1
86
KHUSNUTDINOV et al.
carrier gas helium, ramp from 40 to 300°С at a rate
(9), 79 (19), 91 (36), 92 (9), 93 (11), 105 (19), 119 (3),
133 (45), 134 (7), 157 (7), 159 (7), 171 (5), 212 (24),
213 (100), 214 (25), 215 (93), 216 (12). Found, %: С
40.9; Н 4.75; Br 54.35. C H Br . Calculated, %: С
8
deg/min, vaporizer temperature 280°С, ion source
temperature 200°С, ionizing electrons energy 70 eV).
Elemental analysis was determined on an analyzer
Karlo Erba 1106.
1
0
14
2
40.84; Н 4.79; Br 54.37. М 294.03.
The monitoring of the reaction progress, checking
the purity of compounds obtained and the products
5-Bromoadamantan-2-one (5). Yield 68%, mp
–
1
154–156°С. IR spectrum, ν, cm : 1750, 1735 (C=O),
1
3
composition was performed by GLC on
a
765, 640 (CBr). C NMR spectrum, δ, ppm: 32.60
7
8
1,3
4,6,9
5
chromatograph Chrom-5, column 1200 m × 3 mm, 5%
SE-30 on Chromaton N-AW-HMDS, ramp from 50 to
(С ), 39.25 (С ), 46.91 (С ), 49.43 (С ), 66.48 (С ),
+
214.50 (C=O). Mass spectrum, m/z (Irel, %): 28 [M]
2
80°С at a rate 8 deg/min, carrier gas helium.
(7), 29 (7), 39 (21), 40 (5), 41 (17), 43 (5), 51 (7), 52
(
(
5), 53 (7), 55 (14), 65 (7), 67 (12), 77 (17), 79 (43), 91
14), 93 (36), 121 (24), 148 (7), 149 (100), 150 (12).
Monomer used in the study was of the purity no
less than 99%. Initial compounds were available
commercially (Acros).
Found, %: С 52.45; Н 5.70; Br 34.91. C H BrО.
Calculated, %: С 52.40; Н 5.68; Br 34.93. М 229.11.
10
13
General procedure. The reactions were carried out
in glass ampoules (20 mL) or in a pressure
microreactor of stainless steel (17 mL). The results of
parallel experiments were identical. Into the
microreactor (ampoule) in an argon atmosphere was
1
-Hydroxydamantan-4-one (6). Yield ~98%, mp
13
3
20–321°С (subl.) С NMR spectrum, δ, ppm: 29.95
7
8,10
2,6,9
3,5
(
(
(
(
(
С ), 38.95 (С ), 45.18 (С ), 46.85 (С ), 67.78
1
4
+
С ) 216.21 (С ). Mass spectrum, m/z (I , %): 166 [M]
rel
25), 148 (6), 109 (6), 108 (10), 107 (5), 97 (10), 96
20), 95 (100), 94 (10), 80 (7), 79 (8), 77 (6), 67 (5), 55
10), 53 (11), 43 (12), 41 (24), 39 (23). Found, %: С
charged 0.3 mmol of Fe(acac) , 10 mmol of initial
3
adamantane, 10 mmol of CBr , and 150 mmol of
4
CH Br . The reactor was hermetically closed (the
2
2
7
8
7.48; Н 8.46. C Н О . Calculated, %: С 72.25; Н
10 16 2
ampoule was sealed) and heated while stirring. On the
completion of the reaction the reactor (ampoule) was
cooled to room temperature, opened, the solvent was
distilled off, the residue was crystallized from hexane
or ethanol. Yields are given in respect to converted
adamantane (adamantine derivatives) (GLC procedure,
internal reference decene; correction factor for
adamantane 1.09, for bromoadamantane 1.53). The
structure of compounds obtained was proved by
comparison with known samples and published data.
.49. M 166.217.
-Bromoadamantan-1-amine (8). Yield 80%, mp
3
13
5,7
2
3
(
6
3
97–298°С. C NMR spectrum, δ, ppm: 24.3 (С ),
6
8,10
1
4,9
6.95 (С ), 45.18 (С ), 46.77 (С ), 49.08 (С ), 53.4
2
3
С ), 63.88 (C ). Found, %: С 51.9; Н 7.6; Br 33.9; N
.61. C H BrN. Calculated, %: С 52.19; Н 7.01; Br
4.72; N 6.09. М 230.14.
14 19
1
-Bromo-3,5-dimethyladamantane (12). Yield
1
3
8
(
5%, bp 108°С. C NMR spectrum, δ, ppm:, 29.7
7
3,5
6,10
8
СН ), 32.5 (С ), 35.2 (С ), 41.7 (С ), 47.5 (С ),
3
1
-Bromoadamantane (2). Yield 99%, mp 119.5°С
4
2,9
1
–
1
1
49.6 (С ), 55.0 (С ), 65.2 (C ). Found, %: С 59.41; Н
.81; Br 32.78. C H Br. Calculated, %: С 59.27; Н
7.88; Br 32.86. М 243.18.
(
from ethanol). IR spectrum, ν, cm : 710 (СBr). Н
7
1
2
19
NMR spectrum, δ, ppm: 1.73 s (6Н, 3СН ), 2.08 s (3Н,
2
1
3
3
3
СН), 2.89 s (6Н, 3СН ). С NMR spectrum, δ, ppm:
2
3
,5,7
4,6,10
2,8,9
1
2.63 (С ), 35.72 (С
), 49.41 (С ), 66.10 (С ).
1-Adamantyl bromomethyl ketone (14). Yield
+
Mass spectrum, m/z (I , %): [M] abs., 39 (10), 41
70%, mp 76–79°С. Mass spectrum, m/z (I , %): 256
rel
rel
+
(
(
10), 53 (5), 55 (5), 65 (5), 67 (10), 77 (7), 79 (19), 81
5), 91(7), 93 (14), 107 (7), 135 (100). Found, %: С
[M] (0.5), 213 (0.3), 163 (6.6), 135 (100), 107 (10.3),
93 (19.9), 79 (20.9), 67 (6.7), 55 (3.7), 41 (6.7). Found,
%: С 56.9; Н 6.03; Br 30.9. C H BrО. Calculated, %:
С 56.04; Н 6.66; Br 31.07. М 257.167.
5
5
5.80; Н 6.93; Br 37.27. С Н Br. Calculated, %: С
5.82; Н 7.03; Br 37.15. M 215.13.
1
0
15
12 17
1
,3-Dibromoadamantane (3). Yield 23%, mp
Adamantane-1-carbonyl bromide (16). Yield
~100%, bp 280–283°С. Mass spectrum, m/z (Irel, %):
[M] abs., 135 (100), 119 (0.8), 107 (9.7), 93 (22), 79
1
3
1
10–111°С (from methanol). C NMR spectrum, δ,
ppm: 32.55 (С ), 34.73 (С ), 35.02 (С ), 42.54 (С ),
8.46 (С ), 55.90 (С ), 65.72 (С ). Mass spectrum, m/z
5
,7
6
3
4,10
+
8,9
2
1
4
(
(28), 67 (8), 39 (11). Found, %: С 40.9; Н 4.75; Br
+
I , %): [M] abs., 29 (5), 39 (23), 41 (19), 51 (7), 53
rel
54.35. C11
H15BrО. Calculated, %: С 54.34; Н 6.22; Br
(
7), 55 (9), 55 (9), 65 (19), 66 (5), 67 (5), 77 (21), 78
32.86. М 243.140.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015