Thermomigrationfast azo dyes

Details Thermomigrationfast azo dyes Thermomigrationfast azo dyes

1999-12-14

2001-02-20

Powers, Fiona T. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Azo

C534S731000, C534S753000, C534S788000, C534S853000, C558S056000, C008S466000, C008S471000, C008S680000, C008S693000, C503S227000, C428S195100, C428S913000, C428S914000

Reexamination Certificate

active

06191265

ABSTRACT:

This invention relates to azo dyes of the formula
wherein
D is aryl or hetaryl other than 2,4-dinitro-6-ethanesulphonylphenyl,
A is —CO— or —SO—,
B is optionally substituted C
1
-C
4
-alkyl,
R
1
and R
2
are independently optionally OH— or C
1
-C
4
-alkoxy-substituted C
1
-C
4
-alkyl, and
R
3
and R
4
are independently H or CH
3
,
with the proviso that A is SO
2
when D is a 6-nitrobenzothiazolyl radical.
Useful substituents for the optionally substituted C
1
-C
4
-alkyl B are Cl, C
1
-C
4
-alkoxy, C
1
-C
4
-acyloxy, CO
2
-C
1
-C
4
-alkyl.
Suitable aryls D are substituted benzene derivatives of the formula (II)
wherein
X
1
and X
5
are independently H, F, Cl, Br, —NO
2
, —CN, —SO
2
—B, —CO
2
—B, —OH, —CHO or —CO—B,
X
2
and X
4
are independently H, Cl, Br, NO
2
or B,
X
3
is H, Cl, Br, —NO
2
, —CN, —SO
2
—B, —CO
2
—B, —CH═O or B, and
B is as defined above.
Preferred hetaryls D are thiazoles (IIIa), isothiazoles (IIIb), thiophenes (IIIc), thiadiazoles (IIId), benzothiazoles (IIIe) and benzisothiazoles (IIIf) of the following formulae:
wherein
X
1
to X
5
are each as defined above,
X
6
is H, B, Cl, Br, —SB or —SO
2
B,
X
7
is CN, —CO
2
B or —CO—B, and
B is as defined above.
Preference is given to dyes of the formula (I) wherein
D is a radical of the formula
wherein
X
1
and X
5
are independently H, Cl, Br, CN, —NO
2
, —SO
2
—B or CO
2
—B,
X
2
and X
4
are independently H, B, Cl or Br,
X
3
is H, B, Cl, Br, —NO
2
, CN, —CO
2
—B or —CH═O,
X
7
is —CN, —CO
2
—B, —CO—B, and
B is as defined above.
Particular preference is given to dyes of the formula (I) wherein
D is a radical of the formula
wherein
X
1
is H, Cl, Br, CN or NO
2
,
X
3
is H, CH
3
, Cl, Br or NO
2
,
X
5
is H, Cl, Br or CN,
A is —SO—,
B is optionally Cl-substituted C
1
-C
4
-alkyl, especially methyl,
R
1
and R
2
are each C
1
-C
4
-alkyl, especially methyl, and
R
3
and R
4
are each hydrogen.
The dyes (I) are prepared by generally customary methods. For example, diazo components of the formula
D—NH
2
  (VI)
wherein
D is as defined above,
are diazotized and coupled onto coupling components of the formula
wherein
A, B, R
1
, R
2
, R
3
and R
4
are each as defined above.
The diazotization is effected in the usual manner at −20 to 20° C. with the aid of alkali metal nitrites, nitrosylsulphuric acid or esters of nitrous acid in mineral acids (HCl, H
2
SO
4
, H
3
PO
4
) or lower fatty acids (acetic and/or propionic acid). The coupling is likewise carried out by customary methods, preferably by adding the aqueous solution or dispersion or aqueous/alcoholic solution to the diazonium salt solution and, if appropriate, adjusting the reaction mixture to pH 5-7 by addition of alkali.
A preferred process for preparing inventive 2,6-dicyanoazo dyes of the formula
wherein
R
1
to R
4
, A, B and X
2
to X
4
are each as defined above,
is characterized in that conventionally prepared azo compounds of the formula
wherein
R
1
to R
4
, A, B and X
2
to X
4
are each as defined above, and
Hal is halogen, preferably Cl or Br,
have their halogen atoms exchanged for cyano groups.
This exchange reaction is likewise known per se and described for example in the following patent literature: DE-A 1 544 563=GB 1 125 683; DE-A 2 456 495=GB 1 479 085; DE-A 2 759 103=GB 2 012 799; DE-A 2 846 439=GB 2 034 736; DD 2 17 232 (especially the references cited therein).
Thereafter, the o,o′-dihaloazo compound is reacted with metal cyanides or cyanide ion donor compounds in a polar organic solvent or water at temperatures of 50 to 150° C. until the halogen atoms are virtually completely replaced, which is readily monitorable by reference to thin layer chromatograms.
Suitable cyanides are in particular CuCN and Zn(CN)
2
and complex cyanides of the formula Me
⊕
n
(CuCN)
n+1
(Me=Na, K; n=1-3). Suitable cyanide ion former systems are for example fornaldroxime, cyanohydrins, nitroalkanes or formamide.
Preferred organic solvents are polar aprotic compounds such as, for example, DMF, DMSO, pyridine, N-methylpyrrolidone, chlorobenzene, dichlorobenzenes, etc.
A particularly suitable and preferred way of carrying out the halogen/cyano exchange is by means of a mixture of copper(I) cyanide and zinc cyanide.
Whereas the diazo components are generally known, only the precursors are known of the coupling components, cf. for example EP 313 918 or U.S. Pat. No. 5,194,598.
However, these compounds are readily obtained in a manner known per se, for example by reacting compounds of the formula
wherein
R
1
to R
4
are each as defined above,
with
a) acid anhydrides, for example of the formula
wherein
B is as defined above, or
b) acid chlorides of the formula
B—A—Cl,
wherein
B and A are each as defined above.
The coupling components of the formula (VII) wherein B, R
1
, R
2
, R
3
and R
4
are each as defined under the formula (I) and A is SO
2
are new and likewise form part of the subject-matter of the present invention.
These acylations are preferably carried out in organic, preferably anhydrous, solvents. Water/organic solvent two-phase systems are also suitable.
Examples of suitable solvents are apolar organic solvents such as chlorinated hydrocarbons, for example methylene chloride, carbon tetrachloride, aromatic solvents, for example toluene, xylenes, chlorobenzene, dichlorobenzene, nitrobenzene, but also polar solvents such as acetone, dimethylformamide, N-methylpyrrolidone, sulpholane, etc.
It may be advantageous to use organic or inorganic bases to scavenge the hydrogen chloride formed.
Examples of suitable bases are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydrogenphosphate, sodium acetate and also amines such as, for example, trialkylamines, pyridine, dialkylaminopyridine, quinoline, dialkylanilines, etc.
The dyes of the invention, as is customary for disperse dyes, are virtually insoluble in water. They are particularly useful for dyeing and printing synthetic textile materials, especially textile materials composed of secondary cellulose acetate and cellulose triacetate, polyamide, for example polyhexamethyleneadipamide, and most suitably aromatic polyester, for example polyethylene terephthalate, by the dyeing and printing methods customary for these fibre varieties using aqueous or non-aqueous liquors or print pastes.
The dyes may lastly also be applied to synthetic textile materials by thermal transfer printing.
The dyes are further useful for thermal transfer printing on synthetic recording materials in optical recording processes, for example for printing polyester-coated paper.
The scarlet to blue dyeings on polyester obtained with the new dyes combine good all round fastnesses with high colour strength, bright hues and, in particular, excellent thermomigrationfastness.
Compared with the closest known dyes of JP-A 47 25 487, which have a 6-nitrobenzothiazole diazo component, and JP-A 4725488, which have a 2,4-dinitro-6-ethylsulphonylphenyl diazo component, the new dyes have superior fastness properties.


REFERENCES:
patent: 4249275 (1981-02-01), Hugl et al.
patent: 4619993 (1986-10-01), Baumann
patent: 5194598 (1993-03-01), Hamprecht
patent: 33 00 914 (1985-01-01), None
patent: 217 232 (1985-01-01), None
patent: 15 44 563 (1985-01-01), None
patent: 29 16 861 (1985-01-01), None
patent: 313 918 (1985-01-01), None
patent: 1 125 683 (1968-08-01), None
patent: 1 479 085 (1977-07-01), None
patent: 2 012 799 (1979-08-01), None
patent: 2 034 736 (1980-06-01), None
patent: 47-25488 (1972-10-01), None
patent: 47-25487 (1972-10-01), None

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