ORDER
REPRINTS
2-Arylmethylidene-8-methyl-8-azabicyclo[3.2.1]octan-3-ones
1937
2E-(2-Methoxybenzylidene)-8-methyl-8-azabicyclo[3.2.1]-octan-3-one
1
(3c). Compound 3c was prepared in 35% yield as a brown oil. H NMR
(CDCl3): 7.66 (s, 1H, C55CH), 7.34 (m, 1H, Ph-4-H), 7.14 (dd, J ¼ 7.5,
1.5 Hz, 1H, Ph-6-H), 6.96 (dt, J ¼ 0.6, 7.5 Hz, 1H, Ph-5-H), 6.91 (dd,
J ¼ 8.4, 0.9 Hz, 1H, Ph-3-H), 4.18 (d, J ¼ 6.9 Hz, 1H, CH-1), 3.83 (s, 3H,
OCH3), 3.53 (t, J ¼ 6.0 Hz, 1H, CH-4), 2.87 (ddd, J ¼ 18.6, 5.7, 1.8 Hz,
1H, CH-5), 2.41 (s, 3H, N-CH3), 2.20–2.48 (m, 3H, CH-4, CH-6, and CH-
7), 1.90 (m, 1H, CH-6), 1.71 (m, 1H, CH-7); 13C NMR (CDCl3): 199.54
(C55O), 158.42 (Ph-2-C), 139.29 (C-2), 130.50 (55CH), 130.45 (Ph-4-C),
130.39 (Ph-6-C), 123.95 (Ph-1-C), 120.08 (Ph-5-C), 110.80 (Ph-3-C), 61.21
(C-1), 58.96 (C-5), 55.58 (OCH3), 44.60 (C-4), 37.07 (N-CH3), 30.60 (C-6),
29.17 (C-7); GC: tR ¼ 10.96 min, purity .99% (Only one peak was
observed.); MS m/z: 256 (6), 242 (1), 229 (100), 214 (16), 201 (54), 186
(12), 170 (12), 145 (8), 131 (12), 115 (24), 94 (70), 82 (36), 42 (36); EI-
HRMS: C16H19NO2 calcd. for 257.1410 (obs. 257.1413).
2E-(2,4-Dimethoxybenzylidene)-8-methyl-8-azabicyclo[3.2.1]-octan-
3-one (3d). Compound 3d was prepared in 25% yield as a semisolid. 1H NMR
(CDCl3): 7.68 (s, 1H, C55CH), 7.10 (d, J ¼ 8.4 Hz, 1H, Ph-6-H), 6.51 (dd,
J ¼ 8.4, 2.4 Hz, 1H, Ph-5-H), 6.46 (d, J ¼ 2.4 Hz, 1H, Ph-3-H), 4.21
(d, J ¼ 6.9 Hz, 1H, CH-1), 3.84 (s, 3H, 4-OCH3), 3.82 (s, 3H, 2-OCH3),
3.53 (t, J ¼ 6.3 Hz, 1H, CH-4), 2.87 (ddd, J ¼ 18.6, 5.7, 1.8 Hz, 1H, CH-5),
2.42 (s, 3H, N-CH3), 2.21–2.50 (m, 3H, CH-4, CH-6, and CH-7),
1.91 (m, 1H, CH-6), 1.71 (m, 1H, CH-7); 13C NMR (CDCl3): 199.27
(C55O), 161.96 (Ph-4-C), 160.05 (Ph-2-C), 137.53 (C-2), 131.48 (55CH),
130.62 (Ph-6-C), 116.91 (Ph-1-C), 104.40 (Ph-5-C), 98.56 (Ph-3-C), 61.36
(C-1), 58.89 (C-5), 55.70 (OCH3), 55.67 (OCH3), 44.39 (C-4), 37.01
(N-CH3), 30.80 (C-6), 29.29 (C-7); GC: tR ¼ 12.28 min, purity .99%
(Only one peak was observed.); MS m/z: 287 (2), 259 (100), 244 (9), 231
(54), 216 (13), 200 (14), 187 (7), 175 (6), 161 (6), 149 (6), 115 (14), 94 (71),
82 (19), 42 (24); EI-HRMS: C17H21NO3 calcd. for 287.1516 (obs. 287.1509).
2E-(4-Fluorobenzylidene)-8-methyl-8-azabicyclo[3.2.1]-octan-3-one
(3e). Compound 3e was prepared in 85% yield as a pale yellow solid. M.p.
76–778C; 1H NMR (CDCl3): 7.46 (s, 1H, C55CH), 7.28–7.35 (m, 2H,
Ph-2-H, and Ph-6-H), 7.06–7.20 (m, 2H, Ph-3-H, and Ph-5-H), 4.25
(d, J ¼ 6.9 Hz, 1H, CH-1), 3.54 (t, J ¼ 6.0 Hz, 1H, CH-4), 2.87 (ddd,
J ¼ 18.6, 5.7, 1.8 Hz, 1H, CH-5), 2.41 (s, 3H, N-CH3), 2.24–2.54 (m, 3H,
CH-4, CH-6, and CH-7), 1.89 (m, 1H, CH-6), 1.73 (m, 1H, CH-7); 13C
NMR (CDCl3): 199.15 (C55O), (164.49, 161.18) (C–F), 139.52 (C-2),
133.06 (55CH), (132.12, 132.00) (Ph-2-C and Ph-6-C), (131.00, 130.95)
(Ph-1-C), (115.95, 115.66) (Ph-3-C and Ph-5-C), 61.09 (C-1), 58.99 (C-5),
44.87 (C-4), 37.58 (N-CH3), 30.45 (C-6), 29.07 (C-7); GC: tR ¼ 10.19 min,
purity .99% (Only one peak was observed.); MS m/z: 244 (16), 230 (1),