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Can. J. Chem. Vol. 86, 2008
(50.2), 56 (100). Anal. calcd. for C21H24FN3O5: C 60.42, H
5.80; found: C 60.57. H 5.74.
7-(5-Bromo-2-hydroxybenzyl)-5,6,7,8,9,10-hexahydro-2H-
1,13,4,7,10-benzodioxatriazacyclopentadecine-
3,11(4H,12H)-dione (10)
Rrecrystallization from EtOAc gave compound 10 as a
colorless powder in 73% yield; mp 238 °C (decomposed).
UV–vis (chloroform, nm (log⑀)) λmax: 374 (1.81), 269 (3.22),
246 (3.08) IR (KBr, cm–1) υmax : 3393, 3200, 2900, 1663,
1590, 1542, 1502, 1464, 1425, 1370, 1258, 1218, 1128,
1106, 1056, 823, 750. 1H NMR (DMSO-d6) δH: 9.81 (1H, s),
7.80 (2H, s), 7.38 (1H, d, J = 1.9 Hz), 7.12–6.95 (5H, m),
6.68 (1H, d, J = 8.6 Hz), 4.44 (4H, s), 3.54 (2H, s), 3.40
(4H, t, J = 5.3 Hz), 2.64 (4H, t, J = 5.3 Hz). 13C NMR
(DMSO-d6) δC: 167.2, 155.2, 147.2, 132.3, 130.5, 127.6,
122.2, 117.3, 114.4, 110.3, 68.0, 52.2, 50.1, 35.4. MS m/z
(%): 479 ([M+ + 2], 1.5), 477 ([M+], 1.5), 407 (2.0), 405
(2.0), 292 (29.3), 242 (10.2), 240 (10.2), 225 (27.4), 206
(10.5), 187 (13.4), 185 (13.4), 167 (12.6), 150 (12.5), 121
(22.2), 85 (59.3), 56 (100.0), 43 (89.2). Anal. calcd. for
C21H24BrN3O5: C 52.73, H 5.06; found: C 52.85, H 4.88.
7-[(4-Hydroxy[1,1’-biphenyl]-3-yl)methyl]-5,6,7,8,9,10-
hexahydro-2H-1,13,4,7,10-benzodioxatriazacyclo-
pentadecine-3,11(4H,12H)-dione (13)
Recrystallization from EtOAc gave compound 13 as a col-
orless powder in 79% yield; mp 190 °C. UV–vis (chloro-
form, nm (log⑀)) λmax: 293 (3.28), 253 (3.36). IR (KBr, cm–1)
υ
max: 3380, 3250, 3030, 2950, 2850, 1672, 1598, 1540,
1
1506, 1456, 1264, 1225, 1127, 1049, 752. H NMR (CDCl3)
δH: 8.81(1H, s), 7.61 (2H, s), 7.48–7.01 (8H, m), 6.90–6.82
(4H, m), 4.47 (4H, s), 3.82 (2H, s), 3.55 (4H, t, J = 5.3 Hz),
2.78 (4H, t, J = 5.3 Hz). 13C NMR (CDCl3) δC: 168.4, 156.0,
147.4, 141.0, 133.4, 129.2, 129.0, 128.1, 127.0, 126.9,
123.0, 116.6, 114.6, 68.4, 54.6, 53.3, 36.2. MS m/z (%): 477
([M+ + 2], 0.1), 476 ([M+ + 1], 0.4), 475 ([M+], 1.0), 403
(1.0), 368 (0.4), 352 (1.1), 313 (0.3), 293 (5.5), 249 (5.3),
225 (68.2), 182 (18.1), 167 (23.4), 150 (21.5), 121 (22.8),
113 (22.9), 85 (47.0), 69 (100.0), 56 (89.7), 43 (87.6). Anal.
calcd. for C27H29N3O5: C 68.19, H 6.15; found: C 68.35, H
6.28.
7-(5-Chloro-2-hydroxybenzyl)-5,6,7,8,9,10-hexahydro-
2H-1,13,4,7,10-benzodioxatriazacyclopentadecine-
3,11(4H,12H)-dione (11)
Recrystallization from EtOAc gave compound 11 as a
colorless powder in 75% yield; mp 237 °C (decomposed).
UV–vis (chloroform, nm (log⑀)) λmax: 360 (2.97), 292 (3.25),
272 (3.24), 246 (3.13). IR (KBr, cm–1) υmax: 3394, 3250,
2950, 2850, 1662, 1590, 1540, 1500, 1427, 1370, 1245,
7-(2,5-Dihydroxybenzyl)-5,6,7,8,9,10-hexahydro-2H-
1,13,4,7,10-benzodioxatriazacyclopentadecine-
3,11(4H,12H)-dione (14)
Recrystallization from EtOAc gave compound 14 as a
colorless powder in 71% yield; mp 170 °C. UV–vis
(DMSO, nm (log⑀)) λmax: 301 (3.42), 279 (3.41). IR
(KBr,cm–1) υmax: 3394, 2916, 2825, 1663, 1597, 1541, 1504,
1
1210, 1128, 1056, 823, 756, 653. H NMR (DMSO-d6) δH:
9.78 (1H, s), 7.80 (2H, s), 7.27 (1H, d, J = 2.2 Hz), 6.95–
7.11 (5H, m), 6.72 (1H, d, J = 8.6 Hz), 4.44 (4H, s), 3.54
(2H, s), 3.40 (4H, t, J = 5.3 Hz), 2.64 (4H, t, J = 5.3 Hz).
13C NMR (DMSO-d6) δC: 167.2, 154.8, 147.2, 129.5, 127.6,
127.0, 122.7, 122.2, 116.8, 114.4, 68.0, 52.2, 50.1, 35.4.
MS m/z (%): 435 ([M+ + 2], 0.4), 434 ([M+ + 1], 0.2), 433
([M+], 2.2), 416 (0.3), 361 (2.3), 292 (12.7), 225 (24.3), 196
(11.1), 167 (12.6), 141 (16.9), 121 (19.4), 113 (19.9), 85
(50.9), 77 (60.3), 69 (66.2), 56 (97.9), 43 (100.0). Anal.
calcd. for C21H24ClN3O5: C 58.13, H 5.58; found: C 57.89,
H 5.76.
1
1259, 1213, 1126, 1051, 818, 750. H NMR (DMSO-d6) δH:
8.71 (1H, s), 8.46 (1H, s), 7.67 (2H, s), 7.04–6.88 (4H, m),
6.47–6.32 (3H, m), 4.37 (4H, s), 3.45 (2H, s), 3.31 (4H, t,
J = 5.3 Hz), 2.54 (4H, t, J = 5.3 Hz). 13C NMR (DMSO-d6)
δC: 166.9, 149.3, 148.5, 146.5, 123.3, 121.8, 117.2, 115.6,
114.4, 114.0, 67.6, 51.5, 49.9, 35.0. MS m/z (%): 416
([M+ + 1], 0.2), 294 (1.9), 293 (2.6), 292 (0.7), 249 (5.1),
225 (51.3), 180 (13.3), 167 (18.6), 150 (17.3), 123 (25.6),
121 (23.5), 99 (17.7), 85 (42.4), 69 (83.7), 56 (100). Anal.
calcd. for C21H25N3O6: C 60.71, H 6.07; found: C 60.53, H
5.89.
7-(5-Fluoro-2-hydroxybenzyl)-5,6,7,8,9,10-hexahydro-2H-
1,13,4,7,10-benzodioxatriazacyclopentadecine-
3,11(4H,12H)-dione (12)
7-(3-Chloro-6-hydroxy-2,4-dimethylbenzyl)-5,6,7,8,9,10-
hexahydro-2H-1,13,4,7,10-benzodioxatriazacyclopenta-
decine-3,11(4H,12H)-dione (15)
Purification by flash column chromatography, eluted with
n-hexane – ethyl acetate (1:1), gave compound 12 as a color-
less powder in 81% yield; mp 214 °C. UV–vis (chloro-
form, nm (log⑀)) λmax : 288 (3.21), 270 (3.22), 245 (2.73). IR
(KBr, cm–1) υmax: 3404, 3078, 2916, 2822, 1676, 1549,
Recrystallization from EtOAc gave compound 15 as a col-
orless powder in 79% yield; mp 241 °C (decomposed). UV–
vis (chloroform, nm (log⑀)) λmax: 271 (3.21), 246 (3.15). IR
(KBr, cm–1) υmax: 3375, 3190, 2878, 2806, 1657, 1599,
1
1
1506, 1448, 1259, 1219, 1195, 1130, 1057, 818, 748. H
1541, 1506, 1438, 1211, 1122, 1063, 815, 744. H NMR
NMR (CDCl3) δH: 8.55 (1H, s), 7.46 (2H, s), 7.06–6.91
(4H, m), 6.87–6.63 (3H, m), 4.51 (4H, s), 3.74 (2H, s), 3.54
(4H, t, J = 5.3 Hz), 2.75 (4H, t, J = 5.3 Hz). 13C NMR
(CDCl3) δC: 168.1, 158.2, 154.5, 152.1, 147.2, 122.9, 116.8,
116.3, 115.9, 114.8, 68.5, 56.0, 52.8, 35.7. 19F NMR
(CDCl3) δF: –125.0 (1F). MS m/z (%): 418 ([M+ + 1], 1.0),
417 ([M+], 2.5), 400 (0.2), 346 (0.2), 345 (3.0), 294 (0.8),
293 (3.8), 292 (19.2), 225 (29.7), 206 (14.1), 180 (31.1), 167
(28.1), 150 (16.7), 125 (36.2), 96 (38.1), 85 (49.0), 69
(CDCl3) δH: 9.43 (1H, s), 7.41 (2H, s), 7.07–6.91 (4H, m),
6.50 (1H, s), 4.51 (4H, s), 3.83 (2H, s), 3.54 (4H, t, J =
5.3 Hz), 2.75 (4H, t, J = 5.3 Hz), 2.33 (3H, s), 2.26 (3H, s).
13C NMR (CDCl3) δC: 168.1, 154.8, 147.3, 139.0, 136.8,
123.0, 118.9, 116.1, 115.1, 68.6, 53.8, 52.8, 35.8, 21.1, 16.9.
MS m/z (%): 463 ([M+ + 2], 0.3), 462 ([M+ + 1],1.2), 461
([M+], 3.6), 390 (0.3), 389 (2.4), 294 (5.0), 293 (5.6), 292
(15.4), 225 (50.0), 180 (14.3), 168 (32.8), 150 (18.0), 121
(31.1), 105 (81.7), 85 (64.5), 69 (89.3), 56 (100). Anal.
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