GB1598212A - Water-soluble polyazo dyestuffs - Google Patents
Water-soluble polyazo dyestuffs Download PDFInfo
- Publication number
- GB1598212A GB1598212A GB3739/78A GB373978A GB1598212A GB 1598212 A GB1598212 A GB 1598212A GB 3739/78 A GB3739/78 A GB 3739/78A GB 373978 A GB373978 A GB 373978A GB 1598212 A GB1598212 A GB 1598212A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dyestuff
- parts
- mole
- general formula
- polyazo
- 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
Links
- -1 polyazo Polymers 0.000 title claims description 19
- 239000000975 dye Substances 0.000 claims description 40
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000010168 coupling process Methods 0.000 claims description 23
- 238000005859 coupling reaction Methods 0.000 claims description 18
- 239000010985 leather Substances 0.000 claims description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229910000906 Bronze Inorganic materials 0.000 claims description 10
- 239000010974 bronze Substances 0.000 claims description 10
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002790 naphthalenes Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- HMXWYAIIRSNTEO-UHFFFAOYSA-N 5-oxo-3-phenyl-4H-pyrazole-1-sulfonic acid Chemical group S(=O)(=O)(O)N1N=C(CC1=O)C1=CC=CC=C1 HMXWYAIIRSNTEO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000018553 tannin Nutrition 0.000 claims description 2
- 229920001864 tannin Polymers 0.000 claims description 2
- 239000001648 tannin Substances 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 4
- 238000002360 preparation method Methods 0.000 claims 3
- 238000012505 colouration Methods 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004040 coloring Methods 0.000 claims 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 2
- LWOAIKNLRVQTFT-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzenesulfonamide Chemical compound C1=CC(N)=CC=C1NS(=O)(=O)C1=CC=C(N)C=C1 LWOAIKNLRVQTFT-UHFFFAOYSA-N 0.000 description 2
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- CWJQQASJVVAXKL-UHFFFAOYSA-N 4-(3-Methyl-5-oxo-4,5-dihydro-1H-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1CC(C)=NN1C1=CC=C(S(O)(=O)=O)C=C1 CWJQQASJVVAXKL-UHFFFAOYSA-N 0.000 description 1
- VFMNIJOKAXPZLE-UHFFFAOYSA-N 4-(5-methyl-3-oxo-1h-pyrazol-2-yl)benzenesulfonic acid Chemical compound N1C(C)=CC(=O)N1C1=CC=C(S(O)(=O)=O)C=C1 VFMNIJOKAXPZLE-UHFFFAOYSA-N 0.000 description 1
- DQNAQOYOSRJXFZ-UHFFFAOYSA-N 5-Amino-1-naphthalenesulfonic acid Chemical compound C1=CC=C2C(N)=CC=CC2=C1S(O)(=O)=O DQNAQOYOSRJXFZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical group C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/50—Tetrazo dyes
- C09B35/58—Tetrazo dyes of the type
-
- 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/36—Trisazo dyes of the type
- C09B35/374—D contains two aryl nuclei linked by at least one of the groups —CON<, —SO2N<, —SO2—, or —SO2—O—
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Optical Filters (AREA)
Description
(54) IMPROVEMENTS IN AND RELATING TO NEW WATER
SOLUBLE POLYAZO DYESTUFFS
(71) We, PRODUITS CHIMIQUES UGINE KUHLMANN, a French body corporate, of 25 Boulevard de l'Amiral, Bruix 75116 Paris, France, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention concerns improvements in and relating to new water-soluble polyazo dyestuffs.
The dyestuffs are suitable for dyeing animal fibres, especially silk and leathers, and have a good affinity for the various kinds of leather, whatever type of tanning may have been used.
Our copending Application No. 3738/78 (Serial No. 1598211) describes and claims polyazo dyestuff of the general formula:
wherein one of X and X1 represents a radical of the formula
and the other represents a radical of the formula:
in which A represents the residue of a mono- or di-coupling component AH2 of the hydroxylated and/or aminated benzene series, optionally substituted by one or two methyl groups or a sulphonic acid group, or of the hydroxylated and/or aminated naphthalene series, optionally substituted by a sulphonic acid group, B represents the residue of a diazotisable primary benzene amine BNH2, n is 0 or 1, R repre sents a methyl or carboxylic acid group, R1 and R2 each represent a hydrogen or chlorine atom, R, represents a hydroxy group or a hydrogen atom, and Rz represents a sulphonic acid group or a hydrogen atom, and in which the substituents of the naphthalenic ring system may be attached to either of the rings.
According to the present invention dyestuffs are provided of the general formula:
wherein one of X and X represents a radical of the formula:
and the other represents a radical of the formula:
in which A represents the residue of a mono- or di-coupling component AH2 of the hydroxylated and/or aminated benzene series or the hydroxylated and/or aminated naphthalene series, optionally substituted by a sulphonic acid group, B represents the residue of a diazotisable primary benzene amine BNH2, e.g. aniline or its derivatives, n is 0 or 1, R represents a methyl or carboxylic acid group, R1 and R2 each represent a hydrogen or chlorine atom, Rs represents a hydroxy group or a hydrogen atom, and R4 represents a sulphonic acid group or a hydrogen atom, and in which the substituents of the naphthalene ring system may be attached to either of the rings.
These dyestuffs dye leathers in full shades, very level and fast to light, washing and dry cleaning. They also show an excellent stability and fastness to acids. The dyestuffs of formula (I) provide full shades in light or medium brown tones, bronzes and red browns in particular. It is surprising that derivatives of an asymmetrical base such as 4,4'-diamino-benzenesulphanilide should have superior properties to the derivatives of a symmetrical base such as 4,4'-diaminobenzene-sulphanilide which are mentioned in U.K. Patent No. -,490,283. It is well known that the diamines most used to Obtain satisfactory dyes are symmetrical.
Of the dyestuffs according to the invention we prefer the dyes of formula:
to the dyes of the formula
The dyestuffs according to the invention may be prepared for example by coupling the bis-diazo derivative of a mole of 4,3'-diamino-benzene-sulphanilide with a mole of a N-sulphophenyl-5-pyrazolone substituted in the 3 position by a methyl or carboxylic acid group, then coupling in a basic medium with a mole of a monosulphonated mono-amino-naphthalene coupling component, optionally substituted by a hydroxy and/or sulphonic acid group (formula II), or by effecting these coupling processes in the reverse order (formula III).In the two cases the mono-amino-disazo compound is diazotised and is coupled with a mole of a mono- or di-coupling component AH2, the product obtained being able to be possible coupled with a mole of the diazo derivative of an amine B--NH2, wherein -A- and B- have the meanings given above.
Examples of mono- and di-coupling components AH2 are: - the hydroxylated and/or aminated benzene derivatives such as phenol, 1,3 dihydroxybenzene and 1,3 -diaminobenzene; and - the naphthalenederivatives such as 2-hydroxynaphthalene, 2-amino-8-hydroy- naphthalene-6-sulphonic acid.
Examples of diazotisable benzene amines B-NH2 are aniline and its nitro and/or sulphonated derivatives, 4-amino-diphenylamine substituted by a nitro and/or sulphonic acid group, especially 4-amino-4'-nitro-1,1'-diphenylamine-2'-sulphonic acid.
The invention is illustrated by the following Examples in which the parts indicated are parts by weight.
Example 1.
26.3 parts of 4,3'-diamino-benzene-sulphanilide are dissolved in 400 parts of water with the aid of 50 parts of a 30% solution of hydrochloric acid. The solution is cooled to 50C, a solution of 14 parts of sodium nitrite in 28 parts of water is added, the mixture is stirred for an hour at 5 C, then the slight excess of nitrous acid is destroyed by the addition of a little sulphamic acid. To the solution of the bis diazo derivative thus obtained are added, in a period of twenty minutes, without exceeding a temperature of 10 C, a solution of 25.4 parts of 1-(4'-sulpho-phenyl)-3-methyl-5 pyrazolone in 200 parts of a 7% solution of sodium hydroxide. Then a 20% solution of sodium carbonate is added in a period of an hour so that a pH of 7 is obtained.
When the mono-coupling process has finished, a solution of 34.1 parts of the monosodium salt of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid in 200 parts of a 7% solution of sodium hydroxide is rapidly added and then 20 parts of sodium carbonate. The product is stirred overnight. The product obtained is acidified with 30% hydrochloric acid so that a pH of 4 is attained. Then a solution of 9 parts of sodium nitrite in 18 parts of water is added and the product is run in a period of forty minutes into a mixture containing 100 parts of water, 30 parts of 30% hydrochloric acid and ice. The mixture is diazotised for three hours at 5"C, then the excess of nitrous acid is destroyed by the addition of a little sulphamic acid. The diazo compound obtained is then run in a period of twenty minutes into a solution of 11 parts of resorcinol in 200 parts of water, 40 parts of caustic soda and 30 parts of sodium carbonate while maintaining the temperature below 10"C. When the coupling process is finished, a solution of diazonium salt obtained from 9.3 parts of aniline by the usual method is added. When the reaction is ended, the dyestuff is isolated by the usual processes.
This dyestuff dyes leathers from various tannings in a light bronze shade which is fast to the usual wet tests.
In Table I below other Examples of tris (n = 0) or tetrakis (n = 1) azo dyes according to formula IIa are given, which are prepared according to the details in Example 1 but replacing the 25.4 parts of 1-(4'-sulphophenyl)-3-methyl-5-pyrazolone by an equivalent molar amount of the pyrazolone indicated, and the 11 parts of resorcinol by an equivalent molar amount of the coupling component AH2 and possibly replacing the 9.3 parts of aniline by an equivalent molar amount of the anune
B-NH2.
TABLE I
SO3H Shade on Ex. R R1 R2 position AH2 B-NH2 leather 2 CH3 H H 4' 1,3-dihydroxy- n = 0 light green benzene brown 3 " " " ,, 4-nitro-aniline light bronze 4 " ,, C12' 5' ,, aniline 5 ,, C12' C15' 4' ,, 6 ,, H H ,, " 4-amino-2'- light red sulfo-4' -nitro- brown diphenylamine 7 COOH ,, " " " n = 0 light green brown 8 " " " " ,, aniline light bronze 9 " " " ,, 4-nitro-aniline 10 " " " " " 4-amino-2'- sulfo-4' -nitro diphenylamine Example 11.
If, in Example 6, the 34.1 parts of the monosodium salt of 1-amino-8-hydroxy naphthalene-3,6disulphonic acid are replaced by 23.9 parts of 2-amino-8-hydroxynaphthalene-6-sulphonic acid, a dyestuff is obtained corresponding to formula (lIb) below in which R = CH2, R1 = R2 = H, SO2H in the 4'-position, AH2 being 1,3dihydroxy-benzene and B-NH2 being 4-amino-2'-sulpho-4'-nitro-diphenylamine, and which dyes leather a light red brown shade which is fast to the usual wet tests.
Table II below gives other Examples of polyazo dyes according to formula (IIb) prepared according to the details in Example II following the same rules of use as
Table I.
TABLE II
SO3H Shade on Ex. R R1 R2 position AH2 B-NH2 leather 12 CH3 H H 4' phenol n=O light brown 13 " " ,, ,, 2-hydroxy " light red naphthalene brown 14 ,, ,, ,, ,, 2-amino-8- ,, medium brown hydroxy-6- naphthalene sulphonic acid Example 15.
If, in Example 12, the 23.9 parts of 2-amino-8-hydroxy-naphthalene-6-sulphonic acid are replaced by 22.3 parts of 1-amino-naphthalene-5-sulphonic acid, a dyestuff is obtained corresponding to formula (IIc) below in which n = 0, R = CH2, R1 =
R2 = H, SO3HO is in position 4' and AH2 being phenol, which dyes leather an orange brown shade which is fast to the usual wet tests.
Table III below gives other Examples of polyazo dyes according to the formula (IIc) prepared according to the details in Example 15 following the same rules for use as Table I.
TABLE III
SO,H Shade on Ex. R Rl R2 position AH2 B-NH2 leather 16 CH3 H H 4' 2-amino-8- n = O light green hydroxy- brown naphthalene-6 sulphonic acid 17 COOH ,, ., ,, 1,3-diamino- 2-nitro-aniline light brown benzene 18 ,, ,, ,, ,, ., 4-nitro-aniline 19 ,, ,, ,, ,, ,, n=O light bronze Example 20.
If, in Example 1, the order of the two first coupling processes is reversed, a dyestuff is obtained which dyes leather a yellow brown shade and which corresponds to formula (IIIa) below in which R = CERT, Rl = R2 = H, SO,gH is in position4',
AH2 being 1,3-dihydroxybenzene and BNH2 being aniline.
Example 21.
If, in Example 2, the order of the two first coupling processes is reversed, a dyestuff is obtained which dyes leather a red brown shade and which corresponds to formula (IIIa) above in which n = O, R = CH2, R1 = R, = H, SOsH is in position 4' and AH2 being 1,3-dihydroxybenzene.
Example 22.
If, in Example 20, the 1,3-dihydroxy-benzene is replaced by 1,3-diamino-benzene, a dyestuff is obtained which dyes leather a brown shade.
Example 23.
If, in Example 21, the 1,3-dihydroxy-benzene is replaced by 1,3-diamino-benzene, a dyestuff is obtained which dyes leather a brown shade with a tendency to green.
Example 24.
100 parts of a clear chrome box-calf are rinsed, neutralised, rinsed again and then introduced into a filling machine containing one part of the dyestuff of Example 1 in 500 parts of water at 60"C. It is fulled for 45 minutes at 600 C, then a tawing paste suspended in 50 parts of water by means of a dispersing agent is introduced.
It is again fulled for 30 minutes, then subjected to the usual treatments. A leather is obtained which is dyed uniformly in a light bronze shade and which is dyed uniformly ing a light bronze shade and which is fast to the usual wet tests.
Example 25.
100 parts of a clear chrome suede skin are rewetted in the presence of a little ammonia and then they are introduced into a filling machine containing a solution of 10 parts of the dyestuff of Example 1 in 2000 parts of water at 600 C. The skin is filled for an hour at 600C, then 5 parts of an 85% solution of formic acid are introduced. It is again filled for 30 minutes, rinsed, dried and subjected to the usual treatment. A leather is obtained which is dyed uniformly and in depth in a light bronze shade and which is fast to the usual wet tests.
Example 26.
100 parts of skins chrome-tanned and retanned by means of a synthetic or vegetable tannin, are rewetted in the presence of a little ammonia. Then the skins are introduced ito a filling machine containing 6 parts of the dyestuff of Example 1 in 2000 parts of water at 600 C. They are fulled at 600 C, then 3 parts of an 85% solution of formic acid are introduced. They are fulled again for 30 minutes at 6aOC, rinsed and dried.
Skins dyed uniformly in the same light bronze shade as the leathers of Examples 24 and 25, fast to the usual wet tests, are obtained.
WHAT WE CLAIM IS:
1. Polyazo dyestuffs of the general formula:
wherein one of X and X1 represents a radical of the formula:
and the other represents a radical of the formula:
in which A represents the residue of a mono- or di-coupling compound AH2 of the hydroxylated and/or aminated benzene series or of the hydroxylated and/or aminated naphthalene series, optionally substituted by a sulphonic acid group, B represents the residue of a diazotisable primary benzene amine BNH2, n is o or 1, R represents a methyl or carboxylic acid group R1 and R2 each represent a hydrogen or chlorine atom, R2 represents a hydroxy group or a hydrogen atom and R4 represents a sulphonic acid group or a hydrogen atom, and in which the substituents of the naphthalenic ring system may be attached to either of the rings.
2. Polyazo dyestuff according to claim 1 of the general formula:
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (13)
- **WARNING** start of CLMS field may overlap end of DESC **.ammonia and then they are introduced into a filling machine containing a solution of 10 parts of the dyestuff of Example 1 in 2000 parts of water at 600 C. The skin is filled for an hour at 600C, then 5 parts of an 85% solution of formic acid are introduced. It is again filled for 30 minutes, rinsed, dried and subjected to the usual treatment. A leather is obtained which is dyed uniformly and in depth in a light bronze shade and which is fast to the usual wet tests.Example 26.100 parts of skins chrome-tanned and retanned by means of a synthetic or vegetable tannin, are rewetted in the presence of a little ammonia. Then the skins are introduced ito a filling machine containing 6 parts of the dyestuff of Example 1 in 2000 parts of water at 600 C. They are fulled at 600 C, then 3 parts of an 85% solution of formic acid are introduced. They are fulled again for 30 minutes at 6aOC, rinsed and dried.Skins dyed uniformly in the same light bronze shade as the leathers of Examples 24 and 25, fast to the usual wet tests, are obtained.WHAT WE CLAIM IS: 1. Polyazo dyestuffs of the general formula:wherein one of X and X1 represents a radical of the formula:and the other represents a radical of the formula:in which A represents the residue of a mono- or di-coupling compound AH2 of the hydroxylated and/or aminated benzene series or of the hydroxylated and/or aminated naphthalene series, optionally substituted by a sulphonic acid group, B represents the residue of a diazotisable primary benzene amine BNH2, n is o or 1, R represents a methyl or carboxylic acid group R1 and R2 each represent a hydrogen or chlorine atom, R2 represents a hydroxy group or a hydrogen atom and R4 represents a sulphonic acid group or a hydrogen atom, and in which the substituents of the naphthalenic ring system may be attached to either of the rings.
- 2. Polyazo dyestuff according to claim 1 of the general formula:in which A, B, n, R, R1, R2, R3, R4 have the same significance as in claim 1.
- 3. Polyazo dyestuff according to claim 2, in the free acid state of the general formula:
- 4. Polyazo dyestuff according to claim 2 in the free acid state of the general formula:
- 5. Polyazo dyestuff according to claim 2 in the free acid state of the general formula:
- 6. Polyazo dyestuff of the general formula given in claim 1 substantially as herein described with reference to and as illustrated in any of Examples 1 to 23.
- 7. A process for the preparation of a polyazo dyestuff of the general formula given in claim 1 which comprises coupling the bis diazo derivative of a mole of 4,3'diaminobenzene sulphanilide with a mole of an N-sulphophenyl-5-pyrazolone substituted in the 3-position by a methyl or carboxylic acid group, then coupling the monoazo-diazo compound thus obtained in a basic medium with a mole of a monoamino-monosulphonated-naphthalene coupling componoent, ptionally substituted by a hydroxy and/or sulphonic acid group, the mono-amino-diazo derivatives obtained being then diazotised and coupled with a mole of a mono- or di-coupling component AH2, the dyestuff obtained being able to be possibly coupled with a mole of the diazo derivative of a benzene amine BNH2 wherein -A- and B-have the same significance as in claim 1.
- 8. A process for the preparation of a polyazo dyestuff of the general formula given in claim 1 which comprises coupling the bis diazo derivative of a mole of 4,3'-diarnino-benzene sulphanilide with a mole of a monoamino-sulphonated-naphthalene coupling component, optionally substituted by a hydroxy and/or sulphonic acid group in a basic medium, then coupling the monoazo-diazo compound thus obtained with a mole of an N-sulphophenyl-5-pyrazolone substituted in the 3-poosition by a methyl or carboxylic acid group, the monoamino-disazo derivative obtained being then diazotised and coupled with a mole of a mono- or di-coupling component AH2, the dyestuff obtained being able to be possibly coupled with a mole of the diazo derivative of a benzene amine BNH2 wherein -A- and -B- have the same significance as in claim 1.
- 9. Process for the preparation of a polyazo dyestuff of the general formula given in claim 1 substantially as herein described with reference to and as illustrated in any of Examples 1 to 23.
- 10. Process for the colouration of animal fibre in which the colouring agent is a dyestuff as claimed in any of claims 1 to 6.
- 11. Process according to claim 10 in which the animal fibre is leather.
- 12. Process for the colouration of animal fibre substantially as herein described with reference to and as illustrated in any of Examples 24 to 26.
- 13. Animal fibre dyed with a dyestuff as claimed in any of claims 1 to 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7703177A FR2379579A1 (en) | 1977-02-04 | 1977-02-04 | NEW WATER-SOLUBLE POLYAZOIC DYES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1598212A true GB1598212A (en) | 1981-09-16 |
Family
ID=9186310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3739/78A Expired GB1598212A (en) | 1977-02-04 | 1978-01-31 | Water-soluble polyazo dyestuffs |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5397027A (en) |
| AU (1) | AU3293578A (en) |
| BE (1) | BE863241A (en) |
| BR (1) | BR7800671A (en) |
| DE (1) | DE2804303A1 (en) |
| ES (1) | ES466648A1 (en) |
| FR (1) | FR2379579A1 (en) |
| GB (1) | GB1598212A (en) |
| IT (1) | IT1107049B (en) |
| NL (1) | NL7801176A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE38531E1 (en) * | 1996-09-09 | 2004-06-08 | Clariant Finance (Bvi) Limited | Tetrakisazo dyes, their production and use |
| GB9618779D0 (en) * | 1996-09-09 | 1996-10-23 | Clariant Int Ltd | Improvements in or relating to organic compounds |
-
1977
- 1977-02-04 FR FR7703177A patent/FR2379579A1/en active Granted
-
1978
- 1978-01-24 BE BE184573A patent/BE863241A/en unknown
- 1978-01-31 GB GB3739/78A patent/GB1598212A/en not_active Expired
- 1978-02-01 DE DE19782804303 patent/DE2804303A1/en not_active Withdrawn
- 1978-02-02 NL NL7801176A patent/NL7801176A/en not_active Application Discontinuation
- 1978-02-02 AU AU32935/78A patent/AU3293578A/en active Pending
- 1978-02-02 BR BR7800671A patent/BR7800671A/en unknown
- 1978-02-03 ES ES466648A patent/ES466648A1/en not_active Expired
- 1978-02-03 IT IT67210/78A patent/IT1107049B/en active
- 1978-02-03 JP JP1140578A patent/JPS5397027A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BR7800671A (en) | 1978-08-29 |
| JPS5397027A (en) | 1978-08-24 |
| DE2804303A1 (en) | 1978-08-10 |
| IT1107049B (en) | 1985-11-18 |
| NL7801176A (en) | 1978-08-08 |
| FR2379579B1 (en) | 1980-11-21 |
| IT7867210A0 (en) | 1978-02-03 |
| BE863241A (en) | 1978-07-24 |
| FR2379579A1 (en) | 1978-09-01 |
| AU3293578A (en) | 1979-08-09 |
| ES466648A1 (en) | 1979-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3915952A (en) | Polyazo compounds containing 2,4,2{40 ,4{40 -tetrahydroxy-dibenzylamine as coupling component | |
| HU182574B (en) | Process for producing 1:2 metal complexes of bis-diazo-compounds | |
| GB1598212A (en) | Water-soluble polyazo dyestuffs | |
| EP0016975B1 (en) | Polyazo dyestuffs and their use in dyeing fibre-materials and leather containing amino- and hydroxyl groups | |
| US2833756A (en) | Polyazo dyestuffs | |
| DE1219155B (en) | Process for the preparation of water-soluble azo dyes | |
| US3787387A (en) | 2:1 metal complexes of 2,2',4'-trihydroxy-3,5-dinitroazobenzene bound to a diphenylamine through an azo bridge | |
| US3189593A (en) | Polyazo dyes | |
| GB1598211A (en) | Water-soluble polyazo dyestuffs | |
| US2750375A (en) | Polyazo-dyestuffs | |
| US3179650A (en) | Polyazo dyes | |
| US3943122A (en) | Polyazo compounds containing benzhydrol as a component | |
| US2039898A (en) | Azo-dyestuffs for dyeing leather | |
| US1885609A (en) | Manufacture of polyazo dyestuffs | |
| US4342684A (en) | Hydrosoluble pyrazolone trisazo dyestuffs derived from 4,4'-diamino-benzenesulfanilide | |
| US3267089A (en) | Disazo orange dye | |
| US3380989A (en) | Copper-containing dis-, tris- and tetrakisazo dyestuffs of resorcin with beta-oxyethylsulfone-sulfuric acid ester groups | |
| US4169831A (en) | Water-soluble tetrakisazo dyestuffs derived from 4,4'-diaminoazobenzene | |
| US3862118A (en) | Tetrakisazo compounds | |
| US4052380A (en) | Trisazo dyes containing two different aminonaphtholsulphonic acid coupler components | |
| US1976044A (en) | Azo dye and method for its preparation | |
| US2034304A (en) | Azo dyestuffs and their production | |
| US1565344A (en) | Brown trisazo dyestuffs and process of making same | |
| US4081437A (en) | Water soluble polyazo dyestuffs | |
| US1923944A (en) | Azo dyestuffs for leather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |