Doklady Chemistry, Vol. 375, Nos. 4–6, 2000, pp. 289–292. Translated from Doklady Akademii Nauk, Vol. 375, No. 6, 2000, pp. 782–785.
Original Russian Text Copyright © 2000 by Palyulin, Emets, Potekhin, Lysov, Chertkov, Zefirov.
CHEMISTRY
The Synthesis and Crystal and Molecular Structures
of 3,7-Diacetyl- and 3,7-Bis(thioacetyl)-1,5-dimethyl-3,7-
diazabicyclo[3.3.1]nonanes
V. A. Palyulin, S. V. Emets, K. A. Potekhin, A. E. Lysov, V. A. Chertkov,
and Academician N. S. Zefirov
Received September 29, 2000
Until recently, investigations of the conforma-
tional behavior of 3,7-diazabicyclo[3.3.1]nonanes
have been mainly devoted to the analysis of the cage
conformation [1]. In particular, a large number of
studies have dealt with the comparison of the stabili-
ties of the chair–chair and chair–boat conformations,
depending on the nature and the mutual arrangement
of substituents. Meanwhile, the factors that control
the orientations of substituents at nitrogen have
scarcely been studied, although model compounds
suitable for these studies have long been known [2–
4]. An interesting class of these compounds is repre-
sented by the 3,7-diacyl derivatives of 3,7-diazabicy-
clo[3.3.1]nonane. The substituents in these com-
pounds are either antiparallel (a) or parallel (b), a
being the predominant species in solution; in the
presence of La3+ ions, b predominates. Hence, com-
pounds of this type can potentially serve as molecular
switches [5].
O
Me
Me
Me
Me
N
N
N
N
Me
O O
Me Me
O O
Me
1
2
Me
Me
N
N
Me
S S
Me
3
These compounds were synthesized from 5,7-dime-
thyl-1,3-diazaadamantan-6-one (4), prepared by a pro-
cedure in [6] and then subjected to the Kishner–Wolff
reduction by modified procedure [7] to give 5,7-dime-
thyl-1,3-diazaadamantane (5).
R
R
R
R
3,7-Diacetyl-1,5-dimethyl-3,7-diazabicyclo[3.3.1]-
nonan-9-one (1). A solution of compound 4 (10.0 g,
55 mmol) in acetic anhydride (70 ml) was kept for 24 h
at room temperature and for 2 h at 100–120°C and then
cooled. Water (70 ml) was added, and the mixture was
stirred for 2 h. The subsequent preparation can be per-
formed in two ways: (1) the reaction mixture was evap-
orated in vacuo to dryness, and the residue was recrys-
tallized from dioxane; or (2) the reaction mixture was
treated with a 40–45% KOH to pH ~ 10, and the prod-
uct was filtered off, dried, and recrystallized from diox-
ane.
N
N
N
N
R
O O
a
R
R
O R
b
O
In this paper, we report the results of an X-ray
diffraction study of three model compounds of this
type, namely: 3,7-diacetyl-1,5-dimethyl-3,7-diazabi-
cyclo[3.3.1]nonan-9-one (1), 3,7-diacetyl-1,5-dime-
thyl-3,7-diazabicyclo[3.3.1]nonane (2), and 3,7-
bis(thioacetyl)-1,5-dimethyl-3,7-diazabicyclo[3.3.1]no-
nane (3):
Either procedure gives 9.7–10.4 g of compound 1
(yield 70–75%) as colorless crystals, mp 263–264°C
(lit.: 264–265°C [8]).
1H NMR (400 MHz, CDCl3): 1.00 (s, 6H, CH3),
2.12 (s, 6H, –CO–CH3), 2.72, 3.25, 4.05, and 5.01 (4 dd,
J = 2.8 and 13.35 Hz, 4 × 2H, HCHa–d).
Department of Chemistry, Moscow State University,
Vorob’evy gory, Moscow, 119899 Russia
0012-5008/00/0012-0289$25.00 © 2000 åÄIä “Nauka /Interperiodica”