J. CHEM. RESEARCH (S), 1996 61
Table 2 Reaction of cycloalkenes with I2–CSa at 50 °C
Run Substrate MeCN:H2O
CS:I2 t/h Products (%)b
2.44–2.52 (m, 1 H), 2.57 (brs, 1 H), 3.66 (m, 1 H) and 4.04 (m, 1 H);
dC (CDCl3) 24.2, 27.9, 33.7, 38.6, 43.3 and 75.9 (Found: Mǹ,
225.9819. C6H11IO requires Mr, 225.9855).
trans-2-Iodocycloheptanol (10). vmax/cmꢀ1 (NaCl) 3424; dH
(CDCl3) 1.41–1.79 (m, 7 H), 1.95–2.03 (m, 1 H), 2.11–2.21 (m,
1 H), 2.35–2.43 (m, 1 H), 2.43–2.51 (brs, 1 H), 3.93 (m, 1 H) and
4.24 (m, 1 H); dC (CDCl3) 21.5, 26.5, 26.7, 32.5, 36.7, 47.0 and 79.9
(Found: Mǹ, 240.0000.C7H13IO requires Mr, 240.0012).
1
2
1
1
1
1
2
2
2
2
2
2
3
3
4
4
5
5
6
7
5:1
2
2
3
3
1
2
3
3
3
3
2
3
2
3
2
2
2
2
5
6
3
3
6
6
3
3
3
1
7
3
9
5
6
6
6
3
8 (79)c
8 (67)
1:1
3
5:1
5:1
8 (94)c
8 (93)
4
trans-2-Iodocyclooctanol (11). vmax/cmꢀ1 (NaCl) 3456; dH
(CDCl3) 1.21–1.81 (m, 7 H), 1.96–2.29 (m, 6 H), 4.08 (m, 1 H) and
4.47 (m, 1 H); dC (CDCl3) 25.4, 25.6, 25.8, 26.8, 32.4, 50.3 and 78.2
(Found: Mǹ, 254.0151. C8H15IO requires Mr, 254.0169).
t-2-Iodo-t-1-methylcyclohexan-r-1-ol (12). vmax/cmꢀ1 (NaCl) 3420;
dH (CDCl3) 1.38 (s, 3 H), 1.53–1.61 (m, 1 H), 1.69 (brs, 1 H),
1.73–1.81 (m, 1 H), 2.00–2.11 (m, 3 H), 2.33–2.40 (m, 1 H) and
4.34 (dd, J 4.4, 12.1 Hz, 1 H); dC (CDCl3) 23.2, 25.8, 28.0, 37.4, 50.0
and 72.3 (Found: Mǹ, 239.9979. C7H13IO requires Mr, 240.0012).
t-2-Iodo-t-1,4-dimethylcyclohexan-r-1-ol (13). vmax/cmꢀ1 (NaCl)
3448; dH (CDCl3) 0.98 (d, J 6.2 Hz, 3 H), 1.45 (s, 3 H), 1.56–1.68
(m, 3 H), 1.82 (brs, 1 H), 1.91–2.06 (m, 4 H) and 4.43 (m, 1 H); dC
(CDCl3) 20.1, 28.5, 29.5, 29.7, 33.0, 41.7, 43.6 and 71.8 (Found: Mǹ,
254.0151.C8H15IO requires Mr, 254.0169).
5
10:1
9 (53)
6
10:1
9 (77)
7
10:1
9 (99)c
9 (90)
8
10:1
9
ButOH–H2O(10:1)
9 (81)
9 (72)
10
11
12
13
14
15
16
17
18
DMSO–H2O(10:1)
10:1
10 (76)
10 (97)
11 (9)
11 (14)
12 (35)
12 (36)
13 (24)
14 (86)
10:1
10:1
DMSO–H2O(10:1)
10:1
1:1
10:1
10:1
2-Iodo-1-phenylethanol (14). vmax/cmꢀ1 (NaCl) 3828; dH (CDCl3)
2.53 (brs, 1 H), 3.41 (dd, J 8.8, 10.0 Hz, 1 H), 3.48 (dd, J 3.6, 10.3
Hz, 1 H), 4.83 (dd, J 3.6, 8.8 Hz, 1 H), 7.30–7.38 (m, 5 H); dC
(CDCl3) 15.3, 74.0, 125.7, 128.4, 128.7 and 141.1 (Found: Mǹ,
247.9736. C8H9IO requires Mr, 247.9699).
a
b
c
.
CS:Ce(SO4)2 4H2O. Isolated yields. Isolated yields based on
iodine.
trans-2-Iodocyclopentyl nitrate (15). vmax/cmꢀ1 (NaCl) 1638 and
1278; dH (CDCl3) 1.78–2.03 (m,3 H), 2.07–2.29 (m, 2 H), 2.38–2.48
(m, 1 H), 4.35 (brt, 1 H) and 5.51–5.57 (m, 1 H); dC (CDCl3) 22.6,
25.6, 28.0, 36.3 and 92.5 (Found: Mǹ, 245.9552.C5H8INO2 requires
Mr, 256.9549).
have a trans-diequatorial conformation. The isolated com-
pounds were shown to be one spot on TLC and of high purity
1
by H and 13C NMR spectroscopy.
As can be seen from Table 2, this synthesis of trans-iodo-
hydrins is more efficient than the synthesis described above;
the reaction provides a new simple preparation of trans-iodo-
hydrins. The trans-iodohydrins of trisubstituted alkenes, e.g.
12 and 13, are unstable and sensitive to light. These com-
pounds cannot be allowed to stand for a long time above
30 °C since they decompose.
trans-2-Iodocyclohexyl nitrate (16). vmax/cmꢀ1 (NaCl) 1646 and
1282; dH (CDCl3) 1.35–2.43 (m, 8 H), 4.13 (m, 1 H) and 5.09 (m,
1 H); dC (CDCl3) 23.0, 25.8, 26.4, 29.4, 36.9 and 84.9 (Found: Mǹ,
270.9686. C6H10INO3 requires Mr, 270.9706).
trans-2-Iodocycloheptyl nitrate (17). vmax/cmꢀ1 (NaCl) 1634 and
1280; dH 1.56–2.28 (m, 10 H), 4.32 (m, 1 H) and 5.35 (m, 1 H); dC
(CDCl3) 22.0, 26.6, 27.5, 30.0, 30.1, 36.36 and 90.3 (Found: Mǹ,
284.9826. C7N12INO3 requires Mr, 284.9863).
trans-2-Iodocyclooctyl nitrate (18). vmax/cmꢀ1 (NaCl) 1638 and
1282; dH (CDCl3) 1.31–1.42 (m, 2 H), 1.54–1.65 (m, 2 H),
1.76–1.99 (m, 6 H), 2.04–2.18 (m, 2 H), 4.29 (m, 1 H) and 5.38 (m,
1 H); dC (CDCl3) 25.0, 25.1, 26.6, 26.7, 31.6, 32.0, 36.36 and 90.3
(Found: Mǹ, 299.0031. C8H14INO3 requires Mr, 299.0019).
Experimental
IR spectra were measured using a Hitachi model 215 grating
infrared spectrometer. NMR spectra were measured on a JOEL
GSX 400 spectrometer in deuteriochloroform with TMS as inter-
nal standard. High-resolution MS spectra were measured on a
JOEL JMS-SX 102 mass spectrometer equipped with a JMA-DA
7000 data system.
We thank Miss Kazue Satoh for the measurement of the
high-resolution mass spectra and the SEIMI Chemical Co.
for providing cerium(IV) ammonium nitrate. This work was
supported by a Rikkyo University Grant for the Promotion of
Research.
Typical Procedures.sReaction of Cyclohexene (2) with Iodine–
CAN in Acetonitrile–Water.—A mixture of cyclohexene (2) (1.00 g),
iodine (190 mg, 0.75 mmol) and cerium(IV) ammonium nitrate
(822 mg, 1.50 mmol) in acetonitrile–water (20 ml, 10:1) was stirred
at 50 °C for 8 h. The reaction mixture was poured into water and
extracted with diethyl ether. The ethereal solution was washed with
aqueous sodium hydrogen carbonate and water, dried and then
evaporated. The resulting oil was chromatographed on silica gel,
eluting with hexane–diethyl ether (120 ml, 10:1) to give trans-
2-iodocyclohexanol (9) (164 mg, 47%) and trans-2-iodocyclo-
hexanol nitrate (15) (142 mg, 35%).
Received, 8th August 1996; Accepted, 29th October 1996
Paper E/6/05548F
References
Reaction of Cyclohexene (2) with Iodine–CS in Acetonitrile–
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filtrate was poured into water and extracted with diethyl ether. The
ethereal solution was washed with aqueous sodium hydrogen
carbonate and water, dried with sodium sulfate and evaporated.
The resulting oil gave pure product 9 (336 mg, 99%) after usual
work-up.
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trans-2-Iodocyclopentanol (8). vmax/cmꢀ1 (NaCl) 3372; dH
(CDCl3) 1.65 (m, 1 H), 1.82 (m, 2 H), 2.05 (m, 1 H), 2.13 (m, 1 H),
2.36 (m, 1 H), 2.78 (brs, 1 H), 4.05 (m, 1 H) and 4.45 (m, 1 H); dC
(CDCl3) 22.0, 30.9, 34.2, 35.6 and 82.0 (Found: Mǹ, 211.9706.
C5H9IO requires Mr, 211.9699).
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trans-2-Iodocyclohexanol (9). vmax/cmꢀ1 (NaCl) 3400; dH (CDCl3)
1.21–1.57 (m, 4 H), 1.82–1.88 (m, 1 H), 1.99–2.16 (m, 2 H),
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