GB2165854A

GB2165854A - Monoazo dyestuffs

Info

Publication number: GB2165854A
Application number: GB08525515A
Authority: GB
Inventors: Casa Angelo Della; Peter Liechti
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1984-10-18
Filing date: 1985-10-16
Publication date: 1986-04-23
Also published as: GB8525515D0; JPS61101557A; CH661519A5; FR2572084B1; GB2165854B; JPH0811785B2; FR2572084A1; DE3536718A1

Abstract

Compounds of the formula <IMAGE> (wherein R1 is a branched C3-C7alkyl radical and each of R2 and R3 independently of the other is a C2-C4alkyl radical, as well as to mixtures of these compounds, which mixtures contain at least two different compounds of the above formula, the difference lying in the meaning of at least one of the substituents R1, R2 and R3) impart blue shades to polyester, cellulose 21 DIVIDED 2-acetate, cellulose triacetate, polyamide, polyolefin, polyacrylonitrile and polyvinyl textiles.

Description

SPECIFICATION Monoazo compounds The present invention relates to novel monoazo compounds, to mixtures thereof, to the preparation thereof, as well as to the use thereof as dyes for dyeing and printing substrates, which can be dyed or printed with disperse dyes, in particular polyester materials.

The novel compounds of the present invention are of the formula

wherein R, is a branched C3-C7alkyl radical and each of R2 and R3 independently of the other is a C2 Alkyl radical.

Examples of R, as a branched C3-C7alkyl radical are isopropyl, isobutyl, tert-butyl, 2-methylpropyl, 2 methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl and 1-ethylpentyl. In preferred compounds, R, is a branched C3alkyl or C4alkyl radical, in particular isopropyl, 2-methylpropyl and tert-butyl.

R2 and Rs as a C2-C4alkyl radical are unbranched or branched alkyl radicals; examples of such radicals are ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.

In preferred compounds, R2 and R3 are the same alkyl radical; e.g. a Alkyl or C4alkyl radical, in particular ethyl.

Further preferred compounds are those in which the total number of the carbon atoms of the alkyl radicals R1, R2 and Rs together is at least 7 and not more than 12.

The invention further relates to mixtures of compounds, which mixtures contain at least two different compounds of formula I, with the difference lying in the meaning of at least one of the substituents R1, R2 and Rs. In preferred mixtures, the individual components are present in about equal amounts.

A particularly interesting mixture is that comprising the 2 compounds of the formulae

as well as that comprising the 3 compounds of the formulae

in which formulae each of the substituents Rl is identical and is as defined for formula (I) and is e.g.

isopropyl. Likewise interesting mixtures are obtained by replacing the last compound of each of the two mixtures by a compound wherein each of R2 and R3 is ethyl.

The compounds of the invention and the mixtures thereof can be prepared by different methods which are known per se; thus, for example, the compounds of formula (I) are obtained by diazotising a diazo component of the formula

wherein Hal is a halogen atom, coupling the diazonium compound to a coupling component of the formula

wherein R1, R2 and R3 are as defined for formula (I), and reacting the coupling product of the formula

with a metal cyanide in a polar organic solvent which may or may not contain water. Hal is preferably bromine.

The mixtures of the present invention can also be prepared by different methods, e.g. by: a) mixing at least two compounds of formula (I), or b) fusing together at least two compounds of formula (I), or c) diazotising a diazo component of the formula

wherein Hal is a halogen atom, and coupling the diazonium compound to a mixture of at least 2 different coupling components of the formula

with the difference lying in the meaning of at least one of the substituents R,, R2 and R3 and in which formula R1, R2 and R3 are as defined for formula (I), and reacting the mixture of the coupling product with a metal cyanide in a polar organic solvent which may or may not contain water.

If process variant a) is chosen, the preparation of the mixture of the invention comprises mixing the individual compounds of formula (I) dry or wet at room temperature. It is advantageous to add dispersants, in particular of an anionic or nonionic nature, and water to the mixture and to grind said mixture with the aid of grinding assistants (e.g. glass beads) to a ready-for-use dispersion.

Examples of suitable anionic dispersants are condensation products of naphthalenesulfonic acids and formaldehyde, in particular dinaphthylmethane disulfonate or modified ligninsulfonates.

Examples of known and particular suitable nonionic dispersants are adducts of about 3 to 40 moles of ethylene oxide with alkyl phenols, fatty alcohols or fatty amines.

If the above variant b) is used for the preparation of the mixture of the invention, the compounds are fused together to a homogeneous melt, subsequently allowed to cool and optionally ground with anionic or nonionic dispersant and water in the presence of grinding assistants. This variant also provides a ready-for-use dispersion.

The starting materials of formulae (III) and (IV) are known and can be prepared by known methods.

Thus, for example, the coupling components of formula (III) are obtained e.g. by reacting the corresponding acylaminoanilines of the formula

with alkyl halides of the formula R2-Hal or R3-Hal or alkyl sulfates of the formula R2-O-SO3H or R3-O-SO3H or, if R2 =I R3, mixtures thereof, in the presence of an acid acceptor, e.g. an alkali metal carbonate, in particular sodium carbonate.

The coupling reaction of the coupling components of formula (III) (individually or in admixture) with the diazo compound of formula (IV) is carried out in known manner, affording the coupling product of formula (II) or a mixture thereof. Said coupling product or mixture can be isolated. The halogen atom in the diazo component is subsequently replaced by the cyano group by reacting the compound of formula (II) or a mixture thereof with a metal cyanide. This reaction, which is preferably carried out with copper cyanide, is preferably effected in a polar organic solvent which may or may not contain water, e.g. dimethyl sulfoxide, dimethylformamide, N-methyl-pyrrolidone or a mixture of pyridine and water, at a temperature in the range from about 40 to 1500C, preferably from 80 to 1300C.

A further process for the preparation of coupling components of formula (III) comprises hydrolysing a compound of the formula

to a compound of the formula

and reacting said compound of formula (VI) with a carboxylic acid halide of the formula Hal-CO Rl The novel compounds of formula (I) and the mixtures thereof are used as dyes for dyeing and printing substrates, in particular textile materials, which can be dyed with disperse dyes. Before use, it is advantageous to convert these compounds into dye formulations provided this has not already been done during their preparation. To this end, the compounds can be comminuted to an average particle size of 0.01 to 10 Am. Comminution may be effected in the presence of dispersants.For example the dried dye or mixture of dyes is ground with dispersant or kneaded as a paste with a dispersant and subsequently dried in vacuo or spray dried. After the addition of water, the formulations so obtained can be used for dyeing, padding or printing in long liquor (liquor to goods ratio greater than 1:5) or short liquor (liquor to goods ratio from 1:1 to 1:5).

The novel compounds exhaust from an aqueous suspension or dispersion in excellent manner onto textiles made of fully synthetic or semi-synthetic high molecular substances to give a blue shade. The compounds are particularly suitable for dyeing, padding or printing fibres, filmaments or fleece, wovens or knits made of linear aromatic polyester as well as of cellulose-2 1/2-acetate and cellulose triacetate.

Synthetic polyamides, polyolefines, acrylonitrile polymerisation products and polyvinyl compounds can also be dyed and printed with the novel compounds. Particularly valuable dyeings are obtained on linear, aromatic polyesters. Such polyesters are in general polycondensation products of terephthalic acid and glycols, in particular acid and 1 ,4-bis(hydroxymethyl)hexahydrobenzene.

The polyesters are dyed by procedures known per se, for example by the exhaust method in the presence of carriers and at temperature in the range from about 80 to 125no or in the absence of carriers, under pressure and at a temperature in the range from about 100 to 140 C. Furthermore, these fibres can be padded or printed with aqueous dispersion of the compounds and the resultant impregnation can be fixed at a temperature in the range from about 140 to 2300C, e.g. with the aid of steam, contact heat or hot air. Cellulose-2 1/2-acetate is preferably dyed at a temperature in the range from about 65 to 85"C and cellulose triacetate at a temperature in the range up to 1150C.

The customary dispersants already mentioned, which are preferably anionic or nonionic and which may be employed in admixture, are usually added.

The customary thickeners are used for padding and printing, e.g. modified or unmodified products such as alginates, British gum, Gummi arabicum, crystal gum, carob bean gum, tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products such as polyacrylamides or polyvinyl alcohols.

The dyeing obtained exhibit good coloristic properties; a property to be singled out for special mention is that, when mixed with other dyes, in particular yellow dyes, and applied to textile material the components of the invention do not exhibit catalytic fading and that, in addition, they possess a good pH stability, in particular in exhaust dyeing. The compounds of formula (I) give level dyeings, are very productive and have a very good build-up.

The invention is illustrated further by the following non-limitative Examples. Unless otherwise stated, parts and percentages are by weight.

Example 1 10.5 parts (0.036 mol) of 3-dibutylaminoisobutyrylanilide (prepared by hydrolysing 3-dibutyiaminoace- tanilide with alcoholic aqueous hydrochloric acid and reacting the resultant 3-dibutylaminoaniline with isobutyryl chloride or by reacting isobutyrylaminoaniline with excess butyl bromide) are dissolved in 300 parts of 50 % aqueous acetic acid. A diazonium salt solution, which has been obtained by introducing 9.43 parts (0.036 mol) of 2,4-dinitro-6-bromoaniline into 38 parts of 1N nitrosylsulfuric acid at about 20"C and subsequently stirring for 2 hours at this temperature, is added dropwise to the resultant solution at 0-5 C over 1 hours. The precipitated compound of the formula

is filtered with suction.The fiitrate is washed with water and dried, affording 18.1 parts (89.3 % of theory) of a dark blue powder with a melting point of 153 to 155 C (sintering at 149"C).

16.9 parts (0.03 mol) of said powder are dissolved in 63 parts of pyridine. To this solution are added 2.85 parts of copper(l) cyanide and 36 parts of water The reaction mixture is stirred for 62 hours at 60 70"C and then filtered with suction at 50"C. The filtrate is washed with a 50 C warm mixture of pyridine and water and then with water and is dried, affording the dye of the formula

as a greenish-brown powder with a melting point of 190 to 199 C (sintering at 186"C). Yield: 10.0 parts (65.4 % of theory).

The dyes of the following formulae are obtained in analogous manner:

melting point 204 to 260 C, melting point of the bromium precursor 145 to 150 C;

melting point 185 to 1900C (sintering at 176 C), melting point of the bromium precursor 156 to 160"C (sintering at 144"C);

melting point 185 to 192 C, melting point of the bromium precursor 150 to 156"C;

melting point 173 to 1740C (sintering at 170 C), melting point of the bromium precursor 69 to 820C;;

melting point 118 to 128"C (sintering at 98"C), melting point of the bromium precursor 141 to 148"C (sintering at 130"C);

melting point 214 to 260"C, melting point of the bromium precursor 135 to 180"C.

Example 2 5 parts of the dye of formula (1a) are mixed with 10 parts of a dispersant of low salt content (dinaphthylmethanesulfonic acid type) and the resultant mixture is ground in a microsol mill in 85 parts of water with the aid of 300 parts of glass beads with a diameter of 0.5 mm. The resultant dispersion can be used for dyeing polyester materials.

Dispersions of the dyes of formulae (1b), (1c) and (1d) or mixtures thereof, e.g. equal amounts of the dyes of formulae (1a) and (1d), can be prepared and used in the same manner.

Example 3 The dye mixture containing the dyes of formulae (1a) and (1b) in a ratio of about 50:50 by weight is obtained by coupling equimolar amounts of the two coupling components of the formulae

with a diazotised diazo component of the formula

and reacting the resultant mixture with CuCN to give the corresponding mixture of cyano derivatives.

Diazotisation, coupling and replacement of the bromine atom by cyano are effected under the conditions as indicated in Example 1.

Example 4 A dye mixture containing the dyes of the formulae (lea), (1b) and

is obtained by coupling the isobutyrylaminoanilides obtained by combined alkylation of 3-isobutyrylaniline with equimolar amounts of n-propyl bromide and n-butyl bromide to diazotised dinitrobromoaniline and converting the resultant mixture into a mixture of the corresponding cyano compounds. The individual steps are carried out under the conditions as indicated in Example 1.

Example 5 4,000 parts of polyester fibre (Diolen) are dyed for 1 hour at 1300C in 100,000 parts of a dye bath adjusted to pH.4, which bath contains 192 parts of a dispersion according to Example 2 (corresponding to 9.6 parts of dye) as well as 50 parts of a wetting agent (e.g. fatty acid methyl tauride) and 50 parts of a dispersant (e.g. based on dinaphthylmethane sulfonate). A strong blue dyeing of very good fastness to light is obtained. The dye bath is completely exhausted.

Example 6 By repeating the dyeing procedure of Example 5 but buffering the dye bath at pH 5, 6, 7 and 8, a faint change in shade is observed above pH 6.

Claims

1. A monoazo compound of the formula

wherein R, is a branched C3-C7alkyl radical and each of R2 and R3 independently of the other is a C2 C4alkyl radical.

2. A monoazo compound according to claim 1, wherein B1 is a branched C3alkyl or C4alkyl radical.

3. A monoazo compound according to claim 1, wherein each of R2 and R3 independently of the other is a C3alkyl or C4alkyl radical.

4. A monoazo compound according to claim 1, wherein the total number of the carbon atoms of the alkyl radicals R,, R2 and R3 is at least 7 and not more than 12.

5. A monoazo compound according to claim 1 wherein each of R2 and R3 is ethyl.

6. A mixture containing at least 2 different monoazo compounds as defined in claim 1, the difference lying in the meaning of at least one of the substituents RI, R2 and R3.

7. A process for the preparation of a compound as defined in claim 1, which process comprises diazotising a diazo component of the formula

wherein R,, R2 and R3 are as defined in claim 1, and reacting the coupling product of the formula

with a metal cyanide in a polar organic solvent which may or may not contain water.

8. A process for the preparation of a mixture as defined in claim 6, which process comprises a) mixing at least two different compounds of the formula (I), or b) fusing together at least two different compounds of the formula (I), or c) diazotising a diazo component of the formula

wherein Hal is a halogen atom, coupling the diazonium compound to a mixture of at least 2 different coupling components of the formula

the difference lying in the meaning of at least one of the substituents R,, R2 and R3 and in which formula R,, R2 and R3 are as defined in formula (I), and reacting the mixture of the coupling product with a metal cyanide in a polar organic solvent which may or may not contain water.

9. A process for dyeing or printing substrates which can be dyed or printed with disperse dyes, which comprises applying to or incorporating into said substrates one or more of the compounds defined in claim 1.

10. A process according to claim 9 wherein the substrate to be dyed or printed is textile material.

11. A process according to claim 10 wherein the material is polyester material.

12. Polyester material dyed or printed by the process of claim 11.

13. Monoazo compounds of formula I according to claim 1 substantially as described with reference to any of Examples 1, 3 and 4.

14. Process for producing monoazo compounds of formula I according to claim 7 or 8 substantially as described with reference to any of Examples 1, 3 and 4.

15. Process for dyeing or printing substrates according to claim 9 substantially as described with reference to Example 5 or 6.