2
888 J . Org. Chem., Vol. 64, No. 8, 1999
Muraki et al.
) δ
1
5
9.80; H, 1.66. Found: C, 19.90; H, 1.68. MS (EI) found M+
)
sept, J ) 7.0 Hz), 6.99 (2H, s); 13C NMR (125 MHz, CDCl
3
46, calcd for C
9
H
9
O
3
I
3
M ) 546.
22.88 (p), 24.06 (p), 30.62 (t), 34.09 (t), 121.95, (t), 130.04 (q),
+
1
-Iod o-2,4,6-tr iisop r op yl ben zen e (6b); oil, bp ) 115 °C/
145.58 (q), 147.07 (q); HRMS (EI) found M ) 238.1486, calcd
1
8
35
2
1
.5 mmHg (lit. 173-175 °C/28 mmHg); IR (neat) 2950, 1565,
460, 740 cm ; H NMR (500 MHz, CDCl
for C15H22 Cl M ) 238.1488.
-
1 1
3
) δ 1.24 (12H, d, J
4
-Br om o-2-ch lor o-1-m eth oxyben zen e (9e): oil; IR (neat)
980, 1580, 1480, 1290, 810 cm ; H NMR (400 MHz, CDCl )
3
)
6.8 Hz), 1.25 (6H, d, J ) 7.0 Hz), 2.87 (1H, sept, J ) 7.0
-1 1
2
1
3
Hz), 3.39 (2H, sept, J ) 7.0 Hz), 6.95 (2H, s); C NMR (125
δ 3.88 (3H, s), 6.80 (1H, d, J ) 8.7 Hz), 7.35 (1H, dd, J ) 8.9,
MHz, CDCl
3
) δ 23.43 (p), 23.98 (p), 33.88 (t), 39.26 (t), 105.71
+
2
2
.4 Hz), 7.50 (1H, d, J ) 2.4 Hz); HRMS (EI) found M )
79 35
+
(q), 122.07, (t), 148.83 (q), 150.77 (q); MS (EI) found: M
)
19.9302, calcd for C
7 6
H O Br Cl M ) 219.9291.
3
30, calcd for C15H22I M ) 330.
1
-Br om o-2,4,6-tr iisop r op ylben zen e (10b): oil; bp ) 106
1
9
Diiod om esitylen e (6c): mp 79-80 °C (lit. 82 °C); IR
25
°
1
C/3.0 mmHg (lit. bp 153-154 °C/21 mmHg); IR (neat) 2960,
-
1 1
(KBr) 2975, 1440, 1375, 860 cm ; H NMR (400 MHz, CDCl
3
)
-1 1
3
580, 1460, 740 cm ; H NMR (500 MHz, CDCl ) δ 1.24 (18H,
+
δ 2.42 (6H, s), 2.92 (3H, s), 7.00 (1H, s); MS (EI) found M
72, calcd for C M ) 372.
Iod om esitylen e: mp 30-31 °C (lit. mp 30.5-31 °C); IR
)
d, J ) 7.0 Hz), 2.86 (1H, sept, J ) 7.0 Hz), 3.48 (2H, sept, J )
3
9
H
10
I
2
13
7
2
1
.0 Hz), 6.98 (2H, s); C NMR (125 MHz, CDCl
4.00 (p), 33.54 (t), 34.03 (t), 122.28, (t), 123.57 (q), 147.39 (q),
47.81 (q); MS (EI) found M ) 282, 284, calcd for C15H22 Br
3
) δ 23.09 (p),
2
0
-
1 1
(KBr) 2975, 1440, 1375, 860 cm ; H NMR (400 MHz, CDCl
3
)
+
79
+
δ 2.23 (3H, s), 2.43 (6H, s), 6.88 (2H, s); MS (EI) found M
92, calcd for C 11I M ) 246.
Meth yl 3-iod o-4-m eth oxyben zoa te (6d ): mp 93-94 °C;
)
M ) 282.
2
9
H
2
,4-Dibr om o-1-m eth oxyben zen e (10e): mp 61-62 °C
2
6
-
1
1
(lit. mp 61-62 °C); IR (KBr) 2980, 1580, 1480, 1290, 810
1 1
IR (KBr) 2940, 1710, 1590, 1490, 1270, 820 cm ; H NMR (400
MHz, CDCl ) δ 3.89 (3H, s), 3.94 (3H, s), 6.83 (1H, d, J ) 8.7
Hz), 8.02 (1H, dd, J ) 8.7, 2.0 Hz), 8.46 (1H, d, J ) 2.0 Hz);
-
cm ; H NMR (400 MHz, CDCl
3
) δ 3.88 (3H, s), 6.77 (1H, d,
3
J ) 8.9 Hz), 7.38 (1H, dd, J ) 8.7, 2.1 Hz), 7.66 (1H, d, J )
+
79
+
1.9 Hz); MS (EI) found M ) 264, calcd for C
64.
Desu lfon yloxyiod in a tion Rea ction of Iod a n es 1. A
solution (CH CN, 5 mL) of iodane 1A (0.5 mmol) and iodine
0.3 mmol) was stirred for 16 h under dark conditions at rt.
The reaction mixture was poured into saturated aqueous Na
SO
solution and extracted with ethyl acetate (20 mL × 3).
The organic layer was dried over Na SO . After removal of the
7 6 2
H O Br M )
HRMS (EI) found M ) 291.9594, calcd for C
91.9596.
-Br om o-2-iod o-1-m eth oxyben zen e (6e): oil (lit. mp 64
9 9 3
H O I M )
2
2
2
1
4
C); IR (neat) 2930, 1570, 1470, 1280, 800 cm ; 1H NMR (400
MHz, CDCl ) δ 3.86 (3H, s), 6.62 (1H, d, J ) 8.9 Hz), 7.34 (1H,
dd, J ) 8.9, 2.4 Hz), 7.80 (1H, d, J ) 2.4 Hz); MS (EI) found
-
1
3
°
(
3
2
-
+
79
3
M ) 312, calcd for C
OBrI; C, 26.87; H, 1.93. Found: C, 26.64%; H, 1.93.
7
H
6
7 6
O BrI M ) 312. Anal. Calcd for C H -
2
4
2
2
solvent under reduced pressure, the residue was purified by
preparative TLC on silica gel using hexane as an eluent.
4-Iodotoluene (6m ) was obtained in 57% yield.
Iod otosyloxyla tion Rea ction for Alk yn es. Iodane 1A
(0.5 mmol) and iodine (0.6 mmol) were added to a solution
2
,5-Diiod o-p-xylen e (6f): mp 102-103 °C (lit. mp 103-
1 1
-
1
04 °C); IR (KBr) 2980, 1470, 1330, 880 cm ; H NMR (400
+
MHz, CDCl
58, calcd for C
,6-Diiod o-m -xylen e (6g): mp 70-71 °C (lit. mp 71-72
3
) δ 2.34 (6H, s), 7.65 (2H, s); MS (EI) found M
)
3
8
H
8
I
2
M ) 358.
2
3
4
-
1 1
°
C); IR (KBr) 2980, 1470, 1330, 880 cm ; H NMR (400 MHz,
CDCl ) δ ) 2.37 (6H, s), 7.09 (1H, s), 8.17 (1H, s); MS (EI)
found M ) 358, calcd for C
,4-Diiod o-1-m eth oxyben zen e (6h ): mp 67.5-68.5 °C
(ClCH
stirred overnight (ca. 16 h) under dark conditions at rt. Then
the reaction mixture was poured into saturated aqueous Na
SO
solution and extracted with chloroform (20 mL × 3). The
organic layer was dried over Na SO . After removal of the
2 2
CH Cl, 5 mL) of 11-I (2.5 mmol), and the mixture was
3
+
8
H
8
I
2
M ) 358.
2
-
2
3
2
4
(
lit. mp 68-69 °C); IR (KBr) 2930, 1565, 1470, 1280, 800
2
4
-
1 1
cm ; H NMR (400 MHz, CDCl
3
) δ 3.85 (3H, s), 6.58 (1H, d,
solvent under reduced pressure, the residue was purified by
preparative TLC on silica gel using hexane/ethyl acetate (8:1)
as an eluent. 1,2-Diphenyl-1-iodo-2-(p-toluenesulfonyloxy)-
ethylene 12-I was obtained in 93% yield.
J ) 8.7 Hz), 7.57 (1H, dd, J ) 8.7, 1.9 Hz), 8.04 (1H, d, 2.2
Hz); MS (EI) found M ) 360, calcd for C
+
7 6 2
H OI M ) 360.
4
-Iod o-ter t-bu tylben zen e (6i): oil; bp 90 °C/12.5 mmHg
1
9
(lit. bp 258 °C/760 mmHg); IR (neat) 2960, 1490, 1395, 820
(E)-1-Iod o-2-(p-tolu en esu lfon yloxy)stilben e (12-I): mp
-
1
1
-1
cm ; H NMR (400 MHz, CDCl
J ) 8.7 Hz), 7.53 (2H, d, J ) 8.7 Hz); MS (EI) found M
2
1
3
) δ 1.29 (9H, s), 7.06 (2H, d,
107-108 °C; IR (KBr) 3060, 1640, 1600, 1370, 1180, 780 cm
;
+
1
)
H NMR (400 MHz, CDCl ) δ 2.33 (3H, s), 6.98 (2H, d, J ) 8.0
3
60, calcd for C10
H
13I M ) 260.
Hz), 7.17 (2H, d, J ) 8.5 Hz), 7.25-7.33 (6H, m), 7.42 (2H, dd,
J ) 6.8, 1.7 Hz), 7.50 (2H, dd, J ) 7.9, 1.6 Hz); 13C NMR (125
4
-Iod op h en yl a ceta te (6k ): oil; IR (neat) 2975, 1760, 1580,
-
1 1
480, 1370, 840 cm ; H NMR (400 MHz, CDCl
3
) δ 2.29 (3H,
MHz, CDCl ) δ 21.51 (p), 93.45 (q), 127.69 (t), 127.84 (t), 128.03
3
s), 6.79 (2H, d, J ) 9.0 Hz), 7.60 (2H, d, J ) 8.7 Hz); HRMS
(t), 128.39 (t), 129.18 (t), 129.22 (t), 129.49 (t), 130.45 (t), 133.46
(q), 135.30 (q), 139.84 (q), 144.34 (q), 145.22(q); MS (FAB)
found M ) 476, calcd for C H IO S M ) 476. Anal. Calcd
21 17 3
for C H IO S: C, 52.95; H, 3.60. Found: C, 52.97; H, 3.44.
+
(
EI) found M ) 261.9494, calcd for C
Br om in a t ion of Ar om a t ics. Iodane 1A (0.6 mmol) and
lithium bromide (0.6 mmol) were added to a solution (CH
8 7 2
H O I M ) 261.9491.
+
2
1
17
3
3
-
CN, 5 mL) of 5e (0.5 mmol), and then the solution turned
orange and was vigorously stirred overnight (ca. 16 h) under
dark conditions at rt. Then the reaction mixture was poured
(
E)-4-Iodo-5-(p-tolu en esu lfon yloxy)-4-octen e (12-II): oil;
-1
1
IR (neat) 2960, 1650, 1600, 1370, 1190, 910 cm ; H NMR
500 MHz, CDCl ) δ 0.81 (3H, t, J ) 7.3 Hz), 0.85 (3H, t, J )
.3 Hz), 1.41 (2H, sixtet, J ) 7.3 Hz), 1.47 (2H, sixtet, J ) 7.3
Hz), 2.29 (2H, t, J ) 7.3 Hz), 2.46 (3H, s), 2.62 (2H, t, J ) 7.3
(
7
3
into saturated aqueous Na
ethyl acetate (20 mL × 3). The organic layer was dried over
Na SO . After removal of the solvent under reduced pressure,
2 3
SO solution and extracted with
2
4
13
Hz), 7.36 (2H, d, J ) 7.9 Hz), 7.82 (2H, d, J ) 8.2 Hz);
NMR (125 MHz, CDCl ) δ 12.90 (p), 13.30 (p), 19.98 (s), 21.76
p, tosyl), 22.80 (s), 37.92 (s), 39.46 (s), 100.87 (q), 127.96 (t),
29.94 (t), 134.09 (q), 145.29 (q), 147.30 (q); HRMS (FAB) found
C
the residue was purified by preparative TLC on silica gel using
hexane/toluene (5:1) as an eluent. 2,4-Dibromoanisole 10e was
obtained in 81% yield.
3
(
1
M
1
-Ch lor o-2,4,6-tr iisop r op ylben zen e (9b): oil; IR (neat)
+
) 408.0217, calcd for C15
E )-1-P h e n y l-1-(p -t o lu e n e s u lfo n y lo x y )-2-i o d o -1-
p r op en e (12-IV): mp 90-91 °C; IR (KBr) 3060, 2920, 1650,
3
H21IO S M ) 408.0256.
-1 1
2
(
960, 1580, 1460, 735 cm ; H NMR (500 MHz, CDCl
18H, d, J ) 7.0 Hz), 2.87 (1H, sept, J ) 7.0 Hz), 3.47 (2H,
3
) δ 1.24
(
-1 1
1
(
600, 1370, 1180, 830 cm ; H NMR (500 MHz, CDCl
3
) δ 2.34
(
18) Suzuki, H.; Sngiyama, T.; Goto, R. Bull. Chem. Soc. J pn. 1964,
7, 1858.
19) Kajigaeshi, S.; Kakinami, T.; Moriwaki, M.; Tanaka, T.; Fujisa-
ki, S.; Okamoto, T. Bull. Chem. Soc. J pn. 1989, 62, 439.
3H, s), 2.67 (3H, s), 7.06 (2H, d, J ) 8.5 Hz), 7.13-7.28 (5H,
3
13
m), 7.41 (2H, d, J ) 8.2 Hz); C NMR (125 MHz, CDCl
3
) δ
(
2
1.53 (p), 28.10 (p), 92.37 (q), 127.61 (t), 127.90 (t), 128.98 (t),
(
(
(
(
(
20) Illuminati, G.; Marino, G. J . Am. Chem. Soc. 1956, 78, 4975.
21) Branch, S. J .; J ones, B. J . Chem. Soc. 1957, 3301
22) Suzuki, H.; Goto, R. Bull. Chem. Soc. J pn. 1963, 36, 389.
23) Ogata, Y.; Aoki, K. J . Am. Chem. Soc. 1968, 90, 6187.
24) Suzuki, H.; Yoshida, M. Bull. Chem. Soc. J pn. 1972, 45, 287.
129.32 (t), 130.25 (t), 133.63 (q), 135.02 (q), 144.64 (q), 145.12
(25) Suzuki, H.; Goto, R. Nippon Kagaku Zasshi 1963, 84, 284.
(26) Hussey, A. S.; Wilk, I. J . J . Am. Chem. Soc. 1950, 72, 830.