US2710859A - Trisazo dyestuffs - Google Patents

Description

United States Patent 0 TRISAZO DYESTUFFS Fritz Kehrer, Base], and Walter Wehrli, Riehen, Switzer- 5 land, assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm N0 Drawing. Application September 15, 1952, Serial No. 309,740

Claims priority, application Switzerland September 21, 1951 6 Claims. (Cl. 260-172) flagaaggm HOOC embodiments thereof. In the examples, parts are by weight; temperatures are in degrees centigrade.

Example 1 24.4 parts of 4,4-diamino-3,3'-dimethoxy-1,ldiphenyl are tetrazotized and, while cooling with ice, are coupled on one side in a medium made alkaline with sodium carbonate with 13.8 parts of 2-hydroxybenzene-l-carboxylic acid. Upon completion of the formation of the resultant intermediate, the latter is coupled, preferably in the presence of 5-10% by volume of pyridine base mixture, with 44.8 parts of the monoazo dyestutf obtained by the acid coupling of diazotized 5-nitro-3-amino-2-hydroxybenzenel-carboxylic acid with 2-amino-S hydroxynaphthalehe-7- 'sulfonic acid. The resultant dyestuif is isolated (e. g. by precipitation and filtering off) and dried.

The thus-obtained trisazo dyestutf, which corresponds to the formula HaC O OCHQ OH HOaS- NHz N02 HO door:

dyes cotton and fibers of regenerated cellulose, with good exhaustion capacity, in dull violet shades. Good fastness properties are obtained, and the shade darkened toward the black, by after-coppering. Thus, the fastness to hot washing of cotton dyeings, aftertreated with a HO OOH wherein x is hydrogen, methyl or chlorine, and y is 45 basic cation-active copper complex compound, is particumethyl or ethyl.

These new dyestuffs are conveniently prepared by coupling 1 mol of tetrazotized 4,4'-diamino-3,3-dialkoxyl,l'-diphenyl with 1 mol of Z-hydroxybenzene-l-carboxylic acid or a derivative thereof which can couple and 50 with 1 mol of the monoazo dyestuif obtained by the acid coupling of diazotized 5-nitro-3-amino-2-hydroxybenzenel-carboxylic acid with 2-amino-5-hydroxynaphthalene-7- sulfonic acid.

The dyestuffs thus prepared dye textile fibers, especially cotton and fibers of regenerated cellulose, in violet shades HOOC of superior fastness properties which, moreover, can be 7 enhanced by after-coppering.

The following examples illustrate presently-preferred l HOas larly good. This is true also of the fastness to light of dyeings on unwashed spun rayon which has been creaseproofed with melamine resin and then aftertreated with a cation-active copper complex compound, which may be basic.

Example 2 A verysimilar dyestuff, yielding dyeings similar to those aforedescribed, is obtained when, while otherwise proceeding as described in Example 1, the 24.4 par-ts of 4,4'-dian1ino-3,3-dimethoxy-l,l-diphenyl are replaced by 26.8 parts of 4,4-diamino-3,3-diethoxy-l,1'-diphenyl. The dyestuff thus obtained corresponds to the formula H5020 OCzHs OH NH2 IP10:

l I HO CO OH Example 3 By replacing the 2-hydroxybenzene-l-carboxylic acid in Example 1 by an equivalent quantity of 3-rnethyl-2- 3 4 hydroxybenzene-l-carboxylic, and otherwise proceeding as process, 3-4 parts of Glauber salt are added in the form described in the said example, the dyestuff of the formula of a concentrated aqueous solution. Upon completion Hm H30? CH: (3H

110- N=N N=N HOOC H038 NH: IYTO:

Ho 00011 is obtained, the properties of which are similar to the of the dyeing operation, the material is allowed to cool dyestufi according to Example 1. in the bath down to 50 in the course of -20 minutes,

15 after which the material is rinsed. It may then be sub- Example 4 jected to aftertreatment with copper sulfate or with a By replacing the 2-hydroxybenzene-l-carboxylic acid cation-active copper complex compound, which may e. g. in Example 1 by an equivalent quantity of 4'methyl-2- be a basic compound. hydroxybenzene-l-carboxylic, and otherwise proceeding as The aftertreatment with copper sulfate is carried out described in the said example, the dyestuif of the formula as follows: The rinsed cotton material is added to a fresh ([311: 113C? 00113 (RE H0093 H018 NH: IfOz m) COOH is obtained, the properties of which are similar to the bath containing 300 parts of water of 70 and 0.3 part of dyestufi according to Example 1. copper sulfate. The bath is held for half an hour at 70,

Exam le 5 then the material is rinsed and dried.

p The aftertreatment with a cation-active copper com- By replacing the 2-hydroxybenzene-l-carboxylic acid plex compound is carried out by adding the rinsed cotton in Example 1 by an equivalent quantity of 3-chloro-2- material to a fresh bath containing 300 parts of water and hydroxybenzene-l-carboxylic acid, and otherwise pro- 0.3 part of e. g. the copper complex compound of the ceeding as described in the said example, the dyestulf of condensation product of diethylene triamine and dithe formula cyanodiamide (obtainable f. i. according to the process of (ill 1150C) (I)CHa ?11 B000 H035 NH: IITO:

NZN

HO COOH z i g gf f are similar to the Swiss Patent No. 261,051), holding the bath for half yes u accor mg 0 xa p e an hour at and rinsing and drying the material.

Example 6 Having thus disclosed the invention, what is claimed is: 10 parts of cotton are entered into a dyebath contain- 1. A trisazo dyestufi which corresponds to the formula 1 a i" a HOOC H058 NH: 1Y0:

H0 COOH ing 300 parts of lime-free water at 50. Then a concenwherein x stands for a member selected from the group trated aqueous solution, which contains 0.8 part of any consisting of hydrogen, methyl and chlorine, and y stands one of the aforedescribed dyes, is added to the dyebath for amember selected from the group consisting of methyl and the latter is heated to boiling within a 30-minute and ethyl. period, after which it is maintained at boiling temper- 2. The trisazo dyestufi which corresponds to the ature for 15 minutes. In the course of the dyeing formula H3O? (ROE; OH

HOOC HOaS *NH] DITOz HO COOH 3. The trisazo dyestufi which corresponds to the formula H316 H30? (])CH: CH

H0O( J H018 NHg N0,

NZN

Ho 00H 4. The trisazo dyestufi which corresponds to the formula (EH5 HaC? OCH: OH

HO 0 H013 NH: N 0 2 H 00H 5. The trisazo dyestuff which corresponds to the formula 11 E30? OOH: 0H

H0O H018 NH| NO! H OOH 6. The trisazo dyestuff which corresponds to the formula H502? OCzHs 0H HOO H018 NH| N01 H0 OOH References Cited-in the file of this patent UNITED STATES PATENTS 2,417,306 Krebser et a1. Mar. 11, 1947 2,507,754 Bossard et a1. May 16, 1950 FOREIGN PATENTS 877,209 France Sept. 1, 1942

Claims (1)

1. A TRISAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA