FR2554455A1 - NOVEL MONOAZOIC COMPOUNDS, THEIR PREPARATION AND THEIR USE AS COLORANTS - Google Patents

Abstract

THE SUBJECT OF THE PRESENT INVENTION IS MONOAZOIC COMPOUNDS OF FORMULA I: (DRAWING IN BOPI) IN WHICH D REPRESENTS A DIAZOTATION COMPONENT, R REPRESENTS HYDROGEN, CHLORINE OR BROMINE OR AN ALKYL, ALCOXY OR ALCOXYETHOXY GROUP, HYDROGEN, AN ALKYL-CARBONYLAMINO, ALKYL-CARBONYLAMINO, ALCOXYALKYL-CARBONYLAMINO, FLUORO-, CHLORO- OR BROMO-ALKYL-CARBONYLAMINO, HYDROXY-ALKYL-CARBONYLONYLOXY-ALKYL-CARBONYL-CARBONYL-CARBONYL-OUCOYL-CARBONYL-CARBONYL-OUCO-AMINOYL-OUCO-AMINOYL-OUCO-AMINOYL-CARBONYL-OR R REPRESENTS HYDROGEN OR A SUBSTITUTED OR NON-SUBSTITUTED ALKYL GROUP, A REPRESENTS A LINEAR OR BRANCHED ALKYLENE GROUP, AND R REPRESENTS A NON-SUBSTITUTED BIPHENYL GROUP. THESE COMPOUNDS ARE USED AS COLORANTS.

Description

The subject of the present invention is new monoazo compounds, their

  preparation and their use as dyes

dispersion.

  The present invention more particularly relates to compounds of formula I R1

D-N = N Q N \ (I)

A-OR 5

2

  wherein D represents a diazotization component, R1 represents hydrogen, chlorine or bromine or a C1-C2 alkyl, C1-C4 alkoxy or (C1-C4 alkoxy) ethoxy group, R2 represents hydrogen or a C 1 -C 4 alkyl group,

  C1-C4) -carbonylamino, (C1-C4-alkoxy) - (C1-C3) alkyl -

  carbonylamino, fluoro-, chloro- or bromo-C 1 -C 4 -alkylcarbonylamino, hydroxy-C 1 -C 3 -alkylcarbonylamino, (C 1 -C 4 -alkoxy) -carbonylamino, (C 1 -C 4 -alkoxy) - (C 1 -C 4) alkoxycarbonylamino or (C 1 -C 4) alkylsulfonylamino, R 3 represents hydrogen or unsubstituted C 1 -C 4 alkyl or C 2 -C 3 alkyl substituted by OH, alkoxy

  C1-C4, CN, (C1-C3) alkylcarbonyloxy, (C1-C4) alkoxy -

  carbonyloxy, (C1-C4) alkoxycarbonyl, (C1-C4) alkoxy -

  ethylcarbonyloxy or (C1-C4 alkoxy) ethoxycarbonyloxy, A represents a linear or branched C2-C4 alkylene group, and

  R5 represents an unsubstituted biphenylyl group.

  D preferably means D ', D' meaning a radical

  phenyl, thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazole,

  zolyl, 1,3,4- or 1,2,4-thiadiazolyl, benzothiazolyl or benzoisothiazolyl. D is more preferably D ", D" signifying a group of formula (a) R6 502N <(a)

R7 R8

in which -

  R6 is halogen or CN, NO2 or (C1-C2alkyl) sulphonyl and R7 and R8 are hydrogen or halogen, at least one of R7 and R8 being hydrogen;

  or D "represents a 5-nitrothiazolyl-2,4-methyl-5-

  nitrothiazolyl-2,4-cyanoisothiazolyl-5,3-methyl-4-cyano-

  isothiazolyl-5, 1-phenyl or 1-methyl-4-cyanopyrazolyl-5,

  1-phenyl-3-methyl-4-cyanopyrazolyl-5,1,3-dimethyl-4-cyano-

  pyrazolyl-5,1-allyl- or 1- (C1-C2alkyl) -4,5-dicyanoimidazo

  2,5-alkyl-C 1 -C 2 -alkylmercapto-1,3,4-thiadiazolyl-2,

  3-phenyl-1,2,4-thiadiazolyl-5,5-nitro-2,1-benzoisothiazol

  yl-3,3,5-dinitrothienyl-2,3,5-dicyano-4-methyl-thienyl-2

  or 3-cyano-4-methyl-5 - [(C 1 -C 2 alkoxy) carbonyl] thienyl-2.

  R1 preferably means R'1, R'i meaning

  hydrogen or a methoxy or ethoxy group. R1 means more preferred

hydrogen.

  R2 preferably means R'2, R'2 meaning hydro-

  gene or a methyl group or (C1-C2 alkyl) -carbonylamino, plus

  preferably R "2, R" 2 signifying hydrogen or a methyl group.

  R3 is preferably R'3, R'3 is C1-C4 alkyl, more preferably R "3, R" 3 is a group

methyl or ethyl.

  A is preferably A ', A' being -CH2-CH2-, -CH2-CHCH3 or -CH2CH-C2H5s, more preferably A

means a group -CH2CH2-.

  R5 preferably means R'5, R'5 meaning a remainder

  unsubstituted ortho- or para-biphenylyl.

  R6 preferably means R'6, where R'6 is chlorine, bromine, iodine or a cyano group; R6 more preferably means

chlorine.

  R7 preferably means R'7, where R'7 is hydrogen, chlorine or bromine and R8 is preferably hydrogen. More preferably, R7 and R8 both mean hydrogen. In this application, unless otherwise indicated, any C 1 -C 4 alkyl group preferably means a methyl or ethyl group, and any C 1 -C 4 alkoxy group preferably means a methoxy or ethoxy group. Halogen means fluorine, chlorine, bromine and iodine, more preferably the last three

when R6 is a halogen.

  The preferred compounds of formula I are those of formula II ## STR1 ##

  wherein the symbols are as defined above.

  According to the process of the invention, to prepare the compounds of formula I, the diazo compound of an amine of formula III is

D-NH2 (III)

  in which D has the meaning already given, with a coupling component of formula IV

\ A-OR 5

  R2 in which R1, R2, R3, R5 and A have the meanings already given. Diazotation and copulation are performed according to

known methods.

  The compounds of formula III and IV are known or can be prepared according to known methods from known compounds. The invention also relates to the use of monoazo compounds of formula I as dyes. For their use as dyes, the compounds of

  Formula I can be formulated as dyeing preparations.

  Such dyeing preparations may be obtained according to known methods, for example by grinding in the presence of a dispersing agent or filler, optionally followed by drying under reduced pressure or by spraying. With these preparations one can, after addition of a more or less important quantity of water,

  dye in long or short bath, pad or print.

  The dyes of the invention mount well in aqueous suspension on textile substrates made of organic materials

  high molecular weight, synthetic or semi-hydrophobic

  synthetic. The dyes of the invention are particularly suitable for the dyeing, padding or printing of textile materials consisting of linear aromatic polyesters, cellulose hemipentaacetate, cellulose triacetate and synthetic polyamides. The dyes of the invention are indicated

  by a slight tendency to thermomigration.

  Dyeing, padding or printing can be carried out according to known methods, in particular as described

  in French Patent No. 1,445,371.

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

  are in degrees Celsius unless otherwise indicated.

EXAMPLE 1

  17.3 parts of 2-chloro-4- are stirred for 12 hours.

  nitroaniline in 44 parts of concentrated hydrochloric acid and 125 parts of water and then 45 parts of ice are added. This mixture is reacted for 40 minutes at a temperature between 0 and 2 with 7.0 parts of sodium nitrite dissolved in parts of water. While cooling to a temperature between 0 and 50, the mixture is stirred for a further 2 hours, the excess nitrous acid is destroyed with amidosulfonic acid and the product is filtered to remove traces of solid impurities.

who are present.

  While stirring and cooling with ice at a temperature between 0 and 50, the resulting solution of diazonium salt is added very slowly in minutes to a solution of 33.2 parts of N-ethyl- (2'-o). -biphenylyloxyethyl) -aniline in

  400 parts of glacial acetic acid and 140 parts of ice water.

  When the coupling is complete, the mixture is stirred for a further 2 hours without cooling and filtered. The residue is washed until it is free of acid and salt and dried

at 50 under vacuum.

  The compound of formula la Cl (la) is thus obtained

0 NO = 4 -N // C2H5 X 6H5

EXAMPLE 2

  By proceeding as described in Example 1 and using, in place of N-ethyl-N- (2'-o-biphenylyloxyethyl) -aniline, a

  corresponding amount of N-ethyl-N- (2'-p-biphenylyloxyethyl)

  aniline, the compound of formula 2aCl is obtained

/,.C2H5

N024N = N1 \ (CH2) 2 C6 5

  In ultradispersed form, it dyes polyester fabrics in red-blue shades. The resulting dyes have good fastness.

EXAMPLES 3 to 30

  By proceeding in a manner analogous to that described in Example 1 and using the appropriate starting materials, it can prepare the following monoazo compounds of Table 1 which correspond to the formula

6 R3

NO2 Q

N 2 f t A-0-R5 -

  in which the symbols have the given meanings

board.

TABLE 1

  Ex. R6 R7 R2 R3 A R5 u e Nos. on the red polyeste 3 -Cl H H -CH3 CH2CH2 O-biphenylyl bluish

4 do. H H -C3H7 do. do. do.

do. H H -C4H do. do. do.

  6 do. H H do. do. -p-biphenylyl do.

7 do. H H -C3H7 do. do. do.

8 do. H H -CH3 do. do. do.

/ CH3

9 do. H H -C 2 H 5 -CH 2 CH-. do.

do. H H do. -CH2CH-

12H5 do. do.

11 do. H CH3 do. do. H ruby

  12 do. H do. ddo. o. -0-biphenylyl do.

  13 do. H H do. -CH2CH2- do. bluish red

14 do. H H do. CH2CH-do. do.

C2H5

-B H H do. -CH2CH2- do. do.

16 -I H H do. do. do. do.

17 Cl Cl H do. do. do. do.

  18 do do. H do. do. P-biphenylyle do.

19 -Br H H do. do. do. do.

-CN. H -CH2CH2CN do. do. do.

  21 do H H, do. -do. o-biphenylyl do.

22 do H H do. -CHCH-do. d o.

CH3

  HClCH 2 CH 2 CH 2 COOCH 3 -CH 2 CH 2 -d. do.

  24 Cl H do. -CH2CH20COCH3 do. do. do.

Cl H do. -CH2CH2OCOOCHI do. do. do.

  TABLE I (continued) Ex. R6 R7 R2 R3 A R5 uance Nos. R5 on 5 ..... ___, _ lyester 26 H H -NHCOCH3 CH2CH2CN -CH2CH2- biphenyl- red

27 Cl H do. do. do. do. do.

28 -CN H H -C2H5 do. do. red

leuâtre-

29 do. H H do. -CH2CH-

CH3 do. do.

do. H H do. do.:p-biphenyl- do.

_the

EXAMPLES 31-40

  Compounds of formula

R6 R1

NO2 N = N N 3

NA- O - R5

  R2 in which the symbols are as defined in Table 2 by proceeding in a manner analogous to that of Example 1 from the

appropriate starting materials.

TABLE 2

  Ex. R 2 R23 A R5 R6 R8 Grade on Nos. R8 polyester 31 Cl NHCOCH3H -CH2CH2- -o-biphenyl Cl H red 32H H -C2H5 do. do. Cl Cl reddish brown

33 H H do. -CH2CH do. Cl Cl do.

CH3

  34 H H do. -CH 2 CH 2 -p-biphenylyl Cl Cl do.

H H do. do. o-biphenylyl Br Cl do.

  36 -OCH3 -NHCOCH3H do. do. -NO2 Br navy blue

37-OC2H5 do. H do. do. do. Cl do.

  38 -OCH2CH2OCH3 -NHCOCH3 H do. do. do. Br do.

  39 -OCH3 -NHCOCH3H-CH2CH- do. do. Cl do.

CH3

  do. -CH3 -CH3 -CH2CH2CH2-do. do. C1 do.

Ln-Pl. -1l U'J

EXAMPLES 41-68

  Compounds of formula

RN R

D-N N N? 4 '

A- O- R5

  wherein the symbols are as defined in Table 3 by proceeding analogously to that described in Example 1 at

  from the appropriate starting materials.

TABLE 3

  Ex. R1 R R A R D Nuance on Nos. 1 2 3 5 polyester 41 H H C2H5 -CH2CH2-o-biphenylyl 3-methyl-4-cyanoisothiazolyb-5 bluish ruler

  42 H H do. do. -p-biphenylyl do. do.

  43H H -CH2CH2CN do. o-biphenylyl do. do.

  44 H H do. do. do. 4-cyano-1,2 -isothiazolyl-5d.

H H -C 2 H 5 -CH 2 CH-. do. do.

  CH3 46 H H do. do. do. 4-chloro-5-formylthiazolb-2 violet

47 H H do. -CH2CH2 do. do. do.

  48 H H do. do. do. 5-nitrothiazolyl-2 violetbleuâtre 49 H -CH3 do. do. do. do. their mug

H do. do. -CH2CH2CH2- do. do. do.

  51 -OCH3 do. -C3H7 -CH2CH2- do. do. blue 52H H -C2H5 -CH2CH- do. do. iolet blueAti CH3 53 H -CH3 do. do. do. do. blue raspberry 3 ... blue rmge & tre

  54 H do. do. -CH2CH2- -p-biphenylyl do. do.

H do. do. -CH2C-do. do. do.

  CH3 TABLE 3 (continued) Ex. R1 R2 R3 A R5 D Grade on Nos. 1 23_polyester _.i i._, 56 H H -C 2 H 5 -CH 2 CH 2 -p-biphenylyl 3,5-dinitrothienyl blue

  57 H H do. do. o-biphenylyl do. do.

58 H H do. -CH2 H do. do. do.

  CH3 59H-CH3 do. -CH2CH2 do. 3,5-dicyano-4-methylthienyl-2 blue ugeatrei H H do. do. do. 3-cyano-4-methyl-5-methoxy-bluish red carbonylthienyl-2 61H H do. do. do. 1-ethyl-4,5-dicyanoimidazolyl-2 red 62H-CH3 do. do. do. do. bluish red 63 H H do. do. do. 5-nitro (2,1) -benzoisothiazolyl-3 melt blue 64 H-CH3 do. do. do. do. blue

H H do. -CH2CH do. do. do.

  H3 66 H H do. -CH2CH2- do. 3-methoxycarbonylethyl-mercapto bluish red 1,2,4-thiadiazolyb-5

67H -CH3 -CH2CH2CN do. do. do. do.

  68 H do. do. do. do. 2-methylmercapto-1,3,4-thiadia-red zolyl-5 I Example of application The compound of formula la (Example 1) is ground in a ball mill in the presence of a dispersing agent (for example a commercially available lignin sulphonate) and is then atomized into an ultradispersed dye preparation having a mean particle size of 1M and a cutting ratio of

3.5: 10.

  16 parts of this preparation are dispersed in 1000 parts of water and this dispersion is added to the bath in circulation (13000 parts containing 30 parts of ammonium sulphate and 0.3 parts of formic acid as buffer) . Then a pre-cleaned and pressed cross-coil (1000 parts polyester fiber on a plastic bobbin) is introduced, the dyeing autoclave is closed and heated to 130 in 35 minutes. After 60 minutes, the mixture is cooled to 80 ° C., the dye bath is drained and the dyed substrate is washed with cold water. The dyed substrate is subjected to a reducing treatment of

  stripping, we then wring the cross coil and dry it.

  A strong, bluish red dye is obtained, having excellent wet fastness, heat setting and rubbing and a low tendency to thermomigration. The reels

  are free of dye particles on the fibers.

  Instead of the dye of Example 1, an appropriate amount of any of the dyestuffs of the present invention can be used.

examples 2 hrs 68.

Claims (10)

  1. The monoazo compounds of formula I R D-N = N N (I)   Wherein D is a diazotization component, R 1 is hydrogen, chlorine or bromine, or a C 1 -C 2 alkyl, C 1 -C 4 alkoxy or (C 1 -C 4) alkoxy ethoxy group, R 2 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxy-C 1 -C 3 alkylcarbonylamino, fluoro-, chloro- or bromoalkylcarbonylamino; C1-C4) -carbonylamino, hydroxy- (C1-C3alkyl) -carbonylamino, (C1-C4alkoxy) -carbonylamino, (C1-C4alkoxy) - (C2-C4alkoxy) -carbonylamino or (C1-C4alkyl) C1-C4) -sulfonylamino, R3 is hydrogen or unsubstituted C1-C4 alkyl or C2-C3 alkyl substituted with OH, C1-C4 alkoxy, CN, (C1-C3) alkyl - carbonyloxy, (C 1 -C 4) alkoxycarbonyloxy, (C 1 -C 4) alkoxycarbonyl, (C 1 -C 4) alkoxy-ethylcarbonyloxy or (C 1 -C 4) alkoxyethoxycarbonyloxy, A represents a C 2 -C 4 alkylene group; Linear or branched C4, and   R5 represents an unsubstituted biphenylyl group.   2. A monoazo compound according to claim 1, characterized in that D represents a group of formula (a) R (a) O2N (a) R7 R8   wherein R6 is halogen, CN, NO2 or (C1-C2alkyl) sulphonyl, and R7 and R8 are hydrogen, at least one of R7 and R8 having to represent hydrogen.   3. A monoazo compound according to claim 1, characterized in that D is phenyl, thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, 1,3,4- or   1,2,4-thiadiazolyl, benzothiazolyl or benzoisothiazolyl.   4. A monoazo compound according to claim 3, characterized in that D represents a -Nitrothiazolyl-2,4-methyl-5-nitrothiazolyl-2,4-cyanoisothiazolyl-5,3-methyl-4-cyanoisothiazolyl-5-group. , 1-phenyl   or 1-methyl-4-cyanopyrazolyl-5, 1-phenyl-3-methyl-4-cyano-   pyrazolyl-5,1-dimethyl-4-cyano-pyrazolyl-5,1-allyl or   1- (C1-C2alkyl) -4,5-dicyanoimidazolyl-2,5-alkyl (C1-C2alkyl) -   mercapto-1,3,4-thiadiazolyl-2,3-phenyl-1,2,4-thiadiazolyl-5,1-nitro-2,1-benzoisothiazolyl-3,5,5 dinitrothienyl-2,3,5-dicyano 4-methylthienyl-2 or 3-cyano-4-methyl-5 - [(alkoxy) en Cl-C2) carbonyl] 2-thienyl.   5. A monoazo compound according to any one of   1 or 2, characterized in that it corresponds to the formula II R 'Re 6 R'i NO N = N (II)   Wherein R '1 is hydrogen, methoxy or ethoxy, R'2 is hydrogen, methyl or (C1-C2 alkyl) carbonylamino, R'3 represents hydrogen or an alkyl group C1-C4   A 'represents a group -CH2CH2-, CH2-CH-CH3 or 2 CH-C2H5,   R'5 represents an unsubstituted ortho- or para-biphenylyl group, R'6 represents chlorine, bromine or iodine or a cyano group, and R'7 represents hydrogen, chlorine or bromine. 6. A process for the preparation of the monoazoic compounds of formula I according to claim 1, characterized in that the diazofque is copulated from an amine of formula III D-NH2 (III)   wherein D has the meaning given in claim 1, with a coupling component of formula IV R R Nl- / 3 (IV) \ -A-OR 5   Wherein SR1, R2, R3, R5 and A are as defined in claim 1.   7. The use of the monoazo compounds specified in   any of claims 1 to 5 as dyes for   dyeing, padding or printing organic materials   high molecular weight, synthetic or semi-hydrophobic synthetic.   8. The use of the monoazo compounds specified in   any of claims 1 to 5 as dyes for   dyeing, padding or printing of textile substrates   consisting of linear aromatic polyesters, hemipera-   cellulose acetate, cellulose triacetate or synthetic polyamides.   9. Hydrophobic organic materials having a molecular weight   high, synthetic or semi-synthetic, characterized in that they have been dyed, padded or printed with a compound   monoazo compound as specified in any one of claims 1 5.   10. Textile substrates made of polyester polyesters   linear materials, hemipenta-cellulose acetate, tri-   cellulose acetate or synthetic polyamides, characterized in that they have been dyed, padded or printed with a compound   monoazo compound as specified in any one of claims 1 at 5.