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Helvetica Chimica Acta – Vol. 90 (2007)
(d, J ¼ 2, 1 H); 6.91 (d, J ¼ 8, 1 H). 13C-NMR: 15.5 (q); 28.0 (t); 75.5 (t); 75.8 (t); 120.0 (d); 120.7 (d);
123.1 (d); 140.3 (s); 146.2 (s); 148.1 (s); 204.8 (s). MS: 192 (100, Mþ), 177 (29), 150 (12), 149 (88), 136
(6), 135 (20), 123 (9), 122 (6), 121 (7), 108 (16), 105 (9), 94 (5), 91 (18), 89 (7), 80 (15), 79 (32), 78 (8),
77 (29), 67 (5), 65 (13), 63 (11), 55 (6), 51 (18), 39 (13), 27 (7).
7-Propyl-2H-1,5-benzodioxepin-3(4H)-one (9g). According to the G.P. 1 in 55% yield from 12g. M.p.
32 – 338. 1H-NMR: 0.93 (d, J ¼ 8, 3 H); 1.50 – 1.73 (m, 2 H); 2.50 (t, J ¼ 6, 2 H); 4.66 (s, 2 H); 4.70 (s, 2 H);
6.76 (dd, J ¼ 2, 8, 1 H); 6.80 (d, J ¼ 2, 1 H); 6.90 (d, J ¼ 2, 1 H). 13C-NMR: 13.8 (q); 24.4 (t); 37.1 (t); 75.5
(t); 75.8 (t); 120.5 (d); 120.6 (d); 123.7 (d); 138.7 (s); 146.2 (s); 148.0 (s); 204.8 (s). MS: 206 (50, Mþ), 178
(12), 177 (100), 149 (30), 135 (10), 123 (7), 121 (6), 105 (6), 91 (9), 79 (7), 77 (19), 65 (12), 63 (7), 55
( 9), 51 ( 11), 39 ( 9), 27 ( 7).
6-Propyl-2H-1,5-benzodioxepin-3(4H)-one (9h). According to the G.P. 1 in 41% yield from 12h.
1H-NMR: 0.94 (d, J ¼ 8, 3 H); 1.51 – 1.66 (m, 2 H); 2.59 (t, J ¼ 7, 2 H); 4.70 (s, 4 H); 6.85 (br. s, 3 H).
13C-NMR: 14.0 (q); 23.5 (t); 32.2 (t); 75.4 (t); 75.6 (t); 118.5 (d); 123.1 (d); 124.6 (d); 135.0 (s); 146.7 (s);
148.6 (s); 205.0 (s). MS: 206 (100, Mþ), 178 (14), 177 (100), 164 (7), 150 (14), 149 (85), 135 (15), 121 (8),
115 (5), 107 (10), 105 (12), 103 (8), 94 (10), 93 (24), 91 (31), 89 (8), 79 (22), 78 (10), 77 (43), 65 (31), 63
(14), 55 (7), 53 (7), 51 (26), 42 (8), 39 (25), 29 (17), 27 (19).
7-Isopropyl-2H-1,5-benzodioxepin-3(4H)-one (9i). According to the G.P. 1 in 60% yield from 12i.
1H-NMR: 1.21 (d, J ¼ 7, 6 H); 2.83 (sept., J ¼ 7, 1 H); 4.67 (s, 2 H); 4.70 (s, 2 H); 6.82 (dd, J ¼ 7, 2, 1 H ) ;
6.86 (d, J ¼ 2, 1 H); 6.92 (d, J ¼ 7, 1 H ) . 13C-NMR: 24.0 (2q); 33.3 (d); 75.5 (t); 75.8 (t); 118.5 (d); 120.7
(d); 121.7 (d); 145.0 (s); 146.2 (s); 148.0 (s); 208.2 (s). MS: 206 (45, Mþ), 192 (12), 191 (100), 163 (14),
121 (5), 119 (7), 107 (9), 105 (6), 91 (22), 79 (10), 77 (13), 65 (7).
6-Isopropyl-2H-1,5-benzodioxepin-3(4H)-one (9j). According to the G.P. 1 in 23% yield from 12j.
1H-NMR: 1.21 (d, J ¼ 7, 6 H); 3.30 (sept., J ¼ 7, 1 H); 4.70 (s, 4 H); 6.80 – 6.87 (m, 1 H); 6.89 – 6.95 (m,
2 H). 13C-NMR: 22.9 (2q); 27.2 (d); 75.4 (t); 75.7 (t); 118.3 (d); 120.8 (d); 123.4 (d); 140.9 (s); 146.1 (s);
148.6 (s); 205.0 (s). MS: 206 (69, Mþ), 192 (12), 191 (100), 163 (36), 149 (6), 135 (12), 133 (20), 121 (5),
119 (7), 117 (5), 115 (6), 107 (21), 105 (14), 103 (8), 93 (7), 91 (41), 89 (8), 79 (26), 78 (11), 77 (33), 65
(19), 63 (11), 55 (5), 53 (9), 51 (17), 41 (10), 39 (21), 29 (8), 27 (15).
7-(tert-Butyl)-2H-1,5-benzodioxepin-3(4H)-one (9k). According to the G.P. 1 in 56% yield from
12k. M.p. 98 – 998. 1H-NMR: 1.28 (s, 9 H); 4.68 (s, 2 H); 4.70 (s, 2 H); 6.92 (d, J ¼ 7, 1 H); 6.98 (dd, J ¼ 7, 2,
1 H); 7.01 (d, J ¼ 2, 1 H). 13C-NMR: 31.3 (3q); 34.3 (s); 75.6 (t); 75.7 (t); 117.8 (d); 120.4 (d); 120.7 (d);
145.9 (s); 147.4 (s); 147.7 (s); 204.8 (s). MS: 220 (24, Mþ), 206 (14), 205 (100), 177 (13), 135 (5), 121 (5),
105 (4), 91 (7), 77 (6).
6-(1-Methylpropyl)-2H-1,5-benzodioxepin-3(4H)-one (9l). According to the G.P. 1 in 39% yield
from 12l. 1H-NMR: 0.84 (t, J ¼ 7, 3 H); 1.19 (d, J ¼ 7, 3 H); 1.50 – 1.64 (m, 2 H); 3.01 – 3.14 (m, 1 H); 4.69
(s, 2 H); 4.71 (s, 2 H); 6.85 – 6.94 (m, 3 H). 13C-NMR: 12.2 (q); 20.7 (q); 30.1 (t); 34.0 (d); 75.3 (t); 75.7
(t); 118.2 (d); 121.5 (d); 123.4 (d); 139.8 (s); 146.5 (s); 148.6 (s); 205.1 (s). MS: 220 (32, Mþ), 192 (13),
191 (100), 177 (6), 135 (7), 133 (17), 107 (12), 105 (8), 91 (18), 79 (8), 77 (15), 65 (8), 51 (6), 39 (7), 29
(9), 27 (8).
7-(1-Methylpropyl)-2H-1,5-benzodioxepin-3(4H)-one (9n). According to the G.P. 1 in 49% yield
from 12n. 1H-NMR: 0.84 (t, J ¼ 8, 3 H); 1.19 (d, J ¼ 7, 3 H); 1.50 – 1.63 (m, 2 H); 3.02 – 3.14 (m, 1 H); 4.69
(s, 2 H); 4.72 (s, 2 H); 6.82 – 6.95 (m, 3 H). 13C-NMR: 12.2 (q); 21.8 (q); 31.1 (t); 40.9 (d); 75.5 (t); 75.8
(t); 119.1 (d); 120.6 (d); 122.3 (d); 143.8 (s); 146.2 (s); 148.0 (s); 204.9 (s). MS: 220 (23, Mþ), 192 (13),
191 (100), 177 (5), 107 (6), 91 (13), 79 (5), 77 (10), 65 (6), 55 (5), 39 (4), 29 (5), 27 (5).
7-(1,1-Dimethylpropyl)-2H-1,5-benzodioxepin-3(4H)-one (9o). According to the G.P. 1 in 40% yield
1
from 12o. H-NMR: 0.69 (d, J ¼ 8, 3 H); 1.24 (s, 6 H); 1.49 (d, J ¼ 8, 2 H); 4.69 (s, 2 H); 4.71 (s, 2 H);
6.89 – 6.94 (m, 2 H); 6.95 (br. s, 1 H). 13C-NMR: 9.1 (q); 28.4 (2q); 36.8 (t); 37.5 (s); 75.5 (t); 75.7 (t); 118.5
(d); 120.2 (d); 121.3 (d); 145.7 (s); 145.8 (s); 147.6 (s); 204.8 (s). MS: 234 (14, Mþ), 206 (15), 205 (100),
177 (15), 121 (4), 91 (10), 77 (10), 65 (5), 55 (8), 51 (5), 41 (9), 39 (7), 29 (7), 27 (7).
7-Cyclopentyl-2H-1,5-benzodioxepin-3(4H)-one (9p). According to the G.P. 1 in 46% yield from
12p. 1H-NMR: 1.43 – 1.58 (m, 2 H); 1.59 – 1.72 (m, 2 H); 1.73 – 1.84 (m, 2 H); 1.96 – 2.09 (m, 2 H); 2.83 –
2.96 (m, 1 H); 4.65 (s, 2 H); 4.67 (s, 2 H); 6.82 (dd, J ¼ 7,2, 1 H); 6.87 (d, J ¼ 2, 1 H); 6.90 (d, J ¼ 8, 1 H).
13C-NMR: 25.4 (t); 34.5 (t); 45.1 (d); 75.5 (t); 75.7 (t); 119.2 (d); 120.6 (d); 122.3 (d); 142.6 (s); 146.1 (s);
148.0 (s); 204.8 (s). MS: 232 (100, Mþ), 204 (7), 203 (39), 190 (16), 177 (15), 175 (19), 162 (7), 149 (10),