GB2125811A

GB2125811A - Monoazo dyestuffs

Info

Publication number: GB2125811A
Application number: GB08320877A
Authority: GB
Inventors: Francois Benguerel
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1982-08-06
Filing date: 1983-08-03
Publication date: 1984-03-14
Also published as: GB8320877D0; FR2531442A1; JPS5962668A; IT1169458B; CH654845A5; IT8322432A0; BE897431A; GB2125811B

Abstract

Monoazo compounds containing a single sulphonic acid group correspond to the formula <IMAGE> wherein R1 is C1-6alkyl or C3-6alkyl monosubstituted by hydroxy, chlorine or cyano, R2 is hydrogen or C1-4alkyl, R3 is hydrogen or methyl, n is 1 or 2 and R1 and the optionally substituted phenyl radical together contain 9 to 15 carbon atoms, R4 is hydrogen, halogen, C1-4alkyl or C1-4alkoxy, and R5 is hydrogen or C1-4alkyl, which compounds are in free acid or salt form and are useful for dyeing or printing anionically dyeable substrates such as natural or synthetic polyamides, especially nylon carpet.

Description

SPECIFICATION Improvements in or relating to organic compounds The present invention relates to monoazo compounds containing a single sulphonic acid group, their preparation and use as anionic dyestuffs More particularly, this invention provides compounds, which, in the free acid form, correspond to formula

and mixtures thereof, in which R1 is C1-6 alkyl or C3 6alkyl monosubstituted by hydroxy, chlorine or cyano, R2 is hydrogen or or C4alkyI, n is1 or2, each R3, independently, is hydrogen or methyl, provided that for the N,N-substituted sulphonamido group, R1 and the optionally substituted phenyl radical together contain 9 to 15 carbon atoms, R4 is hydrogen, halogen, C1.4alkyl or C14alkoxy, and R5 is hydrogen orC1.4alkyl, which compounds are in free acid or salt form.

The total number of carbon atoms for R1 and the optionally substituted phenyl radical preferably is 9-12; more preferably, it is 9 or 10 and most preferably, it is 10.

Any unsubstituted alkyl as R1 may be straight chain or branched. Preferably, it contains 1 to 4 carbon atoms. More preferably, it is methyl, ethyl or linear or branched butyl. Most preferably, it is n-butyl.

Any substituted alkyl as R1 may be a straight chain or branched alkyl group, wherein the substituent is bound to a carbon atom other than to the C1-atom. Preferably, it contains 3 or 4 carbon atoms. More preferably, the alkyl group is monosubstituted by hydroxy and then is 2-or 3-hydroxypropyl or 2-, 3-or 4-hydroxybutyl, wherein the propyl- and butyl-radicals may be linear or branched. Even more preferably, it is linear 2-hydroxypropyl or 2-hydroxybutyl. Most preferably, it is linear 2-hydroxybutyl.

R1 is preferably Ria, where Ria is linear or branched C1.4alkyl or linear or branched C3.4alkyl monosubstituted by hydroxy, chlorine or cyano (with the substituent in other than the C1-position). More preferably, it is Rib, where Rib is methyl, ethyl, linear or branched butyl; linear or branched 2-or 3-hydroxypropyl or 2-, 3- or 4-hydroxybutyl. More preferably, it is R1,, where R1, is methyl, ethyl, n-butyl, 2-hydroxypropyl-(n) or 2-hydroxybutyl-(n). Even more preferably, R1 is Rid, where Rld is n-butyl or 2-hydroxybutyl-(n). Especially, R1 is n-butyl.

Any alkyl as R2 is preferably methyl or ethyl, especially methyl.

R2 is preferably R2a, where R2a is hydrogen, methyl or ethyl. Most preferably, it is R2b where R2b is hydrogen or methyl.

When the phenyl radical bound to the nitrogen atom of the sulphonamido group is disubstituted, the two substituents are preferably in the 2,4; 2,5- or 3,5-positions, especially in the 2,4- or 2,5-positions. When this phenyl radical is trisubstituted, the substituents are preferably in the 2,4,6-positions.

Any halogen as R4 is preferably chlorine or bromine, especially chlorine. Any alkyl as R4 is preferably methyl or ethyl, especially methyl; any alkoxy is preferably methoxy or ethoxy, especially methoxy.

The radical R4 is preferably bound to the carbon atom in the 4-, 5- or 6-position of the phenyl residue, more preferably, it is in the 4- or 5-position.

R4 is preferably R4a, where R4a is hydrogen, chlorine, methyl or methoxy. More preferably, it is R4b, where R4b is hydrogen or methyl. Most preferably, R4 is hydrogen.

Any alkyl as R5 is preferably methyl.

R5 is preferably Ursa, where R5a is hydrogen or methyl. Most preferably, Rg is hydrogen.

Preferred compounds correspond, in the free acid form, to formula la,

wherein the N,N-substituents of the sulphonamido group, the radical Ric and the optionally alkylsubstituted phenyl radical together contain a total number of 10 carbon atoms; wherein the radical R4a is in the 4-, 5-or 6-position; and wherein, when the N-phenyl residue contains two substituents, they are in the 2,4-; 2,5- or 3,5-positions, and when it contains three substituents, they are in the 2,4,6-positions.

Even more preferred are compounds of formula la, wherein (1) R4a is R4b; (2) RlciSRld; (3) R2a is R2b; (4) those of (2) or (3), wherein R4a is hydrogen; (5) the compound of group (4), wherein R1, is n-butyl and R2a and R3 are hydrogen.

When the compound of formula I is in the salt form, the cation of the sulpho group is not critical and may be any one of those non-chromophoric cations conventional in the field of anionic dye-stuffs. Examples of such cations are alkali metal cations and unsubstituted or substituted ammonium cations e.g., lithium, sodium, potassium, ammonium, mono- di-, tri- and tetra-methylammonium, triethylammonium, mono-, diand tri-ethanolammonium.

The preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.

In a compound of formula I the cation of the sulpho group may also be a mixture of the above mentioned cations e.g., the compound of formula I may be in a mixed salt form.

The compounds of formula I may be prepared by a process comprising coupling the diazotized amine of formula II

with the compound which, in the free acid form, corresponds to formula III

or a salt thereof, in an acid to neutral reaction medium.

Diazotization and coupling reactions may be effected in conventional manner. Preferably, coupling is carried out in an acid reaction medium, more preferably at pH 3 to 4.5, using water or a mixture of water and a water-miscible organic solvent as reaction medium; the preferred temperature range is 0'to 30"C, especially 0 to 1 0 C for water and 0" to 20"C for a mixed solvent e.g., water/ethanol.

The starting materials, compounds of formula II or Ill, are either known or may be obtained by known processes from available starting materials.

The compounds of formula I may be isolated in accordance with conventional methods. Advantageously, the isolation of the monoazo compounds is effected by salting out, subsequent filtering, washing and drying in vacuo. Depending on the reaction- and isolation-conditions a compound of formula I is obtained in free acid or preferably salt form of even mixed salt forms containing, for example, one or more of the above mentioned cations. It may be converted from free acid form to a salt form or a mixture of salt forms or vice versa or from one salt form to another by conventional means.

The compounds of formula I, especially in salt or mixed salt forms, are useful for dyeing and printing substrates dyeable with anionic dyes such as leather, natural or synthetic polyamides, polyurethanes and basic-modified polyolefins. They are especially suitable for dyeing and printing textile substrates consisting of or containing natural and synthetic polyamides (especially the latter), such as wool, silk, and especially nylon, for example nylon 6 or nylon 66. The compounds are particularly suitable for the dyeing or printing of nylon carpet and especially of nylon 6 or nylon 66 carpet.

The compounds of formula I may be formulated into liquid or solid compositions such as conventionally used for monoazo acid dyes intended for, for example, the dyeing and printing of anionically dyeable substrates such as nylon carpet. The preparation of such compositions in form of stable liquid, for example concentrated aqueous preparations, or solid preparations may be carried out in accordance with conventional methods, for example by dissolving in suitable solvents e.g. water, optionally with the addition of conventional additives such as solubilizing agents, for example urea, or by grinding or granulating.

Further, the compounds of formula I may be made up into preparations which are dispersible in cold water. Such dispersions may be prepared, for example, by grinding the dye dry or wet in an aqueous dispersing medium in the presence of one or more conventional anionic dispersing agents and optionally in the presence of other conventional additives, optionally with subsequent spray-drying. The preparations so obtained are finely dispersed in cold water.

Dyeing and printing may be carried out in accordance with known methods, for example pad dyeing or exhaust dyeing, especially the latter, in as much as the compounds of formula I exhaust from an essentially neutral, aqueous dyebath, i.e., from a weakly alkaline to weakly acid, aqueous dyebath. Furthermore, the compounds of formula I are also useful for use in the "space-dyeing" process. The compounds are further suitable for using the gum displacement technique in carpet dyeing.

The compounds of formula I in salt form are well soluble in water. They build-up well, have a rapid strike, migrate well and give even dyeings, especially on nylon which tends to give stripy dyeings. The dyeings obtained on, for example, nylon possess notably good fastness to light. Furthermore, the compounds of formula I give dyeings which show good all-around fastness properties, such as wet-fastness properties, especially fastness to washing, (cold) water, milling, sweat, or other fastness properties, such as dry and wet fastness to crocking and fastness to ozone. Further, the compounds have good dye strength.

The compounds of formula I further are suitable for combining with other ahionic dyes which exhaust from a neutral dyebath and are particularly useful for combining in important ternary dye mixtures, whereby tone-in-tone dyeings, having the above-mentioned advantageous properties, are obtained. Further, such dyeings do not exhibit catalytic fading.

The following Examples further serve to illustrate the invention. In the Examples, all parts and percentages are by weight and all temperatures are in degrees Centigrade.

Example 1 30.4 Parts 2-aminobenzenesulphonic acid-N-n-butyl-N-phenylamide are dissolved at 45 in 80 parts ethanol by the addition of 56 parts 30% hydrochloric acid. Subsequently, the solution is cooled to -5" in an ice bath. During 20 minutes, a solution of 7.0 parts sodium nitrite in 25 parts water is added dropwise whilst keeping the temperature at -5 to 0'. After a 30 minutes stirring, diazotization is complete. The excess of nitrous acid is decomposed by the addition of a small amount of amidosulphonic acid.

23.9 Parts 2-amino-8-hydroxynaphthalene-6-sulphonic acid are dissolved in 150 parts water by adding of 12 parts 30% sodium hydroxide solution. The pH of the resulting solution is ca. 8. This solution is slowly added dropwise to the diazonium solution as described above within one hour, the pH is maintained at 3.0-3.5 by the addition of 50 % sodium acetate solution. After stirring for 21/2 hours, the coupling reaction is finished. The pH is adjusted to 9 by the addition of 30% sodium hydroxide solution. The dyestuff which precipitates is filtered off, the residue is washed with 200 parts 10% sodium chloride solution and dried in vacuo at 100 . The thus obtained dyestuff which, in the free acid form, corresponds to the formula

which is in the sodium salt form dyes natural and synthetic polyamide fibres in bluish red shades.These dyeings have notable wet fastness and light fastness properties.

Furthermore, the dyestuff is suitable for dyeing in combination with two and especially three component mixtures.

Examples 2-47 In the following Table further compounds corresponding, in the free acid form, to the formula

are listed. They may be prepared in accordance with the method described in Example 1 using appropriate starting materials.

TABLE

Ex.No. R1 R2 R3 R6 R4 R5 2 C2H5 2-CH3 4-CH3 H H H 3 do. do. do. H H CH3 4 do. do. do. H 5-CH3 H 5 do. do. do. H do. CH3 6 do. do. 5-CH3 H H H 7 do. do. do. H 6-OCH3 H 8 do. do. do. H 4-CH3 H 9 do. 2-C2H5 H H do. H 10 do. do. H H H H 11 CH3 2-CH3 4-CH3 6-CH3 H H 12 do. do. 5-CH3 H 4-CH3 H 13 do. 2-C2H5 H H H H 14 do. 3-C2H5 H H 5-CH3 H 15 do. 2-CH3 4-CH3 6-CH3 H CH3 16 -CH2CHCH3 H H H H H I CH3 17 do. H H H 5-CH3 H 18 C3H7(n) 3-CH3 H H H H 19 do. do. H H 4-CI H 20 do. do. H H 5-CH3 H 21 do. 2-CH3 5-CH3 H H CH3 22 C3H7(i) 4-CH3 H H H H TABLE (con't)

Ex. No. R1 R2 R3 R6 R4 R5 23 C4Hg(n) , H H H H CH3 24 do. 2-CH3 H H H H 25 do. 2-C2H5 H H H H 26 do. H H H 4-CI H 27 do. H H H 6-OCH3 H 28 do. H H H 4-CH3 H 29 do. H H H 5-CH3 H 30 do. H H H do. CH3 31 do. H H H 6-OCH3 do. 32 C4Hg(n) 2-CH3 4-CH3 H H H 33 do. do. do. H 5-CH3 H 34 do. H H H 4-CI CH3 35 -CH2CH2CH2OH H H H H H 36 do. 2-CH3 H H H H OH 37 -CH2CHCH3 do. H H H H 38 do. do. H H H CH3 39 do. H H H 4-CH3 H 40 do. H H H do. CH3 41 -CH2CH2CH2CH2OH H H H H H 42 do. H H H H CH3 OH 43 -CH2CHCH2CH3 H H H H H 44 do. H H H H CH3 45 do. H H H 6-OCH3 H 46 do. H H H 5-CH3 H 47 do. 3-CH3 H H H H

The dyestuffs of Examples 2 to 47 dye natural and synthetic polyamide fibres in bluish red shades. These polyamide dyeings show notably good light fastness and wet fastness properties.

In accordance with the reaction- and isolation-conditions as described the dyestuffs of Examples 2 to 47 are obtained in the sodium salt form. The may, depending on the reaction-/isolation-conditions or by reacting the sodium salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms containing one or moe cations indicated in the description hereinbefore.

In the following examples the application of the dyestuffs of this invention is illustrated.

Application Example A (Exhaust dyeing of polyamide fabric) 100 Parts of pre-wetted synthetic polyamide, for example nylon 66, are entered at 40 into a dyebath consisting of: 2 parts dye of Example 1 10 parts anhydrous sodium sulphate 4000 parts water.

The dye liquor is heated over the course of 30 minutes to boiling temperature and kept at this temperature for 1 hour. 4 Parts of glacial acetic acid are then added thereto and dyeing is completed with heating for a further 30 minutes at boiling temperature. The water that evaporates during dyeing is continuously replaced.

The bluish red dyed nylon cloth is then removed from the liquor, rinsed with water and dried. Wool may also be dyed by the same process.

Application Example B (Exhaust dyeing of nylon yarn) 100 Parts of pre-wetted nylon 66 yarn are added to a dyebath at 26"-27" consisting of: 1 part dye of Example 1 1-2 parts oleylamine (a levelling agent) 1 part monosodium phosphate 3000 parts water.

The dyebath is heated to boiling temperature, 1 part of glacial acetic acid is added, and the dyebath is maintained at this temperature for 45 minutes. The water that evaporates during dyeing is continuously replaced. The bluish red dyed nylon 66 yarn is then removed from the dyebath, rinsed with warm water and dried.

Similarly, the dyes of Examples 2 to 47 or mixtures of two or more of the dyes of Examples 1 to 47 may be employed to dye polyamide in accordance with the method given for Application Example A or B.

The dyeings have good light fastness and good wet fastness properties.

Application Example C (Printing of polyamide fabric) Polyamide is printed with a printing paste containing: 30 parts dye of Example 1 50 parts urea 50 parts solubilizing agent (e.g., thiodiethylene glycol) 290 parts water 500 parts thickening agent (e.g., one based on carob bean gum) 20 parts acid-donating agent (e.g., ammonium tartrate) 60 partsthiourea.

The printed textile goods are steamed for 40 minutes at 102" (saturated steam), rinsed cold, washed at 60 for 5 minutes with a dilute solution of a conventional detergent and rinsed again with cold water. A bluish red print is obtained having good light- and wet-fastness.

In an analogous manner printing pastes may be prepared employing the dyes of Examples 2 to 47 or a mixture of two or more dyes of Examples 1 to 47. Such pastes may be employed for printing in accordance with the above given procedure.

Application Example D (Continuous dyeing of polyamide carpet) Polyamide (e.g.., regulator nylon 6 or regular nylon 66) carpet is wetted out with a composition consisting of 1-2 parts of decyl alcohol ethoxylated with 4 moles of ethylene oxide per mole of alcohol or a similar surfactant and 998-999 parts of water and squeezed to impregnate the wetting agent and reduce the total pick-up to 80-100%.

A dye liquor consisting of: 0,5-5 parts dye of Example 1 1 - 2 parts guarthickener (e.g.., Celca Gum D-49-D) 1 - 2 parts decyl alcohol ethoxylated with 4 moles of ethylene oxide per mole of alcohol (or a similar surfactant) 91-97.5 parts water sufficient trisodium phosphate or acetic acid to adjust the pH to 5 for e.g., regular nylon 6 and regular nylon 66 is applied to the wetted polyamide carpet using a continuous applicator (e.g., Kuesters) to achieve a wet pick-up of 300-600%. The bluish red dyed polyamide carpet is then steamed in a vertical or horizontal steamer for 4-10 minutes, rinsed with warm water and dried.

Application Example E (Continuous dyeing of polyamide carpet with gum displacement) To polyamide (e.g., regular nylon 6 or regular nylon 66) carpet, wetted out and squeezed as in Application Example D, a layer of gum consisting of: 10 parts guarthickener (e.g.., Celca Gum D-49-D) 0.25 parts glacial acetic acid 989.75 parts water is applied.

A dye liquor as described in Application Example D is applied to the thus treated polyamide carpet using a continuous applicator (e.g., Kuesters) to achieve a wet pick-up of 300-600%. The bluish red dyed polyamide carpet is then steamed in a vertical or horizontal steamer for 4-10 minutes, rinsed in warm water and dried.

Claims

1. A compound which, in the free acid form corresponds to formula 1,

and mixtures thereof, in which Ri is C18alkyl or C3.6alkyl monosubstituted by hydroxy, chlorine or cyano, R2 is hydrogen or C1 4alkyl, n is 1 or 2, each R3, independently, is hydrogen or methyl, provided that for the N,N-disubstituted sulphonamido group, R1 and the optionally substituted phenyl radical together contain 9 to 15 carbon atoms, R4 is hydrogen, halogen, C1.4alkyl or C1.4alkoxy, and R5 is hydrogen or C1.4alkyl, which compound is in free acid or salt form.

2. A compound according to Claim 1, wherein the total number of carbon atoms for Ri and the optionally substituted phenyl radical is 9-12.

3. A compound according to Claim 2, wherein said total number of carbon atoms is 9 or 10.

4. A compound according to Claim 3, wherein said total number of carbon atoms is 10.

5. A compound according to any one of Claims 1 to 4, wherein R1 is linear or branched C1.4alkyl or linear or branched Alkyl monosubstituted by hydroxy, chlorine or cyano (with the substituent in other than the C1-position).

6. A compound according to Claim 5, wherein R1 is methyl, ethyl, n-butyl, 2-hydroxypropyl-(n) or 2-hydroxybutyl-(n).

7. A compound according to any one of Claims 1 to 6, wherein R2 is hydrogen, methyl or ethyl.

8. A compound according to Claim 4, wherein R1 is n-butyl and R2 and R3 are hydrogen.

9. A compound according to any one of Claims 1 to 8, wherein R4 is hydrogen, chlorine, methyl or methoxy.

10. A compound according to Claim 9, wherein R4 is hydrogen.

11. A compound according to any one of Claims 1 to 10, wherein R5 is hydrogen or methyl.

12. A compound according to Claim 1 which, in the free acid form, corresponds to formula la,

in which R4, is hydrogen, chlorine, methyl or methoxy, which is in the 4-, or 6-position, R1, is methyl, ethyl, n-butyl, 2-hydroxypropyl-(n) or 2-hydroxybutyl-(n), R2a is hydrogen, methyl or ethyl, R3 and n are as defined in Claim 1, the radical R1, and the optionally alkylsubstituted phenyl radical of the N,N-disubstituted sulphonamido group together contain a total number of 10 carbon atoms; and wherein when the N-phenyl residue contains two substituents, they are in the 2,4-, 2,5- or 3,5-positions, and when it contains three substituents, they are in the 2,4,6-positions.

13. A compound according to Claim 12, wherein R4a is hydrogen.

14. A compound according to Claim 12 or 13, wherein R2a is hydrogen or methyl.

15. A compound according to Claim 13, wherein Rip is n-butyl and R2a and R3 are hydrogen.

16. A compound according to any one of Examples 2 to 47.

17. A process for the preparation of a compound of formula I, as defined in Claim 1, comprising coupling the diazotizd amine of formula II

with the compound which, in the free acid form, corresponds to formula lil

our a salt thereof, in an acid to neutral reaction medium.

18. A process for the production of a compound of formula I, as defined in Claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 47.

19. A compound of formula I, whenever obtained by a process according to Claim 17 or 18.

20. A process for dyeing or printing an anionically dyeable substrate comprising applying to an anionically dyeable substrate a compound or mixture according to any one of Claims 1 to 16 or 19 as dyeing or printing agent.

21. A process according to Claim 20, wherein said anionically dyeable substrate is a textile containing or consisting of natural or synthetic polyamides.

22. A process according to Claim 20, wherein said anionically dyeable substrate is nylon carpet.

23. Dyed or printed substrates, whenever obtained by a process according to any one of Claims 20 to 22.