CH236490A - Process for the preparation of 2- (p-aminobenzene-sulfonamido) -pyridine. - Google Patents
Process for the preparation of 2- (p-aminobenzene-sulfonamido) -pyridine.Info
- Publication number
- CH236490A CH236490A CH236490DA CH236490A CH 236490 A CH236490 A CH 236490A CH 236490D A CH236490D A CH 236490DA CH 236490 A CH236490 A CH 236490A
- Authority
- CH
- Switzerland
- Prior art keywords
- pyridine
- sulfonamido
- aminobenzene
- preparation
- nitrobenzene
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- GECHUMIMRBOMGK-UHFFFAOYSA-N sulfapyridine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=CC=N1 GECHUMIMRBOMGK-UHFFFAOYSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 8
- -1 p-nitrobenzene-sulphonamido Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- RFKCCVWFXQAMBJ-UHFFFAOYSA-N 4-nitro-n-pyridin-2-ylbenzenesulfonamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=CC=N1 RFKCCVWFXQAMBJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- NCBOVAWEMBIIFK-UHFFFAOYSA-N (4-nitrophenyl) thiohypochlorite Chemical compound [O-][N+](=O)C1=CC=C(SCl)C=C1 NCBOVAWEMBIIFK-UHFFFAOYSA-N 0.000 description 1
- IZRWZLBCZMYWIG-UHFFFAOYSA-N 1,2-dinitro-3-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC(C=2C=CC=CC=2)=C1[N+]([O-])=O IZRWZLBCZMYWIG-UHFFFAOYSA-N 0.000 description 1
- KWGZRLZJBLEVFZ-UHFFFAOYSA-N 1-nitro-4-[(4-nitrophenyl)disulfanyl]benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1SSC1=CC=C([N+]([O-])=O)C=C1 KWGZRLZJBLEVFZ-UHFFFAOYSA-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
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NHRKXPCRTQULCO-UHFFFAOYSA-N n-(4-nitrophenyl)sulfanylpyridin-2-amine Chemical compound C1=CC([N+](=O)[O-])=CC=C1SNC1=CC=CC=N1 NHRKXPCRTQULCO-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical class NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung von 2-(p-Aminobenzol-sulfonamido)-pyridin. Vorliegende Erfindung bezieht sich auf die Herstellung eines Derivates des p-Amino- benzol-sulfonamids, nämlich des Bekannter weise wichtige therapeutische Anwendungen findenden 2-(p-Aminobenzol-sulfonamido)- ljyridins.
Gemäss dem Verfahren des vorliegenden Patentes stellt man 2-(p-Aminobenzol-sulfon- amido)-pyridin dadurch her, dass man ein p- Nitrobenzol-sulfenylhalogenid der Formel
EMI0001.0011
mit einem die stöchiometrische Menge über steigenden Überschuss an 2-Aminopyridin zur Sulfenamidoverbindung der Formel
EMI0001.0015
umsetzt, letztere durch Oxydation in das 2-(p-Nitrobenzol-sulfonamido)-pyridin über führt und dieses durch Reduktion in das 2-(p-Aminobenzol-sulfonamido)-pyridin um wandelt.
Die Verwendung eines Überschusses an 2-Amino-pyridin über die stöchiometrische Menge hat sich im vorliegenden Verfahren a1'µ sehr vorteilhaft erwiesen, indem er durch Ge währleistung der Alkalinität des Reaktions gemisches die Ausbeute des gewünschten Pro duktes erhöht.
Die Oxydation der Sulfenamidoverbin- dung zum entsprechenden Sulfonamid wird vorzugsweise in alkalischem Medium vor genommen, da das Sulfenamid in sauren Me dien unbeständig ist. Ein geeignetes Oxyda tionsmittel ist z.
B. Kaliumpermanganat, das nicht nur in alkalischer, sondern auch in neu traler Lösung verwendet werden kann, da letztere sogleich nach Einsetzen der Oxyda tion bekanntermassen alkalisch wird. Wenn man neutrale Kaliumpermanganatlösungen verwendet, kann es als Vorsichtsmassnahme wünschenswert sein, der Lösung geringe Men gen Alkali zuzusetzen. Überdies ist es nicht notwendig, das Sulfenamid vor der Oxyda tion zu isolieren und zu reinigen, da gefunden wurde, dass das Rohprodukt direkt oxydiert werden kann.
Das Oxydationsprodukt, nämlich das 2-(p Nitrobenzol-sulfonamido)-pyridin wird dann in die entsprechende p-Aminoverbindung übergeführt, indem man die p-Nitrogruppe z. B. nach irgendeiner bekannten Methode zur Aminogruppe reduziert, wodurch man das 2- (p-Aminobenzol-sulfonamido)-pyridin erhält.
Das Verfahren gemäss der Erfindung wird durch das nachfolgende Beispiel erläutert. Beispiel: Eine Lösung von 19 g p-Nitrobenzol-sul- fenylchlorid, das nach bekannten Methoden aus p,p =Dinitro-diphenyl-disulfid erhalten wurde, in 100 cm' trockenem Äther wurde unter Rühren in eine Lösung von 20 g 2-Amino- pyridin in 100, cm' trockenen Äther eintrop- fen gelassen. Die Reaktion wurde durch schwaches Kühlen geregelt.
Es schied sich eine harzige, aus dem gewünschten Produkt und 2-Aminopy ridin bestehende Masse aus. Nach mehrstündigem Stehen wurde der Äther abgegossen und die nun festgewordene Masse mit Wasser verrieben, um das 2-Amino-pyri- dinchlorhydrat zu entfernen. Das Produkt wurde aus Alkohol und Benzol umkristalli siert, um es von Spuren des p,p'-Dinitrodiphe- nyl-disulfids zu befreien. Das 2-(p-Nitroben- zol-sulfenamido) -pyridin kristallisiert aus Benzol in schweren Prismen vom Smp. 170 bis 173 .
5 g des erhaltenen Produktes wurden in 70 cm- warmem Aceton gelöst und diese Lö sung unter Rühren in 100 cm' einer 5 ö igen Ka.liumliermanganatlösung einlaufen gelas sen. Unter Entwicklung von etwas Wärme fand die Oxydation statt und war in etwa 30 Minuten beendet. Die nun alkalische Lö sung wurde filtriert, um das Mangandioxyd zu entfernen und das gewünschte Sulfonamid durch Ansäuern des Filtrates gewonnen. Es bildet blasse cremefarbige Nadeln, deren Zer setzungspunkt abhängig ist von der Erhit- zungsgesehwindigkeit, in der Regel aber zwi schen 160 und l90 liegt.
Die Reduktion der Nitrogruppe zur Aminogruppe erfolgte dann in bekannter Weise.
Process for the preparation of 2- (p-aminobenzene-sulfonamido) -pyridine. The present invention relates to the preparation of a derivative of p-aminobenzene-sulfonamide, namely 2- (p-aminobenzene-sulfonamido) ljyridine, which is known to have important therapeutic applications.
According to the process of the present patent, 2- (p-aminobenzene-sulfonamido) -pyridine is prepared by using a p-nitrobenzene-sulfenyl halide of the formula
EMI0001.0011
with a stoichiometric amount over increasing excess of 2-aminopyridine to the sulfenamido compound of the formula
EMI0001.0015
converts the latter into 2- (p-nitrobenzene-sulfonamido) -pyridine by oxidation and converts this into 2- (p-aminobenzene-sulfonamido) -pyridine by reduction.
The use of an excess of 2-aminopyridine over the stoichiometric amount has proven to be very advantageous in the present process a1'μ by increasing the yield of the desired product by ensuring the alkalinity of the reaction mixture.
The sulfenamido compound is preferably oxidized to the corresponding sulfonamide in an alkaline medium, since the sulfenamide is unstable in acidic media. A suitable Oxyda tion agent is z.
B. potassium permanganate, which can be used not only in alkaline, but also in neutral solution, since the latter is known to be alkaline immediately after the onset of the Oxyda tion. When using neutral potassium permanganate solutions, it may be desirable as a precautionary measure to add small amounts of alkali to the solution. Moreover, it is not necessary to isolate and purify the sulfenamide prior to oxidation, since it has been found that the crude product can be oxidized directly.
The oxidation product, namely 2- (p-nitrobenzene-sulfonamido) -pyridine is then converted into the corresponding p-amino compound by removing the p-nitro group z. B. reduced to the amino group by any known method, whereby the 2- (p-aminobenzene-sulfonamido) -pyridine is obtained.
The method according to the invention is illustrated by the following example. Example: A solution of 19 g of p-nitrobenzene-sulfenyl chloride, which was obtained by known methods from p, p = dinitro-diphenyl disulfide, in 100 cm 'of dry ether was converted into a solution of 20 g of 2-amino with stirring - pyridine dripped into 100 cm 'of dry ether. The reaction was controlled by gentle cooling.
A resinous mass consisting of the desired product and 2-aminopyridine separated out. After standing for several hours, the ether was poured off and the now solidified mass was rubbed with water in order to remove the 2-aminopyridine chlorohydrate. The product was recrystallized from alcohol and benzene in order to free it from traces of the p, p'-dinitrodiphenyl disulfide. The 2- (p-nitrobenzene-sulfenamido) -pyridine crystallizes from benzene in heavy prisms with a melting point of 170 to 173.
5 g of the product obtained were dissolved in acetone at a temperature of 70 cm and this solution was allowed to run into 100 cm of a 5-strength potassium manganate solution with stirring. The oxidation took place with the development of some heat and was complete in about 30 minutes. The now alkaline solution was filtered to remove the manganese dioxide and the desired sulfonamide obtained by acidifying the filtrate. It forms pale, cream-colored needles, the decomposition point of which depends on the rate of heating, but is usually between 160 and 190.
The reduction of the nitro group to the amino group then took place in a known manner.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB236490X | 1941-06-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH236490A true CH236490A (en) | 1945-02-15 |
Family
ID=10199045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH236490D CH236490A (en) | 1941-06-04 | 1942-06-09 | Process for the preparation of 2- (p-aminobenzene-sulfonamido) -pyridine. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH236490A (en) |
-
1942
- 1942-06-09 CH CH236490D patent/CH236490A/en unknown
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