DE906003C - Process for the production of water-insoluble azo dyes - Google Patents

Description

In the production of azo dyes on the fiber in the manner of ice colors, it is well known that the 2,3-Oxynaphthoic acid in the form of its arylamides is the most important and most widely used primer component With their help, it is possible, by coupling with diazo connections, almost all Create shades from orange to blue. On the other hand, it has not yet been possible to obtain useful green colorations on this basis. This gap was only found when the 2,3-oxyanthracene carbon

OH

CO-NH- _x

where R is any aromatic radical which does not contain any water-solubilizing groups Acid arylamides, which with the so-called blue bases gave ao blue-green colorations, up to a certain point Degree filled out (see patent specification 54g 983).

It has now been found that based on 2,3-oxynaphthoic acid, new valuable, water-insoluble, green azo dyes can also be obtained if the condensation of 2,3-oxynaphthoic acid 2,3-Oxynaphthoesäurearylamide of of the following general composition

.N = C-X

XO-CH-N = N-R

and X is hydrogen or a non-water-solubilizing substituent, with any

Diazo compounds which do not contain any water-solubilizing groups or with diazoazo compounds by itself or on a coupling basis.

Produced in bulk, the new dyes can be used to prepare valuable pigments. she but are especially used for the production of insoluble dyes on the fiber after the dyeing or printing process suitable for developing ice colors.

The dyes obtained in this way show up against the corresponding azo dyes from 2,3-oxynaphthoic anilide usually a shift in color to the yellow side. So z. B. Bases with the 2,3-Oxynaphthoic anilide deliver scarlet tones, with the arylamides used according to the invention orange tones, red bases provide scarlet tones, Corinth and violet bases brown tones and the standard blue bases corinth colored, gray-blue to olive tones. Many of these dyeings have very good light and wet fastness properties.

The coupling products are of particular interest these new 2,3-oxynaphthoic acid arylamides with the diazoazo compounds from amines from Z. B. of the following general composition:

B ^]

0-alkyl

NH,

wherein the nuclei A and B also contain substituents because you can achieve valuable green colorations with these dyes. In numerous In some cases, green tones with a significantly more yellowish tint are obtained than with the greenest tint that has been used in practice up to now Dye from 2,3-oxyanthracenecarboxylic acid-o-toluidide and diazotized 3-methoxy-4-aminodiphenylamine, which provides blue-green tones. In the The new dyes are more lightfast than the familiar ones not after and have very good wet fastness properties. It is also possible as diazo components To use diazoazo compounds of the above formula, in which the core B contains a sulfonic acid group. The greens obtained with these dyes In spite of the sulfonic acid group present in the molecule, dyeings have good wet fastness properties. The ones containing sulfonic acid groups In some cases, dyes are even a little clearer and have a better one Chlorine fastness than the sulfonic acid group-free and the known ones using the 2,3-oxyanthracenecarboxylic acid arylamides available green dyes.

In view of the large number of coupling options, the new dyes are a valuable asset the pigment and ice color class, especially in the field of those previously used in dyeing green water-insoluble azo dyes.

The 2,3-oxynaphthoic acid arylamides used as azo components of the above general composition can after Method of patent 888,733 can be obtained.

example 1

52.8 parts by weight of the 2,3-oxynaphthoic acid arylamide from the following formula

■ /

OH

CO — NH— "

• NC , N = C-CH ₃

'CO-CH-N =

.Cl

OCH,

(obtainable by condensation of 2,3-oxynaphthoic acid with i- (3'-aminophenyl) -3-methyl-4- (2 "-methoxy ~ 5" -chlorobenzene-i "-azo) -5-pyrazolone according to patent 888,733 ) are stirred with 150 parts by weight of alcohol and 40 parts by weight of sodium hydroxide solution of 38 ^° Be until the solution is obtained. The mixture is then poured into parts by weight of water and the arylamide is precipitated from the clear, dark yellow solution by acidification with dilute acetic acid. This suspension is left with stirring 250 parts by weight of a very weakly acidic solution of 4-nitrobenzene-i-diazonium chloride, corresponding to parts by weight of x-amino-4-nitrobenzene, run in within a few minutes at room temperature Dye is a scarlet pigment and has good lightfastness.

Is used instead of 4-nitrobenzene-i-diazonium chloride the diazo compound from i-amino-4- (2'-methoxy-5'-nitrobenzene-i'-azo) -2-ethoxynaphthalene and if a little pyridine is added expediently, a green pigment is obtained.

Example 2

ι part by weight of 2, 3-oxynaphthoic acid and - (3 '-aminophenyl) -3-methyl-4- (2 "-methyl-4" -chlorobenzene-i "-azo) -5-pyrazolone available aryl amides of the following formula

OH

CO —NH-

are stirred with 3 parts by weight of alcohol, 3 parts by weight of water and 0.6 parts by weight of sodium hydroxide solution of 38 ⁰ Be with gentle heating until completely dissolved and then ^{poured into a mixture of 983 parts by weight of water, 7 parts by weight of sodium hydroxide solution of 38 0} Be and 10 parts by weight of Turkish red oil. A clear yellow solution is obtained. In this bath are 50 parts by weight of cotton yarn and treated in ¹ J ₂ hours at 30 to 35 ⁰ with frequent changing. After squeezing and spinning, the yarn is placed in a bath which, in 1000 parts by weight of water, contains 4 parts by weight of a dye salt, consisting of 33% diazonium chloride of i-amino-4- (2 ', 4'-dimethoxy-5'-nitrobenzene- i'-azo) -2-ethoxynaphthalene in addition to aluminum sulfate and Glauber's salt. ^{Develop at 30 ° for} 15 to 20 minutes. After rinsing, a solution containing 50 parts by weight of soap solution 1:20 and 4 parts by weight of sodium hydroxide solution of 38 ^° Be is soaped at the boil twice for 10 minutes each time.

, N = C-CH,

^ CO-CH-N =

This gives a strong, clear, green dyeing with very good wet fastness properties and good light fastness.

If the development is carried out using the same molar amount of diazotized i-amino-4- (2'- methyl - 5'-nitrobenzene-i'-azo) -2-ethoxynaphthalene-6-sulfonic acid in weakly alkaline bath by what z. B. achieved by adding some pyridine a similar, somewhat clearer and somewhat blue-tinged green coloration is obtained, as is the case with good wet fastness properties, chlorine fastness is somewhat better than that described above.

With other diazotized amines and other 2,3-oxynaphthoic acid arylamides of the specified Composition one obtains dyes with similarly good wet fastness properties and good to very good Lightfastness. The following compilation describes a number of more, following this one Invention available water-insoluble azo dyes.

Diazo component Azo component hue Condensation product from 2, 3-oxynaphthoic acid and 35 i-amino-2,5-dichlorobenzene i- (3'-aminophenyl) -3-methyl "4- (2" -methyl- Scarlet fever 4 "-chlorobenzene-i" -azo) -5-pyrazolone i-aminoanthraquinone the same Scarlet fever i-Amino ^ -methoxy ^ -benzoylamino-s-me- the same corinth ethylbenzene 40 4-amino-3-methoxydiphenylamine the same gray-blue i-Amino-2- (4'-nitro-2'-chlorobenzene-i'-azo) - the same Brown 3-methoxy-4-methylbenzene i-Amino-4- (2'-chloro-5'-nitrobenzene-i'-azo) ~ the same clear green 2-ethoxynaphthalene-6-sulfonic acid 45 i-Amino-4- (2'-methyl-5'-nitrobenzene-i'-azo) - the same olive green 7-methoxynaphthalene i-amino-2,5-dichlorobenzene i- (3 '-aminophenyl) -s-methyl ^ - (3' '-chlorben- orange zol-i "-azo) -5-pyrazolone i ~ Amino-4-chloro-2-methylbenzene the same Scarlet fever 50 i-amino-4-nitro-2-methoxybenzene the same Red i-Amino-4-benzoylamino-2,5-diethoxybenzene the same violet gray 4-amino-3-methoxydiphenylamine the same gray-blue i-Amino-4- (4'-nitrobenzene-i'-azo) -2, 5-di- the same in thick coloring methoxybenzene black 55 i-Amino-4- (2 ', 5'-dichlorobenzene-i'-azo) - the same blue green 2-methoxynaphthalene-6-sulfonic acid i-Amino-4- (2'-methoxy-5'-nitrobenzene- the same blue green i'-azo) -2-ethoxynaphthalene i-Amino-4- (2'-methyl-5'-nitrobenzene-i'-azo) - i- (3'-aminophenyl) -3-methyl-4- (2 "-meth- clear green 60 2-ethoxynaphthalene-6-sulfonic acid oxy-5 "-chlorobenzene-i" -azo) -5-pyrazolone i-Amino-4- (2 ', 4'-dimethoxy-5'-nitrobenzene- the same green i'-azo) -2-ethoxynaphthalene

Diazo component Azo component hue i-Amino-4- (2'-methoxy-5'-nitrobenzene- i- (4'-aminophenyl) -3-methyl-4- (3 "-chlor- dark green i'-azo) -2-methoxynaphthalene-6-sulfonic acid benzene-i "-azo) -5-pyrazolone 5- i-amino-2,5-dichlorobenzene the same Scarlet fever 4-aminodiphenylamine i- (3'-aminophenyl) -3-methyl-4- (2 "-trirluor- dark olive methyl-4 "-chlorobenzene-i" -azo) -5-pyrazolone i-Amino-4- (2'-methyl-5'-nitrobenzene-i'-azo) - the same blue green 2-ethoxynaphthalene-6-sulfonic acid ^{10 the} same. i- (3'-aminophenyl) -3-methyl-4- (naphthalene- dark green i "-azo)" 5-pyrazolone the same i- (3'-aminophenyl) -3-carbethoxy- gray-blue 4- (2 "-methyl-4" -chlorobenzene-i "-azo) -
5-pyrazolone
the same * 5 i-Amino-4- (2'-methoxy-5'-nitrobenzene- gray-green i'-azo) -2-ethoxynaphthalene

Claims (1)

Claim: Process for the preparation of water-insoluble azo dyes, characterized in that one OH CO-NH- / X where R is any aromatic radical which does not contain any water-solubilizing groups should, and X is hydrogen or a non-water-solubilizing substituent, with by condensation of 2,3-oxynaphthoic acid with aminoazo dyes of the pyrazolone series available 2,3-oxynaphthoic arylamides of the following general composition , N = = C-X any diazo compounds that do not contain any water-solubilizing groups, or with Diazoazo compounds by themselves or on a 6g basis. © 5812 2.