USRE23380E - Polyazo dyestuffs - Google Patents
Polyazo dyestuffs Download PDFInfo
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- USRE23380E USRE23380E US23380DE USRE23380E US RE23380 E USRE23380 E US RE23380E US 23380D E US23380D E US 23380DE US RE23380 E USRE23380 E US RE23380E
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- -1 Polyazo Polymers 0.000 title description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 20
- 238000005859 coupling reaction Methods 0.000 description 18
- 230000001808 coupling Effects 0.000 description 17
- 238000010168 coupling process Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000008049 diazo compounds Chemical class 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 239000001187 sodium carbonate Substances 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 150000001408 amides Chemical group 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 229920003043 Cellulose fiber Polymers 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001869 cobalt compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 3
- ZVSKZLHKADLHSD-UHFFFAOYSA-N Benzanilide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 description 3
- 125000006519 CCH3 Chemical group 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N Sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000875 corresponding Effects 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VMZXTHCNVOQXRZ-UHFFFAOYSA-N 3,4-dioxohexanedioic acid Chemical compound OC(=O)CC(=O)C(=O)CC(O)=O VMZXTHCNVOQXRZ-UHFFFAOYSA-N 0.000 description 2
- IFVTZJHWGZSXFD-UHFFFAOYSA-N Biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000005591 charge neutralization Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical class [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 2
- 235000019233 fast yellow AB Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960001663 sulfanilamide Drugs 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NNZXDXMEXBYSRF-UHFFFAOYSA-N 2-methyl-4H-pyrazol-3-one Chemical compound CN1N=CCC1=O NNZXDXMEXBYSRF-UHFFFAOYSA-N 0.000 description 1
- AVQFHKYAVVQYQO-UHFFFAOYSA-N 3-amino-4-hydroxybenzenesulfonamide Chemical compound NC1=CC(S(N)(=O)=O)=CC=C1O AVQFHKYAVVQYQO-UHFFFAOYSA-N 0.000 description 1
- NHLAPJMCARJFOG-UHFFFAOYSA-N 3-methyl-1,4-dihydropyrazol-5-one Chemical compound CC1=NNC(=O)C1 NHLAPJMCARJFOG-UHFFFAOYSA-N 0.000 description 1
- VNSFICAUILKARD-UHFFFAOYSA-N 6-chloropyrimidine-4,5-diamine Chemical compound NC1=NC=NC(Cl)=C1N VNSFICAUILKARD-UHFFFAOYSA-N 0.000 description 1
- 229920002955 Art silk Polymers 0.000 description 1
- FQHDMJVMCFEDCJ-UHFFFAOYSA-L C(=O)([O-])C(O)C(O)C(=O)[O-].[Co+2].[Na+] Chemical compound C(=O)([O-])C(O)C(O)C(=O)[O-].[Co+2].[Na+] FQHDMJVMCFEDCJ-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229960002449 Glycine Drugs 0.000 description 1
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 1
- 241000287530 Psittaciformes Species 0.000 description 1
- 240000003670 Sesamum indicum Species 0.000 description 1
- 210000002268 Wool Anatomy 0.000 description 1
- UOSODGDKLLGIRO-UHFFFAOYSA-N [N+](=O)([O-])C1=CC=CC(C1(S(=O)(=O)N)O)N Chemical compound [N+](=O)([O-])C1=CC=CC(C1(S(=O)(=O)N)O)N UOSODGDKLLGIRO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940051880 analgesics and antipyretics Pyrazolones Drugs 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 239000011975 tartaric acid 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
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
- C09B33/12—Disazo dyes in which the coupling component is a heterocyclic compound
Definitions
- valuable new polyazo dyestuffs free from sulfonic acid groups are made by using as a coupling component a compound of the general formula in which R1 represents the radical of a diphenyl bound in the 4- and 4-positions to Pyi and Pyz, and Pyi and Pyz each represent the radical of a pyrazolone bound in the l-position to the diphenyl radical, and using at least once as a diazocomponent a diazo-compound of an amine oi the general formula ents, and also those which contain further sub- 1 stituents, in the diphenyl radical, for example, alkyl groups such as a methyl group, alkoxy groups such as a methoxy group, or halogen atoms such as chlorine.
- the same substituent may be present twice or more in the di-- phenyl radical, or the substituents may difier from one another, and each individual substituent may be present once or more than once.
- the radical R1 represents the following radicals: 3:3'-dimethyldiphenyl-, 3:3 dimethoxydiphenyl-, 3:3-dich1orodiphenyland principally the unsubstituted diphenyl residue.
- the two pyrazolone radicals Pyl and Pyz present in the coupling components of the above formula may, for example, diifer from one another. It is of advantage to use coupling components which contain the same pyrazolone radical twice.
- the pyrazolone radicals may contain a substituent in the 3-position, for example, a carboxyl group.
- a substituent in the 3-position for example, a carboxyl group.
- compounds which contain in that position an alkyl group, especially a methyl group are examples of coupling components which can be used with advantage as starting materials in the process of the invention.
- dipyrazolones obtained from 1 molecular proportion of 4:4'-diaminodiphenyl or 3:3'-dichloro- 4:4-cliaminodiphenyl and 2 molecular proportions of acetoacetic acid ester or oxalyl acetic acid ester the pyrazolones being obtained in the usual manner by tetrazotizing the diamino-diphenylcompound.
- dyestuffs can be obtained, for example, with the dipyrazolone from 4:4-diaminodiphenyl and acetoacetic acid ester.
- X represents a group occupying a position vicinal to the -NH2- group and capable of taking part in the formation of heavy metal complexes, for example, a carboxyl group or a methoxy group.
- heavy metal complexes for example, a carboxyl group or a methoxy group.
- Y in the diazo-components of the above formula represents an acid amide group, for example, a carboxylic acid amide group or a sulfonamide group.
- the nitrogen atom in the acid amide group may be free from substituents, or may have one or two substituents, for example, one or two alkyl radicals such as methyl and/or ethyl, or an aryl radical, or an aryl radical and an alkyl radical, a benzene radical coming principally into consideration as an aryl radical and which benzene radical may, if desired, carry further substituents.
- the acid amide group Y may occupy any desired position in the benzene radical R2. However, owing to their easy accessibility there come into consideration especially those diam-components in which the acid amide group is in the 4-position relatively to the group X and principally when the X represents an alkoxy or hydroxyl group.
- the benzene radical R2 may contain further substituents, for example a nitro group, an alkyl group such as methyl, or a halogen atom such as chlorine.
- diazocomponents of the above formula there may be mentioned: 2-amino-1-hydroxy 4 benzanilide, 2-amino-l-hydroxy 6 chloro 4 benzanilide, Z-amino-l-hydroxy 4 chloro 6 benzanilide,
- 2-amino 1 hydroxy 4 nitro 6 oenzanilide 2-amin0-l-hydr0xy-4-benzoic acid- (4' -dimethylsulfonylphenylanilide), 2 amino 1 hydroxy- 4 sulfonic acid anilide, Q-amino-l-hydroxy- 4-sulfonic acid methyl-anilide, 2-amino-1-methoxy-l-sulfonic acid anilide and Z-amino-l-(ficarboxy-methoxy) -4-benzanilide.
- Especially valuable dyestuffs can be obtained by using as starting materials in the present process diazo-compounds of amines of the general formula in which R2 represents a benzene radical and the groups --NH: and OH occupy positions vicinal to one another.
- amines are, for example, 6 chloro-2-amino-l-hydroxybenzene-4-sulionamide, 6-nitro-2-amino-l-hydroxybenzene-l-sulfonamide, 6-methy1-2-amino-l-hydroxybenzene- 4-sulfonamide and principally 2-amino-1-hydroxybenzene-4-sulfonamide.
- asymmetrical polyazo-dyestufis by coupling 1 molecular proportion of a coupling component of the formula first mentioned above, on the one hand, with 1 molecular proportion of a diazo-compound of an amine of the general formula in which R2, X and Y have the meanings given above and, on the other, with 1 molecular proportion of any desired diam-component.
- the second diazo-component there is advantageously chosen one which, even when it contains no acid amide group, likewise contains as a substituent in ortho-position relatively to the diazotizable amino-group capable of taking part in the formation of heavy metal complexes.
- the second diazo-component may also be a diazotized aminoazo-dyestuff.
- diazo components are: 1 aminobenzene-Z-carboxylic acid, 1-amino-2-phenoXy-acetic acid, 4-amino- 4 hydroxy 1:1'azobenzene-3:3'dicarboxylic acid.
- the coupling reaction may be conducted in an acid, neutral or advantageously an alkaline medium.
- asymmetrical dyestufis are made by the present process by coupling 1 molecular proportion of a dipyrazolone of the formula first mentioned above with 1 molecular proportion of two different diazo-compounds, it is recommended to conduct the first coupling with one diazo-component in an acid medium, advantageously a medium rendered acid with acetic acid, and then the coupling with the other diazocomponent in an alkaline medium.
- the polyazo-dyestuffs obtained by the present process are suitable for dyeing a very wide variety of materials, especially cellulose fibers such as cotton and artificial silk and staple fibers of regenerated cellulose, and also animal fibers such as wool, silk and leather. They can be converted in substance, in the dyebath or on the fiber into complex metal compounds, for example, copper, chromium, iron, nickel or cobalt compounds.
- the conversion into such complex metal compounds is carried out by the known methods in an acid, neutral or alkaline solution with or without suitable additions such as salts of inorganic or organic acids, salts of acids forming complexes such as tartaric acid or aminoacetic acid, in the presence or absence of a diluent or suspending medium such as pyridine or glycerine, and under atmospheric or super-atmospheric pressure.
- a diluent or suspending medium such as pyridine or glycerine
- many of the complex metal compounds produced in substance, especially cobalt and/or nickel compounds can be used for coloring masses and solutions thereof, such as nitrocellulose lacquers, artificial resins and spinning masses.
- the polyazo-dyestufis of the invention contain no sulfonic acid groups they generally have an adequate solubility and a good affinity for cellulose fibers in the metalfree condition. They may with advantage be treated on the fiber or in the dyebath or partly on the fiber and partly in the dyebath by known methods with agents yielding metal. It is, however, of advantage to use the process described in U. S. Patent No. 2,148,659, in which the material is first dyed and then treated in the same bath with an agent yielding metal. As agents yielding metal there come into consideration preferably those which are stable towards alkaline so- 6 lutions, such as complex copper tartrates and the til the diazo-compound disappears. The dyelike.
- dyestuffs in all cases contain groups imcellulose fibers by the single bath or two-bath parting solubility such as sulfonic acid groups after-coppering process fast reddish yellow tints.
- the I product is then coupled with the diazo-compound obtained by diazotizing 1.9 parts of l-hydroxy-2- aminobenzene-4-sulfonamide and neutralization with sodium carbonate, a quantity of sodium carbonate solution is added sufiicient to give a $02 distinctly alkaline reaction with Brilliant Yellow l ⁇ CH paper, and the whole is stirred while cooling un- Example 4 5.6 parts of the compound of the formula are diazotized in the usual manner in solution in hydrochloric acid.
- the resulting suspension of the diazo-compound is neutralized with sodium carbonate, and coupled with a solution of 3.5 parts of l:1'-[diphenylene-(4:4') l-bis-(B-methyl-fi-pyrazolone) in 40 parts of caustic soda solution of 2.5 per cent. strength and 10 parts of sodium carbonate solution of 10 per cent. strength.
- the dyestuff of the formula Nll Example 5 7.44 parts of the dyestuff obtained as described in Example 1 are dissolved in 100 parts of water and 2.7 parts of caustic soda solution of 30 per cent. strength, and the whole is mixed with an alkaline solution of complex sodium-cobalt tartrate in a quantity corresponding to 5.9 parts of cobalt.
- Example 6 100 parts of cotton are entered at 40 C. into a dyebath which contains 0.6 part of the dyestuif obtained as described in Example 1 and 3 parts of sodium carbonate in 3000 parts of Water, the temperature is raised to 90-95% C., 30
- Glauber salt parts are added, and dyeing is carried on for hour at 90-95" C.
- the dyebath is then cooled to C., the necessary quantity of a complex copper tartrate solution rendered weakly alkaline with sodium carbonate, and containing 0.2 part of copper bound in complex union, is added, and the cottom is treated for hour at 80-90 C. It is then thoroughly rinsed and if desired soaped for a short time. The cotton is dyed a fast yellow tint.
- a polyazo dyestuff which is free from sulfonic acid groups and corresponds to the formula in which R3 and R4 each stands for the radical of a diazo component of the benzene series containing in ortho-position to the -NH2- group a substituent which participates in the formation of heavy metal complexes, at least one of these diazo components corresponding to the formula Nll 9 10 in which R2 stands for a benzene radical carry- 3.
- a disazo-dyestuff which is free from sul" ing the OH- and NH2- groups in orthofonic acid groups and corresponds to the formula 1 HO OH in which R2 stands for a benzene radical in which position to one another and Y stands for an acid the N:N--- and the -OH groups occupy posiamide group bound by the acid radical to R4! and tions vicinal to one another and Y stands for a selected from the class consisting of carboxylic sulfonic acid amide group bound by the acid radiacid amide and sulfonic acid amide groups. 20 cal to R2.
- a disazo-dyestuff which is free from sul- 4.
- a disazo-dyestufi which is free from sulfonic acid groups and which corresponds to the formula i on II,;CC:N c on, on N- N on v I l l 1m o.s R,N :l ⁇ -c:o' (
- J:C-N:N-- m s own. 110 OH in which R2 stands for a benzene radical in which fonic acid groups and corresponds to the forthe N N and OH group occupy positions mula Vicinal to one another.
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Description
Reissuecl June 12, 1951 POLYAZO DYESTUFFS Willy Widmer, Bottmin to Ciba Limited, Ba
gen, Switzerland, assignor sel, Switzerland, a Swiss No Drawing. Original No. 2,538,180, dated January 16, 1951, Serial No. 738,489, March 31, 1947. Application for reissue March 26, 1951, Serial No. 217,671. In Switzerland April 16, 1946 7 Claims.
Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
According to this invention valuable new polyazo dyestuffs free from sulfonic acid groups are made by using as a coupling component a compound of the general formula in which R1 represents the radical of a diphenyl bound in the 4- and 4-positions to Pyi and Pyz, and Pyi and Pyz each represent the radical of a pyrazolone bound in the l-position to the diphenyl radical, and using at least once as a diazocomponent a diazo-compound of an amine oi the general formula ents, and also those which contain further sub- 1 stituents, in the diphenyl radical, for example, alkyl groups such as a methyl group, alkoxy groups such as a methoxy group, or halogen atoms such as chlorine. In the latter case the same substituent may be present twice or more in the di-- phenyl radical, or the substituents may difier from one another, and each individual substituent may be present once or more than once. As examples of such coupling components there may be mentioned, among others, those in which the radical R1 represents the following radicals: 3:3'-dimethyldiphenyl-, 3:3 dimethoxydiphenyl-, 3:3-dich1orodiphenyland principally the unsubstituted diphenyl residue. The two pyrazolone radicals Pyl and Pyz present in the coupling components of the above formula may, for example, diifer from one another. It is of advantage to use coupling components which contain the same pyrazolone radical twice. The pyrazolone radicals may contain a substituent in the 3-position, for example, a carboxyl group. There come principally into consideration, however, compounds which contain in that position an alkyl group, especially a methyl group. As examples of coupling components which can be used with advantage as starting materials in the process of the invention there may be mentioned dipyrazolones obtained from 1 molecular proportion of 4:4'-diaminodiphenyl or 3:3'-dichloro- 4:4-cliaminodiphenyl and 2 molecular proportions of acetoacetic acid ester or oxalyl acetic acid ester the pyrazolones being obtained in the usual manner by tetrazotizing the diamino-diphenylcompound. reducing the product to the corresponding dihydrazine, and condensing the latter with acetoacetic acid ester or oxalyl acetic acid ester). Especially valuable dyestuffs can be obtained, for example, with the dipyrazolone from 4:4-diaminodiphenyl and acetoacetic acid ester.
In the diazo-compounds of amines of the general formula also used as starting materials in the present process, X represents a group occupying a position vicinal to the -NH2- group and capable of taking part in the formation of heavy metal complexes, for example, a carboxyl group or a methoxy group. Especially valuable results can be obtained with those diazo-components which contain in that position a hydroxyl group. The substituent Y in the diazo-components of the above formula represents an acid amide group, for example, a carboxylic acid amide group or a sulfonamide group. The nitrogen atom in the acid amide group may be free from substituents, or may have one or two substituents, for example, one or two alkyl radicals such as methyl and/or ethyl, or an aryl radical, or an aryl radical and an alkyl radical, a benzene radical coming principally into consideration as an aryl radical and which benzene radical may, if desired, carry further substituents. The acid amide group Y may occupy any desired position in the benzene radical R2. However, owing to their easy accessibility there come into consideration especially those diam-components in which the acid amide group is in the 4-position relatively to the group X and principally when the X represents an alkoxy or hydroxyl group. In addition to the -NH2, X and Y groups, the benzene radical R2 may contain further substituents, for example a nitro group, an alkyl group such as methyl, or a halogen atom such as chlorine. As examples of diazocomponents of the above formula there may be mentioned: 2-amino-1-hydroxy 4 benzanilide, 2-amino-l-hydroxy 6 chloro 4 benzanilide, Z-amino-l-hydroxy 4 chloro 6 benzanilide,
2-amino 1 hydroxy 4 nitro 6 oenzanilide, 2-amin0-l-hydr0xy-4-benzoic acid- (4' -dimethylsulfonylphenylanilide), 2 amino 1 hydroxy- 4 sulfonic acid anilide, Q-amino-l-hydroxy- 4-sulfonic acid methyl-anilide, 2-amino-1-methoxy-l-sulfonic acid anilide and Z-amino-l-(ficarboxy-methoxy) -4-benzanilide.
Especially valuable dyestuffs can be obtained by using as starting materials in the present process diazo-compounds of amines of the general formula in which R2 represents a benzene radical and the groups --NH: and OH occupy positions vicinal to one another. Such amines are, for example, 6 chloro-2-amino-l-hydroxybenzene-4-sulionamide, 6-nitro-2-amino-l-hydroxybenzene-l-sulfonamide, 6-methy1-2-amino-l-hydroxybenzene- 4-sulfonamide and principally 2-amino-1-hydroxybenzene-4-sulfonamide.
By the present process there may be produced, for example, asymmetrical polyazo-dyestufis by coupling 1 molecular proportion of a coupling component of the formula first mentioned above, on the one hand, with 1 molecular proportion of a diazo-compound of an amine of the general formula in which R2, X and Y have the meanings given above and, on the other, with 1 molecular proportion of any desired diam-component. As the second diazo-component there is advantageously chosen one which, even when it contains no acid amide group, likewise contains as a substituent in ortho-position relatively to the diazotizable amino-group capable of taking part in the formation of heavy metal complexes. The second diazo-component may also be a diazotized aminoazo-dyestuff. Examples of such diazo components are: 1 aminobenzene-Z-carboxylic acid, 1-amino-2-phenoXy-acetic acid, 4-amino- 4 hydroxy 1:1'azobenzene-3:3'dicarboxylic acid.
It is of especial advantage in the present process to couple 1 molecular proportion of a coupling component of the formula first mentioned above with 2 molecular proportions of a diazocompound of an amine of the general formula in which R2, Y and X have the meanings given above, whereby symmetrical disazo-dyestufis are obtained, provided that the coupling component is symmetrical.
The coupling reaction may be conducted in an acid, neutral or advantageously an alkaline medium. When asymmetrical dyestufis are made by the present process by coupling 1 molecular proportion of a dipyrazolone of the formula first mentioned above with 1 molecular proportion of two different diazo-compounds, it is recommended to conduct the first coupling with one diazo-component in an acid medium, advantageously a medium rendered acid with acetic acid, and then the coupling with the other diazocomponent in an alkaline medium. It is in most cases of advantage to dissolve the coupling component with the aid of a small excess of an alkali hydroxide so that it is present in the form of its di-alkali salt, and to add the further quantity of alkali required for coupling in the form, for example, of an alkali carbonate. The working up of the resulting dyestuffs is carried out in a manner in itself known, for example, by filtration and drying.
The polyazo-dyestufls free from sulfonic acid groups obtainable by the present process are new and correspond to the general formula in which R1 represents the radical of a diphenyl bound in the 4- and 4'-positions to Pm and Pyz, Pm and Pyz each represent the radical of a pyrazolone bound in the 1-position to the diphenyl radical and in the 4-position to the -N=N-- group, and R3 and R4 each represent the radical of a diazo-component of which at least one corresponds to the general formula in which R2 represents a benzene radical, X represents a group occupying a position vicinal to the -NH2- group and capable of taking part in the formation of heavy metal complexes, and Y represents an acid amide group bound by the acid radical to R2.
The polyazo-dyestuffs obtained by the present process are suitable for dyeing a very wide variety of materials, especially cellulose fibers such as cotton and artificial silk and staple fibers of regenerated cellulose, and also animal fibers such as wool, silk and leather. They can be converted in substance, in the dyebath or on the fiber into complex metal compounds, for example, copper, chromium, iron, nickel or cobalt compounds. The conversion into such complex metal compounds, which may contain a plurality of metals in the complex, is carried out by the known methods in an acid, neutral or alkaline solution with or without suitable additions such as salts of inorganic or organic acids, salts of acids forming complexes such as tartaric acid or aminoacetic acid, in the presence or absence of a diluent or suspending medium such as pyridine or glycerine, and under atmospheric or super-atmospheric pressure. Furthermore, many of the complex metal compounds produced in substance, especially cobalt and/or nickel compounds, can be used for coloring masses and solutions thereof, such as nitrocellulose lacquers, artificial resins and spinning masses.
Notwithstanding that the polyazo-dyestufis of the invention contain no sulfonic acid groups they generally have an adequate solubility and a good affinity for cellulose fibers in the metalfree condition. They may with advantage be treated on the fiber or in the dyebath or partly on the fiber and partly in the dyebath by known methods with agents yielding metal. It is, however, of advantage to use the process described in U. S. Patent No. 2,148,659, in which the material is first dyed and then treated in the same bath with an agent yielding metal. As agents yielding metal there come into consideration preferably those which are stable towards alkaline so- 6 lutions, such as complex copper tartrates and the til the diazo-compound disappears. The dyelike. stuff of the formula H3CC=N N=CCH3 mnols SOgNHg l J L Q*N=N i=o c=cN=N H on o-o1i HO In U. S. Patent No. 2,228,374 there are deafter being separated and dried is a red-brown scribed polyazo-dyestufis obtained from 1:1'- powder which dissolves in concentrated sulfuric [diphenylene (4:4')] bis (3 methyl 5 acid with a yellow coloration and in dilute alkapyrazolone) and various diazo-components. line with an orange-yellow coloration, and dyes These dyestuffs in all cases contain groups imcellulose fibers by the single bath or two-bath parting solubility such as sulfonic acid groups after-coppering process fast reddish yellow tints.
and/or carboxyl groups, but in no case a sulfon- Dyestuffs having similar properties are obamide group. As compared with these known tained by starting from 1-aminobenzene-2-cardyestuffs the new dyestufifs of the present invenboxylio acid or l-amino-Z-phenoxyacetic acid or tion containing sulfonamide groups have impor- 4-amino-4'-hydroxy-1:1'-azobenzene 3:3 ditant advanta es, for examp y y d dye carboxylic acid instead of from 1-methoxy-2- of better fastness to washing and/or they have amino-benzene-4-sulfonamide, and proceeding a better ailinity towards cellulose fibers. according to the data of this example.
The following examples illustrate the inven- Example 3 tion, the parts being by weight:
4.6 parts of l-hydroxy-2-amino-benzene-4- Example 1 carboxylic acid anilide are diazotized in the usual 3.76 parts of 2-amino-l-hydroxybenzenelmanner in solution in hydrochloric acid. The sulfonamide are diazotized in the usual manner resulting suspension of the diazo-compound is in a hydrochloric acid solution. The resulting neutralized with sodium carbonate, and then coususpension of the diam-compound is neutralized pled with a solution of 3.5 parts of 1: 1'-[diphenby the addition of sodium carbonate, and coupled meme-(424) l-bis-(3-methyl-5-pyrazolone) in with asolution of 3.6 parts of l:l-[diplienyleneparts of caustic soda solution of 2.5 per cent. (414') l-bis(3-methyl5-pyrazolone) in 40 part strength and 10 parts of sodium carbonate soluof a caustic soda solution of 2.5 per cent. strength tion of 10 per cent. strength. When coupling is and 10 parts of a sodium carbonate solution of complete the dyestuff of the formula =N C:( I-N=N 1 m )H g on no IIC--(:N N=C-0Hg O-NH-00 t C 1 o OHN-C N A-N C -N=N4(.F:( CICQJVZNA m 011 OH H0 10 per cent. strength. When the coup-ling is is separated by filtering, and dried. It is a redcomplete the precipitated dyestufi of the formula brown powder which dissolves in concentrated H C cr N N=C-CH3 Parrots SOiNHg I l l I A no on g )H 110 is separated by filtration and dried. It is an Sulfuric acid with a yellow coloration and dyes orange-brown powder, which dissolves in hot cellulose fibers by the single-bath or 2-bath afterwater with an orange-yellow coloration, and dyes ooppering process fast yellow brown tints. A cellulose fibers by the single bath or two-bath imil r yestufi'. which dyes somewhat more 1181- after-coppering process ddish yellow tints lowish tints, is obtained by starting from the which are especially fast to washing and light. comp of the formula Example 2 OH 2 parts of l methoxy2-aminobenzene-4- 1 sulfonamide are diazotized in the usual manner in a hydrochloric acid solution, and then stirred with a suspension, rendered acid with acetic acid and containing sodium acetate, of 3.5 parts of l:1'[diphenylene (4:401 bis (3 methyl- 5-pyrazolone) while cooling with ice until the NH diazo-compound can no longer be detected. The I product is then coupled with the diazo-compound obtained by diazotizing 1.9 parts of l-hydroxy-2- aminobenzene-4-sulfonamide and neutralization with sodium carbonate, a quantity of sodium carbonate solution is added sufiicient to give a $02 distinctly alkaline reaction with Brilliant Yellow l\ CH paper, and the whole is stirred while cooling un- Example 4 5.6 parts of the compound of the formula are diazotized in the usual manner in solution in hydrochloric acid. The resulting suspension of the diazo-compound is neutralized with sodium carbonate, and coupled with a solution of 3.5 parts of l:1'-[diphenylene-(4:4') l-bis-(B-methyl-fi-pyrazolone) in 40 parts of caustic soda solution of 2.5 per cent. strength and 10 parts of sodium carbonate solution of 10 per cent. strength. when the coupling is complete the dyestuff of the formula Nll Example 5 7.44 parts of the dyestuff obtained as described in Example 1 are dissolved in 100 parts of water and 2.7 parts of caustic soda solution of 30 per cent. strength, and the whole is mixed with an alkaline solution of complex sodium-cobalt tartrate in a quantity corresponding to 5.9 parts of cobalt. The whole is heated for a short time at 60-70 C., and the cobalt compound so formed is precipitated by neutralization with acetic acid, separated by filtration, and dried under reduced pressure. 4 parts of the resulting complex cobalt compound of the dyestufi, when dissolved in- 1000 parts of an ordinary commercial nitrocellulose lacquer, yield a coating composition with which yellow coatings which are fast to light can be produced on a suitable support.
Example 6 100 parts of cotton are entered at 40 C. into a dyebath which contains 0.6 part of the dyestuif obtained as described in Example 1 and 3 parts of sodium carbonate in 3000 parts of Water, the temperature is raised to 90-95% C., 30
parts of Glauber salt are added, and dyeing is carried on for hour at 90-95" C. The dyebath is then cooled to C., the necessary quantity of a complex copper tartrate solution rendered weakly alkaline with sodium carbonate, and containing 0.2 part of copper bound in complex union, is added, and the cottom is treated for hour at 80-90 C. It is then thoroughly rinsed and if desired soaped for a short time. The cotton is dyed a fast yellow tint.
What I claim is:
l. A polyazo dyestuff which is free from sulfonic acid groups and corresponds to the formula in which R3 and R4 each stands for the radical of a diazo component of the benzene series containing in ortho-position to the -NH2- group a substituent which participates in the formation of heavy metal complexes, at least one of these diazo components corresponding to the formula Nll 9 10 in which R2 stands for a benzene radical carry- 3. A disazo-dyestuff which is free from sul" ing the OH- and NH2- groups in orthofonic acid groups and corresponds to the formula 1 HO OH in which R2 stands for a benzene radical in which position to one another and Y stands for an acid the N:N--- and the -OH groups occupy posiamide group bound by the acid radical to R4! and tions vicinal to one another and Y stands for a selected from the class consisting of carboxylic sulfonic acid amide group bound by the acid radiacid amide and sulfonic acid amide groups. 20 cal to R2.
2. A disazo-dyestuff which is free from sul- 4. A disazo-dyestufi which is free from sulfonic acid groups and which corresponds to the formula i on II,;CC:N c on, on N- N on v I l l 1m o.s R,N :l\ -c:o' (|J:C-N:N-- m s own. 110 OH in which R2 stands for a benzene radical in which fonic acid groups and corresponds to the forthe N=N and OH group occupy positions mula Vicinal to one another.
inc-mix N(IGII3 on NW MN on i 7/ l \'RQ-N:=N*(J=U (j: n1 y z1,c-c:=N\ /N:C-CHI M l i l YR,N:N4(=C c=c-1v=N R,-Y H0 ))H in which R2 stands for a benzene radical in which the N=N and the OH groups 00- 5. The disazo-dyestuff of the formula mu o n NZCAUHK on no cupy positions vicinal to one another and Y 6. The disazo-dyestuff of the formula H3C ..[:N N:CCH3 mNois some, 1 1 C C:(j C::CN:N
stands for a carboxylic acid amide group bound by the acid radical to R2. 7. The disazo-dyestufi of the formula WILLY WIDMER.
(References on following page) 11 12 REFERENCES CITED Number Neme Date The following references are of record in the 3g: t: J file of thls patent or the orlgmal paten 2,228374 Stusser et a1 Jan. 1941 UNITED STATES PA'I'ENTS 6 2,277,544 Fischer et a] Mar. 24, 1942 Number Name Date 2,135,901 Schmid Jan. 2, 1940 FOREIGN PATENTS 2,195,784 SChmid ADI- 2, 1 4 Number Country Date 2,195,787 hmid p 2, 1940 650,558 Germany Sept, 25, 1937 2,195,788 Schmid Apr. 2, 1940 16 Certificate of Correction Reissue No. 23,380 June 12, 1951 WILLY WIDMER It is hereby certified that error appears in the printed specification of the above numbered patent requiring, correction as follows:
Column 5. line 32, for the Word part read parts; columns 5 and 6, Example 1, for that portion of the formula reading same columns, Example 2, for that portion of the formula reading H1CC=N H;CC=N
l \N- d N N=N 1'88. N=N
m at) same formula, right-hand portion thereof, for
same oolumns, 5 and 6, Example 3, for
column 8, line 25, for 90-95% C. read 90-95 0.;
and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 28th day of August, A. D. 1951.
THOMAS F. MURPHY,
Assistant Commissioner of Patents.
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Cited By (1)
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US2829141A (en) * | 1955-06-20 | 1958-04-01 | Geigy Ag J R | Copperable disazo dyestuffs |
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US2829141A (en) * | 1955-06-20 | 1958-04-01 | Geigy Ag J R | Copperable disazo dyestuffs |
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