FR2514017A1 - NOVEL MONOAZOIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS COLORANTS - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS MONOAZOIC COMPOUNDS OF FORMULA: (CF DRAWING IN BOPI) IN WHICH R REPRESENTS HYDROGEN, CHLORINE, BROMINE OR IODINE, R REPRESENTS HYDROGEN, CHLORINE OR BROMINE, R REPRESENTS AN ALKYLCARBONYL, ALCOXYCARBONYL, ALCOXYETHOXYCARBONYL, ALCOXYETHOXYETHOXYCARBONYL OR ALKYLSULFONYL GROUP AND R REPRESENTS A CYANOALKYL OR G-CHLOROALLYL GROUP. THESE COMPOUNDS MAY BE USED AS A DISPERSION COLORANTS FOR DYING, SCRAPING OR PRINTING HYDROPHOBIC TEXTILE MATERIALS OF HIGH MOLECULAR WEIGHT, SYNTHETIC OR SEMI-SYNTHETIC.

Description

The present invention aims to

  new monoazole compounds and their preparation.

  These compounds can be used as dispersion dyes for dyeing, padding or printing hydrophobic, synthetic or semi-organic

  synthetic, high molecular weight.

  The invention relates more particularly to monoazole compounds of formula I

R 1

  wherein R 1 represents hydrogen, chlorine, bromine or iodine, R 2 represents hydrogen, chlorine or bromine, R 3 represents a group -CO-R 5, -COOR 5, -COOCH 2 CH 2 R 5, -CO- + OCH 2 CH 2 -2 OR 5 -502-R 6 R 5 represents C 1-4 alkyl C 4 and R is methyl or ethyl,

14 6

  and R 4 represents a C 2 -C 3 cyanoalkyl group or

(-chloroal lyle.

  R 1 preferably means R, that is,

  say a chlorine or bromine atom R 2 preferably means hydrogen R 3 preferably means R a, ie a group -CO-R 6, -COOR 6, -COOCH 2 CH 20 -R 6 or -SO 2 CH 3, more preferably one

  group -CO-R 6 o R 6 has the meaning already given.

  R 4 preferably means a -cyanoethyl group. The preferred compounds of formula I are those corresponding to formula II ## STR1 ##

NO 2 N: N 2

  = H-R 'CH 2 -CH = CH Cl in which R' and R 'have the given meanings

previously.

  Among the compounds of formula I,

  especially the form a and 5 of the compound of formula III ci

N 02 O N = N ZCH 2 CH 2 CN (III)

  X-ray diffraction pattern (Cu-Kal radiation) of the α-form having lines with the following d-values: 19.0 (low, diffuse), 15.5 (low), 10.0 (very weak, diffuse), 8.5 (medium), 7.9 (medium), 3.4 o (intense, diffuse) and 3.28 (weak, diffuse) A, and the diffraction spectrum at X-ray (Ou-K al radiation) of the form 5 having lines at the following d-values: 16.0 (very low), 8.4 (intense), 8.0 (low), 6.7 (medium), 5.65 (medium), 5.10 (weak),, 05 (weak), 4.25 (weak), 4.15 (weak), 4.02 (weak), 3.92 (weak), 3, 86 (average), 3.78 (weak), 4017 3.65 (medium), 3.58 (medium), 3.51 (very pronounced), 3.39 (very low), 3.34 ( low), 3.28 (low), 3.22 (low), 3.01 (very low) and 2.74 (very low) A. Form e of the compound of formula III is

  to form a of the same compound.

  According to the process of the invention, the compounds of formula I are prepared by coupling the diazolec of an amine of formula IV

R

  (IV) NO 2 t NH 2 (I) R with a compound of formula V

> / R 4 (V)

NH-R 3 CH 2 CH: CHC

  formulas in which the symbols R 1 to R 4 have

  the meanings given previously.

  The amine of formula IV and the coupler of formula V are known or can be prepared according to known methods from known compounds Diazotation and copulation can be carried out

according to known methods.

  Form e of the compound of formula III can

  be obtained by heating directly after copula-

  the form a (formed during copulation),

  in aqueous suspension and at a pH H greater than 3, preferably

  at a pH of about 4, at a temperature above

  than 65, preferably at a temperature of

  between 75 and 85 Form e can also be obtained by recrystallizing the α-form in an organic solvent, for example

  acetone or a lower alcohol such as ethanol.

  When the conversion of the form to form is carried out in aqueous suspension, it is advantageous to carry out this conversion in the presence of anionic, cationic or nonionic surfactant, preferably a dispersing agent.

  chosen from polyvinylsulphonates, dinaphthyl

  methanesulphonates, alkaline lignin sulphonates and

  sulphite waste liquors.

  The compounds of formula I can be

  used as dispersion dyes for the dyeing

  fabricating, padding or printing textile substrates consisting, in whole or in part, of molecular weight hydrophobic organic materials

  high, synthetic or semi-synthetic

  come particularly well for dyeing,

  padding or the printing of fibers or yarns

  killed, in whole or in part, of aromatic polyesters

  linear ticks, cellulose hemipentaacetate,

  of cellulose triacetate and synthetic polyamides

  ticks, as well as articles made from

these fibers or threads.

  The compounds of formula I can be

  used in the form of dyeing preparations.

  Such preparations are known and can be prepared according to known methods, for example by grinding in the presence of dispersing agents and / or filler, followed optionally by drying under

  reduced pressure or spray With these prepa-

  After addition of a greater or lesser amount of water, it is possible to dye in a long bath or

  short, scarf or print Dyeing, foular-

  and printing, can be done according to

ú 514017

  known methods, for example as described in

French Patent No. 1,445,371.

  The dyes obtained with the compounds

  Formula I have good general solidities.

  rays It should be noted in particular their

  fastness to light, thermofixing, sublimation

  pleating and dyeing.

  have remarkable wet fastness, for example, water, sea water, washing and

  perspiration, to solvents, in particular to the net-

  dry cleaning, lubricating agents, friction, overspray, ozone, flue gases and chlorine; the dyes are very stable with respect to the various methods of permanent pressing and Soil Release.

  corrosion, stability to reduction (in the

  of wool) and the reserve of wool and

cotton are good.

  The form of the compound of formula III

  also feels good stability and is useful in

  especially for dyeing at higher temperatures than

  to 700, especially for the dyeing of cross rolls, dyeing during which the dye bath circulates through the coil It is indeed important in the dyeing of cross rolls that the

  dye does not form large crystals that agglomerate

  on the outer surface of the substrate to be dyed,

  but remains in the bath in the form of a fine diss

  persion, about 1 P in size, under the

dyeing conditions.

  The invention also relates to high molecular weight, synthetic or semi-synthetic hydrophobic organic materials which have been dyed, padded or printed with monoazo compounds of formula I.

  The following examples illustrate the

  Without limiting the scope of the invention, the percentages and parts are by weight and the temperatures are all indicated.

in degrees Celsius.

Example 1

  a) 34.5 parts of

  2-chloro-4-nitroaniline, 88 parts of hydrochloric acid

  Concentrated drique and 250 parts of water After addition of 40 parts of ice, 13.8 parts of sodium nitrite are added in 50 parts of water, in the space of 40 minutes and at a temperature between 0 and 20 while cooling to between 0 and 50, the reaction mixture is stirred for a further 2 hours and the solution of the diazonium salt thus formed is filtered in such a way as to remove any solid residue. To this solution of the diazonium salt is added dropwise, in the amount of 45 minutes, a solution of

  55.5 parts of 1- (N-5-cyanoethyl-N-chloroallyl)

  amino-3-acetylamino-benzene in 100 parts of glacial acetic acid and 200 parts of 30% hydrochloric acid, while stirring and cooling between 0 and addition of ice.

  (b) When the copulation is over, the

  dye host is adjusted to pH 4 with about 400 parts of a 30% solution of sodium hydroxide,

  which raises the temperature to 40-450

  The dye solution is then heated to 80-85 by introducing water vapor directly into the solution and is kept at this temperature for minutes with stirring. The resulting form A is then filtered, washed with water until at

neutrality and dried.

  (c) Instead of treating the suspension as

  Criteria under b) above, the dye can be filtered after copulation, washed neutral with water, dried and recrystallized from ethanol or acetone. In this way also the Xmax form is obtained ( in dimethylformamide)

515 nm.

  d) 1- (N-5-cyanoethyl-N-2-chloroallyl) -

  amino-3-acetylamino-benzene, used as a coupler, can be prepared by reacting 40.6 parts of 1- (N-e-cyanoethyl) amino-3-acetylaminobenzene in

  parts of water with 10 parts magnesium oxide

  27 parts of 1,3-dichloropropene (cis, trans) at 92% and stirring the reaction mixture

  24 hours to 80 Then cool to the temperature

  room temperature, 200 parts of water are added and

  extract the reaction product with chloroform.

  Examples 2 to 12 In the following table, other dyes of formula I and the color of the dyes obtained on polyester were reported. These dyes are prepared in a manner analogous to that described in Example 1a) and subsequent addition of about 500

  parts of water to the suspension of copulation, filtra-

  washing, neutrality washing and drying.

(table see next page)

BOARD

  Example R 1 R 2 R 3 R 4 1 grade iwma> 2 CN frue 1 52 CH -COC 2 H 5 -CH 2 CH 2 CN red 16 3 Br H -COCH 3 do 517 4 HH do scarlet 495 Cl ci CO -OCH 2 CH 20 C 2 H 5do red 517 6 C 1 H -COCH 3 -CH 2 CH = CH Cl 521 7 Cl H CO (CF) 3 CH 3 -CH 2 CH 2 CNdo 516 8 CiH COOCH 3 do C H OH (CH 2) 3 CH 3 do 513 CH COOCH 2 CH 2 OC 25 do 511 il Cl H SO 2 CH 3 do 508 12 Cl H do-CH 2 CH = CHCI do 514 Example d (a) In a ball mill, the form of the dye of Example 1, obtained according to Example 1b) or 1c), is milled in the presence of a dispersing agent such as ligninsulfonate, and the product is dried by spraying. An ultradispersable dye preparation is thus obtained, the average particle size of which is equal to or less than 1 μm and the cutting ratio of which is

from 3:10.

  (b) 6 parts of the tincture

  ultradispersed ring obtained under (a), 1000 parts

  of water and the whole is brought to 600 in a

  dyeing clave comprising a circulation bath consisting of 13,000 parts of water and a buffer solution of 30 parts of ammonium sulfate and 0.3 part of formic acid. A prewashed cross-coil is introduced into the autoclave. comprising 1000 parts

  polyester thread on a plastic spool.

  the autoclave is closed and the temperature is raised

  from 60 to 130 in the space of 35 minutes After heating minutes to 130 ', the

  bath at 80, let it run and wash thoroughly

  the dyed coil with cold water

  spinning, dry the coil in an oven.

  This gives a red dye

  tense, pure, well united and free of particles

  undissolved The dye has good solidification

  wet and rubbed baths The bath is practically

  It is colorless and the equipment used for dyeing is not soiled with dye deposits and can be used as is for the following dyeing.

Claims (11)

  1. New monoazo compounds,   as defined in formula I R) / _ 1 / j R 4 (I) / O N CH-CH = CH-C 1 K 2 NH-R 3 2   in which R 1 represents hydrogen, chlorine, bromine or iodine, R 2 represents hydrogen, chlorine or bromine, R 3 represents a group -CO-R 5, -COOR 5, -COOCH 2 CH 2 OR 5, -CO OCH 2 CH 2 -2 OR 5 or - 502-R 6 R 5 is C 1 -C 4 alkyl and R 6 is methyl or ethyl, and R 4 is C 2 cyanoalkyl -C 3 or Are chloroallyl.   2. Monoazole compounds according to Regulation   claim 1, characterized in that R 1 represents chlorine or bromine.   3. Monoazole compounds according to Regulation   1 or 2, characterized in that R 2 represents smell hydrogen.   4. Monoazole compounds according to one   any of claims 1 to 3, characterized in   R 3 represents a group -CO-R 6, -COOR 6, -COOCH 2 CH 20 -R 6 orSO 2 CH 3 o R 6 has the meaning given in claim 1. The monoazo compounds according to one of the following:   any of claims 1 to 4, characterized in   R 4 is -CH 2 -CH 2 CN. 25140 17 l 1   6. New monoazol compound,   as it corresponds to formula III CH 2 CH 2 CHC 1 NO 2 N = N N, CH = CHC NHCOCH 3 2   7 The monoazol compound according to claim   6, characterized in that it is   the form Y, said form having a spectrum of diffe-   X-ray fraction with lines to -   o d values in A (Cu-Kal radiation): 16.0 (very low), 8.4 (intense), 8.0 (low), 6.7 (medium), 5.65 (medium), 5 , 10 (low), 5.05 (low), 4.25 (low), 4.15 (low), 4.02 (low), 3.92 (low), 3.86 (medium), 3, 78 (low), 3.65 (medium), 3.58 (medium), 3.51 (very pronounced), 3.39 (very low), 3.34 (low), 3.28 (low), 3 , 22 (weak), 3.01   (very weak) and 2.74 (very weak).   8. A process for preparing the compounds   monoazoles specified in claim 1, characterized   in that the diazolec is copied from an amine of formula IV R 2 1 (IV) NO 2 Q NH 2   Wherein R 1 and R 2 have the meanings given in claim 1, with a compound of formula V ## STR1 ## wherein R 3 and R 4 have the same meanings; data in claim 1.   9. A process for preparing the   form of the monoazole compound according to the   7, characterized in that the compound -, onoazolqu =   obtained after copulation of the 2-chloro-4- diazolc   nitroaniline with 3- (N-cyanoethyl-1-chloro)   allylamino) acetanilide is subjected, in aqueous suspension and at a pH greater than 3, to a heating   at a temperature above 65.   A process according to claim 9, characterized in that the aqueous suspension is heated to a temperature of between 75 and 8 and at a temperature of p H of 4.   11. A process for preparing the form of the monoazo compound according to claim 7, characterized in that the monoazo compound obtained is recrystallized from an organic solvent.   after copulation of the diazolque of the 2-ch T Dro-4-   nitroaniline with 3- (N-5-cyanoethyl- allylamino) acetanilide.   12. The use of monoazol compounds   specified in any of the re-   1-7, as dispersion dyes for dyeing   re, padding or printing of organ-mat-   hydrophobic substances with a molecular weight of semi-synthetic.   13. The use of single compounds   azoles specified in any of the claims   cations 1 to 7, as disperse dyes for dyeing, padding or printing fibers, yarns or textiles made wholly or in part of linear aromatic polyesters, cellulose hemipentaacetate, triacetate   cellulose or synthetic polyamides.   14. Hydrophobic organic materials   high molecular weight, synthetic or semi-   synthetic, characterized in that they have been dyed, padded or printed with a mono-azo compound as specified in any of the Claims 1 to 7.   15 Fibers, yarns or textiles made up wholly or in part of polyesters   aromatics, hemipenta-cellulose acetate   cellulose triacetate or synthetic polyamides, characterized in that they have been   dyed, padded or printed with a mono-   azole as specified in any of the Claims 1 to 7.