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I. Suzuki et al. / Tetrahedron 59 (2003) 5691–5704
75 MHz) d 134.4 (C), 129.9 (C), 128.9 (C), 128.5 (CH),
127.7 (CH), 125.0 (CH), 78.1 (CH), 68.7 (CH2), 51.8 (CH2),
50.0 (CH2), 33.3 (CH2), 29.3 (CH2), 25.8 (CH2); IR (CHCl3)
1320, 1215, 1122 cm21; HRMS (EI) calcd for C13H16O3S
(Mþ): 252.0820, found: 252.0838.
3.43 (2H, t, J¼6.5 Hz), 3.29 (2H, t, J¼6.5 Hz), 2.49 (3H, s);
13C NMR (CDCl3, 100 MHz) d 138.5 (C), 130.8 (C), 129.2
(C), 127.7 (CH), 126.5 (CH), 125.5 (CH), 54.5 (CH2), 48.9
(CH2), 26.2 (CH2), 16.0 (CH3); IR (CHCl3) 1322 and
1120 cm21; HRMS (EI) calcd for C10H12O2S2 (Mþ):
228.0279, found: 228.0285; Anal. calcd for C10H12O2S2:
C, 52.60; H, 5.30. Found: C, 52.39; H, 5.24.
4.2.6. 1,3,4-Trihydro-6-(1-hydroxyethyl)-2-thia-
naphthalene 2,2-dioxide (17). Obtained in 15% as a
colorless oil: 1H NMR (CDCl3, 300 MHz) d 7.30–7.22
(2H, m), 7.13 (1H, d, J¼8.5 Hz), 4.91 (1H, q, J¼6.5 Hz),
4.28 (2H, s), 3.53 (1H, brs), 3.40 (2H, t, J¼6.5 Hz), 3.29
(2H, t, J¼6.5 Hz), 1.49 (3H, d, J¼6.5 Hz); 13C NMR
(CDCl3, 75 MHz) d 146.5 (C), 133.4 (C), 130.0 (CH), 127.5
(C), 125.8 (CH), 124.7 (CH), 69.8 (CH), 54.8 (CH2), 49.8
(CH2), 29.2 (CH2), 25.4 (CH3); IR (CHCl3) 3688, 1323,
1122 cm21; HRMS (EI) calcd for C11H14O3S (Mþ):
226.0664, found: 226.0672.
4.2.11. 1,3,4-Trihydro-5-butylamino-2-thia-naphthalene
2,2-dioxide (22). Obtained in 21% as a colorless powder:
mp 1738C; 1H NMR (CDCl3, 400 MHz) d 7.16 (1H, t,
J¼7.5 Hz), 6.64 (1H, d, J¼7.5 Hz), 6.47 (1H, d, J¼7.5 Hz),
4.24 (2H, s), 3.47 (1H, brs), 3.29 (2H, t, J¼6.2 Hz), 3.14
(2H, t, J¼7.0 Hz), 3.09 (2H, t, J¼6.2 Hz), 1.66 (2H, m),
1.45 (2H, m), 0.96 (3H, t, J¼7.0 Hz); 13C NMR (CDCl3,
75 MHz) d 145.9 (C), 128.8 (C), 128.3 (CH), 118.6 (CH),
118.5 (CH), 110.2 (CH), 53.8 (CH2), 47.5 (CH2), 43.8
(CH2), 31.4 (CH2), 24.0 (CH2), 20.3 (CH2), 13.9 (CH3); IR
(CHCl3) 1469, 1323, 1297, 1120 cm21; HRMS (EI) calcd
for C13H19O2S (Mþ): 253.1136, found: 253.1136.
4.2.7. 1,3,4-Trihydro-6-Butylsulfanyl-2-thia-naphtha-
lene 2,2-dioxide (18). Obtained in 32% as a colorless oil:
1H NMR (CDCl3, 400 MHz) d 7.20 (1H, dd, J¼8.0 and
2.0 Hz), 7.16 (1H, d, J¼2.0 Hz), 7.05 (1H, d, J¼8.0 Hz),
4.24 (2H, s), 3.35 (2H, t, J¼6.0 Hz), 3.28 (2H, t, J¼6.0 Hz),
2.93 (2H, t, J¼7.3 Hz), 1.70–1.59 (2H, m), 1.51–1.40 (2H,
m), 0.93 (3H, t, J¼7.3 Hz); 13C NMR (CDCl3, 75 MHz) d
138.3 (C), 133.8 (C), 130.2 (CH), 128.4 (CH), 127.2 (CH),
125.5 (C), 54.7 (CH2), 49.7 (CH2), 32.8 (CH2), 31.0 (CH),
29.0 (CH2), 21.9 (CH2), 13.6 (CH3); IR (CHCl3) 2961,
2932, 1323, 1124 cm21; HRMS (EI) calcd for C13H18O2S2
(Mþ): 270.0748, found: 270.0767.
4.2.12. 1-Thia-cyclodec-3-on-5-en-7-yne 1,1-dioxide (23).
Obtained in 14% as a colorless powder: mp 1098C; 1H NMR
(CDCl3, 400 MHz) d 5.95 (1H, dt, J¼5.4 and 11.0 Hz), 5.62
(1H, dt, J¼2.0 and 11.0 Hz), 4.45 (2H, s), 3.52 (2H,
deformed t J¼5.4 Hz), 3.37 (2H, dd, J¼6.0 and 2.0 Hz),
2.88 (2H, t, J¼6.0 Hz); 13C NMR (CDCl3, 75 MHz) d 197.1
(C), 135.6 (CH), 111.3 (CH), 93.6 (C), 83.7 (C), 66.6 (CH2),
50.9 (CH2), 44.6 (CH2), 15.3 (CH2); IR (CHCl3) 3000,
2926, 1725, 1323, 1121 cm21; HRMS (EI) calcd for
C9H10O3S (Mþ): 198.0351, found: 198.0350; Anal. calcd
for C9H10O3S: C, 54.53; H, 5.08. Found: C, 54.18; H, 5.04.
4.2.8. 1,3,4-Trihydro-5,6-bis(methylsulfanyl)-2-thia-
naphthalene 2,2-dioxide (19). Obtained in 15% as a
1
colorless oil: H NMR (CDCl3, 400 MHz) d 7.14 (1H, d,
4.2.13. 2,3,4-Trihydro-8-butylamino-1-thia-naphthalene
1,1-dioxide (24). Obtained in 4% as a colorless powder: mp
1698C; 1H NMR (CDCl3, 400 MHz) d 7.22 (1H, t,
J¼8.0 Hz), 6.64 (1H, d, J¼8.0 Hz), 6.46 (1H, d, J¼
8.0 Hz), 6.05 (1H, brs), 3.37 (2H, deformed t, J¼6.5 Hz),
3.17 (2H, t, J¼7.0 Hz), 2.95 (2H, t, J¼6.5 Hz), 2.44–2.38
(2H, m), 1.69 (2H, m), 1.46 (2H, m), 0.96 (3H, t, J¼7.0 Hz);
13C NMR (CDCl3, 75 MHz) d 146.6 (C), 138.0 (C), 133.0
(CH), 120.0 (C), 116.7 (CH), 110.6 (CH), 53.1 (CH2), 43.5
(CH2), 30.9 (CH2), 29.3 (CH2), 20.7 (CH2), 20.2 (CH2), 13.8
(CH3); IR (CHCl3) 1469, 1280, 1107 cm21; HRMS (EI)
calcd for C13H19O2S (Mþ): 253.1136, found: 253.1124.
J¼8.0 Hz), 7.04 (1H, d, J¼8.0 Hz), 4.22 (2H, s), 3.79 (2H, t,
J¼6.5 Hz), 3.27 (2H, t, J¼6.5 Hz), 2.44 (3H, s), 2.30 (3H,
s); 13C NMR (CDCl3, 100 MHz) d 147.6 (C), 138.9 (C),
132.0 (C), 130.7 (CH), 125.2 (C), 122.5 (CH), 55.1 (CH2),
50.4 (CH2), 27.3 (CH2), 18.5 (CH3), 15.8 (CH3); IR (CHCl3)
3003, 2924, 1322, 1120 cm21; HRMS (EI) calcd for
C11H14O2S3 (Mþ): 274.0156, found: 274.0148; Anal.
calcd for C11H14O2S3: C, 48.14; H, 5.14. Found: C, 48.50;
H, 4.99.
4.2.9. 1,3,4-Trihydro-1,5-bis(methylsulfanyl)-2-thia-
naphthalene 2,2-dioxide (20). Obtained in 17% as a
colorless powder: mp 85–868C; 1H NMR (CDCl3,
400 MHz) d 7.29 (1H, d, J¼8.0 Hz), 7.18 (1H, t,
J¼8.0 Hz), 7.16 (1H, d, J¼8.0 Hz), 4.74 (1H, d,
J¼2.5 Hz), 4.03 (1H, ddd, J¼14.2, 11.0 and 6.0 Hz), 3.43
(1H, ddd, J¼17.5, 6.0 and 4.0 Hz), 3.29 (1H, ddd, J¼17.5,
11.0 and 6.0 Hz), 3.14 (1H, dddd, J¼14.2, 6.0, 4.0 and
2.5 Hz), 2.52 (3H, s), 2.48 (3H, s); 13C NMR (CDCl3,
100 MHz) d 138.8 (C), 131.6 (C), 129.5 (C), 128.2 (CH),
127.5 (CH), 125.0 (CH), 65.7 (CH), 42.0 (CH2), 26.6 (CH2),
18.2 (CH3), 15.6 (CH3); IR (CHCl3) 3006, 2926, 1325,
1116 cm21; HRMS (EI) calcd for C11H14O2S3 (Mþ):
274.0156, found: 274.0148.
4.2.14. 1,3,4-Trihydro-2-thia-anthracene-2,2 dioxide
(25). Obtained in 21% as a yellow powder: mp 2898C
1
(decomp.); H NMR(CDCl3, 400 MHz) d 7.78–7.67 (2H,
m), 7.63 (1H, s), 7.61 (1H, s), 7.43–7.39 (2H, m), 4.35 (2H,
s), 3.79 (2H, deformed t, J¼6.4 Hz), 3.28 (2H, deformed t,
J¼6.4 Hz); 13C NMR (CDCl3, 100 MHz) d 133.2 (C), 132.4
(C), 131.5 (C), 129.1 (CH), 128.2 (CH), 127.5 (CH), 127.3
(CH), 127.0 (CH), 126.9 (C), 126.5 (CH), 56.2 (CH2), 52.0
(CH2), 29.1 (CH2); IR (KBr) 2934, 1390 and 1119 cm21
;
HRMS (EI) calcd for C13H12O2S (Mþ): 232.0558, found:
232.0565.
4.2.15. 1,3,4-Trihydro-1-cyclohexyl-2-thia-anthracene
1
2,2-dioxide (27). Obtained in 75% as a colorless oil: H
NMR (CDCl3, 400 MHz) d 7.83–7.78 (2H, m), 7.67 (1H, s),
7.64 (1H, s), 7.52–7.47 (2H, m), 4.06 (1H, d, J¼6.4 Hz),
3.64–3.47 (2H, m), 3.39–3.18 (2H, m), 2.50–2.20 (2H, m),
4.2.10. 1,3,4-Trihydro-5-methylsulfanyl-2-thia-naphtha-
lene 2,2-dioxide (21). Obtained in 46% as a colorless oil: 1H
NMR (CDCl3, 400 MHz) d 7.26 (1H, t, J¼7.5 Hz), 7.21
(1H, d, J¼7.5 Hz), 6.93 (1H, d, J¼7.5 Hz), 4.26 (2H, s),