# Patent

## Title
Disperse dyes, their preparation and their use

## Abstract

The present invention provides dyes of the general formula (I)




where D, R1 to R7 and n are each as defined in claim 1, processes for their preparation and their use.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2007/061002, filed Oct. 16, 2007, which claims benefit of German application 10 2006 050642.1, filed Oct. 27, 2006.
BACKGROUND OF THE INVENTION
The present invention relates to disperse azo dyes in which a 2-oxoalkyl ester is linked to the chromophore. Dyes having this structural element are already known and described for example in GB 909843, WO95/20014 and WO05/056690. It has now been found that disperse azo dyes in which the structural element in question is linked to further selected structural elements in a certain manner have excellent properties and provide dyeings having excellent wash fastnesses and very good sublimation fastnesses.
BRIEF SUMMARY OF THE INVENTION
The invention relates to a dye of the formula (I)




where

    D is the radical of a diazo component;
    R1 is hydrogen, (C1-C6)-alkyl, (C1-C4)-alkoxy, hydroxyl, halogen, —NHCHO, —NHCO(C1-C6)-alkyl, —NHCOaryl, —NHSO2(C1-C6)-alkyl or —NHSO2aryl;
    R2 is hydrogen, (C1-C6)-alkyl, (C1-C4)-alkoxy, phenoxy or halogen;
    R3 is hydrogen, (C1-C6)-alkyl, substituted (C1-C6)-alkyl, (C3-C4)-alkenyl or substituted (C3-C4)-alkenyl;

or R2 and R3 combine to form the radical —C*H(CH3)CH2C(CH3)2—, where the carbon atom marked by * is attached to the phenyl nucleus;

    R4 is hydrogen, (C1-C6)-alkyl or phenyl;
    R5 is (C1-C6)-alkyl or substituted (C1-C6)-alkyl;
    R6 is hydrogen or (C1-C6)-alkyl;
    R7 is hydrogen, (C1-C6)-alkyl or phenyl; and
    n 0, 1, 2 or 3;

although the compounds of the formulae







shall be excluded. The invention also relates to the process to make the dye and the process of using the dye.

DETAILED DESCRIPTION OF THE INVENTION
D radicals of a diazo component are in particular those customary in the field of disperse dyes and known to one skilled in the art.
Preferably, D represents a group of the formula (IIa)




where

    T1 and T2 independently are hydrogen, (C1-C6)-alkyl, (C1-C4)-alkoxy, —SO2(C1-C6)-alkyl, —SO2aryl, cyano, halogen or nitro; and
    T4 and T3 independently are hydrogen, halogen, trifluoromethyl, cyano, —SCN, —SO2CH3 or nitro;

although at least one of T1, T2, T3 and T4 is not hydrogen;

or represents a group of the formula (IIb)







where

    T5 and T5′ independently are hydrogen or halogen; and
    T6 is hydrogen, —SO2CH3, —SCN, (C1-C4)-alkoxy, halogen or nitro;

although at least one of T5, T5′ and T6 is not hydrogen;

or represents a group of the formula (IIc)







where

    T12 is hydrogen or halogen;

or represents a group of the formula (IId)







where

    T7 is nitro, —CHO, cyano, —COCH3 or a group of the formula






    where T10 is hydrogen, halogen, nitro or cyano;
    T8 is hydrogen, (C1-C6)-alkyl or halogen; and
    T9 is nitro, cyano, —COCH3 or —COOT11; where T11 is (C1-C4)-alkyl;

or represents a group of the formula (IIe)







where T7 and T8 are each as defined above;

or represents a group of the formula (IIf)





where T13 is phenyl or S—(C1-C4)-alkyl.

(C1-C6)-Alkyl groups may be straight chain or branched and are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or n-hexyl. A similar logic applies to alkoxy groups, which are methoxy or ethoxy for example. (C3-C4)-Alkenyl groups are in particular allyl.
Substituted (C1-C6)-alkyl and (C3-C4)-alkenyl groups are in particular substituted by 1 to 3 substituents from the group consisting of halogen, cyano, hydroxyl, (C1-C6)-alkoxy, —COO(C1-C6)-alkyl, —COOaryl, —OCOO(C1-C6)-alkyl, —OCOOaryl, —OCO(C1-C6)-alkyl, phenyl, —OCOphenyl and phenoxy.
Aryl is in particular phenyl or naphthyl, —NHSO2aryl is in particular phenylsulfonylamino. Halogen preferably represents chlorine or bromine.
R1 is preferably hydrogen, chlorine, methyl, ethyl, hydroxyl, methoxy, ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino or phenylsulfonylamino.
R2 is preferably hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy.
R3 is preferably hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C2H4OCOCH3, —C2H4OCOC2H5, —C2H4COOCH3, —C2H4COOC2H5 or allyl.
R4 and R7 are each preferably hydrogen, methyl or phenyl, more preferably hydrogen. R6 is preferably hydrogen or methyl.
R5 is preferably methyl or ethyl.
n is preferably 0 or 1, more preferably 0.
Preferred dyes according to the present invention conform to the general formula (Ia)




where T1 to T4, R1 to R7 and n are each as defined above, but the compounds of the formulae





shall be excluded.

In preferred dyes of the general formula (Ia), R3 is not ethyl when R1 is hydrogen and n=0. In further preferred dyes of the general formula (Ia), R3 is not n-propyl or n-butyl when R1 is —NHCOCH3 and n=0.
In particularly preferred dyes of the general formula (Ia),

    R1 is acetylamino, propionylamino, benzoylamino or methylsulfonylamino;
    R2 is hydrogen, chlorine, methoxy or ethoxy;
    R3 is hydrogen, methyl, ethyl, allyl or benzyl;
    R4 is hydrogen or methyl;
    R5 methyl or ethyl;
    R6 is hydrogen or methyl and
    R7 is hydrogen, methyl or phenyl.


Particularly preferred dyes of the general formula (Ia) according to the present invention conform to the general formula (Iaa)




where

    T1 is hydrogen, nitro or methyl;
    T2 is hydrogen, nitro or chlorine;
    T3 is hydrogen, cyano, chlorine or bromine;
    T4 is hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;
    R1 is hydrogen, hydroxyl, chlorine, methyl, acetylamino, propionylamino, benzoylamino or methylsulfonylamino;
    R2 is hydrogen, chlorine, methyl, phenoxy, methoxy or ethoxy;
    R3 is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl, phenoxyethyl or allyl;
    R5 is methyl or ethyl; and
    R4 and R7 are hydrogen, methyl or phenyl;

although the compounds of the formulae







shall be excluded.

In preferred dyes of the general formula (Iaa), R3 is not ethyl when R1 is hydrogen. In further preferred dyes of the general formula (Ia), R3 is not n-propyl or n-butyl when R1 is —NHCOCH3.
Further preferred dyes according to the present invention conform to the general formula (Ib)




where T12, R1 to R7 and n are each as defined above.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Iba)




where

    T12 is hydrogen, chlorine or bromine;
    R1 is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
    R2 is hydrogen, methyl, chlorine or methoxy;
    R3 is hydrogen, ethyl, butyl, benzyl or allyl; and
    R5 is methyl or ethyl.


Further preferred dyes according to the present invention conform to the general formula (Ic)




where T5, T5′, T6, R1 to R7 and n are each as defined above.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Ica)




where

    T5 and T5′ independently are hydrogen or halogen;
    T6 is halogen or nitro;
    R1 is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
    R2 is hydrogen, methyl, chlorine or methoxy;
    R3 is hydrogen, ethyl, butyl, benzyl or allyl; and
    R5 is methyl or ethyl.


Further preferred dyes according to the present invention conform to the general formula (Id)




where T7 to T9, R1 to R7 and n are each as defined above.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Ida)




where

    T7 is nitro, —CHO or cyano;
    T8 is hydrogen, methyl or chlorine;
    T9 is nitro, cyano or —COCH3;
    R1 is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
    R2 is hydrogen, methyl, chlorine or methoxy;
    R3 is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl; and
    R5 is methyl or ethyl.


Further particularly preferred dyes of this type according to the present invention conform to the general formula (Idb)




where

    T10 is nitro;
    T9 is cyano or —COCH3;
    1 is hydrogen, methyl or acetylamino;
    3 is methyl, ethyl, butyl or allyl; and
    R5 methyl or ethyl.


Further preferred dyes according to the present invention conform to the general formula (Ie)




where T7, T8, R1 to R7 and n are each as defined above and T7 is in particular nitro, —CHO, COCH3 or cyano.

Particularly preferred dyes of this type according to the present invention conform to the general formula (Iea)




where

    T7 is nitro, —CHO or cyano;
    T8 is hydrogen or chlorine;
    R1 is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
    R2 is hydrogen, methyl, chlorine or methoxy;
    R3 is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl; and
    R5 is methyl or ethyl.


Further preferred dyes according to the present invention conform to the general formula (If)




where

    T13, R1 to R7 and n are each as defined above.


Particularly preferred dyes of this type according to the present invention conform to the general formula (Ifa)




where

    R1 is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;
    R2 is hydrogen, methyl, chlorine or methoxy;
    R3 is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl; and
    R5 is methyl or ethyl.


The dyes of the general formula (I) according to the present invention are obtainable using methods known to one skilled in the art.
For instance, a compound of the general formula (III)

D-NH2  (III)

where D is as defined above, is diazotized and coupled onto a compound of the general formula (IV)





where R1 to R7 and n are each as defined above.

The diazotizing of the compounds of the general formula (III) is generally effected in a known manner, for example using sodium nitrite in an aqueous medium rendered acidic, for example with hydrochloric or sulfuric acid, or using nitrosylsulfuric acid in dilute sulfuric acid, phosphoric acid or in a mixture of acetic acid and propionic acid. The preferred temperature range is between 0° C. and 15° C.
The coupling of the diazotized compounds onto the compounds of the general formula (IV) is generally likewise effected in a known manner, for example in an acidic, aqueous, aqueous-organic or organic medium, particularly advantageously at temperatures below 10° C. Acids used are in particular sulfuric acid, acetic acid or propionic acid.
The compounds of the general formulae (III) and (IV) are known and can be prepared by known methods.
The present invention's dyes of the general formula (I) are very useful for dyeing and printing hydrophobic materials, the dyeings and prints obtained being notable for level hues and high service fastnesses. Deserving of particular mention are excellent wash fastnesses and very good sublimation fastnesses.
The present invention thus also provides for the use of the dyes of the general formula I for dyeing and printing hydrophobic materials, i.e., processes for dyeing or printing such materials in a conventional manner wherein one or more dyes of the general formula (I) according to the present invention are used as a colorant.
The hydrophobic materials mentioned may be of synthetic or semisynthetic origin. Useful hydrophobic materials include for example secondary cellulose acetate, cellulose triacetate, polyamides and, in particular, high molecular weight polyesters. Materials of high molecular weight polyester are in particular those based on polyethylene glycol terephthalates.
The hydrophobic synthetic materials can be present in the form of sheet- or threadlike constructions and can have been processed, for example, into yarns or into woven or knit textile materials. Preference is given to fibrous textile materials, which may also be present in the form of microfibers for example.
The dyeing in accordance with the use provided by the present invention can be carried out in a conventional manner, preferably from an aqueous dispersion, if appropriate in the presence of carriers, at between 80 to about 110° C. by the exhaust process or by the HT process in a dyeing autoclave at 110 to 140° C., and also by the so-called thermofix process, in which the fabric is padded with the dyeing liquor and subsequently fixed/set at about 180 to 230° C.
Printing of the materials mentioned can be carried out in a manner known per se by incorporating the dye of the general formula (I) of the present invention in a print paste and treating the fabric printed therewith at temperatures between 180 to 230° C. with HT steam, high-pressure steam or dry heat, if appropriate in the presence of a carrier, to fix the dye.
The dyes of the general formula (I) of the present invention shall be in a very fine state of subdivision when they are used in dyeing liquors, padding liquors or print pastes.
The dyes are converted into the fine state of subdivision in a conventional manner by slurrying the as-fabricated dye together with dispersants in a liquid medium, preferably in water, and subjecting the mixture to the action of shearing forces to mechanically comminute the original dye particles to such an extent that an optimal specific surface area is achieved and sedimentation of the dye is minimized. This is accomplished in suitable mills, such as ball or sand mills. The particle size of the dyes is generally between 0.5 and 5 μm and preferably equal to about 1 μm.
The dispersants used in the milling operation can be nonionic or anionic. Nonionic dispersants include for example reaction products of alkylene oxides, for example ethylene oxide or propylene oxide, with alkylatable compounds, for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides. Anionic dispersants are for example lignosulfonates, alkyl- or alkylarylsulfonates or alkylaryl polyglycol ether sulfates.
The dye preparations thus obtained should be pourable for most applications. Accordingly, the dye and dispersant content is limited in these cases. In general, the dispersions are adjusted to a dye content up to 50 percent by weight and a dispersant content up to about 25 percent by weight. For economic reasons, dye contents are in most cases not allowed to be below 15 percent by weight. The dispersions may also contain still further auxiliaries, for example those which act as an oxidizing agent, for example sodium m-nitrobenzenesulfonate, or fungicidal agents, for example sodium o-phenylphenoxide and sodium pentachlorophenoxide, and particularly so-called “acid donors”, examples being butyrolactone, monochloroacetamide, sodium chloroacetate, sodium dichloroacetate, the sodium salt of 3-chloropropionic acid, monosulfate esters such as lauryl sulfate for example, and also sulfuric esters of ethoxylated and propoxylated alcohols, for example butylglycol sulfate.
The dye dispersions thus obtained are very advantageous for making up dyeing liquors and print pastes.
There are certain fields of use where powder formulations are preferred. These powders comprise the dye, dispersants and other auxiliaries, for example wetting, oxidizing, preserving and dustproofing agents and the abovementioned “acid donors”.
A preferred method of making pulverulent preparations of dye consists in stripping the above-described liquid dye dispersions of their liquid, for example by vacuum drying, freeze drying, by drying on drum dryers, but preferably by spray drying.
The dyeing liquors are made by diluting the requisite amounts of the above-described dye formulations with the dyeing medium, preferably water, such that a liquor ratio of 5:1 to 50:1 is obtained for dyeing. In addition, it is generally customary to include further dyeing auxiliaries, such as dispersing, wetting and fixing auxiliaries, in the liquors. Organic and inorganic acids such as acetic acid, succinic acid, boric acid or phosphoric acid are included to set a pH in the range from 4 to 5, preferably 4.5. It is advantageous to buffer the pH setting and to add a sufficient amount of a buffering system. The acetic acid/sodium acetate system is an example of an advantageous buffering system.
To use the dye or dye mixture in textile printing, the requisite amounts of the abovementioned dye formulations are kneaded in a conventional manner together with thickeners, for example alkali metal alginates or the like, and if appropriate further additives, for example fixation accelerants, wetting agents and oxidizing agents, to give print pastes.
The present invention also provides inks for digital textile printing by the ink jet process, comprising a present invention dye of the general formula (I).
The inks of the present invention are preferably aqueous and comprise one or more of the present invention's dyes of the general formula (I), for example in amounts of 0.1% to 50% by weight, preferably in amounts of 1% to 30% by weight and more preferably in amounts of 1% to 15% by weight based on the total weight of the ink. They further comprise in particular from 0.1% to 20% by weight of a dispersant. Suitable dispersants are known to one skilled in the art, are commercially available and include for example sulfonated or sulfomethylated lignins, condensation products of aromatic sulfonic acids and formaldehyde, condensation products of substituted or unsubstituted phenol and formaldehyde, polyacrylates and corresponding copolymers, modified polyurethanes and reaction products of alkylene oxides with alkylatable compounds, for example fatty alcohols, fatty amines, fatty acids, carboxamides and substituted or unsubstituted phenols.
The inks of the present invention may further comprise customary additives, for example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in the temperature range of 20 to 50° C. Preferred inks have a viscosity in the range from 1.5 to 20 mPas and particularly preferred inks have a viscosity in the range from 1.5 to 15 mPas.
Useful viscosity moderators include rheological additives, for example polyvinyl-caprolactam, polyvinylpyrrolidone and also their copolymers, polyetherpolyol, associative thickeners, polyureas, sodium alginates, modified galactomannans, polyetherurea, polyurethane and nonionic cellulose ethers.
By way of further additives, the inks of the present invention may include surface-active substances to set surface tensions in the range from 20 to 65 mN/m, which are if appropriate adapted depending on the process used (thermal or piezo technology). Useful surface-active substances include for example surfactants of any kind, preferably nonionic surfactants, butyldiglycol and 1,2 hexanediol.
The inks may further include customary additives, for example chemical species to inhibit fungal and bacterial growth in amounts from 0.01% to 1% by weight based on the total weight of the ink.
The inks of the present invention can be prepared in conventional manner by mixing the components in water.


EXAMPLE 1
4.6 g of 6-chloro-2,4-dinitroaniline are introduced into a mixture of 9.8 ml of sulfuric acid (96%), 0.5 ml of water and 3.5 ml of nitrosylsulfuric acid (40%) at 30 to 35° C. After 3 hours of stirring at 30-35° C., excess nitrite is destroyed with amidosulfonic acid. The diazonium salt solution thus obtained is expediently added dropwise to a mixture of 7.0 g of 2-oxopropyl 3-[(5-acetylamino-2-methoxyphenyl)ethylamino]-propionate, 50 ml of methanol and 200 g of ice. After stirring for one hour the solids are filtered off with suction, washed with water and dried to leave 7.3 g of the dye of the formula (Iab)




(λmax [DMF]=606 nm), which dyes polyester in blue hues having good wash and sublimation fastnesses.

EXAMPLE 2
7.5 g of 2-oxopropyl 3-{[3-acetylamino-4-(2,6-dibromo-4-nitrophenylazo)phenyl]-ethylamino}propionate and 2.15 g of copper(I) cyanide are stirred in 30 ml of N-methylpyrrolidone at 80° C. for 4 hours. After cooling, 200 ml of methanol and 30 ml of water are added dropwise. The precipitate is filtered off with suction, washed with 5% hydrochloric acid and water and dried under reduced pressure to leave 4.9 g of the dye of the formula (Iac)




(λmax [DMF]=612 nm), which dyes polyester in brilliant, blue shades and has excellent wash and sublimation fastnesses.

EXAMPLE 3
Example 2 is repeated except it proceeds from 2-oxopropyl 3-{[3-acetylamino-4-(6-bromo-2,4-dinitrophenylazo)phenyl]ethylamino}propionate and utilizes only one equivalent of copper(I) cyanide. The dye thus obtained has the formula (Iad)




(λmax [DMF]=602 nm) and dyes polyester in brilliant, blue shades and gives excellent wash and sublimation fastnesses.

Examples 4 to 145 of Table 1 were prepared in a similar manner.







TABLE 1













 

































λmax


Exam-












(nm)


ple
T1
T2
T3
T4
R1
R2
R3
R5
R4
R6
R7
n
DMF























4
NO2
H
Br
NO2
NHCOCH3
OCH3
CH2CH3
CH3
H
H
H
0
604


5
NO2
H
H
NO2
NHCOCH3
OCH3
CH2CH3
CH3
H
H
H
0
582


6
NO2
H
Br
CN
NHCOCH3
OCH3
CH2CH3
CH3
H
H
H
0
632


7
NO2
H
Cl
NO2
NHCOCH3
OCH3
CH2CH3
C2H5
H
H
H
0
604


8
NO2
H
Br
NO2
NHCOCH3
OCH3
CH2CH3
C2H5
H
H
H
0
604


9
NO2
H
H
NO2
NHCOCH3
OCH3
CH2CH3
C2H5
H
H
H
0
582


10
NO2
H
Cl
NO2
NHCOCH3
OCH3
CH3
CH3
H
H
H
0
600


11
NO2
H
Br
NO2
NHCOCH3
OCH3
CH3
CH3
H
H
H
0
598


12
NO2
H
H
NO2
NHCOCH3
OCH3
CH3
CH3
H
H
H
0
572


13
NO2
H
Cl
NO2
NHCOCH3
OCH3
CH2CH═CH2
CH3
H
H
H
0
598


14
NO2
H
Br
NO2
NHCOCH3
OCH3
CH2CH═CH2
CH3
H
H
H
0
598


15
NO2
H
H
NO2
NHCOCH3
OCH3
CH2CH═CH2
CH3
H
H
H
0
574


16
NO2
H
Cl
NO2
NHCOCH3
OCH3
CH2C6H5
CH3
H
H
H
0
590


17
NO2
H
Br
NO2
NHCOCH3
OCH3
CH2C6H5
CH3
H
H
H
0
590


18
NO2
H
H
NO2
NHCOCH3
OCH3
CH2C6H5
CH3
H
H
H
0
570


19
NO2
H
CN
NO2
NHCOCH3
OCH3
CH2C6H5
CH3
H
H
H
0
634


20
NO2
H
Cl
NO2
NHCOCH3
OCH3
H
CH3
H
H
H
0
592


21
NO2
H
Cl
NO2
NHCOCH3
OC2H5
H
CH3
H
H
H
0
594


22
NO2
H
Br
NO2
NHCOCH3
OCH3
H
CH3
H
H
H
0
594


23
NO2
H
Br
NO2
NHCOCH3
OCH3
H
C2H5
H
H
H
0
594


24
NO2
H
Cl
NO2
NHCOCH3
OCH3
H
C2H5
H
H
H
0
600


25
NO2
H
H
NO2
NHCOCH3
OCH3
H
C2H5
H
H
H
0
574


26
NO2
H
H
NO2
NHCOCH3
OCH3
H
CH3
H
H
H
0
574


27
NO2
H
H
CF3
NHCOCH3
OCH3
H
CH3
H
H
H
0
542


28
NO2
H
Br
CN
NHCOCH3
OCH3
H
CH3
H
H
H
0
624


29
NO2
H
Br
CF3
NHCOCH3
OCH3
H
CH3
H
H
H
0
562


30
NO2
H
Br
NO2
NHCOC2H5
OCH3
H
CH3
H
H
H
0
596


31
NO2
H
Cl
NO2
NHCOC2H5
OCH3
H
CH3
H
H
H
0
596


32
NO2
H
H
NO2
NHCOC2H5
OCH3
H
CH3
H
H
H
0
576


33
NO2
H
Br
NO2
NHCOC6H5
OCH3
H
CH3
H
H
H
0
586


34
NO2
H
Cl
NO2
NHCOC6H5
OCH3
H
CH3
H
H
H
0
586


35
NO2
H
H
NO2
NHCOC6H5
OCH3
H
CH3
H
H
H
0
572


36
NO2
Cl
H
NO2
NHCOCH3
OCH3
H
CH3
H
H
H
0
576


37
NO2
H
Br
NO2
NHCOC6H5
OCH3
CH2CH3
CH3
H
H
H
0
596


38
NO2
H
Br
NO2
NHCOC2H5
OCH3
CH2CH3
CH3
H
H
H
0
606


39
NO2
H
Cl
NO2
NNCOC2H5
OCH3
CH2CH3
CH3
H
H
H
0
608


40
NO2
H
CN
NO2
NHCOCH3
OCH3
CH2CH3
CH3
H
H
H
0
648


41
NO2
H
Br
NO2
NHCOC6H5
H
CH2CH3
CH3
H
H
H
0
560


42
NO2
H
Br
NO2
NHCOC2H5
H
CH2CH3
CH3
H
H
H
0
558


43
NO2
Cl
H
NO2
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
548


44
NO2
H
Cl
NO2
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
560


45
NO2
H
Cl
NO2
NHCOCH3
H
CH2CH3
C2H5
H
H
H
0
560


46
NO2
H
Br
NO2
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
558


47
NO2
H
Cl
NO2
NHCOCH3
H
n-C4H9
CH3
H
H
H
0
562


48
NO2
H
Cl
H
NHCOCH3
H
n-C4H9
CH3
H
H
H
0
534


49
NO2
H
H
H
NHCOCH3
H
n-C4H9
CH3
H
H
H
0
516


50
NO2
H
Br
CN
NHCOCH3
H
n-C4H9
CH3
H
H
H
0
584


51
NO2
H
CN
NO2
NHCOCH3
H
n-C4H9
CH3
H
H
H
0
604


52
NO2
H
H
NO2
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
548


53
NO2
H
H
CN
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
552


54
NO2
H
Br
CN
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
582


55
NO2
H
Cl
CN
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
582


56
NO2
H
Cl
H
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
534


57
NO2
H
Br
H
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
530


58
NO2
H
H
H
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
514


59
NO2
H
Cl
NO2
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
554


60
NO2
H
H
CN
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
546


61
NO2
H
Br
NO2
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
552


62
NO2
H
Cl
H
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
524


63
NO2
H
H
NO2
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
540


64
NO2
H
H
H
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
506


65
H
Cl
H
Cl
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
476


66
NO2
H
Br
CN
NHCOCH3
H
CH2C6H5
CH3
H
H
H
0
574


67
NO2
H
H
CN
NHCOCH3
H
n-C4H9
CH3
H
H
H
0
554


68
NO2
H
Cl
NO2
NHCOCH3
H
CH2CH═CH2
CH3
H
H
H
0
556


69
NO2
H
H
CN
NHCOCH3
H
CH2CH═CH2
CH3
H
H
H
0
548


70
NO2
H
H
Cl
NHSO2CH3
H
CH2C6H5
CH3
H
H
H
0
534


71
NO2
H
H
H
NHSO2CH3
H
CH2C6H5
CH3
H
H
H
0
494


72
NO2
H
H
CN
CH3
H
CH2CH3
CH3
H
H
H
0
548


73
NO2
H
H
CN
CH3
H
n-C4H9
CH3
H
H
H
0
550


74
NO2
H
H
Cl
CH3
H
n-C4H9
CH3
H
H
H
0
526


75
NO2
H
CN
CN
CH3
H
n-C4H9
CH3
H
H
H
0
600


76
NO2
H
CN
NO2
CH3
H
n-C4H9
CH3
H
H
H
0
590


77
NO2
H
Br
CN
CH3
H
n-C4H9
CH3
H
H
H
0
562


78
NO2
H
Cl
H
CH3
H
CH2CH3
CH3
H
H
H
0
524


79
NO2
H
Cl
H
H
H
CH2CH3
CH3
H
H
H
0
512


80
NO2
H
Cl
Cl
H
H
CH2CH3
CH3
H
H
H
0
440


81
NO2
H
Br
Cl
H
H
CH2CH3
CH3
H
H
H
0
442


82
NO2
H
Br
Br
H
H
CH2CH3
CH3
H
H
H
0
440


83
NO2
H
H
Br
H
H
CH2CH3
CH3
H
H
H
0
508


84
NO2
Cl
H
Cl
H
H
CH2CH3
CH3
H
H
H
0
512


85
NO2
H
Br
Cl
H
H
n-C4H9
CH3
H
H
H
0
444


86
NO2
H
Cl
Cl
H
H
CH2C6H5
CH3
H
H
H
0
432


87
NO2
H
Br
Cl
H
H
CH2C6H5
CH3
H
H
H
0
434


88
NO2
H
Cl
H
H
H
CH2C6H5
CH3
H
H
H
0
500


89
NO2
H
H
CN
H
H
CH2C6H5
CH3
H
H
H
0
526


90
NO2
H
H
CF3
H
H
CH2C6H5
CH3
H
H
H
0
506


91
NO2
H
Br
Br
H
H
CH2C6H5
CH3
H
H
H
0
432


92
NO2
H
H
Br
H
H
CH2C6H5
CH3
H
H
H
0
498


93
NO2
H
Cl
Cl
H
H
CH2CH2C6H5
CH3
H
H
H
0
440


94
NO2
H
Br
Cl
H
H
CH2CH2C6H5
CH3
H
H
H
0
442


95
NO2
H
Cl
Cl
H
H
CH2CH2OC6H5
CH3
H
H
H
0
436


96
NO2
H
Br
Cl
H
H
CH2CH2OC6H5
CH3
H
H
H
0
432


97
NO2
H
H
Cl
H
H
CH2CH2OC6H5
CH3
H
H
H
0
502


98
NO2
H
H
CN
H
H
CH2CH2OC6H5
CH3
H
H
H
0
526


99
NO2
H
Cl
Cl
H
H
CH2CH2CN
CH3
H
H
H
0
424


100
NO2
H
Br
Br
H
H
CH2CH2CN
CH3
H
H
H
0
422


101
NO2
H
Cl
Cl
CH3
H
CH2CH3
CH3
H
H
H
0
462


102
NO2
H
Br
Cl
CH3
H
CH2CH3
CH3
H
H
H
0
460


103
NO2
H
Cl
CN
CH3
H
CH2CH3
CH3
H
H
H
0
562


104
NO2
H
Br
CN
CH3
H
CH2CH3
CH3
H
H
H
0
560


105
NO2
H
CN
CN
CH3
H
CH2CH3
CH3
H
H
H
0
596


106
NO2
H
H
H
CH3
H
CH2CH3
CH3
H
H
H
0
500


107
NO2
H
H
Br
CH3
H
CH2CH3
CH3
H
H
H
0
522


108
NO2
Cl
H
Cl
CH3
H
CH2CH3
CH3
H
H
H
0
524


109
H
NO2
H
H
CH3
H
CH2CH3
CH3
H
H
H
0
452


110
NO2
Cl
Cl
H
H
H
CH2C6H5
CH3
H
H
H
0
500


111
NO2
H
H
H
OH
H
CH2CH3
CH3
H
H
H
0
494


112
NO2
H
H
Cl
OH
H
CH2CH3
CH3
H
H
H
0
530


113
NO2
H
H
CN
OH
H
CH2CH3
CH3
H
H
H
0
544


114
NO2
H
Cl
Cl
OH
H
CH2CH3
CH3
H
H
H
0
486


115
NO2
H
H
H
Cl
OC6H5
H
CH3
H
H
H
0
478


116
NO2
H
H
CN
Cl
OC6H5
H
CH3
H
H
H
0
524


117
NO2
H
H
Cl
Cl
OC6H5
H
CH3
H
H
H
0
498


118
NO2
H
Cl
Cl
Cl
OC6H5
H
CH3
H
H
H
0
444


119
NO2
H
H
H
H
Cl
H
CH3
H
H
H
0
450


120
NO2
H
H
Cl
H
Cl
H
CH3
H
H
H
0
472


121
NO2
H
H
H
H
Cl
H
C2H5
H
H
H
0
450


122
NO2
H
H
NO2
NHCOCH3
Cl
H
CH3
H
H
H
0
520


123
NO2
H
H
H
NHCOCH3
Cl
H
CH3
H
H
H
0
486


124
NO2
H
Cl
NO2
NHCOCH3
Cl
H
CH3
H
H
H
0
536


125
NO2
H
Cl
H
NHCOCH3
Cl
H
CH3
H
H
H
0
508


126
NO2
H
H
CN
NHCOCH3
Cl
H
CH3
H
H
H
0
530


127
NO2
H
Br
NO2
NHCOCH3
OCH3
H
CH3
CH3
H
H
0
596


128
NO2
H
Cl
NO2
NHCOCH3
OCH3
H
CH3
CH3
H
H
0
596


129
NO2
H
Cl
NO2
NHCOCH3
OCH3
H
CH3
H
CH3
H
0
592


130
NO2
H
Cl
NO2
NHCOCH3
OCH3
H
CH3
H
H
H
1
601


131
NO2
H
Br
NO2
NHCOCH3
OCH3
H
CH3
H
H
H
1
600


132
NO2
H
H
NO2
NHCOCH3
OCH3
H
CH3
H
H
H
1
582


133
NO2
H
Br
CN
NHCOCH3
OCH3
H
CH3
H
H
H
1
630


134
NO2
H
Cl
NO2
NHCOCH3
OCH3
H
CH3
H
H
CH3
0
594


135
NO2
H
Br
NO2
NHCOCH3
OCH3
H
CH3
H
H
CH3
0
594


136
NO2
H
H
NO2
NHCOCH3
OCH3
H
CH3
H
H
CH3
0
576


137
NO2
H
Cl
NO2
NHCOCH3
OCH3
H
CH3
H
H
C6H5
0
594


138
NO2
H
Br
NO2
NHCOCH3
OCH3
H
CH3
H
H
C6H5
0
594


139
NO2
H
H
NO2
NHCOCH3
OCH3
H
CH3
H
H
C6H5
0
576


140
NO2
H
Br
NO2
NHCOCH3
CH3
H
CH3
H
H
H
0
558


141
NO2
H
Cl
NO2
NHCOCH3
CH3
H
CH3
H
H
H
0
558


142
NO2
H
Cl
H
NHCOCH3
CH3
H
CH3
H
H
H
0
532


143
NO2
H
Br
CN
NHCOCH3
CH3
H
CH3
H
H
H
0
584


144
NO2
H
H
NO2
NHCOCH3
CH3
H
CH3
H
H
H
0
538


145
CH3
H
CN
CN
NHCOCH3
H
CH2CH3
CH3
H
H
H
0
532









EXAMPLE 146
4.3 g of 3-amino-5-nitrobenzisothiazole are introduced into a mixture of 11 ml of sulfuric acid (96%) and 4 ml of phosphoric acid (85%). Then, 4.6 ml of nitrosylsulfuric acid (40%) are added dropwise at 10 to 15° C. The mixture is subsequently stirred at 10 to 15° C. for 4 hours. The diazonium salt solution thus obtained is speedily added dropwise to a mixture of 6.6 g of 2-oxopropyl 3-[(5-acetylaminophenyl)ethylamino]-propionate, 100 ml of methanol, 1.1 g of urea and 100 g of ice. The mixture is stirred at room temperature overnight and the precipitate is filtered off with suction, washed with 1:1 methanol/water and dried to leave 7.9 g of the dye of the formula (Ibb)




(λmax [DMF]=622 nm), which dyes polyester in greenish blue shades and has very good wash and sublimation fastnesses.

Examples 147 to 173 of Table 2 were prepared in a similar manner.







TABLE 2













 













Exam-





λmax


ple
D
R1
R2
R3
R5
[DMF]





147




NHCOCH3
OCH3
H
CH3
648


 


148




H
H
CH2CH3
CH3
606


 


149




H
H
CH2C6H5
CH3
594


 


150




CH3
H
CH2CH3
CH3
618


 


151




H
H
CH2CH3
CH3
622


 


152




CH3
H
CH2CH3
CH3
636


 


153




CH3
H
CH2CH3
CH3
562


 


154




H
H
CH2CH3
CH3
550


 


155




H
H
CH2C6H5
CH3
540


 


156




NHCOCH3
H
CH2CH3
CH3
564


 


157




CH3
H
CH2CH3
CH3
540


 


158




H
H
CH2CH3
CH3
530


 


159




NHCOCH3
H
CH2CH3
CH3
542


 


160




NHCOCH3
H
CH2CH3
CH3
596


 


161




NHCOCH3
OCH3
H
CH3
608


 


162




NHCOCH3
H
CH2CH3
CH3
556


 


163




NHCOCH3
H
CH2CH3
CH3
526


 


164




NHCOCH3
H
CH2C6H5
CH3
520


 


165




CH3
H
CH2CH3
CH3
520


 


166




NHCOCH3
H
CH2CH3
CH3
644


 


167




CH3
H
CH2CH3
CH3
668


 


168




H
H
CH2CH3
CH3
650


 


169




NHCOCH3
H
CH2CH3
CH3
604


 


170




CH3
H
CH2CH3
CH3
607


 


171




H
H
CH2CH3
CH3
592


 


172




NHCOCH3
OCH3
CH2CH3
CH3
650


 


173




H
H
CH2CH3
CH3
664









EXAMPLE 174
A textile fabric consisting of polyester is padded with a liquor consisting of 50 g/l of 8% sodium alginate solution, 100 g/l of 8-12% carob flour ether solution and 5 g/l of monosodium phosphate in water and then dried. The wet pickup is 70%.
The textile thus pretreated is then printed with an aqueous ink prepared in accordance with the procedure described above and containing

    3.5% of the dye of Example 1,
    2.5% of Disperbyk 190 dispersant,
    30% of 1,5-pentanediol,
    5% of diethylene glycol monomethyl ether,
    0.01% of Mergal K9N biocide, and
    58.99% of water

using a drop-on-demand (piezo) ink jet print head. The print is fully dried. Fixing is effected by means of superheated steam at 175° C. for 7 minutes. The print is subsequently subjected to an alkaline reduction clear, rinsed warm and then dried.

## Claims

1. A dye of the formula (I)



where
D is the radical of a diazo component;
R1 is hydrogen, (C1-C6)-alkyl, (C1-C4)-alkoxy, hydroxyl, halogen, —NHCHO, —NHCO(C1-C6)-alkyl, —NHCOaryl, —NHSO2(C1-C6)-alkyl or —NHSO2aryl;
R2 is hydrogen, (C1-C6)-alkyl, (C1-C4)-alkoxy, phenoxy or halogen;
R3 is hydrogen, (C1-C6)-alkyl, substituted (C1-C6)-alkyl, (C3-C4)-alkenyl or substituted (C3-C4)-alkenyl;
or R2 and R3 combine to form the radical —C*H(CH3)CH2C(CH3)2—, where the carbon atom marked by * is attached to the phenyl nucleus;
R4 is hydrogen, (C1-C6)-alkyl or phenyl;
R5 is (C1-C6)-alkyl or substituted (C1-C6)-alkyl;
R6 is hydrogen or (C1-C6)-alkyl;
R7 is hydrogen, (C1-C6)-alkyl or phenyl; and
n 0, 1, 2 or 3;
although the compounds of the formulae




shall be excluded.

2. The dye as claimed in claim 1, wherein D represents a group of the formula (IIa)



where
T1 and T2 independently are hydrogen, (C1-C6)-alkyl, (C1-C4)-alkoxy, —SO2(C1-C6)-alkyl, —SO2aryl, cyano, halogen or nitro; and
T4 and T3 independently are hydrogen, halogen, trifluoromethyl, cyano, —SCN, —SO2CH3 or nitro;
although at least one of T1, T2, T3 and T4 is not hydrogen;
or represents a group of the formula (IIb)




where
T5 and T5′ independently are hydrogen or halogen; and
T6 is hydrogen, —SO2CH3, —SCN, (C1-C4)-alkoxy, halogen or nitro;
although at least one of T5, T5′ and T6 is not hydrogen;
or represents a group of the formula (IIc)




where
T12 is hydrogen or halogen;
or represents a group of the formula (IId)




where
T7 is nitro, —CHO, cyano, —COCH3 or a group of the formula




where T10 is hydrogen, halogen, nitro or cyano;
T8 is hydrogen, (C1-C6)-alkyl or halogen; and
T9 is nitro, cyano, —COCH3 or —COOT11; where T11 is (C1-C4)-alkyl;
or represents a group of the formula (IIe)




where T7 and T8 are each as defined above;
or represents a group of the formula (IIf)




where T13 is phenyl or S—(C1-C4)-alkyl.

3. The dye as claimed in claim 1, wherein
R1 is hydrogen, chlorine, methyl, ethyl, methoxy, hydroxyl, ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino or phenylsulfonylamino;
R2 is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy;
R3 is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C2H4OCOCH3, —C2H4OCOC2H5, —C2H4COOCH3, —C2H4COOC2H5 or allyl;
R4 and R7 are hydrogen, methyl or phenyl;
R5 is methyl or ethyl;
R6 is hydrogen or methyl; and
n is 0 or 1;
although the compounds of the formulae




shall be excluded.

4. The dye as claimed in claim 2, wherein
R1 is hydrogen, chlorine, methyl, ethyl, methoxy, hydroxyl, ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino or phenylsulfonylamino;
R2 is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy;
R3 is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C2H4OCOCH3, —C2H4OCOC2H5, —C2H4COOCH3, —C2H4COOC2H5 or allyl;
R4 and R7 are hydrogen, methyl or phenyl;
R5 is methyl or ethyl;
R6 is hydrogen or methyl; and
n is 0 or 1;
although the compounds of the formulae




shall be excluded.

5. The dye according to claim 1, conforming to the formula (Ia)



where T1 to T4, R1 to R7 and n are each as defined in claim 1, although the compounds of the formulae




shall be excluded.

6. The dye as claimed in claim 5, wherein
R1 is acetylamino, propionylamino, benzoylamino or methylsulfonylamino;
R2 is hydrogen, chlorine, methoxy or ethoxy;
R3 is hydrogen, methyl, ethyl, allyl or benzyl;
R4 is hydrogen or methyl;
R5 methyl or ethyl;
R6 is hydrogen or methyl and
R7 is hydrogen, methyl or phenyl.

7. The dye as claimed in claim 5, conforming to the formula (Iaa)



where
T1 is hydrogen, nitro or methyl;
T2 is hydrogen, nitro or chlorine;
T3 is hydrogen, cyano, chlorine or bromine;
T4 is hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;
R1 is hydrogen, hydroxyl, chlorine, methyl, acetylamino, propionylamino, benzoylamino or methylsulfonylamino;
R2 is hydrogen, chlorine, methyl, phenoxy, methoxy or ethoxy;
R3 is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl, phenoxyethyl or allyl;
R5 is methyl or ethyl; and
R4 and R7 are hydrogen, methyl or phenyl;
although the compounds of the formulae




shall be excluded.

8. The dye as claimed in claim 7, wherein T3 is chlorine or bromine and R1 is hydrogen or methyl.

9. A process for preparing a dye of the formula (I) as claimed in claim 1, which comprises diazoting a compound of the formula (III)


D-NH2  (III)

where D is as defined in claim 1, and coupling onto a compound of the formula (IV)




where R1 to R7 and n are each as defined in claim 1.

10. A process for dyeing and printing a hydrophobic material which comprises contacting the material with the dye as claimed in claim 1.

11. An ink for digital textile printing by the ink jet process, comprising the dye of the formula (I) as claimed in claim 1.

12. An ink for digital textile printing by the ink jet process, comprising the dye of the formula (I) as claimed in claim 8.