US1934807A - Water-insoluble azo-dyestuffs and fiber dyed therewith - Google Patents

Description

wherein R presents'aradicalof he benzene, 7 l

" 2'31- hydroxynaphthoyl.2-aminoe6+alkoxy-naph- Patented Nov. 14, 1 933 1 1 9? V 'WATER-INSOLUBLE AZO-DYESTUFFS AND FIBER. DYED THEREWITH Leopold Laska and, Arthur Zitscher,.0ffenbachon-the-Main, Germany, assignors to General a Aniline Works, Inc., New York, N. Y., a corpora-' tion of Delaware N oDraw ing. Application January 12, 1933, Serial No. 651,448 ,'and in Germany January 18, 1932 10 Claims. The present invention relates vto newllwate rinsoluble vazodyestuffs and to fiber-dyed therewith, more particularly it relates to compounds of the following general formula:

' N =N R" naphthalene or anthraquinone series;

We have found that valuable water-insoluble azo-dyestufis are obtainable by combining a diazo tetrazoordiazoazo-eompound which does not contain any grouplending solubility: such as the sulfonic acid or carboxylic acid group with a thalene, either in substance, on the fiber or on any of the usual substrata adapted for the production of lakes.

It issurprisingthatf the dyestuifs obtainable according to the present invention, when compared with the dyestuff'sfwhichi are, obtained by using 2 3" hydroxynaphthoyl-Z-amino-naphthalene and 2'3hydroxynaphthoyl j2,jamino-3- methoxy-naphthalene, respectively, are distinguished by anincreasedfastnessto light, ,j j

dium bicarbonate, thereupon, thefyarn is rinsed and soaped whilehotf" V The 2f3'-hydroxynaphthoyl-2-amino-6-alkoxynaphthalenes may beobtained by condensing 2.3-,

hydroxyn'aphthoic acid with I 2-amino-6-allroxy-v naphthalenes according to] one of the usual methods. Y i

The following examples serve to" illustrate the inventionQbutfthe'y are not intended to limit it thereto, the parts beingby weight unless otherwise stated:'- 1 a W (1) Well boiled and dried cotton yarn is padded 'with asolution containing per liter 7 I 2'3 hydroxyna'phthoyl- Z -ama 2.25 gramsof ino-6-n'1ethoxynaphthalene, cc;

j of ust d isq iion 91.3 Be" and. a I a. 10 cc. 'of'Turkey'red-oil,

v the yarn is thoroughly squeezed. and developed in v a diazo-solution which contains'per liter 1.21'grams of l amino 2A dimethylbenzene v and which has been neutralized by :means of so- A saturated red dyeing of very good fastness to light is thus obtained. 7

The dyestufi corresponds to the following formula: I

v (2) "developing dehydrated cotton yarn which has been impregnated as described in example 1 in a liter r V 1.76 grams of 1-amino-4-methyl-2.3-dichlorobenzene, and. which has been neutralized by means of sodium acetate, and by rinsing and soaping the yarn, there is obtained a bluishqeddyeing of very good fastnessto light. r

(3) l2.75'p'arts .of I-aminmB-chlorobenZene are dissolved in; 34.2,parts1of hydrochloric acid of -B and '250 parts; of -water 'andthe whole is diazotized at" about 10 Q. by a'ddition'of a'solution,of7 ;pa'rts'"of sodiumnitrite in 100 parts of Water.- The diazo-solutionis run into a solution of '36 ,'parts' of 2 3'-hydroXynaphthoyl-2- amino-6-methoxy-naphthalene, in [70 0 parts of Water and 244 parts of J caustic soda solution of -40-B, to-which solution there has been added the quantity "or sodium acetate .sufiicient for T'of Turkey red oil. After the coupling .hasbeen diazo" solution, which contains per binding the excess'of mineral acid and 15 parts finished, the dyestuif formed is" filteredby suction and washed well. It may ;be used for the preparation of pigments, advantageously, *in the form, of a paste; The dyestuff forms in the state ayellowish-red powder.

It yieldsflwh'en prepared, in the usual manner a on a substratum a reddish orange pigment dye- (4) Cotton yarn which 'hasappropriately been treated is impregnated with. a paddingrsolution which has been prepared in the usual manner and which containsper liter j 2 grams of 2'3-hydroxynaphthoyl-2-amino-6- ethoxy-naphthalene' and, after havingdehydrated the yarn, it isdeveloped'in a dia'zo solutionwhich contains per zone OCH:

The dyestuffs may also beprepared on other fibers, as, for instance, on regenerated cellulose or on animal fibers, and may also bev applied in the usual printing processes. 1

By using other diazo-, tetrazoor-diazoazocompounds, the process of the present invention may be carried out in like manner.

The following table indicates a number of other combinations obtainable according to the pres;

ent process but it does not comprise all possibilities for the preparation of dyestuffs by using different components; it, therefore, is not intended to limit the invention to the dyestuffs Y i mentioned therein:

1.68 grams of 1-amino-2-methoxy-4-nitrobenappended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate thefastness of the dyestuffs to alkalies. 'Substituents of this kind are, for instance,

the sulfonic acid and carboxylic acid group.

i We claim:

*1; The water-insoluble azo-dyestuffs of the following 1 general formula CO-NH 'o-aik i wherein R represents a radical of the benzene,

naphthalene or anthraquinone series, yielding, when producedon the fiber, dyeings the shades I of which vary from red to blue to black and being distinguished by good iastness properties, particularly by a good fastness tolight.

2. The water-insoluble azo-dyestuffs of the following general formula:

na -R OOHa wherein It represents a radical of the. benzene Diazotizing component Coupling component Tint (1) 1-amino- 3-ch1orobenzene 2'3.-hydroxynaphthoyl-2-amino-6-methoxynophthalene Reddish-orange (2) l-ann'n0-2.5-dich1orobenzene d Brownish-red g3) 1-a nino-2A.fi-trichlorobenzene .do Orange-brown 4) 1-amino-2-methyl-5-ch1orobenzene do Red (5) 1-amino-2-methyl-4-ch1orobenzene do Saturated red (6) 1-amino-2-methyl-4-bromo-5-chlorob do Deep bluish-red (7) 1-amino-3-methyl-4.o-dichlorobenzenem; do 1 Bluish-red (8) 1-amino-2-methoxy-5-ch1orobenzene -do Saturated red (9) 1-amino-2-phenoxy-5-ch1orobenzene do Yellowish-red (10) 1-amino-2-nitrob'en one do Brownish-red (l1) l-amino-S-nitrobenzene Yellowish-red (12) Lamina-4-chloro-2-nitrobenzene Brownish-red (l3) l-arnino-2-methyl-5-nitroben1 ne Clear yellowish-red (14) 1-amino-4-methyl-2-nitrobenzeue Deep bluish-red (15) l-amino-2-methyl-4-nitrob fl1ene Brownish-red (16) l-amino-2-methoxy-5 nitrobenzene do Red (17) 1-amino-2-methoxy-4-nitrobenzene do Bordeaux (18) 1-amino-4-nitronaphthalano do Saturated Bordeaux (19) 'l-amino-S-nitrouaphthalene L; Bordeaux (20) l-amino-5.8-dichloro-naphthalene Do. (21) 4-zgmiuo-3-methoxy-6.4'-(limethyl-2-nitroazodo Blackish-currant enzene. (22) l'-aminoauthraquinone;; '(io 'Brownish-red (23) ,1 -amino-4-benzoyl-amino-2.5-dimethoxyben- Reddish-dark blue zene. i (24) 4-aniino-2.5-dimethoxy-4 nitroazoben Pne Violet-black (25) 1-amino-2.5-dichlorobenzener Brownish-red (26) l,-amino-2.4,5-trichlorobenzene Reddish-brown (27) 1-amino-2-methyl-4bromo-5-ehl Yellowish-red (28) l-amino-2-methoxy-5-chlorobenzene Bluish-red (29) l-amino-2-phenoxy-5-chlorobenzeuel Yellowish-red (30) l-amino-4-chloro-2-nitrobenzene Yellowish-Bordeaux (31) 1-amiuo-4-methyl-2enitrobenzene. Bordeaux '(32) l-arnino-2-methyl-i-nitrobe11ze11e Do; (33) lamina! (2-ethoxy-phenyl l azo)-napl1thado Black one. v

which dyestuffsare insoluble in water and alkalies, it "is to be understood'that the aromatic nuclei of the general formulae appearing in thea series, yielding, when produced on the fiber, dye- 3.The water-insoluble azo-dyestufli of the following formula: I

OCH:

yielding, when produced on the fiber, a Bordeaux dyeing and being distinguished-by good fastness properties, particularly by a good fastness to light.

4. The water-insoluble azo-dyestuff of' the following formula: V r

CONH' OCH:

yielding, when produced on the fiber, a clear yellow-red dyeing and being distinguished by 3 good fastness' properties, particularly by agood fastness t0.light.

5. The water-insoluble azo-dyestufl of the following .formula:

OOH

yielding, when produced on the fiber. an orangebrown. dyeing and being distinguished by good LEoPoLnLAsKA." I ARTHUR ZITSCHER. I