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Study of the bromination of 1,5-dinitro-3-azabicyclo-[3.3.1]non-6-enes

“…The precipitated orange solid was filtered off, washed with a small amount of CCl 4 , and dried in a vacuum desiccator to constant mass. 13 C NMR spectrum (63 MHz), δ, ppm : 83.95 (C (1) ); 66.62 (C (2) ); 64.84 (C (4) ); 84.84 (C (5) ); 47.58 (C (6) ); 75.27 (C (7) ); 35.79 (C (8) ); 31.34 (C (9) ); 57.98 (CH 2 ); 8.59 (CH 3 1.73 (2H, m, CH 2 CH 2 CH 3 ); 0.93 (3H, t, J = 7.32, CH 2 CH 2 CH 3 ); 3.59 (3H, s, CH 3 ). 13 C NMR spectrum (63 MHz), δ, ppm: 83.09 (C (1) ); 67.16 (C (2) ); 65.25 (C (4) ); 84.89 (C (5) ); 47.49 (C (6) ); 75.96 (C (7) ); 35.79 (C (8) ); 31.25 (C (9) ); 63.43 (NCH 2 ); 16 …”

“…A starting point for interpreting the NMR spectra may be served by the low field broadened doublet (5.73 ppm, 3 J = 6.62 Hz) of the H-6 proton at the carbon atom directly linked with halogen, and the singlet of the N-methyl group protons at 3.59 ppm, which have correlation peaks 1 J CH in the 2D HSQC spectrum with the signals of the carbon atoms at 53.06 and 55.01 respectively, and also cross peaks 2 J CH in the HMBC spectrum H-6/C (7) , H-6/C (5) and 3 J CH H-6/C (9) , H-6/C (8) , Me/C (4) , Me/C (2) , and Me/C (7) ( Table 2). The presence of a vicinal coupling constant between the protons of the methyl group and the C (7) atom indicates the formation in the molecule of a covalent bond between the C (7) -N (3) atoms.…”

“…One of the methods of functionalizing the derivatives of 1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes previously synthesized by us [4][5][6][7][8] may be the addition of electrophilic reagents at the double bond. It was shown previously that electrophilic addition of halogenating agents to 2-azanorborn-5-ene leads to the formation of rearranged products [9, 10], and addition of bromine and dihalogen iodates to 2-alkyl-2-azabicyclo[2.2.1]hept-5-ene and 2-alkyl-2-azabicyclo-[2.2.2]oct-5-ene leads to a quaternary ammonium salt containing an aziridinium ring [11,12].…”

“…Since these protons are common to the two rings and occupy an equatorial position in one and an axial in the other, to distinguish them is possible from the 3 J CH H-9endo/C (8) , H-9endo/C (6) , H-9exo/C (4) , H-9exo/C (2) cross peaks in the HMBC spectrum (Table 2), and also with the aid of the 4 J HH H-6e/H-9endo, H-4e/H-9exo, and H-2e/H-9exo correlation peaks in the COSY spectrum. Finally, the signal of the H-8e equatorial proton is split into a doublet of doublets of doublets 2 J = 13.6, 3 J = 7.73, 4 J = 1.47 Hz), and the signal of the H-8a proton into a doublet of doublets ( 2 J = 13.6, 4 J = 2.2 Hz) and were detected at 3.24 and 3.14 ppm respectively.…”

Synthesis and Structure of 1,9-Dinitro-5-oxa-11-azatricyclo[6.4.0.04,9]dodecan-2-one

“…In continuation of investigations [2][3][4][5][6][7][8] on applying anionic σ-adducts of dinitroarenes I to preparation of polyfunctional derivatives of 3-azabicyclo[3.3.1]nonane, an important class of compounds possessing versatile biological activity [9], in the present study syntheses were performed of a series of 6-R-11-R'-1,9-dinitro-5-oxa-11-azatricyclo[6.4.0.0 4,9 ]dodecan-2-ones IIa-IIj. The preparation of compound IIa at reduction of Janovsky σ-adduct of 2,4-dinitrophenol and acetone (Ia) with sodium borohydride was first reported [10], but no reliable proofs of tricyclic compound formation were given.…”