Z.-L. Wang et al. / Tetrahedron 70 (2014) 3788e3792
3791
CDCl3)
d
190.8, 170.6, 146.1, 130.4, 129.6, 128.7, 91.6, 53.7, 21.9.
NMR (100 MHz, CDCl3)
d
184.9, 170.2, 136.9, 136.8, 136.6, 128.8, 92.3,
HRMS(EI) calcd for C11H10O4 [M]þ 206.0579, found: 206.0575.
53.9. HRMS(EI) calcd for C8H6O4S [M]þ 197.9987, found: 197.9982.
4.3.4. Compound 2d.9o A yellowish solid (8 h, 64%, yield). Mixture
of ketone and corresponding hydrated form in ratio of 1:5. Rf¼0.25
(petroleum ether/ethyl acetate¼4:1). Mp: 81e83 ꢀC. Ketone: 1H
4.3.10. Compound 2j. A yellowish solid (12 h, 46%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 1:10. Rf¼0.15
(petroleum ether/ethyl acetate¼3:1). Mp: 86e88 ꢀC. Ketone: 1H
NMR (400 MHz, CDCl3)
d
7.97 (d, J¼9.0 Hz, 2H), 6.99 (d, J¼9.0 Hz,
NMR (400 MHz, CDCl3)
d
7.88 (d, J¼4.2 Hz,1H), 7.07 (d, J¼4.2 Hz,1H),
2H), 3.93 (s, 3H), 3.89 (s, 3H). 13C NMR (100 MHz, CDCl3)
183.6, 165.6, 161.2, 132.7, 124.5, 114.6, 55.7, 53.4. Hydrate: 1H NMR
(400 MHz, CDCl3)
8.06 (d, J¼9.0 Hz, 2H), 6.92 (d, J¼9.0 Hz, 2H),
5.56 (s, 2H), 3.86 (s, 3H), 3.72 (s, 3H). 13C NMR (100 MHz, CDCl3)
189.7, 170.7, 164.8, 132.9, 124.0, 114.2, 91.6, 55.6, 53.6.
d
188.1,
3.97 (s, 3H). Hydrate: 1H NMR (400 MHz, CDCl3)
1H), 6.99 (d, J¼4.2 Hz,1H), 7.12e7.14 (m,1H), 5.30 (s, 2H), 3.79 (s, 3H).
d
7.75 (d, J¼4.2 Hz,
d
13C NMR (100 MHz, CDCl3):
d 183.9, 169.9, 142.9, 136.3, 135.2, 128.3,
92.1, 54.0. HRMS(EI) calcd for C8H5ClO4S [M]þ 231.9597, found:
231.9596.
d
4.3.5. Compound 2e. A white solid (9 h, 85%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 1:7. Rf¼0.20
(petroleum ether/ethyl acetate¼4:1). Mp: 86e88 ꢀC. Ketone: 1H
4.3.11. Compound 2k.17 A yellowish oil (8 h, 65%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 1:3. Rf¼0.20
(petroleum ether/ethyl acetate¼4:1). Ketone: 1H NMR (400 MHz,
NMR (400 MHz, CDCl3)
d
7.96 (d, J¼8.7 Hz, 2H), 7.53 (d, J¼8.7 Hz,
CDCl3)
d
7.89 (dd, J¼7.0, 1.5 Hz, 2H), 7.71e7.66 (m, 1H), 7.54e7.52
2H), 3.96 (s, 3H). 13C NMR (100 MHz, CDCl3)
142.5, 131.6, 131.4, 128.8, 53.6. Hydrate: 1H NMR (400 MHz, CDCl3)
8.03 (d, J¼8.7 Hz, 2H), 7.46 (d, J¼8.7 Hz, 2H), 5.34 (s, 2H), 3.75
d
188.5, 182.8, 160.9,
(m, 2H), 2.54 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 197.5, 193.6,187.2,
135.4, 132.1, 129.6, 129.3, 24.7. Hydrate: 1H NMR (400 MHz, CDCl3)
d
d
8.02 (dd, J¼7.0, 1.5 Hz, 2H), 7.65e7.59 (m, 1H), 7.49e7.44 (m, 2H),
(s, 3H). 13C NMR (100 MHz, CDCl3)
d
190.4, 170.2, 141.5, 131.6, 129.6,
5.57 (s, 2H), 2.14 (s, 3H). 13C NMR (100 MHz, CDCl3)
135.0, 131.5, 130.4, 129.1, 95.1, 23.8.
d 202.8, 193.4,
129.3, 91.8, 53.8. HRMS(EI) calcd for C10H7ClO4 [M]þ 226.0033,
found: 226.0026.
4.3.12. Compound 2l.10c A yellowish solid (16 h, 92%, yield). Mixture
of ketone and corresponding hydrated form in ratio of 10:1. Rf¼0.25
(petroleum ether/ethyl acetate¼6:1). Mp: 71e73 ꢀC. Ketone: 1H
4.3.6. Compound 2f.9o A white solid (8 h, 64%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 1:10. Rf¼0.20
(petroleum ether/ethyl acetate¼4:1). Mp: 86e88 ꢀC. Ketone: 1H
NMR (400 MHz, CDCl3)
d 8.10e8.06 (m, 4H), 7.76e7.67 (m, 2H),
NMR (400 MHz, CDCl3)
d
7.87 (d, J¼8.6 Hz, 2H), 7.69 (d, J¼8.6 Hz, 2H),
7.59e7.51 (m, 4H). 13C NMR (100 MHz, CDCl3)
132.1, 130.2, 129.1. Hydrate: 1H NMR (400 MHz, CDCl3)
(m, 4H), 7.56e7.47 (m, 2H), 7.39e7.31 (m, 4H), 5.96 (s, 2H). 13C NMR
(100 MHz, CDCl3) 194.1, 134.6, 132.0, 130.2, 128.8, 94.1.
d
192.4, 188.3, 135.4,
7.96e7.92
3.96 (s, 3H). 13C NMR (100 MHz, CDCl3)
d
187.9, 182.0, 160.1, 132.6,
d
131.4, 53.6. Hydrate: 1H NMR (400 MHz, CDCl3)
d
7.94 (d, J¼8.7 Hz,
2H), 7.62 (d, J¼8.7 Hz, 2H), 5.40 (s, 2H), 3.74 (s, 3H). 13C NMR
d
(100 MHz, CDCl3) d 190.7, 170.1, 132.3, 131.6, 130.4, 130.0, 91.8, 53.8.
4.3.13. Compound 2m.18 A yellowish oil (9 h, 55%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 5:2. Rf¼0.22
(petroleum ether/ethyl acetate¼6:1). Ketone: 1H NMR (400 MHz,
4.3.7. Compound 2g. A white solid (8 h, 77%, yield). Mixture of ke-
tone and corresponding hydrated form in ratio of 1:10. Rf¼0.20
(petroleum ether/ethyl acetate¼4:1). Mp: 75e77 ꢀC. Ketone: 1H
CDCl3)
d
8.06e8.00 (m, 2H), 7.69e7.63 (m,1H), 7.51 (t, J¼7.8 Hz, 2H),
NMR (400 MHz, CDCl3)
d
8.13 (t, J¼1.7 Hz,1H), 7.92e7.89 (m,1H), 7.81
3.14 (s, 3H), 3.06 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 192.1, 185.6,
(ddd, J¼8.0,1.9,1.0 Hz,1H), 7.41 (t, J¼7.9 Hz,1H), 3.96 (s, 3H).13C NMR
165.5, 135.2, 131.9, 130.3, 128.9, 36.9, 34.5. Hydrate: 1H NMR
(100 MHz, CDCl3)
d
188.5,182.6,160.7,138.4,133.1,132.6,130.7,128.7,
(400 MHz, CDCl3) d 8.06e8.00 (m, 2H), 7.62e7.57 (m, 1H), 7.44
123.4, 53.7. Hydrate: 1H NMR (400 MHz, CDCl3)
d
8.22 (t, J¼1.8 Hz,
(t, J¼7.8 Hz, 2H), 6.00 (s, 2H), 2.97 (s, 3H), 2.76 (s, 3H). 13C NMR
1H), 8.00e7.98 (m, 1H), 7.73 (ddd, J¼8.0, 1.9, 1.0 Hz, 1H), 7.33
(100 MHz, CDCl3)
37.0.
d 194.1, 168.7, 134.7, 131.8, 130.0, 128.9, 91.3, 37.4,
(t, J¼7.9 Hz, 1H), 5.51 (s, 2H), 3.74 (s, 3H). 13C NMR (100 MHz, CDCl3)
d
190.5, 169.9, 137.5, 133.1, 133.0, 130.4, 128.8, 123.1, 92.0, 53.8.
HRMS(EI) calcd for C10H7BrO4 [M]þ 269.9528, found: 269.9524.
4.3.14. Compound 2n.17 A yellowish oil (16 h, 80%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 4:3. Rf¼0.15
(petroleum ether/ethyl acetate¼3:1). Ketone: 1H NMR (400 MHz,
4.3.8. Compound 2h. A yellowish solid (9 h, 88%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 1:6. Rf¼0.20
(petroleum ether/ethyl acetate¼2:1). Mp: 94e96 ꢀC. Ketone: 1H
CDCl3)
d 7.86e7.83 (m, 2H), 7.66e7.61 (m, 1H), 7.56e7.49 (m, 2H),
7.14 (s, 1H), 3.41e3.32 (m, 2H), 1.19 (t, J¼7.3 Hz, 3H). 13C NMR
NMR (400 MHz, CDCl3)
d
8.51 (s, 1H), 8.04 (dd, J¼8.7, 1.7 Hz, 1H),
(100 MHz, CDCl3) d 193.8, 188.9, 159.2, 135.3, 134.4, 129.5, 129.1,
7.96e7.94 (m, 2H), 7.87e7.85 (m, 1H), 7.70e7.52 (m, 2H), 3.98
(s, 3H). 13C NMR (100 MHz, CDCl3)
190.0, 183.5, 161.0, 136.7, 134.0,
132.3,130.1, 130.0, 129.4, 128.8, 128.0,127.4, 123.5, 53.6. Hydrate: 1H
NMR (400 MHz, CDCl3)
8.70 (s, 1H), 8.09 (dd, J¼8.7, 1.7 Hz, 1H),
7.96 (d, J¼6.7 Hz, 1H), 7.90e7.85 (m, 2H), 7.70e7.52 (m, 2H), 5.59
(s, 2H), 3.72 (s, 3H). 13C NMR (100 MHz, CDCl3)
191.4, 170.6, 136.2,
34.5, 14.3. Hydrate: 1H NMR (400 MHz, CDCl3)
d 8.12e8.08 (m, 2H),
d
7.57e7.52 (m, 1H), 7.42e7.37 (m, 2H), 6.68 (s, 1H), 5.86 (s, 2H),
3.26e3.18 (m, 2H), 1.02 (t, J¼7.3 Hz, 3H). 13C NMR (100 MHz, CDCl3)
d
d 194.4, 169.1, 132.1, 131.6, 130.5, 128.5, 93.2, 35.1, 14.2.
d
4.3.15. Compound 3.15 A colorless oil (8 h, 35%, yield). Rf¼0.25 (pe-
133.1, 132.3, 130.2, 129.5, 128.7, 128.6, 127.8, 127.1, 124.8, 92.0, 53.8.
HRMS(EI) calcd for C14H10O4 [M]þ 242.0579, found: 242.0576.
troleum ether/ethyl acetate¼20:1). 1H NMR (400 MHz, CDCl3)
d 8.13
(d, J¼7.5 Hz, 2H), 7.56 (t, J¼7.4 Hz, 1H), 7.45 (t, J¼7.7 Hz, 2H), 5.40
(s,1H), 4.15 (m, 2H),1.47e1.28 (m, 9H),1.15 (m, 6H), 0.98 (s, 3H), 0.81
4.3.9. Compound 2i. A yellowish solid (12 h, 87%, yield). Mixture of
ketone and corresponding hydrated form in ratio of 1:6. Rf¼0.15
(petroleum ether/ethyl acetate¼3:1). Mp: 72e74 ꢀC. Ketone: 1H NMR
(s, 3H). 13C NMR (100 MHz, CDCl3)
d 193.7, 168.2, 134.5, 133.7, 129.8,
128.5, 92.9, 61.7, 60.5, 60.0, 40.2, 40.0, 33.2, 32.5, 20.2, 20.2,17.0,14.0.
(400 MHz, CDCl3)
d
8.03 (dd, J¼3.9,1.0 Hz,1H), 7.89 (dd, J¼4.9,1.1 Hz,
4.3.16. Compound 5. A yellowish oil (53%, yield). Rf¼0.30 (petro-
1H), 7.21 (dd, J¼4.8, 4.1 Hz, 1H), 3.94 (s, 3H). 13C NMR (100 MHz,
leum ether/ethyl acetate¼20:1). 1H NMR (400 MHz, CDCl3)
d 8.17
CDCl3)
d
182.0,179.6,161.8,138.6,137.8,137.3,129.2, 53.4. Hydrate:1H
(dd, J¼8.3,1.0 Hz,1H), 8.07 (dd, J¼8.4,1.0 Hz,1H), 7.85e7.80 (m,1H),
7.78e7.73 (m, 1H), 5.46e5.35 (m, 2H), 4.07 (s, 3H), 3.29e3.23
(m, 2H), 2.20 (q, J¼6.8 Hz, 2H), 2.09e2.01 (m, 2H), 1.94e1.86
NMR (400 MHz, CDCl3)
d
7.94 (dd, J¼3.9, 1.1 Hz, 1H), 7.76 (dd, J¼4.9,
1.0 Hz, 1H), 7.13 (dd, J¼4.7, 4.1 Hz, 1H), 5.54 (s, 2H), 3.74 (s, 3H). 13
C