3
016
R. Sato et al. / Tetrahedron Letters 48 (2007) 3013–3016
(d, J = 8.5 Hz, 1H, ArH); C NMR (101 MHz, CDCl
1
3
4. (a) Davidson, B. S.; Molinski, T. F.; Barrows, L. R.;
3
) d
Ireland, C. M. J. Am. Chem. Soc. 1991, 113, 4709; (b)
Litaudon, M.; Trigalo, F.; Martin, M.-T.; Frappier, F.;
Guyot, M. Tetrahedron 1994, 50, 5323; (c) Litaudon, M.;
Guyot, M. Tetrahedron Lett. 1991, 32, 911; (d) Behar, V.;
Danishefsky, S. J. J. Am. Chem. Soc. 1993, 115, 7018; (e)
Ford, P. W.; Davidson, B. S. J. Org. Chem. 1993, 58, 4522;
16.6, 29.1, 56.6, 114.2, 132.3, 132.5, 141.6, 145.2, 159.14;
IR (KBr) 2960, 2924, 1576, 1543, 1460, 1263, 1236, 1222,
À1
+
1177, 831, 785 cm ; MS (70 eV) m/z 294 (M ); Anal.
Calcd for C
H, 3.42.
9 5
H10OS : C, 36.70; H, 3.42. Found: C, 36.65;
6-Ethyl-9-hydroxybenzopentathiepin (HBPT):
Pale yellow crystals; mp 70.0–70.5 °C;
1
(
f) Ford, P. W.; Narbut, M. R.; Belli, J.; Davidson, B. S. J.
H
NMR
Org. Chem. 1994, 59, 5955; (g) Ishii, A.; Ohishi, M.;
Matsumoto, K.; Takayanagi, T. Org. Lett. 2006, 8, 91.
. (a) Sato, R.; Saito, S.; Chiba, H.; Goto, T.; Saito, M.
Chem. Lett. 1986, 349; (b) Sato, R.; Saito, H.; Chiba, T.;
Goto, T.; Saito, M. Bull. Chem. Soc. Jpn. 1988, 61, 1647;
(400 MHz, CDCl ) d 1.18 (t, J = 7.5 Hz, 3H, CH ), 2.76
3
3
(dq, J = 7.5, 14.0 Hz, 1H, CH ), 2.91 (dq, J = 7.5,
2
5
14.0 Hz, 1H, CH
2
), 6.45 (s, 1H, OH), 6.97, (d,
J = 8.4 Hz, 1H, ArH), 7.15 (d, J = 8.4 Hz, 1H, ArH);
1
3
C NMR (101 MHz, CDCl
3
) d 16.68, 29.12, 118.66,
(
c) Sato, R.; Kimura, T.; Goto, T.; Saito, M. Tetrahedron
128.55, 133.55, 141.67, 143.46, 156.11; IR (KBr)
À1
+
Lett. 1988, 29, 6291–6294; (d) Sato, R.; Kimura, T.; Goto,
T.; Saito, M.; Kabuto, C. Tetrahedron Lett. 1989, 30,
3422 cm (OH); MS (70 eV) 280 m/z (M ); Anal. Calcd
for C OS : C, 34.26; H, 2.87. Found: C, 34.10; H, 2.87.
8
H
8
5
3
456.
4-Ethyl-1-hydroxy-2,3,5,6-tetrabromobenzene (8): Color-
1
6
7
. (a) Sato, R.; Ohyama, T.; Kawagoe, T.; Baba, M.;
Nakajo, S.; Kimura, T.; Ogawa, S. Heterocycles 2001,
less crystals; mp 111.0 °C; H NMR (400 MHz, CDCl )
3
d 1.15 (t, J = 7.4 Hz, 3H, CH ), 3.19 (q, J = 7.4 Hz, 2H,
3
13
55, 145; (b) Searle, P. A.; Molinski, T. F. J. Org. Chem.
CH
2
), 6.10 (s, 1H, OH); C NMR (101 MHz, CDCl
3
) d
À1
1994, 59, 6600–6605.
12.4, 34.1, 113.3, 126.1, 137.9, 149.4; IR (KBr) 3425 cm
+
. (a) Seung, D.-Y; Jung, W.-C; Do, C.-H.; Moon, S.-I.
The Law Offices of Eugene M Lee, PLLC), US, 2002/
55039, 2002; [Chem. Abstr. 2002, 136, 343388]; (b)
(OH); MS (70 eV) m/z 422 (M ÀOH); Anal. Calcd for
(
0
8 6 4
C H Br O: C, 21.95; H, 1.38. Found: C, 21.95; H, 1.45.
6-Ethyl-10-hydroxy[1,2,3]trithiolo[4,5-h]benzopentathiepin
1
Astruc, D. Acc. Chem. Res. 1986, 19, 377–383; (c) Mayor,
M.; Lehn, J.-M.; Fromm, K. M.; Fenske, D. Angew.
Chem., Int. Ed. 1997, 36, 2370–2372; (d) Mayor, M.; Lehn,
J.-M. J. Am. Chem. Soc. 1999, 121, 11231–11232; (e)
Greve, D. R.; Geister, T.; Petersen, J. S.; Bjornholm, T.
Synth. Met. 1999, 102, 1533–1534.
(H–TBPT): Red powder; mp 134.0–135.0 °C; H NMR
3 3
(400 MHz, CDCl ) d 1.17 (t, J = 7.4 Hz, 3H, CH ), 2.89
(dq, J = 7.4, 14.8 Hz, 1H, CH
2
), 2.99 (dq, J = 7.4,
13
14.8 Hz, 1H, CH ),6.75 (s, 1H, OH); C NMR (101
2
MHz, CDCl ) d 22.8, 37.2, 122.0, 123.9, 131.1, 134.9,
3
À1
138.5, 141.3; IR (KBr) 3421, 3401 cm (OH); MS (70 eV)
+
8
. (a) Ogawa, S.; Yomoji, N.; Chida, S.; Sato, R. Chem. Lett.
m/z 374 (M ); Anal. Calcd for C
8
H
6
OS
8
: C, 25.65; H,
1994, 507; (b) Ogawa, S.; Kikuchi, T.; Sasaki, A.; Chida,
1.61. Found: C, 25.61; H, 1.83.
S.; Sato, R. Tetrahedron Lett. 1994, 35, 5469.
. 6-Ethyl-9-methoxybenzopentathiepin (6):
10. (a) Sato, R.; Utsumi, Y.; Nakajo, S.; Ogawa, S.; Kawai, Y.
Heterocycles 2001, 55, 851–854; (b) Ogawa, S.; Yoshim-
ura, S.; Nagahora, N.; Kawai, Y.; Mikata, Y.; Sato, R.
Chem. Commun. 2002, 1918–1919.
9
1
Yellow crystals; mp 91.0–92.0 °C; H NMR (400 MHz,
CDCl ) d 1.18 (t, J = 7.6 Hz, 3H, CH ), 2.82 (dq, J = 7.6,
3
3
1
3.9 Hz, 1H, CH
2
), 2.93 (dq, J = 7.6, 13.9 Hz, 1H, CH
2
),
11. Ogawa, S.; Saito, S.; Kikuchi, T.; Kawai, Y.; Niizuma, S.;
Sato, R. Chem. Lett. 1995, 321–322.
3
3.87 (s, 3H, OCH ), 6.91, (d, J = 8.5 Hz, 1H, ArH), 7.20