Cationic dyes containing an aryloxy group linked through a bridging radical to a quaternized nitrogen atom

Abstract

Disclosed are basic dyes, e.g., azo dyes and anthraquinone dyes free from sulphonic acid groups and which contain, as characteristic group, a group of the formula ##STR1## in which R and R.sub.1, independently, are substituted or unsubstituted C.sub.1-4 alkyl or are linked to form a ring, orOne of R and R.sub.1 is --NH.sub.2 or C.sub.1-4 alkoxy, the other substituted or unsubstituted alkyl,R.sub.2 and R.sub.3, independently, are hydrogen or C.sub.1-4 alkyl,Y is a bridging group,Q is unsubstituted or substituted phenyl, biphenylyl, naphthyl or ##STR2## in which R.sub.7 is ##STR3## where R.sub.8 ic C.sub.1-4 alkyl, andA.sup.- is an anion. These dyes are useful for the dyeing and printing of polymers and copolymers of acrylonitrile and asymmetrical dicyanoethylene as well as polyesters and polyamides modified to contain acid groups. The dyes build-up well and exhibit good pH stability and stability to boiling. The obtained dyeings are level and possess good fastness to light, wet treatments, solvents, heat treatments and cross-dyeing.

Description

The invention relates to basic dyes free from sulphonic acid groups.

The invention provides basic dyes, free from sulphonic acid groups and which contain, as characteristic group, a group of formula T ##STR4## in which either R and R.sub.1, which may be the same or different, each signify an alkyl radical of 1 to 4 carbon atoms, unsubstituted or substituted by hydroxy or phenyl,

or one of R and R.sub.1 signifies-- NH.sub.2 or C.sub.1-4 alkoxy radical, the other having one of the above significances, or R and R.sub.1, together with the nitrogen atom to which they are attached, signify ##STR5## in which Ro signifies a C.sub.1-4 alkyl or phenyl radical, or the group ##STR6## signifies, as a whole, a radical of the formula ##STR7## in which the Ra's, independently, signify hydrogen or alkyl of 1 to 4 carbon atoms, and n signifies 1 or 2, R.sub.2 and R.sub.3, which may be the same or different, each signify hydrogen or C.sub.1-4 alkyl, Y signifies a radical ##STR8## in which x signifies 1 to 6, R.sub.4 signifies one of the above significances of R.sub.2 and R.sub.3, and R.sub.5 signifies ##STR9## in which R.sub.6 signifies hydrogen or C.sub.1-4 alkyl, A.sup.- signifies an anion, and Q signifies a radical of the formula ##STR10## in which R.sub.9 signifies hydrogen; hydroxy; halogen; alkyl or alkoxy of 1 to 4 carbon atoms, unsubstituted or substituted by halogen, hydroxy, cyano, phenyl or phenoxy; cycloalkyl of 5 or 6 carbon atoms, unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; trifluoromethyl; cyano; nitro; phenoxy; naphthyloxy; phenylazo; or a radical of the formula ##STR11## in which the Ro's, independently, signify C.sub.1-4 alkyl or phenyl, and X signifies --CO-- or --SO.sub.2 --, R.sub.10 signifies hydrogen, halogen or alkyl of 1 to 4 carbon atoms, R.sub.11 signifies C.sub.1-4 alkyl, C.sub.1-4 alkoxy, phenyl, phenoxy, halogen, ##STR12## a signifies 0, 1,2 or 3 or, where R.sub.9 signifies halogen, 1,2,3,4 or 5, R.sub.7 signifies ##STR13## in which R.sub.8 signifies C.sub.1-4 alkyl and R.sub.8 ' signifies hydrogen or C.sub.1-4 alkyl Preferably, R and R.sub.1 each signify C.sub.1-4 alkyl, more preferably methyl or ethyl. Preferably, R.sub.2 and R.sub.3, independently, signify hydrogen or methyl, more preferably hydrogen. Preferably, Y signifies ##STR14## in which R.sub.4 ' signifies hydrogen or C.sub.1-4 alkyl, more preferably hydrogen or methyl, most preferably hydrogen. and x' signifies 1, 2 or 3, more preferably 1, or --CH.dbd.CH--CH.sub.2 -- or --C.tbd.C--CH.sub.2 -- or --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --. Most preferably, Y signifies --CH.sub.2 --. Preferably, Q signifies an unsubstituted phenyl, naphthyl, biphenylyl dibenzofuranyl radical, or a phenyl radical substituted by halogen, preferably chlorine, C.sub.1-4 alkyl or alkoxy, --CF.sub.3, cyano or --NO.sub.2, or a phenyl radical substituted by up to 5 chlorine atoms.

Most preferably Q signifies unsubstituted phenyl or 2-naphthyl, or phenyl substituted by up to 5 chlorine atoms.

As examples of anions A.sup.- may be given the halides, such as chloride, bromide or iodide, sulphate, disulphate, methylsulphate, aminosulphate, perchlorate, carbonate, bicarbonate, phosphate, phosphormolybdate, phosphortungstenate, phosphortungstenmolybdate, formate, benzenesulphonate, naphthalenesulphonate, 4-chlorobenzenesulphonate, oxalate, maleimate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, malate, methanesulphonate or benzoate ions, or complex anions such as zinc chloride double salts, e.g. ZnCl.sub.3.sup.-. The preferred anions are the halide methylsulphate ZnCl.sub.3.sup.- ions, acetate ions and sulphate ions.

As examples of the basic dyes provided by the invention may be given the azo series of dyes of formula Ia, ##STR15## in which D signifies a diazo component,

K signifies a coupling component, w signifies a direct bond or a bridging group, T is as defined above, and the group (s) W-T being bound to D and/or K, t signifies 1 or 2.

As examples of preferred compounds of formula Ia, may be given the compounds of formula Iaa, ##STR16## in which K' signifies a radical of formula (m) or (n), ##STR17## in which R.sub.18 signifies hydrogen, C.sub.1-4 alkyl, preferably methyl, C.sub.1-4 alkoxy, preferably methoxy, or halogen, preferably chlorine,

D' signifies a radical of formula (a), ##STR18## in which R.sub.19 signifies hydrogen, nitro, halogen preferably chlorine or bromine, cyano, trifluoromethyl, C.sub.1-4 alkylsulfonyl, preferably methylsulphonyl, phenylsulphonyl,, --CO--Ro, COORo, --CONHRo, alkyl of 1 to 4 carbon atoms, preferably methyl, or alkoxy of 1 to 4 carbon atoms, preferably methoxy or a radical --O.sub.2 S--NR.sub.21 R.sub.22, wherein R.sub.21 and R.sub.22, independently, signify C.sub.1-4 alkyl or are linked to form, together with the nitrogen, ##STR19## in which Rc signifies C.sub.1-4 alkyl, preferably methyl, R.sub.119 and R.sub.119 ', independently, signify hydrogen, nitro, halogen, preferably chlorine or bromine, cyano, C.sub.1-4 alkyl, preferably methyl, trifluoromethyl, C.sub.1-4 alkylsulphonyl or C.sub.1-4 alkoxy, preferably methoxy, R.sub.219 signifies hydrogen, halogen, preferably chlorine, nitro or cyano, with the proviso that radical (a) contains no more than 3 substituents other than halogen, a radical of formula (b) or (c) ##STR20## in which R.sub.319 signifies hydrogen, halogen, preferably chlorine, nitro, cyano, trifluoromethyl or C.sub.1-4 alkylsulphonyl, R.sub.419 signifies hydrogen, halogen, preferably chloro, nitro, cyano, alkyl, preferably methyl, or C.sub.1-4 alkoxy, preferably methoxy, the R.sub.20 's independently, signify hydrogen, alkyl of 1 to 4 carbon atoms, preferably methyl, or alkoxy of 1 to 4 carbon atoms, preferably methoxy, a radical of formula (d) ##STR21## in which R.sub.23 signifies hydrogen, an unsubstituted phenyl radical; a phenyl radical substituted by C.sub.1-4 alkyl, preferably methyl, cyano or nitro; a C.sub.1-4 alkylsulphonyl radical; a C.sub.1-4 alkylsulphoxide radical; a C.sub.1-4 alkylthio radical; halogen, preferably chlorine, or C.sub.1-4 alkyl, preferably methyl, a radical of formula (e) ##STR22## in which R.sub.23 ' signifies hydrogen, phenyl unsubstituted or substituted by C.sub.1-4 alkyl, preferably methyl, cyano, nitro and halogen, preferably chlorine; or C.sub.1-4 alkyl, preferably methyl, a radical of formula (f) ##STR23## in which R.sub.23 " signifies halogen, preferably chlorine, R.sub.23 ''' signifies cyano, --CONHRa in which Ra signifies hydrogen or C.sub.1-4 alkyl, or --COORo, preferably cyano, a radical of formula (g) ##STR24## Rg signifies halogen, preferably bromine, nitro or --CO--Ro, Rg' signifies halogen, preferably bromine, a radical of formula (h) ##STR25## in which Rh signifies nitro, cyano, or trifluoromethyl, preferably nitro, a radical of formula (i) ##STR26## in which Ri signifies nitro or cyano, preferably nitro, a radical of formula (j) ##STR27## in which Rj and Rj'', independently, signify cyano, C.sub.1-4 alkoxycarbonyl, preferably methoxycarbonyl, or --CONHRa, Rj' signifies C.sub.1-4 alkyl, preferably methyl, or phenyl, a radical of formula (k) ##STR28## or a radical of formula (1) ##STR29## R.sub.16 signifies hydrogen; alkyl of 1 to 4 carbon atoms, unsubstituted or substituted by halogen, hydroxy, cyano, phenyl, phenoxy, C.sub.1-4 alkoxycarbonyl, C.sub.1-4 alkylcarbonyloxy, C.sub.1-4 alkoxy, benzoyloxy, ##STR30## or --CON(Ra).sub.2 in which the Ra's, independently, signify hydrogen or C.sub.1-4 alkyl; or phenyl; R.sub.16 preferably signifying an unsubstituted alkyl radical radical of 1 to 4 carbon atoms, more preferably methyl or ethyl, R.sub.17 signifies an alkylene radical of the formula ##STR31## or a radical ##STR32## in which R.sub.25 signifies hydrogen or C.sub.1-4 alkyl, preferably methyl, R.sub.25 most preferably signifying hydrogen; and T is as defined above.

In the compounds of formula Iaa, D' preferably signifies a radical of formula (a'), ##STR33## in which Ra' signifies hydrogen, halogen, preferably chlorine, nitro or cyano,

Ra" signifies hydrogen or halogen, preferably chlorine, a radical of formula (") ##STR34## in which the Ra''''s, independently, signify hydrogen or halogen, preferably chlorine, and either R.sub.1a and R.sub.2a, independently, signify an alkyl radical of 1 to 4 carbon atoms or are linked to form, together with the nitrogen atom, a morpholino radical; a radical (d), in which R.sub.23 signifies a phenyl radical or a 2-cyanophenyl radical; a radical (e), in which R.sub.23 ' signifies a phenyl radical; a radical (i), in which Ri signifies nitro; a radical (f), in which R.sub.23 " signifies chlorine and R.sub.23 "' signifies cyano; a radical (g), in which Rg and Rg' both signify bromine; a radical (h), in which Rh signifies nitro; a radical (j), in which Rj and Rj" each signify cyano and Rj' signifies methyl, or in which Rj signifies methoxycarbonyl, Rj' signifies methyl and Rj" signifies cyano.

K' preferably signifies a radical of formula (m), most preferably a radical of formula (m), in which R.sub.18 signifies hydrogen or methyl.

R.sub.16 most preferably signifies an ethyl radical.

T preferably signifies a radical ##STR35## in which R',R.sub.1 ',R.sub.2 ',R.sub.3 ', Y' and Q' correspond to the preferred significances of R, R.sub.1, R.sub.2, R.sub.3, Y and Q, as given above.

As examples of other preferred compounds of formula Ia may be given the compounds of formula Iab, ##STR36## in which Ka' signifies a coupling component,

Z signifies a bridging group ##STR37## t signifies 1 or 2, preferably 1, and T is as defined above, preferably T', as defined above.

In the compounds of formula Iab, Ka' may, for example, be of the benzene, naphthalene, heterocyclic or aliphatic series. Suitable significances of Ka' will suggest themselves to those skilled in the art and, as will be appreciated, the particular significance of Ka' is of minor consequence in the invention. As examples of Ka' may be given the radicals of formulae ##STR38## in which R.sub.18 ' and R.sub.19 ', which may be the same or different, each signify hydrogen, or an alkyl radical of 1 to 4 carbon atoms unsubstituted or substituted by C.sub.1-4 alkoxycarbonyl, benzoyloxy, phenoxy, halogen, preferably chlorine, hydroxy, cyano, C.sub.1-4 alkoxy, C.sub.1-4 alkylcarbonyloxy or N,N-di(C.sub.1-4) alkylamino,

or one of R.sub.18 ' and R.sub.19 ' signifies phenyl or cyclohexyl, the other having a significance as defined above, or R.sub.18 ' and R.sub.19 ', together with the nitrogen atom to which they are attached, signify ##STR39## R.sub.21 ' signifies a hydrogen atom, a C.sub.1-4 alkyl or alkoxy radical or a halogen atom, R.sub.19 " signifies phenyl, C.sub.1-4 alkyl, preferably methyl, unsubstituted or substituted by phenyl, e.g. benzyl, R.sub.20 " signifies hydrogen, phenyl or C.sub.1-4 alkyl, preferably methyl, R.sub.22 ' signifies C.sub.1-4 alkyl, preferably methyl, the R.sub.23 ''s which may be the same or different, each signifies C.sub.1-4 alkyl, preferably methyl, R.sub.24 ' signifies hydroxy, amino, or monophenylamino, R.sub.25 ' signifies hydrogen or an alkyl radical of 1 to 4 carbon atoms, unsubstituted or substituted by C.sub.1-4 alkoxy, preferably methoxy, R.sub.26 ' signifies hydrogen or halogen, e.g. chlorine or C.sub.1-4 alkyl or alkoxy, preferably hydrogen, R.sub.181 and R.sub.191, independently, signify hydrogen or C.sub.1-4 alkyl, or one of R.sub.181 and R.sub.191 signifies hydrogen or C.sub.1-4 alkyl, and the other has one of the above significances of R.sub.18 ' or R.sub.19 ' and v signifies O or NH.

The preferred significances of Ka' are the above formulae (p), (r) and (y). In the formula (p), above, R.sub.21 ' preferably signifies an alkyl radical of 1 to 4 carbon atoms, more preferably methyl, or a halogen atom, more preferably chlorine, R.sub.18 ' and R.sub.19 ' preferably signify hydrogen, C.sub.1-4 alkyl, preferably ethyl, unsubstituted or substituted by cyano. In the formula (r), R.sub.19 " preferably signifies C.sub.1-4 alkyl, e.g., methyl, or phenyl, R.sub.20 " preferably signifies C.sub.1-4 alkyl, preferably methyl, or hydrogen, R.sub.26 ' preferably signifies hydrogen or halogen, preferably chlorine. In the formula (y), R.sub.23 ' preferably signifies C.sub.1-4 alkyl, preferably methyl, phenyl, R.sub.25 ' preferably signifies hydrogen, C.sub.1-4 alkyl, unsubstituted or substituted by alkoxy, preferably methoxy; or phenyl, and v preferably signifies 0.

As examples of further compounds of formula Ia may be given the compounds of formula Iac. ##STR40## in which R.sub.6c signifies hydrogen, halogen, preferably chlorine, C.sub.1-4 alkyl, preferably methyl, or C.sub.1-4 alkoxy, preferably methoxy,

R.sub.1c and R.sub.2c, independently, signify hydrogen, alkyl of 1 to 4 carbon atoms, preferably methyl, or halogen, preferably chlorine, nitro, cyano or C.sub.1-4 alkoxy, preferably methoxy, R.sub.11c signifies hydrogen, phenoxy, halophenoxy, preferably 4-chlorophenoxy, C.sub.1-4 alkoxy, preferably methoxy, C.sub.1-4 alkyl, preferably methyl, C.sub.1-4 alkoxycarbonyl, preferably ethoxycarbonyl, phenylazo, C.sub.1-4 alkylphenylazo, preferably 4-methylphenylazo, with the proviso that (i) when R.sub.11c signifies phenylazo or C.sub.1-4 -alkylphenylazo R.sub.2c signifies hydrogen and R.sub.1c and R.sub.6c, independently, signify hydrogen, C.sub.1-4 alkyl, preferably methyl, C.sub.1-4 alkoxy, preferably methoxy, more preferably R.sub.1c and R.sub.6c signifying hydrogen and (ii) the diazo component bears up to a maximum of 3 substituents, R.sub.9c signifies cyano, halogen, preferably chlorine, hydrogen or nitro, more preferably cyano, R.sub.10c signifies C.sub.1-4 alkyl, preferably methyl, or phenyl, u signifies 2 or 3, preferably 3. T is as defined above, T preferably signifying T', as defined above.

As still further examples of formula Ia may be given the compounds of formula Iad, may be given the compounds of formula Iad, ##STR41## in which Hal signifies halogen, preferably chlorine,

Ka" signifies a radical (p), given above for Ka', and T is as defined above.

In the compounds Iad, R.sub.21 ' (in radical [p]), preferably signifies methyl or chlorine, R.sub.18 ' and R.sub.19 ', preferably signify, independently, hydrogen, ethyl or cyanoethyl. T preferably signifies T', above, more preferably ##STR42##

As further examples of compounds provided by the invention may be given the dyes of the anthraquinone series and of formula Ib, ##STR43## in which W signifies either a direct bond or a divalent bridging group,

A.sup.- and T are as defined above, z signifies 1 or 2, and when z signifies 2, the W's and T's may be the same or different, the W(s) being bound to ring Z.sub.10 or Z.sub.11, and rings Z.sub.10 and Z.sub.11 are optionally further substituted.

Preferred compounds of formula Ib are the compounds of formula Ib'. ##STR44## in which R.sub.40 signifies a group ##STR45## in which T is as defined above, R.sub.45 signifies hydrogen or hydroxy, preferably hydrogen,

s signifies 1 or 2, or R.sub.40 signifies a hydroxy group or the group --NH--R.sub.46, in which R.sub.46 signifies hydrogen; C.sub.1-4 alkyl, preferably methyl; cyclohexyl; phenyl, unsubstituted or substituted by up to two substituents, selected from C.sub.1-4 alkyl, preferably methyl, C.sub.1-4 alkoxy, benzyloxy and halogen, preferably chlorine, R.sub.41 signifies a group ##STR46## in which x6 signifies 2, 3 or 4, preferably 2 or 3, a group ##STR47## a group ##STR48## hydrogen, halogen, preferably bromine, cyano or --CONH.sub.2, R.sub.42 signifies a group ##STR49## a group in which R.sub.47 signifies halogen, preferably chlorine, or C.sub.1-4 alkyl, preferably methyl, q signifies 0, 1 or 2, Y.sub.2 signifies ##STR50## in which x2 signifies 1 or 2, and x2' signifies 2 or 3, preferably 2; or a group --NH--R.sub.46, in which R.sub.46 is as defined above, R.sub.43 and R.sub.44, which may be the same or different, each signify hydrogen, halogen, --NO.sub.2, --NH.sub.2 or --OH, a mono(C.sub.1-4) alkylamino or di-(C.sub.1-4) alkylamino radical, a monophenylamino, a phenoxy radical or a monocyclohexylamino radical, most preferably both signify hydrogen, with the proviso that the compounds contain one or two T groups.

The preferred compounds of formula Ib' contain only one T group.

As examples of preferred compounds of formula Ib', may be given the compounds of formula Iba, ##STR51## in which R.sub.58 signifies a C.sub.1-4 alkyl radical, preferably methyl or ethyl,

R.sub.69 signifies hydrogen, C.sub.1-4 alkyl, preferably methyl or ethyl, C.sub.1-4 alkoxy, preferably methoxy or ethoxy, benzyloxy or halogen, preferably chlorine, R.sub.70 signifies hydrogen, C.sub.1-4 alkyl, preferably methyl or ethyl, C.sub.1-4 alkoxy, preferably methoxy or ethoxy, or halogen, preferably chlorine R.sub.71 signifies methyl or ethyl, Q" signifies an unsubstituted phenyl, biphenylyl, naphthyl or dibenzofuranyl radical or a phenyl radical substituted by halogen, preferably chlorine, cyano or nitro, x5 signifies 2 or 3, and x4 signifies 2, 3 or 4, the compounds of formula Ibb, ##STR52## in which R.sub.58, R.sub.70, R.sub.71, x4 and Q" are as defined above, and R.sub.72 signifies hydrogen, C.sub.1-4 alkyl, e.g. methyl, ethyl, propyl or butyl, or cyclohexyl, the compounds of formula Ibc, ##STR53## in which R.sub.58, R.sub.70, R.sub.71, R.sub.72, x4 and Q" are as defined above, the compounds of formula Ibd, ##STR54## in which R.sub.58, R.sub.71, R.sub.72, x4 and Q" are as defined above, and the compounds of formula Ibe, ##STR55## in which R.sub.55 signifies hydrogen or methyl, and R.sub.58, R.sub.71, R.sub.72, x4 and Q" are as defined above.

The compounds of the invention may be produced in conventional manner from available starting materials. For example, the compounds can be produced by reacting a compound of formula II, ##STR56## in which R, R.sub.1, R.sub.2, R.sub.3 and Q are as defined above,

with a dyestuff containing a leaving group such as the acid radical of an ester, e.g. a tosylate group, in conventional manner.

Where appropriate, the cleaving group may be an A.sup.- yielding group or, if desired, the required A.sup.- group may be introduced using conventional ion-exchange techniques.

Alternatively, for example, the compounds of the invention may be obtained by reacting a dyestuff containing the group ##STR57## with quaternising agent of the formula R.sub.1 --A, in which R.sub.1 is as defined above, and A is an A.sup.- yielding group, in conventional manner.

The azo compounds of the invention may also be produced using conventional coupling techniques.

As examples of alkyl and alkoxy radicals of 1 to 4 carbon atoms, as used herein, may be given methyl, ethyl, n-propyl, isopropyl and n-butyl and the corresponding alkoxy radicals. Unless otherwise stated, the preferred such radicals are methyl, ethyl, methoxy and ethoxy, methyl and methoxy being most preferred. By the term halogen, as used herein, is meant chlorine, bromine and iodine; chlorine and bromine being preferred, chlorine being most preferred.

The compounds of formula I are useful as dyes. They may be converted into dyeing preparations, e.g. into stable, liquid or solid dyeing preparations, in conventional manner, e.g. by grinding or granulating or dissolving in conventional dyestuff solvents, if necessary with the addition of assistants such as stabilizers. Such preparations may be produced, for example, in accordance with French Pat. Nos. 1,572,030 and 1,581,900.

The compounds of formula I may be used in the dyeing or printing of textile substrates, whether in fibre, yarn or fabric form, which consist of or comprise homopolymers or co-polymers of acrylonitrile or asymmetrical dicyanoethylene. The dyeing of such substrates may be carried out in conventional manner.

The compounds of formula I may also be used for dyeing or printing substrates of synthetic polyamide or synthetic polyester fibres, modified by the introduction of acid groups. Polyamides of this type are described in Belgian Pat. No. 706,104 and polyester fibres of this type are described in U.S. Pat. No. 3,379,723. The dyeing of such substrates may be carried out in conventional manner. It is advantageous to dye in an aqueous, neutral or acid medium at from 60.degree. C to the boil or at temperatures above 100.degree. C under pressure.

The dyeings obtained with the compounds of formula I are level, have stable light fastness as well as good wet fastness properties, e.g. to washing, perspiration, sublimation, pleating, decatizing, pressing, steam, water, sea water, dry cleaning, cross-dyeing and solvents. The dyes are well soluble in water, show good compatibility with salt, good stability to boiling, good pH stability and partly reserve fibres other than those on which they are dyeable. Further, they possess good power of build-up in combination with other basic dyes.

The compounds, which have good solubility in organic solvents, may also be used for the dyeing of natural or synthetic resins in the mass, being incorporated therein in conventional manner, e.g. by intimate admixture therein, for example by milling, optionally with the use of a solvent.

It has been found that mixtures of two or more of the compounds of the present invention or of one of the compounds of the present invention and other cationic dyes can be used with advantage.

The following Examples, in which parts and percentages are by weight and temperatures are in degrees centrigrade, illustrate the invention.

EXAMPLE 1

17.2 Parts 1-amino-2-chloro-4-nitrobenzene are stirred into 30 parts concentrated hydrochloric acid, and then diluted with 200 parts ice and 100 parts water. Diazotization is accomplished according to a known method by the addition of a solution consisting of 7 parts sodium nitrite in 30 parts water. The resulting diazo solution is filtered and the excess sodium nitrite is decomposed with aminosulphonic acid. Finally the diazo solution is added dropwise to 37.8 parts of a coupling component of the formula ##STR58## dissolved in 200 parts water. After coupling, the pH of the solution is adjusted to a value from 4 to 5 by the addition of a 30% aqueous solution of sodium hydroxide and the resulting dye of the formula ##STR59## is filtered, washed with a 2% solution of sodium chloride, dried and ground. 49.5 Parts of a red-brown powder are obtained, which in an acid dye bath gives wet-fast and light-fast dyeings of a brownish-red shade on polyacrylonitrile fibres. Likewise on acid-modified polyester and polyamide fibres the same fast brownish-red dyeings are obtained.

The coupling component used above may be prepared in the following manner:

42.5 parts N,N-diethyl-N-2-phenoxyethyl amine (obtained from the reaction of 1-phenoxy-2-chloroethane with diethylamine) are heated to 80.degree. to 90.degree. in a nitrogen atmosphere, together with 36.8 parts N-ethyl-N-2'-chloroethylaniline in 90 parts water and 10 parts ethyl alcohol. The reaction solution is stirred for 3 hours in this temperature range and the pH is adjusted to between 8 and 9 by the addition of sodium hydroxide. The solution is diluted with 50 parts water, cooled to a temperature between 40.degree. and 50.degree., extracted twice each time with 100 parts of toluene and the toluene phase is separated. The coupling component is obtained in the form of a 40% aqueous solution which may be used directly for the preparation of the dye.

EXAMPLE 2

Instead of the coupling component in Example 1, 45.4 parts of a compound of the formula ##STR60## is employed, using a similar process to yield a dye of the formula ##STR61## which, likewise, gives fast dyeings of a brownish-red shade on polyacrylonitrile and acid-modified polyester and polyamide fibres.

EXAMPLE 3

21 Parts 1-amino-2,6-dichloro-4-nitrobenzene are dissolved in 40 parts concentrated sulphuric acid at a temperature from 20.degree. to 30.degree. and is diazotized by the addition of a 40% solution of nitrosylsulfuric acid in concentrated sulphuric acid. The mixture is stirred into 100 parts water and 200 parts ice, and is stirred for 2 hours after the completion of the diazotization. After the decomposition of the excess nitrosylsulphuric acid with aminosulphuric acid, the cold diazo solution is added dropwise to an aqueous solution consisting of 39.9 parts of the coupling component of the formula ##STR62## and 400 parts water, and the pH of the solution is adjusted to 3 by the addition of a caustic soda solution. After the addition of 40 parts sodium chloride the dye of the formula ##STR63## is precipitated out, filtered by suction, washed with a 2% sodium chloride solution, dried and ground. 51.9 Parts of a yellow-brown powder are obtained, which powder gives light-fast and wet-fact dyeings of a yellow brown shade on polyacrylonitrile fibres dyed in an acid bath. A similar fast dyeing of a yellow brown shade was obtained on acid-modified polyester and polyamide fibres.

EXAMPLE 4

In place of the coupling component of Example 3, 41.8 parts of the compound of formula ##STR64## are used employing a similar process, and the dye of formula ##STR65## is obtained which gives fast yellow brown dyeings on polyacrylonitrile or acid-modified polyester or polyamide fibres.

EXAMPLE 5

In place of the coupling component of Example 4, 43.9 parts of the compound of formula ##STR66## is used employing a similar process and the dye of the formula ##STR67## is obtained, which likewise gives fast dyeings of a yellow brown shade on polyacrylonitrile and acid-modified polyester and polyamide fibres.

The structural composition of further dyes is shown in Table I. They may be produced in accordance with the procedure of Examples 1 to 5 and agree with the formula ##STR68## in which R.sub.1 ' to R.sub.5 ' have the significances given in the columns. A further column I indicates the dye shade on polyacrylonitrile. The anion A.sup.- may be any one of those named in the foregoing description. The symbol K.sup.+ may stand for any of the groups K.sub.1 to K.sub.46 shown in Table A. These groups in any single dye may be exchanged for any of the further groups given for K.sub.1 to K.sub.46.

Table A______________________________________K.sub.1 signifies the group ##STR69##K.sub.2 signifies the group ##STR70##K.sub.3 signifies the group ##STR71##K.sub.4 signifies the group ##STR72##K.sub.5 signifies the group ##STR73##K.sub.6 signifies the group ##STR74##K.sub.7 signifies the group ##STR75##K.sub.8 signifies the group ##STR76##K.sub.9 signifies the group ##STR77##K.sub.10 signifies the group ##STR78##K.sub.11 signifies the group ##STR79##K.sub.12 signifies the group ##STR80##K.sub.13 signifies the group ##STR81##K.sub.14 signifies the group ##STR82##K.sub.15 signifies the group ##STR83##K.sub.16 signifies the group ##STR84##K.sub.17 signifies the group ##STR85##K.sub.18 signifies the group ##STR86##K.sub.19 signifies the group ##STR87##K.sub.20 signifies the group ##STR88##K.sub.21 signifies the group ##STR89##K.sub.22 signifies the group ##STR90##K.sub.23 signifies the group ##STR91##K.sub.24 signifies the group ##STR92##K.sub.25 signifies the group ##STR93##K.sub.26 signifies the group ##STR94##K.sub.27 signifies the group ##STR95##K.sub.28 signifies the group ##STR96##K.sub.29 signifies the group ##STR97##K.sub.30 signifies the group ##STR98##K.sub.31 signifies the group ##STR99##K.sub.32 signifies the group ##STR100##K.sub.33 signifies the group ##STR101##K.sub.34 signifies the group ##STR102##K.sub.35 signifies the group ##STR103##K.sub.36 signifies the group ##STR104##K.sub.37 signifies the group ##STR105##K.sub.38 signifies the group ##STR106##K.sub.39 signifies the group ##STR107##K.sub.40 signifies the group ##STR108##K.sub.41 signifies the group ##STR109##K.sub.42 signifies the group ##STR110##K.sub.43 signifies the group ##STR111##K.sub.44 signifies the group ##STR112##K.sub.45 signifies the group ##STR113##K.sub.46 signifies the group ##STR114## Table I__________________________________________________________________________Ex. R.sub.1 ' R.sub.2 ' R.sub.3 ' R.sub.5 ' R.sub.4 ' K.sup..sym. I__________________________________________________________________________6 Cl H H H C.sub.2 H.sub.5 K.sub.1 brownish- red7 " H H H " K.sub.3 "8 " H H H " K.sub.4 "9 " H H H " K.sub.5 "10 " H H H " K.sub.6 "11 " H H H " K.sub.7 "12 " H H H " K.sub.8 "13 " H H H " K.sub.9 "14 " H H H " K.sub.10 "15 " H H H " K.sub.11 "16 " H H H " K.sub.12 "17 " H H H " K.sub.13 "18 " H H H " K.sub. 14 "19 " H H H " K.sub.15 "20 " H H H " K.sub.16 "21 " H H H " K.sub.17 "22 " H H H " K.sub.18 "23 " H H H " K.sub.19 "24 " H H H " K.sub.20 "25 " H H H " K.sub.21 "26 " H H H " K.sub.22 "27 " H H H " K.sub.23 "28 " H H H " K.sub.24 "29 " H H H " K.sub.25 "30 " H H H " K.sub.26 "31 " H H H " K.sub.27 "32 " H H H " K.sub.28 "33 " H H H " K.sub.29 "34 " H H H " K.sub.30 "35 " H H H " K.sub.31 "36 " H H H " K.sub.32 "37 " H H H " K.sub.33 "38 " H H H " K.sub.34 "39 " H H H " K.sub.35 "40 " H H H " K.sub.36 "41 " H H H " K.sub.37 "42 " H H H " K.sub.38 "43 " H H H " K.sub.39 "44 " H H H " K.sub.40 "45 " H H H " K.sub.41 "46 " H H H " K.sub.42 "47 " H H H " K.sub.43 "48 " H H H " K.sub.44 "49 " H H CH.sub.3 CH.sub.3 K.sub.1 "50 " H H " " K.sub.2 "51 " H H " " K.sub.13 "52 " H CH.sub.3 " " K.sub.17 "53 " H OCH.sub.3 " " K.sub.18 "54 " H Cl " " K.sub.44 yellowish- orange55 " Cl H H C.sub.2 H.sub.5 K.sub.1 yellowish- brown56 " " H H " K.sub.2 "57 " " H H " K.sub.13 "58 " " H H " K.sub.17 "59 " " H H " K.sub.18 "60 " " H H " K.sub.19 "61 " " H H " K.sub.35 "62 " " H H " K.sub.43 "63 " " H H " K.sub.44 "64 " " H H " K.sub.12 "65 " " H H " K.sub.14 "66 " " H H " K.sub.15 "67 " " H H " K.sub.16 "68 " " H H " K.sub.36 "69 " " H H " K.sub.37 "70 " " CH.sub.3 H " K.sub.1 "71 " " " H " K.sub.2 "72 CN H H H " K.sub.1 rubine73 " H H H " K.sub.2 "74 " H H H " K.sub.13 "75 " H H H " K.sub.17 "76 " H H H " K.sub.18 "77 " H H H " K.sub.19 "78 " H H H " K.sub.35 "79 " H H H " K.sub.43 "80 " H H H " K.sub.44 "81 " H H CH.sub.3 CH.sub.3 K.sub.2 "82 NO.sub.2 Br CH.sub.3 H C.sub.2 H.sub.5 K.sub.1 violet83 " " " H " K.sub.2 "84 " " " H " K.sub.13 "85 " " " H " K.sub.17 "86 " " " H " K.sub.18 "87 " " " H " K.sub.19 "88 " " " H " K.sub.35 "89 " " " H " K.sub.43 "90 " " " H " K.sub.44 "91 " " " CH.sub.3 " K.sub.2 "92 " " H H " K.sub.2 reddish- violet93 " Cl CH.sub.3 H " K.sub.2 violet94 CF.sub.3 H H H " K.sub.2 rubine95 SO.sub.2 CH.sub.3 H H H " K.sub.2 "96 CH.sub.3 H H H " K.sub.2 brownish- red97 OCH.sub.3 H H H " K.sub.2 "98 CN CN CH.sub.3 H " K.sub.2 bluish- violet99 NO.sub.2 NO.sub.2 " H " K.sub.2 "100 Cl H H H C.sub.4 H.sub.9 K.sub.2 brownish- red101 " H H H C.sub.2 H.sub.4 CN K.sub.2102 " H H H C.sub.2 H.sub.4COOC.sub.2 H.sub.5 K.sub.2 "103 ##STR115## orange104 ##STR116## red105 ##STR117## bluish- violet106 ##STR118## reddish- blue107 ##STR119## reddish- violet__________________________________________________________________________

The structural composition of further dyes is shown in Table II. They can be produced in accordance with the procedure of Examples 3 to 5 and agree with the formula ##STR120## in which R.sub.1 ' to R.sub.8 ' and K.sup.+ have the significances as shown in the columns of the Table. A further column I shows the dye-shade on polyacrylonitrile. The anion A.sup.- may be any one of those named in the foregoing description.

Table II__________________________________________________________________________Ex. R.sub.1 ' R.sub.2 ' R.sub.3 ' R.sub.5 ' R.sub.6 ' R.sub.7 ' R.sub.8 ' R.sub.4 ' K.sup..sym. I__________________________________________________________________________108 --Cl --Cl H H H --CH.sub.3 --CH.sub.3 --C.sub.2 H.sub.5 K.sub.1 golden-yellow109 " " H H H " " " K.sub.2 "110 " " H H H " " " K.sub.12 "111 " " H H H " " " K.sub.13 "112 " " H H H " " " K.sub.14 "113 " " H H H " " " K.sub.15 "114 " " H H H " " " K.sub.16 "115 " " H H H " " " K.sub.17 "116 " " H H H " " " K.sub.18 "117 " " H H H " " " K.sub.19 "118 " " H H H " " " K.sub.35 "119 " " H H H " " " K.sub.36 "120 " " H H H " " " K.sub.37 "121 " " H H H " " " K.sub.43 "122 " " H H H " " " K.sub.44 "123 " " --CH.sub.3 H H " " " K.sub.2 reddish- yellow124 " " H --CH.sub.3 H " " --CH.sub.3 K.sub.2 "125 " " H H H --(CH.sub.2).sub.5 -- --C.sub.2 H.sub.5 K.sub.2 golden-yellow126 " " H H H --C.sub.2 H.sub.4 --O--C.sub.2 H.sub.4-- " K.sub.2 "127 " " H H H --C.sub.4 H.sub.9 --C.sub.4 H.sub.9 " K.sub.2 "128 " H H H --Cl --CH.sub.3 --CH.sub.3 " K.sub.1 orange129 " H H H " " " " K.sub.2 "130 " H H H " " " " K.sub.12 "131 " H H H " " " " K.sub.13 "132 " H H H " " " " K.sub.14 "133 " H H H " " " " K.sub.15 "134 " H H H " " " " K.sub.16 "135 " H H H " " " " K.sub.17 "136 " H H H " " " " K.sub.18 "137 " H H H " " " " K.sub.19 "138 " H H H " " " " K.sub.20 "139 --Cl H H H --Cl --CH.sub.3 --CH.sub.3 --C.sub.2 H.sub.5 K.sub.35 orange140 " H H H " " " " K.sub.36 "141 " H H H " " " " K.sub.37 "142 " H H H " " " " K.sub.43 "143 " H H H " " " " K.sub.44 "144 " H H --CH.sub.3 " " " --CH.sub.3 K.sub.2 "145 " H H H " --C.sub.2 H.sub.4 --O--C.sub.2 H.sub.4 -- --C.sub.2 H.sub.5 K.sub.2 "146 " H H H " --(CH.sub.2).sub.5 -- " K.sub.2 "__________________________________________________________________________

EXAMPLE 147

17.8 Parts 4-amino-.omega.-dimethylaminoacetophenone (prepared by the reaction between 4 acetamino-.omega.-chloroacetophenone with dimethylamine and saponification of the acetamino group) are diazotized at 0.degree. C employing conventional methods. The pH is adjusted to 8.0 by the addition of sodium carbonate and over the period of 1 hour a solution of 16.3 parts N,N-diethyl-m-toluidine, dissolved in 150 parts water and 50 parts glacial acetic acid, is added dropwise. After completion of the coupling reaction, the dye is salted out with sodium chloride, filtered, washed with a dilute brine solution, dried and ground, 17 Parts of the dye so obtained are dissolved in 75 parts isopropanol and 75 parts ethylmethylketone and over the period of 1 hour are mixed with 20.3 parts 1-phenoxy-4-chlorobut-2,3-ene. After 2 more hours at boiling temperature, the mixture is cooled to room temperature, the dye, after the addition of ether or dioxane, is filtered and washed with acetone and agrees with the formula ##STR121##

Fast red dyeings are obtained on polyacrylonitrile as well as on acid-modified polyester or polyamide fibres.

EXAMPLE 148

In place of the 1-phenoxy-4-chlorobut-2,3-ene used in Example 147, 18.6 parts of the compound of the formula ##STR122## (obtained by condensing sodium phenoxide with 1,4-dichlorobutane in the presence of sodium iodide), is employed using the procedure as described in Example 147 and the dye of the formula ##STR123## is obtained which likewise gives fast red dyeings on polyacrylonitrile as well as on acid-modified polyester and polyamide fibres.

The structural composition of further dyes is shown in the following Table III. The dyes can be produced in accordance with the procedure of Examples 147 and 148 and agree with the formula ##STR124## in which K.sup.+, K"' , X and have the significances as shown in the columns. A further column I indicates the shade of dyeing obtained on polyacrylonitrile. The anion A.sup.- may be any one of those named in the foregoing description.

Table III______________________________________Ex. X Y K.sup..sym. K" I______________________________________149 ##STR125## 1 K.sub.1 ##STR126## red150 " 1 K.sub.2 " "151 " 1 K.sub.13 " "152 " 1 K.sub.17 " "153 " 1 K.sub.18 " "154 " 1 K.sub.19 " "155 " 1 K.sub.35 " "156 " 1 K.sub.43 " "157 " 1 K.sub.44 " "158 SO.sub.2 1 K.sub.2 " "159 ##STR127## 2 K.sub.2 " orange160 " 1 K.sub.1 ##STR128## red- dish- yellow161 " 1 K.sub.2 " "162 " 1 K.sub.1 ##STR129## "163 " 1 K.sub.2 " "164 " 1 K.sub.13 " "165 " 1 K.sub.17 " "166 " 1 K.sub.18 " "167 " 1 K.sub.19 " "168 " 1 K.sub.35 " "169 " 1 K.sub.43 " "170 " 1 K.sub.44 " "171 " 1 K.sub.1 ##STR130## "172 " 1 K.sub.2 " "172a " 1 K.sub.2 ##STR131## "173 " 1 K.sub.2 ##STR132## "174 " 1 K.sub.1 ##STR133## yellow175 " 1 K.sub.2 " "176 " 1 K.sub.16 " "177 " 1 K.sub.17 " "178 " 1 K.sub.18 " "179 " 1 K.sub.19 " "180 " 1 K.sub.35 " "181 " 1 K.sub.43 " "182 " 1 K.sub.44 " "183 " 1 K.sub.12 " "184 " 1 K.sub.1 ##STR134## "185 " 1 K.sub.2 " "186 " 1 K.sub.1 ##STR135## "187 " 1 K.sub.2 " "188 " 1 K.sub.2 ##STR136## "189 " 1 K.sub.2 ##STR137## "______________________________________

EXAMPLE 190

25.6 parts of 4-amino-4'-chloro-diphenyletherchlorohydrate are dissolved in 300 parts water and are diazotized, after the addition of 18 parts of 30% hydrochloric acid with 6.9 parts sodium nitrite, according to conventional methods. This diazo solution is added to 24.7 parts of the coupling component of the formula ##STR138## dissolved in 200 parts 2% hydrochloric acid. After completion of the coupling, the dye of the formula ##STR139## is salted out with sodium chloride at 60.degree., filtered and dried. 15 Parts of the dye so obtained are diluted with 75 parts isopropylalcohol and 75 parts ethylmethylketone, mixed with 9.0 parts 2-phenoxy-1-chloroethane and the mixture is heated for 3 hours. After cooling, the quaternated dye of the formula ##STR140## is precipitated out with ether, dioxane or acetone. After filtering, drying and grinding a dye is obtained which gives light-fast and wet-fast dyeings of a reddish-yellow shade on polyacrylonitrile, acid-modified polyesters and polyamide fibres.

The coupling component may be prepared by condensing cyanoacetic acid-3-dimethylamino-n-propylamide with ethyl acetate.

EXAMPLE 191

In place of the 2-phenoxy-1-chloroethane quaternating agent of Example 190, the compound of the formula ##STR141## is used, employing the same method, to obtain the dye of the formula ##STR142## which dye likewise gives fast reddish-yellow dyeings on polyacrylonitrile as well as on acid-modified polyester and polyamide fibres.

The structural composition of further dyes is shown in the following Table IV. They may be prepared according to the procedure of Examples 190 and 191 and agree with the formula ##STR143## in which R.sub.1 ', R.sub.2 ', R.sub.6 ', R.sub.9 ' to R.sub.11 ', x and K.sup.+ have the significances as shown in the columns. A further column I indicates the dye shade on polyacrylonitrile. The anion A.sup.- may be any one of those named in the foregoing description.

Table IV__________________________________________________________________________Ex. R'.sub.1 R'.sub.2 R'.sub.6 R'.sub.9 R'.sub.10 X K.sup..sym. R'.sub.11 I__________________________________________________________________________192 H H H CN CH.sub.3 3 K.sub.1 ##STR144## yellow193 H H H " " 3 K.sub.2 " "194 H H H " " 3 K.sub.12 " "195 H H H " " 3 K.sub.13 " "196 H H H " " 3 K.sub.14 " "197 H H H " " 3 K.sub.15 " "198 H H H " " 3 K.sub.16 " "199 H H H " " 3 K.sub.17 " "200 H H H " " 3 K.sub.18 " "201 H H H " " 3 K.sub.19 " "202 H H H " " 3 K.sub.35 " "203 H H H " " 3 K.sub.36 " "204 H H H " " 3 K.sub.43 " "205 H H H " " 3 K.sub.44 " "206 Cl H Cl " " 3 K.sub.2 H "207 " H " " " 3 K.sub.17 H "208 " H " " " 3 K.sub.19 H "209 " H " " " 3 K.sub.43 H "210 H H H " " 3 K.sub.2 ##STR145## golden yellow211 H H H " " 3 K.sub.17 " "212 H H H " " 3 K.sub.43 " "213 CH.sub.3 H H " " 3 K.sub.2 ##STR146## reddish- yellow214 H H Cl " " 3 K.sub.2 CH.sub.3 O "215 H H H " " 3 K.sub.2 H greenish- yellow216 H H Cl " " 3 K.sub.2 CH.sub.3 yellow217 H Cl " " " 3 K.sub.2 H greenish- yellow218 H H " " " 3 K.sub.2 H "219 H H " " " 3 K.sub.2 COOC.sub.2 H.sub. 5 "220 H H H " " 2 K.sub.2 ##STR147## yellow221 H H H H " 3 K.sub.2 " "222 H H H Cl " 3 K.sub.2 " "223 H H H NO.sub.2 " 3 K.sub.2 " "224 H H H CN ##STR148## 3 K.sub.2 " "__________________________________________________________________________

EXAMPLE 225

40 Parts nitrosylsulphuric acid with a nitric acid strength of 6.4% is stirred with a mixture of 50 parts acetic acid and 50 parts phosphoric acid under cooling at a temperature from -5.degree. to 0.degree.. 17.7 Parts of 5-amino-3-phenyl-1,2,4-thiadiazole are added to the reaction mixture and the further 60 parts of the mixture of 50 parts acetic acid and 50 parts phosphoric acid is added thereto and stirring is effected at the same temperature for 21/2 hours.

After clarification the clear yellow diazo solution is added dropwise to an aqueous solution consisting of 39.1 parts of the coupling component of the formula ##STR149## in 300 parts water including 2 parts sodium acetate and 5 parts aminosulphonic acid. The mixture is stirred for 1 hour and the pH of the solution is adjusted to a value from 4 to 5 by the addition of sodium hydroxide; then, with the addition of 30 parts sodium chloride, the dye of the formula ##STR150## is salted out. After filtering, washing with a dilute brine solution, drying and grinding, 51 parts of a red powder is obtained which fast bluish-red dyeings on polyacrylonitrile and acid-modified polyester and polyamide fibres.

EXAMPLE 226

In place of the coupling component used in Example 225, 39.9 parts of the compound of the formula ##STR151## is used to obtain a similar dye of the formula ##STR152## which on polyacrylonitrile as well as on acid-modified polyamide and polyester fibres gives fast dyeings of a yellowish red shade.

The structural composition of further dyes is shown in the following Table V. They can be in accordance with the process of Examples 225 and 226 and correspond with the formula ##STR153## in which R.sub.3 ' to R.sub.5 ', R.sub.12 ' and K.sup.+ have the significances as shown in the columns. A further column I indicates the dye-shade on polyacrylonitrile. The anion A.sup.- may be any one of those named in the foregoing description.

Table V__________________________________________________________________________Ex. R'.sub.3 R'.sub. R'.sub.12 K.sup..sym. R'.sub.4 I__________________________________________________________________________227 H H ##STR154## K.sub.1 C.sub.2 H.sub.5 yellowish- red228 H H " K.sub.2 " "229 H H " K.sub.12 " "230 H H " K.sub.13 " "231 H H " K.sub.14 " "232 H H " K.sub.15 " "233 H H " K.sub.16 " "234 H H " K.sub.17 " "235 H H " K.sub.18 " "236 H H " K.sub.19 " "237 H H " K.sub.35 " "238 H H " K.sub.36 " "239 H H " K.sub.37 " "240 H H " K.sub.43 " "241 H H " K.sub.44 " "242 H CH.sub.3 " K.sub.1 CH.sub.3 "243 H " " K.sub.2 " "244 H " " K.sub.12 " "245 H " " K.sub.13 " "246 H " " K.sub.14 " "247 H " " K.sub.15 " "248 H " " K.sub.16 " "249 H " " K.sub.17 " "250 H " " K.sub.18 " "251 H " " K.sub.19 " "252 H " " K.sub.35 " "253 H " " K.sub.36 " "254 H " " K.sub.37 " "255 H " " K.sub.43 " "256 H " " K.sub.44 " "257 CH.sub.3 H ##STR155## K.sub.1 C.sub.2 H.sub.5 bluish- red258 " H " K.sub.3 " "259 " H " K.sub.12 " "260 " H " K.sub.13 " "261 " H " K.sub.14 " "262 " H " K.sub.15 " "263 " H " K.sub.16 C.sub.2 H.sub.5 "264 " H " K.sub.17 " "265 " H " K.sub.18 ""266 " H " K.sub.19 " "267 " H " K.sub.35 " "268 " H " K.sub.36 " "269 " H " K.sub.37 " "270 " H " K.sub.43 " "271 " H " K.sub.44 " "272 " H ##STR156##273 " H ##STR157## K.sub.2 " "274 " H ##STR158## K.sub.2 " "275 " H ##STR159## K.sub.2 " "276 " H CH.sub. 3 SO.sub.2 K.sub.2 " "277 " H CH.sub.3SO K.sub.2 " "278 " H CH.sub.3S K.sub.2 " "279 CH.sub.3 H Cl K.sub.2 C.sub.2 H.sub.5 red280 " H CH.sub.3 K.sub.2 " "281 H CH.sub.3 ##STR160## K.sub.2 CH.sub.3 yellowish- red282 H " ##STR161## K.sub.2 C.sub.4 H.sub.9 "283 H " " K.sub.2 C.sub.2 H.sub.4 CN orange284 H " " K.sub.4 CH.sub.3 yellowish- red__________________________________________________________________________285 ##STR162##286 ##STR163##287 ##STR164##288 ##STR165##289 ##STR166##290 ##STR167##291 ##STR168##292 ##STR169##293 ##STR170##294 ##STR171##295 ##STR172##__________________________________________________________________________

EXAMPLE 296

94.8 Parts 1-methylamino-4-bromoanthraquinone and 1 part copper acetate are added to 90 parts 1-dimethylamino-3-aminopropane and are stirred at 90.degree. to 100.degree. until the condensation reaction is finished as determined by thin-layer chromatography. The mixture is diluted with water until the reaction product begins to separate out. After cooling, the blue dye is filtered with suction, washed with neutral water and dried.

50.5 Parts of the fine pulverized dye so obtained is dissolved in 1000 parts dichlorobenzene and mixed with 31.2 parts 1-phenoxy-2-chloroethane, at 150.degree. and is afterwards stirred at this temperature for 1 hour. After cooling the separated dye is filtered with suction, washed with toluene and dried under vacuum at 50.degree. to 60.degree.. 53 Parts of blue dye of the formula ##STR173## are obtained which dye gives fast blue dyeings on polyacrylonitrile and acid-modified polyamide fibres.

EXAMPLE 297

In place of 1-phenoxy-2-chloroethane as used in Example 296, 36 parts 1-phenoxy-4-chlorobutene-2 is used, employing the same procedure as described in Example 296, to obtain a similar dye of the formula ##STR174## which on polyacrylonitrile and acid-modified polyamide fibres gives fast dyeings of a blue shade.

The structural composition of further dyes is shown in the following Table VI. The dyes may be obtained according to the procedure of the processes hereinbefore described and they correspond with the formula ##STR175## in which R.sub.13 ' to R.sub.15 ', K.sup.+ and X have the significances as shown in the columns of the Table. A further column indicates the dye shade on polyacrylonitrile. The anion A.sup.- may be any one of those named in the foregoing description.

Table VI______________________________________Ex. R'.sub.14 R'.sub.15 X K.sup..sym. R'.sub.13 I______________________________________298 H H 1 K.sub.2 CH.sub.3 blue299 H H 1 K.sub.13 " "300 H H 1 K.sub.17 " "301 H H 1 K.sub.18 " "302 H H 1 K.sub.19 " "303 H H 1 K.sub.35 " "304 H H 1 K.sub.43 " "305 H H 1 K.sub.46 " "306 H H 1 K.sub.2 ##STR176## "307 H OH 1 K.sub.2 CH.sub.3 "308 H H 2 K.sub.2 " "309 H H 1 K.sub.1 ##STR177## greenish- blue310 H H 1 K.sub.2 " "311 H H 1 K.sub.13 " "312 H H 1 K.sub.17 " "313 H H 1 K.sub.18 " "314 H H 1 K.sub.19 " "315 H H 1 K.sub.35 " "316 H H 1 K.sub.44 " "317 H H 1 K.sub.46 ##STR178## greenish- blue318 H OH 1 K.sub.2 " "319 CN H 1 K.sub.2 CH.sub.3 "320 CONH.sub.2 H 1 K.sub.2 " "321 Br H 1 K.sub.2 " "______________________________________

EXAMPLE 322

40.5 Parts of monochloromethylated 1-methylamino-4-(2',4'-xylidine)-anthraquinone, (obtained by reacting 1-methylamino-4-(2',4'-xylidene)-anthraquinone with dichlorodimethylether) are dissolved in 450 parts methanol at 50.degree. and at this temperature is added dropwise to a solution of 15 parts diethylamine in 40 parts methanol. The solution is heated to its boiling point and then cooled to 40.degree., and a solution of 15.7 parts 2-phenoxy-1-chloroethane in 30 parts methanol are added thereto. The mixture is heated to its boiling point and then left to cool. The precipitated dye is filtered and washed with 50 parts methanol. After drying 41.4 parts of a dye of the formula ##STR179## is obtained which on polyacrylonitrile and acid-modified polyester and polyamide fibres gives fast dyeings of a greenish-blue shade.

The structural composition of further dyes is given in the following Table VII. They can be prepared in accordance with the procedure of Example 322 and correspond to the formula ##STR180## in which R.sub.13 ', R.sub.16 ', Y and K.sup.+ have the significances as shown in the columns. A further column I indicates the shade of dyeing obtained on polyacrylonitrile. The anion A.sup.- may be any one of these named in the foregoing description.

Table VII______________________________________Ex. R'.sub.13 R'.sub.16 K.sup..sym. Y I______________________________________323 H H K.sub.2 CH.sub.2 reddish-blue324 H H K.sub.13 " "325 H H K.sub.17 " "326 H H K.sub.18 " "327 H H K.sub.19 " "328 H H K.sub.35 " "329 H H K.sub.43 CH.sub.2 reddish-blue330 H H K.sub.44 " "331 H H K.sub.1 OC.sub.2 H.sub.4 "332 H H K.sub.2 " "333 H H K.sub.13 " "334 H H K.sub.17 " "335 H H K.sub.18 " "336 H H K.sub.19 " "337 H H K.sub.35 " "338 H H K.sub.43 " "339 H H K.sub.44 " "340 H H K.sub.45 CH.sub.2 "341 H H K.sub.46 " "342 H H K.sub.45 OC.sub.2 H.sub.4 "343 H H K.sub.46 " "344 CH.sub.3 CH.sub.3 K.sub.1 CH.sub.2 greenish-blue345 " " K.sub.2 " "346 " " K.sub.13 " "347 " " K.sub.17 " "348 " " K.sub.18 " "349 " " K.sub.19 " "350 " " K.sub.35 " "351 " " K.sub.43 " "352 " " K.sub.44 " "353 " " K.sub.45 " "354 " " K.sub.46 " "355 " " K.sub.4 " "______________________________________

The structural composition of further dyes is shown in the following Table VII. They may be prepared in accordance with the procedure of the foregoing Examples and correspond with the formula ##STR181## in which Y.sub.1 ', R.sub.17 ' to R.sub.20 ' and K.sup.+ have the significances as shown in the columns. A further column I indicates the shade on dyeing on polyacrylonitrile. The anion A.sup.- may be any one of those named in the foregoing description.

Table VIII__________________________________________________________________________Ex. R'.sub.17 R'.sub.18 R'.sub.19 R'.sub.20 Y.sub.1 K.sup. .sym. I__________________________________________________________________________356 H H NH.sub.2 NHCH.sub.3 CONHC.sub.2 H.sub.4 K.sub.2 greenish- blue357 H H " ##STR182## OC.sub.2 H.sub.4 K.sub.2 bluish violet358 OH NH.sub.2 " OH ##STR183## K.sub.2 blue359 H H " NHCH.sub.3 CONHC.sub.3 H.sub.7 K.sub.6 greenish blue360 ##STR184## blue361 ##STR185## red362 ##STR186## red363 ##STR187## blue364 ##STR188## yellow__________________________________________________________________________

APPLICATION EXAMPLE A

20 Parts of the salt of the dye described in Example 1 and 80 parts dextrin are ground for 4 hours in a powder mill. 1 Part of the preparation so obtained is made into a paste with 1 part 40% acetic acid, then 200 parts demineralized water are poured onto the paste and the mixture is boiled for a short time. (The same dye and dextrin mixture can also be formed into a paste with 100 parts water and finally be spray dried.) The mixture is then diluted with 7000 parts demineralized water, mixed with 2 parts glacial acetic acid and is put into a bath at 60.degree. with 100 parts polyacrylonitrile fabric. The fabric may be pretreated for 10 to 15 minutes at 60.degree. in a bath consisting of 8000 parts water and 2 parts glacial acetic acid.

The dye bath is raised to 98.degree. to 100.degree. over a period of 30 minutes, boiled for 11/2 hours and the fabric is rinsed. A bluish-red dyeing with good light and wet fastness properties is obtained.

10 Parts of the dye mentioned in Example 1 are dissolved in 60 parts glacial acetic acid and 30 parts water. A stable concentrated solution, with a dye content of about 10%, is obtained, which solution can be used to dye polyacrylonitrile according to the above-mentioned process.

APPLICATION EXAMPLE B

20 Parts of the dye from Example 1 are mixed with 80 parts dextrin in a ball-mill for 48 hours; 1 part of the preparation so obtained is made into a paste with 1 part 40% acetic acid, 200 parts demineralized water are poured onto the paste and the mixture is boiled for a short time. With this solution the following dyeings are made:

a. The solution is diluted with 7000 parts of demineralized water and mixed with 21 parts of anhydrous sodium sulphate, 14 parts of ammonium sulphate, 14 parts of formic acid and 15 parts of a carrier, based on the reaction product of ethylene oxide with dichlorophenolene are put into a bath at 60.degree. with 100 parts of a polyester fabric, which fabric has been modified with acid groups. The fabric may be pretreated for 10 to 15 minutes at 60.degree. in a bath consisting of 8000 parts of water and 2 parts of glacial acetic acid.

The dyebath is raised to 98.degree.-100.degree. over a period of 30 minutes, boiled for 11/2 hours and the fabric rinsed. A similar bluish-red dyeing with good wet fastness is obtained.

b. The solution is diluted with 3000 parts of demineralized water and mixed with 18 parts of anhydrous sodium sulphate, together with 6 parts of ammonium sulphate and formic acid and put into the bath at 60.degree. with 100 parts of a polyester fabric, which fabric has been modified with acid groups. The closed vessel is heated to 110.degree. over a period of 45 minutes, kept at this temperature for 1 hour with shaking, cooled to 60.degree. within 25 minutes and the dyed fabric rinsed. A similar bluish-red dyeing with good wet fastness is obtained.

c. The same procedure as described in paragraph (b) above is carried out except that the closed vessel is heated for 1 hour at 120.degree..

Formulae of representative dyes of the foregoing Examples are as follows: ##STR189##

Claims

1. A dye of the formula

wherein

G is the residue of a carbocylic monoazodye

R is alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl, amino or alkoxy of 1 to 4 carbon atoms,

R.sub.1 is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl,

R.sub.2 is hydrogen or alkyl of 1 to 4 carbon atoms,

R.sub.3 is hydrogen or alkyl of 1 to 4 carbon atoms,

Q is ##STR190## wherein n R.sub.7 is ##STR191## wherein each R.sub.8 is independently alkyl of 1 to 4 carbon atoms, each R.sub.9 is independently hydroxy, halo, alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy, alkoxy of 1to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy, cycloalkyl of 5 or 6 carbon atoms, cycloalkyl of 5 or 6 carbon atoms substituted by alkyl of 1 to 4 carbon atoms, trifluoromethyl, cyano, nitro, phenoxy, naphthyloxy, -CO-Ro, --CO-O-Ro, --O-CO-Ro, --CO-NH-Ro, --CO-N(Ro).sub.2, --O-CO-N(Ro).sub.2, -NH-CO-Ro, --SO.sub.2 -Ro, -SO.sub.2 -NH-Ro or -O-SO.sub.2 -N(Ro).sub.2, wherein each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl,

R.sub.10 is hydrogen, halo or alkyl of 1to 4 carbon atoms,

R.sub.11 is hydrogen alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenoxy, halo, trifluoromethyl, nitro, cyano, -CO-Ro, --CO-O-Ro, --O-CO-Ro, --CO-NH-Ro, --NH-CO-Ro, -SO.sub.2 -Ro --SO.sub.2 --NH-Ro or -SO.sub.2 -N)Ro).sub.2,

wherein each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl, and

a is 0, 1, 2, 3, 4, or 5, with the proviso that when a is 4 or 5 each R.sub.9 must be halo,

Y is ##STR192## wherein each R.sub.4 is independently hydrogen or alkyl of 1 to 4 carbon atoms,

R.sub.5 is ##STR193## --SO--, --SO.sub.2 --or --CO--, wherein R.sub.6 is hydrogen or alkyl of 1 to 4 carbon atoms, and

x is 1 to 6, and

A.sup.- is an anion,

wherein each halo is independently chloro, bromo or iodo, with the proviso that the molecule is free of sulfo groups.

2. A dye according to claim 1 wherein R is alkyl of 1 to 4 carbon atoms, and R.sub.1 is alkyl of 1 to 4 carbon atoms.

3. A dye according to claim 2 wherein R.sub.2 is hydrogen or methyl, and R.sub.3 is hydrogen or methyl.

4. A dye according to claim 3 wherein Y is ##STR194## --CH.sub.2 O-CH.sub.2 CH.sub.2 --, wherein

R.sub.4 is hydrogen or alkyl of 1 to 4 carbon atoms, and

x' is 1, 2 or 3.

5. A dye according to claim 4

wherein

Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.

6. A dye according to claim 1 having the formula ##STR195## wherein D is a diazo component radical,

K is a coupling component radical,

each

T" is independently ##STR196## W is a bridging group, q is 0 or 1, and

t is 1 or 2,

with the proviso that each --Wa-T" independently is bound to D or K.

7. A dye according to claim 6 having the formula ##STR197## wherein Ka' is a coupling component radical,

Z is -CO- or SO.sub.2,

T" is ##STR198## and t is 1 or 2.

8. A compound of the formula ##STR199## wherein R.sub.16 is hydrogen, phenyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl, phenoxy, alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, benzoyloxy, --CO-N-(Ra).sub.2 or --O-CO-N(Ra).sub.2, wherein each Ra is independently hydrogen or alkyl of 1 to 4 carbon atoms,

R.sub.17 is ##STR200## wherein R.sub.25 is hydrogen or alkyl of 1 to 4 carbon atoms, R.sub.19 is hydrogen, nitro, halo, cyano, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -CO-Ro, --COORo, --CO--NHRo or -SO.sub.2 -N(R.sub.21).sub.2,

wherein each R.sub.21 is independently alkyl of 1 to 4 carbon atoms, and

Ro is alkyl of 1 to 4 carbon atoms or phenyl,

each of

R.sub.119 and R'.sub.119 is independently hydrogen, nitro, halo, cyano, alkyl of 1 to 4 carbon atoms, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms,

R.sub.219 is hydrogen, halo, nitro or cyano, with the proviso that at least one of R.sub.19, R.sub.119, R'.sub.119 and R.sub.219 is hydrogen or halo

K' is ##STR201## wherein R.sub.18 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo,

Ka' is ##STR202## wherein each of R.sub.18 ' and R.sub.19 ' is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R.sub.18 ' and R.sub.19 ' is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl, R.sub.21 ' is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, R.sub.24 ' is hydroxy, amino or anilino, and

each of

R.sub.181 and R.sub.191 is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that at least one of R.sub.181 and R.sub.191 is hydrogen or alkyl of 1 to 4 carbon atoms,

Ka" is ##STR203## wherein each of R.sub.18 ' and R.sub.19 ' is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R.sub.18 ' and R.sub.19 ' is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl, and

R.sub.21 ' is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo,

Z is --CO- or --SO.sub.2,

t is 1 or 2, Hal is halo, and

T" is ##STR204## wherein R is alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl, amino or alkoxy of 1 to 4 carbon atoms,

R.sub.1 is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl,

R.sub.2 is hydrogen or alkyl of 1 to 4 carbon atoms,

R.sub.3 is hydrogen or alkyl of 1 to 4 carbon atoms,

Q is ##STR205## wherein R.sub.7 is ##STR206## wherein each R.sub.8 is independently alkyl of 1 to 4 carbon atoms,

each

R.sub.9 is independently hydroxy; halo; alkyl of 1 to 4 carbon atoms; alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy; alkoxy of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy; cycloalkyl of 5 or 6 carbon atoms; cycloalkyl of 5 or 6 carbon atoms substituted by alkyl of 1 to 4 carbon atoms; trifluoromethyl; cyano; nitro; phenoxy; naphthyloxy; --CO--Ro; --CO--O--Ro; --O--CO--Ro; --CO--NH--Ro; --CO--N(Ro).sub.2 ; --O--CO--N(Ro).sub.2 ; --NH--CO--Ro; --SO.sub.2 --Ro; --SO.sub.2 --NH--Ro or --O--SO.sub.2 --N(Ro).sub.2,

wherein each

Ro is independently alkyl of 1 to 4 carbon atoms or phenyl,

R.sub.10 is hydrogen, halo or alkyl of 1 to 4 carbon atoms,

R.sub.11 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenoxy, halo, trifluoromethyl, nitro, cyano, --CO--Ro, --CO--O--Ro, --O--CO--Ro, --CO--NH--Ro, --NH--CO--Ro, --SO.sub.2 --Ro, --SO.sub.2 --NH--Ro or --SO.sub.2 --N(Ro).sub.2,

wherein each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl, and

a is 0, 1. 2, 3, 4, or 5, with the proviso that when a is 4 or 5 each R.sub.9 must be halo,

Y is ##STR207## wherein each R.sub.4 is independently hydrogen or alkyl of 1 to 4 carbon atoms,

R.sub.5 is ##STR208## --SO--, --SO.sub.2 -- or --CO--, wherein R.sub.6 is hydrogen or alkyl of 1 to 4 carbon atoms, and

x is 1 to 6, and

A.sup.- is an anion,

wherein each halo is independently chloro, bromo or iodo.

9. A compound according to claim 8 having the formula ##STR209## wherein R.sub.16 is hydrogen, phenyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl, phenoxy, alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, benzoyloxy, --CO--N(Ra).sub.2 or --O--CO--2,

R.sub.17 is ##STR210## wherein R.sub.25 is hydrogen or alkyl of 1 to 4 carbon atoms, R.sub.19 is hydrogen, nitro, halo, cyano, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, --CO--Ro, --COORo, --CO--NHRo or --SO.sub.2 --N(R.sub.21).sub.2, wherein each R.sub.21 is independently alkyl of 1 to 4 carbon atoms. each of R.sub.119 and R'.sub.119 is independently hydrogen, nitro, halo, cyano, alkyl of 1 to 4 carbon atoms, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms,

R.sub.219 is hydrogen, halo, nitro or cyano, with the proviso that at least one of R.sub.19, R.sub.119, R'.sub.119 and R.sub.219 is hydrogen,

K' is ##STR211## wherein R.sub.18 is hydrogen or halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, and

T" is ##STR212## wherein each Ra is independently hydrogen or alkyl of 1 to 4 carbon atoms, and each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl.

10. A compound according to claim 9 wherein ##STR213## wherein Ra' is hydrogen, halo, nitro or cyano,

Ra" is hydrogen or halo,

each Ra'" is independently hydrogen or halo, and

each of

R.sub.1a and R.sub.2a is independently alkyl of 1 to 4 carbon atoms.

11. A compound according to claim 10 wherein R.sub.16 is alkyl of 1 to 4 carbon atoms, R.sub.25 is hydrogen or methyl, and

K' is ##STR214##

12. A compound according to claim 11

wherein

R.sub.16 is methyl or ethyl,

R.sub.18 is hydrogen or methyl, and

R.sub.25 is hydrogen.

13. A compound according to claim 9

wherein

R is alkyl of 1 to 4 carbon atoms,

R.sub.1 is alkyl of 1 to 4 carbon atoms,

R.sub.2 is hydrogen or methyl, and

R.sub.3 is hydrogen or methyl.

14. A compound according to claim 13

wherein Y is ##STR215## --CH.dbd.CH--CH.sub.2 --, --C.vertline.C--CH.sub.2 -- or --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --,

wherein

R.sub.4 is hydrogen or alkyl of 1 to 4 carbon atoms, and

x' is 1, 2 or 3.

15. A compound according to claim 14

wherein

Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.

16. A compound according to claim 15

wherein

R is methyl or ethyl,

R.sub.1 is methyl or ethyl,

R.sub.2 is hydrogen,

R.sub.3 is hydrogen,

R.sub.4 is hydrogen or methyl, and

x' is 1.

17. A compound according to claim 16

wherein

Q is phenyl, 2-naphthyl or phenyl substituted by 1 to 5 chloro substituents, and

Y is --CH.sub.2 --.

18. A compound according to claim 8 having the formula ##STR216## wherein Ka' is ##STR217## wherein each of R'.sub.18 and R'.sub.19 is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R'.sub.18 and R'.sub.19 is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl,

R'.sub.21 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo,

R'.sub.24 is hydroxy, amino or anilino, and

each of

R.sub.181 and R.sub.191 is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that at least one of R.sub.181 and R.sub.191 is hydrogen or alkyl of 1 to 4 carbon atoms,

Z is --CO-- or --SO.sub.2 t is 1 or 2, and

T" is ##STR218##

19. A compound according to claim 18

wherein

R is alkyl of 1 to 4 carbon atoms,

R.sub.1 is alkyl of 1 to 4 carbon atoms,

R.sub.2 is hydrogen or methyl, and

R.sub.3 is hydrogen or methyl.

20. A compound according to claim 19

wherein

Y is ##STR219## --CH.dbd.--CH.sub.2 --, --C.vertline.C--CH.sub.2 -- or --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --,

wherein

R.sub.4 is hydrogen or alkyl of 1 to 4 carbon atoms, and

x' is 1, 2 or 3.

21. A compound according to claim 20

wherein

Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.

22. A compound according to claim 21

wherein

R is methyl or ethyl,

R.sub.1 is methyl or ethyl,

R.sub.2 is hydrogen,

R.sub.3 is hydrogen,

R.sub.4 is hydrogen or methyl, and

x' is 1.

23. A compound according to claim 22

wherein

Q is phenyl, 2-naphthyl or phenyl substituted by 1 to 5 chloro substituents, and

Y is --CH.sub.2 --.

24. A compound according to claim 8 having the formula ##STR220## wherein Ka" is ##STR221## wherein each of R'.sub.18 and R'.sub.19 is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R'.sub.18 and R'.sub.19 is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl, and

R'.sub.21 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo,

Hal is halo, and

T" is ##STR222##

25. A compound according to claim 24

wherein

R is alkyl of 1 to 4 carbon atoms,

R.sub.1 is alkyl of 1 to 4 carbon atoms,

R.sub.2 is hydrogen or methyl, and

R.sub.3 is hydrogen or methyl.

26. A compound according to claim 25

wherein

Y is ##STR223## --CH.dbd.CH--CH.sub.2 --, --C.vertline.C--CH.sub.2 -- or --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --,

wherein

R.sub.4 is hydrogen or alkyl of 1 to 4 carbon atoms, and

x' is 1, 2 or 3.

27. A compound according to claim 26

wherein

Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.

28. A compound according to claim 27

wherein

R is methyl or ethyl,

R.sub.1 is methyl or ethyl,

R.sub.2 is hydrogen,

R.sub.3 is hydrogen,

R.sub.4 is hydrogen or methyl, and

x' is 1.

29. A compound according to claim 28

wherein

Q is phenyl, 2-naphthyl or phenyl substituted by 1 to 5 chloro substituents, and

Y is --CH.sub.2 --.

30. A compound according to claim 11 having the formula ##STR224##

31. A compound according to claim 11 having the formula ##STR225##

32. A compound according to claim 11 having the formula ##STR226##

33. A compound according to claim 11 having the formula ##STR227##

34. The compound according to claim 33 wherein A.sup.- is Cl.sup.-.

35. A compound according to claim 11 having the formula ##STR228##

36. The compound according to claim 35 wherein A.sup.- is Cl.sup.-.

37. A compound according to claim 11 having the formula ##STR229##

38. The compound according to claim 37 wherein A.sup.- is Cl.sup.-.

39. A compound according to claim 11 having the formula ##STR230##

40. The compound according to claim 39 wherein A.sup.- is Cl.sup.-.

41. A compound according to claim 11 having the formula ##STR231##

42. The compound according to claim 41 wherein A.sup.- is Cl.sup.-.

43. A compound according to claim 11 having the formula ##STR232##

44. The compound according to claim 43 wherein A.sup.- is Cl.sup.-.

45. A compound according to claim 11 having the formula ##STR233##

46. A compound according to claim 11 having the formula ##STR234##

47. A compound according to claim 11 having the formula ##STR235##

48. The compound according to claim 47 wherein A.sup.- is Cl.sup.-.

49. A compound according to claim 11 having the formula ##STR236##

50. The compound according to claim 49 wherein A.sup.- is Cl.sup.-.

51. A compound according to claim 11 having the formula ##STR237##

52. The compound according to claim 51 wherein A.sup.- is Cl.sup.-.

53. A compound according to claim 11 having the formula ##STR238##

54. A compound according to claim 11 having the formula ##STR239##

55. A compound according to claim 11 having the formula ##STR240##

56. A compound according to claim 11 having the formula ##STR241##

57. A compound according to claim 11 having the formula ##STR242##

58. A compound according to claim 22 having the formula ##STR243##

59. A compound according to claim 22 having the formula ##STR244##

60. A compound according to claim 22 having the formula ##STR245##

61. A compound according to claim 29 having the formula ##STR246##

62. A compound according to claim 29 having the formula ##STR247##