CH470355A - Process for the preparation of sulfamylanthranilonitrile - Google Patents
Process for the preparation of sulfamylanthranilonitrileInfo
- Publication number
- CH470355A CH470355A CH1364068A CH1364068A CH470355A CH 470355 A CH470355 A CH 470355A CH 1364068 A CH1364068 A CH 1364068A CH 1364068 A CH1364068 A CH 1364068A CH 470355 A CH470355 A CH 470355A
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- nitrile
- preparation
- nitriles
- saponification
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 12
- 238000007127 saponification reaction Methods 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- -1 sulfamyl anthranilonitrile Chemical compound 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical group NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FKKJJPMGAWGYPN-UHFFFAOYSA-N thiophen-2-ylmethanamine Chemical compound NCC1=CC=CS1 FKKJJPMGAWGYPN-UHFFFAOYSA-N 0.000 description 2
- VMCZHVHCMSYKTN-UHFFFAOYSA-N 2-chloro-5-cyano-4-(furan-2-ylmethylamino)benzenesulfonamide Chemical compound ClC1=CC(=C(C#N)C=C1S(N)(=O)=O)NCC1=CC=CO1 VMCZHVHCMSYKTN-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- VSSQNHYJSJVUGS-UHFFFAOYSA-N 4-chloro-2-nitro-5-sulfamoylbenzamide Chemical compound S(N)(=O)(=O)C=1C=C(C(=O)N)C(=CC=1Cl)[N+](=O)[O-] VSSQNHYJSJVUGS-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical class NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- ZFRIDTQZUXVNIT-UHFFFAOYSA-N S(N)(=O)(=O)C=1C=C(C#N)C(=CC=1Cl)[N+](=O)[O-] Chemical compound S(N)(=O)(=O)C=1C=C(C#N)C(=CC=1Cl)[N+](=O)[O-] ZFRIDTQZUXVNIT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/37—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung von Sulfamylanthranilonitril
Gegenstand des Hauptpatentes ist ein Verfahren zur Herstellung von Sulfamyl-anthranilsäuren der Formel
EMI1.1
worin Hal ein Chlor oder Bromatom und R den Benzyloder Furfuryfrest bedeuten, das dadurch gekennzeichnet ist, dass man eine Verbindung der Formel
EMI1.2
worin R1 eine Hydroxygruppe, deren Wasserstoffatom auch durch ein Alkalimetall ersetzt sein kann, einen Alkoxy- oder Aralkoxyrest mit bis zu 18 Kohlenstoffatomen, ein Chlor- oder Bromatom oder eine substituierte Amino- oder Hydrazinogruppe bedeutet, mit Benzyl-, Furfuryl- oder 2-Thenylamin in Gegenwart eines organischen Lösungsmittels umsetzt und die erhaltene Verbindung gegebenenfalls anschliessend verseift und erhaltene Salze in die Säure überführt.
In weiterer Ausgestaltung dieses Verfahrens wurde nun gefunden, dass man nach dem Verfahren des Hauptpatentes zu Sulfamyl-anthranilonitrilen der Formel
EMI1.3
worin R' den Benzyl-, Furfuryl- oder Thenylrest bedeutet, gelangt, indem man ein Nitril der Formel
EMI1.4
mit Aminen der Formel
NH2R' (III) umsetzt.
Die Nitrile der Formel II lassen sich durch Wasserabspaltung der entsprechenden Benzoesäureamide, die analog dem Verfahren der deutschen Patentschrift Nr.
1 220436 aus dem 3-Sulfamyl-4-halogen-6-nitro-benzoesäurechlorid mit Ammoniak erhalten sind, herstellen.
Die Wasserabspaltung kann mit üblichen Wasser abspaltenden Mitteln, z. B. Phosphorpentachlorid, Phosphoroxychlorid oder Phosphorpentoxyd durchgeführt werden.
Die Umsetzung der so erhaltenen Nitrile der Formel II mit den Aminen der Formel III kann mit oder ohne Lösungsmittel durchgeführt werden. Als Lösungsmittel eignen sich beispielsweise niedere Alkohole wie Methanol, Äthanol oder Propanol; man kann auch Äther verwenden, z. B. Diäthyläther, Tetrahydrofuran oder Dioxan; ferner werden auch Aceton und Dimethylformamid verwendet. Man kann als Lösungsmittel auch schwache organische tertiäre Basen, beispielsweise Pyridin, Picolin oder Chinolin, verwenden. Diese basischen Lösungsmittel sind insofern vorteilhaft, als sie gleichzeitig die bei der Umsetzung freiwerdende Säure binden.
Zur Bindung der Säure kann man auch mit einem grösseren Überschuss an Amin, also mindestens 2 Mol Amin, arbeiten, was besonders im Falle des billigen Benzylamins von Vorteil ist. Beim Arbeiten mit äquivalenten Mengen Amin ist die Gegenwart eines Säurebindenden Lösungsmittels, insbesondere Pyridin, erforderlich. Zur Säurebindung kommen weiterhin auch fein gepulverte Alkalicarbonate wie Natriumbicarbonat oder Kaliumcarbonat in Gegenwart eines organischen Lösungsmittels wie Methanol oder Äthanol in Frage, wobei man dann in Suspension arbeitet.
Die Reaktionstemperaturen sind dabei in weiten Grenzen variierbar; man kann mit besonderem Vorteil bereits bei Zimmertemperatur umsetzen, andererseits ist es beispielsweise möglich, im Methanol, Äthanol, Aceton oder Diäthyläther bei Rückflusstemperatur des Lösungsmittels zu arbeiten. Die tiefen Reaktionstemperaturen bringen einen besonderen Vorteil mit sich, weil man hier zu praktisch analysenreinen Produkten und annähernd quantitativen Ausbeuten an Nitril gelangt. Die hohe Reaktionsfähigkeit der Ausgangsnitrile der Formel II gestatten es ausserdem, mit äquivalenten Mengen des betreffenden Amins zu arbeiten, wobei auch hier fast quantitative Ausbeuten erhalten werden. Dies ist ein besonderer Vorteil bei den schwerer zugänglichen Aminen 2-Thenylamin und Furfurylamin.
Die Aufarbeitung nach erfolgter Umsetzung mit den Aminen der Formel III ist sehr einfach. Man giesst z. B. in Wasser oder schwache Säuren, wobei sich das Nitril der Formel I kristallin abscheidet.
Die Umsetzung des Nitrils der Formel II mit Aminen zu den Nitrilen der Formel 1 war unerwartet und nicht vorauszusehen.
Der glatte Austausch der Nitrogruppe in den Nitrilen der Formel II gegen eine substituierte Aminogruppe ist überraschend, da nicht damit zu rechnen war, dass die der CN-Gruppe benachbarte Nitrogruppe bei Gegenwart eines Halogenatoms in 4-Stellung bevorzugt austauschbar wäre, während das Halogenatom praktisch nicht in Reaktion tritt. Es hätte vielmehr erwartet werden müssen, dass das Halogenatom in 4-Stellung, entsprechend der in den Chemischen Berichten 99, S. 346 (1966), beschriebenen Umsetzung glatt gegen Amin ausgetauscht wird, während die Nitrogruppe unverändert bleibt.
Die so erhaltenen Nitrile können anschliessend durch alkalische Verseifung in die entsprechenden Carbonsäuren übergeführt werden. Als Alkalien können z. B. wässrige verdünnte Natron- oder Kalilauge, gegebenenfalls unter Zusatz von Tetrahydrofuran oder Dioxan, verwendet werden. Die Verseifungstemperaturen liegen etwa im Bereich zwischen 60 und 100 OC. Die Verseifungsdauer beträgt etwa 1 bis 4 Stunden. Die Carbonsäure wird dann nach erfolgter Verseifung nach Verdünnen mit Wasser bei einem pH-Wert zwischen 2,5 und 3,5 kristallin abgeschieden.
Die bei der Verseifung intermediär gebildeten Carbonsäureamide können gewünschtenfalls isoliert werden, jedoch bringt es für das erfindungsgemässe Verfahren keinen Vorteil, die Verseifung zu den Carbonsäuren stufenweise durchzuführen.
Die Verseifung der Nitrile kann auch in einem Arbeitsgang mit der Herstellung dieser Nitrile durchgeführt werden, indem im Anschluss an die Umsetzung der Nitrile der Formel mit den Aminen, vorteilhaft in einem mit Wasser mischbaren Lösungsmittel wie Dioxan, überschüssige Mengen der Alkalilauge zum Reaktionsgemisch zugegeben werden und in der oben geschilderten Weise verseift wird.
Das erfindungsgemässe Verfahren ist ein besonders einfaches Verfahren, da es apparativ nur minimalen Aufwand benötigt. Die hohen Ausbeuten stellen einen weiteren Vorteil dieses Verfahrens dar.
Beispiel
1,3 g 3-Sulfamyl-4-chlor-6-nitro-benzonitril (0,005 Mol) werden in 40 ccm Propanol mit 1,0 g Furfurylamin (0,01 Mol) 1 Stunde zum Sieden unter Rückfluss erhitzt.
Nach dem Abkühlen wird das Reaktionsgemisch in Salzsäure unter Rühren eingetropft. Die dabei ausfallende bräunliche Substanz wird abgesaugt, gut mit Wasser gewaschen und über P205 getrocknet. Aus Nitromethan umkristallisiert, fällt das 3 -Sulfamyl-4-chlor-6-furfurylamino-benzonitril in feinen, farblosen gebogenen Nadeln und Nadelbüscheln an. Schmp. 238 "C (Block). 1,3 g (84 /o d. Th.).
Herstellung des Nitrils der Formel II (Hal-Chlor) 3 -Sullamyl-4-chlor-6-nitro-benzonitril:
56,0 g 3 -Sulfamyl-4-chlor-6-nitrobenzoesäureamid, hergestellt nach der im Hauptpatent beschriebenen Verfahrensweise, werden mit 80 ccm Phosphoroxychlorid unter Rühren eine Stunde in einem Ölbad von 110 "C erhitzt und nachfolgend das Phosphoroxychlorid im Vakuum abgezogen. Den Rückstand rührt man 5 Minuten bei 80 C mit 0,7 1 Wasser, wobei das gebildete Nitril kristallisiert. Schmp. 282 OC.
Process for the preparation of sulfamylanthranilonitrile
The main patent relates to a process for the preparation of sulfamyl-anthranilic acids of the formula
EMI1.1
wherein Hal is a chlorine or bromine atom and R is the benzyl or furfury radical, which is characterized in that one is a compound of the formula
EMI1.2
where R1 is a hydroxyl group whose hydrogen atom can also be replaced by an alkali metal, an alkoxy or aralkoxy group with up to 18 carbon atoms, a chlorine or bromine atom or a substituted amino or hydrazino group, with benzyl, furfuryl or 2-thenylamine reacted in the presence of an organic solvent and the compound obtained, optionally then saponified and the salts obtained converted into the acid.
In a further embodiment of this process it has now been found that the process of the main patent leads to sulfamyl-anthranilonitriles of the formula
EMI1.3
wherein R 'denotes the benzyl, furfuryl or thenyl radical, obtained by adding a nitrile of the formula
EMI1.4
with amines of the formula
NH2R '(III) converts.
The nitriles of the formula II can be separated by dehydration of the corresponding benzoic acid amides, which are prepared analogously to the process of German Patent No.
1 220436 are obtained from the 3-sulfamyl-4-halogen-6-nitro-benzoic acid chloride with ammonia.
The dehydration can be carried out using conventional water-releasing agents, e.g. B. phosphorus pentachloride, phosphorus oxychloride or phosphorus pentoxide can be carried out.
The reaction of the nitriles of the formula II thus obtained with the amines of the formula III can be carried out with or without a solvent. Suitable solvents are, for example, lower alcohols such as methanol, ethanol or propanol; you can also use ether, e.g. B. diethyl ether, tetrahydrofuran or dioxane; acetone and dimethylformamide are also used. Weak organic tertiary bases, for example pyridine, picoline or quinoline, can also be used as solvents. These basic solvents are advantageous in that they simultaneously bind the acid liberated during the reaction.
To bind the acid, it is also possible to work with a larger excess of amine, i.e. at least 2 mol of amine, which is particularly advantageous in the case of the cheap benzylamine. When working with equivalent amounts of amine, the presence of an acid-binding solvent, in particular pyridine, is required. Finely powdered alkali metal carbonates such as sodium bicarbonate or potassium carbonate in the presence of an organic solvent such as methanol or ethanol can also be used for acid binding, in which case the work is carried out in suspension.
The reaction temperatures can be varied within wide limits; it is particularly advantageous to react at room temperature, on the other hand it is possible, for example, to work in methanol, ethanol, acetone or diethyl ether at the reflux temperature of the solvent. The low reaction temperatures bring a particular advantage, because here you get practically analytically pure products and almost quantitative yields of nitrile. The high reactivity of the starting nitriles of the formula II also make it possible to work with equivalent amounts of the amine in question, almost quantitative yields being obtained here too. This is a particular advantage for the more difficult to access amines 2-thenylamine and furfurylamine.
Working up after the reaction with the amines of the formula III is very simple. You pour z. B. in water or weak acids, the nitrile of the formula I separating out in crystalline form.
The reaction of the nitrile of the formula II with amines to form the nitriles of the formula 1 was unexpected and unforeseeable.
The smooth exchange of the nitro group in the nitriles of the formula II for a substituted amino group is surprising, since it was not to be expected that the nitro group adjacent to the CN group would preferably be exchangeable in the presence of a halogen atom in the 4-position, while the halogen atom is practically not reacts. Rather, it should have been expected that the halogen atom in the 4-position would be exchanged smoothly for amine, in accordance with the reaction described in Chemischeberichte 99, p. 346 (1966), while the nitro group remained unchanged.
The nitriles obtained in this way can then be converted into the corresponding carboxylic acids by alkaline saponification. As alkalis, for. B. aqueous dilute sodium or potassium hydroxide solution, optionally with the addition of tetrahydrofuran or dioxane, can be used. The saponification temperatures are approximately in the range between 60 and 100 ° C. The saponification time is about 1 to 4 hours. The carboxylic acid is then precipitated in crystalline form after saponification, after dilution with water at a pH between 2.5 and 3.5.
The carboxamides formed as intermediates in the saponification can, if desired, be isolated, but it is of no advantage for the process according to the invention to carry out the saponification to the carboxylic acids in stages.
The saponification of the nitriles can also be carried out in one operation with the preparation of these nitriles by adding excess amounts of the alkali to the reaction mixture after the reaction of the nitriles of the formula with the amines, advantageously in a water-miscible solvent such as dioxane is saponified in the manner described above.
The method according to the invention is a particularly simple method since it requires only minimal expenditure in terms of apparatus. The high yields are another advantage of this process.
example
1.3 g of 3-sulfamyl-4-chloro-6-nitro-benzonitrile (0.005 mol) are refluxed with 1.0 g of furfurylamine (0.01 mol) in 40 cc of propanol for 1 hour.
After cooling, the reaction mixture is added dropwise to hydrochloric acid with stirring. The brownish substance which precipitates out is filtered off with suction, washed well with water and dried over P205. Recrystallized from nitromethane, the 3-sulfamyl-4-chloro-6-furfurylamino-benzonitrile is obtained in fine, colorless, curved needles and needle tufts. Mp 238 "C (block). 1.3 g (84 / o of theory).
Preparation of the nitrile of the formula II (Hal-Chlor) 3-Sullamyl-4-chloro-6-nitro-benzonitrile:
56.0 g of 3-sulfamyl-4-chloro-6-nitrobenzoic acid amide, prepared according to the procedure described in the main patent, are heated with 80 cc of phosphorus oxychloride for one hour in an oil bath at 110 ° C. with stirring and then the phosphorus oxychloride is stripped off in vacuo The residue is stirred for 5 minutes at 80 ° C. with 0.7 1 of water, the nitrile formed crystallizing, mp 282 ° C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1364068A CH470355A (en) | 1968-03-08 | 1968-07-08 | Process for the preparation of sulfamylanthranilonitrile |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH343868A CH461523A (en) | 1968-03-08 | 1968-03-08 | Process for the preparation of sulfamyl-anthranilic acids |
| CH1015968A CH466310A (en) | 1968-07-08 | 1968-07-08 | Process for the preparation of sulfamylanthranilic acids |
| CH1364068A CH470355A (en) | 1968-03-08 | 1968-07-08 | Process for the preparation of sulfamylanthranilonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH470355A true CH470355A (en) | 1969-03-31 |
Family
ID=25693010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1364068A CH470355A (en) | 1968-03-08 | 1968-07-08 | Process for the preparation of sulfamylanthranilonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH470355A (en) |
-
1968
- 1968-07-08 CH CH1364068A patent/CH470355A/en not_active IP Right Cessation
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1795344B2 (en) | PROCESS FOR THE PREPARATION OF 3-AMINOISOTHIAZOLS | |
| CH470355A (en) | Process for the preparation of sulfamylanthranilonitrile | |
| DE2406972C3 (en) | Process for the preparation of 5-sulfamoylanthranilic acids | |
| DE2503736A1 (en) | 2-Oxo-quinazoline derivs prepn - by reacting 2-dichloromethyl-phenyl isocyanates with ammonia and cyclizing | |
| CH466309A (en) | Process for the production of sulfamylanthranilonitrile | |
| DE1695067B1 (en) | Process for the preparation of 5-cyanuracils | |
| DE1806581C3 (en) | Process for the preparation of sulfamytanthranilic acids | |
| DE952121C (en) | Process for the production of leuco-sulfuric acid ester salts from hard-to-esterify kuepen dyes of the anthraquinone series | |
| AT206444B (en) | Process for the preparation of new pyridazine derivatives | |
| AT247352B (en) | Process for the preparation of new 5,6,7,8-tetrahydropyrido [4,3-d] pyrimidines | |
| CH466310A (en) | Process for the preparation of sulfamylanthranilic acids | |
| AT254189B (en) | Process for the preparation of new substituted 3- (3-hydroxyphenyl) -1-phenacylpiperidines | |
| AT367394B (en) | METHOD FOR PRODUCING NEW INDANDERIVATES | |
| AT201605B (en) | Process for the preparation of the new α, α -diphenyl-γ-hexamethyleneiminobutyramide | |
| DE602089C (en) | Process for the preparation of neutral water-soluble complex salts of mercaptopyrimidines | |
| AT368154B (en) | METHOD FOR THE PRODUCTION OF NEW LYSERGIC ACID DERIVATIVES | |
| DE942027C (en) | Process for the preparation of substituted 2-iminothiazolidines | |
| AT203496B (en) | Process for the preparation of new tertiary amines | |
| DE842064C (en) | Process for the preparation of 2-diphenylmethoxymethyl-imidazoline | |
| DE1220436B (en) | Process for the preparation of sulfamylanthranilic acids | |
| DE1695067C (en) | Process for the preparation of 5-cyanuracils | |
| DE2008874A1 (en) | Pyrimidine derivs from urea and beta-keto - esters | |
| DE859023C (en) | Process for the production of diphenylsulfone pellets | |
| AT234691B (en) | Process for the preparation of new piperidine derivatives | |
| DE1445916C (en) | Process for the preparation of compounds of the oxazole series |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |