SU1761757A1 - Pyrrolopyrazoloazepines and method of their synthesis - Google Patents

Abstract

Use as physiologically active preparations The essence of the invention: the product 5,7-dimethyl-6-ethyl-2,3-dihydropyrro, 3rd pyrazolo 3,4-аз azepin-3-onBFS1zN14M40 yield 56%, so pl. 247 ° C 5,7-Dimethyl-6-phenyl-2,3-dihydropyrrolo 4,3-e pyrazolo 3, zepin-3-one, BF SPN-nM / 3 O, 77% yield, m.p. 263 ° C, 5,7-dimethyl-2-phenyl-6-ethyl-2,3-dihydropyrrolo 4,3-e pyrazolo 4,3-аз azepin-3-one, BF CigHisN O, yield 90%, m.p. 256 DEG C .; 5,7-dimethyl-2,6-diphenyl-2,3-dihydropyrrolo 4,3-e pyrazolo 3, zepin-3-one, BF C2 3 H 1 G yO, 89% yield, t. Pl. 270iS. The compounds are prepared by reacting the corresponding 3,4-deformylpyrrole with aminopyrazole.

Description

The invention relates to organic chemistry, namely to derivatives of a new heterocyclic pyrrolopyrazoloazepine system of structure I

where Ri is ethyl, phenyl;

R 2 is hydrogen, phenyl and the method for their preparation.

The invention can find wide and varied applications, because Until now, representatives of heterocycles with the indicated fusion of pyrrole, pyrazole and azepine nuclei were not known, which predetermines broad prospects for practical use in many fields. For example, they can be used as physiologically active drugs, because it is known that compounds containing azepine nuclei often exhibit high activity.

Of the closest structural analogues of the claimed compounds are known heterocycles containing simultaneously a pyrrole cycle condensed with a seven-membered nucleus of structure IV

IV

A method of obtaining compounds of structure IV is the interaction of dialdehyde structure II with acetone.

The disadvantage of this method is the impossibility of obtaining in this way new heterocycles that would contain simultaneously pyrrole, azepine and pyrazole rings.

1761757A1

The aim of the invention are compounds related to the new heterocyclic system containing a new combination of known chemical bonds, as well as the development of a convenient preparative way to obtain these compounds.

This goal is achieved by compounds of structure I and the method of their preparation, which consists in the fact that

3,4-diformylpyrrole of formula II

H ₃ C sn = o n ₅ with cn = o _p where Ri is ztyl, phenyl, is reacted with pyrazolone of the formula III o ^P 'where R2 is hydrogen, phenyl

The composition and structure of the synthesized compounds is confirmed by the data of elemental analysis, IR spectra and PMR.

Indeed, in the 1H NMR spectrum of compound 1 (R ₂ = H. Ri = C2H5) in DMSO-D6 (TMS internal standard), proton signals of two methyl groups with a chemical shift of 2.49 ppm are observed, signals of protons of the ethyl group are 1.23 t . and 4.00 sq., signals of aromatic protons - 7.72 and 8.21, and also NH signal of a proton - 11.34.

Example 1,5,7-Dimethyl-6-ethyl-2,3-dihydropyrrolo [4.3-e] pyrazolo- [3,4-b] azepi n-3-one.

A mixture of 0.36 g (2 mmol) of 1-ethyl-2,5-dimethyl-3,4-bisformylpyrrole, 0.2 g (2 mmol) of 3-amino-5-pyrazolone, 5 ml of absolute alcohol is heated to boiling and added 0.1 ml piperidine. Boil for 40 minutes. After cooling, the product is filtered off and crystallized from water. Yield 0.27 g (56%), mp. 27 ° C.

Found,%: C 64.2; H 5.9; N, 23.0.

C13H14N4O

Calculated,%: C 64.43; H 5.84; N, 23.13.

Example 2. 5,7-Dimethyl-6-phenyl-2,3-dihydropyrrolo [4.3-e] pyrazo. By [3,4-b] aze pin-3-one.

A mixture of 0.55 g (2 mmol) of 1-phenyl-2,5-dimethyl-3,4-bisformylpyrrole, 0.2 g (2 mmol) of 3-amino-5-pyrazolone, 5 ml of absolute alcohol is heated to boiling and 0 1 ml of piperidine. Boil for 40 minutes. The product is filtered off from the hot reaction mixture and crystallized from nitromethane. Yield 0.45 g (77%), mp. 263 ° C.

Found,%: C 69.9; H 4.8; N 19.0

C17H14N4O

Calculated,%: C 70.32; H 4.87; N, 19.30.

Example 3. 5.7-Dimethyl-2-phenyl-6ethyl-2,3-dihydropyrrolo [4,3-e] -pyrazolo [3, 4-b] azepin-3-one.

A mixture of 0.54 g (3 mmol) of 1-ethyl-2,5-dimethyl-3,4-bisformylpyrrole, 0.53 g (3 mmol) of 1-phenyl-3-amino-5-pyrazolone, heated to 10 ml of absolute alcohol to a boil and add 0.1 ml of piperidine., Boil for 15 minutes. After cooling, the product is filtered off, crystallized from nitromethane. Yield 0.86 g (90%), mp. 256 ° C.

Found,%: C 71.8; H 5.9; N 18.0

C19H18N4O

Calculated,%: C 71.67; H 5.71; N, 17.60.

Example 4. 5,7-Dimethyl-2,6-diphenyl2,3-dihydropyrrolo [4,3-e] -pyrazolo [3,4-b] azepin-3-one.

A mixture of 0.55 g (2 mmol) of 1-phenyl-2,5-dimethyl-3,4-bisformylpyrrole, 0.35 g (2 mmol) of 1-phenyl-3-amino-5-pyrazolone, 5 ml of absolute alcohol are heated to a boil and add 0.1 ml of piperidine. Boil for 40 minutes. The product is filtered off from the hot reaction mixture and crystallized from nitromethane. Yield 0.65 g (89%), mp. 270 ° C.

Found,%: C 75.7; H 4.9; N 15.5,

C23H18N4O

Calculated,%: C 75.38; H 4.86; N, 15.29.

Thus, from the presented data it is seen that the developed method allows to obtain derivatives of a new heterocyclic system with a previously unknown combination of the known nuclei of pyrrole, azepine and pyrazole.

Claims (2)

Claim 1. Pyrrolopyrazoloazepines of the general formula wherein Ri is ethyl, phenyl; R 2 is hydrogen, phenyl. 2. A method of obtaining pyrrolopyrazoloazepines of the General formula where Ri is ethyl, phenyl; R2 is hydrogen, phenyl, characterized in that the diformylpyrroles of the formula cn ₃ L ^ CH = O CH3 ^ ^- ^ cn = o where Ri is ethyl, phenyl, is reacted with aminopyrazolones of the formula