Structure of the reduction products of N-(m-tolyl)-exo-2,3-epoxybicyclo[2. 2.1]heptane-endo-5,endo-6-dicarboximide with lithium tetrahydridoaluminate

Full text of DOI:10.1007/s11178-005-0111-4

Russian Journal of Organic Chemistry, Vol. 40, No. 12, 2004, pp. 1832–1834. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004,
pp. 1878–1879.
Original Russian Text Copyright © 2004 by L. Kas’yan, Krishchik, A. Kas’yan, Tarabara.
SHORT
COMMUNICATIONS
Structure of the Reduction Products of N-(m-Tolyl)-
exo-2,3-epoxybicyclo[2.2.1]heptane-endo-5,endo-6-dicarboximide
with Lithium Tetrahydridoaluminate
L. I. Kas’yan1, O. V. Krishchik1, A. O. Kas’yan2, and I. N. Tarabara1
1 Dnepropetrovsk National University, per. Nauchnyi 13, Dnepropetrovsk, 49625 Ukraine
2 Rheinisch–Westfälische technische Hochschule, Aachen, Germany
Received April 20, 2004
Reduction of epoxynorbornanes is accompanied by
heterocyclization processes [1]. Gray and Heitmeier
[2] reported on the reduction with lithium tetrahydrido-
aluminate of stereoisomeric epoxy derivatives I (R =
Et, PhCH2CH2, PhCH2CH2CH2) obtained from nor-
bornanedicarboximides; however, the structure of aza-
brendanes II thus obtained was not confirmed by NMR
spectroscopy.
imide (III) under analogous conditions (molar ratio
substrate–reducing agent 1:5, solvent dimethoxy-
ethane or tetrahydrofuran) [2]. Compound III was
prepared by oxidation with peroxyformic acid of
N-(m-tolyl)bicyclo[2.2.1]hept-2-ene-endo-5,endo-6-di-
carboximide (IV) which is available via aminolysis of
endic anhydride. The reduction of epoxy imide III
with 5 equiv of LiAlH4 afforded diol V whose struc-
1
We examined the reduction of N-(m-tolyl)-exo-2,3-
epoxybicyclo[2.2.1]heptane-endo-5,endo-6-dicarbox-
ture was confirmed by the IR and H and 13C NMR
spectra (including two-dimensional NMR techniques).
Al
O
O
HO
O
LiAlH4
CH2OH
Al
O
N
N
N
R
R
O
R
I
II
O
O
O
HCO3H
N
N
Me
Me
O
O
IV
III
11
2
10
9
HO
HO
1
1
2
8
3
9
5
7
3
8
LiAlH4 (5 equiv)
LiAlH4 (3 equiv)
7
10
6
N 4
N6
III
V
+
OH
5
4O
Me
Me
V
VI
1070-4280/04/4012-1832 © 2004 MAIK “Nauka/Interperiodica”

STRUCTURE OF THE REDUCTION PRODUCTS
1833
(according to the TLC data). Excess LiAlH4 was
carefully decomposed with moist diethyl ether and ice
water, the precipitate was filtered off and washed with
chloroform, and the organic phase was dried and
evaporated. Yield of diol V 2.45 g (94%), mp 136–
138°C, Rf 0.45 (diethyl ether). IR spectrum, ν, cm–1:
3344, 3293, 1604, 1583, 1496, 1480, 1365, 1306,
When the reduction of III was carried out with the use
of 3 equiv of LiAlH4 in tetrahydrofuran (65°C, 40 h) or
dimethoxyethane (80°C, 25 h), we isolated by column
chromatography on silica gel diol V and compound VI
in 7.5 and 38.3 or 9.2 and 57.2% yield, respectively.
1
The H NMR spectrum of diol V contained
a doublet and a singlet from 8-H and 9-H (δ 3.85 and
3.74 ppm), signals from the methylene protons on C3
(δ 2.68 and 3.69 ppm) and C5 (δ 2.83 and 3.99 ppm),
a singlet from the methyl group in the aromatic ring
(δ 2.32 ppm), and signals from the aromatic protons
(δ 6.65–7.16 ppm). In the 13C NMR spectrum of V,
the C8 and C9 signals were located at δC 85.3 and
78.4 ppm, respectively. The 5-H signal in the 1H NMR
spectrum of VI appeared at δ 5.50 ppm (due to
deshielding by the oxygen and nitrogen atoms), and
the corresponding carbon nucleus gave a signal at
δC 94.0 ppm in the 13C NMR spectrum. Compound VI
is a probable intermediate in the synthesis of diol V;
it represents a new polyheterocyclic system, 4-oxa-6-
azatetracyclo[5.2.1.13,5.08,9]undecane. The structure of
VI was proved by the X-ray diffraction data.
1
1015, 787. H NMR spectrum (CDCl3), δ, ppm: 7.16–
6.65 (4H, Harom), 3.99 d (1H, 5-HA), 2.83 d.d (1H,
5-HB), 3.69 d (1H, 3-HA), 2.68 d.d (1H, 3-HB), 3.85 d
(1H, 8-H), 3.74 s (1H, 9-H), 2.81 m (1H, 2-H), 2.66 m
(1H, 6-H), 2.42 m (1H, 1-H), 2.32 s (3H, CH3), 2.30 m
(1H, 7-H), 1.89 d (1H, syn-10-H), 1.41 d (1H, anti-
13
10-H). C NMR spectrum (CDCl3), δC, ppm: 149.1–
113.6 (Carom), 85.4 (C8), 78.4 (C9), 51.7 (C5), 51.0 (C3),
48.2 (C1), 45.0 (C7), 42.9 (C2), 41.1 (C6), 37.5 (C10),
22.1 (CH3). Found, %: C 74.18; H 8.14; N 5.45.
C16H21NO2. Calculated, %: C 74.13; H 8.11; N 5.41.
b. Epoxy derivative III was reduced with 3 equiv
of LiAlH4 in anhydrous tetrahydrofuran. After approp-
riate treatment, the products were separated by column
chromatography on silica gel using petroleum ether–
diethyl ether mixtures at different ratios. From the first
fraction we isolated N-(m-tolyl)-4-oxa-6-azatetracyclo-
[5.2.1.13,6.08,9]undecan-exo-2-ol (VI), yield 38.3%,
mp 132–134°C, Rf 0.52 (diethyl ehter). IR spectrum,
ν, cm–1: 3360, 2949, 1604, 1372, 1195, 1015, 761.
1H NMR spectrum (CDCl3), δ, ppm: 7.05–6.45 (4H,
N-(m-Tolyl)-exo-2,3-epoxybicyclo[2.2.1]heptane-
endo-5,endo-6-dicarboximide (III) was synthesized
by oxidation of imide IV with peroxyformic acid
according to the procedure reported in [3]. Yield 99%,
1
mp 216–218°C. H NMR spectrum (CDCl3), δ, ppm:
7.31–6.92 (4H, Harom), 3.24 m (2H, 2-H, 3-H), 3.12 m
(2H, 5-H, 6-H), 3.06 m (2H, 1-H, 4-H), 2.31 s (3H,
CH3), 1.65 d (1H, syn-7-H), 1.05 d (1H, anti-7-H).
Found, %: C 71.32; H 5.54; N 5.16. C16H15NO3. Cal-
culated, %: C 71.38; H 5.58; N 5.20.
Harom), 5.50 d (1H, 5-H), 3.84 d (1H, 3-H), 3.42 d.d
(1H, 7-HA), 3.32 s (1H, 2-H), 3.30 s (1H, OH), 3.12 d
(1H, 7-HB), 2.98 m (1H, 9-H), 2.63 m (1H, 8-H),
2.62 m (1H, 10-H), 2.22 s (3H, CH3), 2.18 m (1H,
1-H), 1.94 d (1H, syn-11-H), 1.48 d (1H, anti-11-H).
13C NMR spectrum (CDCl3), δC, ppm: 146.6–111.5
(Carom), 94.0 (C5), 88.8 (C3), 75.4 (C2), 49.6 (C8),
48.7 (C7), 48.3 (C9), 47.1 (C10), 42.1 (C1), 35.8 (C11),
22.8 (CH3). Found, %: C 74.76; H 7.33; N 5.51.
C16H19NO2. Calculated, %: C 74.71; H 7.39; N 5.45.
From the second fraction we obtained diol V, yield
7.5%, Rf 0.45 (diethyl ether), mp 136–138°C.
N-(m-Tolyl)bicyclo[2.2.1]hept-2-ene-endo-5,endo-
6-dicarboximide (IV) was prepared as described in
[4] from endic anhydride and m-toluidine in boiling
glacial acetic acid. Yield 81%, mp 123–125°C. IR
spectrum, ν, cm–1: 2980, 1686, 1360, 1186, 1045, 845.
1H NMR spectrum (DMSO), δ, ppm: 7.26, 7.12, 6.86
(4H, Harom); 6.22 m (2H, 2-H, 3-H); 3.38 m (4H,
1-H, 4-H, 5-H, 6-H); 2.38 s (3H, CH3); 1.72 d (1H,
syn-7-H); 1.63 d (1H, anti-7-H). Found, %: C 75.83;
H 5.96; N 5.58. C16H15NO2. Calculated, %: C 75.89;
H 5.93; N 5.53.
N-(m-Tolyl)-4-azatricyclo[5.2.1.02,6]decane-
endo-8,exo-9-diol (V). a. Epoxy derivative III, 2.70 g
(0.01 mol), was added to a mixture of 1.90 g
(0.05 mol) of lithium tetrahydridoaluminate and 40 ml
of anhydrous dimethoxyethane, and the mixture was
stirred under reflux until the reaction was complete
The IR spectra were recorded in KBr on a Specord
13
75IR spectrometer. The 1H and C NMR spectra were
measured on a Gemini-BB instrument (400 MHz
1
for H and 100.7 MHz for 13C) from solutions in
DMSO-d6 or chloroform-d; tetramethylsilane was used
as internal reference. The progress of reactions and the
purity of products were monitored by TLC on Silufol
UV-254 plates using diethyl ether as eluent; develop-
ment with iodine vapor. The elemental compositions
were determined on a Carlo Erba analyzer.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

KAS’YAN et al.
2. Gray, A.P. and Heitmeier, D.E., J. Org. Chem., 1969,
1834
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004