Molecules 2018, 23, 1728
8 of 14
acetate:hexanes, v/v) gave light yellow oil 4Da (194 mg, 83%); IR (neat) 3061 (w), 2955 (m) 2926 (s),
2857 (m), 1676 (s), 1583 (m), 1449 (m), 1401 (m), 1379 (w), 1295 (m), 1279 (m), 1248 (w), 1056 (w), 1000
(w), 841 (w) 784 (w), 722 (w) cm−1; 1H-NMR (400 MHz, CDCl3)
δ 0.73 (t, J = 7.2 Hz, 3H), 1.11–1.21 (m,
2H), 1.22–1.35 (m, 2H), 1.51–1.60 (m, 2H), 2.12 (s, 3H), 2.58 (dd, J = 11.6, 16.0 Hz, 1H), 2.83 (dd, J = 2.8
,
,
16.0 Hz, 1H), 3.21–3.29 (m, 1H), 6.88 (t, J = 7.6 Hz, 1H), 7.09 (qd, J = 0.8, 8.0 Hz, 1H), 7.78 (qd, J = 0.4
8.0 Hz, 1H); 13C-NMR (100 MHz, CDCl3)
δ 13.9, 20.1, 22.4, 28.8, 34.4, 40.7, 45.7, 123.9, 126.6, 130.8,
134.5, 135.4, 141.3, 195.2; HRMS (EI-ion trap) m/z: [M]+ calcd. for C14H18OS, 234.1078; found 234.1075.
3.5.5. Synthesis of 6-(tert-Butyl)-2-n-butylthiochroman-4-one (4Ea)
Employing General Procedure B and using 6-tert-butylthiochromone (86 mg, 0.42 mmol) and and
n-BuLi (2.8 M, 0.36 mL, 1.01 mmol), after purification by flash column chromatography (silica gel,
0–2% ethyl acetate:hexanes, v/v) gave light yellow oil 4Ea (89 mg, 77%); IR (neat) 3054 (w), 2955 (s),
2928 (s), 2869 (m), 1678 (s), 1596 (m), 1479 (m), 1463 (m), 1463 (m), 1252 (s), 1119 (m), 824 (m) cm−1
;
1H-NMR (400 MHz, CDCl3)
δ 0.84 (t, J = 7.2 Hz, 3H), 1.24 (s, 9H), 1.21–1.30 (m, 2H), 1.32–1.46 (m, 2H),
1.64 (q, J = 7.6 Hz, 2H), 2.72 (dd, J = 11.2, 16.4 Hz, 1H), 2.97 (dd, J = 3.2, 16.4 Hz, 1H), 3.35–3.45 (m, 1H),
7.13 (d, J = 8.40 Hz, 1H), 7.37 (dd, J = 2.4, 8.4 Hz, 1H), 8.04 (d, J = 2.40 Hz, 1H); 13C-NMR (100 MHz,
CDCl3)
δ 13.9, 22.3, 28.9, 31.1, 34.3, 34.6, 41.6, 46.5, 125.4, 127.4, 130.2, 131.2, 138.5, 148.1, 195.2; HRMS
(EI-ion trap) m/z: [M]+ calcd. for C17H24OS, 276.1548; found 276.1544.
3.5.6. Synthesis of 6-Chloro-2-n-butylthiochroman-4-one (4Fa)
Employing General Procedure B, and using 6-chlorothiochromone (130 mg, 0.66 mmol) and
n-BuLi (2.8 M, 0.57 mL, 1.58 mmol), after purification by flash column chromatography (silica gel,
0–2% ethyl acetate:hexanes, v/v) gave light yellow oil 4Ea (143 mg, 85%); IR (neat) 3057 (w), 2955 (s),
2927 (s), 2857 (m), 1682 (s), 1582 (m), 1452 (s), 1391 (m), 1293 (w), 1253 (m), 1224 (w), 1157 (w), 1094
(m), 898 (w), 815 (w), 730 (w) cm−1; 1H-NMR (400 MHz, CDCl3)
δ 0.94 (t, J = 7.2 Hz, 3H), 1.32–1.40 (m,
2H), 1.41–1.50 (m, 2H), 1.74 (q, J = 7.6 Hz, 2H), 2.81 (dd, J = 11.2, 16.4 Hz, 1H), 3.06 (dd, J = 3.2, 16.4 Hz,
1H), 3.45–3.54 (m, 1H), 7.23 (d, J = 8.4 Hz, 1H), 7.36 (dd, J = 2.4, 8.4 Hz, 1H), 8.06 (d, J = 2.4 Hz, 1H);
13C-NMR (100 MHz, CDCl3)
δ 13.9, 22.3, 28.8, 34.1, 41.7, 45.9, 128.5, 129.1, 131.1, 131.6, 133.4, 140.1,
193.6; HRMS (EI-ion trap) m/z: [M]+ calcd. for C13H15OSCl, 254.0532; found 254.0534.
3.5.7. Synthesis of 6-Bromo-2-n-butylthiochroman-4-one (4Ga)
Employing General Procedure B and using 6-bromothiochromone (130 mg, 0.54 mmol) and n-BuLi
(2.8 M, 0.39 mL, 1.08 mmol), after purification by flash column chromatography (silica gel, 0–2% ethyl
acetate:hexanes, v/v) gave light yellow oil 4Ga (132 mg, 82%); IR (neat) 3054 (w), 2955 (m) 2926 (s),
2856 (m), 1679 (s), 1574 (m), 1474 (m), 1450 (m), 1386 (m), 1291 (w), 1254 (m), 1224 (w), 1091 (m), 1054
(w), 898 (w), 813 (w) cm−1; 1H-NMR (400 MHz, CDCl3)
δ 0.84 (t, J = 7.2 Hz, 3H), 1.21–1.31 (m, 2H),
1.32–1.41 (m, 2H), 1.64 (q, J = 7.6 Hz, 2H), 2.71 (dd, J = 11.2, 16.4 Hz, 1H), 2.97 (dd, J = 2.8, 16.4 Hz,
1H), 3.36–3.45 (m, 1H), 7.07 (d, J = 8.4 Hz, 1H), 7.40 (dd, J = 2.0, 8.4 Hz, 1H), 8.12 (d, J = 2.4 Hz, 1H);
13C-NMR (100 MHz, CDCl3)
δ 13.9, 22.3, 28.8, 34.1, 41.7, 45.8, 118.6, 129.3, 131.5, 131.9, 136.2, 140.7,
193.5; HRMS (EI-ion trap) m/z: [M]+ calcd. for C13H15OSBr, 298.0027; found 298.0033.
3.5.8. Synthesis of 6-Fluoro-2-n-butylthiochroman-4-one (4Ha)
Employing General Procedure B and using 6-fluorothiochromone (100 mg, 0.56 mmol) and n-BuLi
(2.8 M, 0.48 mL, 1.34 mmol), after purification by flash column chromatography (silica gel, 0–2% ethyl
acetate:hexanes, v/v) gave light yellow oil 4Ha (105 mg, 79%); IR (neat) 3066 (w), 2957 (m) 2928 (s),
2858 (m), 1682 (s), 1601 (m), 1464 (s), 1404 (s), 1303 (m), 1262 (s), 1223 (w), 1196 (w), 1089 (w), 895 (w),
817 (w) cm−1; 1H-NMR (400 MHz, CDCl3)
δ 0.94 (t, J = 7.2 Hz, 3H), 1.32–1.41 (m, 2H), 1.42–1.50 (m,
2H), 1.74 (q, J = 7.6 Hz, 2H), 2.81 (dd, J = 11.2, 16.4 Hz, 1H), 3.07 (dd, J = 2.8, 16.4 Hz, 1H), 3.46–3.55
(m, 1H), 7.15 (ddd, J = 2.8, 8.0, 8.4 Hz, 1H), 7.27 (dd, J = 5.2, 8.8 Hz, 1H), 7.79 (dd, J = 3.2, 9.6 Hz, 1H);
13C-NMR (100 MHz, CDCl3) δ 13.9, 22.3, 28.8, 34.0, 41.8, 46.0, 114.9 (d, J = 22 Hz), 121.4 (d, J = 22 Hz),