CH215821A - Process for the preparation of a 1-oxy-4-acylaminonaphthalene-3-sulfonic acid. - Google Patents
Process for the preparation of a 1-oxy-4-acylaminonaphthalene-3-sulfonic acid.Info
- Publication number
- CH215821A CH215821A CH215821DA CH215821A CH 215821 A CH215821 A CH 215821A CH 215821D A CH215821D A CH 215821DA CH 215821 A CH215821 A CH 215821A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- oxy
- sulfonic acid
- acid
- acetylamino
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 3
- 150000008049 diazo compounds Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims 1
- 230000000397 acetylating effect Effects 0.000 claims 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- -1 diacetyl compound Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HWAUAPHDMHWNCM-UHFFFAOYSA-N 4-acetamidonaphthalene-2-sulfonic acid Chemical compound C1=CC=C2C(NC(=O)C)=CC(S(O)(=O)=O)=CC2=C1 HWAUAPHDMHWNCM-UHFFFAOYSA-N 0.000 description 1
- SSQQBRZUIXIPIP-UHFFFAOYSA-N 5-diazo-2-nitrocyclohexa-1,3-diene Chemical compound [O-][N+](=O)C1=CCC(=[N+]=[N-])C=C1 SSQQBRZUIXIPIP-UHFFFAOYSA-N 0.000 description 1
- COYOYULJHHOUIV-UHFFFAOYSA-N CC(NC(C=C1C(OC(C)=O)=C2)=CC=C1C(NC(C)=O)=C2S(O)(=O)=O)=O Chemical compound CC(NC(C=C1C(OC(C)=O)=C2)=CC=C1C(NC(C)=O)=C2S(O)(=O)=O)=O COYOYULJHHOUIV-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung einer 1-Oxy-4-acylaminonaphtalin-3-sulfonsäure. Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von 1-Oxy-4- acetylamino- 7 - aminonaphtalin- 3 - sulfonsäur e.
Das Verfahren ist dadurch gekennzeichnet, dass man auf 1-Oxy-4-amino-7-acetylamino- naphtalin - 3 - sulfonsäure ein acetylierendes Mittel, auf das erhaltene Reaktionsprodukt ein die Acetyloxygruppe verseifendes alkali sches Mittel und schliesslich ein die 7-Acetyl- aminogruppe verseifendes, saures Mittel ein wirken lässt.
Die neue 1-Oxy-4-acetylamino-7-amino- naphtalin-3-sulfonsäure bildet mit salpetriger Säure eine gelbe Diazoverbindung und kuppelt mit Diazoverbindungen. Sie soll zur Herstel lung von Farbstoffen verwendet werden.
Beispiel: 50 Teile 1-Oxy- 4 - amino - 7 - acetylamino- naphtalin-3-sulfonsäure werden in ein Acety- lierungsgemisch aus 150 Teilen Essigsäure anhydrid und 27 Teilen wasserfreiem Natrium- acetat bei 80 0 unter Rühren eingetragen, wo bei unter Selbsterwärmung auf ca 100 0 Auf- lösung eintritt. Man gibt weitere 50 Teile derselben Säure rasch hinzu.
Die Temperatur steigt dadurch weiter auf ca. 120 -125 0, und aus der Lösung scheidet sich nach kurzer Zeit die 1-Acetyloxy- 4,7 - di- (acetylamino)- naphtalin-3-sulfonsäure aus.
Man destilliert im Vakuum den Eisessig ab, löst die zurück bleibende Triacetylverbindung in wenig Was ser auf, stellt mit Natronlauge phenolphtalein- alkalisch, fügt ca. 45 Teile Soda zu und er hitzt 15 Minuten auf 70 0, wobei die Acetyl- oxygruppe verseift wird.
Nach Abkühlung wird mit Schwefelsäure neutral gestellt, 12 Stunden stehen gelassen und der sich aus scheidende Niederschlag gesammelt und ge trocknet; er besteht aus der 1- Oxy - 4,7- di(acetylamino)-naphtalin-3-sulfonsäure, deren Gehalt durch Titration mit p-Nitrodiazobenzol- lösung festgestellt werden kann.
Um die Diacetylverbindung in die 1-Oxy- 4-acetylamino-7-aminonaphtalin- 3-sulfonsäure überzuführen, werden 74 Teile der<B>67,5</B> %igen Diacetylverbindung in 400 Teilen Wasser ge löst, hierauf 44 Teile konzentrierte Schwefel- säure hinzugetropft, in ca. 10 Minuten unter Rühren auf 90 erwärmt und 5 -Minuten auf 90 - 95 gehalten.
Durch diese Behandlung wird vorwiegend die 7 - Acety laminogi-uppe verseift und beim Abkühlen scheidet sich die neue monoacetvlierte Säure seliiin kristalli siert ab. Zur weiteren Reinigung löst man sie unter Zusatz von Natriumaeetat in warmem Wasser, behandelt mit Blutkohle, filtriert und fällt mit Salzsäure aus. Man gewinnt so die Verbindung in reinem Zustande, wovon inan sich durch '1'itration mit Nitritlüsung, wie auch mit p-Nitrodiazobeilzollösung überzeugen kann.
Die neue Säure kuppelt mit Diazov er- bindungeil und Märt sich durch salpetrige Säure in eine gelbe Diazoverbindung über führen.
Die zur Acetylierung verwendete, in der Literatur nicht beschriebene 1-Oxy-4-ainino- 7 - acetylaminonaphtalin - 3 - sulfollsäure kann durch Reduktion des Azofarbstoffes gewonnen werden, den man bei der Kupplung voll 4- Nitro-l-diazobenzol-3-sulfonsäui-e mit 1-Oxy-7- acetylaminonaphtalin-3-sulfonsäui@e in Gegen wart voll Soda erhält,
wobei die Diazover- bindung ausschliesslich in p-Stellung zur Hydroxylgruppe eintritt. Dadurch ist es mög lich, die Reduktion ohne Isolierung des Azo- farbstoffes vorzunehmen. Die 1-Oxy-4-amino- 7-acetyl < iminona.plitalin-3-sulfonsäure ist weder diazotierball,
noch kuppelt sie mit Diazover- bindungen. -Mit soloalkalischer Resoreinlüsung auf Filterpapier gebracht tritt allmählich eine intensive rote Färbung auf.
Process for the preparation of a 1-oxy-4-acylaminonaphthalene-3-sulfonic acid. The subject of the present patent is a process for the preparation of 1-oxy-4-acetylamino- 7 - aminonaphthalene- 3 - sulfonic acid.
The process is characterized in that an acetylating agent is added to 1-oxy-4-amino-7-acetylamino-naphthalene-3-sulfonic acid, an alkaline agent saponifying the acetyloxy group is applied to the reaction product obtained, and finally the 7-acetylamino group is added saponifying, acidic agent.
The new 1-oxy-4-acetylamino-7-amino-naphthalene-3-sulfonic acid forms a yellow diazo compound with nitrous acid and couples with diazo compounds. It is to be used for the produc- tion of dyes.
Example: 50 parts of 1-oxy-4-amino-7-acetylamino-naphthalene-3-sulfonic acid are introduced into an acetylation mixture of 150 parts of acetic anhydride and 27 parts of anhydrous sodium acetate at 80 ° with stirring, where with self-heating at approx. 100 0 resolution occurs. Another 50 parts of the same acid are added rapidly.
As a result, the temperature rises further to approx. 120-125 °, and 1-acetyloxy-4,7-di- (acetylamino) -naphthalene-3-sulfonic acid separates out of the solution after a short time.
The glacial acetic acid is distilled off in vacuo, the remaining triacetyl compound is dissolved in a little water, phenolphthalein alkaline with sodium hydroxide solution, about 45 parts of soda are added and it is heated to 70 ° for 15 minutes, the acetyl oxy group being saponified.
After cooling, it is made neutral with sulfuric acid, left to stand for 12 hours and the precipitate which separates out is collected and dried; it consists of 1-oxy-4,7-di (acetylamino) -naphthalene-3-sulfonic acid, the content of which can be determined by titration with p-nitrodiazobenzene solution.
In order to convert the diacetyl compound into the 1-oxy-4-acetylamino-7-aminonaphthalene-3-sulfonic acid, 74 parts of the 67.5% strength diacetyl compound are dissolved in 400 parts of water, and 44 parts are concentrated thereon Sulfuric acid was added dropwise, heated to 90 in about 10 minutes with stirring and held at 90-95 for 5 minutes.
This treatment mainly saponifies the 7-acetylamine group, and when it cools down, the new monoacetylated acid separates out in crystalline form. For further purification, they are dissolved in warm water with the addition of sodium acetate, treated with blood charcoal, filtered and precipitated with hydrochloric acid. The compound is thus obtained in a pure state, of which one can convince itself by nitration with nitrite solution as well as with p-nitrodiazobeilzoll solution.
The new acid couples with Diazov compound and Märt transforms itself into a yellow diazo compound through nitrous acid.
The 1-oxy-4-ainino-7-acetylaminonaphthalene-3-sulfollic acid used for the acetylation and not described in the literature can be obtained by reducing the azo dye which is obtained in the coupling of full 4-nitro-1-diazobenzene-3-sulfonic acid -e with 1-oxy-7- acetylaminonaphthalene-3-sulfonsäui @ e in the presence of full soda,
the diazo compound entering exclusively in the p-position to the hydroxyl group. This makes it possible to carry out the reduction without isolating the azo dye. The 1-oxy-4-amino-7-acetyl <iminona.plitalin-3-sulfonic acid is neither diazotizing ball,
it still couples with diazo compounds. -With solo alkaline resor solution on filter paper, an intense red color gradually appears.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH212639T | 1939-04-05 | ||
| CH215821T | 1939-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH215821A true CH215821A (en) | 1941-07-15 |
Family
ID=25725281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH215821D CH215821A (en) | 1939-04-05 | 1939-04-05 | Process for the preparation of a 1-oxy-4-acylaminonaphthalene-3-sulfonic acid. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH215821A (en) |
-
1939
- 1939-04-05 CH CH215821D patent/CH215821A/en unknown
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