UNITED STATES PATENT OFFICE Roarr 1965,201 AZO DYES and METHODS for THEIR PREPARATION Arthur Rowan Murphy, Penns Grove, N

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 signorWilmington, 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. ferred. These ethers may be the same or dis 3. A process for producing azo dyes which com Similar, and they inay belong to either the pjises coupling a diazotized aromatic annine of 5 aliphatic or aromatic Series or they nay belong the benzene or naphthalene series which may 90 to both series. It may here be linentioned that have substituted thereon members selected from amino-hydroquinone-dimethyi-ether is preferred, the group consisting of alkyl, halogen, alkoxy, although other ether's Such as the diethyl-ether Sulfonic, carboxylic and nitro radicals, with an and dibenzyl-ether give satisfactory results. This alpha-naphthylamine-sulfonic acid which cou 20 Cornponent may have additional groups, for ex pies in the position para to the amino group, 95 a.inple alkyl groups, Substituted thereon. diazotizing the resulting annino-azo compound The end component is an amino-benzoyl-am and coupling it with amino-hydroquinone-di in C-naphthol-Sulfonic acid Or an amino-benzoyl inlethyl-ether, diazotizing the resulting amino amino-benzoyl-amino-naphthol -sulfonic acid, (disazo compound and coupling it with a men. 2.5 wherein the amino groups may occupy dif ber Selected from the group coinsisting of para 100 ferent positions on the benzoyl nucleus, the J amino - benzoyl-, meta - aimino - benzoyl-, para acid, S-acid and ly-acid derivatives being pre aimino-benzoyi-para-amino-benzoyl-, meta-am ferred. Examples of such compounds are para amino-benzoyl-Ineta-almino-benzoyl-, para-am amino - benzoyl - J - acid, para -amino-benzoyl ino-benzoyl-meta-amino-benzoyl-, and meta 3. o paira - anino - benzoyl-J-acid, Ineta-anino-ben amino-benzoyl-para-amino-benzoyl-J, -S, or -M 105. Zoyl - J-acid, meta-amino-benzoyl-meta-amino acid. benzoyl - J-acid, para-amino-benzoyl-meta-am 4. A process for producing azo dyes which com ino-benzoyl-J-acid, para-amino-benzoyl-S-acid, prises coupling a dia,Zotized amino-benzene-sul and meta-amino-benzoyl-M-acid. Where a yell fonic acid Which may have Substituted thereon 3. 5 low shade of green is desired the S-acid deriva members selected from the class consisting of O tives appear to be preferable. On the other alkyl, halogen, alkoxy, Sulfonic acid, carboxylic hand, the J-acid derivatives have been found to acid and nitro groups with alpha-naphthylamine produce colors which are somewhat faster to 6-Sulfonic acid or alpha-naphthylamine-sul Washing. fonic acid, diazotizing the resulting amino-azo As is well known J-acid is 2-ainino-5-hydroxy Compound and coupling it with 2-5-dimethoxy 15 7-sulfonic acid, S-acid is 1-amino-8-hydroxy-4- aniline, diaZOtizing the resulting amino-disazo Sulfonic acid and Mi-acid is -ainino-5-hydroxy compound and coupling it with a member se '7-Sulfonic acid. lected from the group consisting of para-amino the Several factors such as temperature, benzoyl-, meta-amino-benzoyl-, para-amino time of reactioin and proportions of react benzoyl-para-amino-benzoyl-, meta-amino-bein 20 ing substances inay also be varied within ZOyl-Ineta-amino-benzoyl-, para-aimino-benzoyl rather wide limits without departing from the ineta-amino-benzoyl-, and meta-amino-benzoyl scope of the present invention. In addition, the para-amino-benzoyl-J, -S, or -M acid. customary means whereby undesirable side re 5. A process for producing azo dyes which com actions are eliminated or greatly reduced may be prises coupling a diazotized amino-benzene incorporated herein in the practical application disulfonic acid. With alpha-naphthylamine-7-sul of the present invention. fonic acid, diazotizing the resulting amino-azo The present invention produces dyes of excel Compound and CCupling it with 2-5-dimethoxy lent Stability to light and Washing. These dyes aniline, dia. Zotizing the resulting amino-disazo 5 impart attractive colors to cotton, particularly Compound and coupling it with a member Se i 3. G desirable shades of green. Moreover, the inn lected from the group consisting of para-amino parted colors may be discharged fron the nate benzoyl-, meta-amino-benzoyl-, para-amino rial quite readily and effectively. The shades benzoyl-para-amino-benzoyl-, meta-amino-ben produced are much brighter and more attractive ZOyl-meta-amino-benzoyl-, para-amino-benzoyl than those produced from somewhat related con ineta-amino-benzoyl-, and neta-amino-benzoyl 3. 5 pounds, apparently due to the presence of the para-amino-benzoyl-J, -S, or -M acid. amino-hydroquinone-ether component. 6. A process for producing an azo dye which As many apparently widely different embodi COmprises coupling diaZOtized aniline-2-5-disul ments of this invention may be made without fonic acid with 1-naphthylainine-'7-sulfonic acid, 5 departing from the spirit and Scope thereof, it diazotizing the resulting amino-aZO compound 40 is to be understood that I do not limit nyself to and coupling it with amino-hydroquinone-di the specific embodiments thereof except as de methyl-ether, diazotizing the resulting amino fined in the appended claims. disazo compound and coupling it with para i claim: amino - benzoyl - 2-amino-5-naphthol-7-sulfonic 1. A process for producing azo dyes which com acid. 45 prises coupling a diazotized aromatic amino-azo 7. A process for producing an azo dye which compound. With an aimino-hydroquinone-ether, comprises coupling diazotized 2-naphthylamine diazotizing the resulting amino-disazo compound 4-8-disulfonic acid with 1-naphthylamine-7-sul and coupling it with a member selected from the fonic acid, diazotizing the resulting amino-azo group consisting of amino-benzoyl-amino-naph compound and coupling it with amino-hydro 4. 1,965,201 quinone-dimethyl-ether, diazotizing the resulting amino-benzoyl-meta-amino-benzoyl-, para-am amino-disazo compound and coupling it with ino-benzoyl-meta-amino-benzoyl-, or met a - para-amino-benzoyl-para-amino-benzoyl - 2 - 5 - amino-benzoyl-para-amino-benzoyl-J, -S, or -M naphthol-7-sulfonic acid. acid. 8. A process for producing an azo dye which comprises coupling diazotized amino-terephthalic 12. AZO dyes having the general formula: 80 acid with 1-naphthylamine-l-Sulfonic acid, di OCH's aZotizing the resulting amino-azo compound and coupling it with amino-hydroquinone-dimethyl 0. ether, diazotizing the resulting amino-disaZO ------()--- compound and coupling it with para-amino-ben (boH, 85 Zoyl-l-amino-8-naphthol-4-Sulfonic acid. wherein R, represents the residue of an amino 9. AZO dyes having the following general benzene-Sulfonic acid which may have Substi formula: tuted thereon members Selected from the class 15 OX 90

n-e-r-s-s-()---it-nue 0-{)-- OX NHY 20 95 wherein R and R. lepresent aromatic nuclei, R.' consisting of alkyl, halogen, alkoxy, sulfonic represents a naphthol-Sulfonic acid nucleus, X acid, carboxylic acid and nitro groups, R.' rep represents alkyl or aromatic radicals which may resents the residue of 1-naphthylamine-6-sul be dissimilar and Y represents hydrogen or an fonic acid or 1-naphthylamine-7-sulfonic acid, 1. 25 amino-benzoyl-nucleus. and R' represents the residue of a para-amino- 00 10. Azo dyes having the following general for benzoyl-, meta-amino-benzoyl-, para-amino mula: benzoyl-para-amino-benzoyl-, meta-amino-ben

OX 30 105

OX NHY 35 wherein R and R.' represent aromatic nuclei of ZOyl-meta-amino-benzoyl-, para-amino-benzoyl O the benzene or naphthalene series, R.' represents meta-amino-benzoyl-, or meta-amino-benzoyl a naphthol-sulfonic acid nucleus, X represents para-amino-benzoyl-J, -S, or -M acid. alkyl radicals which may be dissimilar, and Y 13. AZO dyes having the following general for 40 represents hydrogen or an amino-benzoyi nu mula: s cleus. 11. Azo dyes having the following general formula: (CH, O CH R-NstNR- -NsN. N=N-R iss-le-sex > -- OCH 20 (CH, O3H wherein R represents an aromatic nucleus of the Wherein R represents the residue of an amino 50 benzene or naphthalene series which may have benzene-disulfonic acid, and R' represents the 125 substituted thereon alkyl, halogen, alkoxy, Sul residue of a para-amino-benzoyl-, meta-amino fonic, carboxylic and nitro radicals, R.' represents benzoyl-, para-amino-benzoyl-para-amino-ben the residue of an alpha-naphthylamine-Sulfonic Zoyl-, meta-amino-benzoyl-meta-amino-ben acid which couples in the position para to the Zoyl-, para -amino-benzoyl-meta-amino-ben 5 5 amino group, and R' represents the residue of a Zoyl-, or meta-amino-benzoyl-para-amino-ben- 130 para - amino-benzoyl-, meta - amino - benzoyl-, Zoyl-J acid, -S, Or -M acid. para-amino-benzoyl-para-amino-benzoyl-, meta 14. An azo dye having the following formula:

SON a O CH OH 60 35 N-N N NsN so-Na (CH, NH-C 0-{X-NH, 65 do.Na SO3F 40 15. An azo dye having the following formula: SONa OC OH i45 NsN- N-N- NEN b CH N-C 0-{D-NH-c 0-{ X-NH. SONa SONa SONa 150 1,965,201 16. An azo dye having the following formula:

CONa O CH 80 Nsn --()-- CONa (CH, 0. SO3Na 85 ARTHUR, R. MURPHY.

5 90

20 95

25 00

35 10

40 115

45 120

50 25

85 40

70 145

75 150 CERTIFICATE OF CORRECTION. Patent No. 1,965,201. July 3, 1934. ARTHUR ROWAN MURPHY. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, line 32, for "benzy1" read benzoyl; page 2, line 103, for "benzol" read benzoyl; and page 4, line 3, claim 7, after "2-" insert amino-; and that the said Letters Patent should be read with these corrections there in that the same may conform to the record of the case in the Patent Office. Signed and sealed this 7th day of August, A. D. 1934. Leslie Frazer (Seal) Acting Commissioner of Patents.