Products and mechanism of some halogenation reactions of 1-sulfonyl-substituted tricyclo[4.1.0.02,7]heptanes

Article abstract of DOI:10.1134/S1070428012030049

Reactions of 1-methylsulfonyl- and 1-phenylsulfonyltricyclo[4.1.0.0 ^2,7]heptanes with iodine, dioxane dibromide, and dichloro-λ3- iodanylbenzene (under irradiation) gave products of stereoselective syn addition of halogen at the C¹-C⁷ central bicyclobutane bond. 7-Methyl-1-phenylsulfonyltricyclo[4.1.0.0^2,7]- heptane reacted with dioxane dibromide in carbon tetrachloride to produce a mixture of 2-bromo- and 2,3-dibromo- 1-methyl-exo-7-phenylsulfonylnorcaranes at a ratio of 1 : 4 as a result of cleavage of the C¹-C² bicyclobutane bond. 7-Bromo- and 7-methoxycarbonyl-1-phenylsulfonyltricyclo[4.1.0.0 ^2,7]heptanes take up bromine exclusively at the C¹-C ⁷ central bond with strict syn stereoselectively. The regio- and stereoselectivity of the addition and their relations with the halogen nature were interpreted with account taken of structural specificities of intermediate 6-sulfonyl-substituted 6-norpinanyl radicals determined by ab initio quantumchemical calculations using 6-31G basis set. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012030049

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 3, pp. 358–367. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.A. Vasin, P.S. Petrov, V.A. Kalyazin, V.V. Razin, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 3,
pp. 365–373.
Products and Mechanism of Some Halogenation Reactions
of 1-Sulfonyl-Substituted Tricyclo[4.1.0.02,7]heptanes
V. A. Vasina, P. S. Petrova, V. A. Kalyazina, and V. V. Razinb
a Ogarev Mordovian State University, ul. Bol’shevistskaya 68, Saransk, 430005 Russia
e-mail: vasin@mrsu.ru
b St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
Received June 22, 2011
Abstract—Reactions of 1-methylsulfonyl- and 1-phenylsulfonyltricyclo[4.1.0.02,7]heptanes with iodine,
dioxane dibromide, and dichloro-λ3-iodanylbenzene (under irradiation) gave products of stereoselective syn
addition of halogen at the C1–C7 central bicyclobutane bond. 7-Methyl-1-phenylsulfonyltricyclo[4.1.0.02,7]-
heptane reacted with dioxane dibromide in carbon tetrachloride to produce a mixture of 2-bromo- and 2,3-di-
bromo-1-methyl-exo-7-phenylsulfonylnorcaranes at a ratio of 1:4 as a result of cleavage of the C1–C2 bicyclo-
butane bond. 7-Bromo- and 7-methoxycarbonyl-1-phenylsulfonyltricyclo[4.1.0.02,7]heptanes take up bromine
exclusively at the C1–C7 central bond with strict syn stereoselectively. The regio- and stereoselectivity of the
addition and their relations with the halogen nature were interpreted with account taken of structural
specificities of intermediate 6-sulfonyl-substituted 6-norpinanyl radicals determined by ab initio quantum-
chemical calculations using 6-31G basis set.
DOI: 10.1134/S1070428012030049
It is known that elemental halogens and halogen
carriers (such as N-bromosuccinimide, dioxane di-
bromide, dichloro-λ3-iodanylbenzene, etc.) are capable
of acting as both electrophilic and radical reagents in
the addition reactions with olefins. Bicyclo[1.1.0]-
butane derivatives, in particular compounds of the tri-
cyclo[4.1.0.02,7]heptane series, are formally saturated
compounds; however, due to high π-character of bonds
in the bicyclobutane fragment they react with many
reagents as alkenes with rupture of these bonds. Elec-
trophilic addition to tricyclo[4.1.0.02,7]heptanes can
involve both central bicyclobutane C–C bond with
formation of norpinane derivatives and side C–C
bond to give norcarane derivatives [1, 2]; radical ad-
dition occurs exclusively at the central bond [3].
For instance, tricyclo[4.1.0.02,7]heptane (I) and its
1-methyl and 1-phenyl derivatives II and III undergo
halomethoxylation at the C1–C7 bond according to the
electrophilic addition mechanism [4–6]. Study on halo-
methoxylation of methyl tricyclo[4.1.0.02,7]heptane-1-
carboxylate (IV) as substrate possessing reduced
nucleophilicity showed that this reaction also follows
electrophilic pattern [7]. However, the result of action
of other halogenating agents, e.g., elemental iodine, on
the same compound indicated competition between
electrophilic and radical paths of halogenation at the
C1–C7 bond.
R
SO2R'
SO2R'
R
I–IV
V, VI
VII–IX
I, R = H; II, VII, R = Me; III, R = Ph; IV, IX, R = MeOCO;
VIII, R = Br; V, R′ = Me; VI–IX, R = Ph.
In the present work we studied reactions of some
halogenating agents with 1-mono- and 1,7-disubstitut-
ed tricycloheptanes containing in the bridgehead posi-
tion a sulfonyl group which is a stronger electron-with-
drawing substituent than methoxycarbonyl group.
Sulfones V–IX were expected to be largely deactivated
toward electrophilic attack, so that their reactions with
halogenating agents would follow mainly radical
mechanism with formation of norpinane derivatives.
We initially found that none of sulfonyl-substituted
tricycloheptanes V–IX reacted with N-halosuccin-
imides in methanol. Unlike sulfones V–IX, 7-phenyl-
1-phenylsulfonyltricyclo[4.1.0.02,7]heptane was recent-
ly shown [8] to undergo, though slowly, electrophilic
358

PRODUCTS AND MECHANISM OF SOME HALOGENATION REACTIONS
Table 1. Halogenation of tricycloheptanes V and VI
359
Tricycloheptane
Halogenating agent (solvent)
Products
Yield, %
Fraction of syn-adduct, %
V
I2 (Et2O)
X
60
90
~100
VI
V
I2 (Et2O)
XI
~100
Br2·dioxane (CCl4)
Br2·dioxane (CCl4)
PhICl2 (CCl4)
PhICl2 (CCl4)
XIIa, XIIb
XIIIa, XIIIb
XIVa, XIVb
XVa, XVb
70
~095
VI
V
81
~075 [9]
~078
<50<
64
VI
~089 [11]
halomethoxylation at the central C1–C7 bond with ex-
clusive formation of syn-addition product having nor-
pinane structure. This was interpreted in terms of effect
of donor substituent at the bridgehead carbon atom,
which stabilizes intermediate benzyl-type carbocation.
tion. We failed to isolate pure minor anti-adducts
XIIb–XVb, and they were characterized by spectral
methods as mixtures with their major diastereoisomers.
The structure of compounds XIIIa and XVa was
determined previously by X-ray analysis [9, 10];
proofs for the structure of dibromide XIIIb and di-
chloride XVb were given in [9, 11]. The structure of
diiodides X and XI, dibromides XIIa and XIIb, and
dichlorides XIVa and XIVb was confirmed using the
1H and 13C NMR spectra of structurally related com-
pounds XIIIa, XIIIb, XVa, and XVb. syn Orientation
of the halogen atom on C7 follows from the presence
of a triplet signal of anti-7-H (J ≈ 6 Hz) in the
1H NMR spectra [12]. The difference in the chemical
shifts of anti-7-H between stereoisomeric dibromides
XIIa and XIIb and dichlorides XIVa and XIVb
allowed us to assign configuration of the C6 atom with
account taken of weaker long-range deshielding effect
of the bromine or chlorine atom oriented opposite to
anti-7-H, as compared to sulfonyl group (cf. [9, 11]).
The configuration at C6 in diiodides Xa and XIa was
assumed to be the same as in dibromides XIIa and
XIIIa and dichlorides XIVa and XVa on the basis of
similarity of chemical shifts of anti-7-H in all three
couples of compounds. The configuration at C6 in
dibromide XIIa was also confirmed chemically by
stereospecific hydrodebromination with triphenyltin
hydride, which afforded monobromide XVI (cf. [8, 13,
14]); we also identified compound XVI as one of
minor products formed in the reaction of tricyclo-
heptane V with dioxane dibromide. The configuration
of C6 and C7 in compound XVI unambiguously fol-
lowed from the presence of singlet and triplet signals
We then examined reactions of monosubstituted
tricycloheptanes V and VI with elemental iodine,
dioxane dibromide, and dichloro-λ3-iodanylbenzene
(under irradiation). All these reactions occurred fairly
readily at room temperature. The iodination gave nor-
pinane derivative Xa or XIa, respectively, as the only
product corresponding to rigorous syn stereoselectivity
of the addition. The bromination and chlorination
followed analogous pattern, but in each case two dia-
stereoisomeric 6,7-dihalo derivatives were formed
(compounds XIIa–XVa and XIIb–XVb) with appre-
ciable prevalence of the syn-adduct (Table 1; see also
[9–11]). In addition, the bromination of tricyclohep-
tane V gave monobromonorpinane XVI and dibromo-
norcarane XVII as by-products, whereas the chlorina-
tion of the same substrate was accompanied by forma-
tion of dichloronorcarane XVIII. Analogous norcarane
dibromide XIX was formed as an impurity in the
bromination of tricycloheptane VI.
syn-Adducts Xa–XVa were isolated as individual
substances by column chromatography and crystalliza-
Hlg
Hlg
Hlg
SO2R
SO2R
Xa–XVa
Hlg
XIIb–XVb
1
belonging to endo-6-H and anti-7-H in the H NMR
spectrum (cf. [12]).
Br
Hlg
·
The formation of compounds X–XV was rational-
ized in terms of radical mechanism of halogenation of
sulfones V and VI. Our interpretation was based on
both regioselectivity of the addition (cleavage of the
central rather than side C–C bond) and its stereo-
SO2Me
SO2Me
XVI
A
X, XII, XIV, R = Me; XI, XIII, XV, R = Ph; X, XI, Hlg = I;
XII, XIII, Hlg = Br; XIV, XV, Hlg = Cl.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012

VASIN et al.
360
Table 2. Relative energies ΔH,a dihedral angles (α, β, γ, δ), and interatomic distances l1 and l2 in methylsulfonyl-substituted
radicals A, according to quantum-chemical calculations with 6-31G basis setb, c
Radical
Invertomer ΔH, kcal/mol
l1, Å
l2, Å
α, deg
β, deg
γ, deg
δ, deg
ACl
A′
0.84
0.00
0.77
0.00
1.19
0.00
2.513
2.485
2.512
2.471
2.483
2.436
2.782
2.886
2.728
2.825
2.679
2.775
–153.7–
140.0
152.5
155.0
151.0
153.8
146.1
148.1
125.6
110.3
108.7
110.7
109.8
112.4
139.5
137.6
139.6
137.9
153.6
139.4
A″
A′
ABr
AI
–153.7–
141.0
A″
A′
–139.6–
140.2
A″
a
b
c
Zero-point vibration energies (ZPE) of radicals were not estimated.
Radicals AI were calculated with the use of iodine functions from STO-6G basis set.
Selected geometric parameters: l1 stands for the 7-H···C6, l2 stands for the 3-H3 ···C6 distance, α is the dihedral angle between the C1C6C5
plane and C6–S bond, β is the dihedral angle between the C1C2C4C5 and C2C3C4 planes, γ is the angle between the C1C2C4C5 and C1C5C6
planes, and δ is the angle between the C1C5C7 and C1C5C6 planes.
selectivity: isomers “b” could be obtained only accord-
ing to radical rather than ionic (with halogen as elec-
trophile) reaction path. In all cases the addition is
initiated by endo attack by halogen atom on C7 with
formation of 6-norpinanyl radical A, and the subse-
quent reagent transfer to the reaction center in A is
characterized by syn stereoselectivity. The selectivity
depends on the halogen nature and is the highest for
iodine.
are characterized by the same energy, were optimized
for each invertomer A′. In these radicals, the 3-CH2
fragment deviates toward the C6 atom. Invertomers A′
are initially formed via cleavage of the bicyclobutane
system [16]. They are slightly less energetically favor-
able than invertomers A″, and reversible transforma-
tion A′ ↔ A″ is possible (Table 2). The reaction center
in bromo- and chloro-substituted invertomers A′ is
more flattened as compared to analogous invertomers
A″ (cf. the angles α between the C1C6C5 plane and the
C6–S bond). Obviously, adducts “a” should be derived
from invertomers A′, and adducts “b,” from A″.
With a view to reveal factors responsible for stereo-
selectivity in the halogenation of sulfones V and VI,
the electronic and steric structures of halogenated
6-methylsulfonyl-substituted 6-norpinanyl radicals A
were estimated by ab initio quantum-chemical calcula-
tions with 6-31G basis set using PC GAMESS soft-
ware [15]. According to the results of our previous
calculations, analogous 6-methoxycarbonyl-substituted
6-norpinanyl radicals possess planar reaction center
[7]. By contrast, the most stable radicals A had pyram-
idal reaction center and were represented by two
invertomers A′ and A″ (see figure). The structures of
mirror isomers with respect to the C3C6C7 plane, which
The “a/b” stereoisomer ratio can be determined by
several factors, primarily by the relative rates of
reagent transfer to the reaction center in norpinanyl
radical and its inversion. We believe that, unlike anal-
ogous intermediates having a hydrogen atom or alkyl
or phenyl substituent at the radical center (such inter-
mediates are formed from tricycloheptane hydrocar-
bons I–III, e.g., in homolytic sulfonation [17] and
sulfanylation [18] characterized by anti selectivity of
the addition), in our case the rate of inversion of the
radical center may be either lower than or comparable
to the rate of reagent transfer due to d-orbital effect of
the sulfonyl substituent. Then invertomer A′ reacts
mainly as it is generated (cf. [9]), which determines
syn selectivity of the addition as a whole.
C3
C3
C2
C1
C2
C1
Hlg
C4
C5
Hlg
C4
C5
S1
C6
S1
C7
C7
On the other hand, different selectivities in the
halogenation of sulfone V may be related to dif-
ferences in spatial accessibilities of the reaction centers
in invertomers A′ and A″. In all cases, the interatomic
distance anti-7-H···C6 (l1) in A″ is shorter than the
distance C3–C6 (l2) in A′. Furthermore, the methyl
group and atomic orbital bearing unpaired electron in
C6
A′
A″
Steric structure of invertomers A′ and A″ of methylsulfonyl-
substituted radicals according to ab initio calculations.
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PRODUCTS AND MECHANISM OF SOME HALOGENATION REACTIONS
361
A″ are synperiplanar with respect to the C6–S bond,
which gives rise to additional shielding of the reaction
center. The methyl group in A′ is synclinal with
respect to the unpaired electron orbital, and its shield-
ing effect on the reaction center is weaker than in A″.
Thus structure A′ is more favorable for reagent ap-
proach to the reaction center, which also determined
the observed syn stereoselectivity in the halogenation
of tricycloheptane V. Taking into account considerable
differences in steric volumes of iodine, bromine, and
chlorine atoms (their van der Waals radii are 1.97,
1.86, and 1.73 Å, respectively [19]), it becomes clear
why only one product is formed in the iodination reac-
tion. Presumably, the above structural peculiarities of
radicals A generated from tricycloheptane V are also
inherent to radicals derived from tricycloheptane VI.
and (3) asymmetric structure of the π-complex with
a large positive charge on the C2 atom due to stabiliza-
tion by the three-membered carbocycle. Expected
similarity of the NMR spectra of dihalo derivative
XVII, on the one hand, and compounds XVIII and
XIX, on the other, allowed us to assign analogous
structure to the two latter.
Disubstituted tricycloheptanes VIII and IX failed
to react with dioxane dibromide and with iodine. Only
prolonged reaction of VIII and IX with an equimolar
amount of bromine in methylene chloride (7 days at
20°C) afforded compounds XXII and XXIII, the latter
being the syn-addition product at the C1–C7 bond.
The structure of tetrasubstituted norpinanes XXII
and XXIII was proved on the basis of their 1H and 13C
NMR spectra, which were analogous to those of model
compounds [8, 22]. Ester XXIII was characterized by
nonequivalence of the 1-H and 5-H protons and C1 and
C5 carbon nuclei due to staggered conformation of the
ester group which is orthogonal to the C3C6C7 plane
(according to the X-ray diffraction data [23]). By con-
trast, the C1H and C5H fragments in the NMR spectra
of tribromo sulfone XXII are equivalent.
The formation of monobromonorpinane XVI in the
reaction of tricycloheptane V with dioxane dibromide
may be rationalized assuming that norpinanyl radical
A is also involved in side process, abstraction of
hydrogen from solvent molecules. Dihalonorcaranes
XVII–XIX are likely to be formed as a result of partial
isomerization of tricycloheptanes V and VI into nor-
carenes XX and XXI in the presence of traces of
hydrogen halide and subsequent halogen addition at
the C=C bond. This assumption was confirmed by
special experiment: the reaction of bromine with pre-
liminarily synthesized compounds XX and XXI [20]
gave the same dibromonorcaranes XVII and XIX,
respectively.
We believe that sulfones VIII and IX react with
bromine only according to radical mechanism because
of their strong deactivation toward electrophiles. In
fact, the reaction is accelerated under irradiation.
Rigorous syn stereoselectivity in the bromination of IX
may be rationalized by steric factors in intermediate
norpinanyl radical where the methoxycarbonyl (or
phenylsulfonyl) group hampers anti approach of the
reagent to the reaction center.
The structure of norcarane XVII was determined
1
by H and 13C NMR spectroscopy. exo Orientation of
the methylsulfonyl group on C7 was assigned on the
basis of the coupling constant for the α-H proton
(5 Hz), which is typical of trans vicinal coupling in
cyclopropanes [21]. We have no direct proofs for the
assumed configuration of C2 and C3 in molecule XVII,
and the assignment was made on the basis of general
considerations on the formation of dibromide XVII in
the bromination of norcarene XX. These included (1)
anti addition at the double C=C bond, (2) exo approach
of electrophilic bromine to the C=C bond of norcarene,
Disubstituted sulfone VII having an electron-
donating group in the 7-position turned out to be more
reactive than tricycloheptanes VIII and IX, and it
readily reacted with dioxane dibromide at room tem-
perature. However, instead of expected norpinane
dibromide B we obtained two norcarane derivatives,
dibromide XXIV and monobromide XXV at a ratio of
4:1. Compounds XXIV and XXV were identified in
the reaction mixture by NMR and MALDI mass
spectrometry. Bromonorcarane XXV was isolated as
individual substance by column chromatography on
silica gel. It was also synthesized independently by
passing dry hydrogen bromide through a solution of
compound VII in carbon tetrachloride. Dibromonor-
carane XXIV was identified by comparing with
a sample prepared by independent synthesis from nor-
carene XXVI [20] and bromine (Scheme 1).
SO2R
SO2R
Hlg
Br
Br
R
Hlg
SO2Ph
XVII–XIX
XX, XXI
XXII, XXIII
XVII, XVIII, XX, R = Me; XIX, XXI, R = Ph; XVII, XIX, Hlg =
Br; XVIII, Hlg = Cl; XXII, R = Br; XXIII, R = MeOCO.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012

VASIN et al.
362
Scheme 1.
SO2Ph
SO2Ph
Me
XXIV
Br2
Br
Me
Br
HBr
XXVI
SO2Ph
Br
Me
XXV
VII
Br2
Br
Br
SO2Ph
Br
–HBr
H2C
Me
SO2Ph
B
C
of dibromide XIIa under the action of bases with dif-
ferent strengths. However, compound XIIa remained
unchanged on heating in a boiling solution of sodium
hydroxide in aqueous dioxane or by the action of
potassium tert-butoxide in THF at 0°C. Only heating
of XIIa with excess potassium tert-butoxide in DMSO
at 70°C (reaction time 2 h) resulted in its transforma-
tion into sulfone V (Scheme 2).
Presumably, the reaction of tricycloheptane VII
with dioxane dibromide nevertheless involves initial
formation of some amount of dibromonorpinane B as
product of radical addition of bromine. However,
unlike dibromides XXII and XXIII, intermediate B is
unstable, and it undergoes spontaneous dehydro-
bromination [5] to give methylidenenorpinane C. The
latter was not detected in the reaction mixture, prob-
ably because of its fast transformation into further
bromination products. Liberated hydrogen bromide
reacts with tricycloheptane VII along two pathways.
One of these is stereoselective addition at the C1–C2
bond with formation of monobromide XXV, which is
consistent with published data on regio- and stereo-
selectivity of cleavage of tricycloheptane system
initiated by electrophilic hydrogen [1, 2, 20]. The
second path is catalytic isomerization of tricyclohep-
tane VII into norcarene XXVI which takes up bromine
to produce dibromide XXIV, as in the above inter-
pretation of the formation of dibromides XVII and
XIX from tricycloheptanes V and VI.
Scheme 2.
B–
Br
XIIa
V
SO2Me
F
Thus dibromide XIIa undergoes 1,3-debromination
rather than dehydrobromination in the reaction where
dimethyl sulfoxide potassium salt acts as halophilic
reagent capable of generating sulfonyl-substituted
carbanion F [26]. Analogous transformation was re-
ported previously [27] for endo,syn-6,7-diiodobicyclo-
[3.1.1]heptane.
Dihalo sulfones XIIa and XIVa seemed to be
promising from the viewpoint of their further trans-
formation either into 6-methylidenenorpinane deriva-
tive D via Ramberg–Bäcklund reaction [24] or into
tricyclic sulfone E as a result of 1,5-dehydrohalogena-
tion [25]. For this purpose we examined the behavior
EXPERIMENTAL
The elemental compositions were determined on
1
an HP-185B CHN analyzer. The H and 13C NMR
spectra were recorded on a Bruker AC-300 spectrom-
eter at 300.130 and 75.468 MHz, respectively, using
CDCl3 as solvent and tetramethylsilane as internal
reference. The IR spectra were measured in KBr on an
InfraLYuM FT-02 spectrometer with Fourier transform.
Br
Br
CH2
S
O
GLC analyses were performed on a Kristallyuks-
4000 chromatograph equipped with a flame ionization
O
D
E
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012

PRODUCTS AND MECHANISM OF SOME HALOGENATION REACTIONS
363
detector and a 1000×3-mm glass column packed with
3% of OV-17 on Inerton N-Super (0.125–0.160 mm);
carrier gas nitrogen, flow rate 40 ml/min; oven tem-
perature 200°C, injector temperature 240°C. The com-
ponents were quantitated by the internal normalization
method (by peak areas). The chromatograms were
processed using NetChrom 1.5 program. The mass
spectra (electron impact, 70 eV) were obtained on
an Agilent 6890N chromatograph coupled with a mass-
selective detector (Agilent 19091S-433 HP-5MS capil-
lary column, 30 m×0.25 mm; oven temperature prog-
ramming to 300°C; carrier gas helium, 1 ml/min).
a 5% solution of sodium sulfite and water and dis-
solved in 20 ml of chloroform. The solution was dried
over MgSO4 and filtered, and the filtrate was evaporat-
ed under reduced pressure. Crystallization of the resi-
due gave 15.7 g (90%) of sulfone V with mp 75–76°C
(from petroleum ether–diethyl ether, 3:1), Rf 0.22. The
1H and 13C NMR spectra of the product coincided with
the data reported in [25] for the same compound syn-
thesized by us by a different method.
Reaction of sulfones V and VI with molecular
iodine (general procedure). Sulfone V or VI, 1 mmol,
was dissolved in 3 ml of anhydrous diethyl ether,
a solution of 0.25 g (1 mmol) of iodine in 15 ml of
diethyl ether was added, and the mixture was kept for
40 h at 20°C. The mixture was then washed with
a 5% solution of sodium sulfite, dried over MgSO4,
and evaporated, and the solid residue was analyzed by
1H NMR and purified by crystallization.
The MALDI mass spectra were recorded on
a Bruker Autoflex II instrument (FWHM resolution
18000) equipped with a nitrogen laser (λ 337 nm) and
time-of-flight mass analyzer (reflector mode; accel-
erating voltage 20 kV); samples were applied onto
a polished steel support; positive ions were detected.
The resultant spectrum was a sum of 300 spectra re-
corded as different points of a sample. 2,5-Dihydroxy-
benzoic acid (99%, Acros Organics) and α-cyano-4-
hydroxycinnamic acid (99%, Acros Organics) were
used as matrices.
endo-6,syn-7-Diiodo-exo-6-methylsulfonylbicyclo-
[3.1.1]heptane (Xa). Yield 58%, Rf 0.33, mp 157°C
1
(decomp.). H NMR spectrum, δ, ppm: 1.63–1.78 m
and 1.79–1.96 m (1H each, 3-H), 2.35–2.51 m and
2.55–2.71 m (2H each, 2-H, 4-H), 3.16 br.d (2H, 1-H,
5-H, J = 5.9 Hz), 3.34 s (3H, MeSO2), 5.78 t (1H, 7-H,
J = 5.9 Hz). 13C NMR spectrum, δC, ppm: 10.4 (C3),
18.8 (C7), 35.2 (C2, C4), 39.1 (MeSO2), 49.0 (C1, C5),
63.5 (C6). Found, %: C 22.48; H 2.92. C8H12I2O2S.
Calculated, %: C 22.55; H 2.84.
Analytical thin-layer chromatography was per-
formed on Silufol UV-254 plates using hexane–diethyl
ether (2:1) as eluent. Spots were detected by treatment
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.
endo-6,syn-7-Diiodo-exo-6-phenylsulfonylbicyclo-
[3.1.1]heptane (XIa). Yield 90%, mp 175–176°C
1
Quantum-chemical calculations were performed in
terms of the unrestricted Hartree–Fock method (6-31G
basis set supplemented by iodine functions from STO-
6G basis set; initial PM3 parameterization) using PC
GAMESS 7.1 [15].
(from hexane–acetone). H NMR spectrum, δ, ppm:
1.53–1.71 m and 1.73–1.93 m (1H each, 3-H), 2.29–
2.46 m and 2.58–2.67 m (2H each, 2-H, 4-H), 3.26 br.d
(2H, 1-H, 5-H, J = 5.7 Hz), 5.94 t (1H, 7-H, J =
5.7 Hz), 7.59 t (2H, Harom, J = 7.7 Hz), 7.70 t (1H,
H
arom, J = 7.7 Hz), 8.03 d (2H, Harom, J = 7.7 Hz).
Sulfone VI with a purity of no less than 97% was
synthesized from tricycloheptane I by lithiation at the
bridgehead position according to the procedure de-
scribed in [28]. Sulfones VII–IX with the same purity
were prepared as described in [17].
13C NMR spectrum, δC, ppm: 10.5 (C3), 19.2 (C7), 35.4
(C2, C4), 49.6 (C1, C5), 66.0 (C6), 128.7 (2C), 130.7
(2C), 134.3, 136.7 (Carom). Found, %: C 31.97; H 2.94.
C13H14I2O2S. Calculated, %: C 31.99; H 2.89.
1-Methylsulfonyltricyclo[4.1.0.02,7]heptane (V).
A mixture of 15.8 ml of acetonitrile, 4 g of potassium
carbonate, and 14.0 g (0.1 mol) of 1-methylsulfanyl-
tricyclo[4.1.0.02,7]heptane [29] was cooled to 0°C, and
a mixture of 34 ml (0.3 mol) of 30% hydrogen perox-
ide and 30 ml of methanol was added dropwise under
stirring. The progress of the reaction was monitored by
TLC, following the disappearance of the initial sulfide.
The solvent was removed under reduced pressure
(water-jet pump), and the residue was washed with
The reaction of sulfone V with dioxane di-
bromide was carried out according to the procedure
described in [9] for the bromination of tricycloheptane
VI. A solution of 2.15 g (8.7 mmol) of freshly prepared
dioxane dibromide in 60 ml of carbon tetrachloride
was added dropwise over a period of 1 h under stirring
at 0°C to a mixture of 1.5 g (8.7 mmol) of sulfone V,
0.5 g of calcium carbonate, and 25 ml of anhydrous
carbon tetrachloride. The mixture was stirred for 1 h
more until complete decoloration, washed with 15 ml
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012

VASIN et al.
364
of a 5% solution of sodium sulfite and with water, and
dried over CaCl2. According to the GLC and H NMR
tricycloheptane V and 0.82 g (3 mmol) of dichloro-
(phenyl)-λ3-iodane in 20 ml of anhydrous carbon tetra-
chloride, the ampule was tightly capped, and the
mixture was irradiated with a KGL-500 lamp for 5 h at
20°C until it became homogeneous. The solvent was
removed under slightly reduced pressure, and the resi-
due was washed with 5 ml of diethyl ether to remove
iodobenzene. We thus obtained 0.61 g of a product
mixture containing stereoisomers XIVa and XIVb and
norcarane XVIII at a ratio of 4.6:1.3:1. Compounds
XIVa and XVIII were isolated by column chromatog-
raphy, and compound XIVb was identified by spectral
methods in a mixture with XIVa.
1
data, the products were two diastereoisomeric nor-
pinane dibromides XIIa and XIIb and norcarane di-
bromide XVII at a ratio of 8.3 :1 :2.5 with a small
(~5%) impurity of monobromide XVI. Compounds
XIIa and XVII were isolated by column chromatog-
raphy on silica gel. Compound XIIb was identified by
1H NMR in a 2:1 mixture with XIIa. Bromonorpinane
XVI was detected by GC–MS and was identified by
comparing with an authentic sample (see below).
endo-6,syn-7-Dibromo-exo-6-methylsulfonylbicy-
clo[3.1.1]heptane (XIIa). Yield 57%, mp 117–118°C
(from hexane–diethyl ether, 3:1), Rf 0.45, Rt 9.13 min.
1H NMR spectrum, δ, ppm: 1.61–1.77 m and 1.77–
1.92 m (1H each, 3-H), 2.30–2.44 m and 2.46–2.60 m
(2H each, 2-H, 4-H), 3.20 s (3H, MeSO2), 3.30 br.d
(2H, 1-H, 5-H, J = 5.9 Hz), 5.49 t (1H, 7-H, J =
5.9 Hz). 13C NMR spectrum, δC, ppm: 11.7 (C3), 29.3
(C2, C4), 37.9 (MeSO2), 45.5 (C7), 48.8 (C1, C5), 81.7
(C6). Mass spectrum, m/z (Irel, %): 175 (14.4), 173
(15.7), 172 (12.4) [M – Br2], 120 (16.4), 94 (12.2), 93
(100), 92 (9.9), 91 (45.2), 81 (41.9), 79 (25.1), 77
(42.5), 65 (17.0), 53 (12.3). Found, %: C 28.86;
H 3.56. C8H12Br2O2S. Calculated, %: C 28.94; H 3.64.
endo-6,syn-7-Dichloro-exo-6-methylsulfonylbi-
cyclo[3.1.1]heptane (XIVa). Yield 0.27 g (37%),
mp 99–100°C (from hexane–diethyl ether, 4:1),
Rf 0.71, Rt 8.23 min. 1H NMR spectrum, δ, ppm: 1.60–
1.74 m and 1.74–1.88 m (1H each, 3-H), 2.23–2.34 m
and 2.37–2.47 m (2H each, 2-H, 4-H), 3.08 s (3H,
MeSO2), 3.30 d.t (2H, 1-H, 5-H, J = 1.3, 5.9 Hz),
5.27 t (1H, 7-H, J = 5.9 Hz). 13C NMR spectrum, δC,
ppm: 12.2 (C3), 25.5 (C2, C4), 36.7 (MeSO2), 48.5 (C1,
C5), 54.0 (C7), 86.6 (C6). Found, %: C 39.39; H 4.88.
C8H12Cl2O2S. Calculated, %: C 39.52; H 4.97.
exo-6,syn-7-Dichloro-endo-6-methylsulfonylbicy-
clo[3.1.1]heptane (XIVb) was isolated with a stereo-
chemical purity of 50%, Rf 0.45, Rt 6.40 min. 1H NMR
spectrum, δ, ppm: 1.70–1.90 m (1H), 2.12–2.35 m
(3H, 3-H, exo-2-H, exo-4-H) (overlapped by signals of
isomer XIVa); 2.55–2.66 m (2H, 2-H, 4-H), 3.06 s
(3H, MeSO2), 3.16–3.20 m (2H, 1-H, 5-H), 5.05 t (1H,
7-H, J = 5.3 Hz). 13C NMR spectrum, δC, ppm: 12.9
(C3), 24.2 (C2, C4), 39.1 (MeSO2), 54.4 (C1, C5), 56.2
(C7), 73.5 (C6).
exo-6,syn-7-Dibromo-endo-6-methylsulfonylbi-
cyclo[3.1.1]heptane (XIIb). Rf 0.30, Rt 7.35 min.
1H NMR spectrum (XIIa/XIIb, 2:1), δ, ppm: 3.06 s
(3H, MeSO2), 3.20 br.s (2H, 1-H, 5-H), 5.24 t (1H,
anti-7-H, J = 5.3 Hz).
Bromination of tricycloheptane VI according to the
procedure described in [9] gave two diastereoisomeric
norpinanes XIIIa and XIIIb and a small amount
(~5%) of norcarane dibromide XIX which was iden-
tified by comparing with a sample obtained by inde-
pendent synthesis (see below).
endo-2,exo-3-Dichloro-exo-7-methylsulfonylbi-
cyclo[4.1.0]heptane (XVIII). Yield 85 mg (12%),
mp 131–132°C (from hexane–diethyl ether, 4:1),
Rf 0.15, Rt 4.24 min. 1H NMR spectrum, δ, ppm: 1.73–
1.98 m (3H), 2.16–2.23 m (1H), 2.30–2.40 m (2H),
2.55 t (1H, 7-H, J = 4.8 Hz), 3.01 s (3H, MeSO2),
3.93 d.d.d (1H, 3-H, J = 2.4, 5.4, 7.8 Hz), 4.61 d.d
(1H, 2-H, J = 5.7, 7.2 Hz). 13C NMR spectrum, δC,
ppm: 18.2, 20.9, 24.9, 27.0 (C1, C4, C5, C6); 41.0 and
41.4 (Me, C7); 58.9 and 59.2 (C2, C3). Found, %:
C 39.47; H 5.05. C8H12Cl2O2S. Calculated, %:
C 39.52; H 4.97.
endo-2,exo-3-Dibromo-exo-7-methylsulfonylbicy-
clo[4.1.0]heptane (XVII). Yield 20%, mp 155–156°C
(from hexane–diethyl ether), Rf 0.38, Rt 6.51 min.
1H NMR spectrum, δ, ppm: 1.86–2.01 m (2H), 2.09–
2.25 m (2H), 2.31–2.50 m (2H), 2.60 t (1H, 7-H, J =
4.6 Hz), 3.02 s (3H, MeSO2), 4.23–4.32 m (1H, 3-H),
4.94 d.d (1H, 2-H, J = 4.2, 7.6 Hz). 13C NMR spec-
trum, δC, ppm: 18.4, 22.1, 24.8, 26.4, 41.5, 43.1, 50.9
and 51.1 (C2, C3). Found, %: C 28.88; H 3.55.
C8H12Br2O2S. Calculated, %: C 28.94; H 3.64.
The reaction of sulfone V with dichloro(phenyl)-
λ3-iodane was carried out as described in [11] for the
chlorination of tricycloheptane VI [11]. A quartz am-
pule was charged with a mixture of 0.5 g (3 mmol) of
syn-7-Bromo-exo-6-methylsulfonylbicyclo[3.1.1]-
heptane (XVI). A mixture of 0.432 g (1.3 mmol) of
dibromo sulfone XIVa and 0.567 g (2.0 mmol) of
triphenyltin hydride in 15 ml of anhydrous benzene
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PRODUCTS AND MECHANISM OF SOME HALOGENATION REACTIONS
365
containing 5 mg of azobis(isobutyronitrile) was heated
for 4 h under reflux in a weak stream of nitrogen. The
solvent was removed under reduced pressure (water-jet
pump), and the solid residue was subjected to column
chromatography to isolate 0.118 g (36%) of compound
XVI with mp 105–106°C (from chloroform–hexane,
to column chromatography on silica gel to isolate
dibromonorcarane XVII, XIX, or XXIV in 78, 82, or
75% yield, respectively.
endo-2,exo-3-Dibromo-exo-7-phenylsulfonylbi-
cyclo[4.1.0]heptane (XIX). Rf 0.52, mp 149–150°C
1
(from hexane–diethyl ether, 1:1). H NMR spectrum,
1
2:1). H NMR spectrum, δ, ppm: 1.58–1.72 m and
δ, ppm: 1.79–1.95 m (3H), 2.19–2.27 m (1H), 2.30–
2.41 m (1H), 2.49–2.56 m (1H), 2.60 t (1H, 7-H, J =
4.9 Hz), 4.19–4.23 m (1H, 3-H), 4.78 d.d (1H, 2-H, J =
7.8, 4.0 Hz), 7.56 t (2H, Harom, J = 7.6 Hz), 7.66 t (1H,
Harom, J = 7.3 Hz), 7.91 d (2H, Harom, J = 7.8 Hz).
13C NMR spectrum, δC, ppm: 18.2, 23.0, 24.7, 25.8,
44.8 (C7), 49.8 and 51.3 (C2, C3); 127.9 (2C), 129.2
(2C), 133.6, 139.7 (Carom). Found, %: C 39.83; H 3.61.
C13H14Br2O2S. Calculated, %: C 39.62; H 3.58.
1.72–1.88 m (1H each, 3-H), 2.02–2.17 m and 2.26–
2.40 m (2H each, 2-H, 4-H), 2.90 s (3H, MeSO2),
3.11–3.16 m (2H, 1-H, 5-H), 3.60 s (1H, 7-H), 5.42 t
(1H, 6-H, J = 6.3 Hz). 13C NMR spectrum, δC, ppm:
12.8 (C3), 26.2 (C2, C4), 40.0 (MeSO2), 42.4 (C1, C5),
52.2 (C6), 62.6 (C7). Mass spectrum, m/z (Irel, %):
253/251 (24.8/18.2) [M – 1]+, 173/171 (22.2/26.4), 93
(15.9), 92 (47.0), 91 (100), 81 (10.9), 79 (10.2), 77
(19.2), 65 (19.3), 63 (10.1). Found, %: C 38.03;
H 5.06. C8H13BrO2S. Calculated, %: C 37.96; H 5.18.
endo-2,exo-3-Dibromo-1-methyl-exo-7-phenyl-
sulfonylbicyclo[4.1.0]heptane (XXIV). mp 136–
exo-7-Methylsulfonylbicyclo[4.1.0]hept-2-ene
(XX). Perchloric acid, 0.1 ml, was added to a solution
of 1.38 g (8 mmol) of compound V in 50 ml of anhy-
drous benzene. The mixture was kept for 72 h at 20°C,
washed with 5 ml of a 5% aqueous solution of
NaHCO3 and with water, and dried over MgSO4. The
solvent was removed under reduced pressure, and the
residue was subjected to column chromatography on
silica gel to isolate 0.83 g (60%) of compound XX as
1
136.5°C (from hexane–diethyl ether). H NMR spec-
trum, δ, ppm: 1.50 s (3H, Me), 1.75–1.85 m (1H),
1.86–1.96 m (2H), 2.31–2.41 m (1H), 2.45 t (1H, J =
6.4 Hz), 2.61 d (1H, 7-H, J = 6.1 Hz), 4.16 d.d.d (1H,
3-H, J = 2.3, 5.5, 8.3 Hz), 4.39 d (1H, 2-H, J =
6.2 Hz), 7.55 t (2H, Harom, J = 7.7 Hz), 7.64 t (1H,
Harom, J = 7.2 Hz), 7.92 d (2H, Harom, J = 7.3 Hz).
13C NMR spectrum, δC, ppm: 19.2, 19.6, 26.7, 29.1,
31.6 (C1), 49.3 (C7), 52.2 (C3), 59.3 (C2); 127.4 (2C),
129.0 (2C), 133.4, 140.8 (Carom). Mass spectrum
(MALDI), m/z (Irel, %): 428.65 (27.6), 430.54 (40.1),
432.87 (32.3) [M + Na]+·; 444.54 (19.4), 446.55 (56.3),
448.54 (24.3) [M + K]+·. Found, %: C 41.28; H 3.85.
C14H16Br2O2S. Calculated, %: C 41.20; H 3.95.
1
a colorless viscous oily substance, Rf 0.52. H NMR
spectrum, δ, ppm: 1.66–1.81 m (2H), 2.01–2.22 m
(4H, 1-H, 4-H, 5-H, 6-H), 2.59 t (1H, 7-H, J = 4.2 Hz),
2.94 s (3H, MeSO2), 5.64–5.71 m (1H), 5.97–6.03 m
(1H, 2-H, 3-H). 13C NMR spectrum, δC, ppm: 16.5,
17.2, 20.1, 20.4, 40.5, 41.4 (MeSO2), 123.4 and 126.8
(C2, C3). Found, %: C 55.53; H 7.06. C8H12O2S. Cal-
culated, %: C 55.78; H 7.02.
Reaction of tricycloheptane VII with dioxane
dibromide. A solution of 0.74 g (3 mmol) of sulfone
VII in 15 ml of anhydrous carbon tetrachloride con-
taining 0.1 g of CaCO3 was cooled to –10°C, and
a solution of 1.24 g (3 mmol) of freshly prepared di-
oxane dibromide in 35 ml of anhydrous carbon tetra-
chloride was added dropwise over a period of 1 h
under stirring in a nitrogen atmosphere. The mixture
was stirred for ~2 h at 0°C until it turned colorless and
filtered, and the solvent was distilled off from the
filtrate under reduced pressure. The MALDI mass
spectrum of the crystalline residue contained peaks
corresponding to the molecular ions of compounds
1-Methyl-exo-7-phenylsulfonylbicyclo[4.1.0]-
hept-2-ene (XXVI) was synthesized according to the
procedure described in [20]. Its 1H NMR spectrum was
identical to that given in [20]. 13C NMR spectrum
(DEPT), δC, ppm: 16.4 and 19.7 (C4, C5), 17.4 (CH3),
24.8 (C1), 27.7 (C6), 46.4 (C7), 125.4 and 133.0 (C2,
C3); 127.0 (2C), 129.1 (2C), 130.9, 142.0 (Carom).
Reactions of norcarenes XX, XXI, and XXVI
with bromine (general procedure). Sulfone XX, XXI
[20], or XXVI, 4 mmol, was dissolved in 5 ml of
anhydrous methylene chloride, a solution of 0.2 ml
(0.78 g, 4.9 mmol) of bromine in 5 ml of methylene
chloride was added over a period of 10 min under
stirring at 20°C, and the mixture was stirred for 24–
30 h until it turned colorless. The solvent was removed
under reduced pressure, and the residue was subjected
1
XXV and XXIV (ratio 1:4 according to the H NMR
data). Norcarane XXV was isolated as individual sub-
stance by column chromatography on silica gel.
endo-2-Bromo-1-methyl-exo-7-phenylsulfonylbi-
cyclo[4.1.0]heptane (XXV). Yield 0.24 g (24%),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012

VASIN et al.
366
mp 113–114°C (from hexane–diethyl ether), Rf 0.45.
1H NMR spectrum, δ, ppm: 1.15–1.28 m (1H), 1.40–
1.56 (2H), 1.48 s (3H, Me), 1.59–1.73 m (1H), 2.00–
2.09 m (1H), 2.09–2.19 m (1H), 2.38–2.45 m (1H,
6-H), 2.57 d (1H, 7-H, J = 6.1 Hz), 4.13 d.d (1H, 2-H,
J = 5.8, 10.9 Hz), 7.52–7.68 m (3H, Harom), 7.94 d (2H,
Harom, J = 7.1 Hz). 13C NMR spectrum (DEPT), δC,
ppm: 18.2 (Me); 21.7, 22.9, 32.4 (C3, C4, C5); 30.8
(C6), 49.6 (C7), 56.8 (C2); 127.5 (2C), 128.9 (2C),
133.3, 141.0 (Carom). Mass spectrum (MALDI), m/z
(Irel, %): 351.04/353.01 (51.4/48.6) [M + Na]+·;
366.98/368.99 (46.7/53.3) [M + K]+·. Found, %:
C 51.18; H 5.25. C14H17BrO2S. Calculated, %:
C 51.07; H 5.20.
Reaction of dibromide XIIa with potassium tert-
butoxide in DMSO. A solution of 3.32 g (10 mmol) of
compound XIIa in 20 ml of anhydrous DMSO was
added under stirring and cooling (with tap water) in
a dry nitrogen atmosphere to a solution of 5.61 g
(50 mmol) of potassium tert-butoxide in 20 ml of
anhydrous DMSO. The mixture was stirred for 2 h at
70°C, cooled, diluted with 40 ml of water, and ex-
tracted with diethyl ether (5×20 ml). The extracts were
dried over MgSO4, the solvent was distilled off on
a water bath, and the residue was subjected to column
chromatography on Al2O3 to isolate 0.56 g (33%) of
compound V.
REFERENCES
Reaction of tricycloheptane VII with hydrogen
bromide. A solution of 0.62 g (2.5 mmol) of com-
pound VII in 15 ml of anhydrous carbon tetrachloride
was cooled to 0°C, and a weak stream of dry hydrogen
bromide was passed through the solution over a period
of 1 h under stirring [30]. The mixture was then
washed with a 2% solution of sodium carbonate and
with water and dried over MgSO4, the solvent was
removed under reduced pressure, and crystallization of
the residue gave 0.68 g (83%) of norcarane XXV.
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Reactions of sulfones VIII and IX with bromine
(general procedure). A solution of 1.5 mmol of tri-
cycloheptane VIII or IX in 7 ml of anhydrous methyl-
ene chloride was mixed with a solution of 62 μl
(1.5 mmol) of bromine in 3 ml of methylene chloride.
The mixture was kept for 7 days at 20°C in a tightly
capped vessel, washed with 5 ml of a 5% aqueous
solution of Na2SO3 and with water, and dried over
MgSO4. The solvent was removed under reduced
pressure (water-jet pump), and the solid residue was
subjected to column chromatography on silica gel to
isolate compound XXII or XXIII in 82 or 86% yield,
respectively. The physical constants and spectral pa-
rameters of XXIII coincided with those given in [23].
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6,6,7-Tribromo-endo-7-phenylsulfonylbicyclo-
[3.1.1]heptane (XXII). Yield 82%, mp 172–173°C
(from hexane–diethyl ether), Rf 0.73. H NMR spec-
1
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trum, δ, ppm: 1.56–1.67 m and 1.68–1.81 m (1H each,
3-H), 2.47–2.58 m and 2.78–2.89 m (2H each, 2-H,
4-H), 3.96 s (2H, 1-H, 5-H), 7.52 t (2H, Harom, J =
7.7 Hz), 7.60 t (1H, Harom, J = 7.3 Hz), 7.89 d (2H,
H
arom, J = 7.5 Hz). 13C NMR spectrum, δC, ppm: 13.2
(C3), 37.0 (C2, C4), 57.8 (C6), 61.4 (C1, C5), 84.9 (C7),
128.4 (2C), 129.2 (2C), 133.6, 142.4 (Carom). Found,
%: C 32.98; H 2.72. C13H13Br3O2S. Calculated, %:
C 33.01; H 2.77.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 3 2012

PRODUCTS AND MECHANISM OF SOME HALOGENATION REACTIONS
367
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