Synthesis and Antiarrhythmic Activity of 5‐Amino‐exo‐3‐azatricyclo[5.2.1.0 2,6 ]decan‐4‐one.

Хурсан

et al. 2009

Chem Heterocycl Comp

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The hydrogenation at Raney nickel of the pyrazoline ring in methyl exo-3,4-diazatricyclo-[5.2.1.0 2,6 ]dec-4-ene-5-carboxylate takes place quantitatively with the preferential formation of the trans isomer of 5-amino-exo-3-azatricyclo[5.2.1.0 2,6 ]decan-4-one. The 3-methoxycarbonylmethyl-, 3-acetyl-, and 3-nitroso-substituted esters are not hydrogenated under these conditions. Keywords: 5-amino-exo-3-azatricyclo[5.2.1.0 2,6 ]decane, 5-amino-exo-3-azatricyclo[5.2.1.0 2,6 ]decan-4-one, methyl 3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-ene-5-carboxylate, Raney nickel, catalytic hydrogenation.The hydrogenation of pyrazolines is a convenient method for the production of 1,3-propylenediamines [1, 2], which are converted in the presence of an ester group or lactone ring into pyrrolidin-2-ones [3][4][5][6][7]. The latter find use in the synthesis of derivatives of pyrrolidine and analogs of γ-aminobutyric acid -the main neurotransmitter in the central nervous system of mammals [8,9]. The presence of the pyrrolidine ring in the molecule of many natural and synthetic compounds gives rise to a wide range of biological activity [6][7][8][9][10][11][12][13][14][15][16].Recently we showed that 3-aminopyrrolidin-2-one, coupled with a norbornane fragment, exhibits antiarrhythmic, analgesic, nootropic, and anti-inflammatory activity [7].In a continuation of our investigations into the chemistry of pyrazolines [2, 5-7, 17, 18] in the present work we studied the reduction of methyl exo-3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-ene-5-carboxylate (1) and its 3-methoxycarbonylmethyl-, 3-acetyl-, and 3-nitroso-substituted analogs 2-4 respectively.It should be noted that at the beginning of our researches there were no data in the literature on the synthesis of tricyclic γ-lactams based on derivatives of norbornene.As a result of a search for the optimum reaction conditions for the case of the ester 1 it was established that the most effective of the methods that have widespread application for the reduction of C=N and N=N bonds (H 2 -Raney nickel, H 2 -Pdc, H 2 -PtO 2 , H 2 -Rh/Al 2 O 3 , Na-n-BuOH, RhCl(PPh 3 ) 3 -i-PrOH-KOH, LiAlH 4 , NaBH 4 , NaBH 4 -Cu(acac) 2 ) is hydrogenation with hydrogen in the presence of Raney nickel in _______

mentioning

confidence: 99%

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confidence: 99%

Catalytic hydrogenation of methyl 3,4-diazatricyclo-[5.2.1.02,6]dec-4-ene-5-carboxylate

Gorpinchenko

Хурсан

et al. 2009

Chem Heterocycl Comp

Self Cite

mentioning

confidence: 99%

“…The structural features of the polycyclic pyrazolines (in particular those containing a norbornane fragment) might be used to develop routes to the synthesis of various heterocyclic structures and of practically interesting compounds. Hence the pyrazoline -methyl exo-3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-ene-5-carboxylate gave the 5-amino-exo-3-azatricyclo[5.2.1.0 2,6 ]decan-4-one, which has anti-inflammatory, analgesic, nootropic, and marked antiarthritic activity [6,7].With the aim of synthesizing novel 3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-enes we have studied the reactions of exo-3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-ene (1) with methyl acrylate, acrylonitrile, ethylene oxide, acetic acid, and the nitrosonium cation. Compound 1 was prepared by the catalytic isomerization of exo-3,4-diazatricyclo[5.2.1.0 2,6 ]dec-3-ene (2) in THF solution in the presence of Pd(acac) 2 with a yield of 70%.…”

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confidence: 99%

“…Pyrazolines are valuable compounds for the synthesis of differently structured organic compounds and are of interest as pharmacologically active compounds with a broad spectrum of activity (antiviral, analgesic, antitumor, psychotropic etc) [1][2][3][4][5][6][7][8]. There are quite detailed reports in the literature of the alkylation, acylation, and several other chemical reactions of monocyclic pyrazolines [9][10][11][12][13] but norbornane series pyrazolines have not been studied.…”

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confidence: 99%

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Synthesis of 3-N-substituted exo-3,4 diazatricyclo[5.2.1.02,6]dec-4-enes

Shafikova

Докичев

2007

Chem Heterocycl Compd

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Pyrazolines are valuable compounds for the synthesis of differently structured organic compounds and are of interest as pharmacologically active compounds with a broad spectrum of activity (antiviral, analgesic, antitumor, psychotropic etc) [1][2][3][4][5][6][7][8]. There are quite detailed reports in the literature of the alkylation, acylation, and several other chemical reactions of monocyclic pyrazolines [9-13] but norbornane series pyrazolines have not been studied. The structural features of the polycyclic pyrazolines (in particular those containing a norbornane fragment) might be used to develop routes to the synthesis of various heterocyclic structures and of practically interesting compounds. Hence the pyrazoline -methyl exo-3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-ene-5-carboxylate gave the 5-amino-exo-3-azatricyclo[5.2.1.0 2,6 ]decan-4-one, which has anti-inflammatory, analgesic, nootropic, and marked antiarthritic activity [6,7].With the aim of synthesizing novel 3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-enes we have studied the reactions of exo-3,4-diazatricyclo[5.2.1.0 2,6 ]dec-4-ene (1) with methyl acrylate, acrylonitrile, ethylene oxide, acetic acid, and the nitrosonium cation. Compound 1 was prepared by the catalytic isomerization of exo-3,4-diazatricyclo[5.2.1.0 2,6 ]dec-3-ene (2) in THF solution in the presence of Pd(acac) 2 with a yield of 70%. N N H N N N N CH 2 CH 2 R O N N CH 2 CH 2 OH N N O Me CH 2 =CHR Pd(acac) 2 AcOH 1 3, 5 2 4 6 CH 2 =CHCO 2 Me, AcOH 3 R = CO 2 Me; 5 R = CN

Synthesis of norbornane series tetra- and hexahydropyrimidines

Shafikova

Sapozhnikova

et al. 2009

Chem Heterocycl Comp

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Pyrimidine derivatives attract the attention of synthetic chemists and of pharmacologists thanks to their unique properties of low toxicity and broad spectrum of physiological activity (analgesic, immunotropic, anti-inflammatory, antiviral, hepatoprotective, antioxidant, and antiradical) [1-7]. Many compounds used in medical practice are close analogs of pyrimidine nucleosides. Work on the synthesis of novel compounds amongst this class is very actively pursued [8][9][10][11]. It is known that pyrrolidinones containing a condensed norbornane fragment have antiarrhythmic properties and norbornane series amines and their acyl derivatives show neurotropic, anti-inflammatory, antiglycemic, and other types of activity [12][13][14][15]. There is, however, no information in the literature regarding the synthesis and properties of norbornanes containing condensed exoorientated tetra-and hexahydropyrimidine structures at the 2, 3 position of the norbornane ring.This report concerns the targeted synthesis of 3,5-diazatricyclo[6.2.1.0 2,7 ]undecanes containing tetraand hexahydropyrimidine fragments in an exo position to a norbornane structure through study of the condensation reaction of exo-2-amino-exo-3-aminomethylnorbornane (1) with formaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde, acetone, methylcyclopropyl ketone, cyclohexanone, and urea and with formic, acetic, and benzoic acids.The reaction of diamine 1 with an equimolar amount of formaldehyde, acetaldehyde, benzaldehyde, or salicylaldehyde occurs at room temperature with heating of the reaction mass and gives a hard to separate mixture of condensation products.