FR2601391A1 - USE OF MONOAZOIC COMPOUNDS AS COLORANTS. - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS THE USE OF MONOAZOIC COMPOUNDS OF FORMULA I (CF DRAWING IN BOPI) IN WHICH R IS A HALOGEN OR CN, R AND R MEAN HYDROGEN OR ONE OF THE SYMBOLS R AND R IS H AND L 'OTHER A HALOGEN, R MEANS H, HALOGEN, ALKYL OR ALKYLAMINO AND R MEANS CYANO-ETHYL OR A -CH-CH (R) -R GROUP, AS DISPERSION DYES FOR DYING, SCRUB OR PRINTING TEXTILE MATERIALS SYNTHETIC OR SEMI-SYNTHETIC HYDROPHOBIC AND WITH HIGH MOLECULAR WEIGHT.

Description

The subject of the present invention is the use of compounds

  monoazo as dispersion dyes for the dyeing of

textile materials.

  The invention relates in particular to the use of compounds of formula I

R1 R5

0 N N = N N I

R6

R3 R2 R4

  wherein R5 is cyanoethyl or a group of formula a-CH2-CH (R7) -R8 a) wherein R7 is hydrogen or C1-C2 alkyl, and R8 is C1-C4 alkoxy phenoxy, benzyloxy, C 1 -C 4 alkylcarbonyloxy, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxycarbonyloxy, benzylcarbonyloxy, benzyloxycarbonyl or benzyloxycarbonyloxy, R 6 represents an alkyl group C8-C14 or a group of formula b -CH2-CH (R7) -R9 b) wherein R7 is as defined above and R9 is C8-C14 alkoxy, - (C8-C14) alkoxy carbonyl, - (C 8 -C 14) alkylcarbonyloxy or - (C 8 -C 14) alkoxycarbonyloxy, R 2 and R 3 represent hydrogen or one of the symbols R 2 and R 3 represents hydrogen and the other represents a halogen R1 is halogen or cyano, R4 is hydrogen, halogen, C1-C2alkyl or acylamino; only one of R5 and R6 may mean a substituent; containing oxygen,

  as disperse dyes for dyeing high molecular weight hydrophobic synthetic or semisynthetic textile materials.

  The invention also relates to a process for dyeing hydrophobic and high molecular weight synthetic or semisynthetic textile materials, wherein a compound of formula I as defined above is applied to the textile material. When R4 is an acylamino group, it is preferably a - (C1-C4) alkylcarbonylamino or - (C1-C4) alkoxycarbonylamino group in which the alkyl or alkoxy moiety may be substituted by chlorine, bromine or with a C1-C4 alkoxy, - (C1-C4) alkoxycarbonyl, cyano, phenyl or phenoxy group. R1 is preferably other than a cyano group when R2

represents a halogen.

  R5 is preferably RS ', ie cyanoethyl or a group of formula a' -CH2-CH2-R8 'a' wherein R8 'is - (C1-C2alkyl) -carbonyloxy - - (C1-C2alkoxy) -carbonyl or benzyloxy. R5 represents more

  preferably a cyanoethyl group.

  R6 is preferably R6 ', i.e., a C1-C14 alkyl group or a group of the formula b' -CH2-CH2-Rg 'b' wherein R9 'is a C1-C14 alkoxy group, - (C10-C14alkyl) -carbonyloxy, - (C10-C14alkoxy) -carbonyloxy or - (C1-C4alkoxy) -carbonyl. Rg more preferably means a

C10-C12 alkyl group.

  R7 is preferably hydrogen. R 2 is preferably hydrogen.

2 60139 1

  - 3 R1 is preferably RI ', that is to say a halogen

or a cyano group.

  R3 preferably represents hydrogen.

  R4 is preferably R4 ', i.e., hydrogen, chlorine or methyl, - (C1-C3) alkylcarbonylamino or - (C1-C3) alkoxycarbonylamino. R4 in particular means R4 ', where R4 is hydrogen, chlorine or methyl when R1 is cyano, or R4' is - (C1-C2alkyl) carbonylamino when R1 is halogen. Halogen is preferably chlorine or bromine.

  The compounds of formula I are new.

  A preferred group of compounds of formula I is that comprising compounds of formula II.

02N N = N D N - II

  -C1-C12 alkyl NHCO-C1-C2alkyl

  wherein Rla represents chlorine or bromine.

  Another group of preferred compounds of Formula I is that comprising the compounds of formula III ## STR2 ##

02N Q N = N III

R

  Ra 6a Ra 1391-4 wherein R6a is C1-C14alkyl or -CH2CH2-R9a wherein R9a is - (C1-C14) alkoxycarbonyloxy, (C1-C14) alkoxy- (C1-C14alkyl) - carbonyloxy or (C10-C14) alkoxycarbonyl, and

  R4a represents hydrogen, chlorine or a methyl group.

  Another group of preferred compounds of formula I is that comprising the compounds of formula IV R

CH2CH2CN

02N- N N IV

R3 IV

R3 R15 R14

  in which R 1 represents a halogen or a cyano group, R 3 represents hydrogen or halogen, R 15 represents a - (C 1 -C 4 alkyl) carbonylamino or - (C 1 -C 4 alkoxy) carbonylamino group, where the alkyl group or alkoxy is optionally substituted with chlorine, bromine or with a C1-C4 alkoxy, - (C1-C4) alkoxycarbonyl, cyano, phenyl or phenoxy group, and

  R14 represents a C8-C14 alkyl group.

  Another group of preferred compounds of formula I is that comprising compounds of formula V R '

02N N = N N V

2 6 R17

260 1391

  Wherein R2 is hydrogen or halogen, R1 'is halogen or cyano, R16 is hydrogen, halogen or C1-C2 alkyl, R17 is cyanoethyl or a group of the formula c - CH2 - CH - Ro c)

R

  Wherein R 10 is (1-4C) alkoxy, phenoxy, benzyloxy, (1-4C) alkylcarbonyloxy, (1-4C) alkoxycarbonyl, (1-4C) alkoxycarbonyloxy, benzylcarbonyloxy; , benzyloxycarbonyl or benzyloxycarbonyloxy, and R7 is as previously defined, R18 is C8-C14 alkyl or CH2 CH-R11 d).

R7

  wherein R 11 is C 8 -C 12 alkoxy, C 8 -C 12 alkylcarbonyloxy, C 8 -C 12 alkoxycarbonyl or C 8 -C 12 alkoxycarbonyloxy, only one of R 5a and R 6a which may mean a substitute

containing oxygen.

2 601391

  The compounds of formula I can be prepared by coupling the diazo of an amine of formula VI R1a

02N NH2 VI

3 2

with a compound of formula VII R5

ON VII

R6

R4

  wherein the symbols are as previously defined.

  The compounds of formula VI and VII are known or may be prepared from known compounds according to known methods. The copulation and the diazotation can be carried out according to

known methods.

  For their use as dyes, the. Compounds of formula I can be converted into dyeing preparations in accordance with known methods, for example by grinding in the presence of a dispersing agent or a filler, and optionally drying under reduced pressure or by spraying. With these preparations, it is possible, after addition of a greater or lesser amount of water,

  dye in long or short bath, pad or print.

  The compounds of the invention mount very well in aqueous suspension on high molecular weight hydrophobic synthetic or semisynthetic textile materials. They are particularly useful for dyeing, padding or printing textiles made of linear aromatic polyester, cellulose hemipentacetate, cellulose triacetate or synthetic polyamide, especially polyester. The compounds of the invention give dyes having good fastness, especially wet and in contact after heat treatment. Dyeing, padding or printing can be

  carried out according to known methods, in particular according to the method described in British Patent No. 1,114,433.

  The following examples illustrate the present invention

  without in any way limiting its scope. In these examples, percentages and percentages are by weight, and temperatures are given in degrees Celsius unless otherwise indicated.

Example 1

  17.3 parts of 4-nitro-2-chloroaniline are dissolved in 44 parts of 30% HCl and 100 parts of water. The resulting solution is reacted with 75 parts of ice and then diazotized with 7.2 parts of sodium nitrite (as a 5N solution) 0-5. After destroying the excess nitrous acid with aminosulfonic acid, the diazo solution is filtered at 0-5. The solution obtained is poured into a solution consisting of 37.5 parts of the compound of formula Ib ## STR2 ##

HCOCH3 C12H25

  and 1000 parts of glacial acetic acid. The resulting brownish suspension is filtered, the residue is neutralized to 50 with 900 parts of water and the product is dried in vacuo at 40.degree. The

  product can be further purified by recrystallization or by chromatography on silica gel (eluent: toluene / methyl ethyl ketone).

  This gives the compound of formula Ia ## STR1 ##

C12H25

NHCOCH3

  max. in dimethylformamide = 527 nm. It dyes the fibers of

  polyester in a ruby red hue having good fastness, especially in contact and wet after heat treatment.

Examples 2 to 7

  By proceeding in a manner analogous to that described in Example 1 and using the appropriate starting materials, the compounds of the formula

R1 CH2CH2CN

02N t N N

3 R4 6

  wherein R1 to R6 are as defined in the following Table I.

-9

TABLE I

  Ex. No. R1 R3 R6 R4 Grade on polyester X max nm 2 Cl 3 Cl 10 4 Cl Cl 6 Br 7 Br

8 -CN 15 9 do.

Cl

11 H 12 H 20 13 H

14 H 15 Cl

16 -CN

17 Cl H -CllH23 -NHCOCH3

H -C10H21 do.

H do. -NHCOC2H5

H -C12H25 do.

H do. -NHCOCH3

H -C10H21 do.

H do. do.

H -C12H25 do.

H (-C10H21 (50%) do.

% -C12H25 (50%)

H do. do.

H -C10H21 do.

H -C12H25 do.

H do. -NHCOC2H5 H do. -NHCOCH3

H do. do.

C1 -CloH21l do.

  bluish red do. do. do. do. do. reddish purple red bluish red bluish red scarlet do. do. do. bluish red bluish red reddish red

527,527,528,528,528,529,528,548,548,527

506 505 508 509 523 544 524

Example 18

  17.3 parts of 4-nitro-2-cyanoaniline (95.2%) are dissolved

  in 165 parts of 93% sulfuric acid; the solution was cooled to 0-5 ° and the dinitrogen was 0-3 with 33 parts of 40% nitrosylsulfuric acid.

  35 parts of N-B-cyanoethyl-N-n-dodecyl-metachloroaniline and 5 parts of aminosulphonic acid are dissolved in 1200 parts of glacial acetic acid. To this solution of component of

  copulation, the solution of com-

  - 10 diazotization pellet obtained previously, with 750 parts of ice. The red-brown suspension thus obtained is filtered off, the residue is washed neutral with 1000 parts of water at 50 and dried under vacuum at 60 ° C. The product can be further purified by recrystallization or by chromatography on silica gel (eluent: toluene / methyl ethyl ketone). The compound of formula 18a is thus obtained

N C2H4CN

02N-G N N N / - N H (18a)

C 12H25

Cl

  ) Max. in dimethylformamide = 522 nm.

  The product dyes the polyester fibers in a bluish red shade with good fastnesses, especially in contact and wet after heat treatment. EXAMPLE 19 By proceeding in a manner analogous to that described in Example 18, the compound of formula 19a can be prepared.

CN C10H

  ## STR2 ## ## STR1 ## in dimethylformamide = 531 nm, replacing the coupling component of Example 18 with 37.5.

  parts of N-r5-propionyloxyethyl-N-n-dodecyl-meta-chloroaniline.

  The compound of formula 19a dyes the polyester fibers into

  a ruby red hue with good fastness, especially in contact and wet.

  Examples 20 to 50 By proceeding in a manner analogous to that described in Example 18 and using the appropriate starting materials, the compounds of the formula

CN R

02N NN

R6 R4

  wherein the symbols R4 to R6 are as defined in the following Table II.

- 12 TABLE II

  Ex. 5 No. R4 R5 R6 Luance on polyester X max (rim)

C1-CH2CH2CN

21 C1 -CH2CH2CN

22 Cl -CH2CH2CN

23 C1 -CH2CH2CN

24 C1-CH2CH2CN

H 15 26 H

27 H 28 H

29 -CH3

30 -CH3

  31 Cl 32 Cl 33 Cl 34 Cl 25 35 Cl 36 Cl 37 H

-CH2CH2CN

-CH2CH2CN

--CH2CH2CN

-CH2CH2CN

-CH2CH2CN

--CH2CH2CN

-CH2CH20COCH3

-CH2CH20COCH3

-CH2CH20COOCH3

-CH2CH20COOC2H5

-CH2CH20COOCH3

-CH2CH20COC2H5

-CH2CH20COCH3

-CllH23 -ClOH21

-C9H19

-C8H17

-C12H25 (50%) L [10H21 (50%)

-C14H29

-C12H25

-CllH23

-C10H21

-Cl2H25

-C10H21

-ClOH21

-C12H25

-ClOH21 -ClOH21

-C12H25

-C12H25

  -Cl0H21 Red do. do. do. do. ruby red do. do. do. bluish red do. do. do. do. do. do. do. do.

522 522 522 522 522

526 526 526 525 537

537 531 531 529 529 529 531 536

  - 13 TABLE II (continued from previous page) EX. R4 No. R5 R6 Grade on polyester fibers> max (rim)

38H -CH2CH2COO (CH2) 3CH3

39. H -CH2CH2COCH3

H -CH2CH20COOCH3

41H -CH2CH2OCH2C6H5

42H -CH2CH2CN

43H -CH2CH2CN

44H -CH2CH2CN

H -CH2CH2OC6H5

-ClOH21

-C12H25

-C12H25

  -ClOH21 Bluish red do. do. Reddish Violet -CH2CH20C12H25 Red CH2CH20COC10H21 Red Yellowish

-CH2CH2OCOOClOH21 do.

-C10H21 -Redish violet

536 533 544

519,510

507,539

506 501 516

46 Cl -CH2CH2CN

47 C1-CH2CH2CN

48 C1 -CH2CH2CN

49H -CH2CH2CN

-CH3 -CH2CH2CN

  -CH2CH2OCl0H21 Red yellowish -CH2CH20COC10H21 Scarlet

-CH2CH2O0ClOC10H2I do.

  -CH2CH2COOC12H25 Red yellowish -CH2CH2COOC12H25 Bluish red

Example 51

  21.5 parts of 4-nitro-2,6-dichloroaniline (98%) at 0-5 ° are refluxed in 180 parts of 94% sulfuric acid with 34.5 g.

  40% nitrosylsulfuric acid parts.

  29.5 parts of N-1-cyanoethyl-N-decylaniline (97%) and 5.0 parts of aminosulphonic acid are dissolved in 900 parts of glacial acetic acid and 50 parts of water. The solution is cooled to 0-5 and, while stirring and simultaneously adding 700 parts of ice, the diazo solution is slowly added to the coupling solution. To the red-orange suspension obtained, 100 parts of sodium acetate are added, the mixture is stirred rapidly, filtered and washed.

  the residue to neutrality and dried under vacuum at about 40.

  The product may be purified by the method specified in

Example 1

  The compound of formula 51a is thus obtained

C1 CH2CH2CN

  02N> - N N (51a) Cl nCo10H21 max. in dimethylformamide = 437 nm. It dyes the fibers of

  polyester in a yellowish brown shade with good fastness, especially in contact and wet after heat treatment.

  Examples 52 to 66 Proceeding in a manner analogous to that described in Example 51 and using the appropriate starting materials, compounds of formula

R1 R6

02N Q NN: N

DCH_úH_úN

R4

- 15 -

  in which the symbols R1 to Table III following.

R6 are as defined in the

TABLE III

  Ex. R2 R1 R4 R6 max nm N4uance on (in dimethylform fibers) polyester 52 Cl

53 do.

54 do.

do.

56 do. 15 57 do.

Bdo.

58 do.

59 do.

do.

61 do. 20 62 Br

63 do.

64 do.

do.

66 do. 25

  Cl do. do. do. do. do. do. Br do. do. do. do. do. do. do.

H H H

-CH3 do. Cl do. do.

H -CH3 H H H -CH3 Ci

-C8H17

-C12H25

-C14H29

-ClOH21

-C12H25 do.

* -ClOH21 do.

do. do.

-C8H17

-ClOH21

-C12H25

-ClOH21 do.

  437 437 437 451 451 439 439 437 435 448 433 433 433 445 435

  Yellowish brown do. do. Reddish brown Yellowish brown Yellowish brown do. do. do. Brown Brown do. do. Brownish reddish yellowish reddish yellowish Examples 67 to 69 The following compounds can be prepared by

  similarly to that described in Example 51 from the appropriate starting materials.

- 16 -

Example 67

ci C 1 H 2 Cl

02N () N =

 2W N = N - - C N

C2H40COCH3

  max: 513 dyes the polyester in a red shade.

Example 68

This

02N- D N

C 12H25 = N - C N

C2H40COCH3

  max: 513 dyes the polyester in a red shade.

Example 69

Br

02N Q Y-- N = N D N

C 1 0H25 1-11

At max: 514

  dyes the polyester in C2H40COC2H5 a red shade.

  Application Example The compound of formula Ia (prepared according to example 1) is ground in the presence of a lignin-sulfonate (dispersing agent) of the compound and then atomized to obtain an ultra-dispersed dye preparation whose size average particle is equal

  1p and having a cutting ratio of 3.5: 10.

  24 parts of the dye preparation obtained above are dispersed in 1000 parts of water and the whole is added in a dyeing autoclave containing 13000 parts of a 60 ml circulation bath containing 30 parts of ammonium sulphate and , 3 parts of formic acid as a buffer (optionally with a carrier or a unison agent). The autoclave is fed with a cross-coil (1000 parts of polyester yarn on a cone of plastic material) which has been washed beforehand. The autoclave is closed and the mixture is heated to 130 ° C. over a period of 35 minutes. After 90 minutes, the autoclave is cooled to 80, the bath is evacuated, the

  substrate dyed with cold water and subjected to a reducing cleaning. After dewatering and drying the substrate, a ruby red color is obtained which is free of deposit.

  In the application example above, we can replace

  the compound of formula la by an appropriate amount of any of the compounds of Examples 2 to 69.

- 18

Claims (9)

  1. The use of monoazo compounds of formula I R1 02N Q N = N "N" I R3 R2 R4   wherein R5 is cyanoethyl or a group of formula a-CH2-CH (R7) -R8 a) wherein R7 is hydrogen or C1-C2 alkyl, and R8 is C1-C4 alkoxy phenoxy, benzyloxy, - (C1-C4) alkylcarbonyloxy, (C1-C4alkoxy) -carbonyl, (C1-C4alkoxy) -carbonyloxy, benzylcarbonyloxy, benzyloxycarbonyl or benzyloxycarbonyloxy, R6 represents a C8-alkyl group -C 14 or a group of formula b -CH 2 -CH (R 7) -R 9 b) in which R 7 is as defined above and R 8 is C 8 -C 14 alkoxy, -C 8 -C 14 alkoxycarbonyl, - C 8 -C 14 alkylcarbonyloxy or C 8 -C 14 alkoxycarbonyloxy, R 2 and R 3 represent hydrogen or one of the symbols R 2 and R 3 represents hydrogen and the other represents halogen, R1 represents a halogen or a cyano group, R4 represents hydrogen, a halogen or a C1-C2 alkyl or acylamino group, 260139 1 - 19 -   only one of the symbols R5 and R6 may mean an oxygen-containing substituent, as disperse dyes for dyeing, padding or   the printing of high molecular weight hydrophobic synthetic or semi-synthetic textile materials.   2. The use of monoazo compounds of formula II CH2CH2CN   II-C 1 -C 6 alkyl NHCO-C 1 -C 22 alkyl wherein R 1a represents chlorine or bromine,   as disperse dyes for dyeing, padding or printing high molecular weight hydrophobic synthetic or semisynthetic textile materials.   3.- The use of monoazo compounds of formula III N 02N c N = CH2CH2CH2CN   Wherein R 6a is (C 10 -C 14) alkyl or CH 2 CH 2 -R 9a or R 9a is - (C 10 -C 14) alkoxycarbonyloxy, C 10 -C 14 alkoxy, (C 10 -C 14) alkylcarbonyloxy or - (C1-C10 alkoxy) -carbonyl, and R4a represents hydrogen, chlorine or a methyl group, as disperse dyes for dyeing, padding or   the printing of high molecular weight hydrophobic synthetic or semisynthetic textile materials.   4. The use of monoazo compounds of formula IV or V - 20 - 02N CH2CH2CN = N-R N / O '1 \ R R1 14 RI $ IV R3 R ' 02N N = R18 N1   Wherein R 1 is halogen or cyano, R 3 is hydrogen or halogen, R 15 is C 1 -C 4 alkylcarbonylamino or C 1 -C 4 alkoxycarbonylamino the alkyl or alkoxy group is optionally substituted with chlorine, bromine or with a C1-C4 alkoxy, - (C1-C4) alkoxycarbonyl, cyano, phenyl or phenoxy group, and R14 represents an alkyl group C8-C14, R2 is hydrogen or halogen, R1 'is halogen or cyano, R16 is hydrogen, halogen or C1-C2 alkyl, R17 is cyanoethyl or a group of the formula wherein Ro10 is (C1-C4) alkoxy, phenoxy, benzyloxy, (C1-C4) alkylcarbonyloxy, (C1-C4) alkoxycarbonyl, - (C1-C4alkyl) -carbonyloxy; C1-C4 alkoxycarbonyloxy, benzylcarbonyloxy, benzyloxycarbonyl or benzyloxycarbonyloxy, and R7 is as defined in claim 1, and R18 is C8-C14 alkyl group or a group of formula d-CH2-CH-R11 d I   Wherein R 11 is C 8 -C 12 alkoxy, C 8 -C 12 alkylcarbonyloxy, C 8 -C 12 alkoxycarbonyl or C 8 -C 12 alkoxycarbonyloxy, only one of R 5a and R 6a may mean a substituent containing oxygen,   as disperse dyes for dyeing, padding or printing high molecular weight hydrophobic synthetic or semisynthetic textile materials.   5. The use according to any one of claims 1 to 4, characterized in that the textile material consists of linear aromatic polyester.   6. A process for dyeing hydrophobic and high molecular weight synthetic or semisynthetic textile materials, characterized in that a compound as specified in any one of claims 1 to 4 is applied to the textile material.   7.- Synthetic or semi-synthetic textile materials   hydrophobic and high molecular weight ticks, characterized   they have been dyed, padded or printed with a composition as specified in any one of claims 1 to 4.   8. The textile materials according to claim 7, characterized in that they consist of linear aromatic polyester.   9. A monoazo compound as specified in any one of claims 1 to 4.