GB1562991A

GB1562991A - Water-soluble monoazo dyes based on alkoxyaniline sulphonic acid and phenols

Info

Publication number: GB1562991A
Application number: GB3164276A
Authority: GB
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1977-07-08
Filing date: 1977-07-08
Publication date: 1980-03-19

Description

(54) WATER-SOLUBLE MONOAZO DYES BASED ON ALKOXY ANILINE SULPHURIC ACIDS AND PHENOLS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Ozemi- cal 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 de scribed in and by the following statement:- This invention relates to monoazo dyes and their application to textile materials.

According to the invention, there are provided water-soluble monoazo dyes which, in the form of the free acids, have the formula:

wherein R' represents an alkyl radical having from one to twelve carbon atoms, R2 represents hydrogen, halogen, alkoxy, cycloalkyl or an alkyl radical having from one to nine carbon atoms, R3 represents hydrogen or alkyl having from one to nine carbon atoms and the hydroxy group is ortho or para to the azo group.

For ease of preparation it is preferred that the sulphonic acid is ortho to the azo group.

Dyes in which the hydroxy group is ortho te the azo group have higher light fastness than those in which it is in the para position and thus a preferred class of dyes has the formula

wherein Rl, R2 and R" have the meanings given above.

It is also preferred that Rl, R2 and R' together contain from 8 to 14 carbon atoms.

The dyes of Formula I may be prepared by diazotising a 4-alkoxy-aniline sulphonic acid of the formula

wherein R1 has the meaning given above, and coupling the resultmg diazo compound with a phenol of the formula

wherein R2 and R3 have the meanings given above.

Alkoxyaniline suiphonic acids which may be used in making the dyes of the invention include 4 - methoxyaniline - 3 - sulphonic acid, 4 - ethoxyaniline - 3 - sulphonic acid, 4 - n - - propoxyaniline - 3 - sulphonic acid, 4 - iso - propoxyaniline - 3 - sulphonic acid, 4 - n - butoxyaniline - 3 - sulphonic acid, 4 - methoxyaniline - 2 - sulphonic acid, 4ethoxyaniline - 2 sulphonic acid, 4 propoxyaniline - 2 - sulphonic acid, 4 propoxyaniline - 2 - sulphonic acid, 4 butoxyaniline - 2 - sulphonic add, 4 - secbutoxyaniline - 2 - sulphonic acid, 4 heptyloxyaniline - 2 - sulphonic acid, 4 nonyloxyaniline - 2 - sulphonic acid and 4dodecyloxyaniline - 2 - sulphonic acid.

The 4-alkoxyaniline sulphonic acid may be prepared from the 4-alkoxynitrobenzene which can itself be prepared by reacring p-nitrophenol with an alkyl halide under alkaline conditions or, preferably, by reacting p-chloro - nitrobenzene with an alcohol in the presence of aqueous alkali and a phase transfer catalyst, such as a quaternary ammonium salt, as described in our U.K. Patent Application No.

32078/75 (Serial No. 1539183). The resulting 4-alkoxynitrobenzene is reduced to the 4-alkoxyaniline which is converted to the amine sulphate and then heated in a high boiling solvent to give the 4-alkoxyaniline-2sulphonic acid.

Examples of phenols which may be used as coupling components in making the dyes indude phenol, o-, m- and p-cresols, p-isopropylenol, p-tert.-butylphenol, p-cyclohexylphenol, p-heptylphenol, p-octylphenol, a-, m- and p-chlorophenols, 2-, 3- and 4 methoxyphenols, 2,5-, 2,6- and 3,3-dimethyl phenols and 6-chloro-3-methylphenol.

The reactions leading to the formation of the dyes of the invention may be performed under conditions that have been fully described in the prior art for such reactions. Similarly, the dyes may be isolated by known~~metiodi and, as in the case of other dyes, containing sulphonic acid groups, it is often convenient to isolate and use rhe dyes in the form of their water-soluble salts, particularly their alkali metal or ammonium salts an especially sodium salts. It is to be understood that the invention relates to both the free acids and their salts.

The dyes of the invention are particularly suitable for applying to synthetic polyamide textile materials, for example nylon 66, nylon 6 and nylon 11, using any of the general methods known for the application of acid dyes to such materials. The dyes provide yellow shades having a high degree of fast-' ness to wet treatments and to light.

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

Example 1.

To a stirred solution of 1.7 parts of the sodium salt of 2 - amino - 5 - nonoxybenzene sulphonic acid in 30 parts of water are added 10 parts of glacial acetic acid and 2 parts of 36% hydrochloric acid. After cooling the su;- pension to 0--5"C, 2.6 parts of 13.8% sodium nitrite solution are added and stirring is contmued at e-50C for 1 hour. The diazo suspension is then added to a stirred solution of 0.6 part of p-cresol in 5 parts of water and 5 parts of 32% sodium hydroxide solution.

The pH of the coupling suspension is raised to 8 and stirring is continued for a further 16 hours. The product is filtered off, washed with water and dried.

When applied to nylon 66 from a neutral to weakly acid bath, a greenishyellow shade is obtained which exhibits very good fastness to wet treatments and to light.

The following Table gives further examples of dyes of the invention which are prepared by diozotising the 4-alkylaniline sulphonic acid listed in the second column below and coupling with the phenols listed in the third column.

Example Diazo Component Coupling Component 2 4-Methoxyaniline-3-sulphonic acid p-cyclohexylphenol 3 ,, p-octylphenol 4 4-Ethoxyaniline-3-suiphoni c acid p-tert-butylphenol 5 ,, p-tert-amylphenol 6 4Methoxyaniline-2-sulphonic acid m-cresol 7 , p-cyclohexylphenol 8 " p-octylphenol 9 4-lsopropoxyaniline-2-sulphonic acid p-tert-amylphenol 10 ,, p-cyclohexylphenol 11 4-n-Butoxyaniline-2-sulphonic acid p-isopropylphenol 12 " 2,5-dimethylphenol 13 " p-tert-butylphenol 14 " p-tert-amylphenol 15 -4-H eptyloxy ani line-2-sulphoni c acid p-cre sol 16 " p-isopropylphenol 17 ,, p-tert-butylphenol 18 !4*Nonyloxyaniline-2-sulphonic acid p-cresol 19 " 2,5-dimethylphenol 20 ,, p-tert-butylphenol

WHAT WE CLAIM IS: 1. A water-soluble monazo dye which, in the form of the free acid, has the formula:

wherein R1 represents an alkyl radical having one to twelve carbon atoms, R2 represents hydrogen, halogen, alkoxy, cycloalkyl or an alkyl radical having from one to nine carbon atoms, R3 represents hydrogen or alkyl having from one to nine carbon atoms and the hydroxy group is ortho or para to the azo group.

2. A water-soluble monoazo dye as claimed in claim 1 wherein the sulphonic acid grouP is ortho to the azo group.

3. A water-soluble monoazo dye as claimed in claim 2 having the formula:

wherein R1, R2 and R9 have the meanings given in claim 1.

4. A water-soluble monoazo dye as claimed in any one of the preceding claims wherein R1, R2 and R3 together contain from 8 to 14 carbon atoms.

5. A water-soluble monoazo dye as claimed in claim 1 and specifically identified herein.

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

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Example Diazo Component Coupling Component 2 4-Methoxyaniline-3-sulphonic acid p-cyclohexylphenol 3 ,, p-octylphenol 4 4-Ethoxyaniline-3-suiphoni c acid p-tert-butylphenol 5 ,, p-tert-amylphenol 6 4Methoxyaniline-2-sulphonic acid m-cresol 7 , p-cyclohexylphenol 8 " p-octylphenol 9 4-lsopropoxyaniline-2-sulphonic acid p-tert-amylphenol 10 ,, p-cyclohexylphenol 11 4-n-Butoxyaniline-2-sulphonic acid p-isopropylphenol 12 " 2,5-dimethylphenol 13 " p-tert-butylphenol 14 " p-tert-amylphenol 15 -4-H eptyloxy ani line-2-sulphoni c acid p-cre sol 16 " p-isopropylphenol 17 ,, p-tert-butylphenol 18 !4*Nonyloxyaniline-2-sulphonic acid p-cresol 19 " 2,5-dimethylphenol 20 ,, p-tert-butylphenol WHAT WE CLAIM IS:

1. A water-soluble monazo dye which, in the form of the free acid, has the formula:

3. A water-soluble monoazo dye as claimed in claim 2 having the formula:

wherein R1, R2 and R9 have the meanings given in claim 1.

6. A method for the preparation of a water

soluble monoazo dye as defined in claim 1 which comprises diazotising a 4-alkoxyaniline sulphonic acid of rhe formula:

wherein R1 has the meaning given in claim 1 and coupling rhe resulting diazo compound with the phenol of the formula:

wherein R2 and R3 have the meanings given in claim 1.

7. A method as claimed in claim 6 conducted substantially as hereinbefore described with reference to any one of the foregoing Examples.

8. A water-soluble monoazo dye whenever prepared by a method claimed in claim 6 or claim 7.

9. A process for the coloration of synthetic polyamide textile materials which comprises applying thereto a water-soluble monoazo dye as claimed in any one of claims 1-5 and 8.

10. Synthetic polyamide textile materials whenever coloured by the process daimed in claim 9.