CH114625A - Process for the preparation of 6-chlorobenzoxazolone-5-arsic acid. - Google Patents
Process for the preparation of 6-chlorobenzoxazolone-5-arsic acid.Info
- Publication number
- CH114625A CH114625A CH114625DA CH114625A CH 114625 A CH114625 A CH 114625A CH 114625D A CH114625D A CH 114625DA CH 114625 A CH114625 A CH 114625A
- Authority
- CH
- Switzerland
- Prior art keywords
- chlorobenzoxazolone
- acid
- preparation
- arsic
- compound
- Prior art date
Links
- 239000002253 acid Substances 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- -1 amino compound Chemical class 0.000 claims description 4
- 150000008049 diazo compounds Chemical class 0.000 claims description 4
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical group 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- SWFNPENEBHAHEB-UHFFFAOYSA-N 2-amino-4-chlorophenol Chemical compound NC1=CC(Cl)=CC=C1O SWFNPENEBHAHEB-UHFFFAOYSA-N 0.000 description 2
- YNKFDRBTIKYADI-UHFFFAOYSA-N 6-chloro-5-nitro-3h-1,3-benzoxazol-2-one Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1OC(=O)N2 YNKFDRBTIKYADI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- GWMSBABWKBFZCF-UHFFFAOYSA-N 5-amino-6-chloro-3h-1,3-benzoxazol-2-one Chemical compound C1=C(Cl)C(N)=CC2=C1OC(=O)N2 GWMSBABWKBFZCF-UHFFFAOYSA-N 0.000 description 1
- UTQPEXLRBRAERQ-UHFFFAOYSA-N 5-nitro-3h-1,3-benzoxazol-2-one Chemical compound [O-][N+](=O)C1=CC=C2OC(=O)NC2=C1 UTQPEXLRBRAERQ-UHFFFAOYSA-N 0.000 description 1
- MATCZHXABVLZIE-UHFFFAOYSA-N 6-chloro-3h-1,3-benzoxazol-2-one Chemical compound C1=C(Cl)C=C2OC(O)=NC2=C1 MATCZHXABVLZIE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
- C07F9/80—Heterocyclic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
Verfahren zur Darstellung von 6-Chlorbenzoaazolon-5-arsinsäure. Nach dem Verfahren des Hauptpatentes lässt sich, wie gefunden wurde, Benzoxazolon- 5-arsinsäure dadurch gewinnen, dass man 5-Nitrobenzoxazolon reduziert, die so er haltene Aminoverbindung diazotiert und die Diazoverbindung mit einem löslichen Arsenit behandelt.
Es wurde nun gefunden, dass man in gleicher Weise 6-Chlorbenzogazolon-5-arsin- säure erhält, wenn man durch Phosgenieren von 2-Amino-4-chlorphenol und nachfol gendes Nitrieren erhaltenes 5-Nitro-6-chlor- benzoxazolon reduziert, die gebildete Amino- verbindung diazotiert und die Diäzoverbin- dung mit einem löslichen Arsenit behandelt.
Der Verlauf der Reaktionen - wird dureh folgendes Schema veranschaulicht:
EMI0001.0021
Es war nicht vorauszusehen, dass bei allen diesen Operationen der -Benzoxa7olon- ring erhalten bleibt und dass die Arsin- säure auf diesem Wege gewonnen werden kann.
Die neue Verbindung soll als solche therapeutische Verwendung finden, wie auch als Ausgangsstoff für die Darstellung anderer pharmazeutischer Produkte dienen. <I>Beispiel:</I> 6-Chlorbenzoxazolon wird erhalten durch Phosgenieren von 2-Amino-4-chlorphenol; es bildet farblose Nadeln vom Schmelzpunkt 189 bis 190 , die sich in Äther, Benzol, Ligroin, Chloroform schwer, in Alkohol, Aceton, Essigsäure leicht lösen. Sie sind unlöslich in verdünnten Mineralsäuren, da gegen leicht löslich in verdünnten Alkalien.
Durch Nitrieren mit verdünnter Salpeter säure liefert die Verbindung: 5-Nitro-6- ehlorbenzoxazolon, feine, glänzende, schwach gelbe Blättchen vom Schmelzpunkt 207 ". Es löst sich leicht in heissem, schwer in kaltem Alkohol. Von Aceton wird es leicht, von Äther, Benzol, Ligroin schwer auf genommen. Das Natriumsalz bildet schöne gelbe Nadeln, die sich in kaltem Wasser sehwer, in heissem leicht lösen.
Durch Re duktion mit Eisen und Essigsäure erhält man 5-Amino-6-ehlorbenzoxazolon, farblose Kristalle, die sich in Äther, Alkohol, Ace ton, Eisessig und in verdünnten Alkalien leicht, in kaltem Wasser schwer lösen. Die Diazoverbindung kuppelt mit Resorcin orangerot.
Zur Darstellung der 6-Chlor- benzoxazolon-5-arsinsäure werden 105 kg ;i- Amino-6-chloi-benzoxazolon mit 300 hg Salzsäure<B>(1,15),</B> 1000 Liter Wasser und 70 kg Nitrit diazotiert. Die Diazolösüng fliesst unter gutem Rühren in eine auf 45 " gehaltene Lösung von 320 kg Natrium a.rsenit und 500 kg Soda in<B>1000</B> Liter Wasser ein.
Nach dem Ansäuern mit kon zentrierter Salzsäure und Absaugen scheidet sieh aus dem Filtrat beim Stehenlassen und Abkühlen die Chlorbeiizoxazolonarsinsäure in weissen Kristallen ab, die in Wasser ziemlich schwer löslich sind, sich dagegen in verdünnten Alkalien, Sodalösung, sowie warmer Acetatlösung leicht lösen.
Process for the preparation of 6-chlorobenzoaazolone-5-arsic acid. According to the process of the main patent, it has been found that benzoxazolone-5-arsic acid can be obtained by reducing 5-nitrobenzoxazolone, diazotizing the amino compound thus obtained and treating the diazo compound with a soluble arsenite.
It has now been found that 6-chlorobenzazolone-5-arsic acid is obtained in the same way if 5-nitro-6-chlorobenzoxazolone obtained by phosgenating 2-amino-4-chlorophenol and subsequent nitration is reduced, the The amino compound formed is diazotized and the diazo compound treated with a soluble arsenite.
The course of the reactions - is illustrated by the following scheme:
EMI0001.0021
It could not have been foreseen that the benzoxalolone ring would be retained in all of these operations and that arsic acid could be obtained in this way.
The new compound will find therapeutic use as such, as well as serve as a starting material for the preparation of other pharmaceutical products. <I> Example: </I> 6-chlorobenzoxazolone is obtained by phosgenating 2-amino-4-chlorophenol; it forms colorless needles with a melting point of 189 to 190, which dissolve with difficulty in ether, benzene, ligroin, chloroform, and easily in alcohol, acetone, and acetic acid. They are insoluble in dilute mineral acids, as they are easily soluble in dilute alkalis.
Nitriding with dilute nitric acid gives the compound: 5-nitro-6-chlorobenzoxazolone, fine, shiny, pale yellow flakes with a melting point of 207 ". It dissolves easily in hot alcohol, difficult in cold alcohol. It becomes light from acetone, from ether The sodium salt forms beautiful yellow needles, which dissolve very slowly in cold water and easily in hot water.
Re reduction with iron and acetic acid gives 5-amino-6-chlorobenzoxazolone, colorless crystals that dissolve easily in ether, alcohol, acetone, glacial acetic acid and in dilute alkalis, but difficult to dissolve in cold water. The diazo compound couples orange-red with resorcinol.
To prepare 6-chlorobenzoxazolone-5-arsic acid, 105 kg of i-amino-6-chlorobenzoxazolone are diazotized with 300 hg hydrochloric acid (1.15), 1000 liters of water and 70 kg of nitrite . The diazo solution flows into a 45 "solution of 320 kg sodium arsenite and 500 kg soda in 1000 liters of water while stirring well.
After acidification with concentrated hydrochloric acid and suction, the chlorobeiizoxazolonarsinic acid separates from the filtrate on standing and cooling in white crystals, which are rather sparingly soluble in water, but easily dissolve in dilute alkalis, soda solution, and warm acetate solution.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH113832T | 1924-08-05 | ||
| CH114625T | 1924-08-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH114625A true CH114625A (en) | 1926-04-16 |
Family
ID=25708222
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH114624D CH114624A (en) | 1924-08-05 | 1924-08-05 | Process for the preparation of 6-methylbenzoxazolone-5-arsic acid. |
| CH114625D CH114625A (en) | 1924-08-05 | 1924-08-05 | Process for the preparation of 6-chlorobenzoxazolone-5-arsic acid. |
| CH113832D CH113832A (en) | 1924-08-05 | 1924-08-05 | Process for the preparation of benzoxazolone-5-aric acid. |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH114624D CH114624A (en) | 1924-08-05 | 1924-08-05 | Process for the preparation of 6-methylbenzoxazolone-5-arsic acid. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH113832D CH113832A (en) | 1924-08-05 | 1924-08-05 | Process for the preparation of benzoxazolone-5-aric acid. |
Country Status (1)
| Country | Link |
|---|---|
| CH (3) | CH114624A (en) |
-
1924
- 1924-08-05 CH CH114624D patent/CH114624A/en unknown
- 1924-08-05 CH CH114625D patent/CH114625A/en unknown
- 1924-08-05 CH CH113832D patent/CH113832A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH114624A (en) | 1926-04-16 |
| CH113832A (en) | 1926-02-16 |
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