US3287349A

US3287349A - 2-hydroxy-3-carboxyamido-benzene-azo-2-hydroxy-5, 6, 7, 8-tetrahydronaphthalene dyestuffs

Info

Publication number: US3287349A
Application number: US193323A
Authority: US
Inventors: Gaetani Ermanno; Moiso Ugo
Original assignee: ACNA Chimica Organica SpA
Current assignee: Aziende Colori Nazionali Affini ACNA SpA; ACNA Chimica Organica SpA
Priority date: 1961-05-12
Filing date: 1962-05-08
Publication date: 1966-11-22
Anticipated expiration: 1983-11-22
Also published as: GB964673A; ES277263A1; DE1444561A1; CH417805A; BE617544A

Description

United States Patent 13 Claims. (Cl. 260-202) The present invention relates to monoazo dyes which develop brown shades upon subsequent chromation, more particularly by the dyeing and chromation of wool and polyamide fibers in a single neutral or slightly acid bath according to the metachrome process.

These dyes have the general formula:

wherein X is selected from halogen atoms, and N0 groups;

Y is selected from acylamino groups, halogen-containing acylamino groups and alkoxycarboxyamino groups.

Metachrome brown shades have generally been heretofore obtained by the metallization on fibers, of monoazodyes which are the product obtained by coupling the diazo compounds of suitable orthoaminophenols with para-alkyl phenol derivatives, (e.g., para-cresol, paratertiary butylphenol, p-tert.amyl phenol, etc., and preferably tlso with other substitutions, such as, e.g., l-hydroxy- 2-acetamino-4-methyl benzene, 1-hydroxy-2-propionyl amino-4-tertiary-butyl benzene, 1-hydroxy-2-acetamino-4- tert.amyl benzene, etc).

Although a certain number of the aforementioned dyes are known from the literature to have valuable dyeing properties, their preparation presents considerable difiiculties due to the poor coupling tendency of diazotized ortho-aminophenols and the para-alkyl phenols. Moreover, when these phenols are substituted with alkyl chains higher than ethyl, their solubility in alkaline water is very slight.

When Z-hydroxy-naphthalene is used as the coupling agent, although the coupling is facilitated, the shade of the final dye is in the area of violet and the dyes therefore cannot be used as brown.

It has now been surprisingly found that by using 2-hydroxy-5,6,7,8-tetrahydronaphthalene as the coupling agent for dyes to be metallized on the fiber, decidely brown shades are obtained after metallization and, at the same time, the coupling reaction is remarkably facilitated. An object of the present invention is herefore to provide monoazo dyes, for wool and polyamidic fibers, which are metallizable on the fibers during or after dyeing and have the general formula:

Patented Nov. 22, 1966 wherein X and Y have the meaning given above.

Another object of the present invention is to provide textile materials such as fibers, yarns and the like, which are dyed with the instant dyes.

Other objects and advantages of the present invention, will become apparent hereinafter.

These dyes are obtained, according to the present invention, by diazotizing and coupling, in any conventional suitable manner, a compound of the formula:

or: NHQ

in which X and Y have the aforementioned meaning, with 2-hydroxy-5,6,7,8-tetrahydronaphthalene.

The new dyes, obtained according to the present invention, are excellent for W001 and polyamidic fibers and are suitable for a dyeing step followed by a chromation treatment. Preferably, the dyeing and chromation can be carried out in a single bath, which is either neutral or slightly acid, according to the so called metachrome process.

By employing the dyes of general Formula 1, it is surprisingly simple, as is illustrated below, to obtain (after metallization) brown shades which heretofore could be obtained only with certain difiiculties in preparation.

The dyes of the present invention possess further advantages. Thus, they possess good fastness to light even under wet conditions and also good fastness to potting treatments, even in comparison with dyes derived from alkylphenols having a higher molecular weight (e.g., p.tert.butyl, p-tertiary amyl) -and even in comparison with dyes possessing further substituents such as l-hydroxy 2 acetamino-4-methylbenzene and 1-hydroxy-2- acetamino-4-tert.butylbenezene. This improved fastness of the present dyes is probably due to the cyclic structure of the alkyl substitution.

Among the numerous 2-arninophenol derivatives which can be used according to the present invention, there can be mentioned as examples:

1-hydroxy-2-a-mino-4-nitro-6-formyl-amino-benzene,

1-hydroxy-2-amino-4-nitro-6-acetamino-benzene,

1-hydroxy-2-amino-4-nitro-6-chloro-acetamino-benzene,

1-hydroxy-2-amino-4-chloro-6-acetamino-benzene,

1-hydroxy-2-amino-4-nitro-6-propionylamino-benzene,

1 hydroxy-2-amino-4-chloro-6-propionylamino-benzene,

and

1 hydroxy 2 amino-4-nitro-6-methoxycarboxyl-aminobenzene.

The dyeing step may be carried out using any suitable conventional procedure. The present invention is described with reference to some of its preferred embodiments. There are, however, obviously many modifications and variations of the instant invention which will be evident to persons skilled in the art. For example, various phenols may be employed as the o-aminophenol, which is coupled with Z-hydroxy-S,6,7,S-tetTahydrQnap-hthalene in order to obtain a dye to be .metallized with a brown shade. It is to be understood that these and other suitable modifications and variations are within the spirit and scope of the present invention.

The invention is illustrated but not limited by the following examples in which all parts are by weight unless otherwise stated, and the relation between parts by weight enzene are diazotized at 5 10 preferably in the pres- :nce of 0.14 part of'Dispersolo' CV (alkylphenol-e'thyl- :neoxide condensation product), 25 parts of Water, 22

arts of 30% HCl and 25 parts by volume of a 4 N sodium litrite solution, with the addition of 30 parts of ice, and by ising outside cooling.

The suspension of diazo-cornpound is neutralized with odiurn carbonate and is introduced at C. into a soluion of 14.9 parts of 2-hydroXy-5,6,7,8-tetrahydronaphhalene in 100 parts of Water containing 4 parts of sodium iydroxide and 17 parts of sodium carbonate.

When the coupling is ended, the precipitated dye is sepaated by filtration and is suspended in water slightly alk-' llinized with sodium carbonate. It is then filtered and lried.

The monoazodye thus obtained has the following fornula:

The dye is a black-brown powder, which is very suit- ;ble for dyeing wool by the known metachrorne process, hus giving a dark-brown shade with very good wet and ight fastness.

The dyeing can also be carried out by employing suc- :essive chromation.

Example 2 22.5 parts of 1-hydroxy-2-amino-4-nitro-6-propionyltIIliIlO benzene are diazotized by following the procedure )f Example 1. The suspension of d-iazocompound is neuralized with Na CO and is introduced at 0 C. into a olution of 14.9 parts of Z-hydroxy-S,6,7,'8-tetrahydroiaphtha'lene in 40 parts of water, 4 parts of NaOH and 50 parts by volume of pyridine.

The coupling occurs very quickly. The dye product )btained after coupling contains about 30% by volume of Jyri-dine.

The dye, which is isolated and dried, is a brown powder raving the following formula:

CIIH OH CHaGHzOONH- N=N [his dye possesses shade and properties similar to the dye )f Example 1.

Example 3 20 parts of 1hydroxy-Z-amino-4-chloro-6-acetaminoaenzene are diazotized and coupled as in Example 1.

A monoazo dye having the following formula:

(Ina 9H obtained in the form of a dark-brown powder which inges wool using the rnetaclrrome process. A brown :hade, clearer than that of the preceding example, having t violet tint and good wet and light fastness, is obtained.

A p This dye is also suitable for dyeing followed by successive chromation.

Examples 4-7 These examples are conducted by following the procedure of Example 1. In each case, 2-hydroxy-5,6,7,8-tetraihydnonap'hthalene is used as the coupling component. The various other dye components employed and the results obtained are reported in Table I, shown below.

TAB LE I Diazotized base coupled Color shade after chromation Ex. No. with 2-hydroxy-4, 5, 6, 7- and characteristics with retetrahydronaphthalene spect to the dye of Ex. 1.

4 1-hydroxy-2-amino-Lnitro- Substantially the same shade Mormylarnino benzene. of brown; slightly lower light fastness.

5 1-hydroxy-2amino-4-nitro- Brown with a violet tint.

fi-chloroacetamino benzene.

6 l-hydroxy-Zamino--nitro- Almost equal shade; slightly 6-methoxyearbonylaminolower light fastness. benzene.

7 1-hydroxy-2-amin0-4-eh1oro- Brown with a violet tint;

6-propionylamin0benzene. better tastness to fulling.

Many variations and modifications can, of course, be

' made without departing from the spirit and scope of the present invention.

Having thus described the present invention, what it is desired to secure and claim by Letters Patent is:

1. A monoazo dye having the formula (j... p X a wherein X is selected from the group consisting of chlorine, and a N0 group, and Y is selected from the group consisting of a caoboxylamino radical containing from 1 to 4 carbon atoms, a canbo-xylarnino radical containing from 1 to 4 carbon atoms and further containing chlorine in the hydnocanbon chain, and an alkoxy-carboxylamino radical containing from 1 to 4 carbon atoms.-

2. The monoazo dye of claim 1 wherein X is a chlorine atom.

3. The monoazo dye of claim 1 wherein X is a N0 group.

4. The monoazo dye of claim 1 wherein Y is a carboxylamino radical containing from 1 to 4 canbon atoms.

5. The monoazo dye of claim 1 wherein Y is a canboxylamino radical containing from 1 to 4 carbon atoms and further containing chlorine in the hydrocanbon chain.

6. The monoazo dye of claim 1 wherein Y is an :alkoxy-oarboxylamino radical containing from 1 to 4 carbon atoms.

7. The monoazo dye which has the formula:

8. The monoazo dye which has the iormula:

OIH OH NO: H

9. The monoazo dye which has the formula:

10. The monoazo dye which has the formula:

OH OH H 0 0 NH@NN@ 1 N O 2 H 11. The monoazo dye which has the formula:

13. The monoazo dye which has the formula:

OH OH References Cited by the Examiner UNITED STATES PATENTS 4/ 1953 Steinemann 260-151 X 10/1956 Buehler 260151 X FOREIGN PATENTS 2/ 1936 Germany. 5/ 1957 Germany. 3/ 1960 Germany.

OTHER REFERENCES Colour Index, 2nd Edition (1956), V01. 3, TP 910 S6,

Conzetti:

German application, Serial No. G 13,644,

printed January 19, 1956 ('Kl.22a 2).

CHARLES B. PARKER, Primary Examiner. 40 N. S. MILESTONE, R. I. FINNEGAN, F. D. HIGEL,

Assistant Examiners,

Claims

1. A MONOAZO DYE HAVING THE FORMULA