FR2472002A1 - NEW CUPRIFER DYES AND THEIR PREPARATION - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS CUPRIFER COMPOUNDS OF FORMULA: (CF DRAWING IN BOPI) IN WHICH R REPRESENTS A HYDROGEN ATOM OR A SULFO GROUP, R MEANS A HYDROGEN ATOM OR AN ALKYL OR HYDROXYALKYL GROUP, R REPRESENTS A GROUP ALKYL OR PHENYL POSSIBLY SUBSTITUTED, OR R AND R FORM TOGETHER, WITH THE NITROGEN ATOM TO WHICH THEY ARE BOUND, A 6-CHAIN HETEROCYCLIC REMAIN, R MEANS A HYDROGEN ATOM OR AN ALKYL AND HAL-REPRESENT ATOM , OF CHLORINE OR OF BROMINE, 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 copper compounds and their

  preparation. These compounds are suitable as reactive dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen atoms. The invention relates more particularly to the triazine tri-amine compounds corresponding to formula I

\ NOT /

 a, N --- N R3 R. tNN (I)

C0 / I

  wherein R 1 is a hydrogen atom or a sulfo group, R 2 is a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkyl group containing 2 to 4 carbon atoms substituted in the 2-position, 3 or 4 with a hydroxy group, R 3 represents an alkyl group containing from 1 to 4 carbon atoms, an alkyl group containing from 2 to 4 carbon atoms substituted in the 2, 3 or 4 position with a hydroxy group, an alkyl group containing of 1 to 4 carbon atoms substituted by a sulfo or carboxy group, or a phenyl group optionally bearing 1, 2 or 3 substituents selected from halogen atoms and sulfo, carboxy and alkyl and alkoxy groups each containing from -1 to 4 carbon atoms, or R2 and R3 together with the nitrogen atom to which they are bonded form a 6-membered heterocyclic residue optionally containing another heteroatom, R to represent a hydrogen atom when the residue -NR2R3 signifi a p-sulfoanilino group, R4 represents a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms, and Hal means a fluorine, chlorine or bromine atom,

and their salts.

  The invention also includes mixtures of compounds of formula I.

  R1 preferably means a hydrogen atom.

  When R 1 signifies a hydrogen atom, the sulfo group present on ring A is preferably located in position 4 or 5, in particular in position 4. When R 1 represents a sulfo group, both

  Sulfo groups are preferably at positions 4,6.

  When R2 and / or R3 represents an alkyl group, it is preferably a methyl or ethyl group, in particular a methyl group. When R2 and / or R3 is hydroxyalkyl, it is preferably hydroxyethyl or hydroxypropyl,

  in particular a hydroxyethyl group.

  When R 3 is an alkyl group substituted with a sulfo or carboxy group, it is preferably a methyl or ethyl group, especially an ethyl group. The alkyl or alkoxy groups present as substituents on the phenyl group represented by R 3 are preferably methyl, ethyl, methoxy or ethoxy groups, in particular methyl or methoxy groups. When R 3 represents a phenyl group substituted by halogen, the latter preferably represents a fluorine, chlorine or bromine atom, in particular chlorine or bromine, more particularly

chlorine.

  When R 3 represents a substituted phenyl group, it is preferably a phenyl group bearing one or two substituents, in particular one or two substituents chosen from chlorine and sulpho, carboxy, methyl and methoxy groups. More particularly, when R 3 signifies a substituted phenyl group, it is a 3- or 4-sulphophenyl group optionally carrying a chlorine atom, a methyl, methoxy, carboxy or sulpho group, in particular a methyl or sulpho group. this latter substituent being preferably located in

  2, and the sulfo group in position 4 or 5.

  When R2 and R3 together with the nitrogen atom to which they are bonded form a 6-membered heterocyclic residue, it is preferably a residue

piperidino or morpholino.

  R2 preferably R2, that is to say

  a hydrogen atom, a methyl group, ethyl 2-hydroxy-

  ethyl, 2- or 3-hydroxypropyl, or R 1 and R 3 form

2 3

  together with the nitrogen atom to which they are attached, a piperidino or morpholinoo radical R2 is preferably R, this symbol R "

R 2 2

  meaning a hydrogen atom or a methyl group

  or 2-hydroxyethyl, especially a hydrogen atom.

  R preferably means R3, that is to say

  a methyl, ethyl, 2-hydroxyethyl, 2- or 3-

  hydroxypropyl, sulphomethyl, sulphoethyl, carboxymethyl, carboxyethyl or a phenyl group optionally bearing one to two substituents selected from chlorine and sulpho, carboxy, methyl and methoxy groups. More particularly, R 3 has the meaning of R ", this R" symbol representing a methyl, 2-hydroxyethyl, sulphoethyl, carboxyethyl, phenyl or 3-or 4-sulphophenyl group optionally carrying, as other substituents, a chlorine atom or a group methyl, methoxy, carboxy

or sulfo.

  More specifically, R3 means R "', i.e. a group

  2-hydroxyethyl, phenyl, 3- or 4-sulfophenyl, 2-

  methyl-4-sulfophenyl or 2,5-disulfophenyl.

iv c

  R3 especially means R3, that is,

  say 2-hydroxyethyl, 3- or 4-sulfophenyl, 2-methyl-4sulfophenyl or 2,5-disulfophenyl. Most preferably, R 3 is R 3, i.e., 3- or 4-sulfophenyl, 2-methyl-4-sulfophenyl or 2,5-disulfophenyl. When R 4 represents an alkyl group, it is preferably a methyl or ethyl group,

  in particular a methyl group.

  R4 preferably means R ', that is to say

  a hydrogen atom or a methyl group, in particular

a hydrogen atom.

  Hal is preferably a fluorine atom

  or chlorine, especially chlorine.

  The preferred compounds of formula I are: (1) those in which R 1 and the sulfo group on ring A occupy the positions indicated above; (2) those wherein R4 is R, especially hydrogen; (3) those in which Hal represents a fluorine or chlorine atom; (4) those wherein R2 is R2 and R3 is R '; (5) those specified under (4) Ru and R represent R "; 23 (6) those specified under (5) fication of R '; (7) those specified under (6) hydrogen and iv of Rv (8) those specified under (1) in which R2 stands for

in which R3 has the meaning

  in R3 to which R2 is the meaning at (7) in which Hal means a chlorine atom; (9) those specified under (1) to (8) in a hydrogen atom when a sulfophenyl group; (10) those specified under (1) to (8) in represents a hydrogen atom;

which Ri represents

R3 means which R1

2472002.

  (11) compounds of formula Ia NRR3 (Ia) in which RV has the meaning already given,

and their salts.

  When the compounds of formula I are present

  in the form of salts, the nature of the cations is not deter-

  nant; they may be salts usually used in the chemistry of reactive dyes, such as the salts of alkali metals, ammonium or substituted ammonium, for example the lithium, sodium, potassium, ammonium, mono-, di-, tri- or tetramethylammonium,

  triethylammonium or mono-, di- or triethanol-

  ammonium. The preferred cations are the alkali metal cations and the ammonium cation, the sodium being

particularly preferred.

  According to the process of the invention, to prepare the compounds of formula I one or more compounds of formula II (II) are reacted in the free acid state or in the form of a salt with a compound of formula III

R NR R3

Ry 2 3 -

  formulas in which R 1, R 2, R 3 and R 4 have the already given cations and R represents a residue of (III)

signifi-

2472002!

  formula (a) Eaf Q0 (a) a1 where Hal has the meaning already given, and Ry means a hydrogen atom, or Ry means a radical of formula (a) and Rx represents

a hydrogen atom.

  Preferably, a compound of formula II is reacted with a compound of formula III

  wherein Ry means a remainder of formula (a).

  The reaction is carried out according to known methods. It is advantageous to operate in a weakly acidic to slightly alkaline medium, at a temperature of

  between room temperature and 650. It is preferable to use

  an acid-accepting agent, for example sodium carbonate, sodium bicarbonate, hydroxide

sodium or triethylamine.

  The compounds of formula I thus obtained can be isolated according to the usual methods, for example precipitation by addition of salts, filtration and drying.

under reduced pressure.

  The compounds of formulas II and III in which Rx and Ry represent a hydrogen atom are known

  or can be prepared according to known methods.

  Likewise, the compounds of formulas II and III in which R and R denote a radical of formula (a) can x

  be prepared by known methods, by condensation

  a corresponding compound in which R respectively Rysignifies each a hydrogen atom, with a cyanuric halide. This condensation can be carried out as described above for the reaction of the compound of formula II with the compound of formula III. However, in view of the ease of reaction of the first halogen atom, it is possible to operate at a lower temperature, preferably between 0 and 50. The compounds of formula I and their mixtures can be used as reactive dyes for dyeing. or the printing of organic substrates

  containing hydroxy groups or nitrogen atoms.

  The preferred substrates are leather and textiles made wholly or in part of natural or synthetic polyamides such as wool, silk or natural or regenerated cellulose nylon.

  such as cotton, viscose or rayon.

  The dyes can be used in dye baths or printing pastes for

  dyeing or printing according to known methods.

  The new compounds of formula I can also

  be used in combination with other dyes.

  The dyes of the invention give a very good dye yield and show good climbing power and good fixing properties; in particular they are distinguished by a good performance

of fixation.

  The dyes and prints obtained with the new dyes have good wet fastness, especially washing, perspiration, and water, chlorine, bleaching agents

  based on peroxide and light.

  For the printing it is necessary to point out the sharpness of the contours, the facility to eliminate by washing the

  unbound dye and the stability of the printing paste.

  In padding processes, the solubility of the dyes in the padding bath and the stability of that pad are as good as the solidities of the resulting dyes and the ease of removing the unbound dye. The invention further comprises organic substrates containing hydroxy groups or atoms

2472002,

  of nitrogen, which have been dyed or printed with at least one of the copper compounds of formula I. The following examples illustrate the present invention without in any way limiting its scope. Parts and percentages are by weight and temperatures

  are all indicated in degrees Celsius.

Example 1

  94.5 parts of 2-amino-1-

  4-hydroxybenzene-4-sulfonic acid in 300 parts of water and, after addition of 15 parts of 30% hydrochloric acid, the mixture is diazotized at 0-5 for 60 minutes with

  parts of a solution of 4N sodium nitrite.

  167.5 parts of 1-amino-8-

  hydroxy-naphthalene-3,6-disulfonic acid in 625 parts of water and dissolved at pH 6.5 by addition of sodium hydroxide solution. After addition of 50 parts of sodium bicarbonate and 46 parts of sodium chloride and ice, the solution of the diazolec prepared above is added dropwise at 3-6 and in 90 minutes. The reaction mixture is stirred for 6 hours at a temperature of between 3 and 6 ° C and then the temperature is allowed to return to 20 ° C. We rush to. pH 7 the resulting monoazolic cacosate,

  by addition of 310 parts of sodium chloride and filtered.

  900 parts of water and 45 parts of a 30% solution of sodium hydroxide are stirred into the product obtained. To this mixture, 420 parts of a solution of molar copper sulphate are added dropwise at -60 and in the course of 2 to 3 hours, while maintaining the pH at 5 by addition of a solution.

to 30% sodium hydroxide.

  84.5 parts of sulfanilic acid are dissolved in 550 parts of water at pH 7 and then this solution is added dropwise at 0-5 and in the course of one hour to a mixture of 87.5 parts. of cyanuric chloride and 140 parts of a mixture of water and

2472002,

  ice cream. The pH is maintained at 3-4 by addition of a

  20% solution of sodium carbonate.

  The condensation product is added dropwise

  Sulfanilic acid-cyanuric chloride solution to the solution of the mono-cupric compound obtained above and gradually raises the reaction temperature from 40 to 45. The pH is maintained between 5 and 6 by the addition of a 20% solution of sodium carbonate. After adjusting the pH to 7, the solution is clarified with a little activated charcoal. The product is precipitated at 40 by addition of 800 parts of chloride

  of sodium, filtered at 30 and dried.

  The dye thus obtained corresponds to the formula eCu S Na 0 t O 3 O o - N> A N Na S03 Na SO3Na 03R It gives on the natural and regenerated cellulose dyes and purple prints red-red

  having good fastnesses (max (H 2 O) 552 nm).

Example 2

  86.5 parts of sulfanilic acid are dissolved in 500 parts of water by the addition of aqueous sodium hydroxide solution and the mixture is treated as described in Example 1. A solution is then cooled.

  filtered from 189.5 parts of 1-acetylamino-8-hydroxy-

  potassium naphthalene-3,6-disulphonate in 750 parts of water and adjusted to pH 6.5. The suspension of the diazolec in this solution is introduced at 8 and for one hour while maintaining the pH at 6.5 by the addition of sodium carbonate. The compound formed precipitates largely in this solution. After dilution of this solution to 3000 parts by volume 2472002i by addition of water, the mixture is stirred overnight.

at room temperature.

  To this suspension is then added 500 parts of a solution of molar copper sulphate and 50 parts of sodium acetate. 90 parts of sodium perborate are added at 150 under stirring and in the course of 2 hours, then 40 parts of a solution of hydrogen peroxide are added dropwise over one hour. at %. The temperature is gradually raised to 40

  and the mixture is stirred for 3 hours at 40. We specify

  The copper compound is cooled to room temperature by addition of 500 parts of sodium chloride and 2500 parts of methanol and filtered. After adjusting the resulting paste to 1000 parts by volume by addition of water, the acetyl group is stirred and removed by hydrolysis for 4 hours.

  at 600 with 50 parts of solid sodium hydroxide.

  The whole is adjusted to pH 5, the resulting product is isolated by the addition of 225 parts of sodium chloride.

and filtered at 40.

  The paste obtained is again adjusted to 1000

  parts by volume by addition of water and stirred.

  While stirring, about 50 parts of cyanuric chloride are added in portions and the condensation is carried out for 5 hours at a temperature between 0 and 5, the pH being maintained at 5 by addition.

of sodium carbonate.

  To the solution thus obtained, is added dropwise at 60, and approximately in the space of 4 hours,

  56.1 parts of 1-amino-2-methylbenzene-4- acid

  sulfonic acid in 450 parts of water and the pH is maintained at 5

  by adding a solution of sodium carbonate.

  The compound formed precipitates gradually. After having

  adjusted the pH to 6.5, the precipitated product is filtered.

  The compound thus obtained is dissolved at 50 in 1500 parts by volume of water. The solution is treated with a little activated charcoal, filtered to obtain a clear solution, and the dye is precipitated by addition of 150 parts. sodium chloride. After filtration and drying, the dyestuff of the formula Cu 2 O 3 N 3 SO 3 Na 3 (max (H 2 O) 560 nm) is obtained. It gives the natural or regenerated cellulose dyes and impressions of violet nuances.

  pulling blue and having good solidity.

  Proceeding as described in Examples 1 or 2, the compounds of formula I specified in Tables I and II below can be prepared. These compounds

  correspond to formula I in which R4 signifies

  a hydrogen atom and the other symbols have the meanings given in the tables. They are obtained in the form of sodium salts and give on the natural or regenerated cellulose dyes and prints having the shades indicated in column J of Tables I and II. In this column, a means purple pulling red-and purple b

bluish.

  (Tables I and II see following pages)

2472002,

TABLE I

  position g u groupR. Hal R.- R. J Ex. SO Na sur1. ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## 9 4 H C1 R-S03Na a CH3 4 HC H3 -CH2CH2SO3Na a 11 4 HF i -CH2CH20H a 2 2 12 5 H CI H CH3 b 13 5 H Cl H -CH2CH2OH b 14 5 B C1 H b H3 S03Na 5 HF RH - <XFSO3Na b 16 4SO3Na (6) Cl H do. 3 b 17 5 H-C1 H do. b 18 4 do. Ci H CH3 b

2472002.

BOARD

  I (continued) position of the group H Ex. 2 R3 Ex. SO 3Na on R Hal R 3 _ the cycle '_ 19 4 do. C₁CHCH₂CH₂O -CH₂CH₂OH b4d. C1 H. - b 21S _0Na 21 4 do. C1 H3Na b 22 4 do. C1 CH3 b

T A B L E A U II

  position of the group R R2 Ex.o SONa on 1 Hal the cylce A 3

/ CH2- CH 2 '

  ## STR2 ## ## STR2 ## b Ct2-CH2_ 4 H CCl-N O to 4 E ci -N2 "

CH -CH

2 2 26 4 SO3Na (6) C do. b

2472002.

  Application Example A About 400 parts of the dye of Example 1 are dissolved in 100 parts of water and 10 parts of urea. To this solution are added 30 parts of a 30% solution of sodium carbonate and 0.5 part of sodium 1-nitro-benzene-3-sulfonate. With this padding bath, we impregnate a fabric of fibranne, until

  an impregnation rate corresponding to 75% of the dry weight.

  After drying, the fabric is subjected for 5 to 10 minutes to a steam treatment at 1020, rinsed

  and soap it to boiling for 15 minutes.

  After drying, a violet dye is obtained

  on the red and having good solidities.

  Application Example B 2 parts of the dye obtained in Example 7 are dissolved in 50 parts of water and 20 parts of urea. After addition of 15 parts of a% sodium carbonate solution, the bath is diluted to 100 parts by volume by the addition of water. 20 parts of a cotton fabric are impregnated with this padding bath until an impregnation rate corresponding to 80% of the weight of the dry fabric. The fabric is dried and the dye is fixed by steaming for 10 minutes at 103 ° C. The fabric is rinsed, soaped to boiling, washed again and dried. This gives a reddish-purple dye with

good solidity.

  Application example C Mercerized cotton satin is printed according to known methods, with a paste having the following composition parts of the dye of Example 1, parts of urea, 440 parts of water, 400 parts of a solution at 4% alginate-based thickener, parts of 1-nitrobenzene-3-sodium sulfonate, and

parts of sodium bicarbonate. -

  The printed fabric is treated for 4 to 8 minutes by a steam treatment at 102 ° -104 °. The fabric is then washed first cold, then hot, and after a boiling, it is washed again. and dry it. This gives a red-violet impression with good fastness to light

and wet.

Claims (10)

  1.- novel cupric compounds, characterized in that they correspond to the formula I CuR o \ R Rieg 2} M (I) The N1-1 N   wherein R 1 is a hydrogen atom or a sulfo group, R 2 is a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms or an alkyl group containing 2 to 4 carbon atoms substituted in position 2, 3 or 4 with a hydroxy group, R 3 represents an alkyl group containing 1 to 4 carbon atoms, an alkyl group containing 2 to 4 carbon atoms substituted in the 2, 3 or 4 position with a hydroxy group, a group alkyl containing 1 to 4 carbon atoms substituted with a sulfo or carboxy group, or a phenyl group optionally bearing 1, 2 or 3 substituents selected from halogen atoms and sulfo, carboxy and alkyl and alkoxy groups each containing 1 to 4 carbon atoms, or R and R together with the nitrogen atom 2 3   to which they are bonded, a 6-membered heterocyclic residue optionally containing another heteroatom, R 1 to represent a hydrogen atom when the residue -NR 2 R 3 is a p-sulfoanilino group, R 4 is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, and Hal means a fluorine, chlorine or bromine atom, their salts and their mixtures.   2.- New copper compounds, characterized in that they correspond to the formula I Cu R%, 0 N N. n \ 0311 30   wherein R 1 signifies a hydrogen atom or a sulfo group, the sulfo group on ring A being located at the 4 or 5 position when R 1 signifies a hydrogen atom, and the sulfo groups present on ring A at positions 4 and 6 when R 1 is sulfo, R 2 is hydrogen, methyl, ethyl, 2-hydroxyethyl or 2-or 3-hydroxypropyl, and R 3 is methyl, ethyl, 2-hydroxyethyl,   2- or 3-hydroxypropyl, sulfomethyl sulfoethyl, car-   boxymethyl or carboxyethyl or a phenyl group optionally carrying one or two substituents selected from chlorine and sulfo, carboxy, methyl and methoxy, or R2 and R3 together with the nitrogen atom   to which they are bound, a piperidino or morpho-   lino, R4 is a hydrogen atom or a methyl group, and Hal signifies a fluorine or chlorine atom, R1 to be hydrogen, when the residue -NR2R3 is a p-sulfoanilino group, their salts and their mixtures.   3.- Copper compounds according to some   of claims 1 and 2, characterized in that   that R 2 is hydrogen, methyl or 2-hydroxyethyl, and R 3 is   methyl, 2-hydroxyethyl, sulphoethyl, carboxy-   ethyl or phenyl or a 3- or 4-sulphophenyl group,   optionally substituted with a chlorine atom or a methyl, methoxy, carboxy or sulfo group. 4.- New cupric compounds, characterized in that they correspond to the formula Ia (Ia) in which   Rv represents a 3- or 4-sulfophenyl, 2-methyl- R3   4-sulfophenyl or 2,5-disulfophenyl, their salts and their mixtures.   5. New copper compound, characterized in that it meets the formula -NM -0-S03H its salts and mixtures.   6. A Process for Preparing Copper Formulas of Formula I Cu INR R 1 / ,, 4 - - / 2 R- \ R /   N 5 H ',, j --- s3n S03t compounds (I) S03va 2472002.   wherein R 1 is hydrogen or sulfo, R 2 is hydrogen, alkyl of 1 to 4 carbon atoms, or alkyl of 2 to 4 carbon atoms substituted in the 2-position, 3 or 4 with a hydroxy group, R 3 represents an alkyl group containing from 1 to 4 carbon atoms, an alkyl group containing from 2 to 4 carbon atoms substituted in the 2, 3 or 4 position with a hydroxy group, an alkyl group containing from 1 to 4 carbon atoms substituted by a sulfo or carboxy group, or a phenyl group optionally bearing 1, 2 or 3 substituents selected from halogen atoms and sulfo, carboxy and alkyl and alkoxy groups each containing from 1 to 4 carbon atoms or R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic 6-membered residue optionally containing another heteroatom, R 1 being a hydrogen atom when the residue -NR 2 R 3 is a p-sulfoanilino group, R4 is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, and Hal is a fluorine, chlorine or bromine atom, and salts thereof, characterized in that one or more compounds of formula II Cu are reacted ? ' 0 NRR   4 x t L '- 2 X. l (I) in the free acid state or in the form of a salt, with a compound of formula III RyNR2R3 (III)   formulas in which R1, R2, R3 and R4 have the meanings   cations already given and R represents a residue of X formula (a) al 'ai (a) in which Hal has the meaning already given, and R signifies a hydrogen atom, or R represents   a residue of formula (a) and R denotes a hydrogen atom   gene. 7. A process according to claim 6, characterized in that a compound is reacted   of formula III or R is a radical of formula (a).   8. The application of copper compounds   specified in any one of claims 1 to 5,   as dyes for dyeing or printing organic substrates containing hydroxy groups or nitrogen atoms.   9.- The application of the copper compounds   specified in any one of claims 1 to 5,   as dyes for dyeing or printing leather or textile substrates made wholly or in part of natural or synthetic polyamides or of cellulose natural or regenerated.   10.- The application of the copper compounds   specified in any one of claims 1 to 5,   as dyes for dyeing or printing the   cotton, viscose or fibranne.   11. Organic substrates containing hydroxy groups or nitrogen atoms, characterized in that they have been dyed or printed with one to   copper compounds specified in any one conque of claims 1 to 5. -2472002 i   12.- Textile substrates made up of   wholly or in part, synthetic or natural polyamides   regenerated or natural cellulose, and leather, characterized   by being dyed or printed with at least one of the copper compounds specified in   any of claims 1 to 5.   13. Cotton, viscose and fibran, characterized in that they have been dyed or printed, with the copper compounds specified in one   any of claims 1 to 5.