NEW DERIVATIVES OF 2-(3,5-DIOXO-4-AZATRICYCLO[5.2.1.02,6-endo]DEC-...
1303
trum, ν, cm–1: 3310, 3030, 1775, 1710, 1560, 1230,
1160, 860. H NMR spectrum, δ, ppm: 8.89 t (1H,
Found, %: C 58.12; H 4.18; N 8.69. C16H14N2O6. Cal-
culated, %: C 58.18; H 4.24; N 8.48.
1
NH), 4.72 d (2H, 12-H), 4.01 s (2H, CH2), 3.33 m
(2H, 6-H, 10-H), 3.23 m (2H, 2-H, 4-H), 2.87 m (2H,
1-H, 5-H), 1.33 d (1H, syn-11-H), 1.04 d (1H, anti-
11-H). Found, %: N 10.02. C12H13ClN2O4. Calculated,
%: N 9.84.
Epoxy derivatives XIa–XIe (general procedure).
Urea VIi or VIk, carbamate VIIa or VIIb, or amide
VIIIc, 1 mmol, was dissolved in 10 ml of 98% formic
acid, 0.06 ml (2 mmol) of 50% aqueous hydrogen per-
oxide was added under stirring, and the mixture was
stirred until the reaction was complete (TLC). Volatile
substances were removed under reduced pressure
(water-jet pump), and the residue was recrystallized
from water or propan-2-ol.
Triazole derivatives XIIa–XIIf (general proce-
dure). A mixture of 1 mmol of compound VIi, VIk,
VIIa, VIIb, VIIIb, or VIIIc and 0.25 g (1.5 mmol) of
p-nitrophenyl azide in 10 ml of chloroform was heated
for 5–7 h under reflux. The solvent was removed under
reduced pressure (water-jet pump), the residue was
ground with 10 ml of diethyl ether, and the precipitate
was filtered off, dried, and recrystallized from iso-
propyl alcohol.
N-Benzyl-N′-(7,9-dioxo-3-oxa-8-azatetracyclo-
[5.3.1.02,4-exo.06,10-endo]undec-8-ylmethyl)urea (XIa).
Yield 66%, mp 99–100°C, Rf 0.18. IR spectrum, ν,
cm–1: 3370, 1774, 1712, 1690, 1648, 1566, 1258, 850.
1H NMR spectrum, δ, ppm: 7.31–7.14 (5H, Harom),
6.71 t (1H, NH), 6.53 t (1H, NH), 4.70 d (2H, 12-H),
4.14 d (2H, CH2), 3.21 m (2H, 6-H, 10-H), 3.00 m
(2H, 2-H, 4-H), 2.88 m (2H, 1-H, 5-H), 1.35 d (1H,
syn-11-H), 1.03 d (1H, anti-11-H). Found, %: N 12.43.
C18H19N3O4. Calculated, %: N 12.32.
N-Benzyl-N′-(9,11-dioxo-3,4,5,10-tetraazatetra-
cyclo[5.5.1.02,6-exo.08,12-endo]tridec-10-ylmethyl)urea
(XIIa). Yield 87%, mp 107–109°C (decomp.), Rf 0.21.
IR spectrum, ν, cm–1: 3374, 3300, 1774, 1712, 1690,
1
1598, 1516, 1334, 1250, 846. H NMR spectrum, δ,
N-(7,9-Dioxo-3-oxa-8-azatetracyclo[5.3.1.02,4-exo.-
06,10-endo]undec-8-ylmethyl)morpholine-4-carbox-
amide (XIb). Yield 66%, mp 192–193°C (decomp.).
IR spectrum, ν, cm–1: 3405, 3030, 1790, 1715, 1670,
ppm: 8.31 d (2H, Harom), 7.31 d (2H, Harom), 7.26–
6.99 m (5H, Harom), 6.88 t (1H, NH), 6.56 t (1H, NH),
3
4.75 d (2H, 14-H), 4.65 d (1H, 2-H, J2,6 = 9.4 Hz),
4.02 (2H, CH2), 3.81 d (1H, 6-H), 3.31 m (2H, 8-H,
12-H), 3.13 m (1H, 1-H), 3.04 m (1H, 7-H), 1.58 d
(1H, syn-13-H), 1.07 d (1H, anti-13-H). Found, %:
N 20.15. C24H23N7O5. Calculated, %: N 20.04.
1
1560, 1220, 860. H NMR spectrum, δ, ppm: 7.21 t
(1H, NH), 4.70 d (2H, 12-H), 3.49–3.45 m and 3.22–
3.19 m (4H each, NCH2CH2O), 3.19 m (2H, 6-H,
10-H), 3.02 m (2H, 2-H, 4-H), 2.86 m (2H, 1-H, 5-H),
1.33 d (1H, syn-11-H), 1.02 d (1H, anti-11-H). Found,
%: N 13.28. C15H19N3O5. Calculated, %: N 13.08.
N-(9,11-Dioxo-3,4,5,10-tetraazatetracyclo-
[5.5.1.02,6-exo.08,12-endo]tridec-10-ylmethyl)morpho-
line-4-carboxamide (XIIb). Yield 62%, mp 195–
197°C (decomp.), Rf 0.12. IR spectrum, ν, cm–1: 3405,
1790, 1725, 1710, 1665, 1610, 1530, 1340, 1260, 1225,
Methyl (7,9-dioxo-3-oxa-8-azatetracyclo-
[5.3.1.02,4-exo.06,10-endo]undec-8-ylmethyl)carbamate
(XIc). Yield 78%, mp 166–167°C, Rf 0.26. IR spec-
trum, ν, cm–1: 3312, 1778, 1736, 1728, 1690, 1538,
1
870, 855. H NMR spectrum, δ, ppm: 8.33 d (2H,
Harom), 7.41 t (1H, NH), 7.32 d (2H, Harom), 4.74 d (2H,
1
3
1252, 856. H NMR spectrum, δ, ppm: 7.86 t (1H,
14-H), 4.67 d (1H, 2-H, J2,6 = 8.7 Hz), 3.84 d (1H,
NH), 4.63 d (2H, 12-H), 3.49 s (3H, CH3), 3.22 m
(2H, 6-H, 10-H), 3.03 m (2H, 2-H, 4-H), 2.87 m (2H,
1-H, 5-H), 1.34 d (1H, syn-11-H), 1.04 d (1H, anti-
11-H). Found, %: N 10.64. C12H14N2O5. Calculated, %:
N 10.53.
6-H), 3.31 m and 3.12 m (4H each, NCH2CH2O),
3.32 m (2H, 8-H, 12-H), 3.14 m (1H, 1-H), 3.03 m
(1H, 7-H), 1.60 d (1H, syn-13-H), 1.07 d (1H, anti-
13-H). Found, %: N 20.80. C21H23N7O6. Calculated,
%: N 20.89.
Ethyl (7,9-dioxo-3-oxa-8-azatetracyclo-
[5.3.1.02,4-exo.06,10-endo]undec-8-ylmethyl)carbamate
(XId). Yield 63%, mp 134–135°C, Rf 0.30. IR spec-
trum, ν, cm–1: 3314, 1780, 1728, 1712, 1690, 1538,
1248, 854. Found, %: N 10.18. C13H16N2O5. Calculat-
ed, %: N 10.00.
Methyl (9,11-dioxo-3,4,5,10-tetraazatetracyclo-
[5.5.1.02,6-exo.08,12-endo]tridec-10-ylmethyl)carbamate
(XIIc). Yield 85%, mp 189–191°C (decomp.), Rf 0.17.
IR spectrum, ν, cm–1: 3298, 1770, 1728, 1688, 1598,
1
1538, 1514, 1334, 1254, 848. H NMR spectrum, δ,
ppm: 8.32 d (2H, Harom), 7.91 t (1H, NH), 7.32 d (2H,
3
H
arom), 4.72 d (2H, 14-H), 4.62 d (1H, 2-H, J2,6
=
Chloro-N-(7,9-dioxo-3-oxa-8-azatetracyclo-
[5.3.1.02,4-exo.06,10-endo]undec-8-ylmethyl)acetamide
(XIe). Yield 78%, mp 127–128°C, Rf 0.19. IR spec-
8.7 Hz), 3.89 d (1H, 6-H), 3.46 s (3H, CH3), 3.35 m
(2H, 8-H, 12-H), 3.14 m (1H, 1-H), 3.03 m (1H, 7-H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 9 2007