GB1595554A

GB1595554A - Antraquinoid dyes

Info

Publication number: GB1595554A
Application number: GB5417/78A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1977-02-11
Filing date: 1978-02-10
Publication date: 1981-08-12
Also published as: FR2380369B1; DE2705716C2; JPS641510B2; IT7819682A0; DE2705716A1; JPS5399229A; IT1093403B; FR2380369A1; CH631731A5

Abstract

Dyes of the formula (2) <IMAGE> where Y is a) linear or branched saturated C3-C18-alkyl, b) C3-C11-alkoxyalkyl, c) Phen-C1-C6-alkyl (which may be additionally substituted in phenyl by chlorine, bromine, C1-C4-alkyl, methoxy, ethoxy, or methylenedioxy and the alkyl moiety by phenyl), d) C6-C8-cycloalkyl, e) Phenoxy-C2- or C3-alkyl (in which case the phenyl moiety can be substituted by chlorine, bromine, C1-C4-alkyl, methoxy or ethoxy, the number of substituents can be 1 to 3 and the substituents can be identical or different), f) a phenyl radical of formula (2) <IMAGE> where D, E and F are each hydrogen, C1-C8-alkyl, C1-C4-alkoxy, phenoxy, phenyl, chlorine or bromine and the substituents can be identical or different, D and E are each methylenedioxy or ethylenedioxy and D and E are each hydrogen and F is carbon-C1-C4-alkoxy, cyano, benzoyl, trifluoromethyl or C1-C6-alkylcarbonyl, g) a tetrahydropyran radical of the formula (3) <IMAGE> where one A is a methylene group and the remaining As are each hydrogen, or h) a 2- or 3-methylenetetrahydropyran or a 2- or 3-methylenetetrahydrofuran radical, one X is hydrogen and the other X is a <IMAGE> group, where R is optionally substituted C1-C17-alkyl, optionally substituted phenylamino, optionally substituted phenyl C1-C10-alkoxy, alkoxyalkoxy with 3 to 11 carbon atoms, C7-C10-phenalkyl or C1-C4-alkoxycarbonyl-C2-C4-alkyl. The dyes dye cellulose or cellulose-containing fibre material in the presence of swelling agents in reddish blue to greenish blue (turquoise) shades having high fastness properties.

Description

(54) ANTHRAQUINOID DYES (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company, of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to new anthraquinoid dyes based on a-tetra- substituted anthraquinone, to a process for their manufacture, and to the use of these dyes.

The present invention provides anthraquinoid dyes of the general formula

where Y is a) linear or branched saturated alkyl of 3 to 18 carbon atoms, b) alkoxyalkyl of 3 to 11 carbon atoms, c) phenalkyl, where the alkyl moiety is of 1 to 7 carbon atoms, the phenyl moiety is unsubstituted or substituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy, ethoxy or methylenedioxy, the substituents numbering from 1 to 3 and being identical or different, and the alkyl moiety may be substituted by a furher phenyl, d) cycloalkyl of 6 to 8 carbon atoms, e) phenoxyalkyl, where alkyl is of 2 or 3 carbon atoms, and phenyl is unsubstituted or substituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy or ethoxy, the substituents numbering from 1 o 3 and being identical or different, f) a phenyl radical of the formula

where D, E and F are identical or different and are each hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenoxy, phenyl, chlorine or bromine, and D and E may also together be methylenedioxy or ethylenedioxy, or D and E are hydrogen and F is carboalkoxy of 2 to 5 carbon atoms, cyano, benzoyl, trifluoromethyl or alkylcarbonyl of 2 to 7 carbon atoms.

g) a tetrahydropyran radical of the formula

where one A is methylene and the remaining A's are hydrogen, or h) a 2- or 3-methylenetetrabydropyran radical or a 2- or 3-methylenetetrahydrofurane radical, one X is hydrogen and the other X is

where R is alkyl of 1 to 17 carbon atoms which is unsubstituted or substituted by chlorine or bromine, phenylamino which is unsubstituted by chlorine or bromine, phenylamino which is unsubstituted or substituted by chlorine, bromine or alkyl of I to 4 carbon atoms, phenyl which is unsubstituted or substituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy, ethoxy or nitro, alkoxy of 1 to 10 carbon atoms, alkoxyalkoxy of a total of 3 to 11 carbon atoms, phenalkyl of 7 to 10 carbon atoms or alkoxycarbonylalkyl, where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 to 4 carbon atoms.

The dyes may be used, in the presence of carriers (oxyethylene swelling agents), for dyeing, and above all for printing, cellulose and cellulose-containing textile material, e.g. cellulose-polyester union fabric. The dyeings or prints obtained have reddish blue to greenish blue hues and possess very good fastness properties, above all fastness to wet treatments, fastness to crocking, and fastness to light.

Specific examples of the groups mentioned for Y are: a) linear or branched saturated alkyl of 3 to 18 carbon atoms: propyl, isopropyl, n-butyl, isobutyl, butyl-2, pentyl-l, pentyl-2, 2-methyl-butyl-3, hexyl-l, hexyl-3, octyl-l, octyl-2, 2-ethylhexyl, 2,4-dimethylpentyl-3, 1,4-dimethylpentyl, 2-isopropyl 5-methyl-hexyl- 1, 1,5-dimethylhexyl( 6-methylheptyl-2), nonnyl, decyl, dodecyl, tetradecyl, tridecyl, hexadecyl and octadecyl; b) alkoxyalkyl of 3 to 11 carbon atoms: 2-methoxyethyl, 2-propoxyethyl, 2ethoxyethyl, 2-butoxyethyl, 2-'( 2'-ethylhexoxy) -ethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-butoxypropyl, and 3 - C2'-ethylhexoxy) -propyl; c) phenalkyl, where the moiety is 1 to 7, preferably 2 to 6, carbon atoms and the phenyl moiety is unsubstituted or substituted: 2-phenylethyl, 1-phenyl propyl-l, l-phenylpropyl-2, l-phenylbutyl-l, 1 -phenyl-butyl-2, 3 -phenyl-butyl-2, 1phenyl-3-methylbutyl-2, 1 -phenyl-2-methylbutyl-4, 2-phenylpentyl-4, 3-(4'-iso propylphenyl) -butyl- 1, 3- (4'-methylphenyl ) -butyl- 1, 2- (4'-methoxyphenyl ) -butyl- 1, 3 - ( 3',4'-methylenedioxyphenyl -2-methylpropyl- 1, 1,3-diphenylpropyl-2 and 2-phenyl- heptyl-4; d) cycloalkyl of 6 to 8 carbon atoms: cyclohexyl, 4-methylcyclohexyl, 2-,4dimethylcyclohexyl and 3 -metbylcyclohexyl; e) phenoxyalkyl, where the alkyl moiety is of 2 or 3 carbon atoms and the phenoxy moiety optionally has from 1 to 3, preferably 1 or 2, substituents: 2-phenoxypropyl-l, 2-phenoxyethyl-1, 2-1(4'-methylphenoxy) -propyl-l, 2- (4'-chlorophenoxy) - propyl and 2- ( 3',5'-dimethylphenoxy) -ethyl-i; f) phenyl of the formula

where D, E and F have the above meanings: phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 4-n-butylphenyl, 4-tert.-butylphenyl, 4-isopropyiphenyl, 4-noctylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2,3-, 2,4-, 2,5-, 3,4- or 3,5 -dimethyiphenyl, 2,4,6-trimethylphenyl, 2,4-, 2,5- or 3,5-dimethoxyphenyl, 3-isopropyl-4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-bromophenyl, 2,3-, 2,4-, 2,5- and 3,5-dichlorophenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methyiphenyl, 3-chloro-2-methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-methylphenyl 2-bromo4-methylphenyl, 2-chloro-5-methoxyphenyl, 5-chloro-2-methoxyphenyl, 2,4-dimethyi- 6-bromophenyl, 4-chloro-2,5 -dimethoxyphenyl, 5-chloro-2,4-dimethoxyphenyl, 4phenylphenyl, 4-phenyl-2-methylphenyl, 4-phenoxyphenyl, 3-cyanophenyl, 3-carbomethoxyphenyl, 4-acetylphenyl, 4-benzoylphenyl, 3-trifluoromethylphenyl, 3,4methylenedioxyphenyl, and 3,4-ethylenedioxyphenyl = 1,4-dioxa-1,2,3,4-tetrahydro- naphthalene).

g) tetrahydropyran of the above formula: 3 -methylene-4-methyltetrahydropyran, 3 -methylene-3 -methyl-tetrahydropyran and fi- (4'-tetrahydropyranyl) methyl; and f) 2-methylene- and 3 -methylene-tetrahydropyran, 2-methylene-tetrahydrofuran and 3 -methylene-tetrahydrofuran.

For tinctorial and technological reasons, preferred dyes of the formula I are those where Y is phenylalkyl, where alkyl is of 2 to 4 carbon atoms, or a phenyl radical of the formula

where D' and E' are hydrogen, methyl, chlorine, methoxy or phenoxy and are identical or different.

For tinctorial reasons, particularly preferred dyes of the formula I are those where Y is phenyl, 2-, 3- or 4-methylphenyl, 3- or 4-chlorophenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 4-phenoxyphenyl, 2-phenylethyl, 1-phenylpropyl-2 or 3phenylbutyl-2.

Specific examples of R in the group

are: a) unsubstituted or chlorine- or bromine-substituted alkyl of 1 to 17 carbon atoms, preferably unsubstituted alkyl of 1 to 8 carbon atoms and alkyl of 1 to 4 carbon atoms which is monosubstituted or disubstituted by chlorine: methyl, ethyl, propyl, isopropyl, n-butyl,isobutyl, pentyl, hexyl, octyl- 1 ,2-ethylhexyl, heptyl-3, decyl, dodecyl, tetradecyl, hexadecyl, chloromethyl, dichyloromethyl, 2-chloroethyl, 3-chloropropyl and chlorobutyl; b) unsubstituted or substituted phenylamino: 2-, 3-, or 4-methylphenylamino, 4-chlorophenylamino, 4-ethylphenylamino, 4-isopropylphenylamino, 4-n-butylphenylamino, 4-tert.-butylphenylamino and 4-bromophenylamino; c) unsubstituted or substituted phenyl: phenyl, 3-, 4- or 2-methylphenyl, 2-, 3or 4-ethylphenyl, 4-butylphenyl, 4-tert.-butylphenyl, 4-isopropylphenyl, 2-, 3- or 4chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-ethoxyphenyl and 3- or 4-nitrophenyl; d) alkoxy of 1 to 10 carbon atoms: methoxy, ethoxy, propoxy, n-butoxy, nhexoxy, 2-ethylhexoxy, octoxy and isodecoxy; e) alkoxyalkoxy of a total of 3 to 11 carbon atoms; 2-methoxyethoxy, 2-ethoxyethoxy, 2-propoxyethoxy, 2-butoxyethoxy, 2- (2'-ethylhexoxy) -ethoxy, 3-methoxypropoxy, 3-ethoxypropoxy, 3-propoxypropoxy, 3-butoxypropoxy and 3- or 2-(2'-ethylhexoxy) -propoxy; f) phenylalkyl of 7 to 10 carbon atoms: benzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl and phenylbutyl; and g) alkoxycarbonylalkyl, where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 to 4 carbon atoms; methoxycarbonylethyl, ethoxycarbonylethyl, butoxycarbonylethyl, methoxycarbonylpropyl, butoxycarbonylpropyl, ethoxycarbonylpropyl, propoxycarbonylpropyl, methoxycarbonylbutyl, ethoxycarbonylbutyl, propoxycarbonylbutyl and butoxycarbonylbutyl.

Amongst the above groups R, the following are preferred: alkyl of 1 to 8 carbon atoms, alkyl of 1 to 4 carbon atoms monosubstituted or disubstituted by chlorine, alkoxycarbonylalkyl, where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 to 4 carbon atoms, phenylamino, phenyl and alkoxy of 1 to 10 carbon atoms, since dyes ccntaining these substituents have advantageous tinctorial and technological properties.

Particularly preferred substituents R are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl-3, 2-ethylhexyl, octyl-l, 3-chloropropyl, dichloromethyl, methoxycarbonylethyl, butoxycarbonylethyl, methoxycarbonylbutyl, phenylamino, phenyl, methoxy, ethoxy, butoxy, 2-ethylhexoxy and isodecoxy. The substituents R are preferably used in combinations with Y being phenyl, 2-, 3- or 4-methylphenyl, 3or 4-chlorophenyl, 3 ,5-dimethylphenyl, 4-methyoxyphenyl, 4-phenoxyphenyl, 2-phenylethyl, l-phenylpropyl-2, or 3 -phenylbutyl-2.

For tinctorial and technological reasons, very particularly preferred dyes are those of the formula

where Y1 is phenalkyl, where alkyl is of 2 to 4 carbon atoms, or is a phenyl radical of the formula

where D' and E' are hydrogen, methyl, chlorine, methoxy or phenoxy and are identical or different, one X' is hydrogen and the other X' is a radical of the formula

where R' is alkyl of 1 to 8 carbon atoms, alkyl of 1 to 4 carbon atoms which is mcncsubstituted or disubstituted by chlorine, alkoxycarbonylalkyl, where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 to 4 carbon atoms, phenylamino, phenyl or alkoxy of 1 to 10 carbon atoms.

Dyes of the formula Ia to be singled out particularly are those where Y' is phenyl, 2-, 3- or 4-methylphenyl, 3- or 4-chlorophenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 4-phenoxyphenyl, 2-phenylethyl, 1-phenylpropyl-2 or 3phenylbutyl-2 and R' is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, heptyl-3,3-chlcropropyl, dichloromethyl, methoxycarbonylethyl, butoxycarbonylethyl, methoxycarbonylbutyl, butoxycarbonylbutyl, phenylamino, phenyl, methoxy, ethoxy, butoxy, 2-ethylhexoxy or isodecoxy.

The dyes may be obtained from 1,4-diamino-5-hydroxy-8-nitroanthraquinones of the formula IV by the following methods:

02N O NH I NII H0 O NE-Y Acylation Reduction 02N O H,N O cc HO 0 blH-Y HO 0 NH-Y (V) (VI, Reduction | Acylation 9 O 0 H2N O lmi-C-R R-C-HN O llH 1 (Ib) (Ic) In the formulae Ib, Ic, IV, V and VI, Y and R have the above meanings.

The required starting compounds IV may be obtained by condensing l-amino 8-nitro-4,5-dihydroxyanthraquinone with an amine of the general formula Y-NH2 by the process described in German Laid-Open Application DOS 2,029,793.

The compounds of the formula IV are either converted to the 1-acylamino-4amino-5-hydroxy-2-nitroanthraquinones (V) by reaction with acylating agents and then reduced to the 1-acylamino-4,8-diamino-5'-hydroxy-anthraquinones (Ib), or they are first reduced to the 1,4,8-triamino-5-hydroxy-anthraquinones (VI) and then reacted with acylating agents to give the 1,4-diamino-5-hydroxy-8-acylamino anthraquinones (Ic).

The acylation is advantageously carried out by suspending the compounds of the formula IV or VI in an organic liquid which is inert under the reaction conditions, heating the suspension to the reaction temperature and adding the acylating agent dropwise, whilst stirring. Alternatively, the acylating agents may be added to the suspension at room temperature and the mixture then heated to the reaction tem perature. Normally, from 1.0 to 2.0 moles, preferably from 1.1 to 1.5 moles, of acylating agent are used per mole of the compound to be acylated. The acrylaticn is advantageously carried out at from room temperature to 170"C, preferably at from 50 to 1500 C. At these temperatures, the reaction is in general complete after from 0.2 to 6 hours.

The acylation of compounds (VI) is advantageously carried out in the presence of at least the stoichiometric amount of a tertiary amine, e.g. triethylamine.

Suitable acylating agents are e.g. carboxylic acid esters and preferably carboxylic acid chlorides, phenyl isocyanates, chloroformic acid esters and acid chlorides of dicarboxylic acid half-esters.

The reduction of compounds of the formula IV or V may be carried out by conventional methods, e.g. with Na2S in aqueous suspension. Preferably, however, the nitro compounds IV or V are reduced with hydrazine hydrate in an inert organic liquid. This reducing agent has the advantage that the acylation and the reduction, or the reduction and the acylation, can be carried out in a one-vessel reaction, since the same inert organic liquid can be used for both reactions.

Normally, the reduction is carried out by heating a suspension or solution of the nitro compound in the inert organic liquid to the reaction temperature and then adding the hydrazine hydrate dropwise, whilst stirring. Advantageously, the reduction is carried out at from 50 to 1700C, preferably from 80 to 1500C, using from 1.5 to 3.5 moles, preferably from 1.5 to 2.0 moles, of hydrazine hydrate per mole of nitro compound. Under these conditions, the reaction is normally complete after from 0.5 to 6 hours.

Examples of organic liquids which are inert under the reaction conditions are aliphatic chlorohydrocarbons, e.g. chloroform, methylene chloride, carbon tetrachloride, dichloroethane, tetracbloroethane and trichloroethane, aromatic hyldrocarbons, e.g.

toluene and xylene and preferably aromatic chlorohydrocarbons, e.g. chlorobenzene, o-dichlorobenzene and trichlorobenzene; carboxylic acid N,N-dialkylamides, e.g. N,Ndimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N-methylpyrrolidone, nitrobenzene and pyridine.

The amount of organic liquid used is such that the reaction mixture can be stirred or mixed; in general, a 2.5-fold to 15-fold amount by weight, based on the compound to be acylated or reduced, suffices.

To work up the reaction mixture, it may be cooled to room temperature and, if necessary, the reaction product is precipitated by adding a diluent which only dissolves the reaction product slightly, if at all, after which the product may be isolated in the conventional manner.

According to their structure, the dyes according to the invention should exhibit the properties of disperse dyes. However, their affinity for polyester is too low for this purpose. German Patent 1,811,796 discloses a process by means of which dyes which are insoluble or sparingly soluble in water can be printed on cellulose or cellulosecontaining textile material using a carrier, sometimes referred to as a swelling agent, which is usually an oxyethylene compound such as ethylene glycol or a derivative thereof. The information on process conditions given in German Patent 1,811,796 also applies to the dyes according to the invention. Generally the fibres are contacted with water and an oxyethylene swelling agent and, simultaneously or successively while the fibres are still swollen, with the dye.

German Laid-Open Applications DOS 2,524,243 and 2,528,743 disclose other processes by means of which the dyes according to the invention may be applied.

Amongst these, printing processes are preferred.

Accordingly the present invention also provides a process for dyeing cellulose or cellulose-containing fiber material with a dye according to the invention wherein the dyeing is carried out in the presence of a swelling agent, especially a glycol, to assist of the dye from an aqueous phase onto the material, and materials dyed thereby.

For use in the above dyeing processes, the dyes according to the invention are advantageously converted to aqueous formulations. These contain the dye in a finely dispersed form, in addition to one or more dispersants, one or more water-retaining agents and one or more auxiliaries conventionally used in aqueous formulations, e.g.

one or more disinfectants.

Such formulations are advantageously produced by milling a suspension of from 15 to 40, preferably from 20 to 35, parts of dye (I), from 4 to 10 parts of dispersant, from 5 to 15 parts of water-retaining agent and from about 0.5 to 1.5 parts of disinfectant in from about 75.5 to 33.5 parts of water in a stirred ball mill, a bead mill or a sand mill until the particle size is about 0.5 /lm or less. Storage-stable dye dispersions are thus obtained.

Suitable dispersants are the anionic and non-ionic dispersants conventionally used for the preparation of finely divided formulations of disperse dyes. Examples of anionic dispersants include ligninsulfonates, salts of phenol/formaldehyde/sodium sulfite condensation products (German Laid-Open Application DOS 2,301,638), salts of 2-naphthalenesulfonic acid/formaldehyde condensation products, salts of phenol suifonic acid/urea/lormaldehyde condensation products, and salts of condensation products of phenolsulfonic acid/urea/formaldehyde, which have been post-condensed with phenol and formaldehyde.

Suitable non-ionic dispersants include, above all, ethylene oxide adducts and propylene oxide/ethylene oxide adducts. These are described in, for example, U.S.

Patents 2,979,528 and 3,841,888.

The amount of dispersant depends on the dye and on its concentration in the dispersion. As a rule, it is fro m4 to 10 per cent by weight, based on the formaulation.

Suitable water-retaining agents include, especially, glycols, e.g. ethylene glycol, propylene glycol, diethylene glycol and preferably dipropylene glycol. The amount used is in general from 5 to 15, preferably from 8 to 12, per cent by weight based on the formulation.

The Examples which follow illustrate the invention.

EXAMPLE 1.

19.5 parts of 1-amino-4-m-toluidino-5-hydroxy-8-nitroanthraquinone are sus pended in 100 parts of o-dichlorobenzene, 10.2 parts of butyl chlorocarbonate are added and the mixture is heated to 140"C, whilst stirring, and kept at from 140 to 1500C until starting material is no longer detectable (duration: 3 hours). 7.5 parts of 100% strength hydrazine hydrate are then added dropwise in the course of 20 minutes. This causes the temperature of the reaction mixture to drop to 120 1300C. The mixture is kept at this temperature for 1 hour and is then cooled to 70"C, and 120 parts of methanol are added.After the mixture has cooled to room temperature, the reaction product which has precipitated is filtered off, washed with methanol and hot water and dried. 14 parts of 1-butoxycarbonylamino-4-m-toluidino- S-hydroxy-8-amino-anthraquinone are obtained On cotton, blue dyeings are obtained.

EXAMPLE 2.

20.15 parts of 1-amino-4- [1-phenylethylamino- (1) ] -5-hydroxy-8-nitroanthraquinone are suspended in 100 parts of o-dichlorobenzene, 7.1 parts of methyl chloro- carbonate are added and the mixture is heated for 2 hours at 140--150"C, whilst stirring. 7.5 parts of 100% strength hydrazine hydrate are then added dropwise and the reaction mixture is boiled under reflux (from 120 to 1300C) for 1.5 hours. It is then cooled to 800C and 320 parts of methanol are run in. After the mixture has cooled to room temperature, the reaction product which has precipitated is filtered off, washed with methanol and finally with hot water, and dried. 14 parts of 1methoxycarbonylamino - 4 - [1 - phenylethylamino - (1) j - 5 - hydroxy - 8 - aminoanthraquinone are obtained.

On cotton/polyester union fabrics, the dye gives blue dyeings and prints.

EXAMPLE 3.

20.15 parts of 1-amino-4- [1-phenylethylamino- (1) ] -5-hydroxy-8-nitroanthra- quinone and 100 parts of o-dichlorobenzene are heated to 1300C and 4.0 parts of 100% strength hydrazine hydrate are added in the course of 20 minutes, whilst stirring.

After stirring for 2 hours at from 120 to 1300C, 7.1 parts of methyl chlorocarbonate are added and the reaction mixture is stirred for a further 1.5 hours at the same temperature. It is then allowed to cool to 800C and the reaction product is precipitated with 320 parts of methanol. Working up takes place in the manner described in Example 1. 14 parts of 1-amino-4-[1-phenylethylamino-(1)]-5-hydroxy-8-methoxy- carbonylamino-anthraquinone are obtained.

In cotton-polyester union fabrics and cotton, blue prints are obtained.

EXAMPLES 1 TO 56.

The dyes mentioned in the Table which follows were prepared by the methods described in Example 1 or Example 2. The hues of the dyeings obtained on cotton or cotton/polyester fiber mixtures are shown in the right-hand column.

Example Y X Hue on cotton and cotton/polyester

0 4 -CH-CH2-CY.5 -C-OCH3 blue 4 -CH-C blue CH 0 O n 5 -CH-CY.2-CH3 -C-CH-C.Y3 blue C.Y3 CH3 0 6 -CH-CH2 -jj-OCH blue CH; 5 0 7 -CH-CX2 -C-CH blue CH3 0 8 -CH e -C-0CH blue 3 0 9 e -C-CCH.3 blue 0 1 a -C-OCH~ blue \= < S cE.3 11 91 blue -C-0C4H9 12 -"- NH-7 greenish z/ CH3 0 II t, blue 13 OH3 -0-CHOl2 0 0 1' 1 blue 14 e -C-CH2-CH2-C-OCH3 Example Y X Hue on cotton and cotton/polyester

0 15 9 -C-OC2H5 blue - -C-0c2H5 CH3 16 Cn0/\ greenish blaze 17 9 -CO e blue CH 3 0 18 e 3 blue e CH3 -C-CH-(CH)-CH 19 9? blue 2 Oh 2 5 CH3 3 0 20 O -g-OC4Hg reddish - -O-004H9 blue 0 21 Cl greenish blue 22 OH3 0 blue ; blue 23 < CX3 -C-OCH3 blue CH 3 24 ~9 -C -CHC l2 blue CH 3 Example Y X Hue on cotton and cotton/polyester

25 25(cm \ C2h'5 blue - f C2H5 26 -C-00H reddish 3 blue 0 /\0CH -C-(O)-OHOl greenish 27 - 22 blue 0 28 - - -CHe -C,H-(o::)-oH reddish blue O2H5 blue 0 29 O -C-CCH2-CH-(CH2)3-CH~ blue - O2H5 CH3 0 3O ~ -C -OCH2 -^H- ( CH2 ) blue O2H5 0 31 OOCH3 -O"-0OH blue blue 0 32 -OH2-OH-(OH2)3-OH3 -CH-CH3 > reddish C'H3 blue C2H5 CH) blue 0 11 33 -CH2- ,CH- ( CH2 ) 3-CH3 -C -CH3 blue C2H5 CH OH O '3 34 -CH-OH2-OH2 -OH-OH3 -C-OCH2-CH2-OCY.3 blue CH CH O 1/ 1 oc, H9 blue 35 -OH-OH2- OH2-OH-CH3 - O-0O4H9 blue 0 3, 36 ~ ( OH3 09/\N02 reddish Example Y X Hue on cotton and cotton/polyester

0 37 -(OH2)7-CH3 " C=3 gTeE?iSi7.

blue 0 38 -(OH2)12-OH3 D1" 0 tt 39 -CEI2 -CH2 -O-CH? -OH3 O(OH2)2OH3 blue 0 tt 4o -(OH2)3-0-OF-O,.H(OH2)3-OH3 -C-OH blue O2H5 0 II 41 -CH2-CH2-CH2-O-CH3 -C-OC2H5 blue 2 5 0 It 42 -CH-CH-CH-CH-CICR2-CII blue 3 3 0 43 CH2 ,cHOcr3 n blue 4ji C2H5 0 44 -CH-CH2 -C-0C4Hg blue -O-0O4H9 CH2 -CH3 0 II 45 -CH-CH2-CH.4 -C-CH2C1 blue CH3 CH3 0 46 'CH-C,-CH -C OC1 greenish H2-C51ue o CH2-C OH3 0 47 -CH2-CII- Cn 2C s -C-CH-CE;- blue N0, OH 3 Example Y X Hue on cotton and cotton/polyester

48 -CH2-CH2-CH 4 -C e greenish 22C'H3 - blue 49 e -C-(Cn2)l0-CH3 blue 0 CH3 -CH2-O,H-Q -C11-OO4A9 blue CH3 0 II 51 -CH2-CH2-0 e -C-CX2-CH2-CX2C1 blue 0 C CH3 i, ,2H5 reddish 52 CH2 t -C-o-CH2-CH-(CH2)3-CH3 blue 0 OH 0 bltle -CH2t -'O'-NH eC1 blue 2 54 -OH2 X -C-CH -CH3 blue 55 -CH2 4 -C-cH4CH2)3-Co3 blue 56 -CH2 4 -C-O-CH2-CH-(CH2)3-CH~ blue EXAMPLES 57 to 60.

The dyes mentioned in the Table which follows were prepared by the method described in Example 3. The hues which the dyes gave on cotton and cotton/polyester fibers are shown in the right-hand column.

Example Y X Hue on cotton and csttcr./wolyester

a CH3 CH3 a 58 1I blue -O-OOH3 OH 0 59 U -C-OCH3 blue 0 6o blue ) -c-ocqg blue WHAT WE CLAIM IS:1.An anthraquinoid dye of the general formula

where Y is a) linear or branched saturated alkyl of 3 to 18 carbon atoms, b) alkoxyalkyl of 3 to 11 carbon atoms, c) phenalkyl, where the alkyl moiety is of 1 to 7 carbon atoms, the phenyl moiety is unsubstituted or sustituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy, ethoxy or methylenedioxy, the substituents numbering from 1 to 3 and being identical or different, and the alkyl moiety may be substituted by a further phenyl, d) cycloalkyl of 6 to 8 carbon atoms, e) phenoxyalkyl, where the alkyl moiety is of 2 or 3 carbon atoms and the phenoxymoiety is unsubstituted or substituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy or ethoxy, the substituents numbering from 1 to 3 and being identical or different, f) a phenyl radical of the formula

where D, E and F are identical or different and are each hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenoxy, phenyl, chlorine or bromine, and D and E may also together be methylenedioxy or ethylenedioxy, or D and E are hydrogen and F is carboalkoxy of 2 to 5 carbon atoms, cyano, benzoyl, trifluoromethyl or alkylcarbonyl of 2 to 7 carbon atoms,

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

Example Y X Hue on cotton and csttcr./wolyester

a CH3 CH3 a 58 1I blue -O-OOH3 OH 0 59 U -C-OCH3 blue 0 6o blue ) -c-ocqg blue WHAT WE CLAIM IS:1.An anthraquinoid dye of the general formula

where Y is a) linear or branched saturated alkyl of 3 to 18 carbon atoms, b) alkoxyalkyl of 3 to 11 carbon atoms,

c) phenalkyl, where the alkyl moiety is of 1 to 7 carbon atoms, the phenyl moiety is unsubstituted or sustituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy, ethoxy or methylenedioxy, the substituents numbering from 1 to 3 and being identical or different, and the alkyl moiety may be substituted by a further phenyl, d) cycloalkyl of 6 to 8 carbon atoms, e) phenoxyalkyl, where the alkyl moiety is of 2 or 3 carbon atoms and the phenoxymoiety is unsubstituted or substituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy or ethoxy, the substituents numbering from 1 to 3 and being identical or different, f) a phenyl radical of the formula

where D, E and F are identical or different and are each hydrogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenoxy, phenyl, chlorine or bromine, and D and E may also together be methylenedioxy or ethylenedioxy, or D and E are hydrogen and F is carboalkoxy of 2 to 5 carbon atoms, cyano, benzoyl, trifluoromethyl or alkylcarbonyl of 2 to 7 carbon atoms,

g) a tetrahydropyran radical of the formula

where one A is methylene and the remaining A's are hydrogen, or h) a 2- or 3-methylenetetrahydropyran radical of a 2- or 3-methylenetetra hydrofuran radical, one X is hydrogen and the other X is

where R is alkyl of 1 to 17 carbon atoms which is unsubstituted or substituted by chlorine or bromine, phenylamino which is unsubstituted or substituted by chlorine, bromine or alkyl of 1 to 4 carbon atoms, phenyl which is unsubstituted or substituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms, methoxy, ethoxy or nitro, alkoxy of 1 to 10 carbon atoms, alkoxyalkoxy of a total of 3 to 11 carbon atoms, phenalkyl of 7 to 10 carbon atoms or alkoxycarboxyalkyl, where alkoxy is of 1 to 4 carbon atoms and alkkyl is of 2 to 4 carbon atoms.
2. A dye of the formula given in claim 1, where Y is phenylalkyl (where alkyl is of 2 to 4 carbon atoms) or is a phenyl radical of the formula

where D' and E' are hydrogen, methyl, chlorine, methoxy or phenoxy and are the same or different.
3. A dye as claimed in claim 1 or claim 2, wherein one X is a hydrogen and the other X is a radical of the formula

where R' is alkyl of 1 to 8 carbon atoms, alkyl of 1 to 4 carbon atoms, which is mcncsubstituted or disubstituted by chlcrine, alkoxy carbonylalkyl, where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 to 4 carbon atoms, phenylamino, phenyl or alkoxy of 1 to 10 carbon atoms.
4. A dye of the formula given in claim 1, where Y is phenyl, 2-, 3- or 4methylphenyl, 3- or 4-chlorophenyl, 3,5-dimethylphenyl, 4-methoxyphenyl-4-phenoxyphenyl, 2-phenylethyl, 1-phenylpropyl-2 or 3-phenylbutyl-2, one X is halogen and the other X is a radical of the formula

where R' is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, heptyl- 3, octyl- 1, 3-chloropropyl, dichloromethyl, methoxycarbonylethyl, butoxycarbonylethyl, methoxycarbonylbutyl, butoxycarbonylbutyl, phenylamino, phenyl, methoxy, ethoxy, butoxy, 2-ethylhexoxy or isodecoxy.
5. A dye as claimed in claim 1 and as hereinbefore specifically identified.
6. A process for the production of a dye as claimed in claim 1 which process comprises carrying out one of the reaction schemes VI-Ic, IV-VI-Ic, V-Ib or IV-V-Ib as hereinbefore set forth
7. A process as claimed in claim 6 carried out substantially as described in any one of the foregoing specific Examples.
8. A dye as claimed in claim 1 whenever obtained by a process as claimed in either of claims 6 and 7.
9. A dye formulation for dyeing and printing cellulose or cellulose-containing textile material, which formulation contains a dye as claimed in any one of claims 1 to 5 and 8, together with one or more dispersants, one or more water-retaining agents, one or more disinfectants and water.
10. A process for dyeing cellulose or cellulose-containing fiber material which includes applying to the material a dye as claimed in any one of claims 1 to 5 and 8 in the presence of a swellng agent for the material.
11. Uniformly dyed water-swellable cellulosic fibers, said fibers being fast to washing, dry-cleaning, sublimation and light and having been produced by contacting water-swellable cellulosic fibers with water and an oxyethylene swelling agent and, simultaneously or successively, while the fibers are still swollen, with an essentially water-insoluble dye as claimed in any one of claims 1 to 5 and 8.
12. Dyed fibers as claimed in claim fl, wherein in the formula of the dye, Y is phenyl, 2-, 3- or 4-methylphenyl, 3- or 4-chlorophenyl, 3,5-dimethylphenyl, 4methoxyphenyl, 4-phenoxyphenyl, 2-phenylethyl, 1-phenylpropyl-2 or 3-phenylbutyl2, one X is hydrogen and the oth.er X is a radical of the formula

where R' is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, 2-ethylhexyl, heptyl-3, octyl- 1, 3-chloropropyl, dichloromethyl, methoxycarbonylethyl, butoxycarbonylethyl, methoxycarbonylbutyl, butoxycarbonylbutyl, phenylamino, phenyl, methoxy, ethoxy, butoxy, 2-ethylhexoxy or isodecoxy.
13. Dyed fibers as claimed in claim 11 or 12, wherein the cellulosic fibers are cotton fibers.
14. Dyed fibers as claimed in claim 11 or 12, wherein the cellulosic fibers are admixed or blended with synthetic fibers.
15. Dyed fibers as claimed in claim 14, wherein the synthetic fibers are polyester fibers.