DE3446417A1 - Novel pyrrolobenzimidazoles, process for their preparation and medicaments containing these compounds, and novel intermediates - Google Patents

Novel pyrrolobenzimidazoles, process for their preparation and medicaments containing these compounds, and novel intermediates

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Publication number
DE3446417A1
DE3446417A1 DE19843446417 DE3446417A DE3446417A1 DE 3446417 A1 DE3446417 A1 DE 3446417A1 DE 19843446417 DE19843446417 DE 19843446417 DE 3446417 A DE3446417 A DE 3446417A DE 3446417 A1 DE3446417 A1 DE 3446417A1
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Prior art keywords
group
nitro
indolin
alkyl
pyridinoylamino
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DE19843446417
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German (de)
Inventor
Jens-Peter Dr.rer.nat. 6800 Mannheim Hölck
Wolfgang Dr.Rer.Nat. 6805 Heddesheim Kampe
Alfred Dr. 6905 Schriesheim Mertens
Bernd Dr. 6718 Grünstadt Müller-Beckmann
Gisbert Dr.med.vet. 6941 Laudenbach Sponer
Klaus Prof.Dr.med. 6944 Hemsbach Strein
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Roche Diagnostics GmbH
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Boehringer Mannheim GmbH
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Priority to DE19843446417 priority Critical patent/DE3446417A1/en
Priority to PL1985259261A priority patent/PL147842B1/en
Priority to PL1985253246A priority patent/PL144822B1/en
Priority to GR851085A priority patent/GR851085B/el
Priority to IL75120A priority patent/IL75120A/en
Priority to NZ212005A priority patent/NZ212005A/en
Priority to US06/731,500 priority patent/US4666923A/en
Priority to IL84769A priority patent/IL84769A/en
Priority to PH32240A priority patent/PH22863A/en
Priority to ES542976A priority patent/ES542976A0/en
Priority to PT80425A priority patent/PT80425B/en
Priority to AU42222/85A priority patent/AU560349B2/en
Priority to AT85105675T priority patent/ATE62487T1/en
Priority to EP85105675A priority patent/EP0161632B1/en
Priority to DE8585105675T priority patent/DE3582447D1/en
Priority to KR1019850003144A priority patent/KR870001201B1/en
Priority to SU853894709A priority patent/SU1480770A3/en
Priority to DK209585A priority patent/DK209585A/en
Priority to NO851862A priority patent/NO851862L/en
Priority to HU851775A priority patent/HU193754B/en
Priority to FI851869A priority patent/FI81351C/en
Priority to JP60099742A priority patent/JPH0647593B2/en
Priority to CN85103724A priority patent/CN85103724B/en
Publication of DE3446417A1 publication Critical patent/DE3446417A1/en
Priority to KR1019870004128A priority patent/KR870001202B1/en
Priority to IL84769A priority patent/IL84769A0/en
Priority to US07/217,143 priority patent/US4963686A/en
Priority to FI883391A priority patent/FI883391A0/en
Priority to JP5310823A priority patent/JPH0772185B2/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C07D209/34—Oxygen atoms in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/42—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/96—Spiro-condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Novel pyrrolobenzimidazoles of the formula I <IMAGE> in which R1 denotes a hydrogen atom, an alkyl, alkenyl or a cycloalkyl group, R2 denotes a hydrogen atom, an alkyl, alkenyl or cyano group, a carbonyl group substituted by a hydroxyl, alkyl, alkoxy, amino, alkylamino, dialkylamino or hydrazino group, or, together with R1, represents a cycloalkylene group or R1 and R2 together form an alkylidene or cycloalkylidene group, X denotes a valency dash, a C1-C4-alkylene group or the vinyl group, T equals oxygen or denotes sulphur, Py represents a 2- ,3- or 4-pyridyl radical, which optionally carries an oxygen atom on the ring hetero atom and/or can be substituted by one or more alkyl, alkoxy, hydroxyl, cyano or nitro groups, as well as by halogen, their tautomers and their physiologically tolerable salts, process for their preparation, medicaments, which contain compounds of the formula I, for the treatment of cardiac and circulatory disorders, and compounds of the formula IIa <IMAGE> in which R1 and R2 have the meanings given in formula I, A and B denote hydrogen, an amino or nitro group or the group <IMAGE> with the proviso that A and B are different, but can simultaneously represent two amino groups, as intermediates for the preparation of compounds of the formula I.

Description

Neue Pyrrolo-Benzimidazole, Verfahren zu ihrer HerstellungNew pyrrolo-benzimidazoles, process for their preparation

und diese Verbindungen enthaltende Arzneimittel sowie Zwischenprodukte Die vorliegende Erfindung betrifft neue Pyrrolo-Benzimidazole der allgemeinen Formel I in welcher R1 ein Wasserstoffatom, eine Alkyl-, Alkenyl- oder eine Cycloalkylgruppe bedeutet, R2 ein Wasserstoffatom, eine Alkyl-, Alkenyl-, oder Cyangruppe, eine durch eine Hydroxy-, Alkyl-, Alkoxy-, Amino-, Alkylamino-, Dialkylamino- oder Hydrazinogruppe substituierte Carbonylgruppe bedeutet oder mit R1 zusammen eine Cycloalkylengruppe darstellt oder R1 und R2 zusammen eine Alkyliden- oder Cycloalkylidengruppe bilden, X einen Valenzstrich, eine C1-C4-Alkylengruppe oder die Vinylgruppe bedeutet, T gleich Sauerstoff oder Schwefel bedeutet, Py einen 2-, 3- oder 4-Pyridylrest darstellt, der gegebenenfalls am Ringheteroatom ein Sauerstoffatom traegt und/ oder durch eine oder mehrere Alkyl-, Alkoxy-, Hydroxy-, Cyano- oder Nitrogruppen, sowie durch Halogen substituiert sein kann, deren Tautomere und deren physiologisch vertraegliche Salze anorganischer und organischer Saeuren und Verfahren zu ihrer Herstellung, sowie diese Verbindungen enthaltende Arzneimittel.and medicaments containing these compounds, as well as intermediates. The present invention relates to new pyrrolo-benzimidazoles of the general formula I in which R1 denotes a hydrogen atom, an alkyl, alkenyl or a cycloalkyl group, R2 denotes a hydrogen atom, an alkyl, alkenyl or cyano group, one by a hydroxy, alkyl, alkoxy, amino, alkylamino, dialkylamino - or hydrazino group denotes a carbonyl group substituted with R1 or represents a cycloalkylene group together or R1 and R2 together form an alkylidene or cycloalkylidene group, X denotes a valence stroke, a C1-C4 alkylene group or the vinyl group, T denotes oxygen or sulfur, Py denotes a 2 -, 3- or 4-pyridyl radical, which optionally carries an oxygen atom on the ring heteroatom and / or can be substituted by one or more alkyl, alkoxy, hydroxy, cyano or nitro groups, and by halogen, their tautomers and their physiological Compatible salts of inorganic and organic acids and processes for their preparation, as well as medicaments containing these compounds.

Da die Verbindungen der allgemeinen Formel I fuer den Fall, daß R1 nicht gleich R2 ist, ein asymmetrisches Kohlenstoffatom besitzen, sind auch Gegenstand der Erfindung die optisch aktiven Formen und racemischen Gemische dieser Verbindungen.Since the compounds of the general formula I for the case that R1 is not equal to R2, have an asymmetric carbon atom, are also subject of the invention the optically active forms and racemic mixtures of these compounds.

Diese neuen Verbindungen der vorliegenden Erfindung weisen wertvolle pharmakologische Eigenschaften auf, insbesondere steigern sie die Herzkraft und/oder wirken blutdrucksenkend und/oder beeinflussen die Thrombozytenaggregation und verbessern die Mikrozirkulation.These new compounds of the present invention have valuable pharmacological properties, in particular they increase heart strength and / or have an antihypertensive effect and / or influence and improve platelet aggregation the microcirculation.

In der allgemeinen Formel I bzw. VIII, IX, XIII und XIV koennen die Substituenten R1 und R2 gleich oder verschieden sein und Wasserstoff, eine geradkettige oder verzweigte Alkyl-oder Alkenylgruppe mit 1-6 bzw. 2-6 Kohlenstoffatomen, eine Cyanogruppe oder eine durch eine Hydroxy-, Alkyl-, Alkoxy-, Amino-, Alkylamino-, Dialkylamino-, oder Hydrazinogruppe substituierte Carbonylgruppe darstellen, wobei jeder der vorgenannten Alkylteile geradkettig oder verzweigt aus 1-6 bzw. 2-6 Kohlenstoffatomen zusammengesetzt sein kann.In the general formula I or VIII, IX, XIII and XIV, the Substituents R1 and R2 may be identical or different and hydrogen, a straight-chain one or branched alkyl or alkenyl group with 1-6 or 2-6 carbon atoms, a Cyano group or a hydroxy, alkyl, alkoxy, amino, alkylamino, Dialkylamino, or hydrazino group represent substituted carbonyl group, wherein each of the aforementioned alkyl parts straight-chain or branched from 1-6 or 2-6 carbon atoms can be composed.

Insbesondere kommen jedoch Wasserstoff, die Methyl-, Ethyl-, Allyl-, Cyan-, Carboxy-, Acetyl-, Propionyl-, Methoxycarbonyl-, Ethoxycarbonyl-, Aminocarbonyl-, Methylaminocarbonyl-, Dimethylaminocarbonyl- und Hydrazinocarbonylgruppe fuer R1 und R2 in Frage.In particular, however, come hydrogen, the methyl, ethyl, allyl, Cyano, carboxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, Methylaminocarbonyl, dimethylaminocarbonyl and hydrazinocarbonyl group for R1 and R2 in question.

Stellt nur. R2 ein Wasserstoffatom dar, so ist R1 eine geradkettige Alkylgruppe mit 1-6 Kohlenstoffatomen oder eine verzweigte Alkylgruppe, eine Cycloalkyl- oder Alkenylgruppe mit 3-7 Kohlenstoffatomen, eine Cyanogruppe oder eine durch eine Alkyl-, Alkoxy-, Amino-, Alkylamino-, Dialkylamino- oder Hydrazinogruppe substituierte Carbonylgruppe. Bevorzugt in diesem Sinne sind die Methyl-, Ethyl-, Cyclopentyl-, Cyclohexy-,Allyl-, Cyan-, Acetyl-, Propionyl-, Methoxycarbonyl-, Ethoxycarbonyl-, Aminocarbonyl-, Methylaminocarbonyl-, Dimethylaminocarbonyl- und Hydrazinocarbonylgruppe.Just ask. R2 represents a hydrogen atom, then R1 is a straight-chain one Alkyl group with 1-6 carbon atoms or a branched alkyl group, a cycloalkyl or alkenyl group with 3-7 carbon atoms, a cyano group or one through one Substituted alkyl, alkoxy, amino, alkylamino, dialkylamino or hydrazino groups Carbonyl group. Preferred in this sense are the methyl, ethyl, cyclopentyl, Cyclohexy, allyl, cyano, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, Aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl and hydrazinocarbonyl groups.

R1 und R2 koennen zusammen mit dem C-Atom, an das sie gebunden sind, auch einen Cycloalkylring mit 3-8 Kohlenstoffatomen bilden, vorzugsweise handelt es sich dabei um die Spirocyclopropyl-, Spirocyclobutyl-, Spirocyclopentyl- und Spirocyclohexylgruppe.R1 and R2 can, together with the carbon atom to which they are bound, also form a cycloalkyl ring with 3-8 carbon atoms, preferably acts it is the spirocyclopropyl, spirocyclobutyl, spirocyclopentyl and Spirocyclohexyl group.

R1 und R2 koennen zusammen auch eine Alkyliden- oder Cycloalkylidengruppe bilden, vorzugsweise handelt es sich dabei um die Isopropylidengruppe.R1 and R2 together can also be an alkylidene or cycloalkylidene group form, preferably it is the isopropylidene group.

Alkyl- oder Alkoxy-Substituenten des Pyridin-Rings koennen 1-6, vorzugsweise 1-4 C-Atome enthalten. Bevorzugt ist Methyl und Ethyl bzw. Methoxy und Ethoxy. Unter Halogen ist Fluor, Chlor und Brom, vorzugsweise Chlor zu verstehen.Alkyl or alkoxy substituents on the pyridine ring can be 1-6, preferably Contains 1-4 carbon atoms. Methyl and ethyl or methoxy and ethoxy are preferred. Under Halogen is to be understood as fluorine, chlorine and bromine, preferably chlorine.

Stellt Py einen 2-, 3- oder 4-Pyridylrest dar, der gegebenenfalls am Ringheteroatom ein Sauerstoffatom traegt und/oder durch eine oder mehrere Alkyl-, Alkoxy-, Hydroxy-, Cyano-oder Nitrogruppen,sowie durch Halogen substituiert sein kann und X ist ein Valenzstrich, so sind in diesem Sinne bevorzugt der 2-Pyridyl-, 2-(N-Oxy-pyridyl}-, 2-(5-n-Butyl-pyridyll-, 3-Pyridyl-, 3-(N-Oxy-pyridyl)-, 3- (6-Methyl-pyridyl) -, 3-(6-Cyan-pyridyl)-, 3-(6-Nitro-pyridyl)-, 3- (6-Hydroxypyridyl)-, 3-(2-Methoxy-6-methyl-pyridyl)-, 4-Pyridyl-, 4- (N-Oxy-pyridyl) -, 4-(2-Methyl-pyridyl)-, 4-(2-Ethylpyridyl)-, 4-(2-Hydroxy-pyridyl)-, 4-(2-Methoxy-pyridyl)-, 4-(2-Nitro-pyridyl)-, 4-(2-Chlor-pyridyl)- und der 4-(3-Hydroxy-pyridyl)-rest.Py represents a 2-, 3- or 4-pyridyl radical, which optionally on the ring heteroatom carries an oxygen atom and / or by one or more alkyl, Alkoxy, hydroxyl, cyano or nitro groups, and also be substituted by halogen can and X is a valence stroke, so are preferred in this sense the 2-pyridyl-, 2- (N-oxy-pyridyl} -, 2- (5-n-butyl-pyridyl-, 3-pyridyl-, 3- (N-oxy-pyridyl) -, 3- (6-methyl-pyridyl) -, 3- (6-cyano-pyridyl) -, 3- (6-nitro-pyridyl) -, 3- (6-hydroxypyridyl) -, 3- (2-methoxy-6-methyl-pyridyl) -, 4-pyridyl-, 4- (N-oxy-pyridyl) -, 4- (2-methyl-pyridyl) -, 4- (2-ethylpyridyl) -, 4- (2-hydroxypyridyl) -, 4- (2-methoxypyridyl) -, 4- (2-nitro-pyridyl) -, 4- (2-chloropyridyl) and the 4- (3-hydroxypyridyl) radical.

Bedeutet X eine C1-C4 Alkylengruppe oder die Vinylgruppe und Py einen 2-, 3-oder 4-Pyridylrest, so sind in diesem Sinne besonders bevorzugt der 3-Pyridyl-methyl-, 3-Pyridyl-ethyl-, 3-Pyridyl-vinyl-, 4-Pyridyl-methyl-, 4-Pyridyl-ethyl und 4-Pyridyl-vinylrest.X denotes a C1-C4 alkylene group or the vinyl group and Py denotes one 2-, 3- or 4-pyridyl radical, so in this sense the 3-pyridyl-methyl-, 3-pyridyl-ethyl, 3-pyridyl-vinyl, 4-pyridyl-methyl, 4-pyridyl-ethyl and 4-pyridyl-vinyl radicals.

Die Herstellung der Verbindungen der allgemeinen Formel I durch Umsetzung von einem entsprechendem 5,6-Diamino-indolin-2-on der allgemeinen Formel II in der R1 und R2 die oben angegebene Bedeutung besitzen, mit einer Verbindung der Formel III Py-X-CO-Y (III), in der Py und X die angegebene Bedeutung besitzen und Y entweder Wasserstoff oder einen leicht abspaltbaren Rest darstellt, und die anschließende Cyclisierung, sowie vorangehende Verfahrensschritte sind in der deutschen Patentanmeldung P 34 10 168.3 beschrieben.The preparation of the compounds of the general formula I by reacting a corresponding 5,6-diamino-indolin-2-one of the general formula II in which R1 and R2 have the meaning given above, with a compound of the formula III Py-X-CO-Y (III), in which Py and X have the meaning given and Y is either hydrogen or an easily cleavable radical, and the subsequent cyclization and preceding process steps are described in German patent application P 34 10 168.3.

Ausgehend von Verbindungen der Formel IV in denen R1, R2 und T die oben angegebene Bedeutung besitzen, lassen sich durch Umsetzungen mit Verbindungen der allgemeinen Formel III nach allgemein bekannter oder in der deutschen Patentanmeldung P 34 10 168.3 beschriebener Weise auch Verbindungen der Formel VI in denen Rs, R2, T, Py und X die oben angegebenen Bedeutungen besitzen, erhalten und in bekannter Weise durch Nitrierung in Verbindungen der allgemeinen Formel VIII in denen R1, R2, T, Py und X die oben angegebenen Bedeutungen besitzen, ueberfuehren.Starting from compounds of the formula IV in which R1, R2 and T have the meaning given above, compounds of the formula VI can also be converted into compounds of the formula VI by reactions with compounds of the general formula III in a manner generally known or as described in German patent application P 34 10 168.3 in which Rs, R2, T, Py and X have the meanings given above, obtained and in a known manner by nitration in compounds of the general formula VIII in which R1, R2, T, Py and X have the meanings given above, transfer.

Nach Hydrierung der Nitrogruppe in den Verbindungen der allgemeinen Formel VIII bzw. IX zu den entsprechenden Aminoverbindungen X in denen Rt, R2, T, Py und X die oben angegebene Bedeutung besitzen, erhaelt man durch Cyclisierung in einem Loesungsmittel oder Loesungsmittelgemisch wie Ethanol, Isopropanol, Eisessig, Benzol, Toluol, Chlorbenzol, Glycol, Ethylenglycoldimethylether, Sulfolan oder Dimethylformamid bei Temperaturen zwischen OOC und 22O0C, vorzugsweise jedoch bei der Siedetemperatur des Reaktionsgemisches, gegebenenfalls in Gegenwart eines Kondensationsmittels wie Phosphoroxychlorid, Thionylchlorid, p-Toluolsulfonsaeure, Salzsaeure, Schwefelsaeure, Phosphorsaeure, Polyphosphorsaeure oder gegebenenfalls auch in Gegenwart einer Base wie Natriumhydroxid, Natriumethylat oder Kalium-tert.-butylat die gewuenschten Verbindungender allgemeinen Formel I. Die Cyclisierung kann jedoch auch ohne Loesungsmittel und/oder Kondensationsmittel durchgefuehrt werden.After hydrogenation of the nitro group in the compounds of the general formula VIII or IX to give the corresponding amino compounds X in which Rt, R2, T, Py and X have the meaning given above, are obtained by cyclization in a solvent or solvent mixture such as ethanol, isopropanol, glacial acetic acid, benzene, toluene, chlorobenzene, glycol, ethylene glycol dimethyl ether, sulfolane or dimethylformamide at temperatures between OOC and 220 ° C., but preferably at the boiling point of the reaction mixture, optionally in the presence of a condensing agent such as phosphorus oxychloride, thionyl chloride, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid or optionally also in the presence of a base such as sodium hydroxide, sodium ethoxide or potassium tert-butoxide the desired compounds of general formula I. The cyclization can, however, also be carried out without a solvent and / or condensing agent.

Verbindungen der Formel V erhaelt man z.B. durch Nitrierung von Verbindungen der allgemeinen Formel XII in 5-Stellung und nachfolgende Reduktion der Nitro- zur Aminogruppe. Durch in allgemein bekannter Weise uebliche Acetylierung an der 5- bzw. 6-Aminofunktion, nachfolgender Nitrierung und Abspaltung der Acetylschutzgruppen an Verbindungen der allgemeinen Formel IV bzw. V erhaelt man Verbindungen der allgemeinen Formel XIII in denen R1, R2 und T die oben angegebene Bedeutung haben.Compounds of the formula V are obtained, for example, by nitration of compounds of the general formula XII in the 5-position and subsequent reduction of the nitro to the amino group. Compounds of general formula XIII are obtained by acetylation on the 5- or 6-amino function, which is customary in a generally known manner, followed by nitration and cleavage of the acetyl protective groups on compounds of general formula IV or V in which R1, R2 and T have the meaning given above.

Durch Umsetzungen mit Verbindungen der allgemeinen Formel III lassen sich in der oben beschriebenen Weise ebenfalls Verbindungen der allgemeinen Formel VIII bzw. IX erhalten.Let by reactions with compounds of the general formula III Compounds of the general formula can also be found in the manner described above VIII and IX, respectively.

Die oben erwaehnte Hydrierung einer Nitrogruppe wird vorzugsweise in einem Loesungsmittel oder Loesungsmittelgemisch wie Wasser, Methanol, Ethanol, Eisessig, Essigsaeureethylester oder Dimethylformamid mit Wasserstoff in Gegenwart eines Katalysators wie Raney-Nickel, Platin oder Palladium/Kohle, mit Metallen wie Eisen, Zinn oder Zink in Gegenwart einer Saeure, mit Salzen wie Eisen(II)sulfat, Zinn(II)chlorid, Natriumsulfid, Natriumhydrogensulfit oder Natriumdithionit oder mit Hydrazin in Gegenwart von Raney-Nickel bei Temperaturen zwischen 0 und 1000C, vorzugsweise jedoch bei Raumtemperatur, durchgefuehrt.The above-mentioned hydrogenation of a nitro group is preferred in a solvent or solvent mixture such as water, methanol, ethanol, Glacial acetic acid, ethyl acetate or dimethylformamide with hydrogen in the presence a catalyst such as Raney nickel, platinum or palladium / carbon, with metals such as Iron, tin or zinc in the presence of an acid, with salts such as iron (II) sulfate, Tin (II) chloride, sodium sulfide, sodium hydrogen sulfite or sodium dithionite or with hydrazine in the presence of Raney nickel at temperatures between 0 and 1000C, but preferably carried out at room temperature.

Verbindungen der allgemeinen Formel I oder deren tautomere Formen sowie die hierzu fuehrenden verschiedenen Zwischennach produkte lassen sich au3erUden in der deutschen Patentanmeldung P 34 10 168.3 oder oben beschriebenen Verfahren auch nach verschiedenen literaturbekannten Verfahren, z.B. aus Verbindungen der allgemeinen Formel XV mit Py und X in der oben angegebenen Bedeutung, herstellen (siehe hierzu auch R.C. Elderfield (Ed.), P.L. Julian, E.W. Meyer, H.C. Printy, Heterocycl. Comp. Vol. 3, 126-186, John Wiley&Sons 1952, New York>.Compounds of the general formula I or their tautomeric forms and the various intermediate products leading to them can also be found in German patent application P 34 10 168.3 or the processes described above also by various processes known from the literature, for example from compounds of the general formula XV with Py and X in the meaning given above (see also RC Elderfield (Ed.), PL Julian, EW Meyer, HC Printy, Heterocycl. Comp. Vol. 3, 126-186, John Wiley & Sons 1952, New York> .

Entsprechende Verbindungen oder Zwischenprodukte werden auch erhalten durch Umsetzungen von Phenylhydrazin bzw. entsprechend substituierten Phenylhydrazinen nach der von K. Brunner, Monatsh.f.Chemie 18, 95 (1897) beschriebenen Weise oder z.B. durch Alkylierung von 2,4-Dinitrochlorbenzol mit geeignet substituierten Malonsaeurederivaten, z.B. dem Natriumsalz des Methylmalonsaeurediethylesters, nach literaturbekannten Verfahren, anschließende Reduktion der Nitrogruppen und Ringschluß zu Verbindungen der allgemeinen Formel IV.Corresponding compounds or intermediates are also obtained by reactions of phenylhydrazine or appropriately substituted phenylhydrazines according to the manner described by K. Brunner, Monatsh.f. Chemie 18, 95 (1897) or e.g. by alkylating 2,4-dinitrochlorobenzene with appropriately substituted malonic acid derivatives, e.g. the sodium salt of methylmalonic acid diethyl ester, according to the literature Process, subsequent reduction of the nitro groups and ring closure to form compounds of the general formula IV.

Die nachtraegliche Umwandlung einer Verbindung der allgemeinen Formel I in eine andere Verbindung der Formel I wird in der Weise vorgenommen wie in der deutschen Patentanmeldung P 34 10 168.3 beschrieben. Außerdem betrifft die nachtraegliche Umwandlung Verbindungen der allgemeinen Formel I in denen R1 oder R2 eine Carboxylgruppe oder ein reaktionsfaehiges Derivat wie z.B. Carbonsaeureester oder Saeurechlorid darstellt, die sich mit Hydrazin, Ammoniak, einem primaeren oder sekundaeren Amin oder einem reaktionsfaehigen Derivat hiervon zu neuen Verbindungen der allgemeinen Formel I, in denen R1 oder R2 eine durch eine Amino-, Alkylamino-, Dialkylamino- oder Hydrazinogruppe substituierte Carbonylgruppe ist, umsetzen lassen. Die nachtraegliche Umwandlung betrifft auch Verbindungen der allgemeinen Formel I in denen R1 oder R2 eine Aminocarbonylgruppe darstellt zu solchen in denen R1 oder R2 eine Cyanogruppe ist, sowie die nachtraegliche Umwandlung einer Cyanogruppe in eine Carboxyl-, Aminocarbonyl- oder Alkoxycarbonylgruppe. Diese Umwandlungen werden alle nach allgemein ueblichen und literaturbekannten Methoden vorgenommen.The subsequent transformation of a compound of the general formula I into another compound of formula I is made in the manner as in the German patent application P 34 10 168.3. It also affects the subsequent Conversion of compounds of general formula I in which R1 or R2 is a carboxyl group or a reactive derivative such as carboxylic acid ester or acid chloride represents, which is with hydrazine, ammonia, a primary or secondary amine or a reactive derivative thereof to form new compounds of the general Formula I, in which R1 or R2 is an amino, alkylamino, dialkylamino or hydrazino group is substituted carbonyl group. The subsequent Conversion also relates to compounds of the general formula I in which R1 or R2 represents an aminocarbonyl group to those in which R1 or R2 is a cyano group is, as well as the subsequent conversion of a cyano group into a carboxyl, aminocarbonyl or alkoxycarbonyl group. These conversions are all generally customary and methods known from the literature.

Die nachtraegliche Umwandlung zu Verbindungen der allgemeinen Formel I und den zu den Verbindungen der allgemeinen Formel I fuehrenden Zwischenprodukten in denen T ein Schwefelatom bedeutet, aus solchen in denen T ein Sauerstoffatom darstellt, wird nach literaturbekannten Verfahren mit einem das Schwefelatom uebertragenden Reagenz wie z.B. Phosphorpentasulfid oder 2,4-Bis(4-methoxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetan in einem geeigneten Loesungsmittel wie z.B. Tetrahydrofuran, Dioxan, Ethylenglycoldimethylether, Benzol, Toluol oder Pyridin bei Temperaturen zwischen OOC und der Siedetemperatur des Reaktionsgemisches durchgefuehrt.The subsequent conversion to compounds of the general formula I and the intermediates leading to the compounds of general formula I. in which T is a sulfur atom, of those in which T is an oxygen atom represents, is carried out according to methods known from the literature with a sulfur atom transferring Reagent such as phosphorus pentasulfide or 2,4-bis (4-methoxyphenyl) -2,4-dithioxo-1,3,2,4-dithiadiphosphetane in a suitable solvent such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Benzene, toluene or pyridine at temperatures between OOC and the boiling point of the reaction mixture carried out.

Die Verbindungen der allgemeinen Formel VIII, IX, XIII und XIV, in denen R1 ein Wasserstoffatom, eine Alkyl-, Alkenyl- oder eine Cycloalkylgruppe bedeutet, R2 ein Wasserstoffatom, eine Alkyl-, Alkenyl- oder Cyanogruppe, eine durch eine Hydroxy-, Alkyl-, Alkoxy-, Amino-, Alkylamino-, Dialkylamino- oder Hydrazinogruppe substituierte Carbonylgruppe bedeutet oder mit R1 zusammen eine Alkyliden- oder Cycloalkylidengruppe bilden, X einen Valenzstrich, eine C1-C4 Alkylengruppe oder die Vinylgruppe bedeutet, T gleich Sauerstoff oder Schwefel ist, und Py einen 2-,3-, oder 4-Pyridylrest darstellt, der gegebenenfalls durch eine oder mehrere Alkyl-, Alkoxy-, Hydroxy-, Cyano- oder Nitrogruppen, sowie durch Halogen substituiert sein kann, sind neu und ebenfalls Gegenstand der Erfindung.The compounds of the general formula VIII, IX, XIII and XIV, in where R1 is a hydrogen atom, an alkyl, alkenyl or a cycloalkyl group, R2 is a hydrogen atom, an alkyl, alkenyl or cyano group, one by one Hydroxy, alkyl, alkoxy, amino, alkylamino, dialkylamino or hydrazino group substituted carbonyl group or together with R1 is an alkylidene or Form a cycloalkylidene group, X a valence stroke, a C1-C4 alkylene group or denotes the vinyl group, T is oxygen or sulfur, and Py is a 2-, 3-, or 4-pyridyl radical, which is optionally replaced by one or more alkyl, Alkoxy, hydroxyl, cyano or nitro groups, and also be substituted by halogen can, are new and also the subject of the invention.

Erfindungsgemaeße Verbindungen der Formel XIV sind außer den in den Beispielen genannten Verbindungen folgende: 5-Amino-6-nitro-3-acetyl-indolin-2-on 5-Amino-6-nitro-3-acetyl-3-methyl-indolin-2-on 5-Amino-6-nitro-3-allyl-indolin-2-on 5-Amino-6-nitro-3-cyan-3-methyl-indolin-2-on 5-Amino-6-nitro-3-cyclohexyl-indolin-2-on 5-Amino-6-nitro-3-cyclopentyl-indolin-2-on 5-Amino-6-nitro-3,3-diallyl-indolin-2-on 5-Amino-6-nitro-3,3-diethyl-indolin-2-on 5-Amino-6-nitro-3,3-dimethyl-indolin-2-on 5-Amino-6-nitro-3-ethoxycarbonyl-indolin-2-on 5-Amino-6-nitro-3-ethoxycarbonyl-3-ethyl-indolin-2-on 5-Amino-6-nitro-3-ethoxycarbonyl-3-methyl-indolin-2-on 5-Amino-6-nitro-3-ethyl-indolin-2-on 5-Amino-6-nitro-3-methoxycarbonyl-indolin-2-on 5-Amino-6-nitro-3-methoxycarbonyl-3-methyl-indolin-2-on 5-Amino-6-nitro-3-methyl-indolin-2-on 5-Amino-6-nitro-3- (3-pentyl) -indolin-2-on 5-Amino-6-nitro-3- (2-propyl) -indolin-2-on 5-Amino-6-nitro-3-(2-methyl-propyl)-indolin-2-on 5'-Amino-6'-nitro-spiro[cyclohexan-1,3'-indolin]-2'-on S'-Amino-6'-nitro-spiro[cyclopentan-1,3'-indolin]-2'-on 5-Amino-6-nitro-3 , 3-dimethyl-indolin-2-thion 5-Amino-6-nitro-3-ethyl-indolin-2-thion 5-Amino-6-nitro-3-methyl-indolin-2-thion Erfindungsgemaeße Verbindungen der Formel XIII sind außer den in den Beispielen genannten Verbindungen folgende: 6-Amino-5-nitro-indolin-2-on 6-Amino-5-nitro-3-acetyl-indolin-2-on 6-Amino-5-nitro-3-acetyl-3-methyl-indolin-2-on 6-Amino-5-nitro-3-allyl-indolin-2-on 6-Amino-5-nitro-3-cyan-3-methyl-indolin-2-on 6-Amino-5-nitro-3-cyclohexyl-indolin-2-on 6-Amino-5-nitro-3-cyclopentyl-indolin-2-on 6-Amino-5-nitro-3,3-diallyl-indolin-2-on 6-Amino-5-nitro-3,3-dimethyl-indolin-2-on 6-Amino-5-nitro-3-ethoxycarbonyl-indolin-2-on 6-Amino-5-nitro-3-ethoxycarbonyl-3-ethyl-indolin-2-on 6-Amino-5-nitro-3-ethoxycarbonyl-3-methyl-indolin-2-on 6-Amino-5-nitro-3-ethyl-indolin-2-on 6-Amino-5-nitro-3-methoxycarbonyl-indolin-2-on 6-Amino-5-nitro-3-methoxycarbonyl-3-methyl-indolin-2-on 6-Amino-5-nitro-3-methyl-indolin-2-on 6-Amino-5-nitro-3- (3-pentyl) -indolin-2-on 6-Amino-5-nitro-3- (2-propyl) -indolin-2-on 6-Amino-5-nitro-3-(2-methyl-propyl)-indolin-2-on 6'-Amino-5'-nitro-spiroEcyclohexan-1,3'-indolin]-2'-on 6'-Amino-5'-nitro-spiro[cyclopentan-1,3'-indolin]-2'-on 6-Amino-5-nitro-3,3-dimethyl-indolin]-2-thion 6-Amino-5-nitro-3-ethyl-indolin-2-thion 6-Amino-5-nitro-3-methyl-indolin-2-thion Erfindungsgemaeße Verbindungen der Formel VIII sind außer den in den Beispielen genannten Verbindungen folgende: 5-Nitro-6-(3-pyridinoylamino)-indolin-2-on 3-Acetyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3-Acetyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-on 3-Acetyl-3-methyl-5-nitro-6-(3-pyridinoylamino)-indolin-2-on 3-Acetyl-3-methyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-on 3-Allyl-5-nitro-6-(3-pyridinoylamino)-indolin-2-on 3-Allyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-on 3-Cyan-3-methyl-5-nitro-6-(3-pyridinoylamino)-indolin-2-on 3-Cyan-3-methyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-on 3-Cyclohexyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3-Cyclohexyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3-Cyclopentyl-5-nitro-6-(3-pyridinoylamino)-indolin-2-on 3-Cyclopentyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3 ,3-Diallyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3 ,3-Diallyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3 ,3-Dimethyl-5-nitro-6- (2-pyridinoylamino) -indolin-2-on 3 ,3-Dimethyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3,3-Dimethyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-on 3,3-Dimethyl-5-nitro-6-(2-(5-n-butyl-pyridinoylamino))-indolin- 2-on 3,3-Dimethyl-5-nitro-6-(3-(6-cyan-pyridinoylamino))-indolin- 2-on 3,3-Dimethyl-5-nitro-6-(3-(6-methyl-pyridinoylamino))-indolin-2-on 3,3-Dimethyl-5-nitro-6-(4-(2-methyl-pyridinoylamino))-indolin-2-on 3,3-Dimethyl-5-nitro-6-(4-(2-hydroxy-pyridinoylamino))-indolin-2-on 3-Ethoxycarbonyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3-Ethoxycarbonyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3-Ethoxycarbonyl-3-ethyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3-Ethoxycarbonyl-3-ethyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3-Ethoxycarbonyl-3-methyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3-Ethoxycarbonyl-3-methyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3-Ethyl-5-nitro-6-(3-pyridinoylaminoJ-indolin-2-on 3-Ethyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3-Methoxycarbonyl-5-nitro-6-(3-pyridinoylamino)-indolin-2-on 3-Methoxycarbonyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-on 3-Methoxycarbonyl-3-methyl-5-nitro-6- (3-pyridinoylamino) -indolin- 2-on 3-Methoxycarbonyl-3-methyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3-Methyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3-Methyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3- (3-Pentyl) -5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3- (3-Pentyl) -5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3- (2-Propyl) -5-nitro-6- (3-pyridinoylamino) -indolin-2-on 3- (2-Propyl) -5-nitro-6- (4-pyridinoylamino) -indolin-2-on 3-(2-Methyl-propyl)-5-nitro-6-(3-pyridinoylamino)-indolin-2-on 3-(2-Methyl-propyl)-5-nitro-6-(4-pyridinoylamino)-indolin-2-on 5'-Nitro-6'-(3-pyridinoylamino)-spiro[cyclohexan-1,3'-indolin]-2'-on 5'-Nitro-6'-(4-pyridinoylamino)-spiro[cyclohexan-1,3'-indolin]-2'-on 5'-Nitro-6'-(3-pyridinoylamino)-spiro[cyclopentan-1,3'-indolin]-2'-on 5'-Nitro-6'-(4-pyridinoylamino)-spiro[cy indolin]-2'-on 3,3-Dimethyl-5-nitro-6-(2-pyridinoylamino)-indolin-2-thion 3,3-Dimethyl-5-nitro-6-(3-pyridinoylamino)-indolin-2-thion 3,3-Dimethyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-thion 3-Ethyl-5-nitro-6- (2-pyridinoylamino) -indolin-2-thion 3-Ethyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-thion 3-Ethyl-5-nitro-6- (4-pyridionylamino) -indolin-2-thion 3-Methyl-5-nitro-6- (2-pyridinoylamino) -indolin-2-thion 3-Methyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-thion 3-Methyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-thion Erfindungsgemaeße Verbindungen der allgemeinen Formel IX sind außer in den Beispielen genannten Verbindungen folgende: 6-Nitro-5-(3-pyridinoylamino)-indolin-2-on 6-Nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Acetyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3-Acetyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Acetyl-3-methyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3-Acetyl-3-methyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Allyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3-Allyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Cyan-3-methyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3-Cyan-3-methyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Cyclohexyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3-Cyclohexyl-6-nitro-5- (4-pyridinoylamino) -indolin-2-on 3-Cyclopentyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3-Cyclopentyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3,3-Diallyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3,3-Diallyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3,3-Diallyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3,3-Diallyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3 ,3-Dimethyl-6-nitro-5- (2-pyridinoylamino) -indolin-2-on 3,3-Dimethyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3,3-Dimethyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3,3-Dimethyl-6-nitro-5-(2-(5-n-butyl-pyridinoylamino)-indolin-2-on 3,3-Dimethyl-6-nitro-5-(3-(6-cyan-pyridinoylamino))-indol in- 2-on 3,3-Dimethyl-6-nitro-5-(3-(6-methyl-pyridinoylamino)).-indolin-2-on 3,3-Dimethyl-6-nitro-5-(4-(2-methyl-pyridinoylamino))-indolin-2-on 3,3-Dimethyl-6-nitro-5-(4-(2-hydroxy-pyridinoylaminOl]-indol in- 2-on 3-Ethoxycarbonyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3-Ethoxycarbonyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Ethoxycarbonyl-3-ethyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3-Ethoxycarbonyl-3-ethyl-6-nitro-5- (4-pyridinoylamino) -indol in- 2-on 3-Ethoxycarbonyl-3-methyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3-Ethoxyearbonyl-3-methyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Ethyl-6-nitro-(3-pyridinoylamino)-indolin-2-on 3-Ethyl-6-nitro-(4-pyridinoylamino)-indolin-2-on 3-Methoxycarbonyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-on 3-Methoxycarbonyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-on 3-Methoxycarbonyl-3-methyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3-Methoxycarbonyl-3-methyl-6-nitro-5- (4-pyridinoylamino) -indolin-2-on 3-Methyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3-Methyl-6-nitro-5- (4-pyridinoylamino) -indolin-2-on 3- (3-Pentyl) -6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3- (3-Pentyl) -6-nitro-5- (4-pyridinoylamino) -indolin-2-on 3- (2-Propyl) -6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3- (2-Propyl) -6-nitro-5- (4-pyridinoylamino) -indolin-2-on 3- (2-Methyl-propyl) -6-nitro-5- (3-pyridinoylamino) -indolin-2-on 3- (2-Methyl-propyl) -6-nitro-5- (4-pyridinoylamino) -indolin-2-on 6'-Nitro-5'-(3-pyridinoylamino)-spirofcyclohexan-1,3'-indolin]-2'-on 6'-Nitro-5'-(4-pyridinoylamino)-spirorcyclohexan-1,3'-indolin]-2'-on 6'-Nitro-5'-(3-pyridinoylamino)-spiro[cyclopentan-1,3'-indolin]-2'-on 6'-Nitro-5'-(4-pyridinoylamino)-spiro[cyclopentan-1,3'-indolin]-2'-on 3,3-Dimethyl-6-nitro-5-(2-pyridinoylamino)-indolin-2-thion 3,3-Dimethyl-6-nitro-5-(3-pyridinoylamino)-indolin-2-thion 3,3-Dimethyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-thion 3-Ethyl-6-nitro-5- (2-pyridinoylamino) -indolin-2-thion 3-Ethyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-thion 3-Ethyl-6-nitro-5-(4-pyridinoylamino)-indolin-2-thion 3-Methyl-6-nitro-5- (2-pyridinoylamino) -indolin-2-thion 3-Methyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-thion 3-Methyl-6-nitro-5- (4-pyridinoylamino) -indolin-2-thion Zur Ueberfuehrung der Verbindungen der allgemeinen Formel I bzw. deren tautomeren Formen in ihre pharmakologisch unbedenklichen Salze, setzt man diese vorzugsweise in einem organischen Loesungsmittel mit der aequivalenten Menge einer anorganischen oder organischen Saeure, z.B. Salzsaeure, Bromwasserstoffsaeure, Phosphorsaeure, Schwefelsaeure, Essigsaeure, Citronensaeure, Weinsaeure, Maleinsaeure, Fumarsaeure, Benzoesaeure oder Cyclohexylsulfaminsaeure um.Compounds of the formula XIV according to the invention are, in addition to those in the Examples of the following compounds: 5-Amino-6-nitro-3-acetyl-indolin-2-one 5-Amino-6-nitro-3-acetyl-3-methyl-indolin-2-one. 5-Amino-6-nitro-3-allyl-indolin-2-one 5-Amino-6-nitro-3-cyano-3-methyl-indolin-2-one, 5-Amino-6-nitro-3-cyclohexyl-indolin-2-one 5-Amino-6-nitro-3-cyclopentyl-indolin-2-one 5-Amino-6-nitro-3,3-diallyl-indolin-2-one 5-Amino-6-nitro-3,3-diethyl-indolin-2-one 5-Amino-6-nitro-3,3-dimethyl-indolin-2-one 5-Amino-6-nitro-3-ethoxycarbonyl-indolin-2-one 5-Amino-6-nitro-3-ethoxycarbonyl-3-ethyl-indolin-2-one 5-Amino-6-nitro-3-ethoxycarbonyl-3-methyl-indolin-2-one, 5-Amino-6-nitro-3-ethyl-indolin-2-one 5-Amino-6-nitro-3-methoxycarbonyl-indolin-2-one 5-Amino-6-nitro-3-methoxycarbonyl-3-methyl-indolin-2-one 5-Amino-6-nitro-3-methyl-indolin-2-one 5-Amino-6-nitro-3- (3-pentyl) -indolin-2-one 5-Amino-6-nitro-3- (2-propyl) indolin-2-one 5-Amino-6-nitro-3- (2-methyl-propyl) indolin-2-one 5'-Amino-6'-nitro-spiro [cyclohexane-1,3'-indoline] -2'-one S'-Amino-6'-nitro-spiro [cyclopentane-1,3'-indoline] -2 ' -on 5-Amino-6-nitro-3,3-dimethyl-indoline-2-thione 5-Amino-6-nitro-3-ethyl-indoline-2-thione 5-Amino-6-nitro-3-methyl-indoline-2-thione Compounds according to the invention of the formula XIII are, in addition to the compounds mentioned in the examples, the following: 6-Amino-5-nitro-indolin-2-one 6-Amino-5-nitro-3-acetyl-indolin-2-one 6-Amino-5-nitro-3-acetyl-3-methyl-indolin-2- on 6-Amino-5-nitro-3-allyl-indolin-2-one 6-Amino-5-nitro-3-cyano-3-methyl-indolin-2-one 6-Amino-5-nitro-3-cyclohexyl-indolin-2-one 6-amino-5-nitro-3-cyclopentyl-indolin-2-one 6-Amino-5-nitro-3,3-diallyl-indolin-2-one 6-Amino-5-nitro-3,3-dimethyl-indolin-2-one 6-Amino-5-nitro-3-ethoxycarbonyl-indolin-2-one 6-Amino-5-nitro-3-ethoxycarbonyl-3-ethyl-indolin-2-one 6-Amino-5-nitro-3-ethoxycarbonyl-3-methyl-indolin-2-one 6-amino-5-nitro-3-ethyl-indolin-2-one 6-Amino-5-nitro-3-methoxycarbonyl-indolin-2-one 6-Amino-5-nitro-3-methoxycarbonyl-3-methyl-indolin-2-one 6-Amino-5-nitro-3-methyl-indolin-2-one 6-Amino-5-nitro-3- (3-pentyl) -indolin-2-one 6-Amino-5-nitro-3- (2-propyl) indolin-2-one 6-Amino-5-nitro-3- (2-methyl-propyl) indolin-2-one 6'-Amino-5'-nitro-spiroEcyclohexane-1,3'-indoline] -2'-one 6'-Amino-5'-nitro-spiro [cyclopentan-1,3'-indolin] -2'-one 6-amino-5-nitro-3,3-dimethyl-indoline] -2-thione 6-amino-5-nitro-3-ethyl-indoline-2-thione 6-Amino-5-nitro-3-methyl-indoline-2-thione Compounds of the formula according to the invention VIII, in addition to the compounds mentioned in the examples, are the following: 5-Nitro-6- (3-pyridinoylamino) indolin-2-one 3-Acetyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one, 3-acetyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3-acetyl-3-methyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-Acetyl-3-methyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one, 3-allyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-Allyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one, 3-cyano-3-methyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-cyano-3-methyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3-cyclohexyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-cyclohexyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3-Cyclopentyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-Cyclopentyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3, 3-diallyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3,3-Diallyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3,3-Dimethyl-5-nitro-6- (2-pyridinoylamino) indolin-2-one 3,3-Dimethyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3,3-Dimethyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3,3-Dimethyl-5-nitro-6- (2- (5-n-butyl-pyridinoylamino)) indoline - 2-one 3,3-dimethyl-5-nitro-6- (3- (6-cyano-pyridinoylamino)) - indolin- 2-one 3,3-dimethyl-5-nitro-6- (3- (6- methyl-pyridinoylamino)) - indolin-2-one 3,3-Dimethyl-5-nitro-6- (4- (2-methyl-pyridinoylamino)) -indolin-2-one 3,3-dimethyl-5-nitro-6- [4- (2-hydroxypyridinoylamino )) - indolin-2-one 3-ethoxycarbonyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-3-ethyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-3-ethyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-3-methyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-3-methyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3-Ethyl-5-nitro-6- (3-pyridinoylaminoI-indolin-2-one 3-Ethyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one, 3-methoxycarbonyl-5-nitro-6- (3-pyridinoylamino) indolin-2-one 3-methoxycarbonyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3-methoxycarbonyl-3-methyl-5-nitro-6- (3-pyridinoylamino) -indolin- 2-one 3-methoxycarbonyl-3-methyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-one 3-methyl-5-nitro-6- (3-pyridinoylamino) -indolin-2-one 3-methyl-5-nitro-6- (4-pyridinoylamino) indolin-2-one 3- (3-pentyl) -5-nitro-6- (3-pyridinoylamino) -indolin-2-one 3- (3-pentyl) -5-nitro-6- (4-pyridinoylamino) -indolin-2-one 3- (2-propyl) -5-nitro-6- (3-pyridinoylamino) indolin-2-one 3- (2-propyl) -5-nitro-6- (4-pyridinoylamino) -indolin-2-one 3- (2-methyl-propyl) -5-nitro-6- (3-pyridinoylamino) -indolin-2-one 3- (2-methyl-propyl) -5-nitro-6- ( 4-pyridinoylamino) indolin-2-one 5'-nitro-6 '- (3-pyridinoylamino) -spiro [cyclohexane-1,3'-indoline] -2'-one 5'-nitro-6' - (4-pyridinoylamino) -spiro [cyclohexane-1, 3'-indoline] -2'-one 5'-nitro-6 '- (3-pyridinoylamino) -spiro [cyclopentane-1,3'-indoline] -2'-one 5'-nitro-6' - (4-pyridinoylamino) -spiro [cy indolin] -2'-one 3,3-dimethyl-5-nitro-6- (2-pyridinoylamino) indoline-2-thione 3,3-dimethyl-5-nitro-6- (3-pyridinoylamino) indoline- 2-thion 3,3-dimethyl-5-nitro-6- (4-pyridinoylamino) indoline-2-thione 3-ethyl-5-nitro-6- (2-pyridinoylamino) -indoline-2-thione 3-ethyl-5-nitro-6- (3-pyridinoylamino) -indoline-2-thione 3-ethyl-5-nitro-6- (4-pyridionylamino) indoline-2-thione, 3-methyl-5-nitro-6- (2-pyridinoylamino) indoline-2-thione 3-methyl-5-nitro-6- (3-pyridinoylamino) indoline-2-thione 3-methyl-5-nitro-6- (4-pyridinoylamino) -indoline-2-thione Compounds according to the invention of the general In addition to the compounds mentioned in the examples, formula IX are the following: 6-nitro-5- (3-pyridinoylamino) indolin-2-one 6-Nitro-5- (4-pyridinoylamino) indolin-2-one, 3-acetyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-Acetyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one. 3-Acetyl-3-methyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-Acetyl-3-methyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one, 3-allyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-Allyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one, 3-cyano-3-methyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-cyano-3-methyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one 3-cyclohexyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-cyclohexyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one 3-Cyclopentyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one. 3-Cyclopentyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one 3,3-diallyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3,3-diallyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one 3,3-diallyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3,3-diallyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one 3,3-Dimethyl-6-nitro-5- (2-pyridinoylamino) indolin-2-one 3,3-dimethyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3,3-Dimethyl-6-nitro-5- (4-pyridinoylamino) -indolin-2-one 3,3-Dimethyl-6-nitro-5- (2- (5-n-butyl-pyridinoylamino) -indoline- 2-on 3,3-Dimethyl-6-nitro-5- (3- (6-cyano-pyridinoylamino)) -indol-in-2-one 3,3-dimethyl-6-nitro-5- (3- (6-methyl- pyridinoylamino)) .- indolin-2-one 3,3-Dimethyl-6-nitro-5- (4- (2-methyl-pyridinoylamino)) -indolin-2-one 3,3-Dimethyl-6-nitro-5- (4- (2-hydroxypyridinoylamino) ] -indole in-2-on 3-ethoxycarbonyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-3-ethyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-ethoxycarbonyl-3-ethyl-6-nitro-5- (4-pyridinoylamino) indol in-2-one 3-ethoxycarbonyl-3-methyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-ethoxyearbonyl-3-methyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one, 3-ethyl-6-nitro- (3-pyridinoylamino) indolin-2-one 3-Ethyl-6-nitro- (4-pyridinoylamino) indolin-2-one, 3-methoxycarbonyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-methoxycarbonyl-6-nitro-5- (4-pyridinoylamino) indolin-2-one 3-methoxycarbonyl-3-methyl-6-nitro-5- (3-pyridinoylamino) indolin-2-one 3-methoxycarbonyl-3-methyl-6-nitro-5- (4-pyridinoylamino) -indolin-2-one 3-methyl-6-nitro-5- (3-pyridinoylamino) -indolin-2-one 3-methyl-6-nitro-5- (4-pyridinoylamino) -indolin-2-one 3- (3-pentyl) -6-nitro-5- (3-pyridinoylamino) -indolin-2-one 3- (3-pentyl) -6-nitro-5- (4-pyridinoylamino) -indolin-2-one 3- (2-propyl) -6-nitro-5- (3-pyridinoylamino) -indolin-2-one 3- (2-propyl) -6-nitro-5- (4-pyridinoylamino) -indolin-2-one 3- (2-methyl-propyl) -6-nitro-5- (3-pyridinoylamino) -indolin-2-one 3- (2-Methyl-propyl) -6-nitro-5- (4-pyridinoylamino) -indolin-2-one 6'-nitro-5 '- (3-pyridinoylamino) -spirofcyclohexane-1,3'-indoline] -2'-on 6'-nitro-5 '- (4-pyridinoylamino) -spirorcyclohexane-1,3'-indoline] -2'-one 6'-nitro-5' - (3-pyridinoylamino) -spiro [cyclopentane-1,3 ' -indoline] -2'-one 6'-nitro-5 '- (4-pyridinoylamino) spiro [cyclopentan-1,3'-indolin] -2'-one 3,3-Dimethyl-6-nitro-5- (2-pyridinoylamino) indoline-2-thione 3,3-Dimethyl-6-nitro-5- (3-pyridinoylamino) indoline-2-thione 3,3-Dimethyl-6-nitro-5- (4-pyridinoylamino) indoline-2-thione 3-ethyl-6-nitro-5- (2-pyridinoylamino) indoline-2-thione 3-ethyl-6-nitro-5- (3-pyridinoylamino) -indoline-2-thione 3-ethyl-6-nitro-5- (4-pyridinoylamino) -indoline-2-thione 3-methyl-6-nitro-5- (2-pyridinoylamino) indoline-2-thione, 3-methyl-6-nitro-5- (3-pyridinoylamino) indoline-2-thione 3-Methyl-6-nitro-5- (4-pyridinoylamino) -indoline-2-thione To transfer the compounds of the general formula I or their tautomeric forms in their pharmacologically acceptable Salts, these are preferably used in an organic solvent with the equivalent amount of an inorganic or organic acid, e.g. hydrochloric acid, Hydrobromic acid, phosphoric acid, sulfuric acid, acetic acid, citric acid, Tartaric acid, maleic acid, fumaric acid, benzoic acid or cyclohexylsulfamic acid around.

Zur Herstellung von Arzneimitteln werden die Substanzen der allgemeinen Formel 1 in an sich bekannter Weise mit geeigneten pharmazeutischen Traegersubstanzen, Aroma-, Geschmacks- und Farbstoffen gemischt und beispielsweise als Tabletten oder Dragees ausgeformt oder unter Zugabe entsprechender Hilfsstoffe in Wasser oder Oel, wie z.B.For the production of drugs, the substances are used in general Formula 1 in a manner known per se with suitable pharmaceutical carrier substances, Aromas, flavors and colors mixed and for example as tablets or Dragees shaped or with the addition of appropriate auxiliaries in water or oil, such as.

Olivenoel, suspendiert oder geloest.Olive oil, suspended or dissolved.

Die erfindungsgemaeßen neuen Substanzen der allgemeinen Formel I und ihre Salze koennen in fluessiger oder fester Form enteral oder parenteral appliziert werden. Als Injektionsmedium kommt vorzugsweise Wasser zur Anwendung, welches die bei Injektionsloesungen ueblichen Zusaetze wie Stabilisierungsmittel, Loesungsvermittler oder Puffer enthaelt.The novel substances of the general formula I and according to the invention Their salts can be administered enterally or parenterally in liquid or solid form will. The injection medium used is preferably water, which the In the case of injection solutions, the usual additives such as stabilizers, solubilizers or buffer included.

Derartige Zusaetze sind z.B. Tartrat- und Citratpuffer, Ethanol, Komplexbildner (wie Ethylendiamintetraessigsaeure und deren nicht toxische Salze) und hochmolekulare Polymere (wie fluessiges Polyethylenoxid) zur Viskositaetsregulierung. Feste Traegerstoffe sind z.B. Staerke, Lactose, Mannit, Methylcellulose, Talkum, hochdisperse Kieselsaeuren, hochmolekulare Fettsaeuren (wie Stearinsaeure), Gelatine, Agar-Agar, Calciumphosphat, Magnesiumstearat, tierische und pflanzliche Fette und feste hochmolekulare Polymere (wie Polyethylenglykole). Fuer orale Applikation geeignete Zubereitungen koennen gewuenschtenfalls Geschmacks-und Sueßstoffe enthalten.Such additives are e.g. tartrate and citrate buffers, ethanol, complexing agents (such as ethylenediaminetetraacetic acid and its non-toxic salts) and high molecular weight Polymers (such as liquid polyethylene oxide) to regulate viscosity. Solid carriers are e.g. starch, lactose, mannitol, methyl cellulose, talc, highly dispersed silicic acids, high molecular weight fatty acids (such as stearic acid), gelatine, agar-agar, calcium phosphate, Magnesium stearate, animal and vegetable fats and solid high molecular weight polymers (such as polyethylene glycols). Preparations suitable for oral administration can be used if desired contain flavorings and sweeteners.

Bevorzugt im Sinne der vorliegenden Erfindung sind außer den in den Beispielen genannten Verbindungen die folgenden und deren Tautomere.For the purposes of the present invention, preference is given to those in the Examples of compounds mentioned below and their tautomers.

7-Acetyl-2- (3-pyridyl) -6,7-dihydro-3H,5H-pyrrolo[2,3-f]benz imidazol-6-on 7-Acetyl-2-(4-pyridyl) -6 ,7-dihydro-3H,5H-pyrrolo [2,3-f]benzimidazol-6-on 7-Acetyl-7-methyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-Acetyl-7-methyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolor2,3-f] benzimidazol-6-on 7-Aminocarbonyl-7-methyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo [2, 3-f] benzimidazol-6-on 7-Aminocarbonyl-7-methyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-Cyan-7-methyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f] benzimidazol-6-on 7-Cyan-7-methyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolor2,3-fgbenzimidazol-6-on 7-Ethoxycarbonyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f] benzimidazol-6-on 7-Ethoxycarbonyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-EthOxycarbonyl-7-ethyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-Ethoxycarbonyl-7-ethyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-Ethoxycarbonyl-7-methyl-2- (3-pyridyl) -6, 7-dihydro-3H' 5H-pyrrolo[2,3-f]benzimidazol-6-on 7-Hydrazinocarbonyl-7-methyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-Hydrazinocarbonyl-7-methyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-MethOxyzarbonyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo-[2,3-f]benzimidazol-6-on 7-MethOxycarbonyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo-[2,3-f]benzimidazol-6-on 7-MethoxyCarbonyl-7-methyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7-MethOxycarbonyl-7-methyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on 7,7-Dimethyl-2-(2-(5-n-butyl-pyridyl))-6,7-dihydro-3H,5H-pyrrolo t 2 ,3-fl benzimidazol-6 -on 7,7-Dimethyl-2-(3-(6-cyan-pyridyl))-6,7-dihydro-3H,5H-pyrrolot2,3-f]benzimidazol-6-on 7-(2-Methyl-propyl)-2-(3-pyridyl}-6,7-dihydro-3H,5H-pyrrolo [2 ,3-f] benzimidazol-6-on 7-(2-Methyl-propyl)-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo [2,3-f]benzimidazol-6-on 2-(4-Pyridyl)-spiro[cyclohexan-1,7'-6',7'-dihydro-3'H,5'H-pyrrolo[2',3'-flbenzimidazol]-6'-on 7,7-Dimethyl-2-(2-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion 7,7-Dimethyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion 7,7-Dimethyl-2-(3-(6-methyl-pyridyl))-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-thion 7,7-Dimethyl-2-(4-(2-methyl-pyridyl))-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-thion 7-Ethyl-2-(2-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion 7-Ethyl-2-(3-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion 7-Ethyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion 7-Methyl-2-(2-pyridyl) -6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion 7-Methyl-2-(3-pyridyl}-6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion 7-Methyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolor2,3-fabenzimidazol-6-thion Beispiel 1 7-Ethoxycarbonyl-7-methyl-2- (4-pyridyl) -6, 7-dihydro-3H, 5H-pyrrolo [2,3-f]benzimidazol-6-on x HCl Eine Loesung von 5-Amino-3-ethoxycarbonyl-3-methyl-6-(4-pyridinoylamino)-indolin-2-on (10.85 g, 32.2 mmol) in Ethanol (700 ml) mit konz. HCl (50 ml) wird ca. 12 h zum Rueckfluß erhitzt. Anschließend wird abgekuehlt, etwas eingeengt, von den Kristallen abgesaugt und aus Ethanol umkristallisiert. Ausbeute 9.6 g (79 z d.Th.), Mp. 288-2900C.7-Acetyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-Acetyl-2- (4-pyridyl) -6, 7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-acetyl-7-methyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-Acetyl-7-methyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolor2,3-f] benzimidazol-6-one 7-aminocarbonyl-7-methyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-aminocarbonyl-7-methyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-cyano-7-methyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-cyano-7-methyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolor2,3-fgbenzimidazol-6-one 7-ethoxycarbonyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-ethoxycarbonyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-Ethoxycarbonyl-7-ethyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-ethoxycarbonyl-7-ethyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-ethoxycarbonyl-7-methyl-2- (3-pyridyl) -6,7-dihydro-3H '5H-pyrrolo [2,3-f] benzimidazol-6-one 7-hydrazinocarbonyl-7-methyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-hydrazinocarbonyl-7-methyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-Methoxyzarbonyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo- [2,3-f] benzimidazol-6-one 7-methoxycarbonyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo- [2,3-f] benzimidazol-6-one 7-methoxycarbonyl-7-methyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7-Methoxycarbonyl-7-methyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7,7-dimethyl-2- (2- (5-n-butyl-pyridyl)) -6,7-dihydro-3H, 5H-pyrrolo t 2, 3-fl benzimidazol-6-one 7,7-dimethyl-2- (3- (6-cyano-pyridyl)) - 6,7-dihydro-3H, 5H-pyrrolot2,3-f] benzimidazole-6 -on 7- (2-Methyl-propyl) -2- (3-pyridyl} -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 7- (2-Methyl-propyl) -2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one 2- (4-pyridyl) -spiro [cyclohexane-1,7'-6 ', 7'-dihydro-3'H, 5'H-pyrrolo [2', 3'-flbenzimidazol] -6'-one 7,7-Dimethyl-2- (2-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione 7,7-Dimethyl-2- (3-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione 7,7-Dimethyl-2- (3- (6-methyl-pyridyl)) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazole-6-thione 7,7-Dimethyl-2- (4- (2-methyl-pyridyl)) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazole-6-thione 7-ethyl-2- (2-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione 7-ethyl-2- (3-pyridyl) -6, 7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione 7-ethyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione 7-methyl-2- (2-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione 7-methyl-2- (3-pyridyl} -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione 7-Methyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolor2,3-fabenzimidazole-6-thione Example 1 7-Ethoxycarbonyl-7-methyl-2- (4-pyridyl) -6, 7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one x HCl A solution of 5-amino-3-ethoxycarbonyl-3-methyl-6- (4-pyridinoylamino) indolin-2-one (10.85 g, 32.2 mmol) in ethanol (700 ml) with conc. HCl (50 ml) is added to the Heated reflux. The crystals are then cooled down and concentrated a little suctioned off and recrystallized from ethanol. Yield 9.6 g (79% of theory), Mp. 288-2900C.

Die Ausgangsstoffe fuer die in Beispiel 1 beanspruchten Verbindungen koennen wie folgt hergestellt werden: a) 5-Amino-3-ethoxycarbonyl-3-methyl-6- (4-pyridinoylamino) -indolin-2-on Eine Loesung von 3-Ethoxycarbonyl-3-methyl-5-nitro-6-(4-pyridinoylamino)-indolin-2-on (12.4 g, 32.2 mmol) in Ethanol (500 ml) wird an 10pro. Pd/C (1 g) bei Raumtemperatur hydriert. Es wird vom Katalysator abgesaugt, eingeengt und die erhaltene Substanz sofort weiter eingesetzt.The starting materials for the compounds claimed in Example 1 can be prepared as follows: a) 5-Amino-3-ethoxycarbonyl-3-methyl-6- (4-pyridinoylamino) -indolin-2-one A solution of 3-ethoxycarbonyl-3-methyl-5-nitro-6- (4-pyridinoylamino) -indolin-2-one (12.4 g, 32.2 mmol) in ethanol (500 ml) is added to 10pro. Pd / C (1 g) at room temperature hydrogenated. It is filtered off with suction from the catalyst, concentrated and the substance obtained used immediately.

b) 3-Ethoxycarbonyl-3-methyl-5-nitro-6- (4-pyridinoylamino) -indol in- 2-on Zu einer Loesung von 3-Ethoxycarbonyl-3-methyl-6-(4-pyridinoylamino)-indolin-2-on (13 g, 0.038 mol) in konz. H2SO4 (90 ml) wird unter Kuehlung eine Loesung von Kaliumnitrat (3.9 g, 0.038 mol) in konz. H2SO4 (30 ml) zugetropft. Es wird ca.b) 3-ethoxycarbonyl-3-methyl-5-nitro-6- (4-pyridinoylamino) indole in-2-one To a solution of 3-ethoxycarbonyl-3-methyl-6- (4-pyridinoylamino) indolin-2-one (13 g, 0.038 mol) in conc. H2SO4 (90 ml) becomes a solution of potassium nitrate under cooling (3.9 g, 0.038 mol) in conc. H2SO4 (30 ml) was added dropwise. It will be approx.

eine Stunde nachgeruehrt, auf Eis gegossen, unter Kuehlung mit konz. NH3-Loesung auf pH 8 gestellt, die Kristalle abgesaugt und aus Ethanol/Methylenchlorid umkristallisiert.stirred for an hour, poured onto ice, cooled with conc. The NH3 solution was adjusted to pH 8, the crystals were filtered off with suction and removed from ethanol / methylene chloride recrystallized.

Ausbeute: 12.81 g (82 % d.Th.), Mp. 217-219°C.Yield: 12.81 g (82% of theory), mp. 217-219 ° C.

c) 3-Ethoxycarbonyl-3-methyl-6-(4-pyridinoylamino)-indolin-2-on Zu einer gekuehlten Loesung von 6-Amino-3-ethoxycarbonyl-3-methyl-indolin-2-on (13 g, 0.048 mol) in-Methylenchlorid (500 ml) werden Triethylamin (22.1 ml) und Pyridin-4-carbonsaeurechlorid Hydrochlorid (9.4 g, 0.053 mol) gegeben und ca. 2 h bei RT geruehrt. Anschließend wird zur Trockne eingeengt mit Wasser verruehrt, abgesaugt und der Rueckstand aus Ethanol/Methylenchlorid umkristallisiert. Ausbeute: 11.9 g (73 % d.Th.), Mp. 222-2240C.c) 3-ethoxycarbonyl-3-methyl-6- (4-pyridinoylamino) indolin-2-one to a cooled solution of 6-amino-3-ethoxycarbonyl-3-methyl-indolin-2-one (13 g, 0.048 mol) in methylene chloride (500 ml) are triethylamine (22.1 ml) and pyridine-4-carboxylic acid chloride Hydrochloride (9.4 g, 0.053 mol) was added and the mixture was stirred at RT for about 2 h. Afterward is concentrated to dryness, stirred with water, suctioned off and the residue is removed Recrystallized from ethanol / methylene chloride. Yield: 11.9 g (73% of theory), Mp. 222-2240C.

d) 6-Amino-3-ethoxyearbonyl-3-methyl-indolin-2-on Eine Loesung von Methyl-(2,4-dinitro-phenyl)malonsaeurediethylester (27 g, 0.079 mol) in Ethanol (800 ml1 wird an 1Oproz. Pd/C (1 g) bei RT hydriert. Anschließend wird vom Katalysator abgesaugt, mit ethanolischer HCl angesaeuert, eingeengt und durch Zusatz von Isopropanol auskristallisiert. Ausbeute: 13.19 g (71 % d.Th.), Mp. 2480C.d) 6-Amino-3-ethoxyearbonyl-3-methyl-indolin-2-one A solution of Methyl- (2,4-dinitro-phenyl) malonic acid diethyl ester (27 g, 0.079 mol) in ethanol (800 ml1 are hydrogenated on 10 percent Pd / C (1 g) at RT suctioned off, acidified with ethanolic HCl, concentrated and by adding isopropanol crystallized out. Yield: 13.19 g (71% of theory), Mp. 2480C.

Beispiel 2 7,7-Dimethyl-2-(4-pyridyl1-6,7-dihydro-3H,5H-pyrrolo[2,3-f]-benzimidazol-6-thion x 2 H2O Eine Loesung von 7,7-Dimethyl-2-(4-pyridyl)-6,7-dihydro-3H,5H-pyrrolo[2,3-f]benzimidazol-6-on (2.0 g, 7.2 mmol) in Pyridin (35 ml) wird mit P2S10 (4 g) unter gutem Ruehren ca. 5 h auf 100 "C erhitzt. Anschließend wird mit Eiswasser zersetzt, alkalisch gestellt, die gewuenschte Substanz extrahiert und an Kieselgel (Laufmittel: Methylenchlorid/NH3 gesaettigtes Methanol 20:1) gereinigt. Ausbeute: 1,7 g (72 % d.Th.), Mp. 205-2200C.Example 2 7,7-Dimethyl-2- (4-pyridyl1-6,7-dihydro-3H, 5H-pyrrolo [2,3-f] -benzimidazole-6-thione x 2 H2O A solution of 7,7-dimethyl-2- (4-pyridyl) -6,7-dihydro-3H, 5H-pyrrolo [2,3-f] benzimidazol-6-one (2.0 g, 7.2 mmol) in pyridine (35 ml) is mixed with P2S10 (4 g) for approx. Heated to 100 ° C for 5 h. Then it is decomposed with ice water, made alkaline, the desired substance is extracted and dried on silica gel (mobile phase: methylene chloride / NH3 saturated methanol 20: 1). Yield: 1.7 g (72% of theory), Mp. 205-2200C.

Claims (1)

Patentansprueche 1. Verbindungen der Formel I in welcher R1 ein Wasserstoffatom, eine Alkyl-, Alkenyl- oder eine Cycloalkylgruppe bedeutet, R2 ein Wasserstoffatom, eine Alkyl-, Alkenyl-, oder Cyangruppe, eine durch eine Hydroxy-, Alkyl-, Alkoxy-, Amino-, Alkylamino-, Dialkylamino- oder Hydrazinogruppe substituierte Carbonylgruppe bedeutet oder mit R1 zusammen eine Cycloalkylengruppe darstellt oder R1 und R2 zusammen eine Alkyliden- oder Cycloalkylidengruppe bilden, X einen Valenzstrich, eine C1-CI-Alkylengruppe oder die Vinylgruppe bedeutet, T gleich Sauerstoff oder Schwefel bedeutet, Py einen 2-, 3- oder 4-Pyridylrest darstellt, der gegebenenfalls am Ringheteroatom ein Sauerstoffatom traegt und/ oder durch eine oder mehrere Alkyl-, Alkoxy-, Hydroxy-, Cyano- oder Nitrogruppen, sowie durch Halogen substituiert sein kann, deren Tautomere und deren physiologisch vertraegliche Salze anorganischer und organischer Saeurene 2. Verfahren zur Herstellung von Verbindungen der Formel I in welcher Rr ein Wasserstoffatom, eine Alkyl-, Alkenyl- oder eine Cycloalkylgruppe bedeutet, R2 ein Wasserstoffatom, eine Alkyl-, Alkenyl-, oder Cyangruppe, eine durch eine Hydroxy-, Alkyl-, Alkoxy-, Amino-, Alkylamino-, Dialkylamino- oder Hydrazinogruppe substituierte Carbonylgruppe bedeutet oder mit R1 zusammen eine Cycloalkylengruppe darstellt oder R1 und R2 zusammen eine Alkyliden- oder Cycloalkylidengruppe bilden, X einen Valenzstrich, eine C1-C4-Alkylengruppe oder die Vinylgruppe bedeutet, T gleich Sauerstoff oder Schwefel bedeutet, Py einen 2-, 3- oder 4-Pyridylrest darstellt, der gegebenenfalls am Ringheteroatom ein Sauerstoffatom traegt und/ oder durch eine oder mehrere Alkyl-, Alkoxy-, Hydroxy-, Cyano- oder Nitrogruppen, sowie durch Halogen substituiert sein kann, deren Tautomere und deren physiologisch vertraegliche Salze anorganischer und organischer Saeuren, dadurch gekennzeichnet, daß man in an sich bekannter Weise eine Verbindung der Formel II in der R1 und R2 die oben angegebene Bedeutung besitzen, mit einer Verbindung der Formel III Py-X-CO-Y (III), in der Py und X die angegebene Bedeutung besitzen und Y entweder Wasserstoff oder einen leicht abspaltbaren Rest darstellt, umsetzt, anschließend cyclisiert und fuer den Fall, daß T ein Schwefelatom darstellen soll, die erhaltene Verbindung mit Phosphorpentasulfid oder 2,4-Bis-(4-methOxyphenyl)-2,4-dithioxo-1,3,2,4-dithiadiphosphetan zur entsprechenden Thion-Verbindung umsetzt und anschließend die erhaltene Verbindung in ueblicher Weise in physiologisch vertraegliche Salze ueberfuehrt.Claims 1. Compounds of the formula I in which R1 denotes a hydrogen atom, an alkyl, alkenyl or a cycloalkyl group, R2 denotes a hydrogen atom, an alkyl, alkenyl or cyano group, one by a hydroxy, alkyl, alkoxy, amino, alkylamino, dialkylamino - or hydrazino group denotes a carbonyl group substituted with R1 or represents a cycloalkylene group together or R1 and R2 together form an alkylidene or cycloalkylidene group, X denotes a valence stroke, a C1-Cl-alkylene group or the vinyl group, T denotes oxygen or sulfur, Py denotes a 2 -, 3- or 4-pyridyl radical, which optionally carries an oxygen atom on the ring heteroatom and / or can be substituted by one or more alkyl, alkoxy, hydroxy, cyano or nitro groups, and by halogen, their tautomers and their physiological compatible salts of inorganic and organic acids 2. Process for the preparation of compounds of the formula I. in which Rr is a hydrogen atom, an alkyl, alkenyl or a cycloalkyl group, R2 is a hydrogen atom, an alkyl, alkenyl or cyano group, one by a hydroxy, alkyl, alkoxy, amino, alkylamino, dialkylamino - or hydrazino group denotes a carbonyl group substituted with R1 or represents a cycloalkylene group together or R1 and R2 together form an alkylidene or cycloalkylidene group, X denotes a valence stroke, a C1-C4 alkylene group or the vinyl group, T denotes oxygen or sulfur, Py denotes a 2 -, 3- or 4-pyridyl radical, which optionally carries an oxygen atom on the ring heteroatom and / or can be substituted by one or more alkyl, alkoxy, hydroxy, cyano or nitro groups, and by halogen, their tautomers and their physiological Compatible salts of inorganic and organic acids, characterized in that a compound of the formula II is used in a manner known per se in which R1 and R2 have the meaning given above, with a compound of the formula III Py-X-CO-Y (III), in which Py and X have the meaning given and Y is either hydrogen or an easily cleavable radical, is reacted, then cyclized and, in the event that T is to represent a sulfur atom, the compound obtained with phosphorus pentasulfide or 2,4-bis- (4-methoxyphenyl) -2,4-dithioxo-1,3,2,4-dithiadiphosphetane to give the corresponding thione -Compound is converted and then the compound obtained is converted into physiologically acceptable salts in the usual way. 3. Arzneimittel, enthaltend eine Verbindung gemaeß Anspruch 1 neben ueblichen Traeger- und Hilfsstoffen.3. Medicament containing a compound according to claim 1 in addition to usual carrier and auxiliary materials. 4. Verwendung von Verbindungen gemaeß Anspruch 1 zur Prophylaxe bzw. Behandlung von Herz- und Kreislauferkrankungen.4. Use of compounds according to claim 1 for prophylaxis or Treatment of heart and circulatory diseases. 5. Verbindungen der Formel II a in der R1 ein Wasserstoffatom, eine Alkyl-, Alkenyl- oder eine Cycloalkylgruppe bedeutet R2 ein Wasserstoffatom, eine Alkyl-, Alkenyl-, oder Cyangruppe, eine durch eine Hydroxy-, Alkyl-, Alkoxy-, Amino-, Alkylamino-, Dialkylamino- oder Hydrazinogruppe substituierte Carbonylgruppe bedeutet oder mit R1 zusammen eine Cycloalkylengruppe darstellt oder R1 und R2 zusammen eine Alkyliden- oder Cycloalkylidengruppe bilden, A und B Wasserstoff, eine Amino- oder Nitrogruppe oder die Gruppe bedeutet, in der X und Py die in Anspruch 1 angegebene Bedeutung haben, mit der Maßgabe, daß A und B verschieden sind, aber gleichzeitig zwei Aminogruppen darstellen koennen.5. Compounds of the formula II a in which R1 is a hydrogen atom, an alkyl, alkenyl or a cycloalkyl group, R2 is a hydrogen atom, an alkyl, alkenyl or cyano group, a hydroxy, alkyl, alkoxy, amino, alkylamino, dialkylamino or hydrazino group denotes a substituted carbonyl group or represents a cycloalkylene group together with R1 or R1 and R2 together form an alkylidene or cycloalkylidene group, A and B hydrogen, an amino or nitro group or the group means in which X and Py have the meaning given in claim 1, with the proviso that A and B are different but can represent two amino groups at the same time. 6. Verwendung von Verbindungen gemaeß Anspruch 5 zur Herstellung von Verbindungen der Formel I gemaeß Anspruch 1.6. Use of compounds according to claim 5 for the preparation of Compounds of formula I according to claim 1.
DE19843446417 1984-05-12 1984-12-20 Novel pyrrolobenzimidazoles, process for their preparation and medicaments containing these compounds, and novel intermediates Ceased DE3446417A1 (en)

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DE19843446417 DE3446417A1 (en) 1984-12-20 1984-12-20 Novel pyrrolobenzimidazoles, process for their preparation and medicaments containing these compounds, and novel intermediates
PL1985259261A PL147842B1 (en) 1984-05-12 1985-05-06 Method of obtaining novel pyroisobenzimidazoles
PL1985253246A PL144822B1 (en) 1984-05-12 1985-05-06 Method of obtaining novel pyrolobenzimidazoles
GR851085A GR851085B (en) 1984-05-12 1985-05-06
IL75120A IL75120A (en) 1984-05-12 1985-05-07 2-substituted-6-,7-dihydro-3h,5h-pyrrolo(2,3-f)benzimidazole-6-(thi)ones,processes for the preparation thereof and pharmaceutical compositions containing them
NZ212005A NZ212005A (en) 1984-05-12 1985-05-07 Pyrrolobenzimidazoles and pharmaceutical compositions
US06/731,500 US4666923A (en) 1984-05-12 1985-05-07 Pyrrolobenzimidazoles for treating heart or circulatory diseases
IL84769A IL84769A (en) 1984-05-12 1985-05-07 Substituted indolin-2-(thi)ones
PH32240A PH22863A (en) 1984-05-12 1985-05-08 Pyrrolobenzimidazoles and pharmaceutical composition containing them
EP85105675A EP0161632B1 (en) 1984-05-12 1985-05-09 Pyrrolo-benzimidazoles, process for their preparation, medicaments containing them and intermediates
PT80425A PT80425B (en) 1984-05-12 1985-05-09 NEW PYRROLO-BENZIMIDAZOLE METHODS FOR THE PRODUCTION THEREOF, AND MEDICAMENTS CONTAINING SUCH COMPOUNDS, AND INTERMEDIATE PRODUCTS
AU42222/85A AU560349B2 (en) 1984-05-12 1985-05-09 Pyrrolobenzimidazoles
AT85105675T ATE62487T1 (en) 1984-05-12 1985-05-09 NEW PYRROLO-BENZIMIDAZOLES, PROCESSES FOR THEIR PREPARATION AND PHARMACEUTICAL PRODUCTS CONTAINING THESE COMPOUNDS AND INTERMEDIATE PRODUCTS.
ES542976A ES542976A0 (en) 1984-05-12 1985-05-09 PROCEDURE FOR PREPARING PYROLE-BENZMIDAZOLES
DE8585105675T DE3582447D1 (en) 1984-05-12 1985-05-09 NEW PYRROLO-BENZIMIDAZOLES, METHOD FOR THE PRODUCTION THEREOF AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS, AND INTERMEDIATE PRODUCTS.
KR1019850003144A KR870001201B1 (en) 1984-05-12 1985-05-09 Process for preparing pyrrolo-benzimidazols
HU851775A HU193754B (en) 1984-05-12 1985-05-10 Process for preparing pyrrolo-benzimidazoles
FI851869A FI81351C (en) 1984-05-12 1985-05-10 PROCEDURE FOR THE PHARMACOLOGICAL ACTIVATION OF ACTIVE 2-PYRIDYL SUBSTITUTES 6,7-DIHYDRO-3H, 5H-PYRROLO / 2,3-F / BENZIMIDAZOLE-6-ONER O-6-TIONER.
DK209585A DK209585A (en) 1984-05-12 1985-05-10 PYRROLOBENZIMIDAZOLES, PROCEDURES FOR THEIR PREPARATION AND MEDICINES CONTAINING THESE COMPOUNDS AND INTERMEDIATES
NO851862A NO851862L (en) 1984-05-12 1985-05-10 PROCEDURE FOR THE PREPARATION OF NEW PYRROLOBENZIMIDAZOLES
SU853894709A SU1480770A3 (en) 1984-05-12 1985-05-10 Method of producing pyrrolobenzimidazoles or their physiologically compatible salts of inorganic acids
JP60099742A JPH0647593B2 (en) 1984-05-12 1985-05-13 Novel pyrrolo-benzimidazole, a heart containing the same, and a medicament for preventing or treating cardiovascular diseases
CN85103724A CN85103724B (en) 1984-12-20 1985-05-17 Prolesses for the preparation of new pyzzolobenzimidazoles and pharmaceutical compositions containing them
KR1019870004128A KR870001202B1 (en) 1984-05-12 1987-04-27 Process for preparing pyrrolo-benzimidazols
IL84769A IL84769A0 (en) 1984-05-12 1987-12-09 Substituted indolin-2-(thi)ones
US07/217,143 US4963686A (en) 1984-05-12 1988-07-05 Certain pyridinoylamino-indolin-2-one derivatives
FI883391A FI883391A0 (en) 1984-05-12 1988-07-15 SAOSOM MELLANPRODUKTER ANVAENDBARA INDOLINDERIVAT.
JP5310823A JPH0772185B2 (en) 1984-05-12 1993-12-10 Indoline derivative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19843446417 DE3446417A1 (en) 1984-12-20 1984-12-20 Novel pyrrolobenzimidazoles, process for their preparation and medicaments containing these compounds, and novel intermediates

Publications (1)

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DE3446417A1 true DE3446417A1 (en) 1986-06-26

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CN (1) CN85103724B (en)
DE (1) DE3446417A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216165A1 (en) * 1985-08-29 1987-04-01 Roche Diagnostics GmbH Benzodipyrroles, processes for their preparation and pharmaceutical compositions containing these compounds
DE4027592A1 (en) * 1990-08-31 1992-03-05 Beiersdorf Ag NEW PYRROLOBENZIMIDAZOLE, IMIDAZOBENZOXAZINONE AND IMIDAZOCHINOLONE, PROCESS FOR THEIR PREPARATION AND THEIR USE AND THE COMPOUNDS CONTAINING PREPARATIONS

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216165A1 (en) * 1985-08-29 1987-04-01 Roche Diagnostics GmbH Benzodipyrroles, processes for their preparation and pharmaceutical compositions containing these compounds
US4874756A (en) * 1985-08-29 1989-10-17 Boehringer Mannheim Gmbh Benzodipyrroles, processes for the preparation thereof and pharmaceutical compositions containing them
DE4027592A1 (en) * 1990-08-31 1992-03-05 Beiersdorf Ag NEW PYRROLOBENZIMIDAZOLE, IMIDAZOBENZOXAZINONE AND IMIDAZOCHINOLONE, PROCESS FOR THEIR PREPARATION AND THEIR USE AND THE COMPOUNDS CONTAINING PREPARATIONS
US5212186A (en) * 1990-08-31 1993-05-18 Beiersdorf Aktiengesellschaft Cardioactive pyrrolobenzimidazoles

Also Published As

Publication number Publication date
CN85103724B (en) 1988-07-06
CN85103724A (en) 1986-07-02

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