172.2. IR (CHCl3): 3002, 2946, 1734, 1493, 1594, 1486,
1210, 905, 734 cm-1. MS: [M + NH4]+ 274. Anal. Calcd for
C12H16O4S: C, 56.23; H, 6.29; O, 24.96. Found: C, 56.41; H, 6.30;
O, 24.91.
3-(3,4-Dim eth oxyp h en yl)-su lfa n yl-p r op ion ic Acid Meth -
yl Ester 3f. Colorless oil. 1H NMR (300 MHz, CDCl3): δ 2.60
(t, 2H, J ) 7.2 Hz), 3.08 (t, 2H, J ) 7.2 Hz), 3.69 (s, 3H), 3.88 (s,
3H), 3.89 (s, 3H), 6.82 (d, 1H, J ) 8.4 Hz), 7.02 (m, 2H). 13C
NMR (75 MHz, CDCl3): δ 30.8, 34.2, 51.5, 55.8, 111.4, 115.5,
125.0, 125.3, 148.7, 148.9, 172.0. IR (CHCl3): 3008, 2956, 1734,
1584, 1504, 1254, 910, 734 cm-1. M.S: [M + NH4]+ 274. Anal.
Calcd for C12H16O4S: C, 56.23; H, 6.29; O, 24.96. Found: C,
56.14; H, 6.30; O, 24.99.
3-(2,5-Dim eth ylp h en yl)-su lfa n yl-p r op ion ic Acid Meth yl
Ester 3g. Colorless oil. 1H NMR (200 MHz, CDCl3): δ 2.32 (s,
3H), 2.35 (s, 3H), 2.65 (t, 2H, J ) 7.3 Hz), 3.14 (t, 2H, J ) 7.3
Hz), 3.70 (s, 3H), 6.94 (d, 1H, J ) 7.6 Hz), 7.07 (d, 1H, J ) 7.6
Hz), 7.14 (s, 1H). 13C NMR (75 MHz, CDCl3): δ 19.8, 20.8, 28.2,
34.0, 51.6, 127.2, 129.9, 130.0, 133.9, 135.2, 135.9, 172.1. IR
(CHCl3): 3018, 2950, 1739, 1602, 1486, 1434, 1357, 1248, 1171,
812 cm-1. MS: [M + NH4]+ 242. Anal. Calcd for C12H14O2S: C,
64.25; H, 7.19; O, 14.26. Found: C, 64.44; H, 7.17; O, 14.30.
3-(2,4,6-Tr im eth ylph en yl)-su lfan yl-pr opion ic Acid Meth -
yl Ester 3h . Colorless oil. 1H NMR (200 MHz, CDCl3): δ 2.27
(s, 3H), 2.50 (s, 6H), 2.51 (t, 2H, J ) 7.1 Hz), 2.90 (t, 2H, J ) 7.1
Hz), 3.65 (s, 3H), 6.94 (s, 2H). 13C NMR (75 MHz, CDCl3): δ
21.7, 29.9, 34.4, 51.2, 128.8, 128.9, 138.1, 142.9, 172.2. IR
(CHCl3): 3016, 2951, 1739, 1602, 1437, 1357, 1243, 1173, 853
cm-1. MS: [M + NH4]+ 256. Anal. Calcd for C13H18O2S: C, 65.51;
H, 7.61; O, 13.42. Found: C, 65.74; H, 7.59; O, 13.39.
under vacuum. The crude reaction mixture is then washed with
1 N HCl (2 mL), and the aqueous phase is extracted with AcOEt
(3 × 10 mL). The organic phases are dried under MgSO4, filtered,
concentrated under reduced pressure, and dried under vacuum.
The crude 4 is purified by filtration on silica gel.
4-Th io-(N,N-d im eth yl)-ben zen e 4d . Colorless oil. 1H NMR
(300 MHz, CDCl3): δ 2.98 (s, 6H), 6.62 (d, 2H, J ) 8.7 Hz), 7.35
(d, 2H, J ) 8.7 Hz). 13C NMR (75 MHz, CDCl3): δ 40.3, 112.5,
123.3, 134.1, 150.6. IR (CHCl3): 3070, 2920, 1589, 1504, 1445,
1359, 1225, 1194, 1096, 949, 907, 814, 734 cm-1. MS: [M +
NH4]+ 171. Anal. Calcd for C8H11NS: C, 62.70; H, 7.23. Found:
C, 62.92; H, 7.21.
4-Meth oxy-3-th io-br om oben zen e 4j. Colorless oil. 1H NMR
(200 MHz, CDCl3): δ 3.86 (s, 1H), 3.88 (s, 3H), 6.71 (d, 1H, J )
8.8 Hz), 7.30 (m, 2H). 13C NMR (75 MHz, CDCl3): δ 56.0, 111.8,
112.8, 123.1, 128.7, 131.1, 153.8. IR (CHCl3): 3003, 2930, 1576,
1478, 1460, 1439, 1375, 1292, 1248, 1080, 913, 729 cm-1. MS:
[M + NH4]+ 237. Anal. Calcd for C7H7BrOS: C, 38.37; H, 3.22;
O, 7.30. Found: C, 38.26; H, 3.21; O, 7.32.
Typ ica l P r oced u r e for Syn th esis of 4e a n d 4f. A 1 M
solution of t-BuOK in THF (1.65 mL, 1.2 mmol) is added
dropwise at -78 °C to a solution of 4e and 4f (1.0 mmol) in THF
(4.5 mL). The reaction mixture is stirred at -78 °C for 10 min,
quenched by addition of 1 N HCl (1 mL), and concentrated under
vacuum. The crude reaction mixture is then washed with 1 N
HCl (2 mL), and the aqueous phase is extracted with AcOEt (3
× 10 mL). The organic phases are dried under MgSO4, filtered,
concentrated under reduced pressure, and dried under vacuum.
The crude 4 is purified by filtration on silica gel.
1
2,4-Dim eth oxy-th iop h en ol 4e. Colorless oil. H NMR (200
3-(5-Br om o-2-m eth oxyp h en yl)-su lfa n yl-p r op ion ic Acid
Meth yl Ester 3j. White solid. 1H NMR (300 MHz, CDCl3): δ
2.65 (t, 2H, J ) 7.5 Hz), 3.15 (t, 2H, J ) 7.5 Hz), 3.70 (s, 3H),
3.88 (s, 3H), 6.73 (d, 1H, J ) 8.1 Hz), 7.30 (dd, 1H, J ) 8.1, 2.5
Hz), 7.38 (d, 1H, J ) 2.5 Hz). 13C NMR (75 MHz, CDCl3): δ
27.0, 33.8, 52.0, 56.0, 111.0, 112.9, 125.9, 130.1, 132.1, 157.1,
169.2. IR (CHCl3): 3075, 2946, 1731, 1571, 1473, 1434, 1370,
1246, 1173, 1075, 1026, 814 cm-1. MS: [M + NH4]+ 323. Anal.
Calcd for C11H13O3BrS: C, 43.29; H, 4.29; O, 15.72. Found: C,
43.13; H, 4.28; O, 15.68.
3-P h en yl-su lfa n yl-p r op ion ic Acid Meth yl Ester 3i. To a
solution of 1b (290 mg, 1.3 mmol) in DCM (5.5 mL) and benzene
(1 mL) is added dropwise at -40 °C triflic anhydride (0.25 mL,
1.5 mmol). The reaction mixture is stirred at -35 °C for 30 min
and warmed to 0 °C for 30 min and eventually to room
temperature for 12 h. The solvent is removed under reduced
pressure, and the crude 2i is dried under vacuum for 1 h and is
then reacted in a mixture of Et3N (6 mL) and THF (1 mL) at
room temperature for 12 h. The solvents are evaporated under
vacuum. The crude reaction mixture is dried under reduced
pressure and filtered on silica gel to yield the corresponding 3i
as a colorless oil in 80% yield (204 mg, 1.04 mmol). 1H NMR
(200 MHz, CDCl3): δ 2.67 (t, 2H, J ) 7.3 Hz), 3.21 (t, 2H, J )
7.3 Hz), 3.72 (s, 3H), 7.29 (m, 5H). 13C NMR (75 MHz, CDCl3):
δ 29.0, 34.2, 51.2, 126.5, 129.0, 130.1, 135.2, 172.1. IR (CHCl3):
3051, 2986, 1736, 1586, 1436, 1491, 1266, 741 cm-1. MS: [M +
NH4]+ 214. Anal. Calcd for C10H12O2S: C, 61.20; H, 6.16; O,
16.30. Found: C, 61.01; H, 6.18; O, 16.34.
MHz, CDCl3): δ 3.55 (s, 1H), 3.80 (s, 3H), 3.88 (s, 3H), 6.46 (m,
2H), 7.19 (d, 1H, J ) 8.3 Hz). 13C NMR (75 MHz, CDCl3): δ
55.4, 55.8, 98.9, 104.9, 130.6, 133.4, 159.2, 161.4. IR (CHCl3):
3008, 2930, 1597, 1579, 1489, 1463, 1435, 1308, 1210, 1166,
1031, 907, 734 cm-1. MS: [M + NH4]+ 188. Anal. Calcd for
C8H10O2S: C, 56.45; H, 5.92; O, 18.79. Found: C, 56.32; H, 5.94;
O, 18.83.
3,4-Dim eth oxy-th iop h en ol 4f. Colorless oil. 1H NMR (300
MHz, CDCl3): δ 3.42 (s, 1H), 3.86 (s, 3H), 3.87 (s, 3H), 6.76 (d,
1H, J ) 7,9 Hz), 6,86 (d, 1H, J ) 1,9 Hz), 6,91 (dd, 1H, J ) 7,9
Hz, 1,9 Hz). 13C NMR (75 MHz, CDCl3): δ 55.7, 55.8, 111.2,
113.9, 123.3, 128.5, 149.0, 149.4. IR (CHCl3): 2998, 2930, 1582,
1501, 1463, 1442, 1398, 1323, 1254, 1225, 1181, 1137, 1024, 874,
799, 763 cm-1. MS: [M + NH4]+ 188. Anal. Calcd for C8H10O2S:
C, 56.45; H, 5.92; O, 18.79. Found: C, 56.54; H, 5.90; O, 18.76.
2,5-Dim et h yl-t h iop h en ol 4g. Colorless oil. 1H NMR (300
MHz, CDCl3): δ 2.27 (s, 3H), 2.30 (s, 3H), 3.24 (s, 1H), 7.08 (m,
3H). 13C NMR (75 MHz, CDCl3): δ 19.8, 20.5, 128.3, 129.9, 130.1,
130.9, 134.6, 136.2. IR (CHCl3): 3018, 2921, 1600, 1562, 1468,
1435, 907, 732 cm-1. MS: [M + NH4]+ 156. Anal. Calcd for
C8H10S: C, 69.51; H, 7.29. Found: C, 69.73; H, 7.31.
2,4,6-Tr im eth yl-th iop h en ol 4h . Colorless oil. 1H NMR (300
MHz, CDCl3): δ 2.26 (s, 3H), 2.36 (s, 6H), 3.13 (s, 1H), 6.90 (s,
2H). 13C NMR (75 MHz, CDCl3): δ 20.7, 22.0, 127.0, 128.8, 134.7,
136.2. IR (CHCl3): 3023, 2920, 1600, 1561, 1468, 1439, 1372,
1062, 907, 732 cm-1. MS: [M + NH4]+ 170. Anal. Calcd for
C9H12S: C, 70.99; H, 7.94. Found: C, 71.17; H, 7.97.
Typ ica l P r oced u r e for Syn th esis of Ar ylth iols 4a -4d
a n d 4g-4j. A 1 M solution of t-BuOK in THF (5.5 mL, 4.0 mmol)
is added dropwise at -78 °C to a solution of 3 (1.0 mmol) in
THF (4.5 mL). The reaction mixture is stirred at -78 °C for 10
min, quenched by addition of 1 N HCl (1 mL), and concentrated
Ack n ow led gm en t. We thank the Ministe`re de la
Recherche et de l’Enseignement for financial support
of this work through a MENRT grant to J .-M. Becht.
J O034013H
J . Org. Chem, Vol. 68, No. 14, 2003 5761