBSTRATES CONTAINING HYDROXY GROUPS OR NITROGEN ATOMS.

Description

The subject of the present invention is new

  monoazol compounds, their preparation and their application

  as reactive dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen atoms. The invention relates more particularly to monoazole compounds corresponding to formula I Ra

3 R3!

  x4 NN OR where m is 1 or 2, n is 0 or 1, Hal is a halogen atom, R 1 is an alkyl group containing 1 to 4 carbon atoms, R2 is a sulfo group, an alkylsulfonyl group containing 1 to 4 carbon atoms or a residue

7

  (S03H) p -SO2NR8R9 or -NHCOOR10, where p is 0 or 1, R7 is a hydrogen atom or an alkyl or alkoxy group each containing 1 to 4 carbon atoms, R8 and R9 each independently signify on the other side, a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms, a hydroxyalkyl group containing from 2 to 4 carbon atoms whose hydroxyl residue is located in the y position, or f, a cyclohexyl group or a phenyl group optionally bearing 1 or 2 substituents selected from halogens, alkyl and alkoxy groups containing from 1 to 4 carbon atoms, and sulfo and carboxy groups, one of the symbols R8 or R9 to have a meaning different from the cyclohexyl group or an optionally substituted phenyl group, where

  the other symbol R or R8 means a cyclo-

  hexyl or an optionally substituted phenyl group, and R10 represents a group. alkyl containing from 1 to 6 carbon atoms, the triazinyl group being capable of being attached in the 4- or 5-position, this group must however be attached in the 4-position when R2 signifies a -NHCOOR10 residue, R3 represents a hydrogen atom or an alkyl group or alkoxy containing 1 to 4 carbon atoms, R4 is hydrogen or an alkyl group containing 1 to 4 carbon atoms, R5 is a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms a cyclohexyl group optionally substituted by 1, 2 or 3 alkyl groups each containing from 1 to 4 carbon atoms, or a phenyl group optionally bearing 1 or 2 substituents chosen from halogens and alkyl and alkoxy groups each containing from 1 to 4 carbon atoms, and R6 is hydrogen or hydroxy, R6 to be other than hydroxy when R2 is -NHCOOR0lo, with the provisos that: a) n is zero when R2 is a remainder - NHCOOR10, b) the residue -NHR5 and the azo group are located at the adjacent positions 1 and 2 or 2 and 1 of the naphthalenic residue c) R6 is different from a hydroxy group located in

  position 8, where the sulfo group is set at a

  other than the position 4 of the naphthalenic residue, when n is 1, m is 1 and the azo group is in position 1 of the naphthalenic residue, the molecule to contain at least two sulfo groups, and their mixtures, in the form of free acid or under

form of a salt.

  By halogen is meant fluorine, chlorine or bromine. Preferred halogen atoms attached to the triazinyl group are fluorine and chlorine, especially chlorine; the halogen atoms on a benzene ring are preferably chlorine or

bromine, especially chlorine.

  The groups and alkyl residues present in the

  molecule may be linear or branched.

  R1 preferably means an alkyl group containing from 1 to 3 carbon atoms, in particular

a methyl group.

  When R3 represents an alkyl or alkoxy group, it is preferably a methyl group

  or ethyl, preferably a methyl group.

  R3 is preferably R, i.e., hydrogen, methyl, ethyl, methoxy or ethoxy. More particularly, R 3 represents R ", this R" symbol representing a hydrogen atom or a methyl or methoxy group, in particular a

hydrogen atom.

  When R4 is alkyl, it is preferably a methyl group. R4 preferably represents a hydrogen atom or a methyl group,

  in particular a hydrogen atom.

  When R 5 represents an alkyl group,

  it is preferably a methyl or ethyl group.

  When% represents a substituted cyclohexyl group, the latter is preferably substituted with up to 3 methyl groups. When R5 represents a substituted phenyl group, it is preferably a phenyl group bearing 1 or 2 substituents chosen from chlorine and methyl, ethyl, methoxy and ethoxy groups, chosen in particular from chlorine.

  and methyl and methoxy groups.

  R5 preferably represents R, that is to say a hydrogen atom, a methyl, ethyl or cyclohexyl group or a phenyl group optionally monosubstituted with a chlorine atom or with a methyl or methoxy group. R5 in particular R, this R "symbol representing a hydrogen atom or a methyl or phenyl group, more particularly

a hydrogen atom.

  When R 7 represents an alkyl or alkoxy group, it is preferably a methyl, ethyl, methoxy or ethoxy group, in particular a methyl group.

or methoxy.

  R7 preferably represents R, that is to say

  a hydrogen atom or a methyl or methoxy group.

  More particularly, R7 is R ", i.e.

7 7

  a hydrogen atom or a methyl group, in particular

a hydrogen atom.

  When R 8 and / or R 9 are alkyl, it is preferably a methyl or ethyl group. When R 8 and / or R 9 are hydroxyalkyl, this group preferably contains 2 or 3 carbon atoms, and preferably means 2-hydroxyethyl. When R8 or R9 represents a group

  substituted phenyl, this group bears one or two substitutions

  selected from chlorine and the selected methyl, ethyl, methoxy, ethoxy, sulfo and carboxy groups

  in particular from methyl and sulfo groups.

  R8 is preferably Ra, that is to say a hydrogen atom, a methyl or ethyl group or a 2- or 3-hydroxyalkyl group whose alkyl residues

  contain 2 or 3 carbon atoms. More specifically

  R8 represents R ", that is to say a methyl group,

ethyl or 2-hydroxyethyl.

  R9 preferably represents R4, that is to say

  a methyl, ethyl, cyclohexyl, 2- or 3-hydroxy group

  alkyl whose alkyl residues contain 2 or 3

  carbon atoms, or a phenyl group bearing possible

  1 or 2 substituents selected from chlorine and methyl, ethyl, methoxy, ethoxy, sulfo and carboxy groups. More particularly, R9 is R9, that is methyl, ethyl, 2-hydroxyethyl or phenyl optionally having 1 or 2 substituents.

  selected from methyl and sulfo groups.

  R10 is preferably an alkyl group containing from 1 to 4 carbon atoms, in particular

a methyl or ethyl group.

  When R2 represents an alkyl group

  sulfonyl it is preferably a methyl group

sulfonyl or ethylsulfonyl.

  R2 preferably R2a or R2b, R2a

  representing a sulfo, methylsulfonyl, ethyl-

  sulfonyl or a radical R or -SO2NRR, and -SO-

(SO H)

  Wherein R 2b is alkoxycarbonylamino wherein the alkoxy residue contains 1 to 4 carbon atoms. R2a preferably means R, that is to say a sulfo, methylsulfonyl or ethylsulfonyl group or a residue or SNRtR "

R "-S02N 8 9

-S02 7

  More particularly, Ra is R2a, i.e. 2a is a sulfo group or a radical R, any -SO (SO 3 H) p is especially a sulfo group. R2b means of

  preferably R'b i.e. a methoxycarbonyl group

2b,

amino or ethoxycarbonylamino.

  The compounds of formula I preferably contain 2 sulfo groups. When R6 represents a

  hydroxy group, m preferably means 1.

  The substituents present on the naphthalenic residue are preferably the following:

a) n = 1.

  When the remainder -IHR5 is located at position 1 and R6 is hydrogen, the sulfo group is at the 4 position for m = I and the sulfo groups are at the 3,6, 3,8 or 4,6 position of preference to

positions 3,6 or 4,6, for m = 2.

  When the residue -NHR5 is located in position 2 and R6 is hydrogen, the sulfo group is in position 5, 6 or 7 for m = let the groups

  sulfo are located at positions 3.6 or 5.7 for m = 2.

  When the rest -NHR5 is in position

  2 and that R6 represents a hydroxy group (preferably

  in position 8) and m preferably means 1,

  the sulfo group is in position 6.

b) n = 0 and m = 2.

  When the azo group is in position 1, the sulfo groups are fixed at the positions 3,6, 3,8, 4,6 or 4,8; when the azo group is in position 2, the sulfo groups occupy the positions 3.6, 4.8, 5.7

or 6.8.

  The remainder -NHR5 is preferably in

position 2 of the naphthalenic residue.

  Preferred compounds of formula I are: (i) compounds wherein n is 1,

  R2 has the meaning of R2a, Hal represents

  smell fluorine or chlorine, and who knows what.

  hold 2 sulfo groups; (ii) the compounds specified under (i) in which R3 is R "and R is

3 3 4

  a hydrogen atom or a methyl group; (iii) the compounds specified under (i) or (ii) in which R.5 is R; (iv) the compounds of formula Ia NHR "R2a t N = N Ci (Ia) R6 NH-N

GOLD

  (SO3H) m wherein m has the meaning already given, m being 1 when R6 is hydroxy; (v) the compounds specified in (iv) where R "is hydrogen, (vi) - the compounds specified in (iv) or (v) where R 'is R2a, in particular a 2a sulpho group; compounds specified under (iv), (v) or (vi) where R1 represents an alkyl group containing from 1 to 3 carbon atoms, in particular a methyl group, (viii) compounds of formula Ib R2b Hall '- = N + m4 Nb

N = N Q -

  (Ib) OR1 in which Hal 'represents fluorine or chlorine; (ix) the compounds specified under (viii) o R2b means Rb '; and R 2b, - (x) compounds specified under (viii) or (ix) wherein R "and R4 are each

3 4

  hydrogen, Hal 'means chlorine and R represents an alkyl group containing from 1 to 3 carbon atoms, in particular

a methyl group.

  According to the process of the invention, to prepare the compounds of formula I a) the ureou diazolque of several amines of formula II is copulated.

R R2

NH2 (II)

  in which R.sub..a..sub.2 of given meanings for R2 such

- 2

  However, as defined above, while R 'can not represent a radical R2 NHCOORlo, R3 has the meaning already given, X is located in position 4 or 5 and means a nitro group or a residue -NR4Z1 where Z1 represents a protecting group or a remainder of formula (a) or (b) Hal Hal 4 X (a) (b) OR1 OR] o Hal and R have the meanings already given, 1 with one or more compounds of formula III with one or more compounds of formula III

R6 NHR5

  (H03S) m o (III) wherein R5, R6 and m have the meanings

already given ,.

  and when Z 1 signifies a residue (a), the product is condensed with a compound of formula R 10 OH, when X represents a nitro group, this group is reduced, or when Z 1 represents a protective group, this group is eliminated, and the reaction is reacted. remain -NH2 or -NHR4 is with a cyanuryl halide followed by a reaction with a compound of formula RlOH, or with a compound of formula (c) ial Hai (c) OR1 in which Hal and R1 have the meanings already given, to give compounds of formula I is 1, or b) one or more compounds of formula IV are reacted

NHCOOR10

N = N W HR

4 03S (IV)

(HO3S) - NH

  Wherein R 3, R 4 and R 10 have the meanings already given, either with a cyanuryl halide followed by a reaction with a compound of formula R 1 OH, or with a compound of formula (c) specified above, which gives the compounds of formula I in which

n means 0.

  In the processes specified under a) and b), it is preferable to use the compound of formula (c) rather than carrying out the reaction with a cyanuryl halide followed by reaction with a compound of formula R 1OH. The condensation reactions with the cyanuric halide and the compound R1OH or with the compound of formula (c) are carried out according to the known methods. The compound of formula IV is obtained by coupling the diazolec of the compound of formula V NH 2

(HO S) 2 (V)

2 2

with a compound of formula VI

NHCOOR10

H NIR4 (VI)

  R3 in which R3, R4 and Rlo have the meanings already

data.

  The coupling is carried out according to known methods, advantageously in an acid medium, preferably in a medium having a pH between

2.0 and 4.5.

  The compounds of formula I thus obtained

  can then be isolated by known methods.

  According to the reaction and isolation conditions, the compounds of the formula I can be obtained in the form of salts; these salts may comprise, as cations, one of the non-chromophore cations commonly found in salts of reactive dyes. The preferred cations are lithium, sodium and potassium cations,

especially sodium.

  The starting materials of formulas II, III, V and VI are known or can be prepared according to known methods from known starting materials. The compounds of formula I and mixtures thereof can be used as reactive dyes for dyeing or printing organic substrates

  containing hydroxy groups or nitrogen atoms.

  The preferred substrates are leather and textile materials consisting wholly or in part of natural or regenerated celluloses such as cotton, viscose or rayon, or of natural or synthetic polyamides such as wool, silk and / or nylon. The substrates that are particularly preferred are textile substrates consisting, in whole or in part, of

of wool.

  The new dyes of formula I, in the form of dyebaths or printing pastes, can be used to dye or print the substrates mentioned according to the usual methods.

  used for reactive dyes.

  It is best to proceed by the exhaustion methods to dye the substrates

polyamides.

  The dyes and prints obtained with the dyes of the invention are distinguished by their remarkable wet fastness (washing, water,

  sweat), fuller and light.

  In addition, the compounds of formula I may be used in combination with other reactive dyes containing sulfo groups, preferably with anthraquinone reactive dyes. Such mixtures may comprise two or three components, and thus form highly desired ternary mixtures.

for dyeing processes.

  The preferred anthraquinone dyes which can be combined with the compounds of formula I are the compounds corresponding to formula VII NM2 ci <Cl (VII)

S0311 OR1

  in which R 1 represents an alkyl group containing from 1 to 4 carbon atoms, in particular in the form of salts; the cations of these salts may be those mentioned above for the dyes of formula I. To prepare the compounds of formula VII, the compound of formula VIII is condensed

O NV2

(VIII)

  NR 2 with a compound of formula IX (IX)

  in which R1 has the meaning already given.

  The preferred 2 and 3-component mixtures are the mixtures containing the compound of formula Ic in salt form SO 3 H and N> 1-N

NE0> -NR

  OCH3 (Ic) so3H as an orange component, the compound of formula VIIa in salt form,

O <NH

2 N / A

ci 2SNR <"C1Nu

S0311 OCR3

  as the blue component, and / or the compound of formula Id in salt form (formula Id see next page) (VIIa) SO 3 HCl Q N t N 4 (Id) "p> N

OCR3 S03R

as a red component.

  The quantity of each component present

  in 2-component and 3-component mixtures is not deter-

  nant; it depends on the desired shade. The dyes obtained with these mixtures are united, in particular on wool. These dyes have good fastness to light and wet, and do not give a catalytic turn. The invention also includes organic materials containing hydroxy groups or nitrogen atoms which have been dyed or printed with at least one of the compounds of formula I, optionally in combination with reactive anthraquinone dyes,

  especially compounds of formula VII.

  The following examples illustrate the present invention without in any way limiting its scope. Parts are by weight and temperatures are

  all indicated in degrees Celsius.

Example 1

  At pH 8, 23 parts of 4-acetyl-

  amino-2-aminobenzene sulfonic acid in 80 parts of water with 33 parts of a 20% solution of sodium carbonate and this solution is then reacted with 6.9

  parts of sodium nitrite in 25 parts of water.

  This solution is then added dropwise, over 60 minutes and at 0-5, to 25 parts of 30% hydrochloric acid. After allowing to react for minutes, the pH is adjusted to 3 by addition of 6.6 parts of sodium acetate. To the diazo solution thus obtained, a solution of 22.3 parts of 2-aminonaphthalene-5-sulphonic acid in 100 parts of water is added dropwise at 0-5 within 45 minutes. water and 10 parts of a 30% solution of sodium hydroxide. During copulation, the pH is maintained

  at 2.8-3.2 by addition of 12 parts of sodium acetate.

  After 2 hours of reaction, the pH is adjusted to 8.5 by the addition of 14 parts of a 30% solution of sodium hydroxide and the whole is heated for a short time to 800. 33 parts of chloride are then added. of sodium to the clear solution obtained and then filtered at 40 °

product formed.

  The paste thus obtained is stirred for 90 minutes at 90 °, in 300 parts of water and 63 parts of a 30% solution of sodium hydroxide to remove the acetyl group. The pH is adjusted to 9 by the addition of 53 parts of a 30% solution of hydrochloric acid, and then to 36 parts of sodium chloride.

  the product is filtered at room temperature

azole obtained.

  The paste thus obtained is dissolved in 600 parts of water at pH 6.8 and this solution is reacted.

  at room temperature with 18 parts of 2,4-dichloro-

  6-methoxy-1,3,5-triazine. The pH is maintained at 6.7 by the addition of 13 parts of sodium bicarbonate

  and the mixture is stirred for 60 minutes at 30-40 ° C.

  After filtration and drying under reduced pressure, the corresponding compound, in the free acid state, is obtained with the formula (formula see next page).

3 2

  > - N OCH3 In the form of sodium salt, this compound dyes polyamides, in particular wool, in orange shades,

  solid in the wet and in the light.

Example 2

  Proceeding as described in Example 1,

  23 parts of 4-acetylamino-2-amino acid are

  benzene. The solution of the diazolec thus obtained is then added dropwise at 0-5 and in 35 minutes to a suspension of 23.9 parts of 7-amino-1-hydroxynaphthalene-3-sulphonic acid in 140 parts of ethyl acetate. while maintaining the pH at 3.3-3.5 by addition of 31 parts of sodium acetate. After minutes, the temperature of the mixture is allowed to return to 20, stirred at room temperature for 60 minutes and then filtered at room temperature.

room.

  In order to remove the acetyl group, the paste thus obtained is stirred for 14 hours at 90 ° C., in 120 parts of water, 80 parts of ethanol and 80 parts of a 30% solution of hydrochloric acid. The product is filtered at room temperature, suspended in 1000 parts of water at pH 7 and then, during 15 minutes, 18 parts of 2,4-dichloro-6-methoxy are added to this suspension. -1,3,5-triazine, while maintaining the pH at 6.8 by the addition of 32 parts of sodium bicarbonate. After stirring the mixture at room temperature overnight, the product is filtered and dried under reduced pressure. The dye obtained in the form of sodium salt, in the form of a free acid, corresponds to the formula

0 3 H

10 3 S03H3

O> -NKH

OCH.O3

  It dyes polyamides, especially wool, in red shades with good wet fastness

and in the light.

  EXAMPLE 3 23 parts of 2-acetylamino-2-aminobenzene-sulfonic acid are dissolved in 200 parts of water while adding 42 parts of a 20% solution of sodium carbonate and this mixture is then reacted with 6 parts. 9 parts of sodium nitrite in 25 parts of water. This solution is then added dropwise, at 0 ° -5 ° and in the course of 30 minutes, to a mixture of 80 parts of ice and 28 parts of 30% hydrochloric acid. After stirring the mixture for another 15 minutes, the reaction is complete; we obtain a white suspension containing

  the diazo. 34.3 parts of 2- (2,6-

  dimethylphenylamino) -8-hydroxy-naphthalene-6-sulfonic acid in 180 parts of water while adding at the ambient temperature 8 parts of a 30% solution of sodium hydroxide and then, by dropwise addition of 8.5 parts of 30% hydrochloric acid, precipitated

  the compound in the form of a finely divided product.

  To this mixture is added, within 30 minutes, the solution of the diazo, while maintaining the pH at 2.0-3.0 by addition of a 30% solution of sodium hydroxide. When the dropwise addition is complete, the copulation is complete; to isolate the product, it is neutralized with a 30% solution

  sodium hydroxide to pH7, then filtered.

  The acetylamino group is hydrolyzed by stirring the paste obtained, for 45 minutes at 95, in 500

  parts of water and 100 parts of a 30% hydro-

  sodium hydroxide. The product is then precipitated by addition of 140 parts of sodium chloride

and filtered at 60.

  The paste obtained is dissolved at pH 6 in 1200 parts of water. To this solution, 18 parts of 2,4-dichloro-6-methoxy-1,3,5-triazine are added at room temperature and in the course of 15 minutes, while maintaining the pH at 5.5. 6.0 by the sum of 30

  parts of a 20% solution of sodium carbonate.

  The precipitated product is filtered and dried under reduced pressure. The dye obtained in the form of sodium salt, in the form of a free acid, corresponds to the CO 2

N NR

NO> -NHIlN C

C!

OCH O

  -S3H It dyes polyamides, especially wool, in burgundy shades with remarkable solidity

wet and light.

Example 4

  40.6 parts of 1-amino-2-p-

  toluene-sulfonyl-4- (2-chloro-4-methoxy-1,3,5-triazinyl-

  amino) benzene with 25 parts of% hydrochloric acid in 600 parts of a mixture of water and acetone and then this mixture is treated with 7 parts of sodium nitrite in 50 parts of water. After diluting the reaction mixture with 900 parts of water, it is stirred for 1 hour at 0-5 and then the excess acid is destroyed.

  nitrous by addition of sulfamic acid.

  The suspension is added dropwise at 0-5.

  diazolec thus obtained, to a solution of 30.3 parts of 2-aminonaphthalene-3,6-disulfonic acid

  in 600 parts of water, while maintaining the pH at 4.0-

  4.5 by addition of 75 parts of sodium acetate.

  After having diluted the suspension with 600 parts of acetone, the temperature of the mixture is allowed to return to 200 ° C.

  adjust the pH to 8 and filter the precipitated product.

  The compound obtained in the form of sodium salt, in the free acid state, corresponds to the formula

2O> -NH N = N

NOT

OCH3 so2 3 3AS3

CH3

  It dyes polyamides, especially wool, in shades of scarlet red with good fastness

in the light and the wet.

  Proceeding as described in Examples 1 to 4, the dyes specified in Table 1 below can be prepared. The compounds correspond to the formula

-N = N - K

  in which Hal, R1 and R2 have the meanings indicated in the table. The symbol K represents the following naphthalenic groups (K1) to (K15): (K1); SO.sub.3H

$ K. (K,

  S03H (K3); N2SO3u NH2 SO31I (K4); S03H r2

(K5) ;.

S03H (K8); 3H

NR-0

(K7); (K6); (K9); NH-0 HO o3H

(K 10);

SO3H (K11);

NH2 SO3H

$ X S3 (K12);

so3R Mi2 SQ

* - S03H

S03H

(K15).

  In the last column of Table 1 are given the shades of the dyes obtained on the wool: a = orange; b = scarlet red; c = red and d = burgundy. The penultimate column of the table indicates the position of the remainder -NH-Z (ie

  the rest triazinylamino) on the benzene nucleus.

  (Table 1 see following pages) T a b 1 e to 1. positionNuance of the remainder on the R2 R1.i; H-Z - wool] l K1 K1 K1 K5 K5 K5 K1 K1 K1 K1 K2 K3 K3 K K3 K5 SOH S3H do. do. do. do. do. do. do. do. do. do. do. do. do. SO H 3E do.

- S02-- - S03

  Cl Cl F C1 Ci Ci Cl C1 Cl C1 Cl Cl C1 C1 C1 C1 C1 CH3 C2H5 CH3 do. C25 -

-CH (CH3) 2

  do. do. CH. C215 CH3 do. do. do. C2H CH3 do. do. do. -5 a a c c a c d d b b b b b a a c il EIx. positionPuance _ I IHal R2a R1 of the remainder on the 1NH-Z ilaine K5 K4 K1 K2 K3 K4 R15 K5 K6 K8 K8 K9 K9 K19 K9 K12 K12 K13 K9 K9

-SQ _I

/ _03H i2 ci) u

-S02C CH3

  do. do. do. do. do. do. do. S03H do.

-S02-- S03H

  do. do. S03H do. S3 do. do. do. -S do. H3 do. C1 C1 C1 Cl C1 C1 C1 C1 Cl C1 Cl C1 C1 C1 C1 C1 F CH3 CH. do. do. do. do. do.

-CH (CH3) 2

  CH3 do. do. do. do. do. do. do. C2n5 CH3 do. do. c a b b b b c c d b c c d c c c b a b b I q! II I

* 1 i - I uance

  Ex. K Hal -. R position on the R2 1 Jdu rest wool

_ _ _ _ _ _ _ _ _ _ _-NH-Z

  43 K13 -SO-) C1 CH3 5b 44 K12 do. Ci do. 4 b

44 K12

  R14 do. C1 do. 5 b 46 K12 -SO2CH3 Ci do. 4 b 47 K12 do. C1 do. 5 b 48 13 do. ## STR2 ## 5 b 51 K -SOCH C1 do. 5 b 52 R13 -S 24Ho (n) C1 do. 5 b 53 K14 -SO2C3 C do. 4 b 54 K -S02QH C do. 5 b

2

K15 K13 -SO2N (CH3) 2 Ci do. 5 b

56 K1-2 HC

  56 12 -S2 eH 3 Cl do. 5 b 57 K12-SO2N (C2H5) 2 C1 do. 4 -b 58 K12 SO2N (HCH2OH) 2 Ci do. 5 b 59 K12 -FS2ON \ <Cl do. 5 b

C2H.5.

  K13-SO2H CH C1 do. 5b K13 3CH3 61 R13 -S 2NH-H C1 do. 5 b I

Example 67

  30.3 parts of 2-amino acid are stirred

  naphthalene-6,8-disulphonic acid in 180 parts of water, parts of ice and 14 parts of 30% hydrochloric acid and then, within 30 minutes, the mixture is diazotized at 0-5 by addition of 6.9 parts of sodium nitrite in 25 parts of water. After stirring the mixture for another 15 minutes, the reaction is complete. 150 parts of water, 18.4 parts of ethyl 1-aminobenzene-3-carbamate are then stirred, and to this solution, the suspension of the diazolc prepared above is added over a period of 30 minutes. keeping the pH between 4 and 4.5 by adding 20 parts of a 30% solution of sodium hydroxide. The reaction product is precipitated by the addition of 85 parts of sodium chloride and then filtered. The paste obtained is reacted with 2,4-dichloro-6-methoxy-1,3,5-triazine, as described in Example 3. When the condensation is complete, 100 parts of sodium chloride are added. sodium and filter the precipitated product. The dye obtained in the form of the salt of Example E. K R Hal R of the remainder on Ex. - Zlaine 62 - 13 SO2N- / X CH3 4 b CH3 63 Ki -SO2St. -S0] 3 C1 C2H5 5b CH3 64 K5 do. C1 CH3 5 c K4 do. Ci do. 5 b So H S3H 66 K1 i FQ CH3 ci C25 5 b 2CH sodium responds, in the free acid state, to the formula

-C0C2H5 3

  It dyes polyamides such as wool in shades of golden yellow with good fastness to light

and wet.

  Proceeding as described in Example 67, the dyes specified in Table 2 below can be prepared. They correspond to the formula ## STR1 ## in which D, R 1 and R 10 have the meanings given in this table. The shades of the dyes obtained on the wool are indicated in the last

  column; e = yellow and f = golden yellow.

  (Table 2 see next page) T a b 1 e a u 2 Amine allowing Nuance Ex. Prepare component 10 R1 on D_a-ine

2-aminonaphthalene-6,8-acid

disulfonic do. do.

2-aminonaphthalene-4,8-acid

disulfonic do. do.

2-Aminononaphthalene-5,7-acid

disulfonic

2-amino-naphthalic acid-5,7-

disulfonic do.

1-aminonaphthalene-3,6-acid

qisulfonique

l-aminonaphthalene aciae-4,6-

disulfonic

1-aminonaphthalene-4,8-acid

  disulfoic C2H5 CH3 c25 do. do. C4H9 (n) CH3 CPH5 c25 do. do. do. do.

- CH (CH3) 2

CR3 CH c25 CH3 c3

- CH2CH2CH3

CH3 do. do.

- CR (CH3) 2

  CH3 do. do. By the procedure described in Example 1 or 2, and using the appropriate starting materials, the dyestuffs of Examples 80 and 81 below can be prepared.

sodium.

formula

Example 80

  The compound is obtained in the form of a free acid, it corresponds to salt with S03H 0CH3

  It dyes the wool in orange shades.

Example 81

  The compound is obtained in the form of sodium salt. In the free acid state, it corresponds to the formula _QN 0CR CH3 = N s0311

  He dyes wool in red shades.

Example 82

  Dissolved at 40 and at pH 7 49.4 parts

  of 1-amino-4- (4-aminophenylamino) anthraquinone

  Pure 2,3-disulfonic acid in 300 parts of water. This solution is introduced at 40 and in the space of 45

  minutes, 18.1 parts of 2,4-dichloro-6-methoxy-1,3,5

  triazine while maintaining the pH between 7.5 and 8.5 by the addition of a 20% solution of

  sodium. When the reaction is over,

  The product is cipitated by adding 10 parts of sodium chloride and, after stirring the suspension for 30 minutes, it is filtered and the compound is dried under reduced pressure. The compound obtained in the form of sodium salt, in the free acid state, corresponds to the formula

ONH Q E'H - <ON

NOT

S03H. C1

  He gives, on wool, dyes and impressions

  bright blue with good solidity.

  When 2,4-dichloro-6-ethoxy-

  1,3,5-triazine instead of the 6-methoxy compound, a corresponding dye is obtained which gives blue dyes having good fastness to light and wet

on polyamides.

  By proceeding according to known methods, other salts of the dyes of the examples can be prepared.

1 to 82.

  Dyeing Example A One part of the dye of Example 1 or 2 was dissolved in 250 parts of demineralized water. 5 parts of a non-chlorinated, cabled woolen thread are introduced into this bath and the temperature is raised to 400. After adding 5 parts of calcined sodium sulphate, 1.5 parts of glacial acetic acid and a part of a known unison agent, the bath is boiled in the space of 90 minutes and kept boiling for 60 minutes. Every 15 minutes, the water that has evaporated during the dyeing is replaced. The dyed substrate is then washed with hot water and cold water (each operation takes about 3 minutes) and dried at about 70. This gives an orange dye (respectively red with the dye of Example 2) having good fastness

in the light and the wet.

  The synthetic polyamides can be dyed by analogous procedures. Similarly, the dyes of Example 1 or 2 can be replaced by the dyestuffs of Examples 3 to 82 and the dye of the wool can be

  proceeding according to the method described above.

  Example of dyeing B 250 parts of demineralized water are dissolved in a mixture of dyes consisting of 0.94 parts of the dye of Example 1, 0.22 parts of the dye of Example 2 and 0.84 parts After introducing 5 parts of woolen gabardine into this bath, the temperature is raised to 400 and 5 parts of calcined sodium sulfate, 2 parts of acetic acid and 1 part of a known unison agent. This dye bath is then boiled in the space of 90 minutes, and

  keep it at this temperature for 60 minutes.

  Every 15 minutes, the water that has evaporated during boiling is replaced. The fabric is then rinsed with hot water, then cold, and dried at about 700. The olive dye thus obtained has good fastness to light and good

  solidities in a general way.

Claims (15)

  1.- New monoazole compounds, characterized   risen in that they answer formula I (H03S) -   (I) R4 wherein m is 1 or 2, n is O or 1, Hal is a halogen atom, R1 is an alkyl group containing 1 to 4 carbon atoms, R2s R2 is a sulfo group, an alkylsulfonyl group; containing 1 to 4 carbon atoms or a residue -so- So2NR8R9 or -NHCOOR10, op means 0 or 1, R7 represents a hydrogen atom or an alkyl or alkoxy group each containing from 1 to 4 carbon atoms, R8 and R9, independently of one another, means a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms, a hydroxyalkyl group containing from 2 to 4 carbon atoms, the hydroxy residue of which is located in position y, e or a cyclohexyl group, or a phenyl group optionally bearing 1 or 2 substituents selected from   halogens, alkyl and alkoxy groups   1 to 4 carbon atoms, and the sulfo and carboxy groups, one of the symbols R8 or R9 to have a meaning different from the cyclohexyl group or an optionally substituted phenyl group, when   the other symbol R9 or R8 means a cyclo-   hexyl or an optionally substituted phenyl group, and R1o representing an alkyl group containing from 1 to 6 carbon atoms, the triazinyl group being capable of being attached to the 4 or 5 position, this group being however to be attached in position 4 when R2 signifies a residue -NHCOOR0lo R3 represents a hydrogen atom or an alkyl group s15 or alkoxy containing from 1 to 4 carbon atoms, R4 represents a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms, R5 represents an atom of hydrogen, an alkyl group containing from 1 to 4 carbon atoms, a cyclohexyl group optionally substituted by 1, 2 or 3 alkyl groups each containing from 1 to 4 carbon atoms, or a phenyl group optionally carrying 1 or 2 substituents chosen from halogen atoms and alkyl and alkoxy groups each containing from 1 to 4 carbon atoms, and R6 represents a hydrogen atom or a hydroxy group, R6 to be different from a hydroxy group when R2 rep denotes a residue -NHCOORlo0, with the provisos that: a) n is zero when R2 represents a NHCOORlo residue, b) the -NHR5 residue and the azo group are located at the adjacent positions 1 and 2 or 2 and 1 and 1 of the naphthalenic residue, and (c) R6 is different from a hydroxy group located in   position 8, where the sulfo group is set at a   other than the position 4 of the naphthalenic residue, when n is 1, m is 1 and the azo group is in position 1 of the naphthalenic residue, the molecule to contain at least two sulfo groups, and their mixtures, in the form of free acid or under form of a salt.   2. New monoazole compounds, characterized   rises in that they correspond to the formula I R N N Hal N-11 (')   in which m is 1 or 2, n is 1, Hal is a fluorine or chlorine atom, R 1 is an alkyl group containing 1 to 4 carbon atoms, R 2 is a sulfo, methylsulfonyl or ethylsulfonyl group or a residue, R or -SO 2 NR 3 R 3 is O or 1, R is a hydrogen atom or a methyl or methoxy group, R 'is a hydrogen atom or a methyl, ethyl or 2-or 3-hydroxyalkyl group, the remainder of which is alkyl contains 2 or 3 carbon atoms, and   R4 represents a methyl, ethyl, cyclo-   hexyl or 2- or 3-hydroxy-alkyl, the alkyl residue of which contains 2 or 3 carbon atoms, or a phenyl group optionally bearing 1 or 2 substituents chosen from chlorine and the methyl, ethyl, methoxy, ethoxy, sulpho and carboxy groups; wherein the triazinyl group may be attached at the 4 or 5 position to the azo group, R 3 is hydrogen, an alkyl or alkoxy group containing 1 to 4 carbon atoms, R 4 is a hydrogen atom or a alkyl group containing from 1 to 4 carbon atoms, R5 represents a hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms, a cyclohexyl group optionally substituted by 1, 2 or 3 alkyl groups each containing from 1 to 4 carbon atoms, or a phenyl group optionally bearing 1 or 2 substituents selected from halogens and alkyl and alkoxy groups each containing from 1 to 4 carbon atoms, and R6 represents a hydrogen atom or a hydroxy group, with the provisos that (a) the residue -NHR5 and the azo group are located at the adjacent positions 1 and 2 or 2 and 1 of the naphthalenic residue and b) R6 is different from a hydroxy group located in   position 8, where the sulfo group is set at a   other than the position 4 of the naphthalenic residue, when n is 1, m is 1 and the azo group is in position 1 of the naphthalenic residue,   the molecule containing 2 sulfo groups, -   and their mixtures, in the form of free acid or form of a salt.   3. New monoazole compounds, characterized   in that they correspond to the formula: ## STR1 ## wherein m is 1 or 2, R 1 is an alkyl group containing 1 to 4 carbon atoms, R'a means a sulfo group, methylsulfonyl or 2a ethylsulfonyl or a radical RR " 7   -SO or -SO2NRgR. (SO3H) p o p means O or 1, R represents a hydrogen atom or a methyl group,   R 'represents a methyl, ethyl or 2-hydroxy group   ethyl, and R9 has one of the meanings given for R "or represents a phenyl group optionally carrying one or two substituents selected from methyl and sulfo groups, R" signifies a hydrogen atom or a methyl or phenyl group, and R6 represents a hydrogen atom or a hydroxyl group, m having 1 when R 6 is hydroxy, the triazinyl group being attached at the 4 or 5 position with respect to the azo group,   the sulpho group to be located in a different position   at the position 4 of the naphthalenic residue when m is equal to 1, the molecule containing two sulpho groups, and their mixtures, in the form of free acid or in the form of of a salt.   4. Monoazole compounds of formula Ia according to claim 3, characterized in that R " means a hydrogen atom.   5. Novel monoazolph compounds, characterized in that they correspond to the formula Ib R2b U.1} R4 N4 OR1 (Ib) in which R4 signifies a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms Hal 'means a fluorine or chlorine atom, R1 represents an alkyl group containing from 1 to 4 carbon atoms, R2b represents an alkoxycarbonylamino group, the alkoxy residue of which contains 1 to 4 carbon atoms, and R3 represents an atom of hydrogen or a methyl or methoxy group, and mixtures thereof, in the form of free acid or under form of a salt.   6. Novel monoazo compound, characterized in that it corresponds to the formula OCH 3 O '' No o (m3 3 N 0> -NHQ so oc3   in the free acid state or in the form of a salt.   7.- New monoazofcompound, characterized   rised in that it meets the formula ci N sz - N OCR3 SO 3   in the free acid state or in the form of a salt.   8. Monoazo compounds according to one   any of claims 1 to 7, characterized in   what they are in the form of lithium salt, sodium or potassium.   3.- Mixtures of dyes, characterized   in that they contain at least one mono compound   azo as specified in any of the   Claims 1 to 8, and a compound of formula VII   Wherein R1 represents 1 to 4 carbon atoms, 10.Mixtures in that they contain a) the compound of formula Ic SO 3 > O> NH   c N OCH3 in the form of a salt, an alkyl group containing in the form of a salt. dyes, characterized KH2 0 N S   o> 503H (Ic) b) the compound of formula VIIa o0 Ci (VIIa) in the form of a salt, and / or c) the compound of formula Id Sc H), Nt OC "3 KH2 -Né so03H in the form of a salt.   A process for the preparation of the monoazo compounds of the formula I as claimed in claim 1, wherein n is 1, wherein the diazolc is copolymerized with one or more amines of the formula II. R "2   NH2 (II) in which R1 has one of the meanings given for R specified - 2   in claim 1, but R can not represent a remainder -NHCOOR10,   R 3 has the meaning given in claim 1, X is in the 4 or 5 position and means a nitro group or a residue -NR4Z1 where Z1 represents a protecting group or a residue of formula (a) or (b) (Id) Hal Hal $ 4 (a) X (b) Hal OR1 o Hal and R As defined in claim 1, with one or more compounds of formula III IR6 NHR5 (HO3S) (III)   wherein R5, R6 and m have the meanings given in claim 1, and when Z1 signifies a residue (a), the product is condensed with a compound of formula R1OH, when X is nitro, this group is reduced, or when Z1l represents a protecting group, this group is removed / then the residue -NH2 or -NHR4 is reacted either with a cyanuryl halide followed by a reaction with a compound of formula R1OH, or with a compound of formula (c) Hal N {o Hal (c) 30 OR1 in which Hal and R1 have the meanings data in claim 1.   12. A process for the preparation of the monoazo compounds of formula I specified in claim 1, wherein n is O, characterized in that one or more compounds of formula IV are reacted. NHCOOR10 N = N HR4 (IV) (HO3S) X2 (   In which R 3, R 4 and R 10 have the meanings given in claim 1, with a cyanuryl halide followed by a reaction with a compound of formula R 1 OH, or with a compound of formula (c) Hal liai <Q (c) Hal-oC) OR1 in which Hal and R1 have the given meanings in claim 1.   13.- The application of the specified compounds   to any one of claims 1 to 1Q as   dyes for dyeing or printing organic materials containing hydroxy groups or nitrogen atoms. 14.- The application of the specified compounds   in any one of claims 1 to 1, as   dyes for dyeing or printing leather or fibers, yarns or textiles made wholly or in part of natural or synthetic polyamides   or natural or regenerated cellulose.   15.- The application of the specified compounds   in any one of claims 1 to 10, as   dyes for dyeing or printing wool.   16. Organic materials containing hydroxy groups or nitrogen atoms, characterized in that they have been dyed or printed with the   compounds specified in any one of the claims 1 to 10.   17.- Fibers, yarns or textiles made wholly or in part of natural or synthetic polyamides or of natural or regenerated cellulose and leather, characterized in that they have been dyed or printed with the compounds specified in 'a   any of claims 1 to 10.   18.- Wool, characterized in that it has been dyed or printed with the specified compounds   in any one of claims 1 to 1.