202
N. Misawa et al. / Tetrahedron 61 (2005) 195–204
4.4. Purification and identification of the products
(C-5), 120.0 (C-40), 120.4 (C-4), 120.80(C-50), 122.1 0(C-6),
128.2 (C-3a), 136.3 (C-7a), 141.0 (C-2 ), 143.4 (C-1 ).
The liquid phase (2,000 ml) which had been obtained by the
procedure just described was concentrated in vacuo and then
extracted with ethyl acetate (EtOAc) (500 ml!2). The
organic layer was concentrated in vacuo, and analyzed by
thin-layer chromatography (TLC) on silica gel [0.25 mm
E. Merck silica gel plates (60F-254)]. The formed products
were purified by column chromatography on silica gel [20!
250 mm2, Silica Gel 60 (Merck)]. Their structures were
analyzed by mass spectrometry (MS) [MS (EI) and HRMS
(EI), Jeol AX-505W instrument] and nuclear magnetic
resonance (NMR) (400 MHz, Bruker AMX400 instrument).
4.4.4. 3-Benzoxazol-2-ylbenzene-1,2-diol (5; the product
converted from 2-phenylbenzoxazole). The crude extract
(155.0 mg) was subjected to column chromatography
(CH2Cl2–MeOHZ30:1) to yield 76.8 mg of 5. MS (EI) m/z
227 (MC). HRMS (EI) calcd for C13H9NO3 (MC),
1
227.0582; found, 227.0583. H NMR (DMSO-d6) d: 6.88
(dd, 1H, JZ7.8, 7.8 Hz), 7.03 (dd, 1H, JZ1.8, 7.8 Hz), 7.45
(2H), 7.47 (dd, 1H, JZ1.8, 7.8 Hz), 7.82 (dd, 1H, JZ1.4,
8.0 Hz), 7.84 (1H). 13C NMR (DMSO-d6) d: 110.1 (C-7),
110.5 (C-30), 117.3 (C-40), 119.3 (C-4), 119.5 (C-60), 1190.9
(C-50), 125.4 (C-5), 125.8 (C-6), 139.4 (C-3a), 146.2 (C-1 ),
146.9 (C-20), 148.7 (C-7a), 162.8 (C-2).
4.4.1. 3-Morpholin-4-ylbenzene-1,2-diol (1; the product
converted from 1-phenylmorpholine). The crude extract
(86.5 mg) was subjected to column chromatography
(CH2Cl2–MeOHZ30:1) to yield 30.0 mg of 1. MS (EI) m/z
195 (MC). HRMS (EI) calcd for C10H13NO3 (MC),
4.4.5. 3-Benzothiazol-2-ylbenzene-1,2-diol (6; the pro-
duct converted from 2-phenylbenzothiazole). The crude
extract (165.0 mg) was subjected to column chromato-
graphy (hexane–EtOAcZ20:1) to yield 73.5 mg of 6. MS
(EI) m/z 243 (MC). HRMS (EI) calcd for C13H9NO2S
(MC), 243.0355; found, 243.0350. 1H NMR (DMSO-d6) d:
6.82 (dd, 1H, JZ7.2, 7.2 Hz), 6.96 (dd, 1H, JZ1.2, 7.2 Hz),
7.44 (dd, 1H, JZ7.3, 7.3 Hz), 7.53 (dd, 1H, JZ7.3, 8.0 Hz),
7.54 (dd, 1H, JZ1.2, 7.2 Hz), 8.05 (d, 1H, JZ8.0 Hz). 130C
NMR (DMSO-d6) d: 117.7 (C-60), 118.4 (C-30), 118.5 (C-4 ),
119.5 (C-50), 122.0 (C-4), 122.1 (C-7), 125.2 (C-6),
126.6 (C-5), 133.9 (C-7a), 145.7 (C-20), 146.3 (C-10),
151.4 (C-3a), 166.4 (C-2).
1
195.0896; found, 195.0899. H NMR (DMSO-d6) d: 2.87
(m, 4H), 3.71 (m, 4H), 6.38 (dd, 1H, JZ1.4, 7.8 Hz), 6.49
(dd, 1H, JZ1.4, 8.1 Hz), 6.55 (dd, 1H, JZ7.8, 8.1 Hz). 13C
NMR (DMSO-d6) d: 50.8 (C-2, C-6), 66.4 (C-3, C-5), 109.4
(C-40), 110.5 (C-60), 118.7 (C-50), 138.0 (C-20), 140.8 (C-30),
145.5 (C-10).
4.4.2. 3-(2-Pyridyl)benzene-1,2-diol (2; the product
converted from 2-phenylpyridine). The crude extract
(130.0 mg) was subjected to column chromatography
(hexane–EtOAcZ10:1) to yield 26.0 mg of 2. MS (EI) m/z
187 (MC). HRMS (EI) calcd for C11H9NO2 (MC),
4.4.6. 3-(2,3-Dihydroxyphenyl)indan-1-one (7; the pro-
duct converted from 3-phenyl-1-indanone). The crude
extract (148.0 mg) was subjected to column chromato-
graphy (hexane–EtOAcZ2:1) to yield 70.3 mg of 7. MS
(EI) m/z 240 (MC). HRMS (EI) calcd for C15H12O3 (MC),
1
187.0633; found, 187.0633. H NMR (CDCl3) d: 6.92 (dd,
1H, JZ1.2, 7.9 Hz), 6.75 (dd, 1H, JZ7.9, 7.9 Hz), 7.18 (dd,
1H, JZ5.3, 5.6 Hz), 7.27 (dd, 1H, JZ1.2, 7.9 Hz), 7.76
(ddd, 1H, JZ1.6, 5.3, 7.9 Hz), 7.83 (d, 1H, JZ7.9 Hz), 8.42
(dd, 1H, JZ1.6, 5.6 Hz).013C NMR (CDCl3) d: 115.5 (C-60),
116.8 (C-40), 118.1 (C-3 ), 118.6 (C-50), 119.1 (C-3), 1210.6
(C-5), 137.9 (C-4), 145.6 (C-6), 146.0 (C-10), 147.4 (C-2 ),
157.6 (C-2).
1
240.0786; found, 240.0786. H NMR (DMSO-d6) d: 2.60
(dd, 1H, JZ3.4, 18.9 Hz), 3.09 (dd, 1H, JZ8.2, 18.9 Hz),
4.80 (dd, 1H, JZ3.4, 8.2 Hz), 6.34 (dd, 1H, JZ1.9, 7.7 Hz),
6.52 (dd, 1H, JZ7.5, 7.7 Hz), 6.66 (dd, 1H, JZ1.9, 7.5 Hz),
7.28 (dd, 1H, JZ0.8, 7.6 Hz), 7.41 (ddd, 1H, JZ0.8, 7.6,
7.6 Hz), 7.60 (dd, 1H, JZ7.6, 7.6 Hz), 7.65 (d, 1H, JZ
7.6 Hz). 13C NMR (DMSO-d6) d: 39.5 (C-3), 44.3 (C-2),
113.8 (C-60), 118.7 (C-40), 118.9 (C-50), 122.6 (C-7), 1260.5
(C-4), 127.4 (C-6), 130.1 (C-30), 136.3 (C-7a), 143.2 (C-2 ),
145.2 (C-10), 158.2 (C-3a), 205.8 (C-1).
4.4.3. 2-Phenylindol-5-ol (3) and 2-indol-2-ylbenzene-
1,2-diol (4) (the products converted from 2-phenylin-
dole). The crude extract (191.0 mg) was subjected to
column chromatography (hexane–EtOAcZ3:1) to yield
6.8 mg of 3 and 9.0 mg of 4.
3. MS (EI) m/z 209 (MC). HRMS (EI) calcd for C14H11NO
(MC), 209.0841; found, 209.0857. 1H NMR (DMSO-d6) d:
6.61 (dd, 1H, JZ2.0, 8.8 Hz), 6.70 (s, 1H), 6.82 (d, 1H, JZ
2.0 Hz), 7.17 (d, 1H, JZ8.8 Hz), 7.27 (dd, 1H, JZ7.7,
7.7 Hz), 7.42 (dd, 2H, JZ7.7, 7.7 Hz), 7.79 (d, 2H, JZ
7.7 Hz), 8.70 (brs, 1H), 11.20 (brs, 1H). 13C NMR (DMSO-
d6) d: 98.0 (C-3), 103.7 (C-4), 111.7 (C-7), 112.0 (C-6),
124.8 (C-20, C-60), 127.2 (C-40), 128.9 (C-30, C-50), 129.4
(C-3a), 131.7 (C-7a), 132.5 (C-10), 137.9 (C-2), 150.9 (C-5).
4.4.7. 3-(2-Quinolyl)benzene-1,2-diol (8; the product
converted from 2-phenylquinoline). The crude extract
(210.0 mg) was subjected to column chromatography
(hexane–EtOAcZ10:1) to yield 31.3 mg of 8. MS (EI)
m/z 237 (MC). HRMS (EI) calcd for C15H11NO2 (MC),
1
237.0790; found, 237.0788. H NMR (DMSO-d6) d: 6.78
(dd, 1H, JZ7.9, 7.9 Hz), 7.64 (d, 1H, JZ7.9 Hz), 7.65 (dd,
1H, JZ7.2, 7.2 Hz), 7.84 (dd, 1H, JZ7.2, 8.0 Hz), 8.03 (d,
1H, JZ8.0 Hz), 8.04 (d, 1H, JZ7.2 Hz), 8.33 (d, 1H, JZ
8.7 Hz), 8.56 (d, 1H, JZ8.7 Hz). 13C NMR (DMSO-d6) d:
117.5 (C-60), 117.9 (C-40), 118.2 (C-3), 118.3 (C-50), 118.7
(C-30), 126.3 (C-4a), 126.8 (C-8), 127.0 (C-6), 128.0 (C-5),
131.0 (C-7), 138.4 (C-4), 143.9 (C-8a), 146.6 (C-10), 149.1
(C-20), 158.2 (C-2).
4. MS (EI) m/z 225 (MC). HRMS (EI) calcd for C14H11NO2
(MC) 225.0790; found, 225.0786. 1H NMR (CDCl3) d: 6.74
(dd, 1H, JZ1.6, 7.8 Hz), 6.80 (s, 1H), 6.80 (dd, 1H, JZ7.8,
7.9 Hz), 7.06 (dd, 1H, JZ7.8, 7.8 Hz), 7.13 (dd, 1H, JZ7.8,
7.8 Hz), 7.25 (dd, 1H, JZ1.6, 7.8 Hz), 7.36 (d, 1H, JZ
7.8 Hz), 7.58 (d, 1H, JZ7.8 Hz). 13C NMR (CDCl3) d:
100.0 (C-3), 111.0 (C-7), 114.1 (C-60), 119.1 (C-30), 120.0
4.4.8. 1-[(2,3-Dihydroxyphenyl)methyl]piperidin-4-one
(9; the product converted from 1-benzylpiperidone).