Patenied July 3, 1934 1,965,201 UNITED STATES PATENT OFFICE roarr 1965,201 AZO DYES AND METHODS FOR THEIR PREPARATION Arthur Rowan Murphy, Penns Grove, N. J., as Wilmington,signor to E. I. Del,duPont a corporation de Nemours of &Delaware Company, No brawing. Application January 21, 1933, Serial No. 652,927 6. Claims. (CI. 260-72) This invention relates to new a ZO dyes and more Sodium salt was dissolved in 2 liters Water With particularly refers to trisazo dyes having the 40 grams sodium hydroxide. It was diaZOtized at following general formula: 10° C. by adding 91 grams hydrochloric acid 5 OX 55 bx NY it) Wherein R. and R' represent aromatic nuclei (100%) and 69 grams Sodium nitrite. To this 60 which may be further substituted, R.' represents solution was added a solution of 245 grams 1 a naphtho-sulfonic acid nucleus, X representS naphthylamine-7-sodium-sulfonate in 5 liters alkyl or aromatic radicals which may be dissimi water. After the coupling was completed the lar, and Y represents hydrogen or an amino amino-azo compound was diazotized at 10-15 C. benzoyl nucleus; and methods for their produc by adding.91 grams hydrochloric acid (100%) and tion. 69 grams sodium nitrite. To this diazonium Com It is an object of the present invention to pound was added a Solution of 153 grams amino produce azo dyes having excellent stability to hydroquinone-dimethyl-ether and 36 grams hy Washing and light. A further object is to pro drochloric acid (100%) in 2.5 liters Water, and duce azo dyes which impart bright attractive then 272 grams sodium acetate crystals Were colors to cotton, particularly in the various shades added. After stirring several hours the Solution of green. A still further object is to produce was cooled to 5 C. and diazotized with 91 grams dyes which may be developed on the fiber, and hydrochloric acid (100%) and 69 grams Sodium Which nay readily be discharged. Additional nitrite. This diazo compound was then run into objects will appear hereinafter. a Solution of 376 grams para-amino-benzoyl-2- these objects are attained by the present in amino-5-naphthol-l-Sulfonic acid and 170 grams vention wherein a diazotized aromatic amino-aZO ammonia, in 3 liters water cooled to 0°C. with ice. compound is coupled with an amino-hydroquin After the coupling was completed the Solution one ether, the resulting amino-disazo compound was warmed to 40° C. and saturated with salt to being diazotized and coupled With an amino precipitate. the dye Which was then filtered and benzoyl-amino-naphthol-sulfonic acid or an dried. The following formula, represents its con amino-benzyl-amino-benzoyl ramino-naphthol Stitution: SON a O CH OE 35 8 5 SO3Na h CE NH-CO NH ONa O3H 40 90 sulfonic acid. If desired, the resulting trisazo dye The product was a dark blue powder, Soluble in may be developed on the fiber with any of the water with a blue color. It was insoluble in con customary developing compounds Such as 1 centrated Sulfuric acid, but on dilution it went phenyl-3-methyl-5-pyrazolone. into solution as a blue color which then Separated The invention may be more thoroughly under as a blue precipitate. When applied to cotton 9 5 stood by reference to the following illustrative by the usual dyeing method it gave a blue color examples: which on diazotization and development With - Eacample 1 phenyl-3-methyl-5-pyrazolone gave a green dye 275 grams of aniline-2-5-disulfonic acid mono ing of very good fastness and discharging prop 100 2 1,965,201 erties. The constitution of the green developed until coupling WaS completed. The annino-aZO color in its free acid form is probably: compound was then dissolved with 100 grams SO SOH OCH OE O 80 NeN NscN- NN I s s / N Os C3 NHCO N=N- N Cs-N ) SOH SOE ÖH, 85 Eacample 2 dium hydroxide and diazotized at 20-25 C. by 325 grams of the mono-Sodium Salt of 2-naph adding 200 grams hydrochloric acid (100%) and thylamine-4-8-disulfonic acid WaS dissolved in 69 grams Sodium nitrite. The diazonium con 2 liters water with 40 grams Sodium hydroxide, pound was neutralized with 70 grams Sodium ace 90 and diazotized at 10-15° C. by adding 91 grams tate crystals and coupled With 153 granS amino hydrochloric acid (100%) and 69 grams Sodium hydroquinone-dimethyl-ether, which had been nitrite. To this solution was added 245 grams dissolved in 2.5 liters Water with 37 grains hydro 1-naphthylamine-7-Sodium-Sulfonate dissolved chioric acid (100%) and precipitated with 140 in 5 liters Water. After the coupling WaS COIn grains Sodium acetate crystals. After the cou 95 pleted the amino-azo compound was diaZOtized at ping was completed the disaZO compound Was fil 25-30° C. by adding 73 grams hydrochloric acid teled and redissolved in 10 liters Water and 106 (100%) and 69 grams Sodium nitrite. This di grarins Sodium carbonate. It was cooled to 10 C. azonium compound was cooled at 10 C. and the and diazotized by adding 240 grains hydrochloric excess mineral acid WaS neutralized With 70 acid (100%) and 69 grams sodium nitrite. After 100 grams Sodium acetate crystals. There Was added One hour the in Solubie diaZOnium COmpound was to it a Suspension of amino-hydroquinone-di poured into a Solution of 376 grains para-amino methyl-ether made by dissolving 153 grams in 2.5 benzol-1-amino-8-naphthol-4-sulfonic acid and liters water with 37 grams hydrochloric acid 170 grams annonia, in 3 liters water cooled With (100%) and precipitating With 140 grams Sodium ice to 0°C. The Solution Was then Saturated with 05 acetate crystals. After the coupling WaS Con salt, stirred several hours, and the precipitated pleted this disazo compound Was dia.ZOtized. With : coloi was filtered off and died. The following 145 grams hydrochloric acid (100%) and 76 grams follinula, is a graphical representation of its con sodium nitrite. After stirring one hour at 10 C. Stitution: 110 CONa OCH O. NH-C 0-{ X-NB, 15 ()ON -- -----CH Os Na SONa the diazo compound was run beneath the Surface The direct cotton dyeing of this product was a of a Well agitated Solution of 500 grams para greener-blue than was obtained fro; in thc prod- 120 amino-benzoyl-para - amino-benzoyl-2-amino-5- lucts obtained in the first two examples, and naphthol-7-Sulfonic acid and 170 grams am after diazotization and development with 1 nonia in 2 liters Water cooled to 0 C. With ice. phenyl-3-methyl-5-pyrazolone, it gave a yellow The Solution was then heated to 80 C. and the er-green of Similar properties. 5 C dyestuff was salted Out, using about 10% of Salt. It is to be understood that the present inven 125 The precipitate was filtered off and dried. The tion is capable of wide variation and modifica constitution of this product is represented by the tion in the manner of its practical application. following formula: For example, in place of the first conponent, SONa O CE O 5 S 30 -NsN --()--- (CH, NE-C O-( >-NH-C O-K D-NH. 60 SON a SO3Na S OsNa 135 This dyestuff was similar in properties to the one represented by R. in the general formula, here given in example 1, and the developed dye was tofore given, other aromatic amines may be used of about the same Shade. and these annines may have Substituted thereoin alkyl, halogen, alkOXy, Sulfonic acid, carboxylic Eacample 3 acid, nitro and Irelated groups. Among these 181 grams annino-terephthalic acid WaS dis amines are 6-chlor-aniline-3-sulfonic acid, 5 solved in 2 liters water with 80 grams Sodium hy chlor-aniline-2-Sulfonic acid, 2-ainino-4-Sufo droxide. It was cooled to 10 C. and diaZOtized benzoic acid, 2-chlor-5-amino-4-sulfo-benzoic With 128 grans hydrochloric acid (100%) and 69 acid, 5-nitro-aniline-2-sulfonic acid, and 1 grams sodium nitrite, and then neutralized to amino-8-naphthol-3-6-disulfonic acid. Congo red with 70 grams Sodium acetate. To this The Second COInpOnent is an arolinatic amine diazonium compound was added a Solution of 245 which couples pala, to the annino group, and grams 1-naphthylamine-7-Sodium-Sulfonate in 5 which may have additional groups substituted liters water, and the mixture was stirred at 25 C. thereon. Alpha-naphthylamine-Sulfonic acids 10 1,965,201 3 which couple in the 4-position are preferred for thol-Sulfonic acids and amino-benzoyl-alinino this conponent, although the invention is not benzoyl-almino-naphthol-sulfonic acids. limited thereto. Compounds which fall within 2. A process for producing azo dyes which com this class and which have been used with satis prises coupling a diazotized aromatic amino-azo factory results are 1-naphthylamine-2-sulfonic COnpound the COmponents of Which are members 80 acid, 1-naphthylamine-7-sulfonic acid, 2-meth Of the benzene or naphthalene series. With an OXy-1-naphthyiannine-6-sulfonic acid, 2-ethoxy amino-hydroquinone-alkyl-ether, diazotizing the 1-naphthylamine-6-sulfonic acid, and 2-meth resulting amino-disazo compound and coupling oxy-1-naphthylamine-7-sulfonic acid. it with a member selected from the group con 10 The third component is an amino-hydroquin Sisting of amino-benzoyl-amino-naphthol-sul 85 One-ether, either aliphatic or aromatic ethers be fonic acids and amino-benzoyl-amino-benzoyl ing Suitable, although the alkyl ethers are pre amino-naphthol-Sulfonic acids.