US3124566A - Disazo dyestuffs - Google Patents
Disazo dyestuffs Download PDFInfo
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- US3124566A US3124566A US3124566DA US3124566A US 3124566 A US3124566 A US 3124566A US 3124566D A US3124566D A US 3124566DA US 3124566 A US3124566 A US 3124566A
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title description 36
- 239000000243 solution Substances 0.000 description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 210000002268 Wool Anatomy 0.000 description 36
- 239000000975 dye Substances 0.000 description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 26
- 239000002253 acid Substances 0.000 description 26
- 230000001808 coupling Effects 0.000 description 26
- 238000010168 coupling process Methods 0.000 description 26
- 238000005859 coupling reaction Methods 0.000 description 26
- 238000004043 dyeing Methods 0.000 description 26
- -1 methoxy, ethoxy, phenoxy, chlorophenoxy, bromophenoxy, sulfophenoxy, methylphenoxy Chemical group 0.000 description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 24
- 239000000460 chlorine Substances 0.000 description 22
- 229910052801 chlorine Inorganic materials 0.000 description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 18
- 125000004432 carbon atoms Chemical group C* 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 16
- 125000001424 substituent group Chemical group 0.000 description 16
- 150000002431 hydrogen Chemical class 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 14
- 150000004985 diamines Chemical class 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 12
- 239000001632 sodium acetate Substances 0.000 description 12
- 235000017281 sodium acetate Nutrition 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 159000000000 sodium salts Chemical class 0.000 description 12
- 229960000583 Acetic Acid Drugs 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 239000011528 polyamide (building material) Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000001187 sodium carbonate Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N Sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BYONEXGJEYSLBO-UHFFFAOYSA-N 1-amino-4-[(4-amino-9,10-dioxoanthracen-1-yl)amino]anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC=1C=3C(=O)C4=CC=CC=C4C(=O)C=3C(N)=CC=1)=CC=C2N BYONEXGJEYSLBO-UHFFFAOYSA-N 0.000 description 2
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1H-pyrazol-5-amine Chemical compound NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 2
- MVUDWRDRXUICGJ-UHFFFAOYSA-N 3-(5-amino-3-methylpyrazol-1-yl)benzenesulfonic acid Chemical compound N1=C(C)C=C(N)N1C1=CC=CC(S(O)(=O)=O)=C1 MVUDWRDRXUICGJ-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004799 bromophenyl group Chemical group 0.000 description 2
- 230000003139 buffering Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004803 chlorobenzyl group Chemical group 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000006178 methyl benzyl group Chemical group 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004043 oxo group Chemical group O=* 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 230000005068 transpiration Effects 0.000 description 2
- 230000003442 weekly Effects 0.000 description 2
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
- C09B35/02—Disazo dyes
- C09B35/039—Disazo dyes characterised by the tetrazo component
- C09B35/227—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl sulfide or a diaryl polysulfide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
Definitions
- the present invention concerns new disazo dyestuffs, processes for the production thereof, a process for the dyeing of fibres containing natural or synthetic polyamide as well as, as industrial product, the material dyed with the aid of these dyestuffs.
- yellow disazo dyestufi'is which are obtained by coupling (a) One mole of a tetrazotised diamine of formula HzN NHg ll n (I) wherein n is 1 or, preferably, 2, and wherein the benzene rings A and B can be further substituted as explained below.
- the' benzene rings of the diamine of Formula I can be unsubstituted, or they can be substituted further with from one to preferably not more than two of the following substituents which are compatible with the process according to the invention, and are designated in this specification and in the appended claims as monovalent azo-compatible substituents and are alkyl with maximally 4 carbon atoms, preferably methyl or ethyl, chlorine, bromine, one or at most two sulfamyl or lower alkyl-sulfonyl. specification and in the appended claims designates alkyl :with from 1 to 4 carbon atoms.
- the benzene ring (D, E) of the l-phenyl-3-methyl-5- amniopyraz ole used according to the invention as coupling component' can be unsubstituted, or it can be substituted-apart from the above-mentioned water-solubilizing substituent or substituents X, if it is desired that these be present in the coupling component-with one or two of the substituents Whose presence in the coupling component is compatible with the presence according to the present invention and which are designated in this specification and in the appended claims as monovalent coupling-compatible substituents, which are alkyl with maximally 4 carbon atoms, preferably methyl and ethyl, benzyl, methylbenzyl, chlorobenzyl, phenyl, methylphenyl, chlorophenyl, bromophenyl, methoxy, ethoxy, phenoxy, chlorophenoxy, bromophenoxy, sulfophenoxy, methylphen
- the tetrazotised diamine of Formula I is coupled at a temperature of about -10 to C., and preferably at +10 to 25 C. with the 1-phenyl-3-methyl-5- arninopyrazole as defined above, advantageously in an aqueous-acid medium, while, if desired, gradually buffering the acid with an agent which raises the pH value, e.g. with an alkali metal salt of a low-molecular fatty acid such as sodium acetate and, if necessary, in the presence of organic solvents which are miscible with water such as low fatty alcohols, e.g. methanol or ethanol or low aliphatic ketones such as acetone.
- an agent which raises the pH value e.g. with an alkali metal salt of a low-molecular fatty acid such as sodium acetate and, if necessary, in the presence of organic solvents which are miscible with water such as low fatty alcohols, e.g. methanol or ethanol
- disazo dyestuffs according to the invention consists in coupling, in an acid medium,one mol of a tetrazotised diamine of Formula I with two mols of a compound of Lower alkyl as used in this I wherein W is the oxo or imino group, to form a disazo dyestuif of Formula IV @NH-NH:
- the new compounds of Formula I and particularly They yield dyeings with the above-mentioned wet fastness properties, which comprise in particular fastness to washing, to alkali, to milling,.to transpiration and to sea water. They are also distinguished by their excellent solubility in water and the resistance to flocculation of these dyestuffs in hard water. The dyestuffs are also very fast to light, to steaming and are excellently whitedischargeable.
- dyestuffs are their excellent reserve for cotton, viscose and acetate yarn, polyethyleneglycol terephthalate and poly-aorylonitrile fibers (Terylene and Orlon). They are thus very suitable for dyeing blends of wool or synthetic polyamide fibers, especially nylon, with the aforesaid reserved fibers.
- Z is either hydrogen, chlorine, bromine or alkylwith maximally 4 carbon atoms
- Y is either hydrogen, chlorine, bromine, alkyl with maximally 4 carbon atoms, phenoxy, chlorophenoxy, bromophenoxy, methylphenoxy, phenylsulfonyl, meth ylphenyl-sulfonyl, chlorophenylsulfonyl, di(N- alkyl)- sulfamyl with a total of at most 8 carbon atoms, N- phenyl-N-lower alkyl-sulfamyl, or N-lower alkylsulfamyl, and 7 Y is either hydrogen, chlorine or bromine or lower alkyl,
- novel dyestuffs according to the invention are also distinguished from hitherto available wool dyes by their very good levelling power, which latter is, to a considerable extent, independent of the dyeing conditions used. Thus it is excellent over a wide pH range of the dyebath, in particular between about 2 and 6.5.
- Dye-stufiis according to the invention with optimal properties, among those described above, are the dyestuffs of the formula Z is either hydrogen or chlorine, Y is either hydrogen, chlorine or methyl, and Y is either hydrogen or chlorine.
- the coupling solution is stirred for several hours at 1020, the mineral acid is then bufiered by sprinkling in 30 parts of sodium carbonate, 100 parts of sodium chloride are added to the (VII)
- the dried dyesuif is a yellow powder which dissolves in hot water with a greenish yellow colour.- It dyes wool from an acetic acid bath at the boil in very level, greenish yellow shades which are fast to wet, alkali and light.
- EXAMPLE 2 ll II N HOaS 12.4 parts of 4,4'-diamino-1,l'-diphenylsulphone are tetrazotised as described in Example 1 and the tetrazo solution is added dropwise at Ill-20 to the solution of 25.3 parts of 1-(3'-sulphophenyl)-3-methyl-5-aminopyrazole and 50 parts of crystallised sodium acetate in 500 parts of water.
- the coupling solution is then stirred for several hours at -20", the mineral acid is buffered by sprinkling in 30 parts of sodium carbonate, the dyestuif solution is heated to 60 and then the disazo dyestuff is salted out with 100 parts of sodium chloride, the precipitate is filtered off under suction and dried in vacuo at 80.
- the dry dyestuif is a yellow powder which dissolves in hot water with a yellow colour.
- the dyestuff dyes wool from an acetic acid liquor on boiling in pure yellow shades which are fast to wet and light.
- EXAMPLE 3 15.8 parts'of 2,2'-diamino-4,4-dichloro-1,1-diphenylsulphone in 250 parts of glacial acetic acid are dissolved with 19 parts of concentrated sulfuric acid and the solution is tetrazotised at 5l0 while stirring well with a solution of 6.9 parts of sodium nitrite in 20 parts of water. After stirring for 1 hour at 510, the pale yellowish tetrazo solution is diluted with 500 parts of ice water and is then gradually poured at 0-10 into the solution of the sodium salt of 25.3 parts of l-(4-sulphopenyl)-3-methyl-5-aminopyrazole and 50 parts of crystallised sodium acetate in 600 parts of water. Coupling occurs immediately and the solution turns yellow. The coupling solution is stirred for several hours at 0l0, 100 parts of sodium chloride are added, the precipitated disazo dyestufl? is filtered off and dried.
- the dry dyestuff is a yellow powder which dissolves in hot water with a yellow colour.
- disulphonic acid in the form of the sodium salt, are dissolved in 500 parts of water, 6.9 parts of sodium nitrate are added and the solution is added dropwise at 0 to 5 while stirring to 30 parts of concentrated hydrochloric acid and 100 parts of ice. After stirring for 1 hour at 0 to 5, the excess nitrous acid is decomposed and the colourless disazo suspension is poured into the solution of 24.2 parts of l-(3',4-dichlorophenyl)-3-methyl-5-aminopyrazole in 400 parts by volume of ethanol. The couplingoccurs immediately and the solution turns yellow. 50 parts of crystallised sodium acetate are added to the coupling mixture which is then stirred for 6 hours at 0 to 10.
- the dyestufi solution is then diluted with 1000 parts of water, 200 parts of sodium chloride are added and the precipitated yellow disazo dyestuif is filtered otf under suction.
- the disazo dyestuff is washed with a 10% aqueous solution of sodium chloride and dried in vacuo at 80.
- the dyestulf in the form of a yellow powder, dissolves in hot water with a yellow colour. It dyes wool and synthetic polyamide fibers such as nylon from a boiling bath containing ammonium sulfate in level, pure, greenish yellow shades which are very fast to wet, alkali and light.
- N NHZ H2N-C N The dyestufif is identical with that described in Exampie 2.
- EXAMPLE 7 10 --01 o1 100 parts of previously well wetted wool are introduced at 40 into a dyebath which contains, in 3000 parts of water, 2 pans of the disazo dyestuft obtained according to example 2, 10 parts of Glaubers salt and 2 parts of 40% acetic acid. The bath is brought to the boil within 45 minutes and dyeing is performed at the boil for 90 minutes while moving the wool well. After rinsing and G 3 drying, a very level, pure yellow wool dyeing is obtained 0 a Ii 6 N N S02 N N 1i 1i 0H3 which is distinguished by very good fastness properties, NHTC ⁇ particularly to washing, alkali, milling and light.
- EXAMPLE 8 E038 803E 15 3.
- a disazo dyestuff of the formula 100 parts of previously well wetted wool are introduced at 40 C. into a dyeb ath which contains, in 3000 parts of I v water, 2 parts of the disazo dyestufi obtained according A dlsazo dyestuff of the formula to example 1 and 2 parts of sulphuric acid.
- the bath is brought to the boil within 45 minutes and dyeing is performed at the boil for 90 minutes while moving the wool 0 I! H II well. After rinsing and drying, a very level, pure yellow wool dyeing is obtained which is distinguished by very N N good fastness properties, particularly to washing, alkali, I I milling and light.
- Y is a member selected :from the group consisting of f N hydrogen, chlorine, bromine and alkyl with maximally 4 carbon atoms; phenoxy, chlorophenorry, brornophen-oxy, methylphenoxy, phenylsulphonyl, methylphenylsulphonyl, chlorophenylsulphonyl, Y is a member selected from the group consisting of hydrogen, chlorine, bromine, S0311 S0311 g gg fii g g g i g fig fs i References Cited in the file of this patent UNITED STATES PATENTS 2, 19 Exner Dec. 2, 1958 FOREIGN PATENTS 175.217 Germany Sept. 22, 1906
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Description
The present invention concerns new disazo dyestuffs, processes for the production thereof, a process for the dyeing of fibres containing natural or synthetic polyamide as well as, as industrial product, the material dyed with the aid of these dyestuffs.
It is well known that optimal wet fastness properties can be obtained on natural and synthetic polyamide fibers only when dyestuffs are used which draw from a neutral bath. This requires the observation of close limit conditions in particular in dyeing Wool and thus considerably complicates the dyeing with neutral-drawing dyestuffs. Moreover, the dyeing from a neutral bath has the drawback of disadvantageously influencing the physical properties of wool and even particularly damaging the latter. [C. L. Bird, The Theory and Practice of Wool Dyeing, pages 60-64, (1947).] It is, therefore, preferred to dye wool at its isoelectric point. However, this requires the use of dyestuffs drawing from a weakly acid to acid bath, and these dyestuffs suffer from the drawback that it is not possible to obtain dyeings with optimal wet fastness properties; if, in an attempt to solve this problem, neutral-drawing dyestuffs are used for dyeing from an acid bath, the resulting dyeings are not level.
I It is, therefore, an object of the present invention to provide a dyestuif class which affords a combination of the following two advantages: firstly, these dyestuffs must dye from a weakly acid to acid dyebath, and, secondly, they must yield dyeings of optimal wet fastness properties.
It has been found that, surprisingly, this combination of desirable properties is possessed by yellow disazo dyestufi'is according to this invention, which are obtained by coupling (a) One mole of a tetrazotised diamine of formula HzN NHg ll n (I) wherein n is 1 or, preferably, 2, and wherein the benzene rings A and B can be further substituted as explained below.
(b) With two moles of a l-phenyl-3-methyl-5-amino pyrazole the benzene ring of which can be further substituted as explained below to form a compound of formula wherein X is a water-solubilizing group which dissociates acidically in water, namely --COOH or, preferably -SO H (or their sodium, potassium or ammonium salts), .m is an integer ranging from 1 to 4, and preferably 2, n has the same meaning as in Formula I and either the aforesaid diamine of Formula I, or the 5-aminopyrazole coupling component, or both, contain the said United States Patent 0 ice substituent or substituents X, so that the dyestufi of Formula II above contains at least one of said watersolubilizing, acidically-dissociating groups, preferably a sulfonic acid group.
Apart from the latter group or groups, if such is present therein; the' benzene rings of the diamine of Formula I can be unsubstituted, or they can be substituted further with from one to preferably not more than two of the following substituents which are compatible with the process according to the invention, and are designated in this specification and in the appended claims as monovalent azo-compatible substituents and are alkyl with maximally 4 carbon atoms, preferably methyl or ethyl, chlorine, bromine, one or at most two sulfamyl or lower alkyl-sulfonyl. specification and in the appended claims designates alkyl :with from 1 to 4 carbon atoms.
The benzene ring (D, E) of the l-phenyl-3-methyl-5- amniopyraz ole used according to the invention as coupling component'can be unsubstituted, or it can be substituted-apart from the above-mentioned water-solubilizing substituent or substituents X, if it is desired that these be present in the coupling component-with one or two of the substituents Whose presence in the coupling component is compatible with the presence according to the present invention and which are designated in this specification and in the appended claims as monovalent coupling-compatible substituents, which are alkyl with maximally 4 carbon atoms, preferably methyl and ethyl, benzyl, methylbenzyl, chlorobenzyl, phenyl, methylphenyl, chlorophenyl, bromophenyl, methoxy, ethoxy, phenoxy, chlorophenoxy, bromophenoxy, sulfophenoxy, methylphenoxy, -SO NH N-monoand N-di-(lower alkyl)-sulfamyl respectively, N-alkyl-N-phenylsulfonyl with a total of maximally 10 carbon atoms, lower alkyl- ,sulfonyl,.phenylsulfonyl, methylphenylsulfonyl, chlorophenylsulfonyl, sulfophenylsulfonyl, fluorine, chlorine, bromine and cyano, with the proviso that in the end products the above defined total of water-solubilising groups which dissociate acidically in water, does not exceed the limits given above. I
The tetrazotised diamine of Formula I is coupled at a temperature of about -10 to C., and preferably at +10 to 25 C. with the 1-phenyl-3-methyl-5- arninopyrazole as defined above, advantageously in an aqueous-acid medium, while, if desired, gradually buffering the acid with an agent which raises the pH value, e.g. with an alkali metal salt of a low-molecular fatty acid such as sodium acetate and, if necessary, in the presence of organic solvents which are miscible with water such as low fatty alcohols, e.g. methanol or ethanol or low aliphatic ketones such as acetone.
A modification of the process for the production of (ii). N
disazo dyestuffs according to the invention consists in coupling, in an acid medium,one mol of a tetrazotised diamine of Formula I with two mols of a compound of Lower alkyl as used in this I wherein W is the oxo or imino group, to form a disazo dyestuif of Formula IV @NH-NH:
in an acid medium, to form a compound of Formula II. The new compounds of Formula I, and particularly They yield dyeings with the above-mentioned wet fastness properties, which comprise in particular fastness to washing, to alkali, to milling,.to transpiration and to sea water. They are also distinguished by their excellent solubility in water and the resistance to flocculation of these dyestuffs in hard water. The dyestuffs are also very fast to light, to steaming and are excellently whitedischargeable.
Another advantageous feature of these dyestuffs is their excellent reserve for cotton, viscose and acetate yarn, polyethyleneglycol terephthalate and poly-aorylonitrile fibers (Terylene and Orlon). They are thus very suitable for dyeing blends of wool or synthetic polyamide fibers, especially nylon, with the aforesaid reserved fibers.
Further details can be seen from the following nonlimitative examples. W Where not otherwise expressly stated, parts are given as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grams n is one of the numerals 1 and 2,
Z is either hydrogen, chlorine, bromine or alkylwith maximally 4 carbon atoms,
Y is either hydrogen, chlorine, bromine, alkyl with maximally 4 carbon atoms, phenoxy, chlorophenoxy, bromophenoxy, methylphenoxy, phenylsulfonyl, meth ylphenyl-sulfonyl, chlorophenylsulfonyl, di(N- alkyl)- sulfamyl with a total of at most 8 carbon atoms, N- phenyl-N-lower alkyl-sulfamyl, or N-lower alkylsulfamyl, and 7 Y is either hydrogen, chlorine or bromine or lower alkyl,
draw very satisfactorily on to fibers containing natural or synthetic polyamide from a weekly acid, for instance an acetic acid bath, and they produce very pure yellow dyeings which, in spite of the nature of the bath, are unexpectedly of excellent wet fastness properties and are very fast to light.
The novel dyestuffs according to the invention are also distinguished from hitherto available wool dyes by their very good levelling power, which latter is, to a considerable extent, independent of the dyeing conditions used. Thus it is excellent over a wide pH range of the dyebath, in particular between about 2 and 6.5.
Dye-stufiis according to the invention with optimal properties, among those described above, are the dyestuffs of the formula Z is either hydrogen or chlorine, Y is either hydrogen, chlorine or methyl, and Y is either hydrogen or chlorine.
12.4 parts of 3,3-diamino-1,1'-diphenylsulphone are dissolved at 35-40 in 500 parts of water and 40 partsof concentrated hydrochloric acid. The solution is then cooled to 0 to 5 and the diamine is tetrazotised by the dropwise addition of a solution of 6.9 parts of sodium nitrite in 20 parts of water. After stirring for 1 hour at 0-5", the excess nitrous acid is decomposed and the tetrazo solution is poured at 05 into a solution of the sodium salt of 28.8 parts of 1(6-chloro-3-sulfophenyl)- 3-methyl-5-aminopyrazole and parts of crystallised sodium acetate in 500 parts of water. Coupling occurs immediately and the solution turns yellow. The coupling solution is stirred for several hours at 1020, the mineral acid is then bufiered by sprinkling in 30 parts of sodium carbonate, 100 parts of sodium chloride are added to the (VII) The dried dyesuif is a yellow powder which dissolves in hot water with a greenish yellow colour.- It dyes wool from an acetic acid bath at the boil in very level, greenish yellow shades which are fast to wet, alkali and light.
EXAMPLE 2 ll II N HOaS 12.4 parts of 4,4'-diamino-1,l'-diphenylsulphone are tetrazotised as described in Example 1 and the tetrazo solution is added dropwise at Ill-20 to the solution of 25.3 parts of 1-(3'-sulphophenyl)-3-methyl-5-aminopyrazole and 50 parts of crystallised sodium acetate in 500 parts of water. The coupling solution is then stirred for several hours at -20", the mineral acid is buffered by sprinkling in 30 parts of sodium carbonate, the dyestuif solution is heated to 60 and then the disazo dyestuff is salted out with 100 parts of sodium chloride, the precipitate is filtered off under suction and dried in vacuo at 80.
The dry dyestuif is a yellow powder which dissolves in hot water with a yellow colour. The dyestuff dyes wool from an acetic acid liquor on boiling in pure yellow shades which are fast to wet and light.
EXAMPLE 3 15.8 parts'of 2,2'-diamino-4,4-dichloro-1,1-diphenylsulphone in 250 parts of glacial acetic acid are dissolved with 19 parts of concentrated sulfuric acid and the solution is tetrazotised at 5l0 while stirring well with a solution of 6.9 parts of sodium nitrite in 20 parts of water. After stirring for 1 hour at 510, the pale yellowish tetrazo solution is diluted with 500 parts of ice water and is then gradually poured at 0-10 into the solution of the sodium salt of 25.3 parts of l-(4-sulphopenyl)-3-methyl-5-aminopyrazole and 50 parts of crystallised sodium acetate in 600 parts of water. Coupling occurs immediately and the solution turns yellow. The coupling solution is stirred for several hours at 0l0, 100 parts of sodium chloride are added, the precipitated disazo dyestufl? is filtered off and dried.
The dry dyestuff is a yellow powder which dissolves in hot water with a yellow colour. *It dyes wool in the presence of ammonium sulfate at the boil in pure yellow very level shades which are fast to wet and light. The bath is well exhausted.
and the tetrazo-solution is coupled at 10-15" with the solution of the sodium salt of 25.3 parts of 1(3'-sulphophenyl) -3-methyl-5-aminopyrazole and 50 parts of sodium acetate in 500 parts of water. The mixture is stirred for several hours at l0-l5 and then the mineral acid is buffered by sprinkling in 40 parts of sodium carbonate whereupon the disazo dyestuif partly precipitates. The precipitation of the dyestuff is completed by the addition of 100 parts of sodium chloride whereupon it is then EXAMPLE 5 20.4 parts of 3,3'-diamino-1,l-diphenylsulphone-4,4'-
disulphonic acid, in the form of the sodium salt, are dissolved in 500 parts of water, 6.9 parts of sodium nitrate are added and the solution is added dropwise at 0 to 5 while stirring to 30 parts of concentrated hydrochloric acid and 100 parts of ice. After stirring for 1 hour at 0 to 5, the excess nitrous acid is decomposed and the colourless disazo suspension is poured into the solution of 24.2 parts of l-(3',4-dichlorophenyl)-3-methyl-5-aminopyrazole in 400 parts by volume of ethanol. The couplingoccurs immediately and the solution turns yellow. 50 parts of crystallised sodium acetate are added to the coupling mixture which is then stirred for 6 hours at 0 to 10. The dyestufi solution is then diluted with 1000 parts of water, 200 parts of sodium chloride are added and the precipitated yellow disazo dyestuif is filtered otf under suction. The disazo dyestuff is washed with a 10% aqueous solution of sodium chloride and dried in vacuo at 80.
The dyestulf, in the form of a yellow powder, dissolves in hot water with a yellow colour. It dyes wool and synthetic polyamide fibers such as nylon from a boiling bath containing ammonium sulfate in level, pure, greenish yellow shades which are very fast to wet, alkali and light.
EXAMPLE 4 If, instead of the disazo and coupling components given OHa-C-ON=N-C SO-N=N-fiC-GH: V E
ii ii-NH, Nut-o 1H1 I so3H Honsll.6 parts of 4,4-diamino-l,l'-diphenylsulphoxide are in the previous analogous examples, corresponding tetrazotised under the conditions described in Example 1 amounts of the components give'riin the following table 10 oured dyestuff solution and the whole is boiled for 1 hour. 2. A disazo dyestufi": of the formula The solution becomes strongly yellow coloured when the condensation to the disazo dyestufi of the above formula occurs. After cooling the dyestufi solution to 20, the D -Q dyestufi formed is salted out with 200 parts of sodium 5 chloride, filtered off, washed with a 5% aqueous sodium OH3 CO N=N chloride solution and dried. N NHZ H2N-C N The dyestufif is identical with that described in Exampie 2.
EXAMPLE 7 10 --01 o1 100 parts of previously well wetted wool are introduced at 40 into a dyebath which contains, in 3000 parts of water, 2 pans of the disazo dyestuft obtained according to example 2, 10 parts of Glaubers salt and 2 parts of 40% acetic acid. The bath is brought to the boil within 45 minutes and dyeing is performed at the boil for 90 minutes while moving the wool well. After rinsing and G 3 drying, a very level, pure yellow wool dyeing is obtained 0 a Ii 6 N N S02 N N 1i 1i 0H3 which is distinguished by very good fastness properties, NHTC\ particularly to washing, alkali, milling and light. N N
In the same way, the dyestufis given in all the other examples produce fast, level wool dyeing.
EXAMPLE 8 E038 803E 15 3. A disazo dyestuff of the formula 100 parts of previously well wetted wool are introduced at 40 C. into a dyeb ath which contains, in 3000 parts of I v water, 2 parts of the disazo dyestufi obtained according A dlsazo dyestuff of the formula to example 1 and 2 parts of sulphuric acid. The bath is brought to the boil within 45 minutes and dyeing is performed at the boil for 90 minutes while moving the wool 0 I! H II well. After rinsing and drying, a very level, pure yellow wool dyeing is obtained which is distinguished by very N N good fastness properties, particularly to washing, alkali, I I milling and light.
In the same way, the dyestuffs given in all the other examples produce fast, level wool dyeings.
What is claimed is: 1. A member selected from the group consisting of SOaH 03H disazo dyestuffs of the formula OH (}-fiN=N N=N-(H --o-o11, /C NH2 Dig K 1% N (0)n z N/ Y Y1 Y Y;
and the sodium, potassium and ammonium salts thereof, 5, A di d t fl of the f r l wherein Y Z is a member selected from the group consisting of GH3C-CN=N so: N=NC-CGH hydrogen, chlorine, bromine and alkyl with maximal- U, i NH ii I! l 4 carbon atoms NHTC N Y 1 01 Y is a member selected :from the group consisting of f N hydrogen, chlorine, bromine and alkyl with maximally 4 carbon atoms; phenoxy, chlorophenorry, brornophen-oxy, methylphenoxy, phenylsulphonyl, methylphenylsulphonyl, chlorophenylsulphonyl, Y is a member selected from the group consisting of hydrogen, chlorine, bromine, S0311 S0311 g gg fii g g g i g fig fs i References Cited in the file of this patent UNITED STATES PATENTS 2, 19 Exner Dec. 2, 1958 FOREIGN PATENTS 175.217 Germany Sept. 22, 1906
Claims (1)
1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF DISAZO DYESTUFFS OF THE FORMULA
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4083688A (en) * | 1968-04-24 | 1978-04-11 | Ciba-Geigy Ag | Disazo pyrazolyl dyed polyester fibers |
US5545725A (en) * | 1992-09-29 | 1996-08-13 | Ciba-Geigy Corporation | Disazo dyes consisting of two monoazo dyes contaning a 1-phenyl-5-amino pyrazole coupling component and connected by a bridge member |
US20030213405A1 (en) * | 2002-01-15 | 2003-11-20 | Toru Harada | Ink, ink jet recording method and azo compound |
EP1388579A2 (en) * | 2002-08-06 | 2004-02-11 | Fuji Photo Film Co., Ltd. | Ink, ink-jet-recording method and bis-azo compound |
EP2307508B1 (en) * | 2008-07-23 | 2018-09-05 | Archroma IP GmbH | Acid dyes |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE175217C (en) * | ||||
US2862919A (en) * | 1956-05-19 | 1958-12-02 | Bayer Ag | Disazo dyestuffs |
-
0
- US US3124566D patent/US3124566A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE175217C (en) * | ||||
US2862919A (en) * | 1956-05-19 | 1958-12-02 | Bayer Ag | Disazo dyestuffs |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4083688A (en) * | 1968-04-24 | 1978-04-11 | Ciba-Geigy Ag | Disazo pyrazolyl dyed polyester fibers |
US5545725A (en) * | 1992-09-29 | 1996-08-13 | Ciba-Geigy Corporation | Disazo dyes consisting of two monoazo dyes contaning a 1-phenyl-5-amino pyrazole coupling component and connected by a bridge member |
US20030213405A1 (en) * | 2002-01-15 | 2003-11-20 | Toru Harada | Ink, ink jet recording method and azo compound |
US6878196B2 (en) | 2002-01-15 | 2005-04-12 | Fuji Photo Film Co., Ltd. | Ink, ink jet recording method and azo compound |
EP1388579A2 (en) * | 2002-08-06 | 2004-02-11 | Fuji Photo Film Co., Ltd. | Ink, ink-jet-recording method and bis-azo compound |
EP1388579A3 (en) * | 2002-08-06 | 2004-05-19 | Fuji Photo Film Co., Ltd. | Ink, ink-jet-recording method and bis-azo compound |
US20040129172A1 (en) * | 2002-08-06 | 2004-07-08 | Fuji Photo Film Co., Ltd. | Ink, ink-jet-recording method and bis-azo compound |
US6923855B2 (en) | 2002-08-06 | 2005-08-02 | Fuji Photo Film Co., Ltd. | Ink, ink-jet-recording method and bis-azo compound |
EP2307508B1 (en) * | 2008-07-23 | 2018-09-05 | Archroma IP GmbH | Acid dyes |
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