Facile Preparation of 3,4-Dihydro-2,1-benzothiazine
2,2-Dioxides and Related Reaction with 1,3-Diiodo-5,5-dimethylhydantoin
under Photochemical Conditions

Atsushi Moroda; Shusuke Furuyama; Hideo Togo

doi:10.1055/s-0028-1216725

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Synlett 2009(8): 1336-1340
DOI: 10.1055/s-0028-1216725

LETTER

Facile Preparation of 3,4-Dihydro-2,1-benzothiazine 2,2-Dioxides and Related Reaction with 1,3-Diiodo-5,5-dimethylhydantoin under Photochemical Conditions

Atsushi Moroda, Shusuke Furuyama, Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
Fax: +81(43)2902792; e-Mail: togo@faculty.chiba-u.jp;

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Publikationsverlauf

Received 2 February 2009
Publikationsdatum:
17. April 2009 (online)

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Abstract

3,4-Dihydro-2,1-benzothiazine 2,2-dioxides were easily obtained in good yields by the reaction of N-methyl 2-arylethanesulfonamides with 1,3-diiodo-5,5-dimethylhydantoin (DIH) under irradiation with a tungsten lamp. When N-benzyl 2-phenylethanesulfonamide was treated with DIH under the same conditions, the corresponding N-benzyl 3,4-dihydro-2,1-benzothiazine 2,2-dioxide was obtained in good yield, and the N-benzyl group was easily removed by the treatment with hydrogen in the presence of Pd(OH)₂. On the other hand, treatment of N-3-arylpropyl trifluoromethanesulfonamides with DIH under irradiation with a tungsten lamp provided corresponding N-trifluoromethanesulfonyl-1,2,3,4-tetra-hydroquinolines in good yields.

Key words

3,4-dihydro-2,1-benzothiazine 2,2-dioxide - 1,3-diiodo-5,5-dimethylhydantoin - 1,2,3,4-tetrahydroquinoline - tungsten lamp - irradiation - sulfonamidyl radical

References and Notes

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7

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).

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⁺].