Reaction of 1,3-dehydroadamantane with dicarboxylic acid imides

Full text of DOI:10.1134/S1070428013090303

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 9, pp. 1403–1404. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © G.M. Butov, V.M. Mokhov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 9, pp. 1419–1420.
SHORT
COMMUNICATIONS
Reaction of 1,3-Dehydroadamantane
with Dicarboxylic Acid Imides
G. M. Butov and V. M. Mokhov
Volzhsky Polytechnical Institute (Branch), Volgograd State Technical University,
ul. Engel’sa 42a, Volzhskii, Volgograd oblast, 404121 Russia
e-mail: butov@volpi.ru
Received April 10, 2013
DOI: 10.1134/S1070428013090303
Nitrogen-containing adamantane derivatives exhibit
various kinds of biological activity due to lipophilic
properties of the adamantane fragment. Studies in the
field of synthesis of such compounds are performed
with a view to obtain new structures and improve
procedures for the preparation of known adamantane
derivatives [1, 2].
1,3-Dehydroadamantane (I) has been widely used for
the introduction of an 1-adamantyl substituent into
various molecules via addition to O–H, S–H, and other
groups with a labile hydrogen atom [8, 9]. However,
reactions of I with N–H compounds have been poorly
studied. We previously reported [10] on the reaction
of I with lactams derived from ω-amino acids and
demonstrated prospects in using this compounds in the
synthesis of amino derivatives of adamantane.
Known methods for the synthesis of N-(1-adaman-
tyl)imides are based on reactions of functionalized
adamantane derivatives with cyclic amides, such as
phthalimide, succinimide, and maleimide. N-Adaman-
tylphthalimide was prepared in 38% yield from 1-ada-
mantan-1-ol and phthalimide in trifluoroacetic acid [3],
as well as from adamantan-1-amine and phthalic anhy-
dride in dimethylformamide (yield 45%) [4] or in
molten phthalic anhydride (59%) [5]. N-Adamantyl-
succinimide was synthesized in 33% yield from 1-tri-
methylsilylpyrrolidine-2,5-dione and 1-chloroadaman-
The present communication reports on the reactions
of propellane (I) with dicarboxylic acid imides, namely
succinimide and phthalimide. The yields of adducts IIa
and IIb attained 85%. Mixing of a solution of I in
diethyl ether with phthalimide was accompanied by
a weak heat evolution. No adamantylation products at
the aromatic ring or α-carbon atom with respect to the
carbonyl group were detected, which may be rational-
ized by higher reactivity of the N–H proton in dicar-
boxylic acid imides as compared to the corresponding
C–H protons.
tane in the presence of TiCl [6]. Thus the known
4
methods for the preparation of N-adamantyl imides
ensure fairly poor yields of the target products.
Compounds IIa and IIb were purified by recrys-
A promising starting compound for the synthesis of
tallization from propan-2-ol, and their structure was
confirmed by H NMR and IR spectra and elemental
analyses; the physical constants and spectral param-
eters of IIa and IIb were consistent with published
data [3–6]. Compounds IIa and IIb displayed no IR
1
N-adamantyl imides may be 1,3-dehydroadamantane
3
,7
1,3
(
tetracyclo[3.3.1.1. .0. ]decane) (I) which is a repre-
sentative of a class of interesting and unusual com-
pounds, [3.3.1]propellanes containing small rings [7].
O
NH
O
O
O
O
N
H
O
N
N
O
O
IIa
I
IIb
1
403

1
404
BUTOV, MOKHOV
–
1
1
absorption bands in the region 3200–3500 cm , which
are typical of NH stretching vibrations in the initial
imides.
The H NMR spectra were recorded from solutions
in carbon tetrachloride on a Varian Mercury-300 spec-
trometer operating at 300 MHz; hexamethyldisiloxane
was used as internal reference. The IR spectra were
measured on a Specord-82 spectrometer (KBr prism)
from samples dispersed in mineral oil.
Thus we have developed a convenient procedure
for the preparation of N-adamantyl-substituted dicar-
boxylic acid imides under mild conditions with high
yields.
REFERENCES
N-(Adamantan-1-yl)succinimide (IIa). A mixture
of 5 g (0.051 mol) of succinimide and 2 g (0.015 mol)
of 1,3-dehydroadamantane (I) in 20 ml of anhydrous
diethyl ether was heated for 3 h at 34–35°C. The
solvent was distilled off, excess succinimide was
distilled off under reduced pressure, and the residue
was subjected to vacuum distillation. Yield 2.82 g
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1
0.012 mol, 81%), bp 169–171°C (3 mm), mp 119–
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1
1
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spectrum, δ, ppm: 1.60–2.02 m (15H, Ad), 2.49 d (4H,
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COCH CH CO). Found, %: C 72.13; H 8.15; N 6.05.
2
2
C H NO . Calculated, %: C 72.07; H 8.21; N 6.00.
1
4
19
2
N-(Adamantan-1-yl)phthalimide (IIb) was syn-
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8
1
2
5%), mp 138–139°C; published data: mp 140°C [4],
38–139°C [3]. H NMR spectrum, δ, ppm: 1.52–
1
9
.06 m (15H, Ad), 7.30–7.70 m (4H, C H ). Found, %:
6
4
C 76.78; H 6.73; N 5.02. C H NO . Calculated, %:
1
8
19
2
10. No, B.I., Butov, G.M., Mokhov, V.M., and Vishnevets-
C 76.84; H 6.81; N 4.98.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013