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General Procedure
for the Conversion of
N
-Methyl- or
N
-Benzyl 2-Arylethanesulfonamides into the Corresponding
N
-Methyl-3,4-dihydro-2,1-benzothiazine 2,2-dioxides
with DIH
1,3-Diiodo-5,5-dimethylhydantoin (0.6 mmol,
228 mg) was added to a soln of N-methyl
2-arylethanesulfonamide (0.5 mmol) in EtOAc (5 mL). The mixture
was irradiated with a tungsten lamp (500 W) at 30-40 ˚C
for 4 h under an argon atmosphere. After the reaction, the mixture
was poured into sat. aq Na2SO3 soln and extracted
with CHCl3 three times. Then, the organic layer was dried
over Na2SO4. After removal of the solvent
under reduced pressure, the residue was subjected to preparative
TLC on SiO2 using a mixture of hexane, EtOAc, and CHCl3 (6:3:1)
as eluent.
Typical Procedure for the
Reduction of
N
-Benzyl-3,4-dihydro-2,1-benzothiazine
2,2-dioxide
Palladium hydroxide (20 wt% Pd/C,
200 mg) was added to a soln of N-benzyl-3,4-dihydro-2,1-benzothiazine
2,2-dioxide (1 mmol, 273.4 mg) in EtOAc (4 mL) and EtOH (4 mL).
The mixture was stirred at r.t. for 48 h under H2 atmosphere. After
the reaction, the mixture was poured into CHCl3 and washed
with H2O. The organic layer was dried over Na2SO4. After
removal of the solvent under reduced pressure, the residue was subjected
to preparative TLC on SiO2 using a mixture of hexane
and EtOAc (2:1) as eluent.
N
-Methyl-3,4-dihydro-2,1-benzothiazine 2,2-Dioxide
Mp
77.0-79.0 ˚C. IR (KBr): 1580, 1490, 1330,
1170 cm-¹. ¹H NMR
(400 MHz, CDCl3): δ = 3.30
(s, 3 H), 3.32 (t, J = 6.9
Hz, 2 H), 3.43 (t, J = 6.9
Hz, 2 H), 6.96 (dd, J = 8.0,
1.0 Hz, 1 H), 7.05 (td, J = 7.6,
1.0 Hz, 1 H), 7.16 (dd, J = 7.6,
1.2 Hz, 1 H), 7.27 (m, 1 H). ¹³C NMR
(125 MHz, CDCl3): δ = 27.90
(s), 31.97 (p), 45.55 (s), 117.47 (t), 122.82 (q), 123.14 (t), 127.88
(t), 129.30 (t), 141.14 (q). MS (EI): m/z = 197 [M+].
Anal. Calcd (%) for C9H11NO2S:
C, 54.80; H, 5.62; N, 7.10. Found: C, 54.74; H, 5.52; N, 7.07.
N
-Methyl-7-methyl-3,4-dihydro-2,1-benzothiazine
2,2-Dioxide
Mp 78.0-79.0 ˚C.
IR (paraffin oil): 1330, 1200, 1159 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 2.34
(s, 3 H), 3.29 (s, 3 H), 3.32 (t, J = 7.0
Hz, 2 H), 3.40 (t, J = 7.0
Hz, 2 H), 6.77 (s, 1 H), 6.86 (d, J = 7.8
Hz, 1 H), 7.04 (d, J = 7.8
Hz, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 21.27
(p), 27.50 (s), 32.15 (p), 45.55 (s), 118.20 (t), 119.78 (q), 124.02
(t), 129.16 (t), 137.81 (q), 140.92 (q). HRMS-FAB: m/z calcd for C10H13NO2S:
211.0667 [M]; found: 211.0667 [M+].
N
-Methyl-7-fluoro-3,4-dihydro-2,1-benzothiazine
2,2-Dioxide
Mp 67.0-68.0 ˚C.
IR (KBr): 1620, 1590, 1510, 1320, 1300, 1210, 1170, 1140 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 3.28
(s, 3 H), 3.34 (ddd, J = 7.5,
6.3, 1.4 Hz, 2 H), 3.43 (ddd, J = 7.5,
6.3, 1.4 Hz, 2 H), 6.66 (dd, J = 10.6,
2.4 Hz, 1 H), 6.75 (td, J = 8.2,
2.4 Hz, 1 H), 7.09-7.14 (m, 1 H). ¹³C
NMR (100 MHz, CDCl3): δ = 27.36
(s), 31.21 (p), 45.68 (s), 104.34 (t, J
C-F = 26.5
Hz), 109.68 (t, J
C-F = 21.5
Hz), 118.05 (q, J
C-F = 4.2
Hz), 130.67 (t, J
C-F = 9.1
Hz), 142.43 (q, J
C-F = 9.9
Hz), 162.30 (q, J
C-F = 245.6
Hz). MS (EI): m/z = 215 [M+].
Anal. Calcd (%) for C9H10FNO2S:
C, 50.22; H, 4.68; N, 6.51. Found: C, 50.03; H, 4.70; N, 6.50.
N
-Methyl-7-chloro-3,4-dihydro-2,1-benzothiazine
2,2-Dioxide
Mp 93.0-94.0 ˚C.
IR (KBr): 1600, 1490, 1330, 1160 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 3.29
(s, 3 H), 3.34 (t, J = 7.3
Hz, 2 H), 3.43 (t, J = 7.3
Hz, 2 H), 6.93 (d, J = 1.9
Hz, 1 H), 7.02 (dd, J = 8.0,
1.9 Hz, 1 H), 7.09 (d, J = 8.0
Hz, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 27.53
(s), 31.42 (p), 45.52 (s), 117.10 (t), 120.89 (q), 122.96 (t), 130.45
(t), 133.65 (q), 142.11 (q). MS (EI): m/z = 231 [M+].
Anal. Calcd (%) for C9H10ClNO2S:
C, 46.65; H, 4.35; N, 6.05. Found: C, 46.60; H, 4.29; N, 5.94.
N
-Methyl-7-bromo-3,4-dihydro-2,1-benzothiazine
2,2-Dioxide
Mp 103-105 ˚C.
IR (paraffin oil): 1330, 1300, 1200, 1160, 914 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 3.29
(s, 3 H), 3.32-3.37 (m, 2 H), 3.38-3.43 (m, 2
H), 7.03 (d, J = 8.0
Hz, 1 H), 7.08 (d, J = 1.9
Hz, 1 H), 7.17 (dd, J = 8.0,
1.9 Hz, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 27.68
(s), 31.60 (p), 45.54 (s), 120.07 (t), 121.46 (q), 121.54 (q), 125.99
(t), 130.80 (t), 142.35 (q). HRMS-FAB: m/z calcd
for C9H10NO2SBr: 274.9616 [M];
found: 274.9598 [M+].
N
-Benzyl-3,4-dihydro-2,1-benzothiazine
2,2-Dioxide
Mp 71.0-73.0 ˚C.
IR (KBr): 1600, 1580, 1500, 1460, 1330, 1160 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 3.25
(t, J = 6.9 Hz,
2 H), 3.44 (t, J = 6.9
Hz, 2 H), 5.00 (s, 2 H), 6.88 (d, J = 8.2
Hz, 1 H), 7.01 (t, J = 7.5,
1.2 Hz, 1 H), 7.10-7.16 (m, 2 H), 7.23-7.37 (m,
5 H). ¹³C NMR (100 MHz, CDCl3): δ = 28.16
(s), 45.92 (s), 51.11 (s), 119.09 (t), 123.05 (q), 123.46 (t), 127.09
(t), 127.63 (t), 127.81 (t), 128.79 (t), 129.51 (t), 136.57 (q),
140.26 (q). MS (EI): m/z = 273 [M+]. Anal.
Calcd (%) for C15H15NO2S:
C, 65.91; H, 5.53; N, 5.12. Found: C, 65.78; H, 5.53; N, 5.02.
3,4-Dihydro-2,1-benzothiazine 2,2-Dioxide
Mp
150.0-152.0 ˚C. ¹H
NMR (400 MHz, CDCl3): δ = 3.32 (t, J = 6.9 Hz,
2 H), 3.49 (t, J = 6.9
Hz, 2 H), 6.45 (s, 1 H), 6.75 (dd, J = 8.1,
1.1 Hz, 1 H), 7.05 (td, J = 7.5,
1.1 Hz, 1 H), 7.17-7.23 (m, 2 H).
8a
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Nakagawa A.
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Kojima Y.
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J. Antibiot.
1981,
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8d
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8e
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Iliadis T.
Eisenbeis SA.
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1994,
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Toyota M.
Asoh T.
Fukumoto K.
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Togo H.
Hoshina Y.
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10
General Procedure
for the Conversion of
N
-3-Arylpropyl Trifluoromethanesulfonamides into
the Corresponding
N
-(Trifluoromethanesulfonyl)-1,2,3,4-tetrahydroquinolines
with DIH
A soln of N-3-arylpropyl
trifluoromethanesulfonamide (1.0 mmol) and 1,3-diiodo-5,5-dimethylhydantoin
(1.2 mmol, 455.9 mg) in DCE (15 mL) was irradiated with a tungsten lamp
(500 W) for 7 h at 60 ˚C under an argon atmosphere. After
the reaction, the mixture was poured into a sat. aq Na2SO3 soln
and extracted with CHCl3 three times. The organic layer
was dried over Na2SO4. After filtration, the solvent
was removed under reduced pressure, and the residue was subjected
to flash column chromatography on SiO2 using a mixture
of hexane, EtOAc, and CHCl3 (1:10:1) as eluent.
N
-(Trifluoromethanesulfonyl)-1,2,3,4-tetrahydro-quinoline
Oil.
IR (neat): 1580, 1480, 1220, 1200 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 2.11
(quin, J = 6.4
Hz, 2 H), 2.88 (t, J = 6.4
Hz, 2 H), 3.87 (t, J = 6.4
Hz, 2 H), 7.15-7.22 (m, 3 H), 7.52 (d, J = 7.7
Hz, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 23.39
(s), 26.13 (s), 47.94 (s), 120.11 (q, J
C-F = 328
Hz, CF3), 123.34 (t), 126.15 (t), 126.79 (t), 129.46
(t), 130.91 (q), 135.31 (q). HRMS (EI): m/z calcd
for C10H10F3NO2S: 265.0384 [M];
found: 265.0390 [M+].
N
-(Trifluoromethanesulfonyl)-7-chloro-1,2,3,4-tetra-hydroquinoline
Oil.
IR (neat): 1601, 1574, 1454, 1353, 1311, 1025 cm-¹.
¹H
NMR (500 MHz, CDCl3): δ = 2.10
(m, 2 H), 2.85 (t, J = 6.8
Hz, 2 H), 3.86 (t, J = 6.0
Hz, 2 H), 7.08-7.15 (m, 2 H), 7.56 (s, 1 H). ¹³C
NMR (125 MHz, CDCl3): δ = 23.03 (s),
25.80 (s), 47.90 (s), 119.89 (q, J
C-F = 324
Hz, q, CF3), 123.34 (t), 126.30 (t), 129.08 (q), 130.45
(t), 132.14 (q), 136.08 (q)- HRMS-FAB: m/z calcd
for C10H9ClF3NO2S: 298.9995 [M];
found: 299.0006 [M+].
N
-(Trifluoromethanesulfonyl)-7-methyl-1,2,3,4-tetra-hydroquinoline
Oil.
IR (neat): 1620, 1576, 1455, 1393, 1353, 1313 cm-¹.
¹H
NMR (500 MHz, CDCl3): δ = 2.09
(m, 2 H), 2.33 (s, 3 H), 2.83 (t, J = 6.9
Hz, 2 H), 3.84 (t, J = 6.1
Hz, 2 H), 6.97 (d, J = 7.4
Hz, 1 H), 7.04 (d, J = 7.4
Hz, 1 H), 7.33 (s, 1 H). ¹³C NMR (125
MHz, CDCl3): δ = 21.18
(p), 23.44 (s), 25.69 (s), 47.98 (s), 120.00 (q, J
C-F = 324
Hz, q, CF3), 123.75 (t), 127.07 (t), 127.81 (q), 129.19
(t), 135.10 (q), 136.65 (q). HRMS-FAB: m/z calcd
for C11H12F3NO2S: 279.0541 [M]; found:
279.0538 [M+].
N
-(Trifluoromethanesulfonyl)-7-methoxy-1,2,3,4-tetra-hydroquinoline
Oil.
IR (neat): 1617, 1583, 1430, 1293, 1039 cm-¹. ¹H
NMR (500 MHz, CDCl3): δ = 2.08
(m, 2 H), 2.81 (t, J = 6.9
Hz 2 H), 3.78 (s, 3 H), 3.85 (t, J = 6.0
Hz, 2 H), 6.73 (dd, J = 8.2, 2.5
Hz, 1 H), 7.05 (d, J = 8.2
Hz, 1 H), 7.12 (d, J = 2.5
Hz, 1 H). ¹³C NMR (125 MHz, CDCl3): δ = 23.37
(s), 25.47 (s), 48.11 (s), 55.44 (p), 108.55 (t), 112.72 (t), 120.00
(q, J
C-F = 324
Hz, q, CF3), 122.58 (q), 130.08 (t), 135.87 (q), 158.15 (q).
HRMS-FAB: m/z calcd
for C11H12F3NO3S: 295.0490 [M];
found: 295.0482 [M+].
N
-(Trifluoromethanesulfonyl)-7-fluoro-1,2,3,4-tetra-hydroquinoline
Oil.
IR (neat): 1614, 1426, 1315, 1029 cm-¹. ¹H
NMR (500 MHz, CDCl3): δ = 2.10
(m, 2 H), 2.84 (t, J = 6.9
Hz, 2 H), 3.87 (t, J = 6.0
Hz, 2 H), 6.88 (dt, J = 8.2,
2.4 Hz, 1 H), 7.11 (m, 1 H) 7.33 (dd, J = 10.7,
2.4 Hz, 1 H). ¹³C NMR (125 MHz, CDCl3): δ = 23.07
(s), 25.74 (s), 47.96 (s), 110.52 (t, J = 26
Hz), 113.28 (t, J = 21
Hz), 119.92 (q, J
C-F = 323
Hz, q, CF3), 126.00 (q), 130.50 (t, J = 9
Hz), 159.86 (q), 161.81 (q). HRMS-FAB: m/z calcd
for C10H9F4NO2S: 283.0290 [M];
found: 283.0280 [M+].