FR2580289A1 - NOVEL MONOAZOIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS REACTIVE DYES - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS MONOAZOIC COMPOUNDS OF THE FORMULA: (CF DRAWING IN BOPI) IN WHICH P MEANS 1 OR 2, Q MEANS 0 OR 1 AND PQ MEANS 2 OR 3, R AND R REPRESENT VARIOUS RADICALS, W MEANS A BRIDGE , R MEANS A -OR, NH OR AMINOALIPHATIC, CYCLOALIPHATIC, AROMATIC OR HETEROCYCLIC GROUP AND R MEANS HYDROGEN OR AN ALKYL OR PHENYL GROUP. THESE COMPOUNDS MAY BE USED AS REACTIVE COLORS.

Description

The present invention relates to novel compounds

  monoazo compounds, their preparation and their use as reactive dyes. The invention relates to monoazo compounds of formula I F NN? I!

16

X y Ny N l

R2 RA

  (S03H) p (s03H) q wherein p is 1 or 2, q is 0 or 1, and the sum p + q = 2 or 3, R1 is hydrogen or C1-C4 alkyl, C1-C4 alkoxy or S03H, R2 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, -NHCO-C1-C4alkyl or NHCONH2, W is -N-B1-N-, R3 R3 B1 represents a divalent bridge or B1 forms, with the two -N (R3) - groups to which it is attached, a piperazine ring, or B1 forms, with one of the -N (R3) groups to which it is attached, a group (SO3H) n -N1 -C2-4alkyl- or -NN wherein n is 0 or 1, each R3 is independently hydrogen or an optionally substituted C1-C4 alkyl group;

  R4 represents a group -ORs, NH2, or an aliphatic amino group

  tick, cycloaliphatic, aromatic or heterocyclic, and

  R5 represents hydrogen, an optionally substituted C1-C6 alkyl group;

  or substituted phenyl, in the form of free acids or salts.

  The sulfo groups in the diazo-

  naphthalenic acid, preferably occupy the following positions:

  (a) the azo group is located in position 1 and the sum p + q = 2: the sulfo groups preferably occupy the positions 3,6 or 4,6; (b) the azo group is located at position 1 and the sum p + q = 3: the sulfo groups preferably occupy the positions

3, 6, 8;

  (c) the azo group is located in position 2 and the sum p + q = 2: the sulfo groups preferably occupy the positions 1,5, 1,6, 3,6, 4,8, 5, 7 or 6, 8; (ci) they occupy more particularly the positions 3,6, 4,8 or 6,8; (d) the azo group is located at position 2 and the sum p + q = 3: the sulfo groups preferably occupy positions 3,6,8

or 4,6,8.

  The diazotization component is preferably a 2-amino

  naphthalene and contains sulfo groups at

  preferred conditions under (c), more particularly under

(cl), and under (d).

  The sum p + q = 3 is particularly preferred.

  In the present application, the alkyl or alkylene groups are linear or branched unless otherwise indicated. In the hydroxyalkyl or hydroxyalkylene groups attached to a nitrogen atom, the hydroxy group is bonded to a carbon atom other than the Cl atom. When R 1 or R 2 is an alkyl or alkoxy group, the latter preferably contains 1 or 2 carbon atoms and

  especially means a methyl or methoxy group.

  - 3 - When R2 means a halogen, it is preferable

  chlorine or bromine, in particular chlorine. The group -NHCO-

  C1-C4 alkyl is especially an acetamido group.

  R1 preferably means R1a, ie hydrogen or a methyl, methoxy or -SO3H group. R1 means more particularly

  Rlb, i.e. hydrogen or a methoxy group. R1 represents

  especially, hydrogen.

  R2 preferably R2a, ie hydrogen, chlorine or methyl, methoxy, -NHCOCH3 or -NHCONH2. R2 is more particularly R2b, i.e., hydrogen or methyl, NHCOCH3 or -NHCONH2. R2 means more especially

  R2c, i.e., -NHCOCH3 or -NHCONH2.

  When R3 is an alkyl group, it is preferable

  C1-C2 alkyl group. Any substituted alkyl group is preferably a C 1 -C 3 alkyl group preferably substituted by

  hydroxy, chloro, cyano, SO 3 H, OSO 3 H or COOH, in particular

bind with a hydroxy group.

  R3 preferably means R3a, each R3a symbol means

  independently bearing hydrogen or methyl, ethyl, -CH 2 CH 2 OH, - (CH 2) 1-2 SO 3 H, - (CH 2) 1-20 SO 3 H or - (CH 2) 1-3 COOH. R3 is more particularly R3b, each R3b independently signifying hydrogen or a methyl, ethyl or -CH2CH20H group; R3 is especially R3c, each R3c independently signifying hydrogen or a methyl group or

  ethyl. R3 more specifically means hydrogen.

  The alkyl group represented by R 5 is preferably a C 1 -C 4 alkyl group, more preferably a C 1 -C 2 alkyl group. Any substituted alkyl group preferably contains up to four carbon atoms and is preferably monosubstituted by a

  hydroxy group, C1-C2 alkoxy or carboxy.

  R5 preferably means R5a, i.e. hydrogen, C1-C4alkyl, monosubstituted C1-C4alkyl

  hydroxy or C1-C2 alkoxy, or a carboxyl group

  C4-C4 alkyl. R5 more particularly means RSb, that is,

say a C1-C2 alkyl group.

  Any substituted amino group represented by R4 is substituted

  preferably killed by 1 or 2 groups selected from C1-C4alkyl, C5-C6cycloalkyl and phenyl, which groups are unsubstituted or substituted, or the amino group forms a

  optionally saturated 5- or 6-membered heterocycle, said hetero

  can contain up to two other heteroatoms such as N, O or S, and be unsubstituted or substituted. When the amino group is disubstituted, the two substituents may be the same or different. Any substituted alkyl group present in the amino group represented by R4 preferably means a C1-C4 alkyl group

  carrying one or two substituents (more particularly a substitute

  at least one selected from OH, C 1 -C 4 alkoxy, chloro, cyano, COOH, SO 3 H, OSO 3 H, C 2 -C 4 hydroxyalkoxy, phenyl, phenyl

  substituted, NH2, -NH-C1-C4alkyl and -N (C1-C4alkyl) 2.

  Any substituted phenyl group present in the amino group represented by R4 preferably has 1 to 3 substituents selected from halogens (more particularly chlorine) and

  C1-C4 alkyl, C1-C4 alkoxy, SO3H and COOH groups.

  Any substituted cycloalkyl group present in the group

  amino represented by R4 preferably means a cycloalkyl group

  hexyl containing up to three C 1 -C 4 alkyl groups.

  Any heterocyclic amino group represented by R4 signifies

  preferably a saturated 6-membered ring which may contain another oxygen or nitrogen atom. When this ring is substituted, it preferably contains up to three C 1 -C 4 alkyl groups,

  more particularly up to three methyl groups.

  R4 preferably means R4a, that is to say a group -OR5a or a group -NR6R7 in which R6 and R7, independently of each other, represent hydrogen, a C1-alkyl group; -C4, C1-C4 alkyl monosubstituted with OH, C1-C4 alkoxy, COOH, SO3H, C2-C4 hydroxyalkoxy, NH2, -NH-C1-C4alkyl or -N (C1-C4alkyl) 2, a cyclohexyl group optionally substituted with 1 to 3 methyl groups, or a phenyl or phenyl-C 1 -C 4 alkyl group;

  in which the phenyl ring bears optionally 1 or 2

  selected from halogen (preferably chlorine) and C1-C4alkyl, C1-C4alkoxy, SO3H and COOH, or R6

  and R7 together with the nitrogen atom to which they are attached form a hetero

  saturated or unsaturated 5- or 6-membered ring containing, for

  another oxygen or nitrogen atom and possibly

  substituted with 1 to 3 methyl groups.

  R4 more particularly means R4b, i.e.

  group -OR5b or a group -NR6aR7a in which R6a and R7a, independently

  in each case signify hydrogen, a C 1 -C 2 alkyl group, a C 1 -C 3 alkyl group monosubstituted with OH, COOH, SO 3 H, C 2 -C 4 hydroxyalkoxy or -N (C 1 -C 2 alkyl) 2, or a phenyl or phenyl-C 1 -C 2 alkyl group in which the phenyl ring optionally carries 1 or 2 substituents selected from chlorine and methyl, methoxy, SO 3 H and COOH or R 6a and R 7a together with the atom of nitrogen to which they are linked, a cycle

  piperidine, morpholine, piperazine or N-methylpiperazine.

  R4 is especially R4c, i.e. -NR6bR7b wherein R6b and R7b, independently of each other, signify hydrogen or a monosubstituted C2-C3 alkyl group;

  by a hydroxy or 2-hydroxyethoxy group. R4 means everything special

  R4d, i.e., -NR6cR7c wherein R6c and R7c, independently of each other, signify hydrogen or a 2-hydroxyethyl group. - 6 -

  Any bivalent bridge represented by B1 preferably means

  a C2-C6 alkylene chain optionally interrupted by 1 or 2 heteroatoms and / or optionally substituted with 1 or 2 hydroxy groups, a phenylene group or two phenylene groups which are linked together by a divalent bridge such as a -0 bridge; -, -NH-, -N = N-, alkylene, hydroxyalkylene or triazinylamino, which phenylene groups are unsubstituted or each of them bears, independently of one another, one or two substituents chosen from halogens and C1-C4alkyl, C1-C4alkoxy, SO3H and COOH; the phenylene groups are preferably linked

in position 1,3 or 1,4.

  B1 preferably means B1a, that is to say a C2-C6 alkylene group optionally interrupted by -O- or -N (R3) - and optionally monosubstituted with a hydroxy group, a C3-C6 alkylene group substituted with one or two hydroxy groups, a phenylene group optionally monosubstituted with a group SO 3 H or COOH, or a group Al'Q COOH, or a group v 4 b - in which the phenyl rings, independently of one another, are optionally monosubstituted by S03H or COOH, Q being attached at the 3- or 4-position, and 3 'or 4' respectively, and Q being -NH-, -O-, -N = N-, C2-C4 alkylene, C3-C4 hydroxyalkylene or a

-N 'N N-

group I Y R3b, N R3b R4x

  wherein R4x means chlorine or R4c.

  B1 is more particularly Bib, that is to say a C2-C3 alkylene group, C2-C3 alkylene-C2-C3 alkylene, C3-C4 alkylene monosubstituted with a hydroxyl group, a group 1, 3- or 1,4-phenylene optionally monosubstituted with a group SO 3 H, or a group 4 Qa 4'34 in which Qa is attached in position 3 or 4 and 3 'or 4' respectively, and signifies an oxygen atom or - 7 a C2-C3 alkylene group or a residue -NN, N R3 'R3c Cl B1 means more especially Blc, that is to say a C2-C3 alkylene, 2-hydroxypropylene or 1,3- or 1-alkylene group; , 4-phenylene. B1 means especially Bld, that is to say a group

  C2-C3 alkylene or 2-hydroxypropylene.

  W preferably means W1, that is a group

H N--

  N-Bi-N-N-N, N-C 2 -3alkylene-N- OR N R 3b R 3b

(S03IH)

  in which m = 0 or 1. W is more particularly W2,

  that is, a group -'- Blb-N-N-M N-CH2CH2N-

  RR3c 3c or \ - / R3c W means more especially W3, that is to say a group

-i-Bcl-g-

I I

  R3c R3c W is especially W4, i.e., -NH-BldNH-. The preferred compounds are those corresponding to formula Ia

F

  In which the sulfo groups of the naphthalenic residue occupy the positions indicated previously under (c1) or (d),

  in the form of free acids or salts.

  The more particularly preferred compounds are those corresponding to Formula Ia wherein (1) R1b is hydrogen and R2b is R2c, (2) R3c is hydrogen, (3) R4b is R4c, (4) R4b R4d means (5) the compounds of formula Ia in which the sum p + q = 3 and

  the three sulpho groups occupy the positions indicated

  previously under (d), (6) those of (1) to (5), wherein W2 is W3,

  (7) those of (6), wherein W3 is W4.

  When a compound of formula I is in salt form, the cation of the sulfo group and any carboxy group is not critical and may be any of the non-chromophore cations usually present in the reactive dyes, provided that the corresponding salts as obtained are water-soluble. Examples of such cations include alkali metal cations and the optionally substituted ammonium cation, such as lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-,

di- and tri-ethanolammonium.

  The preferred cations are the alkali metal cations and the ammonium cation, the sodium cation being especially preferred. In a compound of formula I, the cations of the sulfo and carboxy groups may be the same or different; in the latter case, the compound of formula I may comprise, for example, a mixture of the cations mentioned above, the compound of formula I

  then presenting as a mixed salt.

- 9 -

  The subject of the invention is also a method for preparing

  of the compounds of formula I, wherein a compound of formula II is reacted

R1

"J / N N-, W - H

Xc5rc R3 y

R2 R

(S03H) p (S03H) q 4

  in which R1, R2, R3, R4, W, p and q have the meanings

  previously, in the form of free acid or in the form of salt,

  with 5-chloro-2,4,6-trifluoropyrimidine.

  The process can be carried out according to the conventional methods

  Siques. The compounds of formula I can then be isolated according to known methods, for example by salting out with a salt.

  alkali metal, filtration and vacuum drying.

  Depending on the reaction and isolation conditions,

  holds a compound of formula I in the form of a free acid or

  preferably in the form of a salt, or even a mixed salt containing, for example, one or more of the cations mentioned above. The free acid can be converted according to the usual methods into salt or mixed salt, or vice versa, or a salt into another salt. The starting compounds of formula II may be prepared by reacting a compound of formula III

R1

N a N N NH "

X R2 III

(S03H) p (S03H) q

- 10-2580289

  in which R 1, R 2, R 3, p and q have the previously given meanings, in free acid or salt form, with cyanuric chloride in a molar ratio of 1: 1, then replacing one of the chlorine atoms by the group R4 and reacting the product obtained with a diamine of formula HWH. The different reactions can be performed according to

known methods.

  The compounds of formula III and the diamines of formula H-W-H are known, or can be prepared according to the methods

known.

  The compounds of formula I and the mixtures of these compounds can be used as reactive dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen. The preferred substrates are leather and fibers containing or consisting of natural or synthetic polyamides and, in particular, natural or regenerated cellulose such as cotton, viscose and fibran. Especially preferred substrates are

  textile materials containing or consisting of cotton.

  Dyeing or printing is done according to the

  known methods usually used for dyeing or

  pressure with reactive dyes. Dyeing is preferably carried out at a temperature between 30 and 600C. In addition, the compounds of formula I are particularly suitable for African printing, carried out on cotton dyed beforehand with

naphthol AS dyes.

  The compounds of the invention can easily be combined with

  born with other reactive dyes; they can be applied alone or in combination with appropriate reactive dyes of

  the same category and having similar dyeing properties

  particular, with regard to the general solidities, the

  see climbing on fiber, etc. The dyes obtained with such mixtures have good fastnesses and are comparable to

  those obtained with a single dye.

25802Z89

- 11 -

  Because of their remarkable climbing power,

  Formulations of formula I give high exhaustion and fixation rates. The unbound dye can be easily removed from the substrate by washing. The dyes and prints obtained, in particular the prints obtained in combination with

  naphthol AS, have special light fastnesses.

  and good wet strength, including washing, water, seawater and perspiration. They

  are stable to oxidation, for example with chlorinated water, with

  chiment with hypochlorites and washing liquors containing

peroxides or perborate.

  The following examples illustrate the present invention without in any way limiting its scope. In these examples, all parts and percentages are by weight or volume, and

  temperatures are given in degrees Celsius.

Example 1

  19.15 parts of 2-aminonaphthalene-3,6,8

  trisulfonic acid in 110 parts of water and dissolved by addition of 6 parts of a 30% sodium hydroxide solution. 18.5 parts of 30% hydrochloric acid are then added. After addition of

  parts of ice, it is diazotized for 45 minutes at a

  between 0 and 5 'by adding a solution of 3.5 parts of sodium nitrite in 10 parts of water and stirred for a further 45 minutes. A solution of 8.3 parts of aminophenylurea in 75 parts of water is then poured into the solution of the diazo. The pH value of the reaction mixture is adjusted to 4.5

  by adding 9 parts of sodium bicarbonate and

  holds for 4.5 minutes for 30 minutes while continuing to add bicarbonate

  sodium bonate until copulation is complete. We

  releasing the monoazoamino compound thus obtained using 90 parts

  of sodium chloride, is isolated by filtration and

shche at 800 under vacuum.

- 12-258289

  32.7 parts of the monoazoamino compound thus obtained are dissolved in 600 parts of water at 20 ° at a pH of 6.0. This solution is poured into a suspension consisting of 12.7 parts of cyanuric chloride and 350 parts of ice water. The pH of the mixture is maintained between 6.0 and 6.5 by adding 22 parts of a 20% sodium bicarbonate solution. Once the condensation is complete,

  the reaction temperature between 0 and 5- is allowed to

  worm at room temperature. We simultaneously increase the value

  from pH to 12.0 by the addition of an aqueous solution of ammonium hydroxide

  monium at 12.5%. After 30 minutes, the reaction mixture is heated to 40 °, the pH is allowed to drop to 9.0 and maintained at this value for three hours by addition of 12.5% aqueous ammonium hydroxide solution. , until the condensation reaction is complete. We use a total of 50 parts of

  aqueous solution of ammonium hydroxide 12.5%.

  The pH of the reaction mixture thus obtained is adjusted to 5.8 by addition of 50 parts of 10% hydrochloric acid. A solution consisting of 9.2 parts of 1,2-propylenediamine, 80 parts of water and 12 parts of 10% hydrochloric acid and having a pH value of 6.2 is then added to this mixture. The mixture is heated to 86 ° within one hour and maintained at this temperature for five hours. The pH value is maintained simultaneously between 5.8 and 6.1 by adding 40 parts of a 20% sodium carbonate solution. For the isolation of the product, the pH value of the solution is adjusted to 3.2 by the addition of 20 parts of 10% hydrochloric acid. The product is salted out using sodium chloride and filtered. The compound corresponding to the formula is obtained

S032

j JoiçYCH3

SG3H SO3HNH'Ohm.

Igl

- 13 - 2580289

- 13 -

  21 parts of this compound are dissolved in 450 parts

  of water. At a pH between 6.5 and 7.0 and at room temperature

  additionally, 8 parts of 5-chloro-2,4,6-

  trifluoro-pyrimidine. During the condensation, the pH value is maintained between 6.5 and 7.0 by addition of 44 parts of a

  sodium carbonate solution 20%. After 6 to 7 hours, the reaction

  condensation is complete. The final product is salted with 50 parts of sodium chloride, isolated by filtration and dried at 50 under vacuum. The compound thus obtained corresponds to the formula NH 2

N to H 3 NH9N H

  S03 3 NCO2 CH3 Cl F and dyes the cotton in a golden yellow shade. The dyes and prints on cotton obtained by the usual methods, and in particular the prints obtained in combination with the naphthol dyes AS, have good fastness to light.

  and wet and resist oxidation.

  Examples 2 to 62 By proceeding in a manner analogous to that described in Example 1 and using suitable starting materials, other compounds of formula I listed in the table below can be prepared. These compounds correspond to the formula

R R

  1 3 13, gN 'D-N to N NH if> N-N (A) R2 Cl F

2 R4

- 14 - 2580289

  in which the symbols are as defined in the table below. The different groups D used in this table have the following definitions: D1 = 3,6,8-trisulfo-2-naphthyl D2 = 4,6,8-trisulfo-2-naphthyl D3 = 3,6,8-trisulfo-1 D4 = 4,8-disulfo-2-naphthyl d5 = 6,8disulfo-2-naphthyl D6 = 3,6-disulfo-2-naphthyl D7 = 1,5-disulfo-2-naphthyl D8 = 3,6-disulfo 1-naphthyl

D = 4,6-disulfo-1-naphthyl.

  Any carbon atom marked with an asterisk in the definition

  B1 bridge is attached to the group -N (R3) - linked to the

Picnic.

  The compounds of Examples 2 to 62 may be applied to cellulosic fibers, in particular to cotton, according to

  usual methods of dyeing or printing by exhaustion.

  The dyes and prints obtained are of a yellow to golden yellow shade. Dyes and prints on cotton, and in

  particularly the impressions obtained in combination with the colors

  naphthol AS, have good fastness to light and

  wet and are stable to oxidation.

  On cotton, a yellow dye is obtained with the dyes of Examples 2-5; 15-18; 22, 26, 27, 30-32; 36, 37, 40-42; 47-49; 52-54, 57-59 and 62 and a yellow-gold dye with the dyes of the examples

  6-14; 19-21; 23-25; 28, 29, 33-35, 38, 39, 43-46; 50, 51, 55, 56,

and 61.

- 15 - 2580289

- 15 -

Board

Ex.No. | R1 R2 R3 R4 B1

2 1 NHCOCH3 H -NH2 * CH2CH-

CH3

3 D1 H do. H do. -CH2CHCI -

OH

4 D1 H do. H -NHCH2CH20H do.

D1 H do. H do. -CH2CH- CH3

6 D1 H NHCONH2 H do. CH2CH (OH) CH2-

7 l H do. H do. * CH2CH-

CH3

8 D1 H do. H -NH2 -CH2CHCH2-

OH

9 D1 H do. H -N (CH 2 CH 2 OH) 2 -CH 2 CH 2

D1 H do. H -NHCH2CH2OCH2CH2O do.

he D2 H do. H -NH2 -CH2CH-

CH3

12 D2 H do. H do. -CH2CHCH2-

OH

13 D2 H do. H -NHCH2CH20H do.

14 02 H do. H do. * CH2CH-

CH3

02 H NHCOCH3 H do. do.

16 D2 H do. H do. CH2CH (OH) CH2-

17 02 H do. H -NH2 do.

18 02 H do. CH3 do. do.

19 D1 H NHCONH2 H do .. I

D2 H do. H do. do.

21 02 H do. H do.

D 2 H NHCOCH 3 H -NHCH 2 COOH

23 D1 OCH3 CH3 H -NH2 CH2CH (OH) CH2-

- 16-2580289

  Table (continued) Ex.No. O R1 R2 R3 R4 81 24 D1 OCH3 CH3 H -NH2 C2CH CH3

  01 do. do. H -NHCH2CH20H -CH2CH (OH) CH2-

26 D3 CH3 do. H -NHCH3 CH2CH-

CH3

27 03 OCH3 H H -NH2 CH2CH2

28 D4 do. CH3 H do. ICH2CH-

CH3

* 29 04 do. do. H -NHCH2CH2SO3H do.

04 H NHCOCH 3 H -NICH 2 CH 2 SO 3 31

CH3

31 D4 H do. H do.

  32 04 H -do. ## STR5 ## -H2CH 34 D5 do. do. 1H do. -CH2HCH2 OH

H NHCONH2 H do. do.

36 D5HHH -N (CH2CH20H) 2 -CH2CH2-

37 H H C2H5 do. do.

38 Ds OCH3 CH3 H -NH2 lCH2CH-

CH3

39 D6 do. do. H do. do.

D6 H do. H do. -CH2CH20CH2CH2-

41 06 S03H NHCOCH3 H do. -CH2CH2-

42 D6 H H CH3 do. H H cl

- 17 -

  Table (continued) Ex.No. D R1 R2 R3 R4 B

43 D6 OCH3 CH3H -NH2 -CH2CH (OH) CH2

-C2H OH) CH2-

44 D6 do. do. H -NHCH2CH20H -CH2CH-

CH3

06 H NHCONH2 H -NH -CH2CH2-

SO 3H 46 D7 H do. H -OC2H5 S3H

COOH S43_

47 07 H NHCOCH3H -NH SO3H CH2CH-

-NH 'SO3H * CH2iCH-

CH3

## STR5 ##

49 08 H NHCOCH3 H -N (CH2CH2OH) 2

D8 H NHCONH2 H do. -CH2CH20CH2CH2-

51 Dg H do. CH3 -NH2 -CH2CH (OH) CH2-

52 9DgH NHCOCH3H-OH do.

  53 D1 HH C2H5 -NH (CH2) 3N (CH3) 2 -CH2CH-

CH3

  ## STR2 ##

01 H NHCONH2H -NH2 - N = N

  56 2 H do. H -NHCH2CH20CH2CH20OH -CH2CH2-

57 D2H NHCOCH3H -NH2

58 D05 S03H do. H -NHCH3 SO H

59 D6 H do. H -NHCH2CH2SO3H do.

02 OCH3 CH3H -NH12 -CH2CH (OH) CH2-

61 02 do. do. H -NHCH2CH20H -CH2CH-

CH3

62 Dl do. H -NHCH2CH2COOH

- 18 -

Examples 63-65

  By proceeding in a manner analogous to that described in Example 1 and using suitable starting materials, other compounds of formula I corresponding to formula F can be prepared.

S03H N -

-M = (B

e <N y N ClS F

S03H S03H R2 NH

NH2 in which for example 63

  R2 represents a group -NHCONH2; W represents a group -N N-

  Cotton shade: golden yellow for Example 64 R2 represents a group -NHCONH2; W represents a group

-N N-CH2CH2NH-

  Grade on cotton: x_ / golden yellow for example 65 R2 represents a group -NHCOCH3; W represents a group

-N N-CH2CH2NH-

  Nuance on cotton: yellow (the nitrogen atom marked with an asterisk is fixed on the triazine cycle).

- 19-2580289

  According to the process described, the dyestuffs of Examples 1 to 65 are obtained in the form of sodium salt. These dyes can also, depending on the reaction / isolation conditions or by reaction of the sodium salts according to the known methods, be obtained in the form of free acid or in the form of other salts, for example salts containing one or many of the cations indicated in

the description. -

  Application Example A (dyeing by exhaustion) 0.3 part of the dye of Example 1 or 44 was dissolved in 300 parts of demineralised water and 15 parts of

  calcined sodium. The dye bath is heated to 40 and introduced

  10 parts of a bleached cotton cloth. After 30 minutes, 0.2, 0.6, 1.2 and finally 4.0 parts of calcined sodium carbonate are added successively every 10 minutes. During the addition of the sodium carbonate, the temperature is maintained at 40. After continuing the dyeing for another hour at, the fabric is rinsed with cold running water for 3 minutes, then with hot running water for 3 minutes. minutes. The dyed fabric is soaped on boiling for 15 minutes in 500 parts of demineralised water and 0.25 parts of sodium lauryl sulfonate. Afterwords

  rinsing with hot running water for 3 minutes and centrifugation

  The fabric is dried in a dryer at about 70 ° C. We obtain

  thus a fabric dyed in a golden yellow shade (for each color)

  rant) with good fastness to light and wet

resistant to oxidation.

  Application example B (printing) A printing paste having the following composition: parts of the dye of Example 1, 6 or 7 parts of urea 340 parts of water 500 parts of a thickener at 4% of sodium alginate and parts of sodium carbonate 1000 parts is applied to a cotton fabric according to the printing methods

classics.

- 20 -

  The printed fabric is dried and the printing is fixed with steam for 1 minute. The fabric is then rinsed with hot water, soaped to boiling according to the method described in Application Example A and dried. With each of the dyes used, we get a golden yellow impression with good

  general fastness and stable to oxidation.

  Application example C (naphthol dye printing AS) A printing paste prepared in accordance with application example B is applied according to conventional printing methods to cotton (leached) cretonne which has been dyed prior to application. printing with a naphthol dye AS. We get prints on cotton

  having remarkably good light fastnesses.

  Similarly, the dyes of the other examples or mixtures of the dyes of Examples 1 to 65 can be used to dye or print the cotton according to the method described in Application Examples A to C.

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Claims (10)

  1. Monoazo compounds of formula I R F   N = N R 3 N Cl FR 4 (SO 3 H) p (SO 3 H) q 4 wherein p is 1 or 2, q is O or 1, and the sum p + q = 2 or 3, R 1 is hydrogen or a group C1-C4alkyl, C1-C4alkoxy or SO3H, R2 is hydrogen, halogen or C1-C4alkyl, C1-C4alkoxy, NHCO-C1-C4alkyl or -NHCONH2, W represents a group -N-B1-N-, R3 R3   81 represents a divalent bridge or B1 forms, with the two -N (R3) groups to which it is attached, a piperazine ring, or else Bi form, with one of the -N (R3) - groups to which it is bound, a (S-H) -N5w -C24alkylene- or -NN group wherein n is O or 1, each R3 is independently hydrogen or an optionally substituted C1-C4 alkyl group; - 22-2580289   R4 represents a group -ORs, NH2, or an aliphatic amino group   tick, cycloaliphatic, aromatic or heterocyclic, and   R5 represents hydrogen, an optionally substituted C1-C6 alkyl group;   or substituted phenyl, in the form of free acids or salts. 2. A monoazo compound according to claim 1, characterized in that R4 represents a group -ORsb or a group -NR6aR7a in which RSb represents a C1-C2 alkyl group and R6a and R7a, independently of one another , signifies hydrogen, a C1-C2 alkyl group, a C1-C3 alkyl group monosubstituted with OH, COOH, SO3H, C2-C4 hydroxyalkoxy or -N (C1-C2alkyl) 2, or a phenyl group or phenyl-C 1 -C 2 -alkyl wherein the phenyl ring optionally carries one or two substituents selected from chlorine and methyl, methoxy, SO 3 H and COOH, or R 6a and R 7a together with the nitrogen atom to which they are linked,   a piperidine, morpholine, piperazine or N-methylpiperazine ring.   3. A monoazo compound according to claim 1 or 2, characterized in that W means a group H   R3b 3b -N N-, -N N-C2-3alkylene-1- or -NJN R3b R3b (SO3H), wherein m = O or 1, Bla means a C2-C6 alkylene group optionally interrupted by -O- or -N and optionally monosubstituted with a hydroxy group, a C3- alkylene group substituted with one or two hydroxyl groups, a phenylene group optionally monosubstituted with a SO3H or COOH group, or a 3-4 N- group. -NyN4 - 23-2580289   wherein the phenyl rings, independently of one another, are optionally monosubstituted by a group SO 3 H or COOH, wherein Q is attached at the 3- or 4-position and 3 'or 4' respectively, and Q is -NH, - 0-, -N = N-, C2-C4 alkylene, C3-C4 hydroxyalkylene or a residue --N N-Y N-   R3b R4x wherein R4x means chlorine or -NR6bR7b wherein R6b and R7b, independently of each other, signify hydrogen or C2-C3 alkyl monosubstituted with hydroxy or 2-hydroxyethoxy, and each R3b symbol independently means hydrogen or a   methyl, ethyl or -CH 2 CH 2 OH.   4. A monoazo compound according to claim 1, characterized in that it corresponds to the formula Ia R F   Wherein the sulfo groups of the naphthalenic residue occupy the positions 3,6, 4,8 or 6,8 when the RZb 3cCl F (SO 3 H) p (SO 3 H) q R 4b p + q = 2, and the positions 3,6,8 or 4,6,8 when p + q = 3, Rlb represents hydrogen or a methoxy group, R2b represents hydrogen or a methyl group, -NHCOCH3 or -NHCONH2, - 24-258289   R4b represents a group -OR5b or a group -NR6aR7a in which   R5b represents a C1-C2 alkyl group and R6a and R7a, inde-   pendently of each other, signify hydrogen, a C 1 -C 2 alkyl group, a C 1 -C 3 alkyl group monosubstituted by OH, COOH, SO 3 H, C 2 -C 4 hydroxyalkoxy or -N (C 1 -C 4) alkyl. -C 2) 2, or phenyl or phenyl-C 1 -C 2 -alkyl wherein the phenyl ring optionally carries one or two substituents selected from chlorine and methyl, methoxy, SO 3 H and COOH, or R 6a and R 7a form, with the nitrogen atom to which they are attached, a piperidine ring,   morpholine, piperazine or N-methylpiperazine.   W2 is N-Blb-N-, O or -N-CH2CH2N-   R3c R3c R3c each R3C independently signifies hydrogen or a methyl or ethyl group, and   Bib represents a C 2 -C 3 alkylene group, C 2 -C 3 alkylene group;   C2-C3 alkylene, C3-C4 alkylene monosubstituted with   hydroxy group, a 1,3- or 1,4-phenylene group   monosubstituted by a group S03H, or a group 3 '   where Qa is set at position 3 or 4 and 3 'or 4' respec-   and signifies an oxygen atom, a C2-C3 alkylene group or a N-N residue. R   2R3. R3c Cl 5.- A monoazo compound according to claim 4, characterized in that Rlb represents hydrogen and R2b means a group -NHCOCH3 or -NHCONH2. - 25 - 2580289 - 25 -   6. A monoazo compound according to claim 4 or 5, characterized in that R4b means a group -NR6cR7c wherein R6c and R7c, independently of each other, signify hydrogen or a 2-hydroxyethyl group.   7. A compound according to any one of claims 4   at 6, characterized in that W2 signifies a group -NH-Bld-NH- o   Bld represents a C 2 -C 3 alkylene or 2-hydroxypropylene group.   8. A process for the preparation of the monoazo compounds of formula I as defined in claim 1, characterized in that a compound of formula II R is reacted; R2 R2 / (S03H) p (S03H) q 4   in which R1, R2, R3, R4, W, p and q have the meanings   in claim 1, in free acid form or in the form of   of salt, with 5-chloro-2,4,6-trifluoropyrimidine.   9.- The use of the monoazo compounds specified in   any of claims 1 to 7 and mixtures thereof.   compounds, as reactive dyes for dyeing or printing   substrates containing hydroxy groups or nitrogen.   10.- The use of the monoazo compounds specified in   any of claims 1 to 7 and mixtures thereof.   compounds, as reactive dyes for dyeing or printing cotton.   11. Substrates containing hydroxy groups or nitrogen, characterized in that they have been dyed or printed using a monoazo compound as specified in any one of the following:   Claims 1 to 7, or a mixture of these compounds.   12. Cotton, characterized in that it has been dyed or im-   Awarded using a monoazo compound as specified in one of the   any of claims 1 to 7, or a mixture of these compounds.