CH239152A - Process for the production of a new benzene sulfonamide derivative. - Google Patents
Process for the production of a new benzene sulfonamide derivative.Info
- Publication number
- CH239152A CH239152A CH239152DA CH239152A CH 239152 A CH239152 A CH 239152A CH 239152D A CH239152D A CH 239152DA CH 239152 A CH239152 A CH 239152A
- Authority
- CH
- Switzerland
- Prior art keywords
- isopropyl
- thiodiazole
- production
- benzene sulfonamide
- amino
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 150000008331 benzenesulfonamides Chemical class 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 2-benzenesulfonamido Chemical group 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- GRDXCFKBQWDAJH-UHFFFAOYSA-N 4-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=C(S(Cl)(=O)=O)C=C1 GRDXCFKBQWDAJH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance 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
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung eines neuen Benzol-sulfonamidderivates. Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung eines neuen Benzolsudonamidderivates, dadurch gekenn zeichnet, dass man ein 2 - Benzolsulfon- amido-5-isopropyl-thiodiazol-(1,3,4), das in p-Stellung einen durch Hydrolyse in die Aminogruppe überführbaren Substituenten aufweist, mit einem hydrolysierenden Mittel behandelt.
Das so erhaltene 2-(p-Amino-benzolsul- fonamido) - 5 - isopropyl - thiodiazol - (1, 3,4) schmilzt bei 192 . Die neue Verbindung soll als Arzneimittel sowie als Zwischenprodukt Verwendung finden.
Das 2 - Benzolsulfonamido - 5 - isopropyl- thiodiazol-(1,3,4). das in p-Stellung zur Sul- fonamidgruppe einen durch Hydrolyse in die Aminogruppe überführbaren Substituenten enthält, kann auf verschiedene Art und Weise gewonnen werden.
Besonders geeignet ist die Umsetzung der entsprechenden reak tionsfähigen Benzolsulfonsäurederivate, ins- besondere der Benzolsulfonsäurehalogenide, mit 5-Isopropyl-thiodiazol-(1,3,4)-verbindun- gen, die in 2-Stellung eine Gruppe enthalten, die mit dem Benzolsulfonsäurederivat ein 2 - Benzolsulf onamido -5-isopropyl-thiodiazol- (1,3,4) zu bilden vermag,
wie mit 2-Amino- 5 - isopropyl-thiodiazol - (1,ä,4). Man kann auch entsprechende Sulfonamide der Formel RSO,NHY, in der Y einen bei der nachfol genden Reaktion sich abspaltenden Rest be deutet, mit 5 - Halogen - 2 - isopropyl - thio- diazolen-(1,3,4) umsetzen. Auch können an dere dem Fachmann geläufige Herstellungs methoden benutzt werden.
<I>Beispiel 1:</I> 26,.4 g p-Carbäthogyamino-benzolsulfo- chlorid werden mit 14,3 g 2-Amino-5-iso- propyl-thiodiazol-(1,3,4) (F. 180 ; herge stellt durch Einwirkung von iso-Butyryl- chlorid auf Thiosemicarbazid) und 50 cm3 Pyridin eine Stunde am Rückflusskühler auf dem Wasserbad erhitzt.
Nach dem Erkalten wird mit Äther im Überschuss gefällt, das ausgefällte Reaktionsprodukt zweimal mit Äther angerieben und nach dem Abdekantie- ren des Äthers werden 400 cm' Wasser hin zugefügt. Aus der ausfallenden Carbäthoxy- verbindung vom F.<B>173'</B> C wird durch Ver- seifung mit 2n-Natronlauge das 2-(,p-Amino- benzolsulfonamido) - 5 -isopropyl - thiodia.zol- (1,3,4) erhalten.
Es schmilzt nach dem Um lösen aus verdünntem Aceton bei 192 C.
Das gebildete p-Aminobenzolsulfonamid- derivat lässt sich auch in Form seiner Salze, z. B. des Natriums oder des Calciums, isolieren.
<I>Beispiel 2:</I> Zu einer Suspension von 1 31o1 ?-Amino- 5-isopropyl-thiodiazol-(1,3,4) in 300 cm' Pyridin wird 1 -Hol p-Acetylamino-benzol- sulfochlorid hinzugegeben, wobei die beiden Substanzen unter Erwärmung in Lösung gehen. Zur Beendigung der Reaktion wird noch 1 Stunde auf dem Wasserbade erhitzt.
Nach dem Erkalten wird das entstandene Reaktionsprodukt mit einem Liter Wasser und 500 cm' 2n-Salzsäure aus der Pyridin- lösung ausgefällt, abgesaugt, gut mit Nasser ausgewaschen und zur Abspaltung der Acetylgruppe in 500 cm' 2n-Salzsäure 2 Stunden auf dem Wasserbad erhitzt. Nach dem Erkalten wird unter Eiskühlung das 2- (p-Amino -benzolsulfonamido)-5-isopropyl- thiodiazol-(1,3,4) durch Abstumpfen der Säure mit Natriumacetat ausgefällt.
Schmelz punkt 192 C (aus Äthylalkohol). Beispiel <I>3:</I> 14,3 g 2- Aniino-5-isopropyl-thiodiazol- (1,i3.4) jvcrden in 25 cm; Pyridin aufgenom men und unter Rühren allmählich mit 23.5 g p - Acetyliimino - benzolsulfochlorid versetzt. Hierauf wird noch eine Stunde auf 95" er hitzt. Durch Eingiessen der erhaltenen Lösung in Eiswasser wird das Kondensationsprodukt in fester Form erhalten.
Es wird abgesogen und durch Kochen in verdünnter Natron lauge verseift. Das mit Essigsäure ausge fällte 2-(p-Amiiio-bezizolsulfonamido)-5-iso- propyl-thiodiazol-(1,3,4) hat nach dem Um kristallisieren aus wässerigem Alkohol den F. 192 .
Die Hydrolyse kann man auch mit an dern alkalischen Mitteln, beispielsweise Erd- all@alihydroxyden, wie Calciumhydrogyd, oder mit sauren Mitteln, z. B. Salzsäure, in Gegenwart von Wasser oder organischen Lö sungsmitteln, wie Alkohol, durchführen.
Process for the production of a new benzene sulfonamide derivative. The present patent is a process for the preparation of a new Benzolsudonamidderivates, characterized in that a 2 - benzenesulfonamido-5-isopropyl-thiodiazole- (1,3,4), which in the p-position by hydrolysis in the Has amino group convertible substituents, treated with a hydrolyzing agent.
The 2- (p-amino-benzenesulfonamido) -5-isopropyl-thiodiazole- (1,3,4) obtained in this way melts at 192. The new compound is to be used as a drug and as an intermediate product.
The 2 - benzenesulfonamido - 5 - isopropyl thiodiazole (1,3,4). which contains a substituent which can be converted into the amino group by hydrolysis in the p-position to the sulfonamide group, can be obtained in various ways.
The reaction of the corresponding reactive benzenesulfonic acid derivatives, in particular the benzenesulfonic acid halides, with 5-isopropyl-thiodiazole- (1,3,4) compounds which contain a group in the 2-position which is associated with the benzenesulfonic acid derivative is particularly suitable 2 - benzenesulfonamido -5-isopropyl-thiodiazole- (1,3,4) is able to form,
as with 2-amino-5-isopropyl-thiodiazole - (1, ä, 4). Corresponding sulfonamides of the formula RSO, NHY, in which Y denotes a radical which is split off in the subsequent reaction, can also be reacted with 5-halogen-2-isopropyl-thio-diazolen- (1,3,4). Other production methods familiar to the person skilled in the art can also be used.
<I> Example 1: </I> 26.4 g of p-carbethogyamino-benzenesulfochloride are mixed with 14.3 g of 2-amino-5-isopropyl-thiodiazole- (1,3,4) (F. 180; produced by the action of isobutyryl chloride on thiosemicarbazide) and 50 cm3 of pyridine, heated on a water bath for one hour in a reflux condenser.
After cooling, it is precipitated with ether in excess, the precipitated reaction product is rubbed twice with ether and after decanting the ether, 400 cm2 of water are added. The 2 - (, p-aminobenzenesulfonamido) -5-isopropyl-thiodia.zol- (1) is obtained from the precipitated carbethoxy compound of F. <B> 173 '</B> C by saponification with 2N sodium hydroxide solution , 3,4).
It melts after dissolving from dilute acetone at 192 C.
The p-aminobenzenesulfonamide derivative formed can also be used in the form of its salts, e.g. B. of sodium or calcium isolate.
<I> Example 2: </I> 1 -hol p-acetylamino-benzenesulfochloride is added to a suspension of 1,311? -Amino-5-isopropyl-thiodiazole- (1,3,4) in 300 cm of pyridine , the two substances going into solution with heating. To end the reaction, the mixture is heated on the water bath for a further hour.
After cooling, the resulting reaction product is precipitated from the pyridine solution with one liter of water and 500 cm 2N hydrochloric acid, filtered off with suction, washed thoroughly with water and heated in 500 cm 2N hydrochloric acid for 2 hours on a water bath to split off the acetyl group. After cooling, the 2- (p-amino-benzenesulfonamido) -5-isopropyl-thiodiazole- (1,3,4) is precipitated by blunting the acid with sodium acetate.
Melting point 192 C (from ethyl alcohol). Example <I> 3: </I> 14.3 g of 2-amino-5-isopropyl-thiodiazole- (1, i3.4) jvcrden in 25 cm; Pyridine was taken up and 23.5 g of p-acetyliimino-benzenesulfochloride were gradually added while stirring. It is then heated to 95 "for a further hour. Pouring the resulting solution into ice water gives the condensation product in solid form.
It is suctioned off and saponified by boiling in dilute sodium hydroxide solution. The precipitated with acetic acid 2- (p-Amiiio-bezizolsulfonamido) -5-isopropyl-thiodiazole- (1,3,4) has after recrystallization from aqueous alcohol the mp 192.
The hydrolysis can also be carried out with other alkaline agents, for example Erdall @ alihydroxides, such as calcium hydrogen, or with acidic agents, eg. B. hydrochloric acid, in the presence of water or organic solvents such as alcohol, perform.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE239152X | 1939-11-23 | ||
| DE239153X | 1939-11-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH239152A true CH239152A (en) | 1945-09-15 |
Family
ID=32963234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH239152D CH239152A (en) | 1939-11-23 | 1940-11-22 | Process for the production of a new benzene sulfonamide derivative. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH239152A (en) |
-
1940
- 1940-11-22 CH CH239152D patent/CH239152A/en unknown
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