KHUSNUTDINOV et al.
1620
General procedure of alcohols and diols
Decene-2-one (XXXI). Yield 90%, bp 81°C
+
oxidation. Into a pressure microreactor of stainless steel
or a glass ampule (the results of parallel runs are virtually
identical) were charged under an argon atmosphere
(15 mm Hg). Mass spectrum, m/z (I , %): 156 [M] (5),
rel
71 (25), 59 (25), 58 (100), 57 (12), 55 (8), 43 (90), 42 (5),
41 (19), 39 (5), 29 (12). Found, %: C 75.82; H 13.86.
C H O. Calculated, %: C 76.92; H 12.82.
0
(
.1 mmol of MO(CO) , 20 mmol of an appropriate alcohol
6
6
20
or 10 mmol of diol), and 20−40 mmol of CCl , and the
4
4
,4,4-Trichloro-2-methylbut-1-ene (XXXIV).Yield
reactor was air-tight closed (the ampule was sealed).
1
4
7%, bp 60–61°C (75 mm Hg). H NMR spectrum, δ,
The reaction was carried out at constant stirring for 1−
h at 120−150°C. Then the reactor was cooled to room
ppm: 5.05−5.30 d (2H, CH ), 3.42 s (2H, CH ), 2.01 s
2
2
6
13
4
(
(
3H, CH ). C NMR spectrum, δ, ppm: 98.33 (C ), 61.69
3
temperature, the reaction mixture was filtered through
a silica gel bed (eluent hexane–ether, 1:1). The solvent
was distilled off, the residue was distilled under the
atmospheric pressure or in a vacuum. The yields are given
with respect to consumed alcohol (GLC, internal
reference). The structure of compounds obtained was
proved by spectral methods and by comparison with
authentic samples and reference data [6–11].
3
2
1
5
C ), 138.25 (C ), 120.08 (C ), 23.66 (C ). Mass
+
spectrum, m/z (I , %): 172 [M] (6), 139 10), 137 (14),
rel
1
1
(
(
(
27 (10), 125 (60), 124 (7), 123 (95), 122 (6), 109 (5),
03 (5), 101 (6), 98 (5), 96 (6), 89 (5), 87 (16), 85 (5), 78
12), 76 (36), 75 (7), 73 (5), 65 (35), 63 (8), 61 (14), 55
61), 53 (10), 51 (17), 50 (11), 49 (6), 41 (78), 40 (30), 39
100), 38 (14), 37 (6), 29 (4). Found, %: C 28.68; H 3.30;
Cl 68.02. C H Cl . Calculated, %: C 28.71; H 3.34;
5
7
3
1
,1-Dimethoxy-2,2,3,3-tetrafluoropropane (XVI).
Cl 67.95.
-Chlorobutan-2-ol (XXXV). Yield 33%. Mass
spectrum, m/z (I , %): 57 (5), 55 (5), 45 (100), 43 (10),
Yield 14%. Mass spectrum, m/z (I , %): 87 (26), 85 (31),
rel
3
7
(
4 (100), 59 (28), 57 (19), 56 (10), 55 (19), 43 (63), 42
10), 39 (14), 31 (5), 29 (57). Found, %: C 34.12; H 4.47;
F 43.17. C H F O . Calculated, %: C 34.09; H 4.58;
rel
2
9 (17). Found, %: C 44.16; H 8.31; Cl 32.50. C H ClO.
4 9
5
8
4
2
Calculated, %: C 44.25; H 8.35; Cl 32.66.
F 43.15.
2
,4,5-Trimethyl-2-ethyl-1,3-dioxolane (XXXVI).
Methyl undecenoate (XVII). Yield 3%. Mass
+
Isolated by preparative GLC. Yield 95%. IR spectrum,
spectrum, m/z (I , %): 200 [M] (3), 169 (5), 157 (8),
rel
–1
1
ν, cm : 1050, 1370, 1400, 2900–2960. H NMR spectrum,
δ, ppm: 0.75–1.1 t (3H, CH ), 1.3 s (9H, 3CH ), 1.5–
.8 q (2H, CH ), 3.5–3.7 m (2H, 2CH). C NMR
2
spectrum, δ, ppm: 109.6 (C ), 78.89 (C ), 78.04 (C ),
5.19 (C ), 33.14 (C ), 8.13 (C ), 16.78 (C ), 16.40 (C ).
1
(
(
43 (7), 101 (5), 87 (5), 75 (11), 74 (100), 69 (10), 59
13), 57 (12), 56 (5), 55 (31), 43 (18), 42 (12), 41 (41), 39
3
3
1
3
1
8), 29 (32). Found, %: C 71.91; H 11.97. C H O .
12
24
2
2
4
5
Calculated, %: C 71.95; H 12.08.
6
7
8
9
10
2
1
,1-Dimethoxyundecene (XVIII). Yield 2%. Mass
Mass spectrum, m/z (I , %): 129 (11), 115 (47), 100 (11),
rel
spectrum, m/z (I , %): 185 (5), 75 (100), 71 (13), 69 (5),
rel
7
(
3 (23), 72 (25), 57 (48), 56 (18), 55 (28), 45 (7), 43
100), 41 (17), 39 (6), 29 (24). Found, %: C 66.50;
H 11.14. C H O . Calculated, %: C 66.63; H 11.18.
5
2
8 (6), 55 (8), 53 (5), 47 (8), 45(8), 43(11), 41(17), 31(5),
9 (16). Found, %: C 72.07; H 12.95. C H O .
1
3
28
2
Calculated, %: C 72.16; H 13.04.
8
16
2
2
-Chlorohexan-5-one (XXXVII). Isolated by prep-
1
-Chloroundecene (XIX). Yield 32%, bp 97°C
arative GLC. Yield 85%. Mass spectrum, m/z (I , %):
34 [M] (5), 58 (41), 57 (14), 56 (8), 55 (16), 43 (100),
2 (29), 41 (10), 39 (6), 29 (6). Found, %: C 53.50; H 8.21;
Cl 26.35. C H ClO. Calculated, %: C 53.59; H 8.24;
(
(
(
(
20 mm Hg). Mass spectrum, m/z (I , %): 105 (10), 97
rel
rel
+
1
4
7), 93 (13), 91 (48), 85 (5), 84 (5), 83 (12), 71 (13), 70
17), 69 (37), 68 (7), 67 (10), 57 (57), 56 (24), 55 (64), 54
6), 53 (5), 43 (100), 42 (23), 41 (87), 39 (17), 31 (7), 39
66). Found, %: C 69.19; H 12.14; Cl 18.67. C H Cl.
6
11
Cl 26.37.
(
11
23
Calculated, %: C 69.26; H 12.15; Cl 18.59.
2,5-Dimethyltetrahydrofuran (XXXVIII). Yield
–1
~
1
100%, bp 91–92°C. IR spectrum, ν, cm : 1090, 1370,
2
-Chlorodecene (XXX). Yield 64%, bp 105°C
1
450, 2850–2950. H NMR spectrum, δ, ppm, trans-
(
(
(
(
(
10 mm Hg). Mass spectrum, m/z (I , %): 140 (5), 112
rel
11), 111 (18), 105 (7), 98 (14), 97 (25), 96 (6), 85 (7), 84
25), 83 (24), 82 (10), 71 (16), 70 (60), 69 (67), 68 (7), 67
7), 63 (7), 57 (23), 56 (41), 55 (81), 54 (8), 53 (6), 43
100), 42 (36), 41 (89), 40 (5), 39 (22), 29 (48). Found,
isomer: 1.20 d (6H, 2CH3), 3.86 m (2H, 2CH), 1.68 m
(4H, 2CH2); cis-isomer: 1.125 d (2CH3), 4.02 m (2H,
13
2CH), 1.68 m (4H, 2CH2). C NMR spectrum, δ, ppm,
6
7
2
5
3
trans-isomer: 21.38 (C , C ), 74.49(C , C ), 33.04 (C ,
4
6
7
2
5
3
%
: C 56.49; H 9.91; Cl 33.60. C H Cl. Calculated, %:
C ); cis-isomer: 21.38 (C , C ), 75.34 (C , C ), 34.15 (C ,
C ). Mass spectrum, m/z (I , %): 100 [M] (6), 73 (23),
10
21
4
+
C 56.60; H 9.97; Cl 33.43.
rel
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 11 2006