HYDRATION OF ALKENES AND CYCLOALKENES
1431
5
4
6
chromatography on silica gel using hexane–methylene
chloride (1:1 by volume) as eluent.
spectrum (CDCl ), δ , ppm: 25.48 (C ), 27.64 (C , C ),
3
C
3
7
2
8
1
22.95 (C , C ), 34.80 (C , C ), 72.03 (C ). Mass spec-
trum, m/z (I , %): 29 (19), 31 (8), 39 (15), 41 (45), 42
rel
Hydration of olefins in the presence of carbon
tetrachloride and chromium–copper catalyst (gen-
eral procedure). A 17-ml stainless steel high-pressure
micro reactor or a 20-ml glass ampule was charged
with 0.01 mmol of Cr(acac) , 0.01 mmol of CuCl ·
(
5
19), 43 (23), 44 (24), 45 (7), 54 (23), 55 (27), 56 (20),
7 (100), 66 (7), 67 (41), 68 (43), 69 (20), 81 (34), 82
(
38), 95 (12), 110 (10). Found, %: C 74.63; H 12.44.
C H O. Calculated, %: C 74.94; H 12.58.
8
16
3
2
2
2
H O, 1 mmol of olefin, 1 mmol of CCl , and
Cyclooctanone (VIb). Yield 4%. Mass spectrum,
m/z (I , %): 126 (19) [M] , 39 (30), 40 (7), 41 (77), 42
2
4
+
0 mmol of water. The reactor was tightly closed (the
rel
ampule was sealed) and heated for 6–12 h at 110–
60°C under continuous stirring. The products were
(76), 43 (17), 53 (7), 54 (9), 55 (80), 56 (37), 57 (9), 58
(8), 67 (22), 68 (18), 69 (25), 70 (23), 71 (8), 79 (4), 80
(5), 82 (42), 83 (40), 84 (46), 85 (4), 93 (5), 97 (20), 98
1
isolated as described above.
(
100), 99 (6), 111 (7). Found, %: C 76.05; H 10.95.
C H O. Calculated, %: C 76.14; H 11.18. M 126.20.
Cyclohexanol (IIa). Yield 39%, bp 49–50°C
8
14
(
5 mm); published data [12]: bp 160–161°C. IR spec-
–1 13
trum: ν 3350 cm (OH). C NMR spectrum (CDCl ),
Bicyclo[2.2.1]heptan-2-exo-ol (IXa). Yield 90%,
3
3
5
4
2
6
13
δ , ppm: 23.93 (C , C ), 25.57 (C ), 35.41 (C , C ),
mp 125–126°C (from EtOH) [12]. C NMR spectrum,
C
1
6
5
7
4
7
0.09 (C ). Found, %: C 71.92; H 12.05. C H O. Cal-
δ , ppm: 24.22 (C ), 27.96 (C ), 34.12 (C ), 35.13 (C ),
C
6
12
3 1 2
culated, %: C 72.35; H 13.87.
41.80 (C ), 43.79 (C ), 74.30 (C ). Mass spectrum, m/z
+
(
I , %): 112 (2) [M] , 29 (49), 31 (12), 39 (46), 40
rel
Cyclohexyl chloride (IIb). Yield 5%. Mass spec-
+
(10), 41 (49), 42 (12), 43 (22), 44 (7), 53 (15), 55 (24),
6 (7), 57 (24), 66 (44), 67 (61), 68 (39), 70 (10), 71
7), 77 (7), 79 (100), 80 (7), 81 (12), 83 (22), 84 (7),
4 (83), 95 (7), 97 (7), 111 (2), 112 (2). Found, %:
C 75.09; H 9.88. C H O. Calculated, %: C 74.95;
trum, m/z (I , %): 118 (2) [M] , 29 (9), 39 (25), 40 (7),
rel
5
(
4
1 (48), 42 (7), 53 (9), 54 (30), 55 (41), 56 (9), 67
(
100), 68 (7), 69 (5), 81 (7), 82 (70). Found, %:
9
C 60.70; H 9.40; Cl 29.90. C H Cl. Calculated, %:
6
11
7
12
C 60.75; H 9.35; Cl 29.90. M 118.60.
H 10.78. M 112.17.
6-exo-Methylbicyclo[2.2.1]heptan-2-exo-ol
Cyclohexanone (IIc). Yield 39%, bp 33–35°C
1
3
(
6 mm); published data [12]: bp 155°C. C NMR
4 3 5
1
3
(XIIa). Yield 98%, bp 78–80°C (5 mm). C NMR
8 7 6
spectrum (CDCl ), δ , ppm: 25.07 (C ), 27.09 (C , C ),
3
C
2
6
1
spectrum, δ , ppm: 21.4 (C ), 30.9 (C ), 31.30 (C ),
C
4
1.99 (C , C ), 210.80 (C ). Mass spectrum, m/z
4
5 3 1
3
5.9 (C ), 37.90 (C ), 42.90 (C ), 49.90 (C ), 74.03
+
(
I , %): 98 (34) [M] , 29 (16), 39 (25), 40 (7), 41 (34),
2
+
rel
(
(
(
(
C ). Mass spectrum, m/z (I , %): 126 (2) [M] , 29
rel
4
2 (84), 43 (20), 54 (5), 55 (100), 56 (16), 69 (23), 70
20), 31 (5), 39 (41), 40 (5), 41 (37), 42 (5), 43 (44), 44
2), 45 (2), 51 (2), 53 (17), 54 (5), 55 (15), 56 (2), 57
5), 58 (2), 59 (2), 65 (2), 66 (2), 67 (44), 68 (2), 69
(
20), 99 (5). Found, %: C 73.45; H 10.30. C H O.
6
10
Calculated, %: C 73.42; H 10.27. M 98.14.
Cyclopentanol (IVa). Yield 80%, bp 35–38°C
(5), 70 (2), 71 (7), 72 (5), 77 (7), 79 (15), 80 (37), 81
1
3
(
6 mm); published data [12]: bp 139–140°C. C NMR
3 4 2 5
(
100), 82 (10), 83 (10), 91 (5), 93 (29), 97 (7), 108
spectrum, δ , ppm: 24.72 (C , C ), 36.28 (C , C ),
(91), 109 (2), 111 (5). Found, %: C 76.13; H 11.05.
C
1
+
7
4
5
4.87 (C ). Mass spectrum, m/z (I , %): 86 (4) [M] ,
C H O. Calculated, %: C 76.14; H 11.18. M 126.20.
rel
8
14
0 (4), 41 (16), 42 (8), 43 (24), 44 (31), 45 (5), 55 (6),
7 (100), 58 (19), 59 (3), 67 (13), 68 (13), 69 (4).
Spiro[bicyclo[2.2.1]heptane-7,1′-cyclopropan]-2-
exo-ol (XIIIa). Yield 81%, bp 71–73°C (3 mm).
Found, %: C 69.70; H 11.73. C H O. Calculated, %:
13
8
9
5
10
C NMR spectrum, δ , ppm: 10.41 (C ), 13.99 (C ),
C
C 69.72; H 11.70. M 86.13.
6
5
7
3
2
1.74 (C ), 31.51 (C ), 31.87 (C ), 36.30 (C ), 46.46
4 1 2
Cyclopentyl chloride (IVb). Yield 20%, bp 114°C
(C ), 53.36 (C ), 73.45 (C ). Found, %: C 78.25;
H 9.99. C H O. Calculated, %: C 78.21; H 10.21.
3
4
[
3
12]. 13C NMR spectrum, δ , ppm: 22.43 (C , C ),
C
9
14
2
5
1
8.61 (C , C ), 60.13 (C ). Found, %: C 57.40; H 8.63;
Cl 33.97. C H Cl. Calculated, %: C 57.42; H 8.67;
3
-exo-(Trichloromethyl)spiro[bicyclo[2.2.1]-
5
9
heptane-7,1′-cyclopropan]-2-endo-ol (XIIIb). Yield
Cl 33.90.
13
2
0%, R 0.69 (hexane–CH Cl ). C NMR spectrum,
f
2
2
8 9 5 6
Cyclooctanol (VIa). Yield 96%, bp 104–105°C
δ , ppm: 5.17 (C ), 10.41 (C ), 22.59 (C ), 24.64 (C ),
C
7 1 4 3 2
(
15 mm); published data [12]: bp 106–108°C (22 mm).
40.73 (C ), 50.99 (C , C ), 62.97 (C ), 73.45 (C ),
–
1
13
10
IR spectrum, ν, cm : 3600, 1150 (OH). C NMR
92.87 (C ). Found, %: C 47.48; H 4.95; Cl 41.52.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013