US2154838A - Monoazo dyestuffs soluble in water - Google Patents
Monoazo dyestuffs soluble in water Download PDFInfo
- Publication number
- US2154838A US2154838A US162059A US16205937A US2154838A US 2154838 A US2154838 A US 2154838A US 162059 A US162059 A US 162059A US 16205937 A US16205937 A US 16205937A US 2154838 A US2154838 A US 2154838A
- Authority
- US
- United States
- Prior art keywords
- parts
- sulfonic acid
- hydroxynaphthalene
- water
- brown
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 10
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 title 1
- 239000000975 dye Substances 0.000 description 15
- 239000010985 leather Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- -1 2-(4'-methylphenylamino)-8- hydroxynaphthalene-6-sulfonic acid Chemical compound 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- VNWVMZDJPMCAKD-UHFFFAOYSA-N 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(N)=CC2=C1O VNWVMZDJPMCAKD-UHFFFAOYSA-N 0.000 description 2
- GDBANHJMXDZUNE-UHFFFAOYSA-N 5-hydroxynaphthalene-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(O)=CC=CC2=C1 GDBANHJMXDZUNE-UHFFFAOYSA-N 0.000 description 2
- QEAYLNJEDDOYNQ-UHFFFAOYSA-N 6-anilino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C2C(O)=CC(S(O)(=O)=O)=CC2=CC=C1NC1=CC=CC=C1 QEAYLNJEDDOYNQ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- IWGIBWVDWATXNW-UHFFFAOYSA-N 2,5-diamino-3-chlorobenzenesulfonic acid Chemical compound NC1=CC(Cl)=C(N)C(S(O)(=O)=O)=C1 IWGIBWVDWATXNW-UHFFFAOYSA-N 0.000 description 1
- QGNJPFLIBOTDKU-UHFFFAOYSA-N 2,5-diaminobenzene-1,3-disulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=C(N)C(S(O)(=O)=O)=C1 QGNJPFLIBOTDKU-UHFFFAOYSA-N 0.000 description 1
- NIXNGYGWQMXMCA-UHFFFAOYSA-N 2,6-dibromobenzene-1,4-diamine Chemical compound NC1=CC(Br)=C(N)C(Br)=C1 NIXNGYGWQMXMCA-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- HGUYBLVGLMAUFF-UHFFFAOYSA-N 2-methoxybenzene-1,4-diamine Chemical compound COC1=CC(N)=CC=C1N HGUYBLVGLMAUFF-UHFFFAOYSA-N 0.000 description 1
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DPIZKMGPXNXSGL-UHFFFAOYSA-N 4-nitro-1,3-phenylenediamine Chemical compound NC1=CC=C([N+]([O-])=O)C(N)=C1 DPIZKMGPXNXSGL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000160765 Erebia ligea Species 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
- C09B29/28—Amino naphthols
- C09B29/30—Amino naphtholsulfonic acid
Definitions
- HaN R N N NH 7 HOSS Y wherein X stands for halogen or SOsH, Y for hydrogen or SOsI-I, Z for hydrogen, alkyl or aryl, and wherein the nucleus R may contain further substituents and the dyestuff contains at least two sulfonic acid groups.
- X stands for halogen or the sulfonic acid group
- Y stands for a diazo-group
- B may contain further substituents, the components being selected in such a manner that the finished dyestuff contains at least two sulfonic acid groups.
- the brown dyestuffs thus obtained are particularly adapted for dyeing leather. With regard to their property of dyeing leather in the grain or of dyeing it throughout they are distinctly superior to the water-soluble monoazodyestuffs obtainable by coupling in an alkaline solution mono-diazotized 1,3-diamino-4-nitrobenzene with 2-hydroXynaphthalene-3,6-disulfonic acid or diazotized l-amino-S-acylaminobenzenes, substituted by a nitro-group, with 2- amino-8-hydroxynaphthalene-3,6-disulfonic acid.
- Chrome-tanned calf is neutralized in known manner, well rinsed and dyed at 60 C. for 1 hour with 3 per cent. of the above dyestufi. After addition of formic acid the dyed leather is greased in a fresh bath and finished in the usual manner. It is well dyed in the grain a bluish-brown tint and may be buffed without changing its tint.
- NHz H2N- N N noss sole (4)
- Example 1 By substituting in Example 1 for the 32 parts of 2-phenylamino-8-hydroxynaphthalene- 6-sulfonic acid 25.3 parts of 2-methylamino-8- hydroxynaphthalene-fi-sulfonic acid and working up the product as usual, a dyestuif of similar properties is obtained.
- the dyestuffs obtained penetrate deeply into the leather and yield brown shades.
- X1 stands for one of the group consisting of halogen and SOsI-I
- X2 for one of the group consisting of hydrogen, halogen, alkyl, alkoxy and SO3H
- Y means a member of the group consisting of hydrogen and SOIBII
- Z a member of the group consisting of hydrogen, alkyl and a radical of the benzene series
- the dyestuff contains at least two sulfonic acid groups, being brown powders, easily soluble in water, penetrating deeply into the leather and yielding brown shades.
- X2 stands for one of the group consisting of hydrogen, halogen, alkyl, alkoxy and SOzI-I, being brown powders, easily soluble in water, penetrating deeply into the leather and yielding brown shades.
- HO3S/ being a brown powder, easily soluble in Water, penetrating deeply into the leather and yielding brown shades.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Patented Apr. 18, 1939 UNITED STATES PATENT OFFICE MONOAZO- DYESTUFFS SOLUBLE IN WATER Erich Fischer and Walter Gmelin, Bad Soden in Taunus, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application September 1, 1937, Se-
rial No. 162,059. 1936 6 Claims.
HaN R N=N NH 7 HOSS Y wherein X stands for halogen or SOsH, Y for hydrogen or SOsI-I, Z for hydrogen, alkyl or aryl, and wherein the nucleus R may contain further substituents and the dyestuff contains at least two sulfonic acid groups.
We have found that valuable monoazo-dyestuffs soluble in water are obtainable by coupling in an alkaline medium with 2-amino-8-hydroxynaphthalene-G-sulfonic acid or 2-amino8-hydroxynaphthalene-3,6disu1fonic acid or an N- alkyl or N-aryl derivative thereof, a diazo-compound of the general formula:
wherein X stands for halogen or the sulfonic acid group, Y stands for a diazo-group and B may contain further substituents, the components being selected in such a manner that the finished dyestuff contains at least two sulfonic acid groups.
The brown dyestuffs thus obtained are particularly adapted for dyeing leather. With regard to their property of dyeing leather in the grain or of dyeing it throughout they are distinctly superior to the water-soluble monoazodyestuffs obtainable by coupling in an alkaline solution mono-diazotized 1,3-diamino-4-nitrobenzene with 2-hydroXynaphthalene-3,6-disulfonic acid or diazotized l-amino-S-acylaminobenzenes, substituted by a nitro-group, with 2- amino-8-hydroxynaphthalene-3,6-disulfonic acid.
The following examples illustrate the invention; the parts are by weight unless otherwise stated; the relationship of parts by weight to parts by volume is that of the kilo to the liter:
(1) 22.25 parts of 2-chloro-1,4-diaminobenzene- 6-sulfonic acid in the form of its sodium salt are dissolved in about 100 parts by volume of water together with 6.9 parts of sodium nitrite. This solution is gradually run at 0 C. to 10 C. into 15 parts by volume of crude hydrochloric acid and ice. The suspension of the diazo-compound thus produced is then added in small In Germany September 5,
portions, while stirring and well cooling, to a solution of 32 parts of 2-phenylamino-8-hydroxynaphthalene-6-sulfonic acid in the presence of 38 parts of sodium carbonate in about 200 parts by volume of water. During the coupling operation 100 parts of sodium chloride are gradually added. The precipitated product is filtered by suction and dried; it is a dark-brown powder. The dyestuff corresponding with the following formula:
SOaH
Chrome-tanned calf is neutralized in known manner, well rinsed and dyed at 60 C. for 1 hour with 3 per cent. of the above dyestufi. After addition of formic acid the dyed leather is greased in a fresh bath and finished in the usual manner. It is well dyed in the grain a bluish-brown tint and may be buffed without changing its tint.
By replacing the 22.25 parts of 2-chloro-1/ldiaminobenzene-6-sulfonic acid by the corresponding quantity of 2-bromo-1,4-diaminobenzene-S-sulfonic acid, a dyestuff of similar prop erties is obtained.
(2) 18.8 parts of lA-diaminobenzenesulfonic acid, dissolved in the equivalent amount of dilute caustic soda solution, are suddenly mixed, while cooling, with 25 parts by volume of crude hydrochloric acid. 6.9 parts of sodium nitrite in an aqueous solution are then run in at 0 C. with addition of a stabilizing agent, such as naphthalenesulfonic acid. The filtered diazo-solution is gradually combined with a solution of 24 parts of Z-amino -8 hydroxynaphthalene 6 sulfonic acid in 600 parts by volume of N-sodium carbonate solution. The dyestuff is precipitated with sodium chloride, filtered by suction and dried. It is a dark-brown powder which dyes leather bluish-brown tints.
(3) 14.25 parts of chloro-lA-diaminobenzene are dissolved in 300 parts of sulfuric acid of per cent. strength and the solution is gradually diazotized at C. to C. with 6.9 parts of sodium nitrite. The filtered diazo-solution is gradually run into a solution of 27.1 parts of 2-amino- 8-hydroxynaphthalene-3,6-disulfonic acid in 400 parts by volume of 2N-sodium carbonate solution. The dyestuff is salted out. In the dry state it is a dark-brown powder which dyes leather well in the grain bluish-brown tints. The dyestuif has the following formula:
NHz H2N- N=N noss sole (4) By substituting in Example 1 for the 32 parts of 2-phenylamino-8-hydroxynaphthalene- 6-sulfonic acid 25.3 parts of 2-methylamino-8- hydroxynaphthalene-fi-sulfonic acid and working up the product as usual, a dyestuif of similar properties is obtained.
(5) 20.2 parts of Z-methyI-IA-diaminobenzene-6-sulfonic acid are diazotized in the usual manner and coupled as described in Example 1 with a solution of 26.7 parts of 2-ethylamino-8- hydroxynaththalene-6-sulfo-nic acid. The dyestuff, isolated in the usual manner, is a.- brown powder which dyes leather well in the grain brown tints.
(6) By combining a diazo-solution obtained in the usual manner from 21.8 parts of 2-methoxy-1,4-diaminobenzene-6-sulfonic a 0 id with parts of 2(4-"nethoxyphenylamino)-8- hydroxynaphthalene-G-s.u1fonic acid, a dyestuif is obtained which dyes leather in the grain bluish-brown tints.
By substituting for the 2-(4-methoxyphenyl amino) 8 hydroXynaphtha-lene 6 sulfonic acid 34 parts of 2-(4'-methylphenylamino)-8- hydroxynaphthalene-6-sulfonic acid or 35.5 parts of 2 (4 chlorophenylamino) 8 hydroxynaphthalene-G-sulfonic acid, dyestuffs of similar properties are obtained.
The following table indicates a number of other azo-dyestuffs which can be made by this invention:
(1) 2,6 dichloro 1,4 diaminobenzene 2- amino 8 hydroxynaphthalene 3,6 disulfonic acid.
(2) 1,4 diaminobenzene 2,6 disulfonic acid 2 phenyla-mino 8 hydroxynaphthalene- 6-sulfonic acid.
(3) 2,6 dibromo 1,4 diaminobenzene+2 amino 8 hydroxynaphthalene 3,6 disulfonic acid.
(4) 2 ethoxy 1,4 diaminobenzene 6 sulfonic acid- 2 phenylamino 8 hydroxynaphthalene-6-sulfonic acid.
(5) 2 methoxy 1,4 diaminobenzene 6 sulfonic acid- 2 phenylamino 8 hydroxynaphthalene-S-sulfonic acid.
(6) 2 methyl 1,4 diarninobenzene 6 sulfonic acid- 2 phenylamino 8 hydroxynaphthalene-G-sulfonic acid.
The dyestuffs obtained penetrate deeply into the leather and yield brown shades.
We claim:
1. The monoazo-dyestuffs of the following general formula:
HOQS/ Y wherein X1 stands for one of the group consisting of halogen and SOsI-I, X2 for one of the group consisting of hydrogen, halogen, alkyl, alkoxy and SO3H, Y means a member of the group consisting of hydrogen and SOIBII, and Z a member of the group consisting of hydrogen, alkyl and a radical of the benzene series, and wherein the dyestuff contains at least two sulfonic acid groups, being brown powders, easily soluble in water, penetrating deeply into the leather and yielding brown shades.
2. The monoaZo-dyestuffs of the following general formula:
SOsH
wherein X2 stands for one of the group consisting of hydrogen, halogen, alkyl, alkoxy and SOzI-I, being brown powders, easily soluble in water, penetrating deeply into the leather and yielding brown shades.
1. The monoazo-dyestuff of the following formula:
HOaS
being a dark-brown powder, easily soluble in water, penetrating deeply into the leather and yielding bluish-brown shades.
5. The monoazo-dyestuff of the following formula:
noss
being a brown powder, easily soluble in water, penetrating deeply into the leather and yielding brown shades.
6. The mcnoazo-dyestuff of the following formula:
i on,
HO3S/ being a brown powder, easily soluble in Water, penetrating deeply into the leather and yielding brown shades.
ERICH FISCHER. WALTER GMELIN.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2154838X | 1936-09-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2154838A true US2154838A (en) | 1939-04-18 |
Family
ID=7987611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US162059A Expired - Lifetime US2154838A (en) | 1936-09-05 | 1937-09-01 | Monoazo dyestuffs soluble in water |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2154838A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3524842A (en) * | 1967-08-04 | 1970-08-18 | Durand & Huguenin Ag | Water-soluble cationic phenylazo-naphthol dyestuffs containing a quaternary ammonium group |
| US4002607A (en) * | 1974-10-25 | 1977-01-11 | Allied Chemical Corporation | Azo dyes having an amino group para to the azo linkage |
-
1937
- 1937-09-01 US US162059A patent/US2154838A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3524842A (en) * | 1967-08-04 | 1970-08-18 | Durand & Huguenin Ag | Water-soluble cationic phenylazo-naphthol dyestuffs containing a quaternary ammonium group |
| US4002607A (en) * | 1974-10-25 | 1977-01-11 | Allied Chemical Corporation | Azo dyes having an amino group para to the azo linkage |
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