Synthesis of Functionalized Vinyl Tellurides
C; ν (KBr)/cm-1: 2926, 1595, 1438, 1319, 1142, 1082, 736; δ
J . Org. Chem., Vol. 66, No. 1, 2001 79
°
H
130.50, 130.12, 128.78, 127.52, 31.57, 31.30, 29.95, 28.88,
+
(500 MHz): 8.16-8.18 (m, 2H), 7.71-7.73 (d, J ) 8.26, 2H),
22.41, 21.72, 14.02; MS (EI) m/z: 551 (M - Br, 2.22), 472
+
7
2
1
3
1
1
4
.57-7.59 (m, 1H), 7.47-7.50 (m, 2H), 7.36-7.37 (d, J ) 8.0,
H), 6.77 (s, 1H), 3.56-3.59 (t, J ) 7.87, 2H), 2.46 (s, 3H),
.61-1.65 (m, 2H), 1.45-1.48 (m, 2H), 0.94-0.97 (t, J ) 7.37,
(M - 2Br, 33.05), 265 (16.65), 207 (36.55), 157 (36.77), 109
(100), 91 (71.51), 77 (56.99); (Found: C, 39.88; H, 4.11. Calcd
for C21
2 2
H26Br O STe: C, 40.04; H, 4.16%).
(E)-1-(4-Meth ylph en ylsu lfon yl)-2-ph en yltellu r yl-2-ph en -
yleth en e (12g): yield 0.146 g (63%); mp 129-130 °C; ν (KBr)/
H
cm : 3046, 1576, 1435, 1322, 1140, 1083, 769; δ (500 MHz):
7.77-7.79 (m, 2H), 7.42 (m, 1H), 7.30-7.32 (m, 4H), 7.26-
7.20 (m, 3H), 7.09-7.12 (m, 4H), 6.39 (s, 1H), 2.36 (s, 1H); δ
C NMR 144.90, 143.66, 140.83, 138.68, 137.26, 132.30,
1
3
H); δ C NMR 157.85, 145.49, 139.91, 137.10, 135.72, 132.46,
30.58, 130.20, 128.79, 127.60, 32.06, 31.38, 22.53, 21.79,
+
+
-1
3.78; MS (EI) m/z: 523 (M - Br, 3.89), 444 (M - 2Br,
9.31), 237 (28.62), 207 (54.21), 139 (41.63), 91 (84.77), 81
2 2
(100); (Found: C, 37.77; H, 3.60; Calcd for C19H22SO Br Te:
1
3
C, 37.92; H 3.68%).
(
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-b u t ylvin yl 4-flu o-
130.29, 129.92, 129.34, 128.66, 127.83, 127.57, 127.41, 114.84,
21.59; MS (EI) m/z: 462 (M , 16.36), 309 (7.44), 207 (24.14),
155 (52.24), 105 (24.68), 91 (100), 77 (66.71); (Found: C, 54.12;
18 2
H, 3.87. Calcd for C21H O STe: C, 54.59; H, 3.93%).
An ti-Tellu r osu lfon a tes of 1-Alk yn es. A solution of alkyne
(1.1 mmol), sodium arylsulfinate (5 mmol), and diorgano
ditelluride (0.5 mmol) in 5 mL of 80% aqueous acetic acid was
heated at 80 °C for the time indicated in Table 3. The reaction
mixture was diluted with 20 mL of AcOEt, washed with
+
r op h en yl tellu r iu m d ibr om id e (13b): yield 0.22 g (71%);
mp 170-171 °C; ν (KBr)/cm : 2930, 1577, 1486, 1390, 1313,
234, 1142, 1081, 811, 777; δ
-
1
1
7
7
2
H
(500 MHz): 8.19-8.21 (m, 2H),
.71-7.73 (d, J ) 11.35, 2H), 7.37-7.38 (d, J ) 7.73, 2H),
.16-7.20 (m, 2H), 6.72 (s, 1H), 3.56-3.59 (t, J ) 7.52, 2H),
.47 (s, 3H), 1.58-1.66 (m, 2H), 1.44-1.48 (m, 2H), 0.94-0.97
1
3
1
(
t, J ) 7.14, 3H); δ C NMR 164.88 (d, J F-C ) 255.3 Hz),
3
1
1
2
(
(
58.07, 145.59, 139.81, 138.33 (d, J F-C ) 8.8 Hz), 136.94,
2
4
30.22, 127.58, 122.81 (d, J F-C ) 3.1 Hz), 117.98 (d, J F-C
)
2 4
saturated aqueous sodium bicarbonate, dried over Na SO , and
2 Hz), 32.02, 31.29, 22.51, 21.78, 13.75; MS (EI) m/z: 541
concentrated in a vacuum. Crude products (entreis 22, 23, and
26) were concentrated under vacuum, and the residues were
purified by preparative TLC on silica gel (AcOEt:hexanes )
1:10) to give compounds 12g, 12h , and 12k . Crude products
(entries 18-21, and 24 and 25) were treated with 1 equiv of
+
+
M
- Br, 8.88), 462 (M - 2Br, 48.20), 225 (39.20), 155
49.04), 139 (45.74), 95 (43,66), 91 (100), 81 (70.99); (Found:
FO STe: C, 36.82; H,
C, 36.70; H, 3.35. Calcd for C19
.41%).
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-p en t ylvin yl p h en yl
tellu r iu m d ibr om id e (13c): yield 0.193 g (64%); mp 97-98
H
21Br
2
2
3
(
Br
2
in AcOEt and concentrated under vacuum. The residues
OH/HCCl3.
were purified by recrystallization with CH
3
-1
°
C; ν (KBr)/cm : 2926, 1595, 1438, 1319, 1143, 1081, 811, 736;
(500 MHz): 8.17-8.19 (m, 2H), 7.71-7.73 (d, J ) 8.27, 2H),
(E)-1-(4-Ch lor oph en ylsu lfon yl)-2-ph en yltellu r yl-2-ph en -
yleth en e (12h ): yield 0.412 g (85%); mp154-155 °C; ν (KBr)/
δ
7
2
1
3
1
2
2
8
H
-
1
.58-7.59 (m, 1H), 7.47-7.50 (m, 2H), 7.35-7.37 (d, J ) 8.17,
H), 6.78 (s, 1H), 3.55-3.58 (t, J ) 7.74, 2H), 2.46 (s, 3H),
.63-1.66 (m, 2H), 1.34-1.41 (m, 4H), 0.88-0.92 (t, J ) 6.94,
H
cm : 3020, 1576, 1326, 1142, 1083, 776, 605, 540; δ (500
MHz): 7.80-7.82 (m, 2H), 7.43-7.45 (m, 1H), 7.31-7.35 (m,
1
3
4H), 7.20-7.24 (m, 3H), 7.08-7.10 (m, 2H), 6.38 (s, 1H); δ
C
1
3
H); δ C NMR 157.86, 145.41, 139.93, 137.04, 135.67, 132.37,
NMR 146.57, 140.94, 140.17, 139.46, 137.13, 131.91, 130.45,
130.13, 129.09, 128.98, 128.93, 128.02, 127.45, 114.81; MS (EI)
m/z: 484 (M , 25.01), 309 (11.57), 277 (7.24), 213 (43.59), 205
30.49, 130.12, 128.79, 127.51, 31.51, 31.28, 29.64, 22.22,
1.73, 13.86; MS (EI) m/z: 523 (M+ - Br, 3.89), 444 (M
+
-
+
Br, 49.31), 237 (28.62), 207 (54.21), 139 (41.63), 91 (84.77),
1 (100); (Found: C, 38.81; H, 3.88. Calcd for C20
(32.02), 175 (36.40), 111 (59.97), 77 (100); (Found: C, 49.69;
H,3.08. Calcd for C20H15ClO STe: C, 49.79; H, 3.13%).
2
H
24Br
2
O
2
-
STe: C, 39.00; H,3.93%).
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-p en t ylvin yl 4-flu o-
r op h en yl tellu r iu m d ibr om id e (13d ): yield 0.199 g (63%);
(E)-2-(P h en ylsu lfon yl)-1-bu tylvin yl p h en yl tellu r iu m
d ibr om id e (13i): yield 0.300 g (51%); mp 135-136 °C; ν (KBr)/
(
-
1
H
cm : 3057, 2930, 1436, 1390, 1147, 1081, 735, 659; δ (500
-
1
mp 158-159 °C; ν (KBr)/cm : 2930, 1578, 1486, 1393, 1313,
MHz): 8.19-8.21 (m, 2H), 7.87-7.88 (m, 2H), 7.69-7.72 (m,
1H), 7.59-7.62 (m, 3H), 7.49-7.52 (m, 2H), 6.79 (s, 1H), 3.60-
3.63 (m, 2H), 1.64-1.68 (m, 2H), 1.46-1.50 (m, 2H), 0.96-
1
7
7
)
4
234, 1141, 1081, 811, 653; δ (500 MHz): 8.19-8.22 (m, 2H),
H
.72-7.73 (d, J ) 8.02, 2H), 7.57-7.59 (d, J ) 8.02, 1H), 7.37-
.38 (m, 2H), 7.17-7.20 (m, 2H), 6.73 (s, 1H), 3.55-3.58 (t, J
1
3
0.99 (m, 3H); δ C NMR 158.33, 139.93, 139.51, 135.66,
7.67, 2H), 2.47 (s, 3H), 1.63-1.66 (m, 2H), 1.34-1.40 (m,
134.22, 132.43, 130.52, 129.53, 128.87, 127.45, 31.99, 31.39,
H), 0.89-0.92 (t, J ) 6.62, 3H); δ 13C NMR 164.92 (d, J F-C
1
22.46, 13.73; MS (EI) m/z: 509 (M - Br, 2.98), 430 (M
+
+
-
3
)
255.1 Hz), 158.13, 145.57, 139.93, 138.32 (d, J F-C ) 8.8 Hz),
2Br, 28.58), 223 (19.10), 207 (38.51), 143 (30.67), 77 (100);
2
1
3
1
9
37.05, 130.21, 127.61, 122.84, 117.98 (d, J F-C ) 22.1), 31.49,
(Found: C, 36.66; H, 3.32; Calcd for C18
H, 3.43%).
2 2
H20Br O STe: C, 36.78;
+
1.33, 29.69, 22.26, 21.75, 13.85; MS (EI) m/z: 553 (M - Br,
+
.14), 476 (M - 2Br, 17.72), 225 (27.04), 157 (31.10), 95(100),
(E)-2-(P h en ylsu lfon yl)-1-h exylvin yl p h en yl tellu r iu m
d ibr om id e (13j): yield 0.376 g (61%); mp 96-98 °C; ν (KBr)/
2 2
1 (59.61); (Found: C, 37,77; H, 3.60. Calcd for C20H23Br FO -
-
1
STe: C, 37.90; H, 3.66%).
E)-2-(4-Met h ylp h en ylsu lfon yl)-1-h exylvin yl 4-flu o-
r op h en yl tellu r iu m d ibr om id e (13e): yield 0.185 g (57%);
H
cm : 3032, 2925, 1446, 1326, 1147, 1081, 792, 635; δ (500
(
MHz): 8.17-8.18 (m, 2H), 7.84-7.86 (m, 2H), 7.66-7.69 (m,
1H), 7.56-7.59 (m, 3H), 7.47-7.50 (m, 2H), 6.78 (s, 1H), 3.56-
3.59 (m, 2H), 1.62-1.68 (m, 2H), 1.38-1.42 (m, 2H), 1.29-
1.31 (m, 4H) 0.89-0.91 (m, 3H); δ 13C NMR 158.52, 140.17,
139.70, 135.71, 134.27, 132.52, 130.65, 129.60, 128.75, 127.58,
-
1
mp 118-120 °C; ν (KBr)/cm : 2926, 2854, 1578, 1486, 1394,
314, 1234, 1141, 1081, 811, 654; δ (500 MHz): 8.19-8.22
m, 2H), 7.71-7.73 (m, 2H), 7.36-7.38 (m, 2H), 7.17-7.20 (m,
H), 6.73 (s, 1H), 3.55-3.58 (m, 2H), 2.47 (s, 3H), 1.61-1.65
m, 2H), 1.38-1.40 (m, 2H), 1.28-1.30 (m, 4H), 0.89-0.91 (m,
1
H
(
2
+
31.70, 31.39, 30.07, 28.99, 22.49, 14.07; MS (EI) m/z: 537 (M
+
(
- Br, 2.32), 458 (M - 2Br, 35.20), 207 (39.46), 143 (40.32),
109 (97.88), 77 (100); (Found: C, 38.85; H, 3.84. Calcd for
1
3
1
3
1
1
3
H); δ C NMR 164.89 (d, J F-C) 255.3 Hz), 158.21, 145.57,
3
39.93, 138.34 (d,
22.85 (d, J F-C)3.2 Hz), 117.98 (d, J F-C) 22.1 Hz), 31.55,
1.34, 29.99, 28.93, 22.46, 21.77, 14.05; MS (EI) m/z: 569 (M
J
F-C) 8.7 Hz), 137.02, 130.21, 127.60,
C
20
H
24Br
2
O
2
STe: C, 39.00; H, 3.93%).
(E )-1-(4-Me t h ylp h e n ylsu lfon yl)-2-(p h e n ylt e llu r yl)-
eth en e (12k ): yield 0.1 g (26%); Mp 124-126 °C; δ (400
4
2
+
H
+
-
Br, 2.60), 490 (M - 2Br, 41.09), 265 (16.94), 225 (40.52),
MHz): 8.57-8.61 (d, J ) 15.83, 1H), 7.76-7.78 (m, 2H), 7.69-
7.72 (m, 2H), 741-7.43 (m, 1H), 730-7.33 (m, 4H), 6.41-6.45
(d, J ) 15.82, 1H), 2.42 (s, 3H); δ 13C NMR 144.32, 140.09,
137.48, 134.77, 130.29, 130.01, 129.72, 127.76, 126.15, 110.83,
1
55 (45.73), 139 (38.03), 109 (100), 91 (74.35); (Found: C,
8.73; H, 3.81. Calcd for C21 FO STe: C, 38.93; H3.89%).
E)-2-(4-Meth ylph en ylsu lfon yl)-1-h exylvin yl ph en yl tel-
lu r iu m d ibr om id e (13f): yield 0.195 g (62%); mp96-97 °C;
3
H
25Br
2
2
(
+
21.69; MS (EI) m/z: 388 (M , 50.83), 207 (40.66), 91 (65.35),
-
1
ν (KBr)/cm : 2924, 1595, 1437, 1319, 1143, 1081, 811, 736,
77 (100); (Found: C, 46.42; H, 3.56; Calcd for C15
C, 46.68; H, 3.66%).
14 2
H O STe:
6
7
44, 539; δ
H
(500 MHz): 8.17-8.19 (m, 2H), 7.72-7.73 (m, 2H),
.57-7.59 (m, 1H), 7.48-7.50 (m, 2H), 7.35-7.37 (m, 2H), 6.78
An ti-Ad d ition of Ar TeI w ith 1-Alk yn es. A mixture of 1
mmol of ArTeI (prepared by the reaction of a diarylditelluride
(
s, 1H), 3.55-3.58 (m, 2H), 2.46 (s, 3H), 1.62-1.65 (m, 2H),
1
.38-1.40 (m, 2H), 1.28-1.31 (m, 4H), 0.89-0.91 (m, 3H); δ
C NMR 157.91, 145.40, 139.95, 137.08, 135.67, 132.38,
(0.5 mmol) with I
2
(0.55 mmol) in THF at 0 °C) and 1 mmol of
1
3
an alkyne was stirred at room temperature for 12 h followed