Nitrochlorination of methyl tricyclo[4.1.0.02,7]heptane-1- carboxylate and phenyl tricyclo[4.1.0.02,7]hept-1-yl sulfone

Article abstract of DOI:10.1134/S1070428008040106

Treatment of methyl tricyclo[4.1.0.0^2,7]heptane-1-carboxylate and phenyl tricyclo[4.1.0.0^2,7]hept-1-yl sulfone with a ～1:8 mixture of N₂O₄ and NOCl in diethyl ether at -5 to 0°C gave products of formal anti-addition of NO₂Cl at the central C ¹-C⁷ bond. In the reaction with phenyl tricyclo[4.1.0.0^2,7]hept-1-yl sulfone nitryl chloride acts as an effective chlorinating agent; as a result, a mixture of diastereoisomeric syn- and anti-6,7-dichlorobicyclo[3.1.1]hept-6-yl phenyl sulfones at a ratio of 7.5:1 is formed.

Full text of DOI:10.1134/S1070428008040106

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 4, pp. 528–531. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.A. Vasin, S.G. Kostryukov, A.V. Semenov, V.V. Razin, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 4,
pp. 533–536.
Nitrochlorination of Methyl Tricyclo[4.1.0.02,7]heptane-
1-carboxylate and Phenyl Tricyclo[4.1.0.02,7]hept-1-yl Sulfone
V. A. Vasina, S. G. Kostryukova, A. V. Semenova, and V. V. Razinb
a Ogarev Mordovian State University, ul. Bol’shevistskaya 68, Saransk, 430000 Russia
e-mail: vasin@mrsu.ru
b St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
Received July 11, 2007
Abstract—Treatment of methyl tricyclo[4.1.0.02,7]heptane-1-carboxylate and phenyl tricyclo[4.1.0.02,7]hept-1-
yl sulfone with a ~1:8 mixture of N2O4 and NOCl in diethyl ether at –5 to 0°C gave products of formal anti-
addition of NO2Cl at the central C1–C7 bond. In the reaction with phenyl tricyclo[4.1.0.02,7]hept-1-yl sulfone
nitryl chloride acts as an effective chlorinating agent; as a result, a mixture of diastereoisomeric syn- and anti-
6,7-dichlorobicyclo[3.1.1]hept-6-yl phenyl sulfones at a ratio of 7.5:1 is formed.
DOI: 10.1134/S1070428008040106
In the preceding communication [1] we showed that
tricycloheptanes I and II react with dinitrogen tetra-
oxide, which behaves as ambident NO2 radikal, to give
addition products at the central C1–C7 bond, the cor-
responding 6,7-dinitro and 6-nitro-7-nitrosooxy deriva-
tives. While performing these studies we found that the
composition of products obtained from compounds I
and II became more complex when dinitrogen tetra-
oxide was purified using CaCl2 instead of P2O5 [2]; in
each case, an additional chlorine-containing compo-
nent was present in the reaction mixture. We presumed
that the source of chlorine is nitrosyl chloride gen-
erated from N2O4 and CaCl2 via exchange reaction. In
order to verify this assumption, we synthesized nitrosyl
chloride by reaction of gaseous N2O4 with anhydrous
KCl according to the procedure described in [3], and
its mixture with N2O4 at a ratio of ~8:1 was brought
into reaction with compounds I and II in diethyl ether
at –5 to 0°C. The only product formed in the reaction
with ester I was nitro chloride III (Scheme 1). Sulfone
II reacted with NOCl/N2O4 to give a mixture of two
compounds at a ratio of 10:1. The major product, nitro
chloride IV, was isolated as individual substance,
while the minor product was not identified. Just chlo-
rides III and IV were the above additional products
formed in the reactions of I and II with N2O4 pre-
liminarily purified using CaCl2.
The structure of compounds III and IV is fairly
1
consistent with their H and 13C NMR spectra. Con-
siderably lower chemical shifts of the C6 atom in the
13C NMR spectra of III and IV as compared to model
dinitro ester and dinitro sulfone [1] indicate the pres-
ence of a chlorine atom rather than nitro group (which
is characterized by the strongest α-effect [4]) in the
geminal position with respect to the X substituent. The
configuration at the C7 atom follows from the 1H NMR
spectra which contain a triplet signal from the anti-7-H
proton [5]. The exo orientation of the chlorine atom at
C6 in III and IV is confirmed by similar chemical
Scheme 1.
N2O4
O2N
·
X
X
I, II
A
NOCl
1
shifts of the 7-H protons in the H NMR spectra of
O2N
X
these compounds. An additional support for the as-
sumed configuration at C6 is provided by downfield
shift of the 1-H/5-H and 2-H/4-H signals in the spec-
trum of sulfone IV relative to the corresponding sig-
Cl
III, IV
I, III, X = MeOCO; II, IV, X = PhSO2.
528

NITROCHLORINATION OF METHYL TRICYCLO[4.1.0.02,7]HEPTANE-1-CARBOXYLATE
529
lowed by recrystallization. Sulfone Vb was character-
ized as a mixture with diastereoisomer Va (stereo-
chemical purity 65%). The norpinane structure and
configuration of the C7 atom in compounds Va and Vb
nals of ester III. This is explained by stronger long-
range deshielding effect of the sulfonyl group as com-
pared to alkoxycarbonyl substituent [6].
Presumably, like the nitration process [1], the nitro-
chlorination follows radical addition mechanism. The
reaction is initiated by NO2 radical generated from
N2O4, and nitrosyl chloride acts as chlorine carrier.
1
were unambiguously determined by H and 13C NMR
spectroscopy. The configuration of C6 was assigned by
comparing the spectral parameters of Va and Vb with
those of model bromine-containing analogs which
were reported previously [8]. The structure of Va was
unambiguously proved by X-ray analysis [9]. Cyclo-
hexenyl sulfone VI was identified on the basis of the
IR and NMR spectra. The IR spectrum of VI contained
an absorption band at 1643 cm–1 due to stretching
vibrations of the double C=C bond. The olefinic proton
It should be noted that intermediate 6-norpinanyl
radical A takes up chlorine atom preferentially at the
spatially more accessible exo side, thus leading to anti-
adducts III and IV. An alternative path for formation
of compounds III and IV could involve preliminary
oxidation of nitrosyl chloride with dinitrogen tetra-
oxide to give nitryl chloride NO2Cl, which could add
to tricycloheptane I or II according to radical mechan-
ism [7]. We examined reactions of ester I and sulfone
II with nitryl chloride prepared by treatment of chloro-
sulfonic acid with a mixture of oleum and fuming
nitric acid. From ester I we obtained a complex mix-
ture of polychlorinated products which we failed to
isolate and identify. Sulfone II reacted with NO2Cl in
chloroform at –5 to 0°C to give a mixture of three
dichloro derivatives Va, Vb, and VI at a ratio of 17:
2.5:1 (Scheme 2). When the reaction was carried out
in diethyl ether, the products were only stereoisomeric
dichlorides Va and Vb at a ratio of 7.5:1 (according to
1
in VI resonated in the H NMR spectrum as a triplet
at δ 7.4 ppm, the CHCl2 proton gave a doublet at
δ 6.6 ppm, and the corresponding carbon signal was
located at δC 74.8 ppm in the 13C NMR spectrum.
Presumably, dichlorides Va and Vb are formed in
the reaction of sulfone II with nitryl chloride according
to radical addition mechanism where NO2Cl acts
as halogenating (chlorinating) agent in a way similar
to the action of CCl4 (chlorination), CBrCl3 or CBr4
(bromination), CCl3I (iodination) [10, 11], and ben-
zenesulfonyl bromide (bromination) [8] toward bicy-
clobutane compounds. The formation of monocyclic
dichloride VI together with dichloronorpinanes Va and
Vb in the reaction of sulfone II with NO2Cl in CHCl3
may be rationalized assuming isomerization of inter-
mediate endo-7-chloro-6-phenylsulfonylnorpinan-6-yl
radical into chloro(2-phenylsulfonylcyclohex-2-en-1-
yl)methyl radical, which is analogous to cyclobutyl–
homoallyl rearrangement [11, 12]. A probable reason
for the formation of a more complex mixture of prod-
ucts in the reaction of ester I with nitryl chloride is that
the tricycloheptane substrate has a considerably lower
ionization potential as compared to sulfone II. There-
fore, nitryl chloride can act here as both radical and
electrophilic reagent [13].
1
the GLC and H NMR data). In no case nitro chloride
IV was detected. Compounds Va and Vb were also
synthesized by independent method, i.e., by reaction of
sulfone II with (dichloro-λ3-iodanyl)benzene in carbon
tetrachloride at 20°C under UV irradiation.*
Scheme 2.
NO2Cl
Cl
Cl
SO2Ph
SO2Ph
II
Va
CHCl2
EXPERIMENTAL
+
+
Cl
SO2Ph
The elemental compositions were determined on
a Hewlett–Packard HP-185B CHN analyzer. The
1H and 13C NMR spectra were measured on a Bruker
AC-300 spectrometer at 300.130 and 75.468 MHz,
respectively, using CDCl3 as solvent. The IR spectra
were recorded in KBr on an InfraLYuM FT-02 spec-
trometer with Fourier transform. GLC analysis was
performed on a Chrom-41 chromatograph equipped
with a flame ionization detector and a glass column,
SO2Ph
Cl
Vb
VI
Compounds Va and VI were isolated as individual
substances by column chromatography on Al2O3, fol-
* We found that treatment of sulfone II with molecular chlorine in
CCl4 at 0°C gives mainly dichloride VI and seven minor prod-
ucts (GLC data) which were not identified (see Experimental).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008

VASIN et al.
530
1200×3 mm, packed with 3% of OV-17 on Inerton
N-Super (0.125–0.160 mm); carrier gas nitrogen, flow
rate 40 ml/min; oven temperature 210°C, injector tem-
perature 260°C. The components were quantitated
using internal normalization technique; the calibrating
factors for all compounds were assumed to be equal to
unity. Analytical thin-layer chromatography was per-
formed on Silufol UV-254 plates using hexane–diethyl
ether (1:1) as eluent; development with iodine vapor.
Aluminum oxide of activity grade II and silica gel L
(40–100 μm) were used for column chromatography;
eluent light petroleum ether–diethyl ether, (2–3):1.
Tricycloheptanes I [14] and II [15] with a purity of no
less than 97% were synthesized by known methods.
OMe), 5.19 t (1H, 7-H, J = 5.5 Hz). 13C NMR spec-
trum, δC, ppm: 11.4 (C3), 22.5 (C2, C4), 51.0 (C1, C5),
53.0 (OMe), 63.4 (C7), 75.2 (C6), 167.0 (C=O). Found,
%: C 46.32; H 5.26; N 5.88. C9H12ClNO4. Calculated,
%: C 46.27; H 5.18; N 5.59.
exo-6-Chloro-syn-7-nitrobicyclo[3.1.1]hept-endo-
6-yl phenyl sulfone (IV). Yield 56%, mp 158–159°C
(from acetone–hexane), Rt 8.7 min. IR spectrum, ν,
cm–1: 563 m, 617 m, 686 m, 721 m, 1153 v.s, 1315 v.s,
1385 s (NO2, asym.), 1446 s, 1527 v.s (NO2, sym.).
1H NMR spectrum, δ, ppm: 1.31–1.52 m and 1.84–
2.04 m (1H each, 3-H), 2.39–2.56 m and 2.92–3.09 m
(2H each, 2-H, 4-H), 3.49 br.d (2H, 1-H, 5-H, J =
5.8 Hz), 5.11 t (1H, 7-H, J = 5.8 Hz), 7.63 t (2H, Harom
,
J = 7.3 Hz), 7.74 t (1H, Harom, J = 7.3 Hz), 7.95 d (2H,
Reaction of tricycloheptanes I and II with a mix-
ture of dinitrogen tetraoxide and nitrosyl chloride
(general procedure). A mixture of anhydrous Pb(NO3)2
and coarse quartz sand (1:2) was heated in a heat-
resistant glass round-bottom flask using a gas burner.
The released dinitrogen tetraoxide was passed through
a 20×250-mm glass tube filled with anhydrous potas-
sium chloride. The yellow–green gas consisting of
NOCl and N2O4 at a ratio of ~8:1 was collected in
a receiver cooled to –15°C using an ice–salt bath.
About 1 ml of the condensate was diluted with 5 ml of
cold anhydrous diethyl ether, and a solution of 6 mmol
of compound I or II in 5 ml of diethyl ether was
added. The mixture was kept for 3 h at –5 to 0°C, and
10 ml of a saturated solution of sodium hydrogen
carbonate was added with care. The organic layer was
separated, the aqueous layer was extracted with diethyl
ether (20×3 ml), the extracts were combined with the
organic phase and dried over MgSO4, and the solvent
was removed under reduced pressure (water-jet pump).
The solid residue was analyzed by GLC and 1H NMR.
From ester I we obtained compound III as the only
product which was purified by recrystallization. The
product mixture obtained from sulfone II contained
two compounds at a ratio of 10:1 (according to the
1H NMR data). The major product, nitro chloride IV,
was isolated by column chromatography on silica gel.
We failed to isolate and identify the minor product.
H
arom, J = 7.3 Hz). 13C NMR spectrum, δC, ppm: 12.5
(C3), 23.8 (C2, C4), 54.3 (C1, C5), 75.3 (C7), 80.1 (C6);
129.1, 129.5, 134.5, 136.6 (Carom). Found, %: C 49.32;
H 4.28; N 4.38. C13H14ClNO4S. Calculated, %:
C 49.45; H 4.47; N 4.44.
Reaction of tricycloheptane II with nitryl
chloride. A solution of 1.17 g of sulfone II in 20 ml of
anhydrous chloroform containing 0.5 g of Na2CO3 was
cooled to –5°C, and a slight stream of NO2Cl {pre-
pared by slowly adding 4.7 ml of chlorosulfonic acid
to a mixture of 3 ml of nitric acid (d = 1.51 g/cm3) and
3 ml of 30% oleum according to the procedure de-
scribed in [3]} was passed through the solution over
a period of 30 min under stirring. The mixture was
then stirred for an additional 1 h at 0°C, excess nitrosyl
chloride was purged off with a slight stream of nitro-
gen (until the mixture turned light yellow), and the
mixture was washed with a 5% solution of sodium
carbonate and with water. The organic phase was dried
over CaCl2 and evaporated under slightly reduced pres-
sure to obtain 1.49 g of a crystallizable oily material
which was analyzed by TLC, GLC, and 1H NMR. The
product contained compounds Va, Vb, and VI at a ra-
tio of 17:2.5:1. By column chromatography on alumi-
num oxide we isolated a mixture of dichlorides Va
and Vb and cyclohexenyl sulfone VI. The subsequent
recrystallizations gave 1.02 g (67%) of compound Va
and 62 mg (4%) of VI. Compound Vb, 0.12 g (8%),
was characterized by spectral methods as a sample
with a stereochemical purity of 65%. Analogous reac-
tion of tricycloheptane II with NO2Cl in diethyl ether
gave a mixture of dichlorides Va and Vb at a ratio of
7.5:1 in an overall yield of 87%.
Methyl exo-6-chloro-syn-7-nitrobicyclo[3.1.1]-
heptane-endo-6-carboxylate (III). Yield 75%,
mp 92–93°C (from diethyl ether), Rf 0.73, Rt 4.5 min
(140°C). IR spectrum, ν, cm–1: 542 m, 690 m, 1094 m,
1126 s, 1385 s (NO2, asym.), 1447 s, 1538 v.s (NO2,
1
sym.), 1741 v.s (C=O). H NMR spectrum, δ, ppm:
1.31–1.46 m (2H, 3-H), 2.20–2.42 m (4H, 2-H, 4-H),
3.31 br.d (2H, 1-H, 5-H, J = 5.5 Hz), 3.87 s (3H,
endo-6,syn-7-Dichlorobicyclo[3.1.1]hept-exo-6-yl
phenyl sulfone (Va). mp 161–162°C (from acetone–
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NITROCHLORINATION OF METHYL TRICYCLO[4.1.0.02,7]HEPTANE-1-CARBOXYLATE
531
hexane), Rf 0.63, Rt 6.0 min. IR spectrum, ν, cm–1:
Reaction of sulfone II with chlorine. A solution of
2970 w, 2937 w, 1452 m, 1324 s, 1307 s, 1151 v.s,
1090 m, 883 m, 692 m, 563 s. H NMR spectrum, δ,
ppm: 1.51–1.68 m and 1.68–1.86 (1H each, 3-H),
2.10–2.26 and 2.30–2.48 (2H each, 2-H, 4-H),
3.35 br.d (2H, 1-H, 5-H, J = 6.0 Hz), 5.51 m (1H, 7-H,
J = 6.0 Hz), 7.60 t (2H, Harom, J = 7.5 Hz), 7.73 t (1H,
0.5 g of sulfone II in 10 ml of carbon tetrachloride was
added under stirring and cooling to 0°C to a saturated
solution of chlorine in 50 ml of carbon tetrachloride.
The mixture was stirred for 30 min (until the initial
sulfone disappeared according to the TLC data). The
solvent was removed under reduced pressure to obtain
0.67 g of a colorless oily material which contained
(according to the GLC data), 55% of compound VI
and 7 unidentified compounds with the following re-
tention times, min: 1.9 (1%), 2.6 (3%), 3.4 (3%), 4.2
(5%), 8.4 (8%), 10.3 (12%), 12.5 (13%). By column
chromatography on aluminum oxide we isolated 0.19 g
(31%) of crystalline compound VI.
1
H
arom, J = 7.5 Hz), 7.99 d (2H, Harom, J = 7.5 Hz).
13C NMR spectrum, δC, ppm: 12.4 (C3), 25.7 (C2, C4),
49.1 (C1, C5), 54.5 (C7), 87.7 (C6); 128.9, 130.5,
134.4, 135.2 (Carom). Found, %: C 50.98; H 4.73.
C13H14Cl2O2S. Calculated, %: C 51.16; H 4.62.
exo-6,syn-7-Dichlorobicyclo[3.1.1]hept-endo-6-yl
1
phenyl sulfone (Vb). Rf 0.63, Rt 5.0 min. H NMR
spectrum, δ, ppm: 1.88–2.09 (2H, 3-H), 2.25–2.50
(2H, overlapped by the signal of Va) and 2.75–2.90
(2H) (2-H, 4-H), 3.11 br.d (2H, 1-H, 5-H, J = 5.7 Hz),
5.01 t (1H, 7-H, J = 5.7 Hz); signals from the aromatic
protons were overlapped by those of isomer Va.
13C NMR spectrum, δC, ppm: 13.2 (C3), 24.6 (C2, C4),
54.6 (C1, C5), 56.3 (C7), 84.4 (C6); 128.9, 129.4,
134.1, 137.0 (Carom). Found, %: C 50.89; H 4.78.
C13H14Cl2O2S. Calculated, %: C 51.16; H 4.62.
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,
J = 7.3 Hz), 7.66 t (1H, Harom, J = 7.3 Hz), 7.88 d (2H,
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off, the solvent was removed from the filtrate under
slightly reduced pressure, and the solid residue was
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 4 2008