FR2532943A1 - NOVEL MONOAZOIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS COLORANTS - Google Patents

Abstract

THE INVENTION CONCERNS THE COMPOUNDS OF FORMULA I: (CF DRAWING IN BOPI) IN WHICH REPRESENTS HYDROGEN OR A HYDROXYALKYL GROUP IN CC, R REPRESENTS A HYDROXYALKYL GROUP IN CC, OR WELL R REPRESENTS HYDROGEN-2, OR A GROUP HYDROXYALKYL 2 AND R REPRESENTS A -CHCHOCHCHOH GROUP, AND MIXTURES OF SUCH COMPOUNDS, IN THE FORM OF FREE ACID OR SALT. THESE COMPOUNDS MAY BE USED FOR DYING OR PRINTING ORGANIC SUBSTRATES CONTAINING HYDROXY GROUPS OR NITROGEN ATOMS.

Description

The subject of the present invention is monoazo chloro

triazinyl, their preparation and

  their use as reactive dyes.

  The invention relates more particularly to compounds which, in free acid form, correspond to formula I, SO 3 I OCH 3 Cil

00 N = N NN I

NH- = KON

SOH CH 3 NRR 2

  in which R 1 represents hydrogen or a C 2 -C 3 hydroxyalkyl group, R 2 represents a C 2 -C 3 hydroxyalkyl group, or R 1 represents hydrogen or a 2-cyanoethyl group and R 2 represents a group -CH 2 CH 20 CH 2 CH 20 H,

  and mixtures of these compounds as free acid or salt.

  In the hydroxyalkyl groups, the hydroxy group is attached to a carbon atom

other than the carbon atom Cl.

  The preferred compounds of formula I are those in which any hydroxyalkyl group represented by R 1 and / or R 2 is a 2-hydroxyethyl group. The compounds of formula I which are more particularly preferred are those in which

  which R 1 represents hydrogen or a 2-hydroxy group

  Ethyl and R 2 is 2-hydroxyethyl The most preferred compound is that wherein R 1 is hydrogen and R 2 is 2-hydroxyethyl. The preferred mixtures of compounds of formula I are those in which, in a compound A, R 1 represents hydrogen and R 2 represents a 2-hydroxyethyl group, and in a compound B, R 1 and R 2 each represent a 2-hydroxyethyl group. Preferably, these mixtures contain compounds A and B in a molar ratio between 90:10 and 10:90, more preferably between

: 25 and 25:75.

  When the compounds of formula I are in the salt form, the cations of the sulfo group may be any non-chromophoric cations common in the chemistry of reactive dyes. Suitable examples of cations include alkali metal cations and unsubstituted ammonium ions. or substituted, such as

  lithium, sodium, potassium, ammonium, mono-, di-, tri-

  and tetramethylammonium, triethylammonium and mono-, di-

and triethanolammonium.

  Preferred cations are metal cations

  alkaline and ammonium, sodium being particularly

highly preferred.

  The present invention also relates to a process for the preparation of the compounds of formula I, comprising the reaction of the following compounds: the diazolc of an amine of formula II 503 H

NH 2

  503 H the coupling component of formula III

OCH 3

H NH 2 III

  CH 3 cyanuric chloride and a compound of formula IV

HNR 1 R 2 IV

  or a mixture of compounds of formula IV, these compounds to be present in a corresponding stoichiometric molar ratio to obtain a compound of formula I by copulation and condensation in any desired order. More particularly, it is preferred to prepare the

  compounds of formula I by condensation of a compound of.

Formula V, So 3H OCH 3 Ci N-K

Q N = N Q NH '= <GN V

O

  In the form of free acid or salt, with a compound of formula IV

HNR 1 R 2 IV

  or a mixture of compounds of formula IV.

  Diazotisation and copulation can be carried out according to the usual methods Substitution of the chlorine atoms in cyanuric chloride by successive condensations can be carried out

  according to the usual methods, for example the sub-

  stitution of the first chlorine atom can be carried out at a temperature between 0 C and 100 C, preferably between 00 C and 50 C Substitution-of the second chlorine atom can be carried out at a temperature between

C and 550 C in alkaline medium.

  The compounds of formula I can be isolated according to known methods, for example by salting out with an alkali metal salt, by filtration and drying.

  Under vacuum conditions of reaction and isolation

  Alternatively, a compound of formula I can be obtained in free acid form or preferably in salt form or even as mixed salts containing, for example, one or more of the above-mentioned cations. free acid into a salt or mixed salts or vice versa, or a salt into another

  salt according to the usual methods.

  The starting materials of formulas II, III and IV are either known or can be prepared according to known methods from

  starting products available.

  The compounds of formula I and mixtures thereof, preferably in the form of salts, are suitable as reactive dyes for dyeing and printing organic substrates containing hydroxy groups or nitrogen atoms. Preferred substrates are leather and textiles Constituted, in whole or in part, of natural or synthetic polyamides such as wool, silk and nylon, or of natural or regenerated cellulose such as cotton, viscose and fibranne The particularly preferred substrate is the textile material

  made in whole or in part of cotton.

  The dyeing or printing is carried out according to the known methods. Whereas the compounds of formula I have a good climbing power, they are suitable for

  all the usual dyeing processes using the

  sold by exhaustion They can be applied according to

  the usual methods, alone or in combination with other

  suitable reactive reagents with similar dyeing properties

  The compounds of formula I are well combinable and can therefore be used as a constituent of trichromic mixtures of great interest. The dyes obtained with such combinations have good fastnesses and do not exhibit

catalytic turn.

  Whereas the reactivity of the compounds of formula I with respect to the substrate does not depend on the temperature at the dyeing temperatures used, the dyeing can be carried out both at 1000 ° C. and without causing a loss of the dye yield, which can even be increased to 1000 C in some cases The dyes of the present invention are of course resistant to hydrolysis at high temperatures and if the dyeing temperature is exceeded, it will not

  not critical for the performance of the dyer.

  The dyeing temperature may advantageously be about 100 ° C, since dyes migrate better at elevated temperatures, thereby producing dyes.

more united.

  In addition, the compounds of the present invention are particularly well soluble in water, even in dye baths containing electrolytes. The dyes obtained with the compounds of formula I have good fastness to light and wet,

  for example, washing, water and

  In addition, they exhibit good fastness to chlorinated water, and are stable to washing baths containing

peroxide and perborate.

  The examples which follow illustrate the invention without, however, limiting its scope; in these examples, the indications of parts and percentages are by weight or by volume and the temperatures are indicated

in degrees Celsius.

Example 1

  75.8 parts of 2-aminonaphthalene-4,8-disulphonic acid are dissolved according to the known methods. To the resulting diazotized suspension is added dropwise.

  drop a solution of 34.3 parts of 2-amino-1-methoxy-

  4-methylbenzene in a mixture of water and chlorinated

  After 4 hours, the resulting monazo dye was isolated by heating the reaction mixture to 600 and adding water. hydrochloric acid to pH 1 The precipitated dye is filtered and washed with a solution containing a

  mixture of water, sodium chloride and chlorinated

30% water.

  The product thus obtained is stirred in 1000 parts of water and completely dissolved by adding about 25 parts of a 30% solution of sodium hydroxide to give a solution of this solution. By adding 500 parts of ice, the temperature is lowered to -1 and then 46 parts of cyanuric chloride are added. The condensation starts at about 70 and the reaction is completed within about 2 hours, the temperature reaching

300 during the last hour.

  For the following condensation step, 19.8 parts of monoethanolamine diluted in 5-0 parts of water are added to the reaction mixture over 5 minutes, the pH increasing to 11.2. After stirring the mixture for a further 20 minutes, the pH falls back to 7 and stirring is continued for a further 3 hours. Next, 2 parts of monoethanolamine diluted in water are added. water and the mixture is stirred until it reaches

  a p H-of about 8.8 which remains unchanged.

  The product is isolated by portionwise addition of 300 parts of sodium chloride, filtered and dried in vacuo. The resulting dye, which is in free acid form, corresponds to the formula SO 3 H OCH 3 ci

Q Q N = N) NH O <N

CH 3 NHCH 2 CH 2 OH

  503 H it is highly soluble in water and dyes cotton in

  yellow shades Dyes have good

  in the light and the wet.

  The following table shows other compounds of formula I which can be obtained in a manner analogous to that described in Example I, but using instead of monoethanolamine the corresponding amount of other mono or disubstituted amines or a mixture of such amines These dyes or dye mixtures

  also dye cotton in yellow shades.

  (see table on the next page) Example N 'R 1 R 2

2 -CH 2 CH 2 OH -CH 2 CH 2 OH

  3 -CH 2 CH 2 CN -CH 2 CH 2 OCH 2 CH 2 OH

4 H do.

  ## STR2 ## 25% by weight The preparation of a dye mixture containing different -NR 1 R 2 groups, for example the mixture of the example 5, can be performed by reacting in stages

  first of all with 3/4 mole equivalent of mono-

  ethanolamine and then with 1/4 mole of diethanolamine equivalent but using a 30% excess of the latter compound This condensation is carried out at 400

and at pH 7 for 10 hours.

  Depending on the conditions of reaction and

  As described above, the dyestuffs of Examples 1 to 4 are obtained in the form of the sodium salt. According to the reaction / isolation conditions or by reaction of the sodium salts according to known methods, these dyes can also be obtained in the form of a sodium salt. free acid or in the form of other salts, for example salts containing 1 or more cations, as indicated in

description above.

  The following examples illustrate the examples

  application of the dyes of the present invention.

  Application example AA a dyeing bath consisting of 1000 parts of water, 20 parts of calcined sodium sulfate, 2.5 parts of calcined sodium carbonate and 1 part of 1Nitrobenzene-3-sulfonicon sodium salt 50 parts of mercerized cotton fabric is added. The bath is heated to 40, then 1 part of the dye of Example 1 is added. The temperature is increased to 980 for minutes and during this time is added after 15 minutes of calcined sodium sulphate. then 15 minutes later, another 20 parts of calcined sodium sulphate are added. At the end of this period, 7.5 parts of calcined sodium carbonate are added. The dyeing is continued to boiling for 45 to 60 minutes. The dyed fabric is then rinsed hot and soaped, boiling for 20 minutes in 500 parts of water and 0.5 parts of sodium alkylsulfonate After rinsing and drying, a yellow dye is obtained on the cotton having a good fastness. Application Example BA a dyeing bath consisting of 1000 parts of water, 60 parts of calcined sodium sulfate, 15 parts of calcined sodium carbonate and 1 part of the sodium salt of 1-nitrobenzene-3-sulfonic acid, 50 parts of cotton fabric are added.

    and 1.5 parts of the dye of Example 1 are added.

  The temperature is maintained at 600 for 15 minutes then

  increased to 980 for 30 minutes.

  The dyed fabric is rinsed with heat and soaped according to the method described in application example A. After rinsing and drying, a yellow dye is obtained on the cotton having a good fastness.

2532943

  Application Example C 1 part of the dye of Example 1 is dissolved in 2000 parts of water 100 parts of fabric are added

  in cotton and increases the temperature of the bath of

  80 minutes for 10 minutes. 100 parts of calcined sodium sulfate are added and 30 minutes later 20 parts of calcined sodium carbonate are added and

  dye for 1 hour at 80 Then rinse -

  the fabric is cold-dyed then hot, and is soaped according to the method described in application example A. After rinsing and drying, a yellow dye is obtained

  on cotton having good strength.

  The dyes or mixtures of Examples 2 to 5 can also be used to dye the cotton according to the method described in application examples A, B or C.

Claims (10)

  Compounds of Formula I 503 N OCH 3 Cl o o M Q I 59 N CH 3 NR 1 R 2   in which R 1 represents hydrogen or a C 2 -C 3 hydroxyalkyl group, R 2 represents a C 2 -C 3 hydroxyalkyl group, or R 1 represents hydrogen or a 2-cyanoethyl group and R 2 represents a group -CH 2 CH 20 CH 2 CH 20 H,   and mixtures of these compounds as free acid or salt.   2 A compound or mixture according to the   1, characterized in that R 1 represents hydro-   gene or a 2-hydroxyethyl group and R 2 represents a 2-hydroxyethyl group.   A compound according to claim 1, wherein R 1 is hydrogen and R 2   represents a 2-hydroxyethyl group.   A mixture according to claim 2, which is composed of a compound A which is a compound of formula I in which R 1 is hydrogen and R 2 is a 2-hydroxyethyl group, and a compound B which is a compound of formula I in which R 1 and R 2 represent a 2-hydroxyethyl group.   A mixture according to claim 4, characterized in that it contains the compounds -A and B in   a molar ratio of between 90:10 and 10:90.   A process for the preparation of the compounds of   Moule I specified in claim 1, and mixtures of these compounds, characterized in that it comprises the reaction of the following compounds: the diazolque of an armine of formula II 53 H N: 2 (II)   503 H the coupling component of formula III OCH 3 -H Q NH? (CH) cyanuric chloride, and a compound of formula IV HNR 1 R 2 (I 2   or a mixture of compounds of formula IV, these compounds to be present in a corresponding stoichiometric molar ratio in order to obtain a compound of formula I, by copulation and condensation in any desired order. A process according to claim 6, characterized in that a compound of formula I is prepared by condensation of a compound of formula V ## STR2 ## CH O C 1   In the form of free acid or salt, with a compound of formula IV HNR 1 R 2 (IV)   in which R 1 and R 2 have the meanings given in claim 1,   or a mixture of compounds of formula IV.   The use of the compounds of formula I and   their specified mixtures to any of the   dications 1 to 5, for the dyeing and printing of sub-   organic strata containing hydroxy groups or nitrogen atoms.   The use of the compounds of formula I and   their specified mixtures to any of the   dications 1 to 5, for dyeing and printing textile materials made up wholly or in part of of cotton.   An organic substrate containing hydroxy groups or nitrogen atoms, characterized in that it has been dyed or printed with a compound of formula I or a mixture of compounds of formula I as specified in one of the following:   any of claims 1 to 5.   A textile material made wholly or in part of cotton, characterized in that it has been dyed or printed with a compound of the formula I or a mixture of compounds of the formula I as specified in either   any of claims 1 to 5.