CA1242190A

CA1242190A - Monoazo dyes, proceses for producing them, and the use thereof

Info

Publication number: CA1242190A
Application number: CA000316855A
Authority: CA
Inventors: Peter Aeschlimann
Original assignee: Individual
Current assignee: BASF Schweiz AG
Priority date: 1977-11-28
Filing date: 1978-11-24
Publication date: 1988-09-20
Also published as: JPS5483031A; CH638551A5; JPS6256187B2; GB2011456B; FR2410023A1; DE2850994A1; DE2850994C2; GB2011456A; FR2410023B1; LU78596A1

Abstract

ABSTRACT OF THE DISCLOSURE

There are described new monoazo dyes of the formula in which X is hydrogen, chlorine, bromine or cyano, R is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, R1 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or substituted by lower alkoxy, aryloxy or aryl, or it is an unsubstituted or substituted phenyl group, R2 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or substituted by hydroxyl, acyloxy, lower alkylsulfonyloxy, aryl, halogen, aryloxy or a hetero ring, or it is an unsubstituted or substituted cycloalkyl group, and Y is a lower alkyl or lower alkoxy with the proviso that R1 must not be an unsubstituted alkyl group if R is methyl, X is chlorine, bromine or cyano and Y is an unsubstituted alkyl group;
and also processes for producing them and their use for dyeing and printing hydrophobic materials.

Description

3~

21489-~362 The inven-tion relates to valuable new blue and navy blue to violet monoazo dyes of the general formula I

~.-o~
O No N=N-\ /~-NH - CH - CH2 - COOR2 0=o 0=~ 1

2 N~-COY R

in which X is hydrogen, chlorine, bromine or cyano, R is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, Rl is an alkyl group which has 1 to carbon atoms and which is unsubstituted or subs-titu-ted by lower alkoxy, aryloxy or aryl, or it is an unsubstituted or substituted phenyl group, R2 is an alkyl group which has 1 to carbon atoms and which is unsubstitu-ted or substituted by hydroxyl, acyloxy, lower alkylsul~onyloxy, aryl, halogen, aryloxy or a hetero ring, or it is an unsubstitu-ted or substituted cycloalkyl group, and Y is lower alkyl or lower alkoxy with the proviso that Rl must not be an unsubs-ti-tuted alkyl group it R is methyl, X is chlo-rine, bromine or cyano and Y is an unsubstituted alkyl group; and also to the production and to the use of these new monoazo dyes.
The terms 'lower alkyl and lower alkoxy' relate to alkyl or alkoxy groups having 1 to I, preEerably 1 or 2 I,, ", carbon atoms, such as methyl, ethyl, methoxy or ethoxy.
As an alkyl group having 1 to carbon atoms, R, Rl and R2 can be identical or different, or straight-chain or branched-chain. They are for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. These alkyl groups can be substituted for example in the case of R by halogen such as bromine or particularly chlorine, lower alkoxy, especially methoxy, ethoxy or propoxy, or by aryloxy, particularly phenoxy;
in the case of Rl by lower alkoxy, especially methoxy or ethoxy, aryloxy, in particular phenoxy, or by aryl, especially phenyl; and in the case of R2 by hydroxyl, an acyloxy group, particularly an acetyloxy group, or a lower alkylsulfonyloxy group, especially methylsulfonyl-oxy, aryl, particularly phenyl or methylphenyl, or by a hetero ring, especially an oxygen-containing hetero ring, for example furfuryl or tetrahydrofurfuryl.
For R there may be mentioned in particular methyl ethyl, methoxymethyl, ethoxymethyl or chloromethyl; for Rl in particular methyl, ethyl, propyl, isopropyl, methoxy-ethyl, phenoxyethyl, benzyl and phenethyl; and for R2 in particular methyl, ethyl, propyl, isopropyl, phenoxyethyl, acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetra-hydrofurfuryl or cyclohexyl.
As a substituted phenyl group, Rl can be for example tolyl, xylyl or chlorophenyl.
As an unsubstituted or substituted cycloalkyl group, R2 is in particular a cycloalkyl group having 5 to 7 carbon atoms, such as the methylcyclohexyl group and especially the cyclohexyl group.
X is preferably chlorine or bromine.
R is preferably unsubstituted alkyl, particularly methyl.

Rl is preferably isopropyl, ethyl or methoxyethyl and in particular methyl.
R2 is preferably an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or substituted by aryloxy, acyloxy, aryl or a hetero ring, or cyclo-hexyl, especially me-thyl, ethyl, propyl, isopropyl, phenoxyethyl, acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetrahydroxyfurfuryl or cyclohexyl; R2 is in particular the unsubstituted methyl or ethyl group.
Y is preferably methyl or ethyl.
In preferred monoazo dyes of the formula I, X is chlorine or bromine, R is methyl, methoxymethyl or ethoxy-methyl, Rl is methyl, ethyl, isopropyl or methoxyethyl, Y is methyl or ethyl, and R2 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or sub-stituted by aryloxy, acyloxy, aryl or a hetero ring, or cyclohexyl, and in particular methyl or ethyl.
Preferred monoazo dyes of the formula I are in particular those wherein X is chlorine or bromine, R
and Rl are methyl, Y is methyl or ethyl, and R2 is methyl, ethyl, propyl, isopropyl, phenoxyethyl, acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetrahydrofurfuryl or cyclohexyl.
The dyes of the formula I are obtained by a process wherein diazo components of amines of the general formula II
~0-~
2 a 2 (II) ~N02 are coupled, in the p-position with respect to the amino group, with coupling components of the general formula III

~ORl -NH - CH - CH2 - COOR2 ~III) NH-COY R

in which X, R, Rl, R2 and Y are as defined under the formula I.
The diazo componen-ts of the formula II are known. The coupling components of the formula III are new but can be obtained by processes known per se, for example by condensation of a ketone of the formula OC - CH2 - COOR, R

with an amine of the formula o/ 1 N~-COY
in which R, Rl, R2 and Y are as defined under the formula I; and subsequent reduction of the condensation product.
The diazotisation of the diazo components mentioned is performed in the customary manner, preferably with the aid of nitrosylsulfuric acid in concentrated sulfuric acid.
The coupling reaction can be performed likewise in a manner known per se, for example in a neutral or advan-tageously acid aqueous solution or suspension, by adding the resulting solution or dispersion of the diazo compound Jo a solution of the coupling component in water, which solution contains an acid and/or an organic solvent miscible with water.
After coupling has been effected, the formed dyes can be readily separated prom the coupling mixture, for example by filtration, since the dyes are virtually insoluble in water.
According to the invention, there is also suggested an alternative process for producing the dyes of the invention, in which process the corresponding dye of the formula I wherein -COY denotes a hydrogen atom is treated with an acylating agent. Examples of acylating agents are acetic anhydride, acetyl chloride and propionyl chloride. This alternative process is performed advan-tageously by reacting the reactants in the presence of a base, for example pyridine.
The new monoazo dyes are excellently suitable or dyeing and printing hydrophobic materials from aqueous dispersions, particularly synthetic textile materials, in any form of make-up, such as fibres, filaments and fabrics, for example of polyamides, especially however of textiles or fibres from aromatic polyesters such as poly-ethylene glycol terephthalate, or condensation products from terephthalic acid and l,~-(bis-hydroxymethyl)-cyclo hexane or cellulose triacetate. The monoazo dyes according to the invention have in particular very good dyeing and build-up properties on aromatic polyester textile materials, in consequence of which it becomes possible to obtain, with uniformly defined monoazo dyes, level, deep and reproducible shades.
The navy blue dyeings and printings obtained on the stated materials with the preferred dyes in which X is chlorine or bromine are clistinguished by a good colour in artificial light and good colouring strength, and by good general fastness properties, especialLy good pH stability, good levelling properties and good fastness to sub-limation and to light. There are used in the process the customary conditions and additives, which are normally used in applying disperse dyes to synthetic textile materials.
Dyeing with the dyes of the formula I is performed by introducing the material to be dyed into an aqueous dispersion of the dyes, preferably at elevated tempera-ture, for example at 40C; optionally adding customary auxiliaries, such as sulfite cellulose degradation products, condensation products from higher alcohols with ethylene oxide, polyglycol ethers of fatty acid amides or alkylphenols, and so forth; and then preferably adding acid agents to the bath, for example organic acids such as formic acid or acetic acid, or inorganic acids such as phosphoric acid. The bath is subsequently heated to the optimum dyeing temperature, preferably, depending on the nature of the fibre materials to be dyed, to a temperature of between 70 and 1~0C. Dyeing is carried out at this temperature until the desired depth of colour is attained.
After cooling of the bath, the dyed material can be subjected to an aftertreatment, for example in the case of acetate fibres to an aftertreatment with soaps, or in the case of fibres formed from aromatic polyesters to a reductive aftertreatment with the addition of alkali.
In the dyeing of aromatic polyesters or triacetate fibres at a temperature of 105C, it is in general advan-tageous to concomitantly use customary carrier substances, such as mono-, di- or trichlorobenzene, benzoic acid, salicylic acid, o- and p-phenylphenol or benzyl alcohol.

To effect thermofixing of the dye, the padded fabric, advantageously after prior drying, for example in a warm stream of air, is heated to temperatures of over 100C, for example between 180 and 210C.
Printing is performed likewise in a manner known per se by applying to the materials a printing paste containing the dye(s) together with the customary auxiliaries, and subsequently subjecting the printing to a heat treatment.
Good fastness properties are likewise obtained with application from organic solven-ts, whereby the dye is applied from a solvent, in which it is dissolved or is present as a fine dispersion, to the substrate to be dyed. Suitable solvents are in particular chlorinated hydrocarbons (for example perchloroethylene), which can be used on their own or as a dispersion together with water.
Dyes, particularly those that convert at atmospneric pressure between 150 and 220C to the extent of at least ~0% in less than 60 seconds into the vapour state, can also be used in the transfer printing process, in which the dyes are -transferred from a provisional carrier, for example paper, to the textile material. As a rule, a brief heating (10 to 60 seconds) under atmospheric pressure, or under vacuum, to 150 to 220C is sufficient for this purpose.
The claimed dyes are superior to the nearest comparable dyes by virtue of better resistance to boiling in the dyeing of polyester materials.
The invention is further illustrated by the Examples which follow. Except where otherwise stated in these Examples, the term 'parts' denotes parts by weight, percentages are given as per cent by weight and tem-peratures in degrees Centigrade.

Example 1 21.8 parts of 6-chloro-2,4-dinitroaniline are suspended in 110 parts of 88% sulfuric acid, and the suspension is diazotised at 20 by the dropwise addition of 32 parts of nitrosylsulfuric acid (40%) within 30 minutes. After 2 hours' subsequent stirring at room temperature, the resulting clear diazo solution is added at 0-5, with stirring, to a solution of 31 parts of a coupling component of the formula ~OCH3 o ~--o~ 11 , -NH-CHCH2COC 3 in 12 parts of concentrated hydrochloric acid and 300 parts of water in the course of 30 minutes.
Coupling is completed immediately. The dye which has precipitated is filtered off, washed with warm water until neutral and then dried.
The dye thus obtained, finely dispersed with suitable agents such as sulfite liquor or dinaphthylmethane-disulfonic acid, exhibits on polyethylene glycol terephthalate fibres good build-up and levelling properties and dyes these fibres in navy blue shades. The dyeings are fast to sublimation and to light.
The coupling component mentioned is produced by hydrogenation of the Schiff base obtained by condensation of ~-propionylamino-2-aminoanisole with methyl acetoacetate according to the following reaction pattern:
~OCH3 -NH + O=C-CH -COOCH

l æ3L~30

3 H 2 N C-CH2 COOCH3 cat.
NHCOCH 2 CE~3 CH3 OCE~3 \. = NH CH - cH2-coocH3 There are obtained in an analogous manner, from the corresponding diazo and coupling components, the dyes listed in the following Table, which dyes dye polyethylene glycol terephthalate fibres likewise in navy blue shades, except for the Examples 29 to 33 and 35 and 36 which give pure blue and violet shades, respectively.

X OR

02N~ -N=N- -NH-CH-CH2-COOR2 3~

Table ~0. X R 1 l 2 _ _ I
2 -Cl -CH3 -CH3 -CH3 -CH3 3 ,. ll ,. ,. 2 3

4 ,l .. ,. -CH2C~3 ,.
S ,. .. 2 6 5 -CH3 ,.
6 .. .. -CH3 2 3 -CH3 7 -Br ,. .. ,. ..
8 .. .. .. ,. -ca2CH3 9 .. .. .. -CH3 ..
.. .. -CH2CH3 -CH3 11 ll .. ll -CH2CH2CH3 ..
12 ,. .. -CH2CH3 -CH3 ..
13 .. ,. ,. ,. -CH2C~3 14 .. .. -CH(CH3)2 .. ..
lS -Cl .. ,. .. ..
16 -Br .. -CH2CH20CH3.. -CH3 17 -Cl .. .. 2 3 -CH2C~3 18 .. .. .. -,CH3 -CH3 19 .. -CH20C~3 -CH3 .. -C~,2,cH3 -Br .. ..
21 .. -CH20CH2CH3 .. -CH2CH3 -CH3 22 -Cl -CH3 .. 2 2 6 5 -CH3 23 -Br 24 ll ll ll 2 2 3 ..
-Cl ll .. " -C~2C~3 26 .. 2 .. -CH3 -CH3 27 -Br -CH3 .. .. -~CH3 28 .. .. ll --\ H I- -CH3 29 -CN ll ,. -CH3 ll ll .. --CH(CH3)2 " "

Table (continuation N o . x R 1 1 . R2 .

31 -CN -CH3 -Ca2CH20CH -CH3 -CH3 32 .. ,. -C~2CH3 2 3 2 3 33 ,. ,. .. ll 2 3 34 -or -CH3 -CH3 -CH2C~2Cl -c~3 _~ ,. ,. -CH3 2 3 36 .l ,l -CH(CH3)2 ,.
37 -Br ll -CH3 -CH -11 11 -CH3 38 -Br ,. ll .. 2 3 39 -Cl .. ,. " _ . ,.
,. -C~2-41 -Br .. " 2 6 5 42 ,. ,. -CH2CH20CE3 ,- ,.
43 ,. ll ,. ,. o~3 44 -Cl " 2 3 ,. -CH2CH3 -Br ,.-CH3 -CH2CH2CH3 -CH3 46 -Cl ll " -CH2CH(CH3)2 "
47 .. ,. ,. -C~(Ca3)2 ,.
48 ,. ,. ,. 2 2 2 3 ,.
49 -Br .- ,. I_. ,.
,. ,. ,. I-\ H /-CH3 "

._ ~c~3 51~ ,. 1. 1. --/EI\- 1.

Dyeing Instructio-ns 1 part of the dye obtained according to Example 1 is ground in the wet state with 2 parts ox a 5~% aqueous solution of the sodium salt of dinaph-thylmethane-disulfonic acid, and the mixture is then dried.
This dye preparation is stirred up with 40 parts of a 10% aqueous solution of the sodium salt of N-butyl-Ju-heptadecylbenzimidazoledisulfonic acid and 4 parts of a 40%
acetic acid solution. A dye bath of 4000 parts is prepared therefrom by dilution with water.
100 parts of a cleansed polyester fibre material is introduced into this bath at 50; the temperature is raised within half an hour to 120 to 130, and dyeing is performed at this temperature for one hour in the closed vessel.
The material is subsequently rinsed. The result is a level, full navy blue dyeing having excellent fastness to light and good fastness to sublimation.
Printing Instructions 25 parts of the dye according to Example 1, which has previously been finely ground, 550 parts of an 8% thickening from modified locust bean flour, 50 parts of a 10% solution of the sodium salt of m-nitrobenzenesulfonic acid, and 10 parts of a mixture of potassium oleate and pine-oil are mixed together, and the amount is made up with water to 1000 parts.
With the aid of a high-speed stirrer, the mixture is stirred until the dye is completely dispersed, and poly-ethylene glycol terephthalate fabric is then printed with this paste. After printing, the fabric is dried, and steamed for 20 minutes at 1 1/2 atm. (excess pressure); it is rinsed for 10 minutes with cold water, soaped twice hot with the addition ox a small amount of hydrosulfite, subsequently rinsed cold and dried. The result is a fast navy blue printing.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A monoazo dye of the general formula I

(I) in which X is hydrogen, chlorine, bromine or cyano, R is an alkyl group having 1 to 4 carbon atoms which is un-substituted or substituted by lower alkoxy, halogen or aryloxy, R1 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or substituted by lower alkoxy, aryloxy or aryl, or it is a phenyl group optionally substituted by lower alkyl or chlorine, R2 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or substituted by hydroxyl, acyloxy, lower alkylsulfonyloxy, aryl, halogen, aryloxy or a hetero ring, or it is a cycloalkyl group optionally substituted by lower alkyl, and Y is lower alkyl or lower alkoxy with the proviso that R1 must not be an unsubstituted alkyl group if R is methyl, X is chlo-rine, bromine or cyano and Y is an unsubstituted alkyl group.

2. A monoazo dye according to claim 1, wherein X is chlorine or bromine.

3. A monoazo dye according to claim 1, wherein R is methyl, methoxymethyl or ethoxyethyl, R1 is methyl, ethyl, isopropyl or methoxyethyl, and Y is methyl or ethyl.

4. A monoazo dye according to claims 1 to 3, wherein R2 is an alkyl group which has 1 to 4 carbon atoms and which is unsub-stituted or substituted by aryloxy, acyloxy, aryl or a hetero ring, or it is cyclohexyl.

5. A monoazo dye according to claim 1, wherein R2 is an unsubstituted alkyl group having 1 or 2 carbon atoms.

6. A monoazo dye according to claim 1, wherein X is chlor-ine or bromine, R is methyl, R1 is an alkyl group which has 1 to 4 carbon atoms, and which is substituted by lower alkoxy, aryloxy, or aryl, or it is a phenyl group unsubstituted or substituted by lower alkyl or chlorine, Y is methyl or ethyl, and R2 is methyl, ethyl, propyl, isopropyl, phenoxyethyl, acetyloxyethyl, chloro-ethyl, benzyl, furfuryl, tetrahydrofurfuryl or cyclohexyl.

7 A process for producing monoazo dyes of the formula I

(I) in which X is hydrogen, chlorine, bromine or cyano, R is an alkyl group having 1 to 4 carbon atoms which is unsubstituted or substit-uted by lower alkoxy, halogen or aryloxy, R1 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or sub-stituted by lower alkoxy, aryloxy or aryl, or it is a phenyl group optionally substituted by lower alkyl or chlorine, R2 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or substituted by hydroxyl, acyloxy, lower alkylsulfonyloxy, aryl, halogen, aryloxy or a hetero ring, or it is a cycloalkyl group optionally substituted by lower alkyl, and Y is lower alkyl or lower alkoxy, with the proviso that R1 must not be an unsubstituted alkyl group if R is methyl, X is chlorine, bromine or cyano and Y
is an unsubstituted alkyl group in which process the diazo component of an amine of the general formula II

(II) is coupled, in the p-position with respect to the amino group, with a coupling component of the general formula III

in which X, R, R1, R2 and Y are as defined under the formula 1.

8. A process according to Claim 7, wherein there are used amines of the formula II in which X is chlorine or bromine.

9. A process according to Claim 7, wherein there are used coupling components of the formula III in which R is methyl, methoxymethyl or ethoxyethyl, R1 is methyl, ethyl, isopropyl or methoxyethyl, and Y is methyl or ethyl.

10. A process according to Claim 9, wherein there are used coupling components of the formula III in which R2 is an alkyl group which has 1 to 4 carbon atoms and which is unsubstituted or substituted by aryloxy, acyloxy, aryl or a hetero ring, or it is cyclohexyl.

11. A process according to Claim 7, wherein there are used coupling components of the formula III in which R2 is an unsub-stituted alkyl group having 1 or 2 carbon atoms.

12. A process according to Claim 7, wherein there are used diazo components of the formula II in which X is chlorine or bromine, and coupling components of the formula III in which R is methyl, R1 is an alkyl group which has 1 to 4 carbon atoms, and which is substituted by lower alkoxy, aryloxy, or aryl, or it is a phenyl group unsubstituted or substituted by lower alkyl or chlorine, Y is methyl or ethyl, and R2 is methyl, ethyl, propyl, isopropyl, phenoxyethyl, acetyloxyethyl, chloroethyl, benzyl, furfuryl, tetrahydrofurfuryl or cyclohexyl.

13. A process for dyeing and printing hydrophobic materials with the use of a monoazo dye according to claim 1.

14. A process according to claim 13 for dyeing and printing aromatic polyester and cellulose triacetate fibres.

15. A process according to claim 13 for dyeing and printing aromatic polyethylene glycol terephthalate fibres.

16. Dyeing and printing preparations containing the monoazo dyes according to claim 1.

17. A hydrophobic material dyed and printed with the monoazo dyes according to claim 1.

18. A material according to claim 17 which is a textile or fibre material made from aromatic polyester or cellulose triacetate.