US679172A - Orange dye and process of making same. - Google Patents
Orange dye and process of making same. Download PDFInfo
- Publication number
- US679172A US679172A US5394301A US1901053943A US679172A US 679172 A US679172 A US 679172A US 5394301 A US5394301 A US 5394301A US 1901053943 A US1901053943 A US 1901053943A US 679172 A US679172 A US 679172A
- Authority
- US
- United States
- Prior art keywords
- primulin
- acid
- orange
- sulfonic acid
- pyrazolone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 6
- 239000001048 orange dye Substances 0.000 title description 5
- YDIKCZBMBPOGFT-PWUSVEHZSA-N Malvidin 3-galactoside Chemical compound [Cl-].COC1=C(O)C(OC)=CC(C=2C(=CC=3C(O)=CC(O)=CC=3[O+]=2)O[C@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)=C1 YDIKCZBMBPOGFT-PWUSVEHZSA-N 0.000 description 16
- PXUQTDZNOHRWLI-QOPOCTTISA-O Primulin Natural products O(C)c1c(O)c(OC)cc(-c2c(O[C@H]3[C@H](O)[C@@H](O)[C@@H](O)[C@H](CO)O3)cc3c(O)cc(O)cc3[o+]2)c1 PXUQTDZNOHRWLI-QOPOCTTISA-O 0.000 description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- -1 phenyl-pyrazolone carboxylic acid Chemical class 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000000344 soap Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNICRWVQYFRWDK-UHFFFAOYSA-N naphthalen-2-ylhydrazine Chemical compound C1=CC=CC2=CC(NN)=CC=C21 VNICRWVQYFRWDK-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
- C09B29/0051—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
Definitions
- 'amin derivative are somewhat less bright than llnirnn Srnrns nrnr trier.
- PAUL JULIUS OF LUDWIGSHAFEN, GERMANY, ASSIGNOR TO BADISGHE ANILIN & SODA FABRIK, OF SAME PLACE.
- My invention relates to the production of orange coloring matter on the fiber by means of certain pyrazolone-carboXylic-acid derivatives.
- phenyl-pyrazolone carboxylic acid the so-called tartrazinogen
- tartrazinogen which can be obtained by saponifying the condensation product of phenyl-hydrazin and oxalyl-acetic ester, see W. Wislicenus, Annale'n, Vol. 246, page 321,
- phenyl-pyrazolone carboxylic acid the so-called tartrazinogen
- phenyl-pyrazolone carboxylic acid in place of phenyl-pyrazolone carboxylic acid another homologous or analogous derivative thereof can be employed, such as can be prepared, for example,by condensing ortho or para tolylhydrazin, alpha or beta naphthyl-hydrazin, or para-nitro-phen yl-hydrazin with oXalyl-acetic ester and subsequent saponification of the condensation products thus obtained.
- the shades produced by combining these pyrazolone products with diazotized primulin sulfonic acid differ but little from one another. Those produced by means of the alpha-naphthylthe others. In the present state of knowledge my new coloring-matter can be regarded as a mono-azo compound.
- the procedure for obtaining these new shades consists in diazotizing primulin snlfonic acid on the fiber of the material to be dyed in the known manner and then passing the goods thus treated through a solution of the alphyl-pyrazolone carboxylic acid chosen made alkaline by carbonate of soda. After leaving the goods in this solution for from ten (10) to twenty (20) minutes they are wrung out, rinsed, and 0therwise treated as required.
- the mono-azo coloring-matter which I wish to claim generically and which can be obtained by combining diazotized primulin sulfonic acid with phenyl-pyrazolone carboxylic acid or one ofits hereinbefore-mentioned derivatives is difficultly soluble to practically insoluble in cold water, as it contains but the sulfo group due to the primulinsulfonic acid.
- On reducing with zinc-dust and common-salt solution primulin sulfonic acid is regenerated.
- the shades obtained on cotton by means thereof are orange and are hardly a1 tered by treatment with dilute carbonate-ofsoda solution or dilute hydrochloric acid. They are exceeding fast to soap and light.
- the mono-azo coloring-matter which I desire to claim specifically and which can be de-' rived from diazotized primulin sulfonic acid and para-nitro-phenyl-pyrazolone carboxylic acid is difticultly soluble in cold water with an orange color, the solution becoming redder on the addition of caustic-soda solution.
- lution lution
- the shades obtained on cotton by means thereof are orange and are hardly altered by treatment with dilute carbonate-of-soda solution or dilute hydrochloric acid. They are also exceedingly fast to soap and to light.
- the new mono-azo dye which can be obtained from diazotized primulin sulfonic acid and a hereinbefore-defined phenyl-pyrazolone-carboxylic-acid body, which is difficultl y soluble to practically insoluble in cold water, which on reduction with zinc-dust and common-salt solution yields primulin sulfonic acid, and which when developed on the cotton fiber produces orange shades, which shades are hardly altered on treatment with dilute carbonate-of-soda solution or with dilute hydrochloric acid and are exceedingly fast to light and soap, substantially as described.
- the new mono-azo dye which can be obtained from diazotized primulin sulfonic acid and para-nitro-phenyl-pyrazolone carboxylic acid, which is difficultlysoluble in cold water with an orange color which solution becomes redder on the addition of caustic-soda solution and which on reduction with zinc-dust and common-saltsolntion yields petitionin sulfonic acid, and which when developed on the cotton fiber produces orange shades which are hardly altered on treatment with dilute carbonate-of-soda solution or on treatment with dilute hydrochloric acid and which are exceedingly fast to light and soap, substantially as described.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
'amin derivative are somewhat less bright than llnirnn Srnrns nrnr trier.
PAUL JULIUS, OF LUDWIGSHAFEN, GERMANY, ASSIGNOR TO BADISGHE ANILIN & SODA FABRIK, OF SAME PLACE.
ORANGE DYE AND PROCESS-OF MAKING SAME.
SPECIFICATION forming" part of Letters Patent No. 679,172, dated July 23, 1901. Application filed April 1, 1901. Serial No. 53,943. (No specimens.)
To all whom it may concern.-
Be it known that vI, PAUL JULIUS, a doctor of philosophy and a chemist, a subject of the Emperor ofAustria-Hungary,residing at Lud- Wigshafen-on-the-Rhine in the Kingdom of Bavaria, Germany, have invented new and useful Improvements in Orange Dyes, of which the following is a specification.
My invention relates to the production of orange coloring matter on the fiber by means of certain pyrazolone-carboXylic-acid derivatives.
I have found that phenyl-pyrazolone carboxylic acid, the so-called tartrazinogen, (which can be obtained by saponifying the condensation product of phenyl-hydrazin and oxalyl-acetic ester, see W. Wislicenus, Annale'n, Vol. 246, page 321,) combines readily with primulin sulfonic acid which has been diazotized on the fiber, giving rise to an orange tartrazin coloring-matter. In place of phenyl-pyrazolone carboxylic acid another homologous or analogous derivative thereof can be employed, such as can be prepared, for example,by condensing ortho or para tolylhydrazin, alpha or beta naphthyl-hydrazin, or para-nitro-phen yl-hydrazin with oXalyl-acetic ester and subsequent saponification of the condensation products thus obtained. The shades produced by combining these pyrazolone products with diazotized primulin sulfonic acid differ but little from one another. Those produced by means of the alpha-naphthylthe others. In the present state of knowledge my new coloring-matter can be regarded as a mono-azo compound. The procedure for obtaining these new shades consists in diazotizing primulin snlfonic acid on the fiber of the material to be dyed in the known manner and then passing the goods thus treated through a solution of the alphyl-pyrazolone carboxylic acid chosen made alkaline by carbonate of soda. After leaving the goods in this solution for from ten (10) to twenty (20) minutes they are wrung out, rinsed, and 0therwise treated as required.
I give an example of a method for obtaining pyrazolone bodies which can be used for the purposes of myinvention; but I do not wish to claim the same.
Example: Heat together at a temperature of about one hundred (100) degrees centigrade, twenty-one (21) parts of the sodium compound of oXalyl-acetic ester, sixteen (16) parts of ortho-tolyl-hydrazin hydrochlorid, and one hundred (100) parts of Xylene for about one hour. I-Iydrazone formation ap pears to take place at first, and this is followed by further condensation. To complete the latter, add about one hundred and fifty (150) parts of water to the mixture, distil off the Xylene by blowing in steam, and when no more hydrocarbon passes over add about eleven (11) parts of calcined soda to the mixture. Keep it boiling for about half an hour longer by continuing to pass in steam, and then add about eleven and a half (11%) parts of caustic-soda solution, (containing about thirty-five per cent. of NaOH.) Heat on the boiling-water bath until the condensation product formed is saponified, filter from any resinous matter formed, cool, and precipitate the ortho tolylpyrazolone carboxylic acid from the filtrate by carefully acidifying it with hydrochloric acid. The ortho-tolyl-pyrazolone carboXylic acid thus obtained can be purified by recrystallization from hot dilute alcohol. In a similar manner para-tolyl, alpha, and beta naphthyl, and para-nitro-phenyl-pyrazolone carboxylic acids can be prepared.
The mono-azo coloring-matter which I wish to claim generically and which can be obtained by combining diazotized primulin sulfonic acid with phenyl-pyrazolone carboxylic acid or one ofits hereinbefore-mentioned derivatives is difficultly soluble to practically insoluble in cold water, as it contains but the sulfo group due to the primulinsulfonic acid. On reducing with zinc-dust and common-salt solution primulin sulfonic acid is regenerated. The shades obtained on cotton by means thereof are orange and are hardly a1 tered by treatment with dilute carbonate-ofsoda solution or dilute hydrochloric acid. They are exceeding fast to soap and light.
The mono-azo coloring-matter which I desire to claim specifically and which can be de-' rived from diazotized primulin sulfonic acid and para-nitro-phenyl-pyrazolone carboxylic acid is difticultly soluble in cold water with an orange color, the solution becoming redder on the addition of caustic-soda solution. On reduction with zinc-dust and common-salt so lution primulin sulfonic acid is regenerated. The shades obtained on cotton by means thereof are orange and are hardly altered by treatment with dilute carbonate-of-soda solution or dilute hydrochloric acid. They are also exceedingly fast to soap and to light.
The following example will serve to illustrate the nature of my invention and a manner of carrying it into practical effect; but my invention is not confined to the example. The parts are by weight.
Example: Dye one hundred (100) kilograms of cotton with three (33) kilograms of primulin sulfonic acid and diazotize the primulin sulfonic acid on the fiber in the well-known manner. Rinse the material thus treated in cold water and pass it through a hath made up of ten kilograms of para-nitro-phenylpyrazolone carboxylic acid'and a snfficient excess of carbonate of soda in five thousand (5,000) liters of water. Allow the material to remain in this bath for about twenty minutes, rinse, and dry.
Now what I claim is l. The process of producing orange dye on the fiber by combining primulin sulfonic acid which has been diazotized on the fiber with a hereinbefore-defined phenyl-pyrazolone-carboxylic-acid body,substantially as described.
2. The process of producing orange dye by combining diazotized primulin sulfonic acid with a hereinbefore-defined phenyl-pyrazolonecarboxylic-acid body, substantially as described.
3. The process of producing orange dye by combining diazotized primulin sulfonic acid with para-nitro-phenyl-pyrazolone carboxylic acid, substantially as described.
4. The new mono-azo dye which can be obtained from diazotized primulin sulfonic acid and a hereinbefore-defined phenyl-pyrazolone-carboxylic-acid body, which is difficultl y soluble to practically insoluble in cold water, which on reduction with zinc-dust and common-salt solution yields primulin sulfonic acid, and which when developed on the cotton fiber produces orange shades, which shades are hardly altered on treatment with dilute carbonate-of-soda solution or with dilute hydrochloric acid and are exceedingly fast to light and soap, substantially as described.
5. The new mono-azo dye which can be obtained from diazotized primulin sulfonic acid and para-nitro-phenyl-pyrazolone carboxylic acid, which is difficultlysoluble in cold water with an orange color which solution becomes redder on the addition of caustic-soda solution and which on reduction with zinc-dust and common-saltsolntion yields primulin sulfonic acid, and which when developed on the cotton fiber produces orange shades which are hardly altered on treatment with dilute carbonate-of-soda solution or on treatment with dilute hydrochloric acid and which are exceedingly fast to light and soap, substantially as described.
In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.
PAUL JULIUS.
\Vitnesses:
JOHN L. HEINKE, JACOB ADRIAN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5394301A US679172A (en) | 1901-04-01 | 1901-04-01 | Orange dye and process of making same. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5394301A US679172A (en) | 1901-04-01 | 1901-04-01 | Orange dye and process of making same. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US679172A true US679172A (en) | 1901-07-23 |
Family
ID=2747718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US5394301A Expired - Lifetime US679172A (en) | 1901-04-01 | 1901-04-01 | Orange dye and process of making same. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US679172A (en) |
-
1901
- 1901-04-01 US US5394301A patent/US679172A/en not_active Expired - Lifetime
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