US2032463A - Fibers dyed with water-insoluble azo-dyestuffs - Google Patents

Description

Patented Mar. 3, 1936 [TED STATEg insane FEQEE FIBERS KEYED WE'EIH WATER-=HNSGLUIELE AZQ-DYESTUFJFS Alfred Bergdolt, Cologne-on-the-Rhine, Anton Ossenbeck, Cologne/Mulheim, and Ernst Tietze and Felix Gund, Cologne-on-the-Rhine, Germany, assignors to General Aniiine Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application March 25, 1933, Serial No. 662,826. In Germany April l, 1932 8 Claims.

wherein a: and y stand for radicals of the aromatic-, araliphaticor aliphatic series, which are attached to the C-atoms of the carbonyl groups by carbon atoms, and which in case a: and 3 stand for aliphatic radicals may be linked together, R stands for the radical of a diazotized diazotization component suitable for producing azo-dyestuifs, and wherein all nuclei may bear substituents which do not cause solubility in water; :1: and 1!; may stand f. i., for methyl, ethyl, propyl, butyl, phenyl, naphthyl and benzyl. As substituents which may be present there are enumerated by way of example alkyl, alkoxy, halogen, and the nitro group, while the sulfonic acid group and the carboxylic acid group are excluded.

As coupling components coming into consideration for the purpose of our invention there may be mentioned for example acetylacetone, benzoylacetone, dibenzoylmethane, phenylacetylbenzoylmethane, the homologues and substitution products thereof.

As diazotization components there may be used all the bases free from groups inducing solubility in water generally used in the manufacture of azo-dyestuffs, for instance, amines of the benzene-, naphthaleneand carbazoleseries.

Our new dyeings are obtainable in the usual manner by diazotizing a primary amine and coupling on the fiber with a diketone of the kind referred to above; thereby generally yellowish to orange shades of good fastness properties are obtained, the dyeings being dischargeable, yielding clear white discharges.

The invention is illustrated by the following examples, without being limited thereto:

Ewample 1.15 grams of dlbenzoylmethane are intimately mixed with. 60 cos. of alcohol, 30 ccs. of water and 7.5 ccs. of aqueous caustic soda lye of 38 B. strength and stirred into 900 cos. of water containing 5 ccs. of aqueous caustic soda lye of 38 B. strength and ccs. of aqueous Turkey red oil of 50% strength.

Cotton yarn is impregnated in this solution for about half an hour, squeezed, dried, and the dyeing is developed by passing the yarn for half an hour into a diazo solution prepared from 22.5 grams of 1-methyl-2-amino-4-chloro-S-benzoylaminobenzene, said diazo solutioncontaining 11 cos. of aqueous acetic acid of 50% strength.

The cotton is rinsed, washed, soaped in a boiling bath, washed again and dried. A clear greenish-yellow dyeing of good fastness to boiling and light is thus obtained, said dyeing being dischargeable, yielding thereby clear white discharges. The dyestufi corresponds to the following formula:

(His

CHI-O Example 3.--In an'analogous manner as described in Example 1, the dyestuff produced from p-toluylbenzoylmethane and diazotized 2.4'-di methyl 5 methoxy- 2' -nitro-4-aminoazobenzene The dyestuff corresponds to the following formula:

In the following table there are given some combinations and the shades obtained thereby when prepared on celulosic fibres according to the directions given in Example 1:

ggg g Diazotization component Shade Acetylacetone l.4-diethoxy-2-amino-5-ben- Orange.

zoylaminobenzene. Benzoylacetone- S-nitro-l-aminobenzene Yellow. Diketohydrindene a-aminoanthraquinone Orange. Dibenzoylrnethane 1-amino-2-chloro-4-benzoyl- Reddish yelamino-S-methoxybenzene. low. Do 2.4-dimethyl--methoxy-2- Orange.

nitro-4 arninoazobenzene. l-amino-2-chloro-4-benzoyl- Reddish yelarnino-5-methylbenzene. low. D0 l-amino-2-methyl-4-benzoyl- Golden orange.

amino-'5-methoxybenzene. Do 1-amino-2-chloro-4-benzoyl- Golden yellow. amino-fi-etlioxybenzene. Do l-amino-2-methoxy-4-ben- Orange.

zoylamino-iethoxybenzene. D0 l-amino-ZS-dirnethoxy-4- Orange.

benzoylaminobenzene. Do 1-amino-2.5-dietl1oxy-4-ben- Orange.

zoylaminobenzene. D0 l-amino-2-ethoxy-4-benzoyl- Golden yellow. amino-Mnethylbenzene. l-amino- 2 -methoxy 4 ben- Golden yellow.

zoylamino-5-clilorobenzene. I l-amino-2-chlor0-4-benzoyl- Reddish yelaminobenzene. low. l-amino-Z-chloro-l-methyl- Reddisli yelfi benzoylaminobenzene. w. 1-amino-2-methyl-4-chloro- Greenish yel- B-benzoylaminobenzene. low. 1-amino-2-chloro-4-methoxy- Reddish yel- 5-benzoylaminobenzene. w. l-amino-Z-methoxy--chloro- Greemsh yel- 5-benzoylaminobenzene. low. 2 methylbenzoyl 1-amino-2-methyl-tbenzoyl- Reddish yelbenzoylrnethane. amino-5-chl0robenzene. low. 4 chlorobenzoyl 2.5-dichloroaniline Yellow.

benzoylmethane.

Do 1.3 dimetliyl 4 amino 6 Greenlsh yelbenzoylaminobenzene. w. Do 2.3'-dimethyl-4-amino- Yellowlsh azobenzene. brown.

We claim:

1. Cellulosic fibers dyed with a water-insoluble azo-dyestuif of the following general formula:

wherein a: and 1/ stand for radicals of the aromatic-, aromatic-aliphaticor aliphatic series, R stands for the radical of a diazotized substituted amine of the aromatic series, and wherein the nuclei bear only substituents which do not cause solubility in water and which are selected from the group consisting of alkyl, alkoxy, halogen, nitro and acylamino, the shades produced being generally yellow to orange and being dischargeable to a pure white.

2. Cellulosic fibers dyed with a water-insoluble azo-dyestufi of the following general formula:

wherein a: and 1,! stand for radicals of the phenyl series, R stands for the radical of a diazotized substituted amine of the aromatic series, and wherein the nuclei bear only substituents which do not cause solubility in water and which are selected from the group consisting of alkyl, alkoxy, halogen, nitro and acylamino, the shades produced being generally yellow to orange and being dischargeable to a pure white. I

4. Cellulosic fibers dyed with a water-insoluble azo-dyestuff of the following general formula:

wherein a: and y stand for radicals of the phenyl series, B. stands for a substituted radical of the benzeneor naphthalene series, andwherein the nuclei bear only substituents which do not cause solubility in water and which are selected from the group consisting of alkylpalkoxy, halogen,

nitro and acylamino, the shades produced being generally yellow to orange and being dischargeable to a pure white.

5. Cellulosic fibers dyed with a water-insoluble azo-dyestuii oi the following formula:

yielding clear greenish-yellow, dischargeable dyeings of good fastness to boiling and light.

6. Celluloslc fibers dyed with a water-insoluble azo-dyestufi of the following formula:

yielding clear reddish yellow dyeings of good fastness to boiling and light.

'7. Cellulosic fibers dyed with a Water-insoluble azo-dyestufi of the following general formula:

wherein a: and y stand for methyl groups, R stands for the radical of a diazotized substituted amine of the aromatic series, and wherein the nuclei may bear substituents selected from the group consisting of alkyl, alkoxy, halogen, nitro and acylamino, the shades produced being generally yellow to orange and being dischargeable to a pure white.

8. Cellulosic fibers dyed with a water-insoluble azo-dyestufi of the following general formula:

wherein m and 1 stand for methyl groups, R stands for a substituted radical of the benzeneor naphthalene series, and wherein the nuclei may bear substituents selected from the group consisting of alkyl, alkoxy, halogen, nitro and acylamino, the shades produced being generally 9 yellow to orange andbeing dischargeable to a pure white.

ED BERGDOLT. ON OSSENBECK. ERNST TIETZE. I" J G.