770
A. PUSTENKO ET AL.
General procedure for the synthesis of 1,4-disubstitutedtriazolyl 1-(2,2-Dioxido-3H-1,2-benzoxathiepin-7-yl)-4-(3-methoxyphenyl)-
1H-1,2,3-triazole (11)
compound (9–17)
To a solution of corresponding alkyne (1 eq.) in tBuOH/H2O 1:1
mixture (10 ml)7-azido-3H-1,2-benzoxathiepine 2,2-dioxide (8) (1
eq.), CuSO4ꢃ5H2O (2 eq.) and sodium ascorbate (4 eq.) were added
and reaction mixture was stirred at room temperature for 10 min.
AcOH (19–21 eq.) was added and mixture was stirred for add-
itional 30 min. Solvent was driven off in vacuum and the crude
product was purified by reversed phase chromatography (C-18,
H2O–MeCN gradient MeCN 10–90%).
Compound 11 was prepared according to the general procedure
from 3-ethynylanisole (17 mg, 0.13 mmol), azide
8
(30 mg,
0.13 mmol), CuSO4ꢃ5H2O (63 mg, 0.25 mmol), sodium ascorbate
(100 mg, 0.50 mmol), AcOH (0.14 ml, 2.45 mmol) as yellowish
solid (24 mg, 51%). Mp210–211 ꢁC.IR (KBr, cmꢂ1
)
mmax¼1372
(S¼O), 1162 (S¼O); 1H NMR (400 MHz, DMSO-d6) d ¼ 3.84 (s, 3H),
4.61 (dd, 2H, J ¼ 5.8, 1.2 Hz), 6.09–6.16 (m, 1H), 6.94–6.99 (m,
1H), 7.02 (d, 1H, J ¼ 11.5 Hz), 7.39–7.45 (m, 1H), 7.48–7.55 (m,
2H), 7.63 (d, 1H, J ¼ 8.9 Hz), 8.03 (dd, 1H, J ¼ 8.9, 2.7 Hz), 8.12 (d,
1H, J ¼ 2.7 Hz), 9.36 (s, 1H); 13C NMR (100 MHz, DMSO-d6)
d ¼ 51.7, 55.2, 110.6, 114.1, 117.6, 120.1, 121.6, 122.1, 122.6,
124.0, 129.6, 130.1,130.2, 131.4, 135.0, 146.3, 147.4, 159.8; HRMS
(ESI) m/z [M þ H]þ calcd for C18H16N3O4S: 370.0862, found
370.0876.
N
N
N
S
O
O
O
N
N
1-(2,2-Dioxido-3H-1,2-benzoxathiepin-7-yl)-4-phenyl-1H-1,2,3-
triazole (9)
N
F
Compound 9 was prepared according to the general procedure
S
O
O
from phenylacetylene (13 mg, 0.13 mmol), azide
8
(30 mg,
O
0.13 mmol), CuSO4ꢃ5H2O (65 mg, 0.26 mmol), sodium ascorbate
(103 mg, 0.52 mmol), AcOH (0.14 ml, 2.45 mmol) as white solid
(41 mg, 95%). Mp 203–204 ꢁC. IR (KBr, cmꢂ1) mmax¼1368 (S¼O),
1-(2,2-Dioxido-3H-1,2-benzoxathiepin-7-yl)-4–(4-fluorophenyl)-
1H-1,2,3-triazole (12)
1
1171 (S¼O); H NMR (400 MHz, DMSO-d6) d ¼ 4.61 (dd, 2H, J ¼ 5.9,
1.2 Hz), 6.09–6.16 (m, 1H), 7.02 (d, 1H, J ¼ 11.3 Hz), 7.37–7.43 (m,
1H), 7.48–7.54 (m, 2H), 7.63 (d, 1H, J ¼ 8.8 Hz), 7.92–7.97 (m, 2H),
8.04 (dd, 1H, J ¼ 8.8, 2.6 Hz), 8.13 (d, 1H, J ¼ 2.6 Hz), 9.35 (s, 1H); 13C
NMR (100 MHz, DMSO-d6) d ¼ 51.7, 119.9, 121.6, 122.1, 122.7, 124.0,
125.3, 128.4, 129.1, 129.6, 130.0, 130.1, 135.0, 146.3, 147.5; HRMS
(ESI) m/z [M þ H]þ calcd for C17H14N3O3S: 340.0756, found 340.0755.
Compound 12 was prepared according to the general procedure
from 1-ethynyl-4-fluorobenzene (30 mg, 0.25 mmol), azide
8
(60 mg, 0.25 mmol), CuSO4ꢃ5H2O (126 mg, 0.50 mmol), sodium
ascorbate (200 mg, 1.02 mmol), AcOH (0.28 ml, 5.05 mmol) as
yellowish solid (60 mg, 66%). Mp 200–201 ꢁC. IR (KBr, cmꢂ1
)
mmax¼1369 (S¼O), 1167 (S¼O); 1H NMR (400 MHz, DMSO-d6)
d ¼ 4.61 (d, 2H, J ¼ 5.4 Hz), 6.07–6.17 (m, 1H), 7.01 (d, 1H,
J ¼ 11.3 Hz), 7.30–7.71 (m, 2H), 7.63 (d, 1H, J ¼ 8.8 Hz), 7.94–8.05
(m, 3H), 8.11 (s, 1H), 9.34 (s, 1H); 13C NMR (100 MHz, DMSO-d6)
d ¼ 51.7, 116.1 (d, J ¼ 21.9 Hz), 119.9, 121.6, 122.1, 122.7, 124.1,
126.6, 127.4 (d, J ¼ 8.3 Hz), 129.7, 130.1, 135.0, 146.3, 146.6,
162.1 (d, J ¼ 245.3 Hz); HRMS (ESI) m/z [M þ H]þ calcd for
C17H13FN3O3S: 358.0662, found 358.0656.
N
N
N
Cl
S
O
O
O
N
N
4-(4-Chlorophenyl)-1–(2,2-dioxido-3H-1,2-benzoxathiepin-7-yl)-
1H-1,2,3-triazole (10)
N
O
F C
3
Compound 10 was prepared according to the general procedure
S
O
from 1-chloro-4-ethynylbenzene (17 mg, 0.12 mmol), azide
8
O
O
(29 mg, 0.12 mmol), CuSO4ꢃ5H2O (61 mg, 0.24 mmol), sodium ascor-
bate (97 mg, 0.49 mmol), AcOH (0.13 ml, 2.27 mmol) as yellowish
solid (34 mg, 74%). Mp 191–192 ꢁC. IR (KBr, cmꢂ1) mmax¼1369
(S¼O), 1356 (S¼O), 1168 (S¼O); 1H NMR (400 MHz, DMSO-d6)
d ¼ 4.61 (dd, 2H, J ¼ 5.9, 1.2 Hz), 6.09–6.16 (m, 1H), 7.01 (d, 1H,
J ¼ 11.5 Hz), 7.55–7.61 (m, 2H), 7.63 (d, 1H, J ¼ 8.9 Hz), 7.92–7.98
(m, 2H), 8.02 (dd, 1H, J ¼ 8.9, 2.7 Hz), 8.11 (d, 1H, J ¼ 2.7 Hz), 9.38
(s, 1H); 13C NMR (100 MHz, DMSO-d6) d ¼ 51.7, 120.3, 121.6, 122.1,
122.7, 124.1, 127.0, 129.0, 129.1, 129.6, 130.1, 132.8, 135.0, 146.3,
146.4; HRMS (ESI) m/z [M þ H]þ calcd for C17H13ClN3O3S: 374.0366,
found 374.0366.
1-(2,2-Dioxido-3H-1,2-benzoxathiepin-7-yl)-4-[4-
(trifluorometoxy)phenyl]-1H-1,2,3-triazole (13)
Compound 13 was prepared according to the general proced-
ure from 4-(trifluoromethoxy) phenylacetylene (40 mg,
0.21 mmol), azide 8 (50 mg, 0.21 mmol), CuSO4ꢃ5H2O (105 mg,
0.42 mmol), sodium ascorbate (167 mg, 0.84 mmol), AcOH
(0.23 ml, 4.02 mmol) as yellowish solid (74 mg, 83%). Mp
168–169 ꢁC. IR (film, cmꢂ1) mmax¼ 1357 (S¼O), 1166 (S¼O); 1H
NMR (400 MHz, CDCl3) d ¼ 4.13 (dd, 2H, J ¼ 6.0, 1.1Hz),
6.06–6.13 (m, 1H), 6.93 (d, 1H, J ¼ 11.3 Hz), 7.30–7.35 (m, 2H),
7.51 (d, 1H, J ¼ 8.8 Hz), 7.79 (dd, 1H, J ¼ 8.8, 2.5 Hz), 7.85 (d,
1H, J ¼ 2.5 Hz), 7.91–7.98 (m, 2H), 8.25 (s, 1H); 13C NMR
(100 MHz, CDCl3) d ¼ 51.8, 120.6 (q, J ¼ 257.9 Hz), 121.4, 121.7,
122.1, 122.9, 124.7, 127.5, 128.8, 130.0, 131.5, 135.6, 147.3,
N
N
N
O
S
O
O
O