Polycondensed nitrogen heterocycles. Part24. Pyrrolo[3,4-c]isoquinolinone by thermal rearrangement of a pyrrolylbenzotriazinone

Rearrangement under acidic conditions of the pyrrolylbenzotriazinone 7 afforded the pyrrolylbenzamides 10 and 11. By thermal rearrangement instead, the first fully aromatic derivative of the pyrrolo[3,4-c]isoquinoline ring system 9 was obtained.

Polycondensed nitrogen heterocycles. XXII. A new synthesis of 5,6-dihydro-7H-pyrazolo[1,5-d][1,4]benzodiazepin-6-ones

A new synthesis of 2-methyl-9-R'-10-R-5,6-dihydro-7H-pyrazolo[1,5-d][1,4]benzodiazepin-6-ones (4a-c) is deserved. Reaction of ethyl hydrazinoacetate hydrochloride with 1,3-diketones 1a-c gave both 3-methyl-5-(4R'-5-R-2-nitrophenyl)pyrazol-1-yl-acetate acids (2a-c) and the corresponding ethyl esters 3a-c. Reduction with the appropiate reducing agent of compounds 2a-c and 3a-c directly gave the title compounds. Compound 4a showed insecticidal properties against the house fly.

ChemInform Abstract: Polycondensed Nitrogen Heterocycles. Part 25. Aminopyrrolo(1,2-f) phenanthridines by Decomposition of 2-(3-Azidophenyl)-1-arylpyrroles.

Acid catalyzed decomposition of the azido derivatives 4a-c gave rise to amino-hydroxy-phenylpyrroles of type 7 and 8 upon hydrolysis of the intermediate aryl nitrenium ions, together with the hydrogen abstraction compounds of type 3. The aminopyrrolo[1,2-f]phenanthridines 10, 11, and 12 were obtained by treatment with TFMSA of the azide 4d in which the ring being attacked was made more nucleophilic by the introduction of the methoxy group.

ChemInform Abstract: Polycondensed Nitrogen Heterocycles. Part 24. Pyrrolo(3,4-c) isoquinolinone by Thermal Rearrangement of a Pyrrolylbenzotriazinone.

Rearrangement under acidic conditions of the pyrrolylbenzotriazinone 7 afforded the pyrrolylbenzamides 10 and 11. By thermal rearrangement instead, the first fully aromatic derivative of the pyrrolo[3,4-c]isoquinoline ring system 9 was obtained.

ChemInform Abstract: Polycondensed Nitrogen Heterocycles. Part 23. Pyrrolo(3,2-c)cinnolines by a Japp-Klingemann-Type Reaction.

Pyrrolo[3,2-c]cinnoline derivatives were obtained by an unusual Japp-Klingemann reaction involving an intramolecular azadehalogenation on the pyrrole nucleus. Such an azadehalogenation represents the first example of Japp-Klingemann reaction in which the extrusion of positive chlorine ion is verified.

3-Diazopyrroles—IV. Structure determination using 13C NMR spectroscopy

Abstract On the basis of the 13 C NMR chemical shifts, it is proposed that, although b is the major canonical structure, structure c , in which a negative charge resides at C-3, provides an important contribution to the resonance stabilization of the 3-diazopyrroles, 1–4 .

Sintesi e studi QSAR di nuovi derivati 3(5)-(2-X)-1R-1H-4-nitrosopirazoli: una classe di composti con potente attività antifungina in vitro.

New syntheses of condensed heterocycles from isoxazole derivatives. V. Pyrrolo[3,4-b]pyridin-4-ones

Hydrogenolysis with Raney-Nickel or iron powder in acetic acid of 2,5-diphenyl-4-nitro-3-(3,5-R,R-4-isoxazolyl)pyrrolyl ketones, prepared by the Grignard reaction of 2,5-diphenylpyrrole and 3,5-R,R-4-isoxazolecarboxilic acid chlorides followed by nitration, afforded directly the desired 6H-pyrrolo[3,4-b ]pyridin-4-ones.

Polycondensed nitrogen heterocycles. Part13. Pyrrolo[3,2-b]indole by intramolecular nucleophilic substitution reaction in the pyrrole series

An intramolecular nucleophilic substitution in the pyrrole series has been generalized. The behaviour of nitro, chlorine, bromine and iodine as leaving groups towards the nucleophilic amino group was observed. An acid catalyzed mechanism has been proposed.

ChemInform Abstract: Polycondensed Nitrogen Heterocycles. Part 22. Pyrrolo(3,4-d)-1,2,3-triazines: A New Ring System as Potential Antineoplastic Agent.

Diazotization of the 3-aminopyrrole-4-carboxamides 6a,b under different conditions directly led to the new ring system pyrrolo[3,4-d]-1,2,3-triazine in excellent yields through an intramolecular coupling reaction. In all the cases it was impossible to isolate the intermediate 3-diazopyrroles.

Sinthesys and Antifungal Activity of New 3(5)-methyl-5(3)-(2-thiophenyl and 2-furanyl)-1H-1-R-4-cyanopyrazoles

Synthesis of new 2,2′-disubstituted 5,5′-dimethyl-4,4′-bitriazoles and 2-(4-Triazolyl)quinoxalines

Thermal rearrangement of 3-acylisoxazole arylhydrazones allowed facile preparation of 2H-1,2,3-triazoles which were firstly reacted with isoamyl nitrite and then with an opportune arylhydrazine to produce the corresponding α-hydroxyiminohydrazones 8a-h. The reaction of compounds 8a-h with phosphorus pentachloride afforded the desired 4,4′-bitriazoles 1a-h. The α-hydroxyiminoketone derivative 7 or the α-diketone 14 reacted easily with 1,2-phenylenediamine to afford 1,2,3-triazoles 2a-c bearing the quinoxaline moiety at position 4. Improved yields of the quinoxalines 2a-c were obtained when 1,2-phenylenediamine was reacted with the dioxime 15.

Facile synthesis of pyrazoles and pyrroles via thermolysis of tetrazolo[1,5-b]pyridazines, tetrazolo[1,5-a]pyrimidines and tetrazolo[1,5-a]pyridines

Abstract A simple and high yielding preparation of pyrazoles and pyrroles is described. Thermolysis of tetrazolo[1,5- b ]pyridazines, tetrazolo[1,5- a ]pyrimidines and tetrazolo[1,5- a ]pyridines allowed easy ring contraction thus providing a facile preparation of cyanopyrazole and cyanopyrrole heterocycles. Since the cyano group is a versatile precursor of other functionalities, the reaction appears of particular interest for the construction of a variety of pyrazoles and pyrroles. The simple preparation of the starting tetrazole derivatives, the relatively mild conditions employed, and the very short reaction times make this versatile procedure of great synthetic utility and applicable bo…

Synthesis of 3-triazenopyrroles

Abstract The 3-triazenopyrroles, a new class of pyrrole derivatives, were synthesized in quantitative yield by coupling 3-diazopyrroles with secondary amines.

ChemInform Abstract: 3-Diazopyrroles: Key Intermediates in the Synthesis of Antineoplastic Agents

4-Nitrosopyrazole Derivatives as a New Class of Compounds with Potent in vitro Antifungal Activity

Synthesis and Antimicrobial Activity of New 1,5-Dimethyl-3-Heteroaryl.1H-4-ONN-Azoxycyanides

Synthesis and antimicrobial activity of new 3-(1-R-3(5)-methyl-4-nitroso-1H-5(3)-pyrazolyl)-5-methylisoxazoles.

A number of new 3-(1-R-3(5)-methyl-4-nitroso-1H-5(3)-pyrazolyl)-5-methylisoxazoles 6a-g (7b-f) were synthesized and tested for antibacterial and antifungal activity. Some of these compounds displayed antifungal activity at non-cytotoxic concentrations. Derivative 6c was 9 times more potent in vitro than miconazole and 20 times more selective against C. neoformans. 6c was also 8- and 125-fold more potent than amphotericin B and fluconazole, respectively. None of the compounds was active against bacteria. Preliminary structure-activity relationship (SAR) studies showed that the NO group at position 4 of the pyrazole ring is essential for the activity. Lipophilicity of the pyrazole moiety, N-a…

FLUORINATED 2-PHENYLBENZOXAZOLES AS POTENT AND SELECTIVE ANTITUMOUR AGENTS.

Polycondensed nitrogen heterocycles. Part25. Aminopyrrolo[1,2-f]-phenanthridines by decomposition of 2-(3-azidophenyl)-1-arylpyrroles

Acid catalyzed decomposition of the azido derivatives 4a-c gave rise to amino-hydroxy-phenylpyrroles of type 7 and 8 upon hydrolysis of the intermediate aryl nitrenium ions, together with the hydrogen abstraction compounds of type 3. The aminopyrrolo[1,2-f]phenanthridines 10, 11, and 12 were obtained by treatment with TFMSA of the azide 4d in which the ring being attacked was made more nucleophilic by the introduction of the methoxy group.

ChemInform Abstract: Polycondensed Nitrogen Heterocycles. Part 17. Isoxazolo(4,3-d)pyrazolo-(3,4-f)(1,2,3)triazepine. A New Ring System.

The title compounds were prepared by nitration of compounds 2, reduction of the dinitro derivatives 4 and diazotization of the diamino derivatives 6 followed by an intramolecular coupling reaction. Compound 4a showed good activity against Salmonella cholerasuis and Clostridium perfringens bacteria.

Polycondensed nitrogen heterocycles. Part19. Pyrrolo[1,2-f]phenanthridines by pschorr-type cyclization brought about by hypophosphorous acid

Pyrrolo[1,2-f]phenanthridines were prepared in good yields by the diazotization in acetic acid of the amines la,b and subsequent treatment with hypophosphorous acid. The necessity for hypophosphorous acid in the reaction was demonstrated.

Polycondensed nitrogen heterocycles. Part 23. Pyrrolo[3,2-c]cinnolines by a japp-klingemann type reaction

Pyrrolo[3,2-c]cinnoline derivatives were obtained by an unusual Japp-Klingemann reaction involving an intramolecular azadehalogenation on the pyrrole nucleus. Such an azadehalogenation represents the first example of Japp-Klingemann reaction in which the extrusion of positive chlorine ion is verified.

Stilbene-based anticancer agents: Resveratrol analogues active toward HL60 leukemic cells wit a non-specific phase mechanism

Several stilbenes, related to known resveratrol, have been synthesized and tested for their anticancer effect on HL60 leukemia cell line, taking particular care of the cell cycle analysis. The most potent compound was the known (Z)-3,4',5-trimethoxystilbene (6b) which was active as apoptotic agent at 0.24 microM. Differently from other stilbenes (including resveratrol) that induced a prevalent recruitment of cells in S phase of cell cycle, we found a peculiar behavior of 6b that caused a decrease of cells in all phases of cell cycle (G0-G1, S, and G2-M) and a proportional increase of apoptotic cells. The potent pro-apoptotic activity shown by compound 6b and its effects on cell cycle make t…

Protonation of 3-aminopyrroles

Abstract The protonation of 3-aminopyrroles has been investigated using H and 13C n.m.r. spectroscopy. The spectral data are compatible with predominant protonation of the amino group with no evidence for protonation of the pyrrole ring.

Polycondensed nitrogen heterocycles. Part17. Isoxazolo[4,3-d]pyrazolo[3,4-f][1,2,3]triazepine. A new ring system

The title compounds were prepared by nitration of compounds 2, reduction of the dinitro derivatives 4 and diazotization of the diamino derivatives 6 followed by an intramolecular coupling reaction. Compound 4a showed good activity against Salmonella cholerasuis and Clostridium perfringens bacteria.

ChemInform Abstract: Facile Synthesis of Pyrazoles and Pyrroles via Thermolysis of Tetrazolo[1,5-b]pyridazines, Tetrazolo[1,5-a]pyrimidines and Tetrazolo[1,5-a]pyridines.

Abstract A simple and high yielding preparation of pyrazoles and pyrroles is described. Thermolysis of tetrazolo[1,5- b ]pyridazines, tetrazolo[1,5- a ]pyrimidines and tetrazolo[1,5- a ]pyridines allowed easy ring contraction thus providing a facile preparation of cyanopyrazole and cyanopyrrole heterocycles. Since the cyano group is a versatile precursor of other functionalities, the reaction appears of particular interest for the construction of a variety of pyrazoles and pyrroles. The simple preparation of the starting tetrazole derivatives, the relatively mild conditions employed, and the very short reaction times make this versatile procedure of great synthetic utility and applicable bo…

Polycondensed nitrogen heterocycles. Part 22. Pyrrolo[3,4-d]-1,2,3-triazines: A new ring system as potential antineoplastic agent

Diazotization of the 3-aminopyrrole-4-carboxamides 6a,b under different conditions directly led to the new ring system pyrrolo[3,4-d]-1,2,3-triazine in excellent yields through an intramolecular coupling reaction. In all the cases it was impossible to isolate the intermediate 3-diazopyrroles.

Polycondensed nitrogen heterocycles. X. 5,6,7,8-Tetrahydropyrrolo[1,2-e][1,5]benzodiazocin-7-ones. A new ring system

The synthesis of a new heterocyclic ring system is described. Condensation of 1,4-diketones 1a,b with β-alanine gave the substituted propionic acids 2a,b which upon reduction with palladium on charcoal afforded compounds 3a,b. Title compounds 4a,b were obtained by refluxing 3a,b in toluene with p-toluenesulphonic acid as catalyst.

ChemInform Abstract: Synthesis of 3-Triazenopyrroles.

Abstract The 3-triazenopyrroles, a new class of pyrrole derivatives, were synthesized in quantitative yield by coupling 3-diazopyrroles with secondary amines.

New synthesis of condensed heterocycles from isoxazole derivatives VI. 2,5-Dimethyl-3-aeetyl-7-amino-1H-pyrrolo[3,2-b] pyridine

A new synthesis of pyrrolo[3,2-b] pyridine starting with pyrrole ring is described. The procedure allows the synthesis of 4-azaindoles bearing a sensitive group at C-7. The nitration of 4b with nitric acid and acetic anhydride at −15° gave 5. The hydrogenation of 5 led to simultaneous reduction of N-hydroxy and nitro groups and to hydrogenolysis of the isoxazole nucleus, affording an appropriate chain of atoms to building up the pyrrolo[3,2-b] pyridine ring.

Preparation of monohalopyrroles

Monobromo-, monochloro- and monoiodopyrroles are obtained in excellent yields by using N-halosuccinimides in dimethylformamide as halogenating agents.