1
652
S. Imazeki et al.
PAPER
1
3
C NMR (100 MHz, CDCl ): d = 161.06, 134.22, 132.00, 131.23,
IR (KBr): 3466, 3071, 3015, 2986, 1587, 1491, 1446, 1404, 1309,
1240, 1165, 1103, 1066, 995, 844, 815, 756, 686 cm .
3
–
1
1
31.14, 125.46, 124.54, 122.38, 120.56, 116.65, 56.49.
1
LC–MS (ESI): m/z (%) = 279 (80), 264 (100), 216 (15).
UV (MeOH): lmax = 203 (48774), 292 nm (4055).
H NMR (400 MHz, CDCl ): d = 8.11–8.07 (m, 2 H, Ph), 7.88–7.86
3
(
1
m, 4 H, Ph), 7.79–7.69 (m, 6 H, Ph), 7.44–7.39 (m, 2 H, Ph).
3
C NMR (100 MHz, CDCl ): d = 167.37, 164.79, 134.89, 134.79,
3
Anal. Calcd for C H BrOS: C, 61.13; H, 4.59. Found: C, 61.01; H,
1
9
17
1
1
34.61, 131.68, 131.36, 125.14, 120.23, 119.39, 119.15.
4
.90.
9
F NMR (376 MHz, CDCl ): d = –99.89.
3
4
-n-Butoxyphenyldiphenylsulfonium Bromide (2i)
LC–MS (ESI): m/z (%) = 281 (100), 203 (60), 185 (40), 77 (15).
White crystals; mp 130.4–132.5 ºC (i-PrOH–hexanes); R = 0.3
f
UV (MeOH): lmax = 204 (47073), 234 nm (17709).
(
CH Cl –MeOH, 12:1).
2 2
Anal. Calcd for C H BrFS: C, 59.84; H, 3.91. Found: C, 59.86; H,
IR (KBr): 3483, 3406, 3192, 3080, 3022, 2957, 2874, 2575, 1900,
18 14
4
.08.
1
1
1
767, 1682, 1587, 1475, 1444, 1415, 1309, 1261, 1178, 1120, 1068,
022, 999, 964, 856, 763, 688 cm .
–
1
4
-Chlorophenyldiphenylsulfonium Bromide (2m)
H NMR (400 MHz, CDCl ): d = 7.87 (d, J = 8.8 Hz, 2 H, Ph), 7.80–
3
White crystals; mp 221.6–222.6 ºC (i-PrOH–hexanes); R = 0.3
f
7
2
2
.68 (m, 10 H, Ph), 7.19 (d, J = 9.0 Hz, 2 H, Ph), 4.06 (t, J = 6.3 Hz,
H, OCH ), 1.79 (dt, J = 6.3, 21.5 Hz, 2 H, CH ), 1.49 (dq, J = 7.5,
(
CH Cl –CH OH, 9:1).
2 2 3
2
2
IR (KBr): 3478, 3069, 3003, 2953, 1570, 1475, 1446, 1400, 1313,
1.5 Hz, 2 H, CH ), 0.97 (t, J = 7.5 Hz, 3 H, CH ).
2
3
–
1
1
282, 1184, 1091, 1068, 1008, 997, 933, 841, 815, 754, 684 cm .
1
3
C NMR (100 MHz, CDCl ): d = 163.59, 1333.92, 133.77, 131.19,
3
1
H NMR (400 MHz, CDCl ): d = 8.05–7.73 (m, 6 H, Ph), 7.72–7.61
1
30.59, 125.61, 117.46, 112.64, 68.76, 30.87, 19.12, 13.76.
3
(
m, 8 H, Ph).
LC–MS (ESI): m/z (%) = 335 (20), 279 (100), 258 (50), 217 (30),
02 (50).
1
3
C NMR (100 MHz, CDCl ): d = 141.13, 134.30, 132.71, 131.41,
2
3
1
31.30, 130.98, 124.14, 122.74.
UV (MeOH): lmax = 204 (40780), 263 nm (12945).
LC–MS (ESI): m/z (%) = 297 (100), 263 (70), 219 (80).
UV (MeOH): lmax = 204 (47858), 239 nm (21492).
Anal. Calcd for C H BrOS: C, 63.61; H, 5.58%. Found: C, 63.51;
22
23
H, 5.60.
Anal. Calcd for C H BrClS: C, 57.24; H, 3.74. Found: C, 57.28;
H, 3.78.
1
8
14
4
-Methoxy-3,5-dimethylphenyldiphenylsulfonium Bromide (2j)
White crystals; mp 174.2–175.2 ºC (i-PrOH–hexanes); R = 0.3
f
(
CH Cl –MeOH, 9:1).
2 2
Diphenyl-4-trifluoromethylphenylsulfonium Bromide (2n)
Pale yellow crystals; mp 108.1–110.7 ºC (i-PrOH–hexanes); R =
IR (KBr): 3474, 3406, 3047, 3005, 2982, 2918, 1574, 1475, 1446,
402, 1313, 1275, 1230, 1169, 1111, 1072, 999, 893, 767, 752, 684
f
0
.3 (CH Cl –MeOH, 4:1).
1
2 2
–
1
cm .
IR (KBr): 3439, 3026, 1604, 1477, 1446, 1402, 1325, 1176, 1134,
–
1
1
1060, 1010, 844, 752, 702, 684 cm .
H NMR (400 MHz, CDCl ): d = 7.86–7.41 (m, 4 H, Ph), 7.75–7.69
3
(
m, 6 H, Ph), 7.50 (s, 2 H, Ph), 3.81 (s, 3 H, OCH ), 2.35 (s, 6 H,
1
3
H NMR (400 MHz, CDCl ): d = 8.18 (d, J = 8.3 Hz, 2 H, Ph), 7.96–
3
CH3).
7.94 (m, 6 H, Ph), 7.82–7.72 (m, 6 H, Ph).
1
3
C NMR (100 MHz, CDCl ): d = 162.17, 135.30, 134.09, 131.69,
13
3
C NMR (100 MHz, CDCl ): d = 135.68, 135.35, 134.65, 132.06,
3
1
31.28, 131.01, 125.17, 117.47, 60.05, 16.72.
1
31.51, 131.47, 129.55, 127.97, 127.94, 123.85, 121.11.
LC–MS (ESI): m/z (%) = 321 (30), 307 (60), 245 (20), 230 (100).
UV (MeOH): lmax = 204 (57704), 255 nm (15151).
19
F NMR (376 MHz, CDCl ): d = –64.48.
3
LC–MS (ESI): m/z (%) = 331 (100), 263 (30), 178 (15).
UV (MeOH): lmax = 204 (45223), 233 nm (18415).
Anal. Calcd for C H BrOS: C, 62.84; H, 5.27. Found: C, 62.85; H,
2
1
21
5
.33.
Anal. Calcd for C H BrF S: C, 55.49; H, 3.43. Found: C, 55.32;
1
9
14
3
H, 3.39.
Diphenyl-4-methylthiophenylsulfonium Bromide (2k)
White crystals; mp 160.8–161.8 ºC (i-PrOH–hexanes); R = 0.3
f
Bis(4-methylphenyl)phenylsulfonium Bromide (3b)
White crystals; mp 207.8–208.9 ºC (i-PrOH–hexanes); R = 0.3
(
CH Cl –MeOH, 12:1).
2 2
f
IR (KBr): 3447, 3045, 2990, 2943, 1566, 1547, 1475, 1441, 1402,
(
CH Cl –MeOH, 15:1).
2 2
–
1
1
313, 1201, 1178, 1099, 1062, 997, 825, 804, 761, 748, 682 cm .
IR (KBr): 3617, 3065, 3003, 2955, 1589, 1491, 1443, 1402, 1315,
1290, 1213, 1186, 1124, 1068, 1014, 825, 806, 760, 688 cm .
1
H NMR (400 MHz, CDCl ): d = 7.86–7.78 (m, 6 H, Ph), 7.76–7.69
–1
3
(
m, 6 H, Ph), 7.48 (d, J = 8.5 Hz, 2 H, Ph), 2.53 (s, 3 H, CH S).
3
1
H NMR (400 MHz, CDCl ): d = 7.78 (d, J = 7.8 Hz, 2 H, Ph), 7.73–
3
1
3
C NMR (100 MHz, CDCl ): d = 149.17, 134.02, 131.44, 131.18,
3
7.68 (m, 7 H, Ph), 7.48 (d, J = 8.6 Hz, 4 H, Ph), 2.45 (s, 6 H, CH ).
3
1
30.67, 127.17, 124.85, 117.94, 14.75.
1
3
C NMR (100 MHz, CDCl ): d = 145.64, 133.94, 131.93, 131.15,
3
LC–MS (ESI): m/z (%) = 309 (90), 233 (100), 218 (80), 156 (40).
UV (MeOH): lmax = 204 (47465), 302 nm (22930).
1
30.94, 130.66, 125.17, 120.97, 21.63.
LC–MS (ESI) m/z (%) = 219 (100), 213 (100), 199 (45), 123 (30).
UV (MeOH): lmax = 204 (54869), 241 nm (22077).
Anal. Calcd for C H BrS : C, 58.61; H, 4.40. Found: C, 56.82; H,
19
17
2
4
.54.
Anal. Calcd for C H BrS: C, 64.69; H, 5.16. Found: C, 64.52; H,
2
0
19
5
.00.
4
-Fluorophenyldiphenylsulfonium Bromide (2l)
White crystals; mp 222.0–223.2 ºC (i-PrOH–hexanes); R = 0.3
f
Bis(4-methoxyphenyl)phenylsulfonium Bromide (3c)
(
CH Cl –MeOH, 12:1).
2 2
Colorless oil; R = 0.3 (CH Cl –MeOH, 12:1).
f
2
2
Synthesis 2004, No. 10, 1648–1654 © Thieme Stuttgart · New York