Synthesis of (3-Hydroxyadamantan-1-yl)methanols

Article abstract of DOI:10.1134/S107042801809004X

A convenient procedure has been developed for the synthesis of (3-hydroxyadamantan-1-yl)-methanols on the basis of nitroxylation of adamantan-1-ylmethanols with fuming nitring acid and subsequent reduction of intermediate nitric acid esters with hydrazine hydrate. The title diols have also been obtained by the reduction of 1-nitroxy-3-(nitroxymethyl)adamantanes. The nitroxylation process is accompanied by oxidation with the formation of substituted adamantane-1-carboxylic acids.

Full text of DOI:10.1134/S107042801809004X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 9, pp. 1294–1300. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © E.A. Ivleva, A.V. Pogulyaiko, Yu.N. Klimochkin, 2018, published in Zhurnal Organicheskoi Khimii, 2018, Vol. 54, No. 9,
pp. 1283–1289.
Synthesis of (3-Hydroxyadamantan-1-yl)methanols
a
a
a
E. A. Ivleva ,* A. V. Pogulyaiko , and Yu. N. Klimochkin
a
Samara State Technical University, ul. Molodogvardeiskaya 244, Samara, 443100 Russia
*
e-mail: elena.a.ivleva@yandex.com
Received March 28, 2018
Abstract—A convenient procedure has been developed for the synthesis of (3-hydroxyadamantan-1-yl)-
methanols on the basis of nitroxylation of adamantan-1-ylmethanols with fuming nitring acid and subsequent
reduction of intermediate nitric acid esters with hydrazine hydrate. The title diols have also been obtained by
the reduction of 1-nitroxy-3-(nitroxymethyl)adamantanes. The nitroxylation process is accompanied by
oxidation with the formation of substituted adamantane-1-carboxylic acids.
DOI: 10.1134/S107042801809004X
In recent time, new methods of synthesis of
polysubstituted adamantanes have been extensively
developed, and the scope of their application has been
extended [1–13]. The unique geometry of almost
spherical adamantane core in combination with the
tripod and quadripod configurations of 1,3,5-tri- and
The known methods of synthesis of (3-hydroxy-
adamantan-1-yl)methanol include reduction of 3-hy-
droxyadamantane-1-carboxylic acid [44–47], hydrol-
ysis of 1-bromo-3-(hydroxymethyl)adamantane [48],
and hydroxymethylation of 1-hydroxy-3-iodoadaman-
tane [49]. The synthesis of (3-hydroxyadamantan-1-
yl)methanol by reduction of 3-(nitroxymethyl)adaman-
tan-1-ol has also been reported [50].
1
,3,5,7-tetrasubstituted derivatives makes it possible to
build up molecular assemblies with fixed orientation of
substituents responsible for functional properties of
materials based thereon [14–28]. However, there are
a few published data on methods of synthesis of poly-
functionalized adamantane derivatives in which, on the
one hand, the position of substituents is firmly fixed
and, on the other hand, their conformational mobility is
restricted due to the presence of spacers, e.g., one or
several methylene units [29–34]. The use of such com-
pounds as starting materials in the synthesis of molec-
ular assemblies is predetermined by a set of properties
which could be imparted to the final products; e.g., the
latter could be used as photosensors, systems for
targeted drug delivery to damaged cells, and materials
for medical diagnostics [35–39].
Each of the above listed procedures utilizes disub-
stituted adamantanes as starting compounds. In this
work we selected adamantan-1-ylmethanols 1a–1d as
initial substrates for the synthesis of (3-hydroxyada-
mantan-1-yl)methanols 4a–4d. The structure of the
target compounds suggested that oxidation of com-
mercially available adamantan-1-ylmethanols 1a–1d
could be appropriate since such methods ensured good
results in the synthesis of a wide series of polyfunc-
tional adamantane derivatives [30, 31, 51–55]. How-
ever, our attempts to oxidize adamantan-1-ylmethanol
(
1a) with a mixture of nitric and sulfuric acids were
unsuccessful; when 2.2 equiv of fuming nitric acid was
used, we isolated only 3-(nitroxymethyl)adamantane
[56]. Increase of the amount of fuming nitric acid to
6 equiv and reaction time led to the formation of
a complex mixture of compounds containing mainly
products of oxidation of the hydroxymethyl group
(adamantane-1-carboxylic acid, 3-hydroxyadaman-
tane-1-carboxylic acid, and 3-nitroxyadamantane-1-
carboxylic acid). No homoadamantane derivatives
were detected since the initial compound was added
to a preliminarily prepared mixture of sulfuric and
nitric acids.
Development of new synthetic approaches to poly-
hydric alcohols with restricted conformational mobility
is important for functionalization of cage structures,
which is especially significant taking into account
prospects of using adamantane polyesters as main
components of oils for high-temperature gas turbine
engines [40–43]. Therefore, the goal of the present
work was to develop a preparative procedure for the
synthesis of difficultly accessible (3-hydroxyadaman-
tan-1-yl)methanols.
1
294

SYNTHESIS OF (3-HYDROXYADAMANTAN-1-YL)METHANOLS
1295
Scheme 1.
ONO2
ONO2
HNO , 20°C
3
+
OH
ONO2
R
R
R
COOH
R'
R'
R'
1
a–1d
2a–2d
3a–3d
OH
OH
N H ·H O, BuOH, ∆
2
4
2
+
OH
R
R
COOH
R'
R'
4
a–4d
5a–5d
R = R′ = H (a); R = Me, R′ = H (b); R = Et, R′ = H (c); R = R′ = Me (d).
Mono- and dinitroxy derivatives of adamantane
were used as starting compounds in the synthesis of
a wide series of polyfunctional adamantane derivatives
Some adamantane derivatives containing a nitroxy-
methyl group in the bridgehead position were reported
to exhibit neuroprotective and vasodilator activities
[68]. Therefore, we isolated dinitroxy derivatives 2a–
2d with a view to studying their biological activity.
The yields of 2a–2d were 63–70%, and 3-(nitroxy-
methyl)adamantane-1-carboxylic acids 3a–3d were
[57–62], including alcohols [63–67]. Nitroxy deriva-
tives in which the ONO group is separated from the
2
adamantane skeleton by a methylene unit are excep-
tionally hydrolytically stable neopentyl type structures
1
[50]. We have developed a procedure for the prepara-
isolated as by-products in 7–14% yield. The H NMR
tion of (3-hydroxyadamantan-1-yl)methanols 4a–4d
spectra of 2a–2d displayed a singlet at δ 4.15–
via initial nitroxylation of adamantan-1-ylmethanols
4.20 ppm due to protons of the CH ONO group. The
2
2
1
a–1d to the corresponding 3-(nitroxymethyl)adaman-
quaternary carbon atom linked to the ONO group
2
1
3
tan-1-yl nitrates 2a–2d and subsequent reduction of the
latter (without preliminary isolation) with hydrazine
hydrate (Scheme 1).
resonated in the C NMR spectra at δ 89–91 ppm,
C
and the CH ONO carbon signal was located at δ 80–
2
2
C
1
81 ppm. The H NMR spectra of acids 3a–3d con-
tained a downfield singlet at δ 12.00 ppm due to OH
proton of the carboxy group, and the carbonyl carbon
Alcohols 1a–1d were subjected to nitroxylation
with 40–70 equiv of fuming nitric acid at room tem-
perature. Dinitroxy derivatives 2a–2d thus formed
were extracted into butan-1-ol, hydrazine hydrate was
added to the extract, and the mixture was refluxed for
signal was observed at δ 181 ppm. The isolated
C
dinitroxy derivatives 2a–2d were reduced to diols 4a–
4
d in 88–93% yield.
3
h. The yields of diols 4a–4d were 67–75%. The OH
The nitroxylation of adamantane-1,3-diyldimeth-
1
protons of 4a–4d resonated in the H NMR spectra at
δ 4.18–4.32 ppm. In the C NMR spectra of 4a–4d,
the signal of the quaternary carbon atom linked to the
hydroxy group was located at δ 68–69 ppm, and the
anol (1e) with fuming nitric acid at 20°C afforded
1,3-bis(nitroxymethyl)adamantane (6) as the only
isolated product. When the reaction was carried out in
a mixture of nitric acid with acetic anhydride, the
product was 3-(nitroxymethyl)adamantane-1-carbox-
ylic acid (7) (Scheme 2). The reaction was not accom-
panied by oxidation of the unsubstituted bridgehead
carbon atom, presumably due to acceptor effect of two
1
3
C
CH OH signal was observed at δ 70–71 ppm. In ad-
2
C
dition, we isolated 3-hydroxyadamantane-1-carboxylic
acids 5a–5d as by-products (8–15%) formed as a result
of oxidation of the hydroxymethyl group.
Scheme 2.
ONO2
OH
ONO2
HNO , 20°C
HNO –Ac O, 0–5°C
3 2
3
ONO2
OH
COOH
6
1e
7
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 9 2018

1
296
IVLEVA et al.
1
3
nitroxymethyl groups. The C NMR spectrum of 7
5-Methyl-3-(nitroxymethyl)adamantan-1-yl
nitrate (2b) was synthesized from 2 g (0.011 mol) of
1b and 24 mL of fuming nitric acid. Yield 2.0 g (63%),
showed a signal at δ 178 ppm due to carbonyl carbon
atom and CH ONO signal at δ 82 ppm, whereas no
signal assignable to quaternary carbon atom linked to
the ONO group was present (δ ~90 ppm).
C
2
2
C
–
1
mp 35–37°C. IR spectrum, ν, cm : 2952, 2912, 2852
1
(C–HAd), 1612 (ONO
), 1274 (ONO ). H NMR spec-
2
C
2 2
trum, δ, ppm: 0.94 s (3H, CH ); 1.31–1.39 m (4H),
3
In summary, we have developed a simple procedure
for the synthesis of (3-hydroxyadamantan-1-yl)-
methanols 4a–4d in high yields from commercially
available starting compounds. The isolated compounds
can be used in the synthesis of new materials with
valuable properties, as well as substrates for studying
biological activity.
1
.42–1.47 m (2H), 1.79–1.81 m (2H), 1.90–1.93 m
(
(
2H), and 2.00–2.02 m (2H) (CH , Ad); 2.35–2.39 m
2
1
3
1H, CH, Ad), 4.15 s (2H, OCH ). C NMR spectrum,
2
δ , ppm: 29.6 (CH ), 30.4 (CH), 34.0, 37.0 (CH ),
C
3
2
3
7.8 (CH ), 38.2 (CH ), 40.5 (CH ), 42.1 (CH ), 44.6
2 2 2 2
(
CH ), 45.5, 80.2 (CH ), 89.8. Found, %: C 50.42;
2 2
H 6.40; N 9.84. C H N O . Calculated, %: C 50.35;
12
18
2
6
H 6.34; N 9.79.
-Methyl-3-nitroxyadamantane-1-carboxylic
acid (3b). Yield 0.28 g (10%), mp 85–86°C. IR spec-
EXPERIMENTAL
5
The mass spectra were recorded on a Thermo
Finnigan DSQ GC/MS instrument [ZB5MS quartz
capillary column, 30 × 0.32 mm, film thickness
.25 μm; carrier gas helium, flow rate 1.5 mL/min;
oven temperature programming from 80°C (1 min) to
–
1
trum, ν, cm : 2945, 2914, 2864 (C–H ), 1691 (C=O),
Ad
1
1
612 (ONO ), 1274 (ONO ). H NMR spectrum, δ,
2 2
0
ppm: 0.97 s (3H, CH ); 1.43–1.45 m (2H), 1.63 s (2H),
3
1
2
.80 s (2H), 1.83 s (2H), 1.98–2.08 m (2H), and 2.18–
3
3
40°C at a rate of 20 deg/min; injector temperature
00°C; electron impact, 70 eV). The H and C NMR
.26 m (2H) (CH , Ad); 2.39–2.43 m (1H, CH, Ad),
2
1
13
1
3
11.19 br.s (1H, OH). C NMR spectrum, δ , ppm:
C
spectra were measured on a Jeol JNM ECX-400
2
9.7 (CH ), 30.5 (CH), 34.0, 36.7 (CH ), 38.1 (CH ),
3
2
2
1
spectrometer at 400 MHz for H using DMSO-d as
6
39.7 (CH ), 41.9 (CH ), 44.2 (CH ), 44.2, 45.4 (CH ),
2 2 2 2
solvent. The IR spectra were recorded on a Shimadzu
IR Affinity-1 spectrometer equipped with an ATR
accessory. The elemental analyses were obtained on
a Euro Vector 3000 EA analyzer using L-cystine as
calibration standard.
8
9.7, 182.1. Found, %: C 56.53; H 6.78; N 5.54.
C H NO . Calculated, %: C 56.46; H 6.71; N 5.49.
1
2
17
5
3
-Ethyl-5-(nitroxymethyl)adamantan-1-yl
nitrate (2c) was synthesized from 2 g (0.01 mol) of 1c
and 20 mL of fuming nitric acid. Yield 2.1 g (67%),
n
2
0
–1
Dinitroxy derivatives 2a–2d and acids 3a–3d
= 1.4982. IR spectrum, ν, cm : 2962, 2912, 2852
D
1
(
2
general procedure). Adamantan-1-ylmethanol 1a–1d,
g, was added in portions over 5–10 min with vigor-
(
C–H ), 1612 (ONO ), 1274 (ONO ). H NMR spec-
Ad
2
2
trum, δ, ppm: 0.82 t (3H, CH , J = 7.56 Hz), 1.23–
1
3
ous stirring to fuming nitric acid at 15–20°C. The
resulting solution was vigorously stirred for 1 h at
.28 m (2H, CH CH ); 1.41–1.49 m (2H), 1.53–1.61 m
3 2
(
2H), 1.79 s (4H), and 1.90–2.05 m (4H) (CH , Ad);
2
2
0°C and poured onto 500 g of crushed ice. The
product was extracted into methylene chloride (3×
0 mL), the extract was washed with 5% aqueous
2
.39–2.42 m (1H, CH, Ad), 4.17 s (2H, OCH ).
2
1
3
C NMR spectrum, δ , ppm: 7.2 (CH ), 30.3 (CH),
C
3
1
3
5.2 (CH ), 36.7, 37.4 (CH ), 38.6 (CH ), 39.6 (CH ),
2 2 2 2
potassium hydroxide (4×10 mL) and then with water
until neutral washings. The organic phase was dried
and evaporated to dryness, and the residue was recrys-
tallized from aqueous methanol. The alkaline washings
were acidified with hydrochloric acid, and the precip-
itate of 3-nitroxyadamantane-1-carboxylic acid 3a–3d
was filtered off.
4
9
0.8 (CH ), 42.3 (CH ), 43.2 (CH ), 44.1, 80.3 (CH ),
2 2 2 2
0.1. Found, %: C 52.06; H 6.78; N 9.40. C H N O .
13 20 2 6
Calculated, %: C 51.99; H 6.71; N 9.33.
3
-Ethyl-5-nitroxyadamantane-1-carboxylic acid
(
3c). Yield 0.33 g (12%), mp 88–89°C. IR spectrum, ν,
–1
cm : 2945, 2914, 2860 (C–H ), 1691 (C=O), 1612
Ad
1
(ONO ), 1274 (ONO ). H NMR spectrum, δ, ppm:
2 2
3
-(Nitroxymethyl)adamantan-1-yl nitrate (2a)
was synthesized from 2 g (0.0012 mol) of 1a and
0 mL of fuming nitric acid. Yield 2.3 g (70%),
mp 62–64°C; published data [50]: mp 63–64°C.
-Nitroxyadamantane-1-carboxylic acid (3a).
0
1
1
2
.83 t (3H, CH , J = 7.36 Hz), 1.29 q (2H, CH CH );
3 3 2
.40–1.47 m (2H), 1.58–1.65 m (2H), 1.81 s (4H),
2
.99–2.11 m (2H), and 2.19–2.29 m (2H) (CH , Ad);
2
.40–2.45 m (1H, CHAd), 11.00 br.s (1H, OH).
1
3
3
C NMR spectrum, δ , ppm: 7.1 (CH ), 30.4 (CH),
C
3
Yield 0.2 g (7%), mp 144–145°C; published data [50]:
mp 145–147°C.
35.2 (CH ), 36.8, 37.1 (CH ), 38.4 (CH ), 39.4 (CH ),
2 2 2 2
40.1 (CH ), 41.9 (CH ), 43.1 (CH ), 44.4, 90.0, 181.9.
2
2
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 9 2018

SYNTHESIS OF (3-HYDROXYADAMANTAN-1-YL)METHANOLS
1297
Found, %: C 58.07; H 7.16; N 5.24. C H NO .
Calculated, %: C 57.98; H 7.11; N 5.20.
24 mL of fuming nitric acid. Yield 1.45 g (67%),
1
3
19
5
–
1
mp 126–128°C. IR spectrum, ν, cm : 3317 (OH),
1
2
0
1
962, 2912, 2850 (C–H ). H NMR spectrum, δ, ppm:
5
,7-Dimethyl-3-(nitroxymethyl)adamantan-1-yl
Ad
.80 s (3H, CH ); 0.90 s (2H), 1.49–1.59 m (4H),
.65–1.77 m (4H), and 2.03 s (2H) (CH , Ad); 2.06 br.s
nitrate (2d) was synthesized from 2 g (0.01 mol) of 1d
3
and 30 mL of fuming nitric acid. Yield 2.0 g (65%),
2
–
1
(
1H, CH, Ad), 2.96–2.97 m (2H, OCH ), 4.20 s (1H,
mp 70–72°C. IR spectrum, ν, cm : 2952, 2910, 2862
2
1
3
1
OH), 4.26 s (1H, OH). C NMR spectrum, δ , ppm:
(
C–H ), 1612 (ONO ), 1274 (ONO ). H NMR spec-
C
Ad
2
2
2
4
9.9 (CH), 30.3 (CH ), 33.1, 42.7 (CH ), 44.6 (CH ),
trum, δ, ppm: 0.96 s (6H, CH ); 1.17–1.35 m (6H),
3 2 2
3
6.2 (CH ), 50.7 (CH ), 51.6 (CH ), 68.8, 71.0 (CH ).
1
.72–1.79 m (4H), and 1.87 s (2H) (CH , Ad); 4.20 s
2
2
2
2
2
+
1
3
Mass spectrum, m/z (I , %): 196 (20) [M] , 165 (100),
(
2H, OCH ). C NMR spectrum, δ , ppm: 29.4
rel
2
C
1
21 (22), 109 (56), 107 (74), 91 (12). Found, %:
(
CH ), 34.2, 38.2, 39.9 (CH ), 44.1 (CH ), 44.9 (CH ),
3 2 2 2
C 73.48; H 10.33. C H O . Calculated, %: C 73.43;
4
9.5 (CH ), 80.0 (CH ), 90.4. Found, %: C 52.05;
12 20
2
2
2
H 10.27.
H 6.77; N 9.38. C H N O . Calculated, %: C 51.99;
13
20
2
6
H 6.71; N 9.33.
,7-Dimethyl-3-nitroxyadamantane-1-carboxylic
acid (3d). Yield 0.39 g (14%), mp 99–100°C. IR
3-Hydroxy-5-methyladamantane-1-carboxylic
acid (5b). Yield 0.25 g (11%), mp 163–165°C;
published data [64]: mp 163–164°C.
5
–
1
spectrum, ν, cm : 2951, 2900, 2862 (C–H ), 1693
Ad
(
3-Ethyl-3-hydroxyadamantan-1-yl)methanol
4c) was synthesized from 2 g (0.01 mol) of 1c and
0 mL of fuming nitric acid. Yield 1.55 g (72%),
1
(
C=O), 1618 (ONO ), 1282 (ONO ). H NMR spec-
2 2
(
2
trum, δ, ppm: 0.89 s (6H, CH ); 1.06–1.10 m (2H),
3
1
.35 s (8H), and 1.65–1.71 m (2H) (CH , Ad); 12.18 s
–1
2
mp 113–115°C. IR spectrum, ν, cm : 3324 (OH),
1
3
(
1H, OH). C NMR spectrum, δ , ppm: 29.5 (CH ),
1
C
3
2
958, 2908, 2850 (C–H ). H NMR spectrum, δ, ppm:
Ad
3
9
4.5, 39.4 (CH ), 42.3 (CH ), 44.4 (CH ), 49.8 (CH ),
2.3, 178.28. Found, %: C 58.05; H 7.17; N 5.26.
2 2 2 2
0
.70 t (3H, CH , J = 7.32 Hz), 1.09 q (2H, CH CH ,
3
2
3
J = 7.32 Hz); 1.18 s (2H), 1.45–1.53 m (4H), and
.64–1.76 m (4H) (CH , Ad); 2.01–2.06 m (3H, CH ,
C H NO . Calculated, %: C 57.98; H 7.11; N 5.20.
1
3
19
5
1
2
2
Diols 4a–4d and acids 5a–5d (general procedure).
CH, Ad), 2.98–3.00 m (2H, OCH ), 4.18 s (1H, OH),
2
1
3
Adamantan-1-ylmethanol 1a–1d was added in portions
over 5–10 min with vigorous stirring to fuming nitric
acid at 15–20°C. The resulting solution was vigorously
stirred for 1 h at 20°C and poured onto 500 g of
crushed ice. The product was extracted into butan-1-ol
4
.24 s (1H, OH). C NMR spectrum, δ , ppm: 7.6
C
(
(
(
(
CH ), 29.7 (CH), 35.2, 35.5 (CH ), 42.7 (CH ), 44.6
3 2 2
CH ), 46.2 (CH ), 50.7 (CH ), 51.6 (CH ), 68.7, 70.9
2
2
2
2
+
CH ). Mass spectrum, m/z (I , %): 210 (14) [M] , 179
2
rel
100), 121 (68), 95 (26), 79 (18). Found, %: C 74.31;
(
6 mL), the organic layer was separated, 20 mL of
H 10.60. C H O . Calculated, %: C 74.24; H 10.54.
1
3
22
2
hydrazine hydrate was added, and the mixture was
refluxed for 3 h. The mixture was cooled, diluted with
5
-Ethyl-3-hydroxyadamantane-1-carboxylic acid
(
5c). Yield 0.29 g (13%), mp 163–164°C [64].
1
2
0 mL of butan-1-ol, and washed with water (2×
0 mL), 5% aqueous potassium hydroxide (3×15 mL),
(3-Hydroxy-5,7-dimethyladamantan-1-yl)metha-
and water again (2×10 mL). The organic phase was
dried and evaporated under reduced pressure, and the
residue was recrystallized from toluene. The alkaline
washings were acidified with aqueous HCl, and the
precipitate of 3-hydroxyadamantane-1-carboxylic acid
nol (4d) was synthesized from 2 g (0.01 mol) of 1d
and 30 mL of fuming nitric acid. Yield 70%, mp 136–
–
1
137°C. IR spectrum, ν, cm : 3300 (OH), 2960, 2910,
1
2
852 (C–H ). H NMR spectrum, δ, ppm: 0.79 s (3H,
Ad
CH ), 0.91–0.99 m and 1.14 s (6H each, CH , Ad),
3
2
5
a–5d was filtered off.
2
.99–3.00 m (2H, OCH ), 4.27 s (1H, OH), 4.32 s (1H,
2
1
3
(
3-Hydroxyadamantan-1-yl)methanol (4a) was
OH). C NMR spectrum, δ
45.1 (CH ), 46.2 (CH ), 50.7 (CH
71.1 (CH ). Mass spectrum, m/z (I , %): 210 (5) [M] ,
C
, ppm: 30.4 (CH
3
), 33.7,
), 68.9,
2
synthesized from 2 g (0.012 mol) of 1a and 20 mL of
fuming nitric acid. Yield 1.6 g (75%), mp 140–142°C;
published data [50]: mp 139–141°C.
2
2
2
), 51.7 (CH
+
2
rel
178 (100), 122 (40), 120 (84), 94 (10), 54 (10). Found,
%
: C 74.30; H 10.59. C H O . Calculated, %:
3
-Hydroxyadamantane-1-carboxylic acid (5a).
13 22 2
C 74.24; H 10.54.
Yield 0.18 g (8%), mp 203–205°C; published data
[
64]: mp 202–203°C.
3-Hydroxy-5-methyladamantan-1-yl)methanol
4b) was synthesized from 2 g (0.011 mol) of 1b and
3
-Hydroxy-5,7-dimethyladamantane-1-carbox-
(
ylic acid (5d). Yield 0.33 g (15%), mp 228–230°C;
published data [64]: mp 235–236°C.
(
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 9 2018

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298
IVLEVA et al.
2. Hussainy, R.A., Verbeek, J., van der Born, D., Booij, J.,
(
Adamantane-1,3-diyl)bis(methylene) dinitrate
and Herscheid, J.D.M., Eur. J. Med. Chem., 2011,
vol. 46, p. 5728.
(
2
(
6) was synthesized from 0.5 g (0.002 mol) of 1e and
0 mL (0.2 mol) of fuming nitric acid. Yield 0.6 g
–
1
3. Wang, M., Wang, C., Hao, X.-Q., Li, X., Vaughn, T.J.,
Zhang, Y.-Y., Yu, Y., Li, Z.-Y., Song, M.-P., Yang, H.-B.,
and Li, X., J. Am. Chem. Soc., 2014, vol. 136, no. 29,
p. 10499.
. Tominaga, M., Ohara, K., Yamaguchi, K., and
Azumaya, I., J. Org. Chem., 2014, vol. 79, no. 14,
p. 6738.
82%), mp 110–112°C. IR spectrum, ν, cm : 2943,
922, 2893 (C–H ), 1618 (ONO ), 1273 (ONO ).
2
Ad
2
2
1
H NMR spectrum, δ, ppm: 1.15–1.23 m (10H) and
.32 s (2H) (CH , Ad), 1.51–1.56 m (2H, CH, Ad),
.12 s (4H, OCH ). C NMR spectrum, δ , ppm: 30.4
1
4
(
(
2
4
1
3
2
C
CH), 31.3, 39.5 (CH ), 44.6 (CH ), 50.2 (CH ), 81.1
2 2 2
OCH ), 90.4. Found, %: C 50.41; H 6.40; N 9.84.
C H N O . Calculated, %: C 50.35; H 6.34; N 9.79.
5. Bagrii, E.I., Nekhaev, A.I., and Maksimov, A.L., Pet.
Chem., 2017, vol. 57, no. 3, p. 183.
2
1
2
18
2
6
6
7
8
9
. Klimochkin, Yu.N., Shiryaev, V.A., and Leonova, M.V.,
Russ. Chem. Bull., Int. Ed., 2015, vol. 64, no. 7, p. 1473.
. Shokova, E.A. and Kovalev, V.V., Pharm. Chem. J.,
3
-(Nitroxymethyl)adamantane-1-carboxylic acid
(
7). A solution of 0.8 g (0.004 mol) of 1,3-bis(hy-
droxymethyl)adamantane (1e) in 7 mL (0.169 mol) of
fuming nitric acid was cooled to 5°C, and 2 mL
0.018 mol) of acetic anhydride was added dropwise
with vigorous stirring. The resulting solution was kept
for 36 h at 0–2°C and was then poured onto ice. The
precipitate was filtered off, washed with water, and
dried. Yield 0.45 g (45%), mp 140–141°C. IR spec-
trum, ν, cm : 2926, 2906, 2858 (C–H ), 1689 (C=O),
612 (ONO ), 1271 (ONO ). H NMR spectrum, δ,
ppm: 1.45–1.50 m (2H), 1.52–1.59 m (4H), and 1.64–
.79 m (6H) (CH , Ad); 2.01 br.s (2H, CH, Ad), 4.17 s
2H, OCH ), 12.12 br.s (1H, OH). C NMR spectrum,
δ , ppm: 27.7 (CH), 33.7, 35.7 (CH ), 37.9 (CH ), 38.2
CH ), 38.3 (CH ), 40.1 (CH ), 82.0 (CH ), 178.5
2
016, vol. 50, no. 2, p. 63.
. Shokova, E.A. and Kovalev, V.V., Russ. Chem. Rev.,
011, vol. 80, p. 927.
(
2
. Štimac, A., Šekutor, M., Mlinarić-Majerski, K.,
Frkanec, L., and Frkanec, R., Molecules, 2017, vol. 22,
no. 2, p. 297.
10. Tsai, C.W., Wu, K.H., Yang, C.C., and Wang, G.P.,
–
1
React. Funct. Polym., 2015, vols. 91–92, p. 11.
Ad
1
1
11. Zhu, X., Shao, B.,Van den Bout, D.A., and Plun-
2
2
kett, K.N., Macromolecules, 2016, vol. 49, p. 3838.
1
1
1
1
2. Ling, Y., Ren, X., Lai, W., and Luo, J., Eur. J. Org.
Chem., 2015, p. 1541.
3. Fleck, C., Franzmann, E., Claes, D., Rickert, A., and
Maison, W., Synthesis, 2013, vol. 45, p. 1452.
4. Schwenger, A., Birchall, N., and Richert, C., Eur. J.
Org. Chem., 2017, p. 5852.
5. Vainer, A.Ya., Dyumaev, K.M., Kovalenko, A.M., Be-
renshtein, L.E., Krichevskaya, S.A., and Fridzon, R.Z.,
Dokl. Chem., 2017, vol. 474, no. 2, p. 129.
6. Klitsche, F., Ramcke, J., Migenda, J., Hensel, A.,
Vossmeyer, T., Weller, H., Gross, S., and Maison, W.,
Beilstein J. Org. Chem., 2015, vol. 11, p. 678.
7. Alexandre, P.-E., Schwenger, A., Frey, W., and
Richert, C., Chem. Eur. J., 2017, vol. 23, p. 9018.
1
(
2
1
3
2
C
2
2
(
(
2 2 2 2
C=O). Found, %: C 56.52; H 6.75; N 5.54.
C H NO . Calculated, %: C 56.46; H 6.71; N 5.49.
1
2
17
5
Reduction of compounds 2a–2d (general proce-
dure). A mixture of 0.5 g of dinitrate 2a–2d, 1 mL of
butan-1-ol, and 3 mL of hydrazine hydrate was
refluxed for 3 h. The resulting solution was cooled,
diluted with 10 mL of water, and extracted with butan-
1
1
1
1
1
-ol (3 × 5 mL). The extract was washed with water
and dried, the solvent was evaporated under reduced
pressure, and the residue was recrystallized from
toluene. Listed below are compound no., yield, and
melting point: 4a, 89%, 140–142°C; 4b, 87%, 127–
8. Sayed, S.M., Lin, B.-P., and Yang, H., Soft Matter,
2
016, vol. 12, p. 6148.
9. Zulfiqar, S., Mantione, D., Tall, O.E., Sarwar, M.I.,
Ruip’erez, F., Rothenbergere, A., and Mecerreyes, D.,
J. Mater. Chem. A, 2016, vol. 4, p. 8190.
1
29°C; 4c, 88%, 114–115°C; 4d, 93%, 137–138°C.
2
2
0. Zhu, D.Y., Guo, J.W., Xian, J.X., and Fu, S.Q., RSC
Adv., 2017, vol. 7, p. 39270.
1. Watson, B.L., Rolston, N., Bush, K.A., Taleghania, L.,
and Dauskardt, R.H., J. Mater. Chem. A, 2017, vol. 5,
p. 19267.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (project no. 14.577.21.0237;
ID RFMEFI57716X0237).
2
2
2. Fang, Q., Gu, S., Zheng, J., Zhuang, Z., Qiu, S., and
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