# Patent

## Title
Disperse azo dyestuffs

## Abstract

The present invention claims dyestuffs of formula (I), wherein D, R1 to R7 and n are defined as given in claim 1, a process for their preparation and their use

## Background
RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C. 371) of PCT/EP2004/011590 filed Oct. 15, 2004 which claims benefit to United Kingdom application 0324584.2 filed Oct. 21, 2003.
The present invention relates to the field of disperse dyes.
Disperse dyestuffs containing cyanomethyl ester groups are known from literature and are described for example in GB 909,843, DE-A 2130992, GB 1,457,532, GB 1,536,429, FR-A 1,531,147, U.S. Pat. No. 3,776,898, JP 55161857, GB 2,104,088, EP 0 685 531 A1 and WO 95/20014.
The inventor of the present invention has surprisingly found that dyeings on polyester with very good wet fastness properties can be obtained if selected dyestuffs containing one cyanomethylester group as defined below are used.
The present invention claims dyestuffs of the formula I




wherein

    D is a group of the formula (IIa)






    
    
        wherein
        T1, T2 and T3 are, independently, hydrogen, halogen or nitro;
        T4 is hydrogen, halogen, cyano or nitro;
        wherein at least one of T1, T2, T3 and T4 is not hydrogen;
    
    
    or a group of the formula (IIb)






    
    
        wherein
        T5 is hydrogen or halogen; and
        T6 is hydrogen —SO2CH3, —SCN or nitro;
        wherein at least one of T5 and T6 is not hydrogen;
    
    
    or a group of the formula (IIc)






    or a group of the formula (IId)






    
    
        wherein
        T7 is nitro, —CHO or a group of the formula
    
    






    wherein T10 is —H, halogen, nitro and cyano;
    
        T8 is hydrogen or halogen; and
        T9 is nitro, cyano, —COCH3 or —COOT10, wherein T10 is (C1-C4)-alkyl;
    
    
    or a group of the formula (IIe)






    R1 is hydrogen, (C1-C4)-alkyl or —NCOR6, where R6 is (C1-C4)-alkyl or phenyl;
    R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl;
    R3 is hydrogen or methyl;
    R4 is hydrogen or methyl;
    R5 is hydrogen, methyl or phenyl;
    R7 is hydrogen, chloro, methoxy or ethoxy;
    n is 0, 1 or 2;
    s is 0 or 1;
    with the proviso that
    in the case R1, R3, R4, R5 and R7 are hydrogen and n=0
    D is a group of the formula (IIc), (IId), (IIe) or (IIa) wherein T1 is not nitro
    
        if T2, T3 and T4 are hydrogen,
        if T2 and T3 are hydrogen and T4 is chlorine or cyano and
        if T2 and T4 are hydrogen and T3 is chlorine; and
    
    
    with the further proviso that
    R2 is unsubstituted (C1-C6)-alkyl if R1 is methyl, R3, R4, R5 and R7 are hydrogen and n=0.


Alkyl groups standing for R1, R8 or T10 may be straight-chain or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. The same applies to alkyl groups standing for R2, which can in addition be pentyl or hexyl. Substituted alkyl groups standing for R2 are preferably substituted by hydroxyl, (C1-C4)-alkoxy or halogen.
Halogen standing for T1, T2, T3, T4, T5 or T8 are preferably chlorine or bromine.
Preferred examples for D derive from the following amines:

    2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2-nitroaniline, 2-bromo-4-nitroaniline, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 2-cyano-4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 2-cyano-6-chloro-4-nitroaniline, 2,4-dinitroaniline, 2-chloro-4,6-dinitroaniline, 2-bromo-4,6-dinitroaniline, 2,6-dicyano-4-nitroaniline, 2-cyano-4,6-dinitroaniline, 2-amino-5-nitrothiazole, 2-amino-3,5-dinitrothiophene, 2-amino-3-ethoxycarbonyl-5-nitrothiophene, 2-amino-3-acetyl-5-nitrothiophene, 2-amino-3-cyano-5-nitrothiophene, 2-amino-3-cyano-4-chloro-5-formylthiophene, 7-amino-5-nitrobenzoisothiazole, 2-amino-6-nitrobenzothiazole, 2-amino-6-methylsulphonylbenzothiazole; 2-amino-6-thiocyanatobenzothiazole, 2-amino-5,6-dichlorobenzothiazole and 2-amino-6,7-dichlorobenzothiazole (mixture).


Preferred disperse dyestuffs according to the present invention are of the general formula (Ia)




wherein

    D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
    R1 is (C1-C4)-alkyl;
    R2 is unsubstituted (C1-C6)-alkyl, benzyl or phenylethyl; and
    n is 0, 1 or 2.


In especially preferred dyestuffs of formula (Ia) R1 is methyl, R2 is ethyl and n is 0.
Other preferred disperse dyestuffs according to the present invention are of the general formula (Ib)




wherein

    T3 is bromo or chloro; and
    R2 is unsubstituted (C1-C8)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl;


In especially preferred dyestuffs of formula (Ib) R2 is ethyl, benzyl or phenethyl.
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ic)




wherein

    D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
    R1 is hydrogen, (C1-C4)-alkyl or —NCOR6, where R6 is (C1-C4)-alkyl or phenyl;
    R2 is unsubstituted (C1-C8)-alkyl, substituted (C1-C8)-alkyl, benzyl or phenylethyl; and
    R3 is hydrogen and R4 is methyl or R3 is methyl and R4 is hydrogen.


Still other preferred disperse dyestuffs according to the present invention are of the general formula (Id)




wherein

    D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
    R1 is hydrogen, (C1-C4)-alkyl or —NCOR6, where R6 is (C1-C4)-alkyl or phenyl;
    R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl; and
    R5 is methyl or phenyl;


Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ie)




wherein

    D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
    R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl;
    R6 is (C1-C4)-alkyl or phenyl;
    R7 is chloro, methoxy or ethoxy; and
    n is 0, 1 or 2.


Still other preferred disperse dyestuffs according to the present invention are of the general formula (If)




wherein

    R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl;
    R8 is nitro; and
    n is 0, 1 or 2;


Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ig)




wherein

    D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
    R1 is hydrogen, (C1-C4)-alkyl or —NCOR6, where R6 is (C1-C4)-allyl or phenyl;
    R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl; and
    R3 is hydrogen or methyl.


The compounds of the formula I may be obtained by usual methods for the preparation of azo compounds such as by diazotisation of an amine of the formula III

D-NH2  (III)

wherein D is defined as given above,

and coupling onto a compound of the formula IV





wherein R1, R2, R3, R4, R5 and R7 are defined as given above.

Typically the amine of the formula (III) may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from −10° C. to 10° C. Coupling onto the compound of the formula (IV) may be achieved by adding the diazotised amine to the compound of the formula (IV) under conditions described in literature and known to the skilled persons.
After coupling the compound of the formula (I) may be recovered from the reaction mixture by any convenient means such as filtration.
The compounds of the formulae (III) and (IV) are known and can be obtained by methods described in literature or known to the skilled person.
The compounds of the formula (I) are useful for dyeing and printing of synthetic textile material particularly polyester textile materials and fibre blends thereof with for example cellulosic materials like cotton, to which they impart colours which have excellent wet fastness properties.
Dyeing of the fibre goods mentioned with the dyestuffs of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions, if appropriate in the presence of carriers, at between 80 and 110° C., by the exhaust process or by the HT process in a dyeing autoclave at 110 to 140° C., and by the so-called thermofixing process, in which the goods are padded with the dye liquor and then fixed at about 180 to 230° C.
The fibre goods mentioned can as well be printed in a manner known per se by a procedure in which the dyestuffs of the formula (I) are incorporated into a printing paste and the goods printed with the paste are treated, if appropriate in the presence of a carrier, with HT steam, pressurized steam or dry heat at temperatures between 180 and 230° C. to fix the dyestuff.
The dyestuffs of the formula (I) should be present in the finest possible dispersion in the dye liquors and printing pastes employed in the above applications.
The fine dispersion of the dyestuffs is effected in a manner known per se by a procedure in which the dyestuff obtained during preparation is suspended in a liquid medium, preferably in water, together with dispersing agents and the mixture is exposed to the action of shearing forces, the particles originally present being comminuted mechanically to the extent that an optimum specific surface area is achieved and sedimentation of the dyestuff is as low as possible. The particle size of the dyestuffs is in general between 0.5 and 5 m, preferably about 1 m.
The dispersing agents used can be nonionic or anionic. Nononic dispersing agents are, for example, reaction products of alkylene oxides, such as, for example, ethylene oxide or propylene oxide, with alkylatable compounds, such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines. Anionic dispersing agnets are, for example, lignin-sulphonates, alkyl- or alkylarylsulphonates or alkylaryl polyglycol ethersulphates. For most methods of use, the dyestuff formulations thus obtained should be pourable. The dyestuff and dispersing agent content is therefore limited in these cases. In general, the dispersions are brought to a dyestuff content of up to 50 percent by weight and a dispersing agent content of up to 25 percent by weight. For economic reasons, the dyestuff contents usually do not fall below 15 percent by weight.
The dispersions can also comprise other auxiliaries, for example those which act as oxidizing agents or fungicidal agents. Such agents are well known in the art. The dyestuff dispersion thus obtained can be used very advantageously for the preparation of printing pastes and dye liquors.
For certain fields of use, powder formulations are preferred. These powders comprise the dyestuff, dispersing agents and other auxiliaries, such as, for example, wetting agents, oxidizing agents, preservatives and dust removal agents.
A preferred preparation process for pulverulent dyestuff formulations comprises removing the liquid from the liquid dyestuff dispersions described above, for example by vacuum drying, freeze drying, by drying on roller dryers, but preferably by spray drying.


EXAMPLE 1
4-(4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-cyanomethoxy-carbonylethyl)aniline




4-nitroaniline (4.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (11.4 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution obtained was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (7.3 parts), methanol (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl)aniline (6.5 parts) λmax=486 nm (acetone).
When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.
The following examples of dyes of formula (Iaa):




were prepared by the procedure of Example 1 (see Table 1)














TABLE 1











λmax


Example
T11
T12
T13
T14
R8
(nm)





















2
—H
—H
—NO2
—H
—C2H5
479


3
—H
—NO2
—H
—H
—C2H5
468


4
—NO2
—H
—Cl
—H
—C2H5
508


5
—Cl
—H
—NO2
—H
—C2H5
501


6
—NO2
—H
—Br
—H
—C2H5
507


7
—NO2
—H
—Cl
—Cl
—C2H5
450


8
—NO2
—H
—Br
—Br
—C2H5
449


9
—NO2
—H
—Cl
—Br
—C2H5
449


10
—NO2
—Cl
—H
—Cl
—C2H5
518


11
—NO2
—H
—CN
—H
—C2H5
534


12
—NO2
—H
—CN
—Br
—C2H5
544


13
—NO2
—H
—CN
—Cl
—C2H5
545


14
—NO2
—H
—NO2
—H
—C2H5
535


15
—NO2
—H
—Br
—NO2
—C2H5
542


16
—NO2
—H
—Cl
—NO2
—C2H5
544


17
—NO2
—H
—CN
—CN
—C2H5
582


18
—NO2
—H
—CN
—NO2
—C2H5
590


19
—NO2
—H
—H
—H
—C4H9
490


20
—NO2
—H
—Cl
—H
—C4H9
513


21
—NO2
—H
—Cl
—Cl
—C4H9
453


22
—NO2
—H
—Cl
—Br
—C4H9
453


23
—NO2
—H
—Br
—Br
—C4H9
452


24
—NO2
—H
—CN
—H
—C4H9
539


25
—NO2
—H
—NO2
—H
—C4H9
540


26
—NO2
—H
—CN
—Br
—C4H9
549


27
—NO2
—H
—CN
—Cl
—C4H9
548


28
—NO2
—H
—Br
—NO2
—C4H9
548


29
—NO2
—H
—Cl
—NO2
—C4H9
549


30
—H
—H
—NO2
—H
—C4H9
483


31
—NO2
—H
—CN
—CN
—C4H9
586


32
—NO2
—H
—H
—H
—CH2[C6H5]
479


33
—NO2
—H
—NO2
—H
—CH2[C6H5]
530


34
—H
—H
—NO2
—H
—CH2[C6H5]
470


35
—H
—NO2
—H
—H
—CH2[C6H5]
460


36
—NO2
—H
—Cl
—H
—CH2[C6H5]
498


37
—NO2
—H
—Cl
—Cl
—CH2[C6H5]
446


38
—NO2
—H
—Br
—Br
—CH2[C6H5]
445


39
—NO2
—H
—Br
—Cl
—CH2[C6H5]
444


40
—NO2
—H
—CN
—H
—CH2[C6H5]
528


41
—NO2
—H
—CN
—Br
—CH2[C6H5]
539


42
—NO2
—H
—CN
—Cl
—CH2[C6H5]
539


43
—NO2
—H
—Br
—NO2
—CH2[C6H5]
538


44
—NO2
—H
—Cl
—NO2
—CH2[C6H5]
537


45
—NO2
—H
—CN
—NO2
—CH2[C6H5]
580


46
—NO2
—H
—CN
—CN
—CH2[C6H5]
577


47
—NO2
—H
—H
—H
—C3H7
487


48
—NO2
—H
—Cl
—H
—C3H7
509


49
—NO2
—H
—Cl
—Cl
—C3H7
452


50
—NO2
—H
—Cl
—Br
—C3H7
451


51
—NO2
—H
—Br
—Br
—C3H7
452


52
—NO2
—H
—CN
—H
—C3H7
536


53
—NO2
—H
—NO2
—H
—C3H7
537


54
—NO2
—H
—CN
—Br
—C3H7
546


55
—NO2
—H
—CN
—Cl
—C3H7
548


56
—NO2
—H
—Br
—NO2
—C3H7
544


57
—NO2
—H
—Cl
—NO2
—C3H7
545


58
—H
—H
—NO2
—H
—C3H7
480


59
—NO2
—H
—CN
—CN
—C3H7
584


60
—NO2
—H
—Cl
—H
—CH3
504


61
—NO2
—H
—CN
—H
—CH3
529


62
—NO2
—H
—Cl
—CN
—CH3
543


63
—NO2
—H
—Br
—CN
—CH3
542


64
—NO2
—H
—Br
—NO2
—CH3
539









EXAMPLE 65
4-(2,6-dichloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxy-carbonylethyl) aniline




2,6-dichloro-4-nitroaniline (6.2 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (11.4 parts) was added below 5° C. and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2(cyanomethoxycarbonylethyl)-aniline (8.3 parts), methanol (50 parts), water (300 parts) and sulphamic acid (1 part). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(2,6-dichloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylethyl)aniline (9.5 parts) λmax=432 nm (acetone).
When applied to polyester materials from aqueous dispersion, yellow brown shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iba)




were prepared by the procedure of Example 65 (see Table 2)












TABLE 2









λmax


Example
T15
T16
R9
(nm)







66
—Cl
—Cl
—C3H7
433


67
—Cl
—Cl
—C4H9
434


68
—Cl
—Cl
—CH2[C6H5]
420


69
—Cl
—Cl
—CH3
425


70
—Cl
—Br
—C2H5
430


71
—Cl
—Br
—C3H7
431


72
—Cl
—Br
—C4H9
433


73
—Cl
—Br
—CH2[C6H5]
420


74
—Cl
—Br
—CH3
424


75
—Br
—Br
—C2H5
430


76
—Br
—Br
—C3H7
432


77
—Br
—Br
—C4H9
431


78
—Br
—Br
—CH2[C6H5]
421


79
—Br
—Br
—CH3
424









EXAMPLE 80
4-(6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline




2-amino-6-nitrobenzothiazole (3.9 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (7.6 parts) was added below 5° C. and the mixture was stirred for 1 hour. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (5.9 parts), methanol (25 parts), water (200 parts) and sulphamic acid (0.5 parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl ethyl)aniline (2.4 parts) λmax=545 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iab):




were prepared by the procedure of Example 80 (see Table 3)













TABLE 3





Example
T17
T18
R10
R11
λmax nm




















81
—SO2CH3
—H
—CH3
—CH3
527


82
—NO2
—H
—CH3
—CH3
543


83
—NO2
—H
—CH3
—C3H7
545


84
—NO2
—H
—CH3
—C4H9
548


85
—NO2
—H
—CH3
—CH2[C6H5]
538


86
—Cl
—Cl
—CH3
—C2H5
526


87
—Cl
—Cl
—CH3
—CH3
522


88
—Cl
—Cl
—CH3
—C3H7
528


89
—Cl
—Cl
—CH3
—C4H9
530


90
—Cl
—Cl
—CH3
—CH2[C6H5]
521


91
—SO2CH3
—H
—CH3
—C3H7
531


92
—SO2CH3
—H
—CH3
—C4H9
533


93
—SO2CH3
—H
—CH3
—CH2[C6H5]
525


94
—SCN
—H
—CH3
—C2H5
534


95
—SCN
—H
—CH3
—CH3
530


96
—SCN
—H
—CH3
—C3H7
535


97
—SCN
—H
—CH3
—C4H9
537


98
—SCN
—H
—CH3
—CH2[C6H5]
529


99
—NO2
—H
—H
—C4H9
535


100
—NO2
—H
—H
—CH2[C6H5]
525


101
—SCN
—H
—H
—C4H9
523


102
—SCN
—H
—H
—CH2[C6H5]
516


103
—Cl
—Cl
—H
—C4H9
519


104
—Cl
—Cl
—H
—CH2[C6H5]
509


105
—SO2CH3
—H
—H
—C4H9
521


106
—SO2CH3
—H
—H
—CH2[C6H5]
512









EXAMPLE 107
4-(3,5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline




2-amino-3,5-dinitrothiophene (3.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts) Nitrosyl sulphuric acid 40% (5.7 parts) was added below 5° C. and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonyethyl)-m-toluidine (4.0 parts), acetone (50 parts), water (300 parts) and sulphamic acid (0.5 parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(3,5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl-ethyl)aniline (3.0 parts) λmax=640 nm (acetone).
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iac):




were prepared by the procedure of Example 107 (see Table 4)














TABLE 4





Ex-





λmax


ample
T19
T20
T21
R12
R13
(nm)





















108
—NO2
—NO2
—H
—H
—C2H5
620


109
—NO2
—NO2
—H
—H
—C4H9
625


110
—NO2
—NO2
—H
—H
—C3H7
622


111
—NO2
—NO2
—H
—H
—CH2[C6H5]
611


112
—NO2
—NO2
—H
—CH3
—C4H9
645


113
—NO2
—NO2
—H
—CH3
—C3H7
640


114
—NO2
—NO2
—H
—CH3
—CH2[C6H5]
632


115
—COOC2H5
—NO2
—H
—CH3
—C2H5
595


116
—COOC2H5
—NO2
—H
—H
—C4H9
583


117
—COCH3
—NO2
—H
—CH3
—C2H5
599


118
—COCH3
—NO2
—H
—CH3
—C4H9
603


119
—COCH3
—NO2
—H
—H
—C4H9
585


120
—CN
—NO2
—H
—CH3
—C2H5
604


121
—CN
—NO2
—H
—CH3
—CH2[C6H5]
595


122
—CN
—CHO
—Cl
—CH3
—C2H5
585


123
—CN
—CHO
—Cl
—CH3
—C4H9
591


124
—CN
—CHO
—Cl
—H
—C4H9
579


125
—COOC2H5
—NO2
—H
—H
—CH2[C6H5]
565


126
—COOC2H5
—NO2
—H
—CH3
—C4H9
601









EXAMPLE 127
4-(5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl)aniline




7-amino-5-nitrobenzoisothiazole (2.9 parts) was added to a mixture of sulphuric acid 98% (15 parts) and phosphoric acid (4 parts) stirring at room temperature. The mixture was heated to 55° C. and was stirred at that temperature for 30 mins. Nitrosyl sulphuric acid 40% (6.1 parts) was added below 5° C. and the mixture was stirred for 2 hrs.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (4.8 parts), acetone (50 parts), water (100 parts) and sulphamic acid (0.5 parts). Sodium acetate was added to increase the pH to 4.0 and the mixture was stirred for 1 hour. The product was isolated by filtration, washed with cold water and dried to yield, 4-(5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl)aniline (2.4 parts) λmax=601 nm (acetone).
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iad)




were prepared by the procedure of Example 127 (see Table 5)











TABLE 5








λmax


Example
R14
R15
(nm)







128
—H
—C2H5
588


129
—H
—CH2[C6H5]
578


130
—H
—C4H9
589


131
—CH3
—C3H7
603


132
—CH3
—CH2[C6H5]
593


133
—CH3
—C4H9
608









EXAMPLE 134
4-(5-nitrothiazol-yl-azo)-N-butyl-N-(2-cyanomethoxy-carbonylethyl)aniline




2-amino-5-nitrothiazole (2.9 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (7.0 parts) was added below 5° C. and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-butyl, N-2(cyanomethoxycarbonylethyl)-aniline (5.2 parts), acetone (50 parts), water (200 parts) and sulphamic acid (0.5 parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(5-nitrothiazol-yl-azo)-N-butyl-N-(2-cyanomethoxycarbonylethyl)aniline (2.9 parts) λmax=571 nm (acetone).
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iae)




were prepared by the procedure of Example 134 (see Table 6)











TABLE 6








λmax


Example
R16
R17
(nm)







135
—H
—CH2[C6H5]
557


136
—CH3
—C2H5
575


137
—CH3
—C4H9
582


138
—CH3
—CH2[C6H5]
569









EXAMPLE 139
4-(2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2-cyanomethoxycarbonylethyl)-aniline




2-chloro-4-nitroaniline (3.5 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (7.0 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of 3(N-ethyl, N-cyanomethoxycarbonylethyl)-amino-acetanilide (6.3 parts), methanol (40 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2-cyanomethoxy-carbonylethyl)-aniline (4.1 parts) λmax=525 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of formula (Iea):




were prepared by the procedure of Example 139 (see Table 7)













TABLE 7










λmax


Example
D′
R18
R19
R20
(nm)







140




—CH3
—H
—C2H5
550


 


141








—H
—C2H5
553


 


142




—CH3
—H
—C4H9
552


 


143




—C2H5
—H
—C2H5
550


 


144




—CH3
—OCH3
—C2H5
596


 


145




—CH3
—OCH3
—C4H9
603


 


146








—OCH3
—H
600


 


147




—C2H5
—OCH3
—C2H5
596


 


148




—CH3
—H
—C4H9
551


 


149




—CH3
—H
—C2H5
574


 


150




—C2H5
—H
—C2H5
550


 


151




—CH3
—H
—C4H9
525


 


152




—CH3
—OCH3
—C2H5
628check


 


153




—CH3
—H
—C2H5
539


 


154




—CH3
—OCH3
—C2H5
574


 


155




—CH3
—H
—C2H5
634


 


156




—CH3
—OCH3
—C2H5
660









EXAMPLE 157
4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(4-cyanomethoxycarbonylbutyl)-aniline




2-cyano-4-nitroaniline (3.2 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (7.6 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(4-cyanomethoxycarbonylbutyl)-m-toluidine (6.0 parts), methanol (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(4-cyanomethoxycarbonylbutyl)-aniline. (5.3 parts) λmax=548 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iaf)




were prepared by the procedure of Example 157 (see Table 8)













TABLE 8





Ex-




λmax


ample
D′′
R21
R22
n
(nm)







158




—H
—C2H5
4
491


 


159




—H
—C2H5
3
486


 


160




—CH3
—C2H5
4
649


 


161




—CH3
—C2H5
3
642


 


162




—CH3
—C2H5
4
561


 


163




—CH3
—C2H5
3
556


 


164




—CH3
—C3H7
3
558


 


165




—CH3
—C2H5
4
535


 


166




—CH3
—C2H5
4
548


 


167




—CH3
—C2H5
3
536


 


168




—H
—C2H5
4
529









EXAMPLE 169
4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1-cyanoethoxy) carbonylethyl)-aniline




2-cyano-4-nitroaniline (2.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (4.9 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1-cyanoethoxy)carbonylethyl)-m-toluidine (3.7 parts), acetone (50 parts), water (300 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1-cyanoethoxy)carbonylethyl)-aniline (3.5 parts) λmax=534 nm (acetone).
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ida)




were prepared by the procedure of Example 169 (see Table 9)













TABLE 9










λmax


Example
D′′′
R23
R24
R25
(nm)







170




—CH3
—C2H5




533


 


171




—CH3
—C2H5




544


 


172




—CH3
—C2H5




507


 


173




—CH3
—C2H5




446


 


174




—CH3
—C2H5




580


 


175




—H
—C2H5




523


 


176




—H
—C2H5




494


 


177




—H
—C2H5
—CH3
522


 


178




—H
—C2H5
—CH3
473


 


179




—H
—C4H9
—CH3
480


 


180




—H
—C2H5
—CH3
494


 


181




—H
—C2H5
—CH3
439


 


182




—H
—C4H9
—CH3
441


 


183




—H
—C2H5
—CH3
521


 


184




—H
—C2H5
—CH3
533


 


185




—H
—C2H5
—CH3
590


 


186




—CH3
—C2H5
—CH3
449


 


187




—CH3
—C2H5
—CH3
544


 


188




—CH3
—C2H5
—CH3
581


 


189




—CH3
—C2H5
—CH3
544


 


190




—CH3
—C2H5
—CH3
533


 


191




—CH3
—C2H5
—CH3
601


 


192




—CH3
—C2H5
—CH3
506


 


193




—H
—C2H5
—CH3
640









EXAMPLE 194
4-(2-chloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylpropyl)-aniline




2-chloro-4-nitroaniline (parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (4.9 parts) was added below 5° C. and the mixture The diazo solution was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2-(cyanomethoxycarbonylpropyl)-aniline (parts), acetone (50 parts), water (300 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-chloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylpropyl)-aniline (3.5 parts) λmax=534 nm (acetone).
When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ica)




were prepared by the procedure of Example 194 (see Table 10)













TABLE 10










λmax


Example
D′′′′
R26
R27
R28
(nm)







195




—H
—H
—CH3
521


 


196




—H
—H
—CH3
473


 


197




—H
—H
—CH3
440


 


198




—H
—H
—CH3
521


 


199




—H
—H
—CH3
569


 


200




—CH3
—H
—CH3
505


 


201




—CH3
—H
—CH3
448


 


202




—CH3
—H
—CH3
532


 


203




—CH3
—H
—CH3
541


 


204




—CH3
—H
—CH3
579


 


205




—CH3
—H
—CH3
525


 


206




—CH3
—H
—CH3
541


 


207




—CH3
—H
—CH3
599


 


208




—H
—H
—CH3
588


 


209




—CH3
—CH3
—H
535


 


210




—CH3
—CH3
—H
544


 


211




—CH3
—CH3
—H
594


 


212




—CH3
—CH3
—H
549









EXAMPLE 213
4-(4-nitrophenylazo)-N-ethyl-N-(2-(1-cyanoethoxy)carbonylpropyl)-aniline




4-nitroaniline (2.0 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (50 parts). Nitrosyl sulphuric acid 40% (5.7 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1-cyanoethoxy)carbonylpropyl)-aniline (4.7 parts), acetone (50 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(4-nitrophenylazo)-N-ethyl-N-(2-(1-cyanoethoxy)carbonylpropyl)-aniline (2.9 parts) λmax=473 nm (acetone).
When applied to polyester materials from aqueous dispersion, scarlet shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ih):




were prepared by the procedure of Example 213 (see Table 11)













TABLE 11





Ex-




λmax


ample
D′′′′′
R29
R30
R31
(nm)







214




—H
—CH3
—CH3
519


 


215




—CH3
—CH3
—CH3
504


 


216




—CH3
—CH3
—CH3
531


 


217




—CH3
—CH3
—CH3
537


 


218




—CH3
—CH3
—CH3
597


 


219




—H
—CH3
—CH3
517


 


220




—H
—CH3
—CH3
428


 


221




—H
—CH3
—CH3
428


 


222




—CH3
—CH3
—CH3
449


 


223




—CH3
—CH3
—CH3
539


 


224




—CH3
—CH3
—CH3
524









EXAMPLE 225
4-(2-cyano-4-nitrophenylazo)-N-ethyl-N-(1-cyanomethoxycarbonylethyl)-m-toluidine




2-cyano-4-nitroaniline (3.1 parts) was set stirring at 5° C. with a mixture of acetic acid and propionic acid, 86:14 (40 parts). Nitrosyl sulphuric acid 40% (6.6 parts) was added below 5° C. and the mixture was stirred for 30 minutes.
The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(1-cyanomethoxycarbonylethyl)-m-toluidine (4.1 parts), methanol (40 parts), water (200 parts) and sulphamic acid (1 part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4-nitrophenylazo)-N-ethyl-N-(1-cyanomethoxycarbonylethyl)-m-toluidine (3.9 parts) λmax=510 nm (acetone).
When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.

## Claims

1. Dyestuff of the formula I




wherein
D is a group of the formula (IIa)





wherein
T1, T2 and T3 are, independently, hydrogen, halogen or nitro;
T4 is hydrogen, halogen, cyano or nitro;
wherein at least one of T1, T2, T3 and T4 is not hydrogen;
or a group of the formula (IIb)





wherein
T5 is hydrogen or halogen; and
T6 is hydrogen, —SO2CH3, —SCN or nitro;
wherein at least one of T5 and T6 is not hydrogen;
or a group of the formula (IIc)




or a group of the formula (IId)





wherein
T7 is nitro, —CHO or a group of the formula





wherein T10 is —H, halogen, nitro and cyano;
T8 is hydrogen or halogen; or
T9 is nitro, cyano, —COCH3 or —COOT10′, wherein T10′ is (C1-C4)-alkyl;
or a group of the formula (IIe)




R1 is hydrogen, (C1-C4)-alkyl or —NHCOR6, where R6 is (C1-C4)-alkyl or phenyl;
R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl and wherein said substituted (C1-C6)-alkyl is substituted by hydroxyl, (C1-C4)-alkoxy or halogen;
R3 is hydrogen or methyl;
R4 is hydrogen or methyl;
R5 is hydrogen, methyl or phenyl;
R7 is hydrogen, chloro, methoxy or ethoxy;
n is 0, 1 or 2;
s is 0 or 1;
with the proviso that
in the case R1, R3, R4, R5 and R7 are hydrogen and n=0
D is a group of the formula (IIc), (IId), (IIe) or (IIa) wherein T1 is not nitro
if T2, T3 and T4 are hydrogen,
if T2 and T3 are hydrogen and T4 is chlorine or cyano and
if T2 and T4 are hydrogen and T3 is chlorine; and

with the further proviso that

in the case R1 is methyl, R3, R4, R5 and R7 are hydrogen and n=0 then
R2 is unsubstituted (C1-C6)-alkyl.

2. Dyestuff according to claim 1 of the formula (Ia)




wherein
D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
R1 is (C1-C4)-alkyl;
R2 is unsubstituted (C1-C6)-alkyl, benzyl or phenylethyl; and
n is 0, 1 or 2.

3. Dyestuff according to claim 1 of the formula (Ib)




wherein
T3′ is bromo or chloro; and
R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl and wherein said substituted (C1-C6)-alkyl is substituted by hydroxyl, (C1-C4)-alkoxy or halogen.

4. Dyestuff according to claim 1 of the formula (Ic)




wherein
D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
R1 is hydrogen, (C1-C4)-alkyl or —NHCOR6, where R6 is (C1-C4)-alkyl or phenyl;
R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl and wherein said substituted (C1-C6)-alkyl is substituted by hydroxyl, (C1-C4)-alkoxy or halogen; and
R3 is hydrogen and R4 is methyl or R3 is methyl and R4 is hydrogen.

5. Dyestuff according to claim 1 of the formula (Id)




wherein
D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
R1 is hydrogen, (C1-C4)-alkyl or —NHCOR6, where R6 is (C1-C4)-alkyl or phenyl;
R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl and wherein said substituted (C1-C6)-alkyl is substituted by hydroxyl, (C1-C4)-alkoxy or halogen; and
R5 is methyl or phenyl.

6. Dyestuff according to claim 1 of the formula (Ie)




wherein
D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl and wherein said substituted (C1-C6)-alkyl is substituted by hydroxyl, (C1-C4)-alkoxy or halogen;
R6 is (C1-C4)-alkyl or phenyl;
R7 is chloro, methoxy or ethoxy; and
n is 0, 1 or 2.

7. Dyestuff according to claim 1 of the formula (If)




wherein
R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl and wherein said substituted (C1-C6)-alkyl is substituted by hydroxyl, (C1-C4)-alkoxy or halogen;
R8 is nitro; and
n is 0, 1 or 2.

8. Dyestuff according to claim 1 of the formula (Ig)




wherein
D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe);
R1 is hydrogen, (C1-C4)-alkyl or —NHCOR6, where R6 is (C1-C4)-alkyl or phenyl;
R2 is unsubstituted (C1-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl and wherein said substituted (C1-C6)-alkyl is substituted by hydroxyl, (C1-C4)-alkoxy or halogen; and
R3 is hydrogen or methyl.

9. Process for the preparation of a dyestuff as claimed in claim 1, which comprises diazotizing an amine of the formula III


D-NH2  (III)


wherein D is a group of the formulae (IIa), (IIb), (IIc), (IId) or (IIe),
and coupling onto a compound of the formula IV





wherein R1, R2, R3, R4, R5 and R7 are defined in claim 1.

10. A process for dyeing and printing of synthetic textile material and fibre blends thereof which comprises contacting the dyestuff as claimed in claim 1 with the material.