DE4103803A1

DE4103803A1 - NEW 4,5,6,7-TETRAHYDRO-IMIDAZO- (4,5, LJK) (1,4) - BENZODIAZEPIN-2- (1H) -THIONE, METHOD FOR THE PRODUCTION THEREOF, AND MEDICINAL PRODUCTS AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION OF THESE COMPOUNDS

Info

Publication number: DE4103803A1
Application number: DE19914103803
Authority: DE
Inventors: Alfred Dr Rer Nat Mertens; Herbert Dr Ing Leinert
Original assignee: Boehringer Mannheim GmbH
Current assignee: Roche Diagnostics GmbH
Priority date: 1991-02-08
Filing date: 1991-02-08
Publication date: 1992-08-13
Also published as: WO1992013860A1; AU1186292A

Abstract

The invention concerns compounds of the formula (I), in which R1, R2, R3 and R4 represent groups defined in the claims. The invention also concerns a method of preparing these compounds, drugs containing them for the treatment of viral illnesses, and intermediates uses in the preparation of compounds of formula (I).

Description

Gegenstand der Erfindung sind neue 4,5,6,7-Tetrahydro-imidazo- [4,5,ljk] [1,4]-benzodiazepin-2-(1H)-thione, ein Verfahren zu deren Herstellung sowie Arzneimittel und neue Zwischenprodukte zur Herstellung dieser Verbindungen.The invention relates to new 4,5,6,7-tetrahydro-imidazo- [4,5, ljk] [1,4] -benzodiazepine-2- (1H) -thione, a method too their manufacture as well as pharmaceuticals and new intermediates to make these connections.

In der Zeitschrift Nature, Vol. 343, S. 470 wird die Wirkung von 4,5,6,7-Tetrahydro-5-methyl-6-(3-methyl-2-butenyl)- imidazo-[4,5,ljk] [1,4]-benzodiazepin-2-(1H)-thion und dessen 9-Chlor-Derivat beschrieben. Diese Verbindungen hemmen die HIV-1 Replikation, aber nicht HIV-2 oder andere DNA- oder RNA-Viren, sodaß diese Verbindungen zur Behandlung von AIDS in Frage kommen. Diese Verbindungen sind auch Gegenstand der EP-A 03 84 522.In the journal Nature, Vol. 343, p. 470, the effect of 4,5,6,7-tetrahydro-5-methyl-6- (3-methyl-2-butenyl) - imidazo- [4,5, ljk] [1,4] -benzodiazepine-2- (1H) -thione and its 9-chloro derivative described. These compounds inhibit HIV-1 Replication, but not HIV-2 or other DNA or RNA viruses, so these compounds are considered for the treatment of AIDS come. These compounds are also the subject of EP-A 03 84 522.

In der vorliegenden Erfindung werden nun neue 4,5,6,7-Tetra hydo-imidazo-[4,5,ljk] [1,4]-benzodiazepin-2-(1H)-thione mit verbesserter Wirkung auf die HIV-1 Replikation beschrieben.In the present invention new 4,5,6,7-tetra hydo-imidazo- [4,5, ljk] [1,4] -benzodiazepin-2- (1H) -thione with improved effect on HIV-1 replication.

Eine Methode zur Herstellung von 4,5,6,7-Tetrahydo-imidazo- [4,5,ljk] [1,4]-benzodiazepin-2-(1H)-thione ist zwar in der europäischen Patentschrift 03 84 522 beschrieben. Nach diesem Verfahren lassen sich die gewünschten Produkte jedoch nur in geringer Gesamtausbeute herstellen.A method for the preparation of 4,5,6,7-tetrahydo-imidazo- [4,5, ljk] [1,4] -benzodiazepin-2- (1H) -thione is in the European patent specification 03 84 522. After this However, the desired products can only be processed in produce low overall yield.

In der deutschen Patentschrift P 40 36 552.2-44 ist ein neues allgemein durchführbares Verfahren beschrieben, das die Herstellung von 4,5,6,7-Tetrahydo-imidazo-[4,5,ljk] [1,4]- benzodiazepin-2-(1H)-thionen auf wirtschaftliche Art und Weise erlaubt.In the German patent specification P 40 36 552.2-44 there is a new one described generally feasible process that the Preparation of 4,5,6,7-tetrahydo-imidazo- [4,5, ljk] [1,4] - benzodiazepine-2- (1H) -thions in an economical way allowed.

Gegenstand der Erfindung sind neue 4,5,6,7-Tetrahydro-imidazo- [4,5,ljk] [1,4]-benzodiazepin-2-(1H)-thione der allgemeinen Formel IThe invention relates to new 4,5,6,7-tetrahydro-imidazo- [4,5, ljk] [1,4] -benzodiazepine-2- (1H) -thione of the general Formula I.

in welcher
R₁ ein Wasserstoffatom, einen geradkettigen oder verzweigten Alkylrest von 1-6 Kohlenstoffatomen,
R₂ einen geradkettigen oder verzweigten C₁-C₆-Alkylrest, der durch eine oder mehrere Hydroxy-, C₁-C₆-Alkoxy-, Mercapto- oder C₁-C₆-Alkylmercaptogruppen oder einen substituierten oder unsubstituierten Phenylrest substituiert sein kann; einen C₃-C₇-Cycloalkylrest, einen substituierten oder unsubstituierten Phenylrest, einen substituierten oder unsubstituierten Aralkylrest, einen substituierten oder unsubstituierten gesättigten heterocyclischen oder einen aromatischen heterocyclischen Rest oder einen substituierten oder unsubstituierten Heteroarylalkylrest, oder zusammen mit R₁ einen C₃-C₇-Cycloalkylring bilden kann,
R₃ ein Wasserstoffatom, einen geradkettigen oder verzweigten C₁-C₆-Alkylrest, der durch eine oder mehrere Hydroxy- oder C₁-C₆-Alkoxygruppen, eine substituierte oder unsubstituierte Aminogruppe oder Halogen substituiert sein kann; einen geradkettigen oder verzweigten C₂-C₆-Alkenylrest, der noch eine oder mehrere Hydroxy- oder C₁-C₆-Alkoxygruppen, eine substituierte oder unsubstituierte Aminogruppe oder Halogen tragen kann; oder einen substituierten oder unsubstituierten Aralkyl- oder Heteroarylalkylrest,
wobei einer der Reste R₁ oder R₂ auch zusammen mit dem Rest R₃ einen substituierten oder unsubstituierten heterocyclischen Ring bilden kann,
mit der Maßgabe, daß R₁ auch Wasserstoff bedeuten kann, wenn R₂ nicht Wasserstoff oder einen unsubstituierten C₁-C₆-Alkylrest darstellt und
R₄ ein Wasserstoffatom, ein Halogenatom, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Alkylendioxygruppe, eine C₁-C₆-Alkylgruppe, eine ein- oder mehrfach substituierte Aminogruppe, oder eine substituierte oder unsubstituierte Benzyloxygruppe,
bedeuten, sowie deren pharmakologisch unbedenkliche Salze.in which
R₁ is a hydrogen atom, a straight-chain or branched alkyl radical of 1-6 carbon atoms,
R₂ is a straight-chain or branched C₁-C₆ alkyl radical which can be substituted by one or more hydroxyl, C₁-C Alk alkoxy, mercapto or C₁-C Alkyl alkyl mercapto groups or a substituted or unsubstituted phenyl radical; a C₃-C₇-cycloalkyl radical, a substituted or unsubstituted phenyl radical, a substituted or unsubstituted aralkyl radical, a substituted or unsubstituted saturated heterocyclic or an aromatic heterocyclic radical or a substituted or unsubstituted heteroarylalkyl radical, or together with R₁ can form a C₃-C₇-cycloalkyl ring
R₃ is a hydrogen atom, a straight-chain or branched C₁-C₆-alkyl radical which may be substituted by one or more hydroxy or C₁-C₆-alkoxy groups, a substituted or unsubstituted amino group or halogen; a straight-chain or branched C₂-C₆ alkenyl radical which can also carry one or more hydroxy or C₁-C₆ alkoxy groups, a substituted or unsubstituted amino group or halogen; or a substituted or unsubstituted aralkyl or heteroarylalkyl radical,
where one of the radicals R₁ or R₂ together with the radical R₃ can also form a substituted or unsubstituted heterocyclic ring,
with the proviso that R₁ can also be hydrogen if R₂ is not hydrogen or an unsubstituted C₁-C₆ alkyl radical and
R₄ represents a hydrogen atom, a halogen atom, a hydroxy group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylenedioxy group, a C₁-C₆ alkyl group, a mono- or polysubstituted amino group, or a substituted or unsubstituted benzyloxy group,
mean, and their pharmacologically acceptable salts.

R₁ bedeutet ein Wasserstoffatom, einen geradkettigen oder verzweigten Alkylrest von 1-6 Kohlenstoffatomen, wie z. B. den Methyl-, Ethyl-, n-Propyl-, Isopropyl-, Butyl-, Pentyl- oder Hexylrest.R₁ represents a hydrogen atom, a straight chain or branched alkyl radical of 1-6 carbon atoms, such as. B. the methyl, ethyl, n-propyl, isopropyl, butyl, Pentyl or hexyl.

R₂ bedeutet ein Wasserstoffatom oder eine geradkettige oder verzweigte Alkylgruppe von 1-6 Kohlenstoffatomen, die noch durch eine oder mehrere Hydroxy-, Alkoxy-, Mercapto- oder Alkylmercaptogruppen oder durch einen substituierten oder unsubstituierten Phenylrest substituiert sein kann. Bevorzugt sind die Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, n-Pentyl-, Isopentyl-, n-Hexyl und die Isohexylgruppe. Unter Alkoxygruppen versteht man im allgemeinen Methoxy- oder Ethoxygruppen. Als Alkylmercaptogruppen kommen die Methylmercapto- oder die Ethylmercaptogruppe in Betracht. Die Substituenten des Phenylrestes können sein, eine Alkylgruppe, wie die Methyl- oder Ethylgruppe, eine Alkoxygruppe wie die Methoxy-, Ethoxy- oder Propoxygruppe oder ein Halogenatom, wie Chlor, Brom oder Fluor.R₂ represents a hydrogen atom or a straight chain or branched alkyl group of 1-6 carbon atoms still by one or more hydroxy, alkoxy, mercapto or Alkyl mercapto groups or by a substituted or unsubstituted phenyl radical may be substituted. The methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl and the isohexyl group. Alkoxy groups are understood in general methoxy or ethoxy groups. As alkyl mercapto groups come the methylmercapto or the Ethyl mercapto group into consideration. The substituents of the Phenylrestes can be an alkyl group like that Methyl or ethyl group, an alkoxy group like that Methoxy, ethoxy or propoxy group or a halogen atom, such as chlorine, bromine or fluorine.

Stellt R₂ einen Cycloalkylrest dar, versteht man darunter einen Cyclopentyl- oder Cyclohexylrest. Bedeutet R₂ einen substituierten Phenylring, so kommen als Substituenten in Betracht eine oder mehrere Alkylgruppen, wie Methyl-, Ethyl-, Propyl-, Isopropyl- oder Butylgruppen, eine oder mehrere Hydroxygruppen, eine oder mehrere Alkoxygruppen, wie Methoxy-, Ethoxy- oder Propoxygruppen, ein oder mehrere Halogenatome, wie Fluor, Chlor, Brom oder Jod oder eine unsubstituierte oder substituierte Aminogruppe, wie die Methylamino-, Ethylamino-, Dimethylamino- oder Diethylaminogruppe.R₂ represents a cycloalkyl radical, it is understood a cyclopentyl or cyclohexyl radical. R₂ means one substituted phenyl ring, come as substituents in Consider one or more alkyl groups, such as methyl, Ethyl, propyl, isopropyl or butyl groups, one or several hydroxyl groups, one or more alkoxy groups, such as methoxy, ethoxy or propoxy groups, one or several halogen atoms, such as fluorine, chlorine, bromine or iodine an unsubstituted or substituted amino group, such as the methylamino, ethylamino, dimethylamino or Diethylamino group.

Stellt R₂ einen unsubstituierten Aralkylrest dar, so versteht man darunter den Benzylrest. Bedeutet R₂ einen substituierten Aralkylrest, so versteht man darunter einen substituierten Benzylrest. Die Substituenten können sein eine oder mehrere Alkylgruppen, wie Methyl-, Ethyl-, n-Propyl-, Isopropyl- oder Butylgruppen, eine Hydroxygruppe oder eine oder mehrere Alkoxygruppen, wie Methoxy- oder Ethoxygruppen, ein oder mehrere Halogenatome, wie Fluor, Chlor, Brom oder Jod oder eine unsubstituierte oder substituierte Aminogruppe, wie die Methylamino-, Ethylamino-, Dimethylamino- oder Diethylaminogruppe.R₂ represents an unsubstituted aralkyl radical, so is the benzyl radical. R₂ means one substituted aralkyl radical, one understands this substituted benzyl radical. The substituents can be one or more alkyl groups, such as methyl, ethyl, n-propyl, Isopropyl or butyl groups, a hydroxy group or one or more alkoxy groups, such as methoxy or Ethoxy groups, one or more halogen atoms, such as fluorine, Chlorine, bromine or iodine or an unsubstituted or substituted amino group, such as the methylamino, Ethylamino, dimethylamino or diethylamino group.

Stell R₂ einen gesättigten heterocyclischen Ring dar, versteht man darunter einen Piperidin- oder Pyrrolidinring. Bedeutet R₂ einen unsubstituierten oder substituierten heteroaromatischen Rest, versteht man darunter einen unsubstituierten oder substituierten Pyridinring, der in 2-, 3- oder 4-Stellung verknüpft sein kann, wobei als Substituenten ein oder mehrere Halogenatome, wie Chlor, Brom oder Fluor, Alkoxygruppen wie die Methoxy- oder Ethoxygruppe oder Alkylgruppen wie die Methyl-, Ethyl- oder Propylgruppe in Betracht kommen.Make R₂ a saturated heterocyclic Ring, it means one Piperidine or pyrrolidine ring. R₂ means one unsubstituted or substituted heteroaromatic Rest, is it an unsubstituted or substituted pyridine ring in the 2-, 3- or 4-position may be linked, with one or several halogen atoms, such as chlorine, bromine or fluorine, Alkoxy groups such as the methoxy or ethoxy group or Alkyl groups such as the methyl, ethyl or propyl group in Come into consideration.

Unter einem Heteroarylalkylrest für R₂ versteht man einen Pyridylmethylrest, z. B. den Pyridyl-2-methyl-, Pyridyl-3-methyl- oder den Pyridyl-4-methylrest, den Indolyl-3-methylrest oder den Imidazolyl-4-methylrest.A heteroarylalkyl radical for R₂ means one Pyridylmethyl, e.g. B. the pyridyl-2-methyl, pyridyl-3-methyl or the pyridyl-4-methyl radical, the indolyl-3-methyl radical or the imidazolyl-4-methyl radical.

R₃ kann ein Wasserstoffatom oder eine geradkettige oder verzweigte C₁-C₆-Alkylgruppe bedeuten, die noch durch eine oder mehrere Hydroxy-, Alkoxy- oder Aminogruppen, oder ein Halogenatom substituiert sein. Bevorzugt sind die Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, Isobutyl-, n-Pentyl-, n-Hexyl-, Isohexyl-, Hydroxyethyl-, Methoxymethyl-, Ethoxyethyl-, 2-Hydroxypropyl-, 2,3-Methylendioxypropyl-, Dimethylmethylendioxypropyl-, 2-Hydroxy-3-dimethylaminopropyl-, 2-Dimethylaminoethyl- und die (2-Hydroxy-ethoxy)-methylgrupe. Unter einem Halogenatom versteht man Chlor oder Brom. Bevorzugt sind die 2-Chlorethyl-, 2-Bromethyl-, 3-Chlorpropyl-, 3-Brompropyl-, 4-Chlorbutyl- und die 4-Brombutylgruppe.R₃ can be a hydrogen atom or a straight chain or branched C₁-C₆ alkyl group mean by one or more hydroxyl, alkoxy or amino groups, or one Halogen atom may be substituted. Those are preferred Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, isohexyl, Hydroxyethyl, methoxymethyl, ethoxyethyl, 2-hydroxypropyl, 2,3-methylenedioxypropyl, dimethyl methylenedioxypropyl, 2-hydroxy-3-dimethylaminopropyl, 2-dimethylaminoethyl and the (2-hydroxy-ethoxy) methyl group. A halogen atom means chlorine or Bromine. The 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl and the 4-bromobutyl group.

R₃ kann auch eine geradkettige oder verzweigte C₂-C₆-Alkenylgruppe bedeuten, die noch durch eine Hydroxy- oder Alkoxygruppe oder ein Halogenatom substituiert sein kann. Bevorzugt sind die Vinyl-, Allyl-, 2-Methylallyl-, Isobutenyl-, Pentenyl-, Isopentenyl-, Hexenyl-, Isohexenyl-, 5-Hydroxy-penten-3-yl und die 5-Methoxy-penten-3-ylgruppe. Unter einem Halogenatom versteht man Chlor oder Brom.R₃ can also be a straight-chain or branched C₂-C₆ alkenyl group mean by a hydroxy or alkoxy group or a halogen atom may be substituted. The vinyl, allyl, 2-methylallyl, isobutenyl, Pentenyl, isopentenyl, hexenyl, isohexenyl, 5-hydroxy-penten-3-yl and the 5-methoxy-penten-3-yl group. A halogen atom means chlorine or bromine.

Bedeutet R₃ einen Aralkylrest, versteht man darunter einen Benzylrest. Bedeutet R₃ einen substituierten Aralkylrest versteht man darunter einen substituierten Benzylrest. R₃ is an aralkyl group, one means one Benzyl radical. R₃ is a substituted aralkyl group this means a substituted benzyl radical.

Als Substituenten kommen in Frage, eine oder mehrere Hydroxygruppen, eine oder mehrere Alkoxygruppen, wie z. B. Methoxy-, Ethoxy- oder Allyloxygruppen oder ein oder mehrere Halogenatome wie Chlor, Brom oder Fluor oder eine oder mehrere Alkylgruppen, wie z. B. Methyl-, Ethyl- oder Propylgruppen.Possible substituents are one or more Hydroxy groups, one or more alkoxy groups, such as. B. Methoxy, ethoxy or allyloxy groups or one or several halogen atoms such as chlorine, bromine or fluorine or one or more alkyl groups, such as. B. methyl, ethyl or Propyl groups.

Bedeutet R₃ einen Heteroarylalkylrest versteht man darunter einen 2-, 3- oder 4-Pyridylmethylrest, der noch durch eine oder mehrere Alkoxygruppen, wie Methoxy- oder Ethoxygruppen durch eine oder mehrere Alkylgruppen, wie z. B. Methyl-, Ethyl- oder Propylgruppen oder durch ein oder mehrere Halogenatome, wie Chlor oder Brom substituiert sein kann.R₃ is a heteroarylalkyl group is understood a 2-, 3- or 4-pyridylmethyl radical, which is still by one or more alkoxy groups, such as methoxy or ethoxy groups through one or more alkyl groups, such as. B. Methyl, ethyl or propyl groups or by one or several halogen atoms, such as chlorine or bromine, are substituted can be.

R₄ kann Wasserstoff, ein Halogenatom, wie Fluor, Chlor oder Brom, eine Hydroxygruppe, eine Alkylgruppe, wie die Methyl- oder Ethylgruppe, eine Alkoxygruppe, wie die Methoxy- oder Ethoxygruppe, eine Alkylendioxygruppe, wie die Methylendioxygruppe oder eine substituierte oder unsubstituierte Benzyloxygruppe bedeuten, wobei als Substituenten eine oder mehrere Alkoxygruppen, wie Methoxy- oder Ethoxygruppen, ein oder mehrere Halogenatome, wie Chlor, Fluor oder Brom und ein oder mehrere Alkylgruppen, wie die Methyl-, Ethyl- oder Propylgruppe in Frage kommen.R₄ can be hydrogen, a halogen atom, such as fluorine, chlorine or Bromine, a hydroxy group, an alkyl group like that Methyl or ethyl group, an alkoxy group like that Methoxy or ethoxy group, an alkylenedioxy group, such as the methylenedioxy group or a substituted or unsubstituted benzyloxy group, where as Substituents one or more alkoxy groups, such as Methoxy or ethoxy groups, one or more halogen atoms, such as chlorine, fluorine or bromine and one or more alkyl groups, like the methyl, ethyl or propyl group in question come.

Bildet einer der Reste R₁ und R₂ zusammen mit dem Rest R₃ einen substituierten oder unsubstituierten heterocyclischen Ring, versteht man darunter einen Pyrrolidin- oder Hydroxy-pyyrolidinring.Forms one of the radicals R₁ and R₂ together with the rest R₃ is a substituted or unsubstituted heterocyclic ring, one means one Pyrrolidine or hydroxy-pyyrolidine ring.

Bilden die Reste R₁ und R₂ zusammen einen C₃-C₇-Ring, versteht man darunter einen Spiro-Cyclopropyl-, Spiro-Cyclobutyl-, Spiro-Cyclopentyl-, Spiro-Cyclohexyl- oder Spiro-Cycloheptylring. Form the residues R₁ and R₂ together a C₃-C₇ ring, is a spiro-cyclopropyl, Spiro-Cyclobutyl-, Spiro-Cyclopentyl-, Spiro-Cyclohexyl- or spiro-cycloheptyl ring.

Die erfindungsgemäßen Verbindungen der allgemeinen Formel I können ein oder mehrere asymmetrische Kohlenstoffatome besitzen. Gegenstand der Erfindung sind daher auch sämtliche optisch aktiven und diastereomeren Formen und racemische und diastereomeren Gemische.The compounds of the general invention Formula I can have one or more asymmetric carbon atoms have. The subject of the invention are therefore also all optically active and diastereomeric forms and racemic and diastereomeric mixtures.

Die Verbindungen der allgemeinen Formel IThe compounds of general formula I

in der R₁, R₂, R₃ und R₄ die angegebenen Bedeutungen besitzen, werden hergestellt, indem man eine Verbindung der allgemeinen Formel IIin which R₁, R₂, R₃ and R₄ have the meanings given, are made by connecting a general Formula II

in der R₁, R₂, R₃ und R₄ die angegebenen Bedeutungen besitzen, nach einer herkömmlichen Methode mit einem die Thiocarbonyl-Gruppe übertragenden Reagenz, wie z. B. mit Schwefelkohlenstoff, Thiocarbonyl-diimidazol, Thiophosgen oder Thioharnstoff umsetzt.in which R₁, R₂, R₃ and R₄ have the meanings given, using a conventional method with a thiocarbonyl group transmitting reagent, such as. B. with carbon disulfide, Thiocarbonyl-diimidazole, thiophosgene or thiourea.

Die Verbindungen der allgemeinen Formel II werden hergestellt, indem man in einer Verbindung der allgemeinen Formel IIIThe compounds of the general formula II are prepared by in a compound of the general formula III

in der R₁, R₂, R₃ und R₄ die angegebenen Bedeutungen besitzen, nach einer dem Fachmann bekannten üblichen Methode die Nitrogruppe in eine Aminogruppe überführt.in which R₁, R₂, R₃ and R₄ have the meanings given, the nitro group by a conventional method known to those skilled in the art converted into an amino group.

Die Verbindungen der allgemeinen Formel III können dargestellt werden, indem man eine Verbindung der allgemeinen Formel IVThe compounds of general formula III can be represented by using a compound of general formula IV

in der R₁, R₂ und R₄ die angegebenen Bedeutungen besitzen, mit einer Verbindung der allgemeinen Formel Vin which R₁, R₂ and R₄ have the meanings given, with a compound of the general formula V

R₃-X (V)R₃-X (V)

in der X ein Halogenatom oder eine Sulfonestergruppierung darstellt, zur Reaktion bringt.in the X a halogen atom or a sulfonic ester grouping represents, brings to reaction.

Die Verbindungen der allgemeinen Formel IV können dargestellt werden, indem man eine Verbindung der allgemeinen Formel VIThe compounds of general formula IV can be represented by using a compound of general formula VI

in der R₁, R₂ und R₄ die angegebenen Bedeutungen besitzen und Y ein Halogenatom bedeutet, einer Cyclisierungsreaktion unterwirft.in which R₁, R₂ and R₄ have the meanings given and Y represents a halogen atom, undergoes a cyclization reaction.

Die Verbindungen der allgemeinen Formel VI werden dargestellt, indem man eine Verbindung der allgemeinen Formel VIIThe compounds of the general formula VI are shown by using a compound of the general formula VII

in der R₁, R₂, R₄ und Y die angegebenen Bedeutungen besitzen, einer Reduktion mit Borwasserstoff oder Diboran unterwirft.in which R₁, R₂, R₄ and Y have the meanings given, subject to a reduction with hydrogen boride or diborane.

Die Verbindungen der allgemeinen Formel VII können dargestellt werden, indem man eine Verbindung der allgemeinen Formel VIIIThe compounds of the general formula VII can be represented by using a compound of general formula VIII

in der R₁, R₂, R₄ und Y die angegebenen Bedeutungen besitzen, und R₅ Wasserstoff oder einen Alkylrest bedeutet nach dem Fachmann bekannten Methoden einem Amidierungsreaktion unterzieht.in which R₁, R₂, R₄ and Y have the meanings given, and R₅ is hydrogen or an alkyl radical after Methods known to those skilled in the art undergo an amidation reaction.

Die Verbindungen der allgemeinen Formel VIII können dargestellt werden, indem man die Verbindung der allgemeinen Formel IXThe compounds of general formula VIII can be represented by using the compound of general formula IX

in der R₄ und Y die angegebenen Bedeutungen besitzen mit einem Aminosäureester der allgemeinen Formel Xin which R₄ and Y have the meanings given with a Amino acid esters of the general formula X

in der R₁ und R₂ die angegebenen Bedeutungen besitzen und einer der Reste R₁ oder R₂ mit der Aminogruppe zusammen gegebenenfalls einen Pyrrolidin- oder Hydroxypyrrolidinring bilden kann und R₅ Wasserstoff oder einen Alkylrest bedeutet nach einer dem Fachmann bekannten Methoden zur Reaktion bringt.in which R₁ and R₂ have the meanings given and one the radicals R₁ or R₂ together with the amino group, if appropriate can form a pyrrolidine or hydroxypyrrolidine ring and R₅ is hydrogen or an alkyl radical according to one Brings known methods to the reaction.

Die Verbindungen der allgemeinen Formel IX sind literaturbekannt oder können nach literaturbekannten Methoden dargestellt werden.The compounds of general formula IX are known from the literature or can be represented by methods known from the literature will.

Die Verbindungen der allgemeinen Formel X sind literaturbekannt oder können nach bekannten Methoden hergestellt werden. The compounds of the general formula X are known from the literature or can be produced by known methods.

Die Umsetzungen der Verbindungen der allgemeinen Formel II mit einem eine Thiocarbonylgruppe übertragenden Reagenz zu einer Verbindung der allgemeinen Formel I werden durchgeführt, indem man z. B. eine Verbindung der allgemeinen Formel II mit Schwefelkohlenstoff in einer wäßrig-alkoholischen Lösung in Gegenwart von Alkali nach einer dem Fachmann bekannten Methode zur Reaktion bringt oder indem man eine Verbindung der allgemeinen Formel II mit Thiocarbonyldiimidazol in einem inerten Lösungsmittel, wie z. B. Dimethylformamid zur Reaktion bringt.The reactions of the compounds of general formula II with a reagent transferring a thiocarbonyl group to a Compounds of general formula I are carried out by one z. B. with a compound of general formula II Carbon disulfide in an aqueous-alcoholic solution Presence of alkali by a method known to those skilled in the art react or by using a compound of the general Formula II with thiocarbonyldiimidazole in an inert Solvents such as B. brings dimethylformamide to the reaction.

Die Verbindungen der allgemeinen Formel II werden hergestellt, indem man in einer Verbindung der allgemeinen Formel die Nitrogruppe nach einer dem Fachmann bekannten Methode in eine Aminogruppe überführt.The compounds of the general formula II are prepared by the nitro group in a compound of the general formula into an amino group by a method known to those skilled in the art transferred.

Die Umsetzung der Verbindungen der allgemeinen Formel IV mit Verbindungen der allgemeinen Formel V zu Verbindungen der allgemeinen Formel III werden durchgeführt, daß man die Verbindungen der allgemeinen Formel IV mit Verbindungen der allgemeinen Formel V in einem inerten Lösungsmittel, wie z. B. Dimethylformamid, Dimethylacetamid, Aceton, Methylethylketon oder Alkohol bei Temperaturen zwischen Raumtemperatur und Rückflußtemperatur des Lösungsmittels, vorzugsweise zwischen 40°C und 60°C in Gegenwart eines alkalischen Kondensationsmittels, wie z. B. Natriumkarbonat oder Kaliumcarbonat nach dem Fachmann bekannten Methoden zur Reaktion bringt.The reaction of the compounds of general formula IV with Compounds of the general formula V to compounds of general formula III are carried out that the compounds of the general formula IV with compounds of the general Formula V in an inert solvent, such as. B. Dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone or alcohol at temperatures between room temperature and Reflux temperature of the solvent, preferably between 40 ° C and 60 ° C in the presence of an alkaline condensing agent, such as B. sodium carbonate or potassium carbonate after Brings known methods to the reaction.

Die Cyclisierung einer Verbindung der allgemeinen Formel VI zu einer Verbindung der allgemeinen Formel IV kann durchgeführt werden, indem man eine Verbindung der allgemeinen Formel VI in einem inerten Lösungsmittel, wie z. B. Dimethylformamid, Dimethylacetamid, Aceton, Methylethylketon oder Alkohol in Gegenwart eines alkalischen Kondensationsmittels, wie z. B. Natriumkarbonat oder Kaliumkarbonat bei Temperaturen zwischen Raumtemperatur und Rückflußtemperatur des Lösungsmittels zur Reaktion bringt.The cyclization of a compound of general formula VI to a compound of general formula IV can be carried out by using a compound of general formula VI in an inert solvent, such as. B. dimethylformamide, Dimethylacetamide, acetone, methyl ethyl ketone or alcohol in Presence of an alkaline condensing agent such as e.g. B. Sodium carbonate or potassium carbonate at temperatures between Room temperature and reflux temperature of the solvent Brings reaction.

Die Cyclisierungsreaktion einer Verbindung der allgemeinen Formel VI zu einer Verbindung der allgemeinen Formel IV kann auch durchgeführt werden, daß man eine Verbindung der allgemeinen Formel IV in Gegenwart eines alkalischen Kondensationsmittels, wie z. B. Natriumkarbonat oder Kaliumkarbonat ohne Zusatz eines Lösungsmittels auf Temperaturen zwischen 100°C und 200°C, vorzugsweise zwischen 130°C und 170°C erhitzt.The cyclization reaction of a compound of the general Formula VI to a compound of general formula IV can also be carried out that a compound of general Formula IV in the presence of an alkaline condensing agent, such as B. sodium carbonate or potassium carbonate without Add a solvent to temperatures between 100 ° C and 200 ° C, preferably heated between 130 ° C and 170 ° C.

Die Verbindungen der allgemeinen Formel VI werden dargestellt, daß man eine Verbindung der allgemeinen Formel VII mit Borwasserstoff oder Diboran in einem inerten Lösungsmittel, wie z. B. Tetrahydrofuran, Dioxan, Diethylether oder Methylenchlorid bei Temperaturen zwischen Raumtemperatur und Rückflußtemperatur des Lösungsmittels zur Reaktion bringt oder indem man eine Verbindung der allgemeinen Formel VI in einem inerten Lösungsmittel, wie z. B. Methylenchlorid der Reduktion mit einem Tetraalkylammoniumborhydrid unterwirft.The compounds of the general formula VI are shown that one has a compound of general formula VII with hydrogen boron or diborane in an inert solvent, such as e.g. B. tetrahydrofuran, dioxane, diethyl ether or methylene chloride at temperatures between room temperature and reflux temperature of the solvent or by reacting one Compound of the general formula VI in an inert solvent, such as B. methylene chloride reduction with a tetraalkylammonium borohydride submits.

Die Verbindungen der allgemeinen Formel VII werden dargestellt, indem man eine Verbindung der allgemeinen Formel VIII nach dem Fachmann und literaturbekannten Methoden einer Amidbildungsreaktion unterzieht.The compounds of the general formula VII are shown by using a compound of general formula VIII according to Expert and methods known from the literature of an amide formation reaction undergoes.

Die Verbindungen der allgemeinen Formel VIII können dargestellt werden, indem man eine Verbindung der allgemeinen Formel IX nach dem Fachmann bekannten Methoden mit einer Verbindung der allgemeinen Formel X zur Reaktion bringt.The compounds of general formula VIII can be represented by using a compound of general formula IX by methods known to those skilled in the art with a compound of general formula X brings to reaction.

Besonders bevorzugte Verbindungen der allgemeinen Formel I sind folgende Verbindungen:
4,5,6,7-Tetrahydro-5,5-dimethyl-6-(3-methyl-2-butenyl)-imidazo-[4,5,-ljk] [1,4-]benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-phenyl-6-(3-methyl-2-butenyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-chlor-phenyl)-6-(3-methyl-2-butenyl)-imidazo--[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methyl-phenyl)-6-(3-methyl-2-butenyl)-imidaz-o-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-ethyl-phenyl)-6-(3-methyl-2-butenyl)-imidazo--[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-Methoxy-phenyl)-6-(3-methyl-2-butenyl)-imida-zo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dichlor-phenyl)-6-(3-methyl-2-butenyl)-imi-dazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-benzyl-6-(3-methyl-2-butenyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-chlor-benzyl)-6-(3-methyl-2-butenyl)-imidazo--[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-Methoxy-benzyl)-6-(3-methyl-2-butenyl)-imida-zo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methyl-benzyl)-6-(3-methyl-2-butenyl)-imidaz-o-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dichlor-benzyl)-6-(3-methyl-2-butenyl)-imi-dazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dimethoxy-benzyl)-6-(3-methyl-2-butenyl)-i-midazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dimethoxy-phenyl)-6-(3-methyl-2-butenyl)-i-midazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-phenyl-6-(3-methyl-2-butenyl)-imidazo-[-4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-chlor-phenyl)-6-(3-methyl-2-butenyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methyl-phenyl)-6-(3-methyl-2-butenyl-)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-ethyl-phenyl)-6-(3-methyl-2-butenyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methoxy-phenyl)-6-(3-methyl-2-buteny-l)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dimethoxy-phenyl)-6-(3-methyl-2-bu-tenyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dichlor-phenyl)-6-(3-methyl-2-bute-nyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-benzyl-6-(3-methyl-2-butenyl)-imidazo-[-4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methoxy-benzyl)-6-(3-methyl-2-buteny-l)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5,5-dimethyl-6-(3-methyl-2-butenyl)-imida-zo-[4,5,1,jk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-chlor-benzyl)-6-(3-methyl-2-butenyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dichlor-benzyl)-6-(3-methyl-2-bute-nyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dimethoxy-benzyl)-6-(3-methyl-2-bu-tenyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5,5-dimethyl-6-(3-methyl-2-butenyl)-imidaz-o-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-phenyl-6-(3-methyl-2-butenyl)-imidazo-[4-,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-chlorphenyl)-6-(3-methyl-2-butenyl)-i-midazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-methyl-phenyl)-6-(3-methyl-2-butenyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-ethyl-phenyl)-6-(3-methyl-2-butenyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-methoxy-phenyl)-6-(3-methyl-2-butenyl-)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(3,4-dimethoxy-phenyl)-6-(3-methyl-2-but-enyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(3,4-dichlor-phenyl)-6-(3-methyl-2-buten-yl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(benzyl)-6-(3-methyl-2-butenyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-methoxy-benzyl)-6-(3-methyl-2-butenyl-)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-chlor-benzyl)-6-(3-methyl-2-butenyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(3,4-dichlor-benzyl)-6-(3-methyl-2-buten-yl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5,5-dimethyl-6-(3-methyl-butyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-phenyl-6-(3-methyl-butyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-chlor-phenyl)-6-(3-methyl-butyl)-imidazo-[4,-5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methyl-phenyl)-6-(3-methyl-butyl)-imidazo-[4-,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-ethyl-phenyl)-6-(3-methyl-butyl)-imidazo-[4,-5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methoxy-phenyl)-6-(3-methyl-butyl)-imidazo-[-4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dimethoxy-phenyl)-6-(3-methyl-butyl)-imida-zo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dichlor-phenyl)-6-(3-methyl-butyl)-imidazo--[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-benzyl-6-(3-methyl-butyl)-imidazo-[4,5,ljk] [1,4-]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-chlor-benzyl)-6-(3-methyl-butyl)-imidazo-[4,-5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methoxy-benzyl)-6-(3-methyl-butyl)-imidazo-[-4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methyl-benzyl)-6-(3-methyl-butyl)-imidazo-[4-,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dichlor-benzyl)-6-(3-methyl-butyl)-imidazo--[4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dimethoxy-benzyl)-6-(3-methyl-butyl)-imida-zo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5,5-dimethyl-6-(3-methyl-butyl)-imidazo-[-4,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-phenyl-6-(3-methyl-butyl)-imidazo-[4,5,-ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-chlor-phenyl)-6-(3-methyl-butyl)-imi-dazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methyl-phenyl)-6-(3-methyl-butyl)-im-idazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-ethyl-phenyl)-6-(3-methyl-butyl)-imi-dazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methoxy-phenyl)-6-(3-methyl-butyl)-i-midazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dimethoxy-phenyl)-6-(3-methyl-buty-l)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dichlor-phenyl)-6-(3-methyl-butyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-benzyl-6-(3-methyl-butyl)-imidazo-[4,5,-ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-chlor-benzyl)-6-(3-methyl-butyl)-imi-dazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methoxy-benzyl)-6-(3-methyl-butyl)-i-midazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methyl-benzyl)-6-(3-methyl-butyl)-im-idazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dichlor-benzyl)-6-(3-methyl-butyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dimethoxy-benzyl)-6-(3-methyl-buty-l)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5,5-dimethyl-6-(3-methyl-butyl)-imidazo-[4-,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-phenyl-6-(3-methyl-butyl)-imidazo-[4,5,l-jk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-chlor-phenyl)-6-(3-methyl-butyl)-imid-azo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-methyl-phenyl)-6-(3-methyl-butyl)-imi-dazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-ethyl-phenyl)-6-(3-methyl-butyl)-imid-azo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-methoxy-phenyl)-6-(3-methyl-butyl)-im-idazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(3,4-dimethoxy-phenyl)-6-(3-methyl-butyl-)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(3,4-dichlor-phenyl)-6-(3-methyl-butyl)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-benzyl-6-(3-methyl-butyl)-imidazo-[4,5,l-jk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-chlor-benzyl)-6-(3-methyl-butyl)-imid-azo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-methoxy-benzyl)-6-(3-methyl-butyl)-im-idazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(4-methyl-benzyl)-6-(3-methyl-butyl)-imi-dazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(3,4-dichlor-benzyl)-6-(3-methyl-butyl)--imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-brom-5-(3,4-dimethoxy-benzyl)-6-(3-methyl-butyl-)-imidazo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-5,5-dimethyl-6-isopropyl-imidazo-[4,5,ljk] [1,4]-b-enzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-phenyl-6-isopropyl-imidazo-[4,5,ljk] [1,4]-benzo-diazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-chlor-phenyl)-6-isopropyl-imidazo-[4,5,ljk] [-1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-brom-phenyl)-6-isopropyl-imidazo-[4,5,ljk] [1-,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methoxy-phenyl)-6-isopropyl-imidazo-[4,5,ljk-] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dimethoxy-phenyl)-6-isopropyl-imidazo-[4,5-,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dichlor-phenyl)-6-isopropyl-imidazo-[4,5,l-jk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-benzyl-6-isopropyl-imidazo-[4,5,ljk] [1,4]-benzo-diazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-chlor-benzyl)-6-isopropyl-imidazo-[4,5,ljk] [-1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-brom-benzyl)-6-isopropyl-imidazo-[4,5,ljk] [1-,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dichlor-benzyl)-6-isopropyl-imidazo-[4,5,l-jk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(4-methoxy-benzyl)-6-isopropyl-imidazo-[4,5,ljk-] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-5-(3,4-dimethoxy-benzyl)-6-isopropyl-imidazo-[4,5-,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5,5-dimethyl-6-isopropyl-imidazo-[4,5,ljk-] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-phenyl-6-isopropyl-imidazo-[4,5,ljk] [1,-4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-chlor-phenyl)-6-isopropyl-imidazo-[4-,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-brom-phenyl)-6-isopropyl-imidazo-[4,-5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methoxy-phenyl)-6-isopropyl-imidazo--[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dichlor-phenyl)-6-isopropyl-imidaz-o-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dimethoxy-phenyl)-6-isopropyl-imid-azo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-benzyl-6-isopropyl-imidazo-[4,5,ljk] [1,-4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-chlor-benzyl)-6-isopropyl-imidazo-[4-,5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-brom-benzyl)-6-isopropyl-imidazo-[4,-5,ljk] [1,4]-benzodiazepin-2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dichlor-benzyl)-6-isopropyl-imidaz-o-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(4-methoxy-benzyl)-6-isopropyl-imidazo-[4,5,ljk]1,4]-benzodiazepin- 2(1H)-thion
4,5,6,7-Tetrahydro-9-chlor-5-(3,4-dimethoxy-benzyl)-6-isopropyl-imid-azo-[4,5,ljk] [1,4]-benzodiazepin- 2(1H)-thionThe following compounds are particularly preferred compounds of the general formula I:
4,5,6,7-tetrahydro-5,5-dimethyl-6- (3-methyl-2-butenyl) imidazo- [4,5, -jk] [1,4-] benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-5-phenyl-6- (3-methyl-2-butenyl) imidazo [4,5, ljk] [1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-5- (4-chlorophenyl) -6- (3-methyl-2-butenyl) imidazo - [4,5, ljk] [1,4] -benzodiazepine 2 (1H) thione
4,5,6,7-tetrahydro-5- (4-methylphenyl) -6- (3-methyl-2-butenyl) imidaz-o- [4,5, ljk] [1,4] benzodiazepine - 2 (1H) thione
4,5,6,7-tetrahydro-5- (4-ethylphenyl) -6- (3-methyl-2-butenyl) imidazo - [4,5, ljk] [1,4] benzodiazepine 2 (1H) thione
4,5,6,7-tetrahydro-5- (4-methoxyphenyl) -6- (3-methyl-2-butenyl) imida-zo- [4,5, ljk] [1,4] benzodiazepine - 2 (1H) thione
4,5,6,7-tetrahydro-5- (3,4-dichlorophenyl) -6- (3-methyl-2-butenyl) -imi-dazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5-benzyl-6- (3-methyl-2-butenyl) imidazo [4,5, ljk] [1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-5- (4-chlorobenzyl) -6- (3-methyl-2-butenyl) imidazo - [4,5, ljk] [1,4] -benzodiazepine 2 (1H) thione
4,5,6,7-tetrahydro-5- (4-methoxy-benzyl) -6- (3-methyl-2-butenyl) imida-zo- [4,5, ljk] [1,4] -benzodiazepine - 2 (1H) thione
4,5,6,7-tetrahydro-5- (4-methyl-benzyl) -6- (3-methyl-2-butenyl) imidaz-o- [4,5, ljk] [1,4] benzodiazepine - 2 (1H) thione
4,5,6,7-tetrahydro-5- (3,4-dichlorobenzyl) -6- (3-methyl-2-butenyl) -imi-dazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dimethoxy-benzyl) -6- (3-methyl-2-butenyl) -i-midazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dimethoxyphenyl) -6- (3-methyl-2-butenyl) -i-midazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5-phenyl-6- (3-methyl-2-butenyl) imidazo - [- 4,5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-chlorophenyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methylphenyl) -6- (3-methyl-2-butenyl -) - imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-ethylphenyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methoxyphenyl) -6- (3-methyl-2-buteny-l) -imidazo- [4,5, ljk] [1, 4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dimethoxyphenyl) -6- (3-methyl-2-bu-tenyl) imidazo- [4,5, ljk] [ 1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dichlorophenyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [ 1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-chloro-5-benzyl-6- (3-methyl-2-butenyl) imidazo - [- 4,5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methoxy-benzyl) -6- (3-methyl-2-buteny-l) -imidazo- [4,5, ljk] [1, 4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-chloro-5,5-dimethyl-6- (3-methyl-2-butenyl) imida-zo- [4,5,1, jk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-chloro-benzyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dichlorobenzyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [ 1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dimethoxy-benzyl) -6- (3-methyl-2-bu-tenyl) imidazo- [4,5, ljk] [ 1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-bromo-5,5-dimethyl-6- (3-methyl-2-butenyl) imidaz-o- [4,5, ljk] [1,4] benzodiazepine - 2 (1H) thione
4,5,6,7-tetrahydro-9-bromo-5-phenyl-6- (3-methyl-2-butenyl) imidazo- [4-, 5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-chlorophenyl) -6- (3-methyl-2-butenyl) -i-midazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-methylphenyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-ethylphenyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-methoxyphenyl) -6- (3-methyl-2-butenyl -) - imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (3,4-dimethoxyphenyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [ 1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-bromo-5- (3,4-dichlorophenyl) -6- (3-methyl-2-buten-yl) imidazo- [4,5, ljk] [ 1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-bromo-5- (benzyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-methoxy-benzyl) -6- (3-methyl-2-butenyl -) - imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-chlorobenzyl) -6- (3-methyl-2-butenyl) imidazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (3,4-dichlorobenzyl) -6- (3-methyl-2-buten-yl) imidazo- [4,5, ljk] [ 1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-5,5-dimethyl-6- (3-methylbutyl) imidazo [4,5, ljk] [1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-5-phenyl-6- (3-methylbutyl) imidazo [4,5, ljk] [1,4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-5- (4-chlorophenyl) -6- (3-methylbutyl) imidazo- [4, -5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-5- (4-methylphenyl) -6- (3-methylbutyl) imidazo- [4-, 5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-5- (4-ethylphenyl) -6- (3-methylbutyl) imidazo- [4, -5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-5- (4-methoxyphenyl) -6- (3-methylbutyl) imidazo - [- 4,5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dimethoxyphenyl) -6- (3-methylbutyl) imida-zo [4,5, ljk] [1,4] benzodiazepine - 2 (1H) thione
4,5,6,7-tetrahydro-5- (3,4-dichlorophenyl) -6- (3-methylbutyl) imidazo - [4,5, ljk] [1,4] benzodiazepine 2 (1H) thione
4,5,6,7-tetrahydro-5-benzyl-6- (3-methylbutyl) imidazo [4,5, ljk] [1,4 -] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-5- (4-chlorobenzyl) -6- (3-methylbutyl) imidazo- [4, -5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-5- (4-methoxy-benzyl) -6- (3-methylbutyl) imidazo - [- 4,5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-5- (4-methyl-benzyl) -6- (3-methyl-butyl) imidazo- [4-, 5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dichlorobenzyl) -6- (3-methylbutyl) imidazo - [4,5, ljk] [1,4] benzodiazepine 2 (1H) thione
4,5,6,7-tetrahydro-5- (3,4-dimethoxybenzyl) -6- (3-methylbutyl) imida-zo [4,5, ljk] [1,4] benzodiazepine - 2 (1H) thione
4,5,6,7-tetrahydro-9-chloro-5,5-dimethyl-6- (3-methylbutyl) imidazo - [- 4,5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-9-chloro-5-phenyl-6- (3-methyl-butyl) imidazo- [4,5, -jk] [1,4] -benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-9-chloro-5- (4-chlorophenyl) -6- (3-methylbutyl) -imi-dazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methylphenyl) -6- (3-methylbutyl) imidazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-ethylphenyl) -6- (3-methylbutyl) -imi-dazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methoxyphenyl) -6- (3-methylbutyl) -i-midazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dimethoxyphenyl) -6- (3-methylbutyl-l) imidazo- [4,5, ljk] [1, 4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dichlorophenyl) -6- (3-methylbutyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5-benzyl-6- (3-methylbutyl) imidazo- [4,5, -jk] [1,4] -benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-9-chloro-5- (4-chloro-benzyl) -6- (3-methyl-butyl) -imi-dazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methoxy-benzyl) -6- (3-methyl-butyl) -i-midazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methyl-benzyl) -6- (3-methyl-butyl) -im-idazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dichlorobenzyl) -6- (3-methylbutyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dimethoxy-benzyl) -6- (3-methyl-buty-l) -imidazo- [4,5, ljk] [1, 4] benzodiazepine-2 (1H) thione
4,5,6,7-tetrahydro-9-bromo-5,5-dimethyl-6- (3-methylbutyl) imidazo- [4-, 5, ljk] [1,4] -benzodiazepine-2 ( 1H) -thione
4,5,6,7-tetrahydro-9-bromo-5-phenyl-6- (3-methylbutyl) imidazo- [4,5,1-jk] [1,4] -benzodiazepine-2 (1H ) -thion
4,5,6,7-tetrahydro-9-bromo-5- (4-chlorophenyl) -6- (3-methylbutyl) imide azo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-methylphenyl) -6- (3-methylbutyl) -imi-dazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-ethylphenyl) -6- (3-methylbutyl) imide azo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-methoxy-phenyl) -6- (3-methylbutyl) -im-idazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (3,4-dimethoxyphenyl) -6- (3-methylbutyl -) - imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (3,4-dichlorophenyl) -6- (3-methylbutyl) imidazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5-benzyl-6- (3-methylbutyl) imidazo [4,5,1-jk] [1,4] benzodiazepine-2 (1H ) -thion
4,5,6,7-tetrahydro-9-bromo-5- (4-chlorobenzyl) -6- (3-methylbutyl) imide azo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-methoxy-benzyl) -6- (3-methyl-butyl) -im-idazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (4-methyl-benzyl) -6- (3-methyl-butyl) -imi-dazo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (3,4-dichlorobenzyl) -6- (3-methylbutyl) imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-bromo-5- (3,4-dimethoxybenzyl) -6- (3-methylbutyl -) - imidazo- [4,5, ljk] [1,4 ] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5,5-dimethyl-6-isopropyl-imidazo- [4,5, ljk] [1,4] -b-enzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5-phenyl-6-isopropyl-imidazo- [4,5, ljk] [1,4] -benzo-diazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (4-chlorophenyl) -6-isopropyl-imidazo- [4,5, ljk] [-1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (4-bromophenyl) -6-isopropyl-imidazo- [4,5, ljk] [1-, 4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (4-methoxy-phenyl) -6-isopropyl-imidazo- [4,5, ljk-] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dimethoxy-phenyl) -6-isopropyl-imidazo- [4,5-, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dichlorophenyl) -6-isopropyl-imidazo- [4,5, l-jk] [1,4] -benzodiazepine-2 (1H) - thion
4,5,6,7-tetrahydro-5-benzyl-6-isopropyl-imidazo- [4,5, ljk] [1,4] -benzo-diazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (4-chlorobenzyl) -6-isopropyl-imidazo- [4,5, ljk] [-1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (4-bromo-benzyl) -6-isopropyl-imidazo- [4,5, ljk] [1-, 4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dichlorobenzyl) -6-isopropyl-imidazo- [4,5, l-jk] [1,4] -benzodiazepine-2 (1H) - thion
4,5,6,7-tetrahydro-5- (4-methoxy-benzyl) -6-isopropyl-imidazo- [4,5, ljk-] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-5- (3,4-dimethoxy-benzyl) -6-isopropyl-imidazo- [4,5-, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5,5-dimethyl-6-isopropyl-imidazo- [4,5, ljk-] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5-phenyl-6-isopropyl-imidazo- [4,5, ljk] [1, -4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-chlorophenyl) -6-isopropyl-imidazo- [4-, 5, ljk] [1,4] -benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-9-chloro-5- (4-bromo-phenyl) -6-isopropyl-imidazo- [4, -5, ljk] [1,4] -benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-9-chloro-5- (4-methoxyphenyl) -6-isopropyl-imidazo - [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dichlorophenyl) -6-isopropyl-imidaz-o- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dimethoxy-phenyl) -6-isopropyl-imide-azo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5-benzyl-6-isopropyl-imidazo- [4,5, ljk] [1, -4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-chloro-benzyl) -6-isopropyl-imidazo- [4-, 5, ljk] [1,4] -benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-9-chloro-5- (4-bromo-benzyl) -6-isopropyl-imidazo- [4, -5, ljk] [1,4] -benzodiazepine-2 (1H) -thion
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dichlorobenzyl) -6-isopropyl-imidaz-o- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (4-methoxy-benzyl) -6-isopropyl-imidazo- [4,5, ljk] 1,4] -benzodiazepine-2 (1H) -thione
4,5,6,7-tetrahydro-9-chloro-5- (3,4-dimethoxy-benzyl) -6-isopropyl-imide-azo- [4,5, ljk] [1,4] -benzodiazepine-2 (1H) -thione

Gegenstand der Erfindung sind auch Arzneimittel, die diese Verbindungen enthalten. Die Verbindungen der vorliegenden Erfindung weisen wertvolle pharmakologische Eigenschaften auf. Insbesondere eignen sie sich zur Therapie und Prophylaxe von Krankheiten die durch das Humanes-Immunschwäche-Virus HIV-1 verursacht werden.The invention also relates to pharmaceuticals that use them Connections included. The compounds of the present Invention have valuable pharmacological properties. They are particularly suitable for the therapy and prophylaxis of Diseases caused by the human immunodeficiency virus HIV-1 caused.

Besonders geeignet erscheinen die Verbindungen der Formel I zur Behandlung der klinischen Manifaktion der retroviralen HIV-Infektion beim Menschen und dem klinischen Vollbild von AIDS. Die Verbindungen der allgemeinen Formel I hemmen die Vermehrung von HIV-1 auf der virusspezifischen RNA-Transkription. Sie hemmen über die Inhibierung des Enzyms Reverse Transkriptase die Vermehrung von Retroviren und sind daher besonders zur Behandlung der Immunschwäche-Erkrankung AIDS geeignet.The compounds of the formula I appear to be particularly suitable for Treatment of clinical manipulation of retroviral HIV infection in humans and the clinical picture of AIDS. The compounds of general formula I inhibit propagation of HIV-1 on virus-specific RNA transcription. they inhibit by inhibiting the enzyme reverse transcriptase the multiplication of retroviruses and are therefore particularly for Treatment of the immune deficiency disease AIDS suitable.

Zur Behandlung von AIDS ist heute nur 3′-Azido-3′-desoxymidin (DE-A 36 08 606) bei AIDS-Patienten zugelassen. Jedoch machen toxische Nebenwirkungen des 3′-Azido-3′-desoxythyidins auf das Knochenmark bei etwa 50% der Patienten Bluttransfusionen erforderlich. Die Verbindungen der allgemeinen Formel I besitzen diese Nachteile nicht. Sie wirken antiviral, ohne in pharmakologisch relevanten Dosen cytotoxisch zu sein.Only 3′-azido-3′-deoxymidine is used to treat AIDS today (DE-A 36 08 606) approved for AIDS patients. However, do toxic side effects of 3'-azido-3'-deoxythyidine on that Bone marrow blood transfusions in about 50% of patients required. The compounds of the general formula I do not have these disadvantages. They have an antiviral effect without to be cytotoxic in pharmacologically relevant doses.

Die Verbindungen der vorliegenden Erfindung und ihre pharmazeutischen Zubereitungen können auch in Kombination mit anderen Arzneimitteln zur Behandlung und Prophylaxe der oben genannten Infektionen eingesetzt werden. Beispiele dieser weiteren Arzneimittel beinhalten Mittel, die zur Behandlung und Prophylaxe von HIV-Infektionen oder diese Krankheit begleitende Erkrankungen einsetzbar sind wie 3′-Azido-3′-desoxythymidin, 2′,3′-Didesoxynukleoside wie z. B. 2′,3′-Didesoxycytidin, 2′,3′-Didesoxyadenosin und 2′,3′-Didesoxyinosin, acyclische Nukleoside (z. B. Acyclovir), Interferone wie z. B. A-Interferon, renale Ausscheidungs-Inhibitoren wie z. B. Probenicid, Nukleosid-Transport-Inhibitoren wie z. B. Dipyridamol, als auch Immunmodulatoren wie z. B. Interleukin II oder Stimulierungs-Faktoren wie z. B. der Granulocyten-Makrophagen-Kolonie-Faktor. Die Verbindungen der vorliegenden Erfindung und das andere Arzneimittel können jeweils einzeln, gleichzeitig gegebenenfalls in einer einzigen oder zwei getrennten Formulierungen oder zu unterschiedlichen Zeiten verabreicht werden, so daß ein synergistischer Effekt erreicht wird.The compounds of the present invention and their pharmaceutical Preparations can also be used in combination with others Medicines for the treatment and prophylaxis of the above Infections are used. Examples of these other drugs include means of treatment and prophylaxis of HIV infections or diseases accompanying this disease can be used like 3'-azido-3'-deoxythymidine, 2 ', 3'-dideoxynucleosides such as B. 2 ', 3'-dideoxycytidine, 2', 3'-dideoxyadenosine and 2 ′, 3′-dideoxyinosine, acyclic nucleosides (e.g. acyclovir), interferons such as e.g. B. A interferon, renal excretion inhibitors such as B. probenicid, Nucleoside transport inhibitors such as B. dipyridamole, as well Immunomodulators such as B. Interleukin II or stimulation factors such as B. the granulocyte-macrophage colony factor. The compounds of the present invention and the other Medicines can be taken individually, at the same time if necessary in a single or two separate formulations or administered at different times, so that a synergistic effect is achieved.

Die Verbindungen der allgemeinen Formel I enthalten basische Gruppen, die mit geeigneten Säuren in Säureadditionssalze überführt werden können. Als Säuren kommen hierfür beispielsweise in Betracht: Salzsäure, Bromwassersäure, Schwefelsäure, Phosphorsäure, Fumarsäure, Bernsteinsäure, Weinsäure, Zitronensäure, Milchsäure, Maleinsäure oder Methansulfonsäure.The compounds of general formula I contain basic Groups with suitable acids in acid addition salts can be transferred. Examples of these are acids considered: hydrochloric acid, hydrobromic acid, sulfuric acid, Phosphoric acid, fumaric acid, succinic acid, tartaric acid, citric acid, Lactic acid, maleic acid or methanesulfonic acid.

Die Arzneimittel enthalten Verbindungen der Formel I zur Behandlung von viralen Infektionen können in flüssiger oder fester Form enteral oder parenteral appliziert werden. Hierbei kommen die üblichen Applikationsformen in Frage, wie beispielsweise Tabletten, Kapseln, Drag´es, Sirupe, Lösungen oder Suspensionen. Als Injektionsmedium kommt vorzugsweise Wasser zur Anwendung, das die bei Injektionslösungen üblichen Zusätze wie Stabilisierungsmittel, Lösungsvermittler und Puffer enthält. Derartige Zusätze sind z. B. Tartrat- und Zitratpuffer, Ethanol, Komplexbildner, wie Ethylendiamintetraessigsäure und deren nichttoxischen Salze, hochmolekulare Polymere, wie flüssiges Polyethylenoxid zur Viskositätsregulierung. Flüssige Trägerstoffe für Injektionslösungen müssen steril sein und werden vorzugsweise in Ampullen abgefüllt. Feste Trägerstoffe sind beispielsweise Stärke, Lactose, Mannit, Methylcellulose, Talkum, hochdisperse Kieselsäuren, höhermolekulare Fettsäuren, wie Stearinsäure, Gelatine, Agar-Agar, Calciumphosphat, Magnesiumstearat, tierische und pflanzliche Fette, fest hochmolekulare Polymere, wie Polyethylenglykole, etc. Für orale Applikationen geeignete Zubereitungen können gewünschtenfalls Geschmacks- oder Süßstoffe enthalten. The medicaments contain compounds of the formula I for Treatment of viral infections can be in liquid or solid form can be applied enterally or parenterally. Here the usual forms of application come into question, such as Tablets, capsules, drages, syrups, solutions or Suspensions. Water is preferably used as the injection medium to the application, which is the usual additives for injection solutions such as stabilizers, solubilizers and buffers. Such additives are e.g. B. tartrate and citrate buffers, Ethanol, complexing agents such as ethylenediaminetetraacetic acid and their non-toxic salts, high molecular weight polymers, such as liquid polyethylene oxide for viscosity regulation. Liquid Carriers for injection solutions must be sterile and are preferably filled into ampoules. Solid carriers are, for example, starch, lactose, mannitol, methyl cellulose, Talc, highly disperse silicas, higher molecular fatty acids, such as stearic acid, gelatin, agar agar, calcium phosphate, Magnesium stearate, animal and vegetable fats, solid high molecular weight Polymers, such as polyethylene glycols, etc. For oral Preparations suitable for applications can, if desired Contain flavorings or sweeteners.

Die Dosierung kann von verschiedenen Faktoren, wie Applikationsweise, Spezies, Alter oder individuellem Zustand abhängen. Die erfindungsgemäßen Verbindungen werden üblicherweise in Mengen von 0,1-100 mg, vorzugsweise 0,2-80 mg pro Tag und pro kg Körpergewicht appliziert. Bevorzugt ist es, die Tagesdosis auf 2-5 Appikationen zu verteilen, wobei bei jeder Applikation 1-2 Tabletten mit einem Wirkstoffgehalt von 0,5-500 mg verabreicht werden. Die Tabletten können auch retardiert sein, wodurch sich die Anzahl der Applikationen pro Tag auf 1-3 vermindert. Der Wirkstoffgehalt der retardierten Tabletten kann 2-1000 mg betragen. Der Wirkstoff kann auch durch Dauerinfusion gegeben werden, wobei die Mengen von 5-1000 mg pro Tag normalerweise ausreichen.The dosage can depend on various factors, such as the mode of administration, Species, age or individual condition depend. The compounds of the invention are common in amounts of 0.1-100 mg, preferably 0.2-80 mg per Applied per day and per kg body weight. It is preferred that Distribute daily dose over 2-5 applications, with each Application 1-2 tablets with an active ingredient content of 0.5-500 mg be administered. The tablets can also be delayed be, which increases the number of applications per day to 1-3 reduced. The active substance content of the prolonged-release tablets can Amount to 2-1000 mg. The active ingredient can also be given by continuous infusion be given, the amounts being 5-1000 mg per day usually enough.

Weiterer Gegenstand der Erfindung sind Zwischenprodukte der allgemeinen Formel IIAnother object of the invention are intermediates general formula II

Hierzu gehören insbesondere:
9-Amino-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-2-butenyl)-(1H)--1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-2-butenyl)-(1H)-1,4--benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-2-butenyl)--(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-2-buteny-l)-(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl-2-bute-nyl)-(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-methyl-2-bu-tenyl)-(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-2-butenyl)-(1H)-1,4--benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-2-butenyl)--(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-2-buteny-l)-(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl-2-bute-nyl)-(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-methyl-2-bu-tenyl)-(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-ethyl-4-(3-methyl-2-butenyl)-(1H)-1,4-b-enzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-2-buteny-l)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-2-butenyl)-(-1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methy-l-2-butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-met-hyl-2-butenyl)-(1H)-1,4-benzodiaze- pin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-2-butenyl)-(-1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methy-l-2-butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-met-hyl-2-butenyl)-(1H)-1,4-benzodiaze- pin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-ethyl-4-(3-methyl-2-butenyl)-(1-H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-2-butenyl-)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-2-butenyl)-(1-H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-2-b-utenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-meth-yl-2-butenyl)-(1H)-1,4-benzodiaze- pin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-2-butenyl)-(1-H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-2-b-utenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-meth-yl-2-butenyl)-(1H)-1,4-benzodiaze- pin
9-Amino-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-butyl)-(1H)-1,4--benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-butyl)-(1H)-1,4-benz-odiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-butyl)-(1H-)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-butyl)-(-1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl-butyl)--(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-methyl-buty-l)-(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-butyl)-(1H)-1,4-benz-odiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-butyl)-(1H-)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-butyl)-(-1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl-butyl)--(1H)-1,4-benzodiazepin
9-Amino-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-methyl-buty-l)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-butyl)-(-1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-butyl)-(1H)--1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-bu-tyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methy-l-butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-met-hyl-butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-butyl)-(1H)--1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-bu-tyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methy-l-butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-met-hyl-butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-chlor-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-butyl)-(1H)--1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-butyl)-(1-H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-butyl)-(1H)-1-,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-but-yl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-b-utyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-meth-yl-butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-butyl)-(1H)-1-,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-but-yl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-b-utyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-meth-yl-butyl)-(1H)-1,4-benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3,3-dimethyl-4-isopropyl-(1H)-1,4--benzodiazepin
9-Amino-7-brom-2,3,4,5-tetrahydro-3-benzyl-4-benzyl-(1H)-1,4-benzodi-azepinThese include in particular:
9-Amino-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl-2-butenyl) - (1H) - 1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3-phenyl-4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methyl-2-buteny-l) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-methyl-2-bu-tenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-2-buteny-l) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-methyl-2-bu-tenyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3-ethyl-4- (3-methyl-2-butenyl) - (1H) -1,4-b-enzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl-2-buteny-l) - (1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3-phenyl-4- (3-methyl-2-butenyl) - (- 1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl-l-2-butenyl) - (1H) -1, 4-benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-methyl-2-butenyl) - (1H) -1, 4-benzodiaze-pin
9-Amino-7-chloro-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-2-butenyl) - (- 1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl-l-2-butenyl) - (1H) -1, 4-benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1, 4-benzodiaze-pin
9-Amino-7-chloro-2,3,4,5-tetrahydro-3-ethyl-4- (3-methyl-2-butenyl) - (1-H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl-2-butenyl -) - (1H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3-phenyl-4- (3-methyl-2-butenyl) - (1-H) -1,4-benzodiazepine
9-amino-7-bromo-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-2-b-utenyl) - (1H) -1,4- benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl - 2-butenyl) - (1H) -1.4 -benzodiazepine
9-amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-meth-yl-2-butenyl) - (1H) -1, 4-benzodiaze-pin
9-Amino-7-bromo-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-2-butenyl) - (1-H) -1,4-benzodiazepine
9-amino-7-bromo-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-2-b-utenyl) - (1H) -1,4- benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl - 2-butenyl) - (1H) -1.4 -benzodiazepine
9-amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-meth-yl-2-butenyl) - (1H) -1, 4-benzodiaze-pin
9-Amino-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3-phenyl-4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methylbutyl) - (1H -) - 1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methylbutyl) - (- 1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-methylbutyl-1) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-chlorobenzyl) -4- (3-methylbutyl) - (1H -) - 1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-butyl) - (- 1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-Amino-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-methyl-buty-l) - (1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methylbutyl) - (- 1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3-phenyl-4- (3-methylbutyl) - (1H) - 1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl-1-butyl) - (1H) -1,4- benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-phenyl) -4- (3-methyl-butyl) - (1H) -1,4- benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3-benzyl-4- (3-methylbutyl) - (1H) - 1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl-1-butyl) - (1H) -1,4- benzodiazepine
9-amino-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-methyl-butyl) - (1H) -1,4- benzodiazepine
9-Amino-7-chloro-2,3,4,5-tetrahydro-3-benzyl-4- (3-methylbutyl) - (1H) - 1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methylbutyl) - (1-H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3-phenyl-4- (3-methylbutyl) - (1H) -1-, 4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-but-yl) - (1H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methyl-b-utyl) - (1H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-phenyl) -4- (3-meth-yl-butyl) - (1H) -1,4- benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3-benzyl-4- (3-methylbutyl) - (1H) -1-, 4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-but-yl) - (1H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-b-utyl) - (1H) -1,4-benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-amino-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-meth-yl-butyl) - (1H) -1,4- benzodiazepine
9-Amino-7-bromo-2,3,4,5-tetrahydro-3,3-dimethyl-4-isopropyl- (1H) -1,4-benzodiazepine
9-amino-7-bromo-2,3,4,5-tetrahydro-3-benzyl-4-benzyl- (1H) -1,4-benzodi-azepine

Gegenstand der Erfindung sind auch Verbindungen der allgemeinen Formel IIIThe invention also relates to compounds of the general Formula III

Hierzu gehören insbesondere:
9-Nitro-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-2-butenyl)-(1H-)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-2-butenyl)-(1H)-1,4--benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-2-butenyl)--(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-2-buteny-l)-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl-2-bute-nyl)-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-methyl-2-bu-tenyl)-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-2-butenyl)-(1H)-1,4--benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-2-butenyl)--(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-2-buteny-l)-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl-2-bute-nyl)-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-methyl-2-bu-tenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-2-buteny-l)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-2-butenyl)-(-1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methy-l-2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-dichlor-phenyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-met-hyl-2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-2-butenyl)-(-1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methy-l-2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methy-l-2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-met-hyl-2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-2-butenyl-)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-2-butenyl)-(1-H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-2-b-utenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-meth-yl-2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-2-butenyl)-(1-H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-2-b-utenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-2--butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl--2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-meth-yl-2-butenyl)-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-butyl)-(1H)-1,4--benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-butyl)-(1H)-1,4-benz-odiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-butyl)-(1H-)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-butyl)-(-1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl-butyl)--(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-methyl-buty-l)-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-butyl)-(1H)-1,4-benz-odiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-butyl)-(1H-)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-butyl)-(-1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl-butyl)--(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-methyl-buty-l)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-butyl)-(-1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-butyl)-(1H)--1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-bu-tyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methy-l-butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-met-hyl-butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-butyl)-(1H)--1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-bu-tyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methy-l-butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-met-hyl-butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3-methyl-butyl)-(1-H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-phenyl-4-(3-methyl-butyl)-(1H)-1-,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-4-(3-methyl-but-yl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-4-(3-methyl-b-utyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-4-(3-meth-yl-butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-benzyl-4-(3-methyl-butyl)-(1H)-1-,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-4-(3-methyl-but-yl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-4-(3-methyl-b-utyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-4-(3-methyl--butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-4-(3-meth-yl-butyl)-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3,3-dimethyl-4-isopropyl-(1H)-1,4--benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-benzyl-4-benzyl-(1H)-1,4-benzodi-azepinThese include in particular:
9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl-2-butenyl) - (1H -) - 1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3-phenyl-4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methyl-2-buteny-l) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-methyl-2-bu-tenyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-2-buteny-l) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-methyl-2-bu-tenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl-2-buteny-l) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3-phenyl-4- (3-methyl-2-butenyl) - (- 1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methyl - 2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl-l-2-butenyl) - (1H) -1, 4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-dichlorophenyl) -4- (3-methyl - 2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-phenyl) -4- (3-methyl-2-butenyl) - (1H) -1, 4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-2-butenyl) - (- 1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl-l-2-butenyl) - (1H) -1, 4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl-l-2-butenyl) - (1H) -1, 4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1, 4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl-2-butenyl -) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3-phenyl-4- (3-methyl-2-butenyl) - (1-H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-2-b-utenyl) - (1H) -1,4- benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl - 2-butenyl) - (1H) -1.4 -benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-meth-yl-2-butenyl) - (1H) -1, 4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-2-butenyl) - (1-H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-2-b-utenyl) - (1H) -1,4- benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-2-butenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl - 2-butenyl) - (1H) -1.4 -benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-meth-yl-2-butenyl) - (1H) -1, 4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methylbutyl) - (1H) -1,4 - benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3-phenyl-4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methylbutyl) - (1H -) - 1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methylbutyl) - (- 1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-methylbutyl-1) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3-benzyl-4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-chlorobenzyl) -4- (3-methylbutyl) - (1H -) - 1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-butyl) - (- 1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-Nitro-2,3,4,5-tetrahydro-3- (3,4-dimethoxybenzyl) -4- (3-methylbutyl-1) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methylbutyl) - (- 1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3-phenyl-4- (3-methylbutyl) - (1H) - 1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methyl-1-butyl) - (1H) -1,4- benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-phenyl) -4- (3-methyl-butyl) - (1H) -1,4- benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3-benzyl-4- (3-methylbutyl) - (1H) - 1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-butyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methyl-l-butyl) - (1H) -1,4- benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-methyl-butyl) - (1H) -1,4- benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methylbutyl) - (1-H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3-phenyl-4- (3-methylbutyl) - (1H) -1-, 4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-chlorophenyl) -4- (3-methyl-but-yl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) -4- (3-methyl-b-utyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) -4- (3-meth-yl-butyl) - (1H) -1,4- benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3-benzyl-4- (3-methylbutyl) - (1H) -1-, 4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) -4- (3-methyl-but-yl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) -4- (3-methyl-b-utyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) -4- (3-methylbutyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) -4- (3-meth-yl-butyl) - (1H) -1,4- benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3,3-dimethyl-4-isopropyl- (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3-benzyl-4-benzyl- (1H) -1,4-benzodi-azepine

Gegenstand der Erfindung sind auch Verbindungen der allgemeinen Formel IVThe invention also relates to compounds of the general Formula IV

Hierzu gehören insbesondere:
9-Nitro-2,3,4,5-tetrahydro-3,3-dimethyl-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-phenyl-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-(1H)-1,4-benzodiazepin-
9-Nitro-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-(1H)-1,4-benzodiazep-in
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-(1H)-1,4-benzodi-azepin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-(1H)-1,4-benzodiaz-epin
9-Nitro-2,3,4,5-tetrahydro-3-benzyl-(1H)-1,4-benzodiazepin
9-Nitro-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-(1H)-1,4-benzodiazepin-
9-Nitro-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-(1H)-1,4-benzodiazep-in
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-(1H)-1,4-benzodiaz-epin
9-Nitro-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-(1H)-1,4-benzodi-azepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3,3-dimethyl-(1H)-1,4-benzodiazep-in
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-phenyl-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-(1H)-1,4-benzo-diazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-(1H)-1,4-ben-zodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-(1H)-1,4--benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-(1H)-1,4-b-enzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-benzyl-(1H)-1,4-benzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-(1H)-1,4-benzo-diazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-(1H)-1,4-ben-zodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-(1H)-1,4-b-enzodiazepin
9-Nitro-7-chlor-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-(1H)-1,4--benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3,3-dimethyl-(1H)-1,4-benzodiazepi-n
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-phenyl-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-phenyl)-(1H)-1,4-benzod-iazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-phenyl)-(1H)-1,4-benz-odiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-phenyl)-(1H)-1,4--benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-phenyl)-(1H)-1,4-be-nzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-benzyl-(1H)-1,4-benzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-chlor-benzyl)-(1H)-1,4-benzod-iazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(4-methoxy-benzyl)-(1H)-1,4-benz-odiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dichlor-benzyl)-(1H)-1,4-be-nzodiazepin
9-Nitro-7-brom-2,3,4,5-tetrahydro-3-(3,4-dimethoxy-benzyl)-(1H)-1,4--benzodiazepinThese include in particular:
9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl- (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3-phenyl- (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) - (1H) -1,4-benzodi-azepine
9-nitro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) - (1H) -1,4-benzodiaz-epine
9-nitro-2,3,4,5-tetrahydro-3-benzyl- (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) - (1H) -1,4-benzodiazepine
9-nitro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) - (1H) -1,4-benzodiaz-epine
9-nitro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) - (1H) -1,4-benzodi-azepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3,3-dimethyl- (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3-phenyl- (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-chlorophenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) - (1H) -1,4-ben-zodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) - (1H) -1,4 - benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) - (1H) -1,4-b-enzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3-benzyl- (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) - (1H) -1,4-benzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) - (1H) -1,4-ben-zodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) - (1H) -1,4-b-enzodiazepine
9-nitro-7-chloro-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3,3-dimethyl- (1H) -1,4-benzodiazepi-n
9-nitro-7-bromo-2,3,4,5-tetrahydro-3-phenyl- (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-chlorophenyl) - (1H) -1,4-benzod-iazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxyphenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxyphenyl) - (1H) -1,4 - benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorophenyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3-benzyl- (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-chloro-benzyl) - (1H) -1,4-benzod-iazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (4-methoxy-benzyl) - (1H) -1,4-benz-odiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dichlorobenzyl) - (1H) -1,4-benzodiazepine
9-nitro-7-bromo-2,3,4,5-tetrahydro-3- (3,4-dimethoxy-benzyl) - (1H) -1,4-benzodiazepine

Experimental part 4,5,6,7-tetrahydro-5,5-dimethyl-6- (3-methyl-2-butenyl) imidazo [4,5, ljk] [1,4] benzodiazepine-2- (1H) thione 1st stage: 2 - [(2-bromo-3-nitro-benzyl) amino] -2,2-dimethyl ethyl acetate

2,9 g Aminoisobuttersäureethylester-Hydrochlorid werden in 30 ml Methylenchlorid suspendiert. Hierzu gibt man 5,2 ml Triethylamin und tropft anschließend unter Rühren eine Lösung von 4 g 2-Brom-3-nitrobenzoylchlorid in 20 ml Methylenchlorid bei Raumtemperatur zu. Man rührt noch 10 Std. bei Raumtemperatur weiter, säuert die Mischung mit verdünnter Salzsäure an und trennt die Phasen. Die organische Phase wird über Natriumsulfat getrocknet und eingedampft. Der Rückstand wird aus Essigester umkristallisiert. Man erhält 4,5 g weiße Kristalle vom Schmp.: 140-141°C.2.9 g of ethyl isobutyrate hydrochloride are suspended in 30 ml of methylene chloride. For this are added 5.2 ml of triethylamine and then added dropwise with stirring, a solution of 4 g of 2-bromo-3-nitrobenzoyl chloride in 20 ml methylene chloride at room temperature to. The mixture is stirred for a further 10 hours at room temperature further, the mixture acidifies with dilute Hydrochloric acid and separates the phases. The organic Phase is dried over sodium sulfate and evaporated. The residue is recrystallized from ethyl acetate. 4.5 g of white crystals of mp: 140-141 ° C.

2nd stage: 2 - [(2-bromo-3-nitro-benzyl) amino] -2,2-dimethyl acetamide

4,5 g N-(2-Brom-3-nitro-benzoyl-aminoisobuttersäureethylester werden in 100 ml konz. Ammoniak suspendiert und über Nacht bei Raumtemperatur geführt. Dann wird der Niederschlag abgesaugt und mit Alkohol und Ether gewaschen. Man erhält 3,8 g Kristalle vom Schmp.: 217-220°C. 4.5 g of N- (2-bromo-3-nitro-benzoyl-aminoisobutyric acid ethyl ester are concentrated in 100 ml. ammonia suspended and overnight at room temperature guided. Then the precipitate is suctioned off and with Washed alcohol and ether. 3.8 g are obtained Crystals of mp: 217-220 ° C.

3rd stage: 2 - [(2-bromo-3-nitro-benzyl) amino] -2,2-dimethyl ethylamine

Zu 35 ml einer molaren Lösung von Borwasserstoff ein Tetrahydrofuran tropft man im Verlauf von 5 min eine Lösung von 1,65 g N-(2-Brom-3-nitro-benzoyl)-aminoisobuttersäureamid in 30 ml Tetrahydrofuran. Man rührt noch 1 Stunde bei Raumtemperatur weiter und erhitzt dann eine weitere Stunde auf Rückflußtemperatur. Man kühlt auf Raumtemperatur ab und versetzt die Mischung mit 10 ml 6 N Bromwasserstoffsäure. Dann wird das Tetrahydrofuran abdestilliert, der Rückstand mit verdünnter Natronlauge alkalisch gestellt und mit Essigester extrahiert. Die Essigesterphase wird über Natriumsulfat getrocknet und eingedampft. Man erhält 1,4 g eines amorphen Rückstandes von 2- [(2-Brom-3-nitro-benzyl)-amino]-2,2-dimethyl ethylamin.To 35 ml of a molar solution of hydrogen boron Tetrahydrofuran is added dropwise in the course of 5 min Solution of 1.65 g of N- (2-bromo-3-nitro-benzoyl) aminoisobutyric acid amide in 30 ml of tetrahydrofuran. Man continue stirring for 1 hour at room temperature and then heated to reflux for another hour. It is cooled to room temperature and added Mix with 10 ml of 6 N hydrobromic acid. Then the tetrahydrofuran is distilled off, the residue made alkaline with dilute sodium hydroxide solution and extracted with ethyl acetate. The ethyl acetate phase is dried over sodium sulfate and evaporated. 1.4 g of an amorphous residue of 2- [(2-bromo-3-nitro-benzyl) amino] -2,2-dimethyl ethylamine.

4th stage: 9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl- (1H) -1,4- benzodiazepine

1 g 2-(2-Brom-3-nitro-benzylamino)-2,2-dimethylethylamin werden in 25 ml Dimethylformamid gelöst und die Lösung nach Zugabe von 1,5 g Kaliumkarbonat 3 Stunden auf 110°C erwärmt. Dann wird von Dimethylformamid i. Vak. abdestilliert, der Rückstand mit Essigester extrahiert und die Essigesterlösung i. Vak. eingedampft. Das zurückbleibende, rotbraune Öl wird zur Reinigung an einer Kieselgelsäule chromatographiert. Laufmittel: Aceton/Toluol. Man erhält 320 mg (=50% d. Th.) 9-Nitro-2,3,4,5-tetrahydro-3,3-dimethyl-(1H)-1,4-benzodiazepin als rotbraunes Öl. 1 g of 2- (2-bromo-3-nitro-benzylamino) -2,2-dimethylethylamine are dissolved in 25 ml of dimethylformamide and the solution after adding 1.5 g of potassium carbonate for 3 hours heated to 110 ° C. Then from dimethylformamide i. Vac. distilled off, the residue with Extracted ethyl acetate and the ethyl acetate solution i. Vac. evaporated. The remaining red-brown oil is chromatographed on a silica gel column for purification. Mobile solvent: acetone / toluene. 320 mg are obtained (= 50% of theory) 9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl- (1H) -1,4-benzodiazepine as a red-brown oil.

5th stage: 9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3-methyl- 2-butenyl) - (1H) -1,4-benzodiazepine

310 mg 9-Nitro-2,3,4,5-tetrahydro-3,3-dimethyl-(1H)-1,4-benzodiazepin werden in 5 ml Dimethylformamid gelöst. Hierzu gibt man 1 g Kaliumkarbonat und 0,2 ml 3,3-Dimethylallylbromid und erwärmt die Mischung 1 Stunde auf 50°C. Dann wird vom Dimethylformamid abdestilliert und der Rückstand zur Reinigung an einer Kieselgelsäule chromatographiert. Laufmittel: Ether/Isohexan (1 : 3). Die Säulenfraktionen werden eingedampft und der Rückstand aus Methanol umkristallisiert. Man erhält 300 mg Kristalle vom Schmp. 125°C.310 mg of 9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl- (1H) -1,4-benzodiazepine are in 5 ml of dimethylformamide solved. 1 g of potassium carbonate and 0.2 ml are added 3,3-dimethylallyl bromide and warm the mixture for 1 hour to 50 ° C. Then dimethylformamide distilled off and the residue for cleaning chromatographed on a silica gel column. Eluent: Ether / isohexane (1: 3). The column fractions are evaporated and the residue recrystallized from methanol. 300 mg of crystals of mp. 125 ° C.

6th stage: 4,5,6,7-tetrahydro-5,5-dimethyl-6- (3-methyl-2- butenyl) imidazo- [4,5, ljk] [1,4] benzodiazepine-2 (1H) - thion

1 g 9-Nitro-2,3,4,5-tetrahydro-3,3-dimethyl-4-(3- methyl-2-butenyl)-(1H)-1,4-benzodiazepin werden in 10 ml konz. Salzsäure gelöst. Hierzu gibt man im Verlauf von einigen Minuten 2 g Zinkstaub, wobei sich die rote Lösung sofort entfärbt. Die Reduktionslösung wird unter Kühlung mit Natronlauge alkalisch gestellt und mit Essigester extrahiert. Die Essigesterlösung wird über Natriumsulfat getrocknet und eingedampft. Der Eindampfrückstand wird mit einer Lösung von 250 mg Kaliumhydroxid in einer Mischung aus 1 ml Wasser und 5 ml Ethanol versetzt und nach Zugabe von 0,25 ml Schwefelkohlenstoff 3 Stunden am Rückfluß erhitzt. Die Reaktionslösung wird abgekühlt, mit Salzsäure angesäuert und mit Essigester extrahiert. Die Essigesterphase wird verworfen. Die salzsaure Lösung wird alkalisch gestellt und mit Essigester extrahiert. Die Essigesterphase wird über Natriumsulfat getrocknet und eingedampft. Der Rückstand wird zur Reinigung an einer Kieselgelsäule chromatographiert. Man erhält 600 mg der Titelverbindung vom Schmp. 166-168°C.1 g 9-nitro-2,3,4,5-tetrahydro-3,3-dimethyl-4- (3- methyl-2-butenyl) - (1H) -1,4-benzodiazepine are dissolved in 10 ml conc. Hydrochloric acid dissolved. This is indicated in the course of a few minutes 2 g of zinc dust, the red solution decolorized immediately. The reducing solution is made alkaline with cooling with sodium hydroxide solution and extracted with ethyl acetate. The ethyl acetate solution is dried over sodium sulfate and evaporated. The evaporation residue is with a solution of 250 mg Potassium hydroxide in a mixture of 1 ml of water and 5 ml of ethanol were added and after adding 0.25 ml Carbon disulfide heated at reflux for 3 hours. The reaction solution is cooled with hydrochloric acid acidified and extracted with ethyl acetate. The The ethyl acetate phase is discarded. The hydrochloric acid solution is made alkaline and with ethyl acetate extracted. The ethyl acetate phase is over sodium sulfate dried and evaporated. The backlog will chromatographed on a silica gel column for purification. 600 mg of the title compound of M.p. 166-168 ° C.

Analog wurden dargestellt:
4,5,6,7-Tetrahydro-5-benzyl-6-(3-methyl-2-butenyl)-imidazo- [4,5,1,jk] [1,4]-benzodiazepin-2(1H)-thion aus 2-Brom-3-nitrobenzolsäure und Phenylalanin
4,5,6,7-Tetrahydro-5-phenyl-6-(3-methyl-2-butenyl)-imidazo- [4,5,1,jk] [1,4]-benzodiazepin-2(1H)-thion aus 2-Brom-3-nitrobenzolsäure und Phenylglycin
4,5,6,7-Tetrahydro-9-chlor-5-benzyl-6-(3-methyl-2-butenyl)- imidazo-[4,5,1,jk] [1,4]-benzodiazepin-2(1H)-thion aus 2,5-Dichlor-5-nitrobenzolsäure und Phenylalanin
4,5,6,7-Tetrahydro-9-chlor-5-phenyl-6-(3-methyl-2- butenyl)-imidazo-[4,5,1,jk] [1,4]-benzodiazepin-2(1H)-thion aus 2,5-Dichlor-5-nitro-benzolsäure und Phenylglycin
[2,3,4,5]-Tetrahydro-[2,1c]-pyryrolo-[4,5,1,jk]-imidazo- (4M)(9M)[1,4]-benzodiazepin-2(1H)-thion aus 2-Brom-3-nitrobenzolsäure und Prolin
11-Chlor-[2,3,4,5]-tetrahydro-[2,1c]-pyrrolo-[4,5,1,jk]- imidazo-(4M)(9M)[1,4]-benzodiazepin-2(1M)-thion aus 2,5-Dichlor-3-nitrobenzolsäure und Prolin.The following were represented in an analogous manner:
4,5,6,7-tetrahydro-5-benzyl-6- (3-methyl-2-butenyl) imidazo- [4,5,1, jk] [1,4] -benzodiazepine-2 (1H) - thione from 2-bromo-3-nitrobenzenic acid and phenylalanine
4,5,6,7-tetrahydro-5-phenyl-6- (3-methyl-2-butenyl) imidazo- [4,5,1, jk] [1,4] -benzodiazepine-2 (1H) - thione from 2-bromo-3-nitrobenzenic acid and phenylglycine
4,5,6,7-tetrahydro-9-chloro-5-benzyl-6- (3-methyl-2-butenyl) imidazo- [4,5,1, jk] [1,4] -benzodiazepine-2 (1H) -thione from 2,5-dichloro-5-nitrobenzenic acid and phenylalanine
4,5,6,7-tetrahydro-9-chloro-5-phenyl-6- (3-methyl-2-butenyl) imidazo- [4,5,1, jk] [1,4] -benzodiazepine-2 (1H) -thione from 2,5-dichloro-5-nitro-benzenic acid and phenylglycine
[2,3,4,5] tetrahydro- [2,1c] -pyryrolo- [4,5,1, jk] -imidazo- (4M) (9M) [1,4] -benzodiazepine-2 (1H) -thione from 2-bromo-3-nitrobenzenic acid and proline
11-chloro [2,3,4,5] tetrahydro- [2,1c] pyrrolo- [4,5,1, jk] - imidazo- (4M) (9M) [1,4] benzodiazepine 2 (1M) -thione from 2,5-dichloro-3-nitrobenzenic acid and proline.

Claims

1. Compounds of formula I. in which
R₁ is a hydrogen atom, a straight-chain or branched alkyl radical of 1-6 carbon atoms,
R₂ is a straight-chain or branched C₁-C₆-alkyl radical which can be substituted by one or more hydroxy, C₁-C₆-alkoxy, mercapto or C₁-C₆-alkyl mercapto groups or a substituted or unsubstituted phenyl radical, a C₃-C₇-cycloalkyl radical , a substituted or unsubstituted phenyl radical, a substituted or unsubstituted aralkyl radical, a substituted or unsubstituted saturated heterocyclic or an aromatic heterocyclic radical or a substituted or unsubstituted heteroarylalkyl radical, or together with R₁ can form a C₃-C₇-cycloalkyl ring,
R₃ is a hydrogen atom, a straight-chain or branched C₁-C₆-alkyl radical which may be substituted by one or more hydroxy or C₁-C₆-alkoxy groups, a substituted or unsubstituted amino group or halogen; a straight-chain or branched C₂-C₆ alkenyl radical which can also carry one or more hydroxyl or C₁-C₆ alkoxy groups, a substituted or unsubstituted amino group or halogen or a substituted or unsubstituted aralkyl or heteroarylalkyl radical,
where one of the radicals R₁ or R₂ together with the radical R₃ can also form a substituted or unsubstituted heterocyclic ring,
with the proviso that R₁ can also be hydrogen if R₂ is not hydrogen or an unsubstituted C₁-C₆ alkyl radical and
R₄ represents a hydrogen atom, a halogen atom, a hydroxy group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylenedioxy group, a C₁-C₆ alkyl group, a mono- or polysubstituted amino group, or a substituted or unsubstituted benzyloxy group,
mean, and their pharmacologically acceptable salts, optically active and diastereomeric forms.

2. Process for the preparation of compounds of formula I. in which
R₁ is a hydrogen atom, a straight-chain or branched alkyl radical of 1-6 carbon atoms,
R₂ is a straight-chain or branched C₁-C₆ alkyl radical which can be substituted by one or more hydroxyl, C₁-C Alk alkoxy, mercapto or C₁-C Alkyl alkyl mercapto groups or a substituted or unsubstituted phenyl radical; a C₃-C₇-cycloalkyl radical, a substituted or unsubstituted phenyl radical, a substituted or unsubstituted aralkyl radical, a substituted or unsubstituted saturated heterocyclic or an aromatic heterocyclic radical or a substituted or unsubstituted heteroarylalkyl radical, or together with R₁ can form a C₃-C₇-cycloalkyl ring
R₃ is a hydrogen atom, a straight-chain or branched C₁-C₆-alkyl radical, which can be substituted by one or more hydroxy or C₁-C Alk-alkoxy groups, a substituted or unsubstituted amino group or halogen, a straight-chain or branched C₂-C₆-alkenyl radical, the can also carry one or more hydroxy or C₁-C₆ alkoxy groups, a substituted or unsubstituted amino group or a halogen atom or a substituted or unsubstituted aralkyl or heteroarylakyl radical,
where one of the radicals R₁ or R₂ together with the radical R₃ can also form a substituted or unsubstituted heterocyclic ring,
with the proviso that R₁ can also be hydrogen if R₂ is not hydrogen or an unsubstituted C₁-C₆ alkyl radical and
R₄ represents a hydrogen atom, a halogen atom, a hydroxy group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylenedioxy group, a C₁-C₆ alkyl group, a mono- or polysubstituted amino group, or a substituted or unsubstituted benzyloxy group,
mean, and their pharmacologically acceptable salts, optically active and diasteromeric forms, characterized in that in a manner known per se

a) a compound of formula IX in which R₄ and Y have the meanings given,
with a compound of formula X in which R₁ and R₂ have the meanings given and one of the radicals R₁ and R₂ together with the amino group can optionally form a pyrrolidine or hydroxypyrrolidine ring and R₅ represents hydrogen or an alkyl radical
b) the compound of formula VIII obtained in which R₁, R₂, R₄ and Y have the meanings given, and R₅ is hydrogen or an alkyl radical, is subjected to an amidation reaction by customary methods.
c) the compound VII obtained in which R₁, R₂, R₄ and Y have the meanings given, reduced with hydrogen boron or diborane,
d) the compound of formula VI obtained in which R₁, R₂ and R₄ have the meanings given and Y represents a halogen atom, cyclizes,
e) the compound of formula IV obtained in which R₁, R₂ and R₄ have the meaning given, with a compound of the formula VR₃-X (V) in which R₃ has the meaning given and X represents a halogen atom,
f) in the compound of formula III obtained in which R₁, R₂, R₃ and R₄ have the meanings given, the nitro group is converted into an amino group in the usual manner and
g) the compound of formula II obtained in which R₁, R₂, R₃ and R₄ have the meanings given with carbon disulfide, thiocarbonyldiimidazole, thiophosgene or thiourea in a compound of the general formula I

3. Medicament containing a compound according to claim 1 in addition to the usual carriers and auxiliaries.

4. Use of compounds according to claim 1 for Treatment of antiviral diseases.

5. Compounds of formula II in which
R₁ is a hydrogen atom, a straight-chain or branched alkyl radical of 1-6 carbon atoms,
R₂ is a straight-chain or branched C₁-C₆ alkyl radical which can be substituted by one or more hydroxyl, C₁-C Alk alkoxy, mercapto or C₁-C Alkyl alkyl mercapto groups or a substituted or unsubstituted phenyl radical; a C₃-C₇-cycloalkyl radical, a substituted or unsubstituted phenyl radical, a substituted or unsubstituted aralkyl radical, a substituted or unsubstituted saturated heterocyclic or an aromatic heterocyclic radical or a substituted or unsubstituted heteroarylalkyl radical, or together with R₁ can form a C₃-C₇-cycloalkyl ring
R₃ is a hydrogen atom, a straight-chain or branched C₁-C₆-alkyl radical which may be substituted by one or more hydroxy or C₁-C₆-alkoxy groups, a substituted or unsubstituted amino group or halogen; a straight-chain or branched C₂-C₆ alkenyl radical which may also carry one or more hydroxy or C₁-C₆ alkoxy groups, a substituted or unsubstituted amino group or a halogen atom; or a substituted or unsubstituted aralkyl or heteroarylalkyl radical,
where one of the radicals R₁ or R₂ together with the radical R₃ can also form a substituted or unsubstituted heterocyclic ring,
with the proviso that R₁ can also be hydrogen if R₂ is not hydrogen or an unsubstituted C₁-C₆ alkyl radical and
R₄ represents a hydrogen atom, a halogen atom, a hydroxy group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylenedioxy group, a C₁-C₆ alkyl group, a mono- or polysubstituted amino group, or a substituted or unsubstituted benzyloxy group,
mean.

6. Compounds of formula III in which
R₁ is a hydrogen atom, a straight-chain or branched alkyl radical of 1-6 carbon atoms,
R₂ is a straight-chain or branched C₁-C₆-alkyl radical which can be substituted by one or more hydroxy, C₁-C₆-alkoxy, mercapto or C₁-C₆-alkyl mercapto groups or a substituted or unsubstituted phenyl radical, a C₃-C₇-cycloalkyl radical , a substituted or unsubstituted phenyl radical, a substituted or unsubstituted aralkyl radical, a substituted or unsubstituted saturated heterocyclic or an aromatic heterocyclic radical or a substituted or unsubstituted heteroarylalkyl radical, or together with R₁ can form a C₃-C₇-cycloalkyl ring,
R₃ is a hydrogen atom, a straight-chain or branched C₁-C₆-alkyl radical which may be substituted by one or more hydroxy or C₁-C₆-alkoxy groups, a substituted or unsubstituted amino group or halogen; a straight-chain or branched C₂-C₆ alkenyl radical which may also carry one or more hydroxy or C₁-C₆ alkoxy groups, a substituted or unsubstituted amino group or a halogen atom; or a substituted or unsubstituted aralkyl or heteroarylakyl radical,
where one of the radicals R₁ or R₂ together with the radical R₃ can also form a substituted or unsubstituted heterocyclic ring,
with the proviso that R₁ can also be hydrogen if R₂ is not hydrogen or an unsubstituted C₁-C₆ alkyl radical and
R₄ represents a hydrogen atom, a halogen atom, a hydroxy group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylenedioxy group, a C₁-C₆ alkyl group, a mono- or polysubstituted amino group, or a substituted or unsubstituted benzyloxy group,
mean.

7. Compounds of formula IV in which
R₁ is a hydrogen atom, a straight-chain or branched alkyl radical of 1-6 carbon atoms,
R₂ is a straight-chain or branched C₁-C₆ alkyl radical which can be substituted by one or more hydroxyl, C₁-C Alk alkoxy, mercapto or C₁-C Alkyl alkyl mercapto groups or a substituted or unsubstituted phenyl radical; a C₃-C₇-cycloalkyl radical, a substituted or unsubstituted phenyl radical, a substituted or unsubstituted aralkyl radical, a substituted or unsubstituted saturated heterocyclic or an aromatic heterocyclic radical or a substituted or unsubstituted heteroarylalkyl radical, or together with R₁ can form a C₃-C₇-cycloalkyl ring and
R₄ represents a hydrogen atom, a halogen atom, a hydroxy group, a C₁-C₆ alkoxy group, a C₁-C₆ alkylenedioxy group, a C₁-C₆ alkyl group, a mono- or polysubstituted amino group, or a substituted or unsubstituted benzyloxy group,
mean.