Page 5 of 7
The Journal of Organic Chemistry
1.2 Hz, 1H), 7.79 (s, 1H), 7.55ꢀ7.52 (m, 2H), 7.51ꢀ7.43 (m, 3H),
3ꢀ(4ꢀ(tertꢀButyl)phenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3ae) (43.5 mg,
74%) H NMR (300 MHz, Chloroformꢀd) δ 8.61ꢀ8.51 (m, 1H),
7.38ꢀ7.26 (m, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 178.2,
137.5, 136.8, 136.8, 135.5, 132.8, 131.2, 129.5, 128.9, 128.3, 128.0,
127.78, 126.5. GCꢀMS (EIꢀ70 eV): m/z(%)=238 (100 ), 136 (55),
108 (40).
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7
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7.79 (s, 1H), 7.56ꢀ7.44 (m, 3H), 7.43ꢀ7.35 (m, 4H), 1.28 (s, 9H).
13C{1H} NMR (75 MHz, CDCl3) δ 178.4, 151.0, 136.8, 136.7,
134.9, 134.5, 132.8, 131.1, 129.5, 128.6, 127.7, 126.5, 125.3, 34.6,
31.3. GCꢀMS (EIꢀ70 eV): m/z(%)=294 (36), 279 (100), 136 (20),
115 (27), 108 (25). HRMS (ESI): calcd. for C19H19OS [M + H]+,
295.1157; found 295.1154.
6ꢀMethylꢀ3ꢀphenylꢀ4Hꢀthiochromenꢀ4ꢀone (3ba)1 (36.8 mg, 73%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.48 (dp, J = 2.3, 0.8 Hz,
1H), 7.90 (s, 1H), 7.59ꢀ7.53 (m, 3H), 7.50ꢀ7.35 (m, 4H), 2.53 (s,
3H). 13C{1H} NMR (75 MHz, CDCl3) δ 178.2, 138.1, 137.7,
136.6, 135.4, 133.8, 132.7, 132.6, 129.2, 128.9, 128.2, 127.9, 126.4,
21.4. GCꢀMS (EI, 70 eV): m/z (%)=252 (100), 150 (30), 121
(39).
3ꢀ(4ꢀMethoxyphenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3af) (41.8 mg,
1
78%) H NMR (300 MHz, Chloroformꢀd) δ 8.61ꢀ8.51 (m, 1H),
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7.76 (s, 1H), 7.60ꢀ7.33 (m, 5H), 6.97ꢀ6.81 (m, 2H), 3.77 (s, 3H).
13C{1H} NMR (75 MHz, CDCl3) δ 178.4, 159.5, 136.8, 136.3,
134.4, 132.8, 131.1, 130.1, 129.9, 129.5, 127.7, 126.5, 113.7, 55.4.
GCꢀMS (EIꢀ70 eV): m/z(%)=268 (100), 136 (36), 117 (24), 108
(50), 89 (37), 63 (25). HRMS (ESI): calcd. for C16H13O2S [M +
H]+, 269.0637; found 269.0641.
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16
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24
25
26
27
28
29
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34
35
36
37
38
39
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43
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6ꢀMethoxyꢀ3ꢀphenylꢀ4Hꢀthiochromenꢀ4ꢀone (3ca) (43.4 mg,
1
81%) H NMR (300 MHz, Chloroformꢀd) δ 8.12 (d, J = 2.9 Hz,
1H), 7.93 (s, 1H), 7.62ꢀ7.37 (m, 6H), 7.28 (dd, J = 8.8, 2.9 Hz,
1H), 3.96 (s, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ 177.8, 159.6,
137.7, 135.7, 135.4, 134.2, 129.0, 128.8, 128.2, 127.9, 127.8, 121.8,
109.7, 55.7. GCꢀMS (EI, 70 eV): m/z (%)=268 (100), 123 (25).
HRMS (EI): calcd. for C16H12O2S [M]+ 268.0552, found 268.0550.
6ꢀFluoroꢀ3ꢀphenylꢀ4Hꢀthiochromenꢀ4ꢀone (3da) (33.8 mg, 66%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.23 (ddd, J = 9.7, 2.9, 0.4
Hz, 1H), 7.83 (s, 1H), 7.55 (ddd, J = 8.8, 4.9, 0.5 Hz, 1H), 7.48ꢀ
7.41 (m, 2H), 7.39ꢀ7.26 (m, 4H). 13C{1H} NMR (75 MHz,
CDCl3) δ 177.3, 162.2 (d, J=249.75 Hz) 137.1, 135.9, 135.7, 134.7
(d, J=6.82 Hz), 132.2 (d, J=2.24 Hz), 128.9, 128.7 (d, J=7.54 Hz),
128.3, 128.2, 120.2 (d, J=24.33 Hz), 115.0 (d, J=22.88 Hz). 19F
NMR (282 MHz, CDCl3) δ ꢀ117.27. GCꢀMS (EIꢀ70 eV):
m/z(%)=256 (100), 154 (25), 126 (33). HRMS (EI): calcd. for
C15H9OFS [M]+ 256.0353, found 256.0354.
3ꢀ(3ꢀFluorophenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3ag) (36.4 mg, 71%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.56 (ddd, J = 7.7, 1.0 Hz,
1H), 7.83 (s, 1H), 7.63ꢀ7.42 (m, 3H), 7.35ꢀ7.19 (m, 3H), 7.06ꢀ6.92
(m, 1H). 13C{1H} NMR (75 MHz, CDCl3) δ 177.9, 162.6 (d,
J=245.85 Hz), 139.4 (d, J=8.04 Hz), 136.6, 136.2, 135.5, 132.7,
131.4, 129.7 (d, J=8.64 Hz), 129.5, 127.9, 126.5, 124.6 (d, J=2.92
19
Hz), 116.1 (d, J=22.56 Hz), 114.9 (d, J=21.09 Hz). F NMR (282
MHz, CDCl3) δ ꢀ113.32. GCꢀMS (EIꢀ70 eV): m/z(%)=256 (100),
136 (67), 120 (20), 108 (48). HRMS (EI): calcd. for C15H9OFS
[M]+ 256.0353, found 256.0349.
3ꢀ(4ꢀChlorophenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3ah) (37.5 mg, 69%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.65 (ddd, J = 7.8, 1.0 Hz,
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1H), 7.91 (s, 1H), 7.69ꢀ7.56 (m, 3H), 7.54ꢀ7.39 (m, 4H). C{1H}
6ꢀChloroꢀ3ꢀphenylꢀ4Hꢀthiochromenꢀ4ꢀone (3ea)11 (37.5 mg, 66%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.54 (ddd, J = 1.6, 1.2, 0.5
Hz, 1H), 7.81 (s, 1H), 7.52ꢀ7.50 (m, 2H), 7.47ꢀ7.42 (m, 2H), 7.40ꢀ
7.30 (m, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ 177.1, 137.0,
136.8, 135.4, 134.9, 134.4, 133.9, 131.7, 129.1, 128.9, 128.3, 128.3,
128.0. GCꢀMS (EIꢀ70 eV): m/z(%)=272 (100), 170 (23), 142
(29), 102 (24).
NMR (75 MHz, CDCl3) δ 178.0, 136.7, 135.8, 135.7, 135.6, 134.0,
132.6, 131.4, 130.3, 129.5, 128.5, 127.9, 126.6. GCꢀMS (EIꢀ70 eV):
m/z(%)=272 (82), 136 (100), 108 (67). HRMS (EI): calcd. for
C15H9OClS [M]+ 272.0057, found 272.0055.
3ꢀ(3ꢀChlorophenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3ai) (39.7 mg, 73%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.61ꢀ8.51 (m, 1H), 7.83 (s,
1H), 7.64ꢀ7.43 (m, 4H), 7.43ꢀ7.20 (m, 3H). 13C{1H} NMR (75
MHz, CDCl3) δ 177.9, 139.1, 136.6, 136.2, 135.4, 134.1, 132.7,
131.4, 129.5, 129.5, 129.0, 128.1, 127.9, 127.2, 126.6. GCꢀMS (EIꢀ
70 eV): m/z(%)=272 (100), 136 (75), 108 (48), 69 (24). HRMS
(EI): calcd. for C15H9OClS [M]+ 272.0057, found 272.0054.
3ꢀ(4ꢀBromophenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3aj) (36.1 mg, 57%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.64 (dt, J = 7.8, 1.2 Hz,
3ꢀ(pꢀTolyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3ab) (37.8 mg, 75%) 1H
NMR (300 MHz, Chloroformꢀd) δ 8.61ꢀ8.50 (m, 1H), 7.77 (s,
1H), 7.57ꢀ7.41 (m, 3H), 7.40ꢀ7.30 (m, 2H), 7.22ꢀ7.10 (m, 2H),
2.31 (s, 3H). 13C{1H} NMR (75 MHz, CDCl3) δ 178.3, 137.9,
136.8, 136.7, 134.9, 134.6, 132.8, 131.1, 129.5, 128.9, 128.8, 127.7,
126.5, 21.3. GCꢀMS (EIꢀ70 eV): m/z(%)=252 (100), 136 (33),
115 (59), 108 (44). HRMS (EI): calcd. for C16H12OS [M]+
252.0603, found 252.0601.
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1H), 7.90 (s, 1H), 7.72ꢀ7.50 (m, 5H), 7.50ꢀ7.35 (m, 2H). C{1H}
NMR (75 MHz, CDCl3) δ 177.9, 136.7, 136.3, 135.8, 135.6, 132.6,
131.4, 130.6, 129.5, 127.9, 126.6, 122.3. GCꢀMS (EIꢀ70 eV):
m/z(%)=317 (100), 136 (85), 108 (61), 101 (27), 75 (29). HRMS
(EI): calcd. for C15H9OBrS [M]+ 315.9552, found 315.9549;
HRMS (EI): calcd. for C15H9O81BrS [M]+ 317.9532, found
317.9534.
3ꢀ(oꢀTolyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3ac) (31.8 mg, 63%) 1H
NMR (300 MHz, Chloroformꢀd) δ 8.70ꢀ8.60 (m, 1H), 7.79 (s,
13
1H), 7.73ꢀ7.51 (m, 3H), 7.39ꢀ7.15 (m, 4H), 2.24 (s, 3H). C{1H}
NMR (75 MHz, CDCl3) δ 178.0, 138.1, 137.6, 137.1, 136.9, 135.9,
132.5, 131.2, 130.1, 129.8, 129.5, 128.3, 127.8, 126.6, 125.8, 20.0.
GCꢀMS (EIꢀ70 eV): m/z(%)=252 (45), 235 (100), 115 (69), 108
(39). HRMS (EI): calcd. for C16H12OS [M]+ 252.0603, found
252.0604.
3ꢀ(4ꢀ(Trifluoromethyl)phenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone
(3ak)
1
(41.0 mg, 67%) H NMR (300 MHz, Chloroformꢀd) δ 8.61ꢀ8.51
(m, 1H), 7.86 (s, 1H), 7.63ꢀ7.42 (m, 7H). 13C{1H} NMR (75
MHz, CDCl3) δ 177.9, 140.9, 136.7, 136.6, 135.4, 132.6, 131.5,
130.0 (q, J=32.26 Hz)., 129.5, 129.3, 128.1, 126.6, 125.2, 123.8 (q,
3ꢀ(2,4ꢀDimethylphenyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3ad) (32.5 mg,
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61%) H NMR (300 MHz, Chloroformꢀd) δ 8.69ꢀ8.59 (m, 1H),
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7.78 (s, 1H), 7.71ꢀ7.53 (m, 3H), 7.24ꢀ7.08 (m, 2H), 7.03 (dp, J =
2.0, 0.6 Hz, 1H), 2.36 (s, 3H), 2.19 (s, 3H). 13C{1H} NMR (75
MHz, CDCl3) δ 178.1, 138.2, 137.4, 137.2, 135.7, 135.2, 133.7,
132.5, 131.2, 130.4, 129.9, 129.4, 129.0, 127.7, 126.6, 20.9, 19.5.
GCꢀMS (EIꢀ70eV): m/z(%)=266 (60), 249 (100), 234 (29), 128
(35), 115 (34), 108 (41). HRMS (ESI): calcd. for C17H15OS [M
+H]+, 267.0844; found 267.0840.
J = 265.6 Hz). F NMR (282 MHz, CDCl3) δ ꢀ62.57. GCꢀMS (EI,
70 eV): m/z (%)=306 (100), 237 (27), 151 (20), 136 (42), 108
(41), 69 (50). HRMS (EI): calcd. for C16H9OF3S [M]+ 306.0321,
found 306.0313.
3ꢀ(Thiophenꢀ3ꢀyl)ꢀ4Hꢀthiochromenꢀ4ꢀone (3al) (30.7 mg, 63%)
1H NMR (300 MHz, Chloroformꢀd) δ 8.63ꢀ8.53 (m, 1H), 7.97 (s,
1H), 7.85 (dd, J = 3.0, 1.4 Hz, 1H), 7.59ꢀ7.40 (m, 3H), 7.40ꢀ7.23
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