GB1565531A

GB1565531A - Diperse monoazo dyestuffs

Info

Publication number: GB1565531A
Application number: GB457376A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1976-02-05
Filing date: 1976-02-05
Publication date: 1980-04-23
Also published as: DE2704333A1; IT1075101B; ES455650A1; FR2340352A1; JPS5295743A; BE850586A; NL7701026A; BR7700532A

Description

(54) DISPERSE MONOAZO DYESTUFFS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperical Chemical House, Millbank, London, SW1P 3JF, a British Company, 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:- This invention relates to disperse monoazo dyestuffs which are valuable for colouring synthetic textile materials.

According to the invention there are provided the disperse monoazo dyestuffs of the formula:

.wherein W is hydrogen, chlorine, bromine, nitro or cyano; Y is an acylamine group; Z is hydrogen, lower alkyl or lower alkoxy; R is lower alkyl; and X is a hydrogen atom or an acyl group.

Throughout this specification the terms "lower alkyl" and "lower alkoxy" are used to denote alkyl and alkoxy radicals respectively containing from 1 to 4 carbon atoms.

The acylamino groups represented by Y are preferably of the formula -NHCOT1 and -NHSO2 wherein T1 is hydrogen, phenyl, amino, lower alkylamino or preferably lower alkyl and T2 is lower alkyl.

The acyl group represented by X is preferably of the formula WOTS wherein T3 is phenyl or preferably lower alkyl.

As examples of lower alkyl represented by Z, R, Tt, T2 and T8 there may be mentioned n-butyl, n-propyl, ethyl and, above all, methyl.

As examples of lower alkoxy represented by Z there may be mentioned ethoxy and, above all, methoxy. As examples of lower alkylamino represented by T1 there may be mentioned methylamino and ethylamino.

A preferred class of the dyestuffs of the invention comprises the dyestuffs of the for mula :-

wherein W and T2 have the meanings stated, Z1 is lower alkoxy, and Xl is hydrogen or especiallyCOT2. Preferably W is chlorine or bromine.

According to a further feature of the invention there is provided a process for the manufacture of the said dyestuffs which comprises diazotising an amine of the formula:

and coupling the resulting diazo compound with a coupling component of the formula:

wherein W, R, X, Y and Z have the meanings stated above.

The process of the invention can be conveniently carried out by, for example, adding the amine to a solution of nitrosylsulphuric acid, if necessary destroying any residual nitrous acid present by the addition of sulphamic acid, adding the resulting solution or suspension of the diazo compound to a solution of the coupling component in water containing an acid and/or a water-soluble organic liquid such as acetone, if necessary adjusting the pH of the mixture so as to facilitate coupling, and isolating the resulting dyestuff in conventional manner.

The said amines are 2:4-dinitroaniline and 2:4-dinitro-6-(chloro-, bromo-, cyano- or nitro-)aniline.

The said coupling components can themselves be obtained, for example, by condensing an allrylene oxide with the appropriate compound of the formula:

to give the corresponding coupling component wherein X is a hydrogen atom, and such coupling components can be converted to the coupling components wherein X is an acyl group by treatment with an acylating agent.

As specific examples of the said coupling components there may be mentioned 2methoxy - 5 - acetylamino - (N hydroxy - n - propyl)aniline, 3 - propionylamino - N - (ss - hydroxy - n - propyl)aniline and 2 - methoxy - 5 - acetylamino N - (p - acetoxy - n - propyl)aniline.

The disperse monoazo dyestuffs of the invention wherein X is an acyl group can also be obtained by treating the corresponding dyestuffs wherein X is a hydrogen atom with an acylating agent. This reaction is preferably carried out in the presence of a basic organic liquid, such as pyridine, the resulting acylated dyestuff being isolated by pouring the reaction mixture into water and filtering off the precipitated solid.

As examples of acylating agents there may be mentioned acetyl chloride, acetic anhydride and propionic anhydride.

The disperse monoazo dyestuffs of the invention in the form of aqueous dispersions are valuable for colouring synthetic textile materials, such as cellulose acetate, nylon and especially aromatic polyester textile materials, by dyeing, padding or printing processes using the conditions and other additives which are conventionally employed in colouring such synthetic textile materials. As the conclusion of such processes the coloured textile material is rinsed in water and is preferably given a clearing treatment in order to remove loose dyestuff from the surface of the textile material. This clearing treatment can be carried out in conventional manner by immersing the coloured textile material in a warm aqueous alkaline solution of sodium hydrosulphite.

When so applied to synthetic textile materials blue to navy blue colourations are obtained which have very good to excellent fastness to the tests conventionally applied to coloured synthetic textile materials. The said dyestuffs are particularly valuable for colouring aromatic polyester textile materials as they have very good dyeing properties in respect of affinity and build-up on such textile materials so that heavy depths of shade can be readily obtained. The resulting colourations have very good to excellent fastness to light, to wet treatments including perspiration, and to dry heat treatments.

The dyestuffs of the invention can also be used for the mass-colouration of aromatic polyesters, or can be applied to synthetic textile materials by the process of transfer colour printing opticnally under vacuum or under wet or humid conditions.

The invention is illustrated but not limited by the following Examples in which the parts and percentages are by weight.

Example 1.

26.2 Parts of 2:4 - dinitro - 6 - bromoaniline are added to a solution of nitrosyl sulphuric acid (which had been prepared by dissolving 7.0 parts of sodium nitrite in 130 parts of sulphuric acid monohydrate and 4 parts of water at 70"C) at 250C, and the resulting mixture is stirred for 1 hour. The resulting solution of the diazo compound is then added to a solution of 23.8 parts of 2methoxy - 5 - acetylamino - N - (ss - hydroxy- n - propyl)aniline in a mixture of 200 parts of water and 5 parts of a concentrated aqueous solution of hydrochloric acid which had been cooled to 0 C by the addition of ice. Sodium acetate is added until the pH of the mixture is 5, and the mixture is stirred for 30 minutes at S"C. The precipitated dyestuff is then filtered off, washed with water and dried.

The dyestuff is dispersed in aqueous medium and the resulting dispersion incorporated into a print paste which is applied to a polyethylene terephthalate textile material in conventional manner. A blue print is obtained which has excellent fastness to light, to wet treatments, to perspiration and to dry heat treatments.

The 2 - methoxy - 5 - acetylamino - N (ss - hydroxy - n - propyl ) aniline used in the above Example was itself obtained by stirring a mixture of 18 parts of 2 - methoxy - 5acetylaminoaniline, 10.4 parts of propylene oxide and 250 parts of methanol for 8 hours at the boil, and then removing all the methanol by evaporation.

Example 2.

In place of the 23.8 parts of 2 - methoxy5 - acetylamino - N - (ss - hydroxy - propyl) aniline used in Example 1 there are used equivalent amounts of a) 2 - methoxy - 5 - acetylamino - N acetoxy - n - propylaniline, b) 2 - methoxy - 5 - acetylamino - N propionyloxy - n - propyl)aniline, and c) 2 - methoxy - 5 -acetylamino - N n - butyryloxy - n - propyl) aniline, whereby similar dyestuffs are obtained, which dye polyester from an aqueous bath in navyblue shades.

The coupling components used in this Example were themselves obtained by treating 2 - methoxy - 5 - acetylamino - N hydroxy - n - propyl) aniline with acetic anhydride, propionic anhydride and n-butyric anhydride respectively, in the presence of hydrogen chloride.

Example 3.

A mixture of 5.6 parts of the dyestuff of Example 1, 1.4 parts of propionic anhydride and 120 parts of pyridine is stirred for 2 hours at 45" + 2"C. The mixture is then poured into 600 parts of water, and the precipitated dyestuff is filtered off, washed with water and dried.

The resulting dyestuff is 2 - acetylamino 4 - [N - (p - propionyloxy - n - propyl) aminoj - 5 - methoxy - 2' - bromo - 4' dinitroazobenzene.

When dispersed in aqueous medium the dyestuff dyes aromatic polyester textile materials in navy blue shades of excellent fastness properties.

Further Examples of the dyestuffs of formula:

in which W, Y, Z, R and X have the previously defined meanings, are given in the following Table 1. The final column gives the shade when dyed on polyester. These examples are all prepared by the method described in Examples 1 and 2.

TABLE I

No. W Y Z R X Shade 4 H NHCOCH3 OCH3 CH3 H Reddish-blue 5 H NHCOCH3 OCH3 CH3 COCH3 blue-violet 6 Cl NHCOCH3 OCH3 CH3 COCH3 navy-blue 7 Br NHCOCH3 OCH3 C2H5 COCH3 8 C1 NHCOCH3 OCH3 C2H5 COCH3 9 Br NHCOC2H5 OCH3 CH3 COCH3 10 Br NHCOC3H7 OCH3 CH3 COCH3 11 Cl NHCOPh OCH3 CH3 COCH3 12 Cl NHCOCH3 OCH3 CH3 COPh 13 Br NHSO2C2H5 OCH3 CH3 COC2H5 " 14 Br NHCONH2 OCH3 CH3 COC2H5 " 15 Br NHCONHCH3 OCH3 CH3 COCH3 " 16 Br NHCOCH3 H CH3 COCH3 violet 17 Br NHCOCH3 OC2H5 CH3 COCH3 navy-blue 18 Cl NHCOCH3 OC2H5 CH3 COCH3 " 19 Br NHCOCH3 CH3 CH3 COCH3 blue-violet 20 Cl NHCOC2H5 OCH3 CH3 COC2H5 navy-blue 21 Cl NHCOC2H5 OC2H5 CH3 COC2H5 " 22 Br NHCOC2H5 OC2H5 CH3 COC2H5 " 23 Cl NHCOCH3 OCH3 CH3 COC2H5 " 24 Cl NHCOCH3 OC2H5 CH3 COC2H5 " 25 Br NHCOCH3 OC2H5 CH3 COC2H5 " 26 Br NHCOC2H5 OCH3 CH3 COC2H5 " 27 Cl NHCOC2Hs OCH3 CH3 COC2Hs 28 Cl NHCOC2H5 OC2H5 CH3 COC2H5 " 29 Br NHCOC2H5 OC2H5 CH3 COC2H5 " 30 Br NHCOCH3 OCH3 C2H5 COC2H5 " TABLE I (Continued)

No W Y Z R X Shade 31 Cl NHCOCH3 OCH3 C2H5 COC2H5 navy-blue 32 Cl NHCOC2H5 OCH3 C2H5 COCH3 " 33 Br NHCOC2HE OCH3 C2H5 COCH3 34 Cl NHCOCH3 OC2H5 C2H3 COCH3 35 Cl NHCOCH3 O C2 C3H5 COC2H3 36 Cl NHCOC2H5 0C3H5 C3H5 COCH3 Example 37.

15.6 parts of 2 - cyano - 4,6 - nitroaniline are added to a solution of nitrosyl sulphuric acid (which had been prepared by dissolving 5.7 parts of sodium nitrite in 110 parts of 98% sulphuric acid at 70 C) at - 10 to -5 C and the resulting mixture stirred for 3 hours. The resulting solution is then added to a solution of 17.25 parts of 3 - (3- hydroxybutylamino) - 4 - methylacetanilide in a mixture of 200 parts of water and 5 parts of a concentrated aqueous solution of hydrochloric acid which is maintained at 0 to 5 C by addition of ice. Sodium acetate is then added until the pH of the mixture is 4 and the precipitated dyestuff is filtered off, washed with water and dried.

The dyestuff is dispersed in aqueous medium and the resulting dispersion is used to dye polyethylene terephthalate textile material form an aqueous dyebath at 1300C.

The resulting greenish-blue dyeing has excellent fastness to light, wet treatments, perspiration and dry heat.

Example 38.

A mixture of 3 parts of the dyestuff of Example 1, 4 parts of acetic anhydride and 100 parts of pyridine is stirred for 3 hours at 450 C. The mixture is then poured into 500 parts of ice-cold water and the precipitated dyestuff filtered off, washed with water and dried.

When dispersed in aqueous medium the dyestuff dyes aromatic polyester textile materials in blue shades having excellent fastness properties.

Examples 39 to 53.

In the following Table 2, in which the column headings W, Y, Z, R and X have the previously defined meanings with reference to the formula immediately preceding Table 1, Example 39 was prepared by the method described in Example 37 and Examples 40 to 53 were prepared by the method described in Example 38, i.e. by acylation of the corresponding dyestuff in which X=H. The final column gives the shade when dyed on polyester.

TABLE 2

No. W Y Z R X Shade 39 CN NHCOCH3 CH3 CH3 H greenish-blue 40 CN NHCOCH3 CH3 CH3 COCH3 blue 41 CN NHCOCH3 CH3 CH3 COC2H5 " 42 CN NHCOCH3 CH3 CH3 COCH3H7 43 CN NHCOC2H5 CH3 C2H, COCH, 44 CN NHCOCH, CH3 C2H5 COC,H, 45 CN NHCOCH3 CH3 C2H5 COC3H7 " 46 CN NHCOCH, OCH3 CH3 OCOC2H3 greenish-blue 47 CN NHCOCH3 OCH3 CH3 OCOCH, 48 CN NHCOCH3 OCH3 C2H5 OCOCH, 49 CN NHCOCH3 OC2H5 CH3 OCOCH3 50 CN NHCOC2H5 OCH3 CH3 OCOCH3 51 NO2 NHCOCH3 OCH3 CH3 OCOCH3 52 NO2 NHCOCH3 OCH3 CH3 OCOC2H5 53 NO2 NHCOCH3 OCH3 C2H5 OCOCH3 WHAT WE CLAIM IS:1. Disperse monoazo dyestuffs of the formula:

wherein W is hydrogen, chlorine, bromine, nitro or cyano; Y is an acylamino group; Z is hydrogen, lower alkyl or lower alkoxy; R is lower alkyl; and X is a hydrogen atom or an acyl group.

2. Dyestuffs as claimed in Claim 1 wherein the acylamino groups represented by Y are of the formula --NHCOT' and -NHSO,T2 wherein T' is hydrogen, phenyl, amino, lower alkylamino or lower alkyl and T2 is lower alkyl.

3. Dyestuffs as claimed in Claim 2 wherein T1 is lower alkyl.

4. Dyestuffs as claimed in any one of Claims 1 to 3 wherein the acyl group represented by X is of the formula -COT3 wherein T3 is lower alkyl or phenyl.

5. Dyestuffs as claimed in Claim 4 wherein T3 is lower alkyl.

6. Dyestuffs as claimed in Claim 2 or Claim 3 wherein the lower alkyl groups represented by Z, R, T' and T2 are methyl.

7. Dyestuffs as claimed in Claim 4 or Claim 5 wherein the lower alkyl group repre

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

Claims

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

TABLE 2

No. W Y Z R X Shade 39 CN NHCOCH3 CH3 CH3 H greenish-blue 40 CN NHCOCH3 CH3 CH3 COCH3 blue 41 CN NHCOCH3 CH3 CH3 COC2H5 " 42 CN NHCOCH3 CH3 CH3 COCH3H7 43 CN NHCOC2H5 CH3 C2H, COCH, 44 CN NHCOCH, CH3 C2H5 COC,H, 45 CN NHCOCH3 CH3 C2H5 COC3H7 " 46 CN NHCOCH, OCH3 CH3 OCOC2H3 greenish-blue 47 CN NHCOCH3 OCH3 CH3 OCOCH, 48 CN NHCOCH3 OCH3 C2H5 OCOCH, 49 CN NHCOCH3 OC2H5 CH3 OCOCH3 50 CN NHCOC2H5 OCH3 CH3 OCOCH3 51 NO2 NHCOCH3 OCH3 CH3 OCOCH3 52 NO2 NHCOCH3 OCH3 CH3 OCOC2H5 53 NO2 NHCOCH3 OCH3 C2H5 OCOCH3 WHAT WE CLAIM IS:1. Disperse monoazo dyestuffs of the formula:

wherein W is hydrogen, chlorine, bromine, nitro or cyano; Y is an acylamino group; Z is hydrogen, lower alkyl or lower alkoxy; R is lower alkyl; and X is a hydrogen atom or an acyl group.
2. Dyestuffs as claimed in Claim 1 wherein the acylamino groups represented by Y are of the formula --NHCOT' and -NHSO,T2 wherein T' is hydrogen, phenyl, amino, lower alkylamino or lower alkyl and T2 is lower alkyl.
3. Dyestuffs as claimed in Claim 2 wherein T1 is lower alkyl.
4. Dyestuffs as claimed in any one of Claims 1 to 3 wherein the acyl group represented by X is of the formula -COT3 wherein T3 is lower alkyl or phenyl.
5. Dyestuffs as claimed in Claim 4 wherein T3 is lower alkyl.
6. Dyestuffs as claimed in Claim 2 or Claim 3 wherein the lower alkyl groups represented by Z, R, T' and T2 are methyl.
7. Dyestuffs as claimed in Claim 4 or Claim 5 wherein the lower alkyl group repre

sented by T2 is methyl.
8. Dyestuffs as claimed in any one of Claims 1 to 5 and 7 wherein the lower alkoxy group represented by Z is methoxy.
9. Dyestuffs as claimed in Claim 1 and having the formula:

wherein W has the meaning stated in Claim 1, T2 is lower alkyl, Z1 is lower alkyl, and Xl is hydrogen or -COT2.
10. Dyestuffs as claimed in Claim 9 wherein X1 is -COT2.
11. Dyestuffs as claimed in Claim 9 or Claim 10 wherein W is chlorine or bromine.
12. Disperse monoazo dyestuffs substantially as hereinbefore descnbed in any one of the foregoing Examples 1 to 3.
13. Disperse monoazo dyestuffs substantially as hereinbefore described in any one of the foregoing Examples 4 to 53.
14. A process for the manufacture of the disperse monoazo dyestuffs claimed in Claim 1 which comprises diazotising an amine of the formula:

and coupling the resulting diazo compound with a coupling component of the formula:

wherein W, R, X, Y and Z have the meanings stated in Claim 1.
15. A process as claimed in Claim 14 substantially as hereinbefore described in the foregoing Example 1 or Example 2.
16. A process as claimed in Claim 14 substantially as hereinbefore described in any one of the foregoing Examples 4 to 37 and 39.
17. A process for the manufacture of the disperse monoazo dyestuffs claimed in Claim 1 wherein X is an acyl group which comprises treating the corresponding dyestuff wherein X is a hydrogen atom with an acylating agent.
18. A process as claimed in Claim 17 wherein the reaction is carried out in the presence of a basic organic liquid.
19. A process as claimed in Claim 17 substantially as hereinbefore described in the foregoing Example 3.
20. A process as claimed in Claim 17 substantially as hereinbefore described in any one of the foregoing Examples 38 and 40 to 53.
21. A process for the colouration of synthetic textile materials which comprises applying to the synthetic textile by a dyeing, padding or printing process a disperse monoazo dyestuff as claimed in Claim 1, followed by rinsing of the coloured synthetic textile material in water.
22. A process as claimed in Claim 21 wherein the coloured textile material is given a clearing treatment in order to remove loose dyestuff from the surface thereof, by immersing the coloured textile material in a warm aqueous alkaline solution of sodium hydrosulphite.
23. Synthetic textile materials wherever coloured by a process as claimed in Claim 21 or Claim 22.