US1843634A - Metal compounds of azo-dyestuffs and process of making same - Google Patents
Metal compounds of azo-dyestuffs and process of making same Download PDFInfo
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- US1843634A US1843634A US345588A US34558829A US1843634A US 1843634 A US1843634 A US 1843634A US 345588 A US345588 A US 345588A US 34558829 A US34558829 A US 34558829A US 1843634 A US1843634 A US 1843634A
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- 150000002736 metal compounds Chemical class 0.000 title description 16
- 238000000034 method Methods 0.000 title description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 239000000975 dye Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000011651 chromium Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- 229940001593 sodium carbonate Drugs 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229920002955 Art silk Polymers 0.000 description 7
- 150000008049 diazo compounds Chemical class 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 229910021563 chromium fluoride Inorganic materials 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 5
- 235000013311 vegetables Nutrition 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 229960000355 copper sulfate Drugs 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000004627 regenerated cellulose Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 244000172533 Viola sororia Species 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- QXYMVUZOGFVPGH-UHFFFAOYSA-N picramic acid Chemical compound NC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O QXYMVUZOGFVPGH-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- AQSOTOUQTVJNMY-UHFFFAOYSA-N 7-(dimethylamino)-4-hydroxy-3-oxophenoxazin-10-ium-1-carboxylic acid;chloride Chemical compound [Cl-].OC(=O)C1=CC(=O)C(O)=C2OC3=CC(N(C)C)=CC=C3[NH+]=C21 AQSOTOUQTVJNMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940013688 formic acid Drugs 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- LHYQAEFVHIZFLR-UHFFFAOYSA-L 4-(4-diazonio-3-methoxyphenyl)-2-methoxybenzenediazonium;dichloride Chemical compound [Cl-].[Cl-].C1=C([N+]#N)C(OC)=CC(C=2C=C(OC)C([N+]#N)=CC=2)=C1 LHYQAEFVHIZFLR-UHFFFAOYSA-L 0.000 description 1
- QYFYIOWLBSPSDM-UHFFFAOYSA-N 6-aminonaphthalen-1-ol Chemical compound OC1=CC=CC2=CC(N)=CC=C21 QYFYIOWLBSPSDM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101100243951 Caenorhabditis elegans pie-1 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000154870 Viola adunca Species 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940108928 copper Drugs 0.000 description 1
- ICIDZHMCYAIUIJ-UHFFFAOYSA-N dinaphthalen-1-yldiazene Chemical compound C1=CC=C2C(N=NC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ICIDZHMCYAIUIJ-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000012047 saturated solution 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/26—Disazo or polyazo compounds containing chromium
-
- 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
- C09B33/18—Trisazo or higher polyazo dyes
- C09B33/22—Trisazo dyes of the type A->B->K<-C
-
- 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
-
- 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/28—Disazo or polyazo compounds containing copper
Definitions
- the present invention relates to new and valuable metal compounds of azo-dyestuffs derivmg from metals of atomic weights ranging from 52 to 58,7. These metal com, pounds may contain either one metal'alone or several metals. In the latter case one or several metals may also not belong'to the above mentioned range of atomic weights.
- the dyestuffs according to the present invention are made by treating the poly-aZo-dyestuff of the general formula in which R and R are aryl residues, from which at least the one of these contains morda'nt bindinggroup.
- the sulfogroups being in meta-positionto the OH- groups, further in which, the two azo-groups are linked in ortho-position to the OH- groups and in which at most one OH-group stands 1n 8-pos1t1on,,w1th agents yielding metals of atomic Weights ranging from 52 to 58.7,.these agents being chosen in such a- Way that either one or several metals enter the dyestufi' molecule whereby in the latter case other metals may alsoenter the dyestufi molecule.
- the treatment may beapplied in the course ofthe production of the said polyazo-dy'estufi' or to the finished dyestuff, either in the fiber, in the dye-bath or in substance.
- These dy'estufi's do not dye the artificialsilks from cellulose esters or cellulose ethers.
- HOaS- Eaaamfole 2 In presence of sodium carbonate 53,5 parts of the dyestuif 2: 1-azonaphthalen e-5 5- dihydroxy-2-amino-7 7-disulfonic acid are coupled with lO parts of diazotized picramic acid and the azo-dyestuff of the formula powder which dissolves in water, dilute alkalies and concentrated sulfuric acid to greenish-grey solutions. It dyes cotton, viscose and silk fast uniform green-grey tints.
- Example 4 54 parts of thesodium salt of the monoazo-dyestuff obtained in acetic acid solution from dia-zotized 2-amino-5-hydroxynaphtha- 'lene-7-sulfonic acid are dissolved in 600 parts of Water and this solution is mixed with parts of sodium carbonate. The diazo-compound from 32 parts of anthranilic acid is then added and the dyes'tulf formed after some time is isolated. By boiling the dyestuf't' of the formula OOH parts of 4-chloro-2-amino l-phenol and after thus formed with; a solution of chromium some time the diaZo-compound from 19,9 fluoride containing 25-parts of Cr o in 3000 parts of picramic acid.
- the chro; azo-dyestufi thus produced of the-formula mium compound of the new dyestufl' is is filtered and dissolved in 4000 parts of hot water. There are then added 30 parts of @150 in the form of a chromium fluoride solution and the whole is heated for 24 hours in a reflux apparatus.
- Example 5 54 parts of the mono-azo dyestuif obtained from diazotized 2-amino 5-hydroxynaphthalene-7-sulfonic acid and 2-amino-5-hydroxynaphthalene-'Y-sulfonic acid (acetic acid coupled) are dissolved. in 500 parts of water and combined in the presence of sodium carbonate with the diazo-conipound from 22,3 parts of l-chloro 2 amino 1 phenol 6 sulfonic acid.
- the dyestuff of the formula By treating the azo 'dyestufi of the first paragraph of'this example with a solution of 25 sloin on parts of copper sulfate and 20 parts of Cr 3 in the form of a chromium salt (fluoride,
- the metal compounds deriving from a group of metaljstheatomic weights of which range general formula in which R and R are benzene radicles, from which at least the one of these contains a mordant binding group in ortho-position to the -N N- group, in which one of the ws and one of the ys stand for an OH-group and the other w and the other 3/ for a hydrogen atom, one of the ws and one of the zs represent a SO H-group, and the other a and the other a a hydrogen atom, the sulfo-groups being in meta-position to the OH-groups, further in which the two azogroups are linked in ortho-position to the OH-groups, and in which at most one OH- group stands in 8-position, which products are when dry dark colored powders, soluble in water and dilute alkalies to blue to grey-blue and grey solutions and in concentrated sulfuric acid to blackish-
- the OH-groups further in which the two azogroups are linked inortho-position to the OI-I-groups, and in which at most one UH- vgroup stands in 8-position, containing besides a group of metals the atomic weights of which range from 52 to 58.? still ther metals which products are when dry dark col.- ored powders, soluble in water and dilute alkalies to blue to grey-blueand grey soluin which R and R are benzene radicles, contions and in concentrated sulfuric'acid to blackish-blue to blue and grey solutions, and dyeing vegetable fiber and especially artificial silk from so-called regenerated cellulose fast violet to blue and grey tints.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
- "FRITZ srnAUB AND w Patented Feb. 2, 1932 if NITEID STATES PATENT OFFICE FIRM sooIE'rY F ALTER Anne-Ran, on BASEL, swrrznnnnlvn, AssIeNoRs r0 THE CHEMICAL INDUSTRY IN BASLE, or BASE-L, SWITZERLAND METAL COMPOUNDS 0F AZO-DYESTUFF S AND I ROCESS OF MAKING SAME .iNoIir aw-ingx' Application filed March s, 1929, Serial No. 345,588, and. in Switzerland March 10, 1928.
The present invention relates to new and valuable metal compounds of azo-dyestuffs derivmg from metals of atomic weights ranging from 52 to 58,7. These metal com, pounds may contain either one metal'alone or several metals. In the latter case one or several metals may also not belong'to the above mentioned range of atomic weights. The dyestuffs according to the present invention are made by treating the poly-aZo-dyestuff of the general formula in which R and R are aryl residues, from which at least the one of these contains morda'nt bindinggroup. in ortho-position to jesithe N=N- group, and in whichone ofthe ws and one of the ys stand foran OH- group and the other to and the other 1 for a hydrogen atom, one of the ocs and one of the es represent a SO l-l-group and the otherv go a? andfthe other a a hydrogen atom, the sulfogroups being in meta-positionto the OH- groups, further in which, the two azo-groups are linked in ortho-position to the OH- groups and in which at most one OH-group stands 1n 8-pos1t1on,,w1th agents yielding metals of atomic Weights ranging from 52 to 58.7,.these agents being chosen in such a- Way that either one or several metals enter the dyestufi' molecule whereby in the latter case other metals may alsoenter the dyestufi molecule. The treatment may beapplied in the course ofthe production of the said polyazo-dy'estufi' or to the finished dyestuff, either in the fiber, in the dye-bath or in substance.
5 Tliedyestuffs of the above formula may be made, for example, by coupling twomolecu- L lar proportions of-diazo-compound-s, at least r the one component of which contains a mordant binding group in'ortho-position to the 50, l l=l l group, with a mono-azo-dyestuff which is obtained by coupling a diazotized amino-naphthol of the general formula in vvhich the one wrepresents one OHegroup and the other to a hydrogen atom, the one a:
a, SO H-group and the other m a hydrogen atom, and in which the sulfo-group stands in meta-position to the OH-group, in weak acid medium with an amino-naphthol of the general formula in which the two ys and the two .es have the same meaning as above indicated, these two ammo-naphthols being chosen 1n such a manner that the resulting azo-dyestuffs contain at most in one 8-position one OH-group. The metal compounds of the azo-dye'stufi's of the above explained general formula derivingfrom metals of atomic Weights rang from the .mono-azo-dyestufi produced by coupling'one molecular proportion of diazotized 2 amino 5 -hydroxynapl1thalene-7-su1- fonic acid with a second molecular proportion of the same aminonaphthol-sulfonic acid in a feebly acid medium. These dy'estufi's, however, do not dye the artificialsilks from cellulose esters or cellulose ethers.
The following examples illustrate the invention, the parts being by weight Edam/pic 1 23,9 parts of diazotized 2-amino-5-hydroxynaphthalene-7-sulfonic acid are coupled in the presence of acetic or formic-acid with 23,9 parts of the same aminonaphthol-sulfonic acid; when coupling is complete the azo-compound thus formed is combined after addition of sodium carbonate until alkaline reaction occurs, with the diaZo-compound from 28,7 parts of l-chloro-2-amino-1-phe- 1101. In the course of some hours the dyestulf of the formula is formed and then filtered. It is dissolved in 300 parts of water and mixed with asolu- N02 on tion of 15.5 parts of Cr O in caustic potash and glycerine which is made according to German patent specification No. 866,095 of 21st February 1921. The whole is heated for 1 116 hours in a reflux apparatus and then neutralized with dilute acid. The dyestuff thus produced is salted out. When dry this chromium compound is a dark powder, dissolving in water and dilute alkalies to a greyblue coloration and in concentrated sulfuric acid to a blackish-blue solution. Thevegetable fiber and artificial silk are dyed in neutral or alkaline baths containing Glaubers salt grey tints having good levelling properties. A very similar d'yestufi? is obtained if the chroming process is conducted with chromium fluoride. i
If in the above example a part of the chromic hydroxide be replaced by nickel hydroxide, more reddish tints are obtained. For example boiling is conducted with a solution containing nickel hydroxide according to 9,3
HOaS- Eaaamfole 2 In presence of sodium carbonate 53,5 parts of the dyestuif 2: 1-azonaphthalen e-5 5- dihydroxy-2-amino-7 7-disulfonic acid are coupled with lO parts of diazotized picramic acid and the azo-dyestuff of the formula powder which dissolves in water, dilute alkalies and concentrated sulfuric acid to greenish-grey solutions. It dyes cotton, viscose and silk fast uniform green-grey tints.
If the conditions are altered so that 7,6 parts of (E 0 in the form of chromium flu- SO33 N=N OH 1-1 N02,
is isolated after 15 hours. It is dissolved in The dyestuff oride solution are used, heating conducted for 24% hours and there is then added a saturated solution of 30 parts of crystallized cop per sulfate in water, the dystufi subsequently isolated as usual dyes cotton and viscose fast uniform blue-grey tints.
If two molecules of diazotized 5-nitro-2- amino-l-phenol are used instead of two molecules of diazotized picramic acid and the dyestuff is treated with agents yielding copper and then'with those yielding chromium, adark'powderis. obtained which dissolves in water and dilute alkalies to blue-grey solu tions and dyes cotton in an alkaline bathcon-v 2 1" -;azonaphthalene 5' dihydroxy 2 m amino-7 7-disulfonic acid dyes viscose greengrey tints.
E wample 3 58,5 parts of the dyestuff 2: 1-az0naphtha lone-5:5 dihydroxy-2-amino-7:7'disulfonic acid are dissolved together with parts of calcined sodium carbonate in 600 arts of Water. Into this solution, at 6-8 there is introduced the diazo-compound from 14,4
parts of crystallized copper sulfate and after some minutes, a new dyestufl. When this is dry it is a dark powder which dissolves in water and dilute alkalies to grey solutions and dyes cotton and artificialsilk uniform grey tints in a bath containing Glaubers salt and neutral or alkaline.
Example 4 54 parts of thesodium salt of the monoazo-dyestuff obtained in acetic acid solution from dia-zotized 2-amino-5-hydroxynaphtha- 'lene-7-sulfonic acid are dissolved in 600 parts of Water and this solution is mixed with parts of sodium carbonate. The diazo-compound from 32 parts of anthranilic acid is then added and the dyes'tulf formed after some time is isolated. By boiling the dyestuf't' of the formula OOH parts of 4-chloro-2-amino l-phenol and after thus formed with; a solution of chromium some time the diaZo-compound from 19,9 fluoride containing 25-parts of Cr o in 3000 parts of picramic acid. After16 hours the partsof water during 15-20 hours, the chro; azo-dyestufi thus produced of the-formula mium compound of the new dyestufl' is is filtered and dissolved in 4000 parts of hot water. There are then added 30 parts of @150 in the form of a chromium fluoride solution and the whole is heated for 24 hours in a reflux apparatus. Thenew dyestuif can he salted out with common salt. lVhen dry it is a dark powder which dissolves in water and dilute alkalies to greenish-gray solutions and dyes cotton andartificial silk fast uni: form grey tints in a bath containing Glaubers salt and neutral or alkaline with sodium car bonate.
If the azo-dyestulf is dissolved in 4000 parts of water and the solution mixed with only 7,6 parts of Gr O in the form of chromium fluoride solution and then heated for 24 hours at the boil, there is obtained, after addition of 30 formed. When dry'the same is a darkpowchar, dissolving in water and diulte alkalies to'a' violet coloration, and in concentrated sulfuric acid to a grey-blue solution. The vegetable fiber is dyed violet tints in a neutral or alkaline bath with sodium carbonate. 4
By treating the az0-dyestuif of the first paragraph of this example with asolution of 25 parts of copper sulfate and 20 parts of 01 203111 the form of chromium fluoride, there are obtained metal compounds with similar dyeing properties yielding red-violet tints.
Example 5 54 parts of the mono-azo dyestuif obtained from diazotized 2-amino 5-hydroxynaphthalene-7-sulfonic acid and 2-amino-5-hydroxynaphthalene-'Y-sulfonic acid (acetic acid coupled) are dissolved. in 500 parts of water and combined in the presence of sodium carbonate with the diazo-conipound from 22,3 parts of l-chloro 2 amino 1 phenol 6 sulfonic acid.
' and then coupled with the diazo-compound 01 1103s +N=N l E) s 2 from 15.7 parts of anthranilic acid. The dyestufi is precipitated by addition of common salt.
The dyestuff of the formula By treating the azo 'dyestufi of the first paragraph of'this example with a solution of 25 sloin on parts of copper sulfate and 20 parts of Cr 3 in the form of a chromium salt (fluoride,
acetate), there. are obtained violet or blueviolet dyeing metal compounds with similar dyeing properties as the chromium compound.
Ewample 6 23,9 parts of diazotized 2-a1nino-5-'hydr0xynaphthalene-'Z-sulfonic acid are coupled in the presence of acetic or formic acid with 28,9 parts of 2-amino-5-hydroxynaphthalene-7- sulfonic acid; when coupling is complete the solution is rendered alkaline by addition of 60 parts of sodium carbonate. It is then added to the diazo-compound from 1%,?) parts of 4c-chloro-2-amino-l-phenol and after this compound has disappeared, the diazo-compound from 22,5 parts of p-nitraniline-osulfonic acid is then further introduced into the solution. After a short time the whole is heated and thedyestufi of the formula NIZN thus produced is precipitated by means of common salt. It is dissolved in 3000 parts of water and heated for 36 hours in a reflux apparatus with 15 parts of Cr O in the form of chromium fluoride. 'The chromiumcompound is separated by addition of common salt. When dry it'is a blackish powder, dissolving in water and dilute alkalies to blue solutions in concentrated sulfuric acid to a blackishblue solution. Cotton and viscose flOOH are dyed grey level tints in a neutral bath or i in a hath made alkaline by addition of sodium carbonate.
What we claim is 1. A manufacture of new metal compounds of azo-dyestuffs by treating arpoly-azo-dyestuff of the general formula in which R and R are benzene radicles from which at least the one of these contains a mordant binding group in ortho-position to the -N=N- group, in which one of the ws and one of the ys stand for an Oil-group and the other 10 and the other y for a hydrogen atom, one of the ws and one of the zs represent a SO H-group, and the other w and the other e a hydrogen atom, the sulfo-groups being in meta-position to the Oil-groups, further in which the two azo-groups are linked in ortho-position to the OH-groups, and in which at most one Old-group stands in 8- position, with a group of agents yielding metals the atomic weights of which range from 52 to 58.7.
2. A manufacture of new metal compounds of azo-dyestuifs by treating a poly-azo-dyestuff of the general formula 1 in which R and R are benzene radicles, from which at least the one of these contains a in ortho-position to the OH-groups, and in Which at most one OH-group stands in 8- position, with a group of agents yielding vmetals the atomic weights of which range from 52 to 58.7, together with agents yielding other metals which are capable to form with the lake forming groups of the poly-azo-dyestufi complex metal compounds. I r
3. A manufacture of new metal compounds of azo-dyestuifs bytreating a poly azo-dyestuffof the general formula in which R and R are benzene radicles, containing a mordant binding group in orthoposition to the N=N group, in which one of the 'ws and one of the ys stand for an OH-group and the other on and the other y for a hydrogen atom, one of the ms and one of the 2s represent a SO H-group, and the other 00 and the other a a hydrogen atom, the 'sul fo-groups being in meta-position to the OH-groups, further in which the two azogroups are linked in o rthoposition to the OH-groups, and in which at most'one OH- group stands in 8-position, with agents yield ing chromium.
i. A manufacture of new metal "compounds of azo-dyestuffs by treating a polya'zo-dyestuif of the general formula v Y in which B and R are benzene radicles,
containing ajhydroxy-group in OIlZhO-POSI- tion to the 'N=N group, in which one of the ws and'one of the ys'stand for an OH- group andv the other w and the other y for a hydrogen atom, one of the ws and one of the zs represent a 'SO HgI011p, and the other 00 and the other 2 a hydrogen atom, the sulfo-groups being in meta-position to the OHgroups, further in which the two azogroups are linked in ortho-positiontjo the OH-groups, and in which at most one OH- group stands in 8-position, with agents yielding chromium. V
5. A manufacture of new metal compounds of azo-dyestufis'by treating a polyazo-dyestuff of the general formula in whichR and R are benzene radicles, containing a hydroxy-group in ortho-position to the N=N group, with agents yielding chromium.
6. A manufacture of new metal compounds of azo-dyestufi's by treating a polya zoedyestuif of the formula 1 V j j in which R and R are benzene radicles, containing a hydroXy-group in ortho-position to the, N=N- group, with salts 'of the trivalent chromium. L
7. As -new*productsof manufacture the metal compounds deriving from a group of metaljstheatomic weights of which range general formula in which R and R are benzene radicles, from which at least the one of these contains a mordant binding group in ortho-position to the -N=N- group, in which one of the ws and one of the ys stand for an OH-group and the other w and the other 3/ for a hydrogen atom, one of the ws and one of the zs represent a SO H-group, and the other a and the other a a hydrogen atom, the sulfo-groups being in meta-position to the OH-groups, further in which the two azogroups are linked in ortho-position to the OH-groups, and in which at most one OH- group stands in 8-position, which products are when dry dark colored powders, soluble in water and dilute alkalies to blue to grey-blue and grey solutions and in concentrated sulfuric acid to blackish-blue to blue and grey solutions, and dyeing vegetable fiber and especially artificial silk from socalled regenerated cellulose fast violet to blue and grey tints.
8. As new products of manufacture the metal compounds of the azo-dyestufi's of the general formula in which R and R are'benzene radicles,
- from which as least the one of these contains a mordant binding group in ortho-position to the N=N group, in which one of the ws and one of the ys stand for an OH- group and the other w and the other y for a hydrogen atom, one of the ws and one of the zs represent a SO H-group, and the other a; and the other 2 a hydrogen atom,
the sulfo-groups beingin meta-position to .v
the OH-groups, further in which the two azogroups are linked inortho-position to the OI-I-groups, and in which at most one UH- vgroup stands in 8-position, containing besides a group of metals the atomic weights of which range from 52 to 58.? still ther metals which products are when dry dark col.- ored powders, soluble in water and dilute alkalies to blue to grey-blueand grey soluin which R and R are benzene radicles, contions and in concentrated sulfuric'acid to blackish-blue to blue and grey solutions, and dyeing vegetable fiber and especially artificial silk from so-called regenerated cellulose fast violet to blue and grey tints.
9. As new products of manufacture the metal compounds of the azo-dyestufis of the general formula:
in which R and R are benzene radicles, containing a hydroxy group in ortho-position to the --N=N- group, in which one of the ws and one of the ys stand for an OH-group and the other 10 and the other 3 for a hydrogen atom', one of the ms and one of the 2s represent a sO H-group, and the other a: and the other 2 a hydrogen atom, the'sulfogroups being in meta-position to the OH- groups, further in which the two azo-groups are linked in ortho-position to the OH- groups, and in which at most one OH-group stands in 8-position, containing chromium, which products are when dry dark colored powders, soluble in water and dilute alkalies 'to blue to grey-blue and grey solutions and in concentrated sulfuric-acid to blackish- .blue to blue and grey solutions, and dyeing vegetable fiber and especially artificial silk from so-called regenerated cellulose fast blue and grey tints.
10. As new products of manufacture the metal compounds of the azo-dyestufis of the general formula taining a hydroxy-group in ortho-position to the N=N group, which products contain chromium, forming when dry dark colored powders, soluble in water and dilute alkalies to blue to grey-blue and grey solutions, and
in concentrated sulfuric acid to blackishblue to blue and grey solutions, and dyeing 11. As a new product of manufacture the chromium compound of the azo-dyestuff of the formula Which product forms when dry a dark colored powder, soluble in Water and dilute alkalies to grey-blue solutions, in concentrated sulfuric acid to a blackish-blue solution and dyeing vegetable fiber and especially artificial silk from so-called regenerated cellulose fast grey tints.
In Witness Whereof We have hereunto signed our names this 21st day of February,
FRITZ STRAUB. WALTER ANDERAU.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH307705X | 1928-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1843634A true US1843634A (en) | 1932-02-02 |
Family
ID=4493250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US345588A Expired - Lifetime US1843634A (en) | 1928-03-10 | 1929-03-08 | Metal compounds of azo-dyestuffs and process of making same |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US1843634A (en) |
| CH (5) | CH133478A (en) |
| GB (1) | GB307705A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2891047A (en) * | 1955-08-20 | 1959-06-16 | Bayer Ag | Metal containing polyazo dyestuffs |
| US2984635A (en) * | 1957-06-03 | 1961-05-16 | Monsanto Chemicals | Composition comprising alumina particles coated with polymer of ethylenically unsaturated monomer |
-
1928
- 1928-03-10 CH CH133478D patent/CH133478A/en unknown
-
1929
- 1929-03-08 US US345588A patent/US1843634A/en not_active Expired - Lifetime
- 1929-03-11 GB GB7920/29A patent/GB307705A/en not_active Expired
- 1929-06-01 CH CH144215D patent/CH144215A/en unknown
- 1929-06-01 CH CH144212D patent/CH144212A/en unknown
- 1929-06-01 CH CH144213D patent/CH144213A/en unknown
- 1929-06-01 CH CH144214D patent/CH144214A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2891047A (en) * | 1955-08-20 | 1959-06-16 | Bayer Ag | Metal containing polyazo dyestuffs |
| US2984635A (en) * | 1957-06-03 | 1961-05-16 | Monsanto Chemicals | Composition comprising alumina particles coated with polymer of ethylenically unsaturated monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CH144213A (en) | 1930-12-15 |
| GB307705A (en) | 1930-06-11 |
| CH133478A (en) | 1929-06-15 |
| CH144214A (en) | 1930-12-15 |
| CH144212A (en) | 1930-12-15 |
| CH144215A (en) | 1930-12-15 |
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