Application of copper(I) halides to modifying reactivity of Polyhalomethanes and arenesulfonyl chlorides in free-radical addition. "cross-halogenation" reaction

Article abstract of DOI:10.1134/S1070428006080033

In the free-radical addition of a number of organohalogen reagents to cyclic alkenes and dienes in the presence of copper(I) halides the composition of the reaction products is governed by the stage of a fast halogen transfer from the copper derivative to

Full text of DOI:10.1134/S1070428006080033

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 8, pp. 1120-1130. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó A.S. Dneprovskii, A.N. Kasatochkin, V.P. Boyarskii, A.A. Ermoshkin, A.A. Yakovlev, 2006, published in Zhurnal
Organicheskoi Khimii, 2006, Vol. 42, No. 8, pp. 1142-1152.
Application of Copper(I) Halides to Modifying Reactivity
of Polyhalomethanes and Arenesulfonyl Chlorides in Free-Radical
Addition. “Cross-Halogenation” Reaction
†
A.S. Dneprovskii , A.N. Kasatochkin, V.P. Boyarskii,A.A. Ermoshkin, andA.A. Yakovlev
St. Petersburg State University, St. Petersburg, 198504 Russia
e-mail: vadimpb@newmail.ru
Received September 19, 2005
Abstract—In the free-radical addition of a number of organohalogen reagents to cyclic alkenes and dienes in the
presence of copper(I) halides the composition of the reaction products is governed by the stage of a fast halogen
transfer from the copper derivative to the alkyl radical. Under these conditions in contrast to the free-radical
addition reactions initiated by UV light or peroxide initiators the intramolecular rearrangements are suppressed,
the stereoselectivity of the reaction changes, and also some adducts contain halogen atoms different from those
present in the organohalogen reagent employed.
DOI: 10.1134/S1070428006080033
the metal atom to the radical-adduct A occurs efficiently
even with the low reactive benzyl and allyl radicals. This
results in significantly longer kinetic chains as compared
to the typical free-radical conditions (Scheme 2), namely,
at UV irradiation or in the presence of peroxide initiators,
e.g., benzoyl peroxide.
The free-radical addition of organohalogen reagents
to multiple bonds in the presence of transition metals
compounds is a promising method for the synthesis of
various halogen derivatives [1]. The sequence of
elementary stages of this process advanced in [2] may
be considered nowadays as general by accepted
(Scheme 1, addition of CCl4, M = Cu).
We formerly [3] demonstrated that in the free-radical
addition of polyhalomethanes to double bonds of
cycloalkenes in the presence of palladium(II) halogen
complexes the transfer of a halogen atom to the primarily
arising radical-adduct occurred not only from the molecule
of the oganohalogen reagent [Scheme 2, stage (3)], but
also from the metal complex [Scheme 1, stage (3)]. In
the presence of different halogens in the palladium
complex and the polyorganomethane the resulting product
contained a mixture of organohalogen compounds. In the
presence of palladium compounds we also observed the
changes in the stereochemical composition of the reaction
products and in the relative amounts of the rearranged
and nonrearranged compounds.
It was established [2] that the reaction proceeded via
the formation of free radical A. Stage (1) is a one-electron
transfer from the metal atom to the polyhalomethane
molecule. Stage (3) consisting in the ligand transfer from
Scheme 1.
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(3)
Scheme 2.
KQ
In this study we used for modification of the reactivity
of the organohalogen reagents and also for preparation
of halides containing a halogen atom foreign to the
composition of the employed addend more accessible
copper(I) derivatives. We investigated in the presence
of copper(I) chloride or bromide the reactions of
tetrachloromethane, bromotrichloromethane, chloroform,
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$ꢀꢁꢀ&&O
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†
1120

APPLICATION OF COPPER(I) HALIDES
1121
Scheme 3.
62 3K
&O
,
9,,
5
5
;
;
9,,,D 9,,,J
,;D ,;H
,,
VIII, X = H, R = CCl3 (a); X = Cl, R = CHCl2 (b), CCl3 (c), CCl-2CN (d), Ts (e); X = Br, R = CHCl2 (f), CCl3 (g);IX, X = Cl, R = CHCl2
(a), CCl3 (b), CCl2CN (c); X = Br, R = CHCl2 (d), CCl3 (e).
&&O
5
;
5
;
%U
,,,
;,D ;,I
;,,D ;,,I
;
X = Cl, R = Ts (a), CCl3 (b); X = Br, R = CCl3 (c), Ts (d); R = p-FC6H4SO2, X = Cl (e), Br (f).
&&O
;
5
;
5
5
;
5
;
,9
;9
;,9Dꢁꢂ;,9E
R = CCl3, X = Cl (a); R = CCl2CN, X = Cl (b), Br (c).
;,,,D ;,,,F
5
;
5
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;
&O
9
;9,,D ;9,,F
;9,
X = Cl, R = CCl3 (a), Ts (b); X = Br, R = Ts (c).
2
2
&O
&O
2
&O &
2
9,
;
;9,,,Dꢀꢁ;9,,,E
X = Cl (a), Br (b).
and trichloroacetonitrile with cyclohexene (I), norbornene
(II), norbornadiene (III), cis-cyclooctene (IV), and
cis,cis-cycloocta-1,5-diene (V), the intramolecular
cyclization of the allyl trichloroacetate (VI), and also the
reactions of arenesulfonyl chlorides with hydrocarbons
I–III, and V (Scheme 3). These reactions were compared
with the typical free-radical processes carried out under
UV irradiation or by thermolysis of the benzoyl peroxide.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRYVol. 42 No. 8 2006

DNEPROVSKII et al.
Table 1. Products of organochlorine reagents addition to cycloalkenes I–V in the presence of CuCla
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a Solvent acetonitrile.
b Reaction under typical free-radical conditions [No CuCl , (PhCOO)2 initiator].
c Solvent excess reagent.
d Added 80 mol% of 1,10-phenanthroline with respect to CuCl.
The cyclic substrates were chosen in order to follow not
only the regioselectivity but also the stereoselectivity of
the reaction.
and mass spectra and elemental analyses. The reaction
mixtures arising at the addition of polyhalomethanes and
trichloroacetonitrile were analyzed by GLC and NMR
spectroscopy, the products formed were identified by
retention times on two columns of different polarity in
comparison with the parameters of authentic samples,
and by the presence of characteristic signals in the NMR
spectra. The reference compounds were synthesized by
independent methods, and their structure was confirmed
The known main restriction to the addition of low
reactive agents like organochlorine reagents under the
typical conditions of the free-radical reactions is the
competition between the chlorine atom transfer to radical-
adduct A and this radical addition to the double bond of
the substrate leading to the formation of a telomers mixture
and decreased yield of the 1:1 adducts [4]. Yet the addition
of the organohalogen reagents in the presence of
copper(I) halides involves the halogen atom transfer to
radical-adduct A from the copper(II) derivatives
(Scheme1). The rate of this process is close to that of
the diffusion-controlled reaction: the rate of a chlorine
atom transfer from CuCl2 to an alkyl radical is equal to
1
by H NMR spectra.
As seen from the findings in Table 1, the addition of
CHCl3 to norbornene in the presence of CuCl used as the
reaction initiator proceeded at the C–Cl and not C–H
bond leading to the formation accordingly of adduct VIIIb
(Table 1, run no. 3) and not VIIIa as occurred under the
typical conditions of the free-radical reactions (Table 1,
run no. 2) [7].
–1 –1
1.1´109 l mol s [5], and this value is 105 times larger
that the transfer rate of a chlorine atom from carbon (for
instance, from CCl4 [6]). Consequently in the presence
of copper(I) halides the addition even of the low reactive
chlorides occurs at the multiple carbon-carbon bond
avoiding the telomerization of alkenes and giving rise
mainly to 1:1 adducts.
In going from the reaction initiated with the UV light
or peroxides to the reaction in the presence of CuCl the
rate of a halogen transfer to the intermediately formed
alkyl radical A (Scheme 1) increases resulting in pre-
dominance of the addition to the double bond in the alkene
or alkadiene over the other competing process, intra-
Thus by the addition of polyhalomethanes and arene- molecular rearrangement. For instance, it is known that
sulfonyl chlorides in the presence of copper(I) chloride the addition of CCl4 initiated photochemically or at heating
we prepared the corresponding adducts (Table 1). The provides with the cis-cyclooctene a product of 1,4-addition
structure of the reaction products was proved using NMR XIVa [8], and with the cis,cis-cycloocta-1,5-diene
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

APPLICATION OF COPPER(I) HALIDES
1123
Table 2. Products of organochlorine reagents addition to substrates II–V in the presence of CuBra
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a Solvent acetonitrile.
b Solvent excess reagent.
c Added 80 mol% of 1,10-phenanthroline with respect to CuBr.
1
d Content in the reaction mixture (by the H NMR data).
e Content in the reaction mixture (according to GLC) .
f Preparative yield.
of cis- and trans-isomers of 1-chloro-2-trichloromethyl-
cyclooctane XIIIa altered from 50:50 [8] to 43:57.
bicyclo[3.3.0]octane derivative XVI [9]. We demonstrated
that the addition of CCl4 to cis-cyclooctene (IV) and
cis,cis-cycloocta-1,5-diene (V) in the presence of CuCl
(both in the stoichiometric and catalytic quantities) gave
rise mainly to the nonrearranged adducts XIIIa and
XVIIa respectively (Table 1, runs nos. 10, 14). Under
the typical conditions of the free-radical reactions only
traces of compound XIIIa were obtained (Table 1, run
no. 9), and no formation of compound XVIIa was
observed (Table 1, run no. 13). The formation of
unsaturated compound XV in a considerable amount
(Table 1, run no. 10) in the course of polyhalomethanes
addition to the cis-cyclooctene in the presence of
copper(I) halides may be satisfactorily rationalized as due
to the oxidation of the intermediate 2-(trichloromethyl)-
cyclooctyl radical with the copper(II) derivatives [10]
arising in the initiation stage.
The variations in the stereoselectivity observed are
caused by the fact that in the presence of the copper(I)
chloride the reaction products form mainly as a result of
a chlorine atom transfer to radical A from the copper(II)
chloride. The contribution of the chlorine transfer from
the organochlorine reagent is here negligibly small.
An important feature of the reactions carried out in
the presence of copper(I) halides is the formation of the
so-called “cross-halogenation” products containing a halo-
gen atom lacking in the composition of the initial organo-
halogen addend. Thus by the addition of polychloro-
methanes and arenesulfonyl chlorides to the double bond
of cycloalkenes in the presence of stoichiometric and
superstoichiometric amounts of CuBr we prepared the
corresponding bromo derivatives (Table 2).
The other characteristic feature of the reaction in the
presence of copper derivatives is the change in the
reaction stereoselectivity. For instance, the addition of
polyhalomethanes and related compounds to the
norbornene under typical conditions of the free-radical
reactions (Table 1, runs nos. 2, 4) led exclusively to the
formation of exo,endo-disubstituted norbornanes VIII,
whereas the reaction in the presence of CuCl yielded
notable amounts of exo,exo-disubstituted isomer IX
(Table 1, runs nos. 3, 5, 6). Likewise in the reaction of
CCl4 with cis-cyclooctene in going from the typical free-
radical process to that in the presence of CuCl the ratio
It was found that CCl4 addition to norbornadiene in
acetonitrile in the presence of a double excess CuBr led
to the formation prevailingly of diastereomers of 3-tri-
chloromethyl-5-bromotricyclo[2.2.1.02,6]heptane (XIc +
XIIc) in an overall yield 60% (Table 2, runs nos. 4, 5),
the addition of trichloroacetonitrile to the cis-cyclooctene
under these conditions gave rise to a mixture containing
24% of (2-bromocyclooctyl)dichloroacetonitrile (XIIIc)
and 11% of (2-chlorocyclooctyl)dichloroacetonitrile
(XIIIb) (Table 2, run no. 8), the addition of arenesulfonyl
chlorides ArSO2Cl (Ar = p-CH3C6H4, p-FC6H4) to the
norbornadiene in the presence of over three-fold excess
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

DNEPROVSKII et al.
Table 3. Dependence on the reaction conditions of the yield and products ratio in the intramolecular cyclization of ester VIa
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Solvent acetonitrile, reaction time 20 h.
of CuBr provided a mixture of 5-halotricyclo[2.2.1.02,6]-
hept-3-yl aryl sulfones XI and XII in an overall yield up
to 55% and bromides content up to 80–85% (Table 2,
runs nos. 6, 7).
of chloroalkyl aryl sulfones.Actually, the ratios of chloro-
alkyl aryl sulfones to bromoalkyl aryl sulfones obtained
are well consistent with the published values of the halogen
transfer rate to alkyl radical from CuCl2 and CuBr2
–1
(1.1 ´ 109 and 4.3 ´ 109 l mol s–1, respectively) [12].
Similar relationships were observed also in the reaction
of intramolecular cyclization suffered by allyl
trichloroacetate (VI) (Scheme 3). In the reaction carried
out in the presence of equimolar or superequimolar
quantities of CuBr alongside lactone XVIIIa was also
obtained bromine-containing lactone XVIIIb.
This cross-halogenation reaction is obviously of
synthetic interest for it provides a possibility to prepare
difficultly accessible bromine-containing organic com-
pounds starting with organochlorine reagents. We plan
further to optimize the process for preparative application
of the reaction.
The analysis of data in Table 3 shows that the yield of
compounds XVIIIa and XVIIIb grows with the rising
temperature and with decreasing compound VI
concentration in the reaction mixture. The
superstoichiometric content of CuBr resulted in an
increased relative yield of bromine-containing lactone
XVIIIb in the mixture of the reaction products and in a
considerably reduced overall yield of the products. This
effect is due to the capability of alkyl radicals to react
with the cations of bivalent copper [11] arising in the
initiation stage of the process under study [Scheme 1,
equation (1)]. The copper(II) cations oxidize radical-
adducts A [Scheme 1, equation (2)] into the corresponding
carbocations which react with the initial unsaturated
substrates initiating their telomerization and thus
decreasing the yield of the target 1:1 adducts.
EXPERIMENTAL
NMR spectra were registered on a spectrometer
Bruker AMX-300 (300 MHz) in CDCl3. The structure
of the reaction products was confirmed by 1H, 13C, 1H-
1
2D-COSY, and H-2D-NOESY NMR spectra. Mass
spectra were measured on an MKh-1321 instrument. The
composition of the reaction products was determined by
means of GLC and NMR spectroscopy. The GLC
analysis was performed on a chromatograph Chrom-5
Scheme 4.
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Based on Scheme 1 describing the addition mechanism
of organohalogen compounds to the multiple bonds in the
presence of transition metal compounds we suggest as
the most probable the mechanism of the cross-halogena-
tion reaction involving CuBr represented on Scheme 4
by an example of arenesulfonyl chloride addition.
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a transfer of a halogen atom to the radical-adduct from
the mixed salt ClCuBr formed in the initiation stage. Thus
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

APPLICATION OF COPPER(I) HALIDES
1125
equipped with packed glass columns 2500´3mm,
stationary phases 10% SE-30 on Chromaton N-Super
and 5% OV-225 on the same carrier, carrier gas helium,
a flame-ionization detector.
was evaporated, and the residue was passed through
a column 4 cm high packed with silica gel (eluent
tetrachloromethane). The solvent was evaporated to
obtain 81% of a mixture of compounds VIIIb and IXa in
1
a ratio 1:0.3. H NMR spectrum, d, ppm: 5.7 m (0.7H,
Norbornene (99%), norbornadiene (99%), cis-
cyclooctene (99%), cis,cis-cycloocta-1,5-diene (99%),
bromotrichloromethane (99%), p-toluenesulfonyl chloride
(99%), p-fluorobenzenesulfonyl chloride (99%), benzene-
sulfonyl chloride (99%) were commercial products.
Benzoyl peroxide, acetonitrile, chloroform, and tetra-
chloromethane were purified by standard procedures [13,
14]. Cyclohexene (99.5% by GLC data) [14], trichloro-
acetonitrile (99% by GLC data) [15], allyl trichloroacetate
(99% by GLC data) [14], copper(I) chloride [16], and
copper(I) bromide [17] were prepared by known
methods.
HCCl2), 5.57 m (0.3H, HCCl2), 4.14 m (0.7H, HCCl),
4.0 m (0.3H, HCCl), 2.64 s (1H, H4), 2.54 m (2H,
HCHCl2 + H1), 2.1 m (2H), 1.75–1.36 (4H). These data
are well consistent with the spectra of compounds VIIIb
and IXa described in [18]. Mass spectrum, m/z (Irel, %):
179 (0.1), 177 (0.18), 175 (0.23), 143 (0.25), 141 (0.67),
131 (0.32), 129 (1), 115 (0.23), 113 (0.32), 109 (0.23),
105 (0.85).
exo-2-(Trichloromethyl)-endo-3-chlorobicyclo-
[2.2.1]heptane (VIIIc) and exo-2-(trichloromethyl)-
exo-3-chlorobicyclo[2.2.1]heptane (IXb). In an
ampule of 40 ml capacity was charged 0.8 g of
norbornene, 12 ml of tetrachloromethane, 0.02 g (5 mol%)
CuCl, and 20 ml of acetonitrile. A weak argon flow was
passed for 15 min through the solution to remove the
dissolved oxygen, the ampule was sealed and heated for
16 h at 140°C. On completion of the reaction the ampule
was opened, the solvent was evaporated, and the residue
was passed through a column packed with silica gel
(eluent tetrachloromethane). The solvent was evaporated
to obtain 87% of a mixture of compounds VIIIc and IXb
in a ratio 1:16. 1H NMR spectrum, d, ppm: 4.23 m (0.84H,
HCCl), 4.18 m (0.16H, HCCl), 4.18 m (0.16H, HCCl),
2.95 d (0.16H, HCCl3), 2.76 s (0.16H, H1), 2.64 m
(1.84H, HCCCl3 + H4), 2.55 c (0.84H, H1), 2.1 m (2H),
1.78–1.38 (4H). The signals from the minor set cor-
respond to exo,exo-adduct IXb [19]. Mass spectrum,
m/z (Irel, %): 249 (0.1), 247 (0.3), 245 (0.2), 215 (0.1),
213 (0.28), 211 (0.32), 177 (0.6), 175 (1), 149 (0.2), 147
(0.28), 139 (0.24), 135 (0.24), 111 (0.64), 109 (0.8).
exo-2-(Trichloromethyl)bicyclo[2.2.1]heptane
(VIIIa). A mixture of 1.1 g of norbornene, 16 ml of
chloroform, and 0.1 g of benzoyl peroxide were boiled at
reflux for 15 h in a weak flow of argon. On completion
of the reaction (GLC monitoring)the unreacted chloro-
form was distilled off, the residue was passed through
a column 4 cm high packed with silica gel (eluent
petroleum ether–tetrachloromethane, 1:2). The solvent
mixture was evaporated to obtain 80% of compound
VIIIa in a mixture with exo-2-(dichloromethyl)-endo-
3-chlorobicyclo-[2.2.1]heptane (VIIIb) in a ratio
1:0.02. 1H NMR spectrum of the mixture of compounds
VIIIa and VIIIb, d, ppm: 5.7 m (0.02H, HCCl2), 4.14 m
(0.02H, HCCl), 2.65 m (2H, HCCl3 + H1), 2.38 s (1H,
H4), 1.92 d (1H, H3), 1.72–1.16 (7H). The spectral data
are identical to those published in [18].
exo-2-(Trichloromethyl)-endo-3-chlorobicyclo-
[2.2.1]heptane (VIIIc) was prepared by the addition
of tetrachloromethane to the norbornene in a similar way.
exo-2-(Dichlorocyanomethyl)-endo-3-chloro-
bicyclo[2.2.1]heptane (VIIId) and exo-2-(dichloro-
cyanomethyl)-exo-3-chlorbicyclo[2.2.1]heptane
(IXc) were obtained by adding trichloroacetonitrile to
norbornene along a similar procedure. The yield of
compounds VIIId and IXc was 86%, the ratio of the
adducts 1:0.06. The spectrum of the mixture contained
characteristic signals identical in position and multiplicity
to the peaks in the published spectrum of compound VIIId
[20]. At the same time the spectrum of the reaction
mixture contained less strong resonances which by
analogy to the spectrum of the mixture of compounds
VIIIc and IXb might be assigned to exo,exo-isomer IXc.
1H NMR spectrum, d, ppm: 4.19 m (0.94H, HCCl),
1
Yield 80%. H NMR spectrum, d, ppm: 4.23 m (1H,
HCCl), 2.64 m (2H, HCCl3 + H4), 2.55 s (1H, H1), 2.1 m
(2H), 1.78–1.38 (4H). The 1H NMR spectrum was similar
to that published in [19].
exo-2-(Dichloromethyl)-endo-3-chlorobicyclo-
[2.2.1]heptane (VIIIb) and exo-2-(dichlormethyl)-
exo-3-chlorobicyclo[2.2.1]heptane (IXa). In an
ampule of 20 ml capacity was charged 1.3 g of nor-
bornene, 10 ml of chloroform, 0.07 g of copper(I) chloride,
and 0.1 g of 1,10-phenanthroline.Aweak argon flow was
passed for 15 min through the solution to remove the
dissolved oxygen, the ampule was sealed and heated for
9 h at 140°C. Then the ampule was opened, the solvent
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

DNEPROVSKII et al.
1126
endo-5-Bromo-exo-6-(trichloromethyl)bicyclo-
[2.2.1]hept-2-ene (X), exo-3-bromo-exo-5-
(trichloromethyl)tricyclo[2.2.1.02.6]heptane (XIc),
and endo-3-bromo-exo-5-(trichloromethyl)tricyclo-
[2.2.1.02.6]heptane (XIIc) were obtained by a modified
method [22]. Into a test tube of 50 ml capacity was
charged a solution of 3 ml (29.5 mmol) of diene III in
29.5 ml (300 mmol) of bromotrichloromethane; a weak
argon flow was passed for 15 min through the solution to
remove the dissolved oxygen, then the reaction mixture
was for 20 min placed under UV irradiation (of a mercury
lamp of medium pressure) at 30°C while stirring in a
weak flow of argon. On completion of the reaction the
unreacted bromotrichloromethane was distilled off, and
the residue was distilled in a vacuum. The fraction boiling
within 100–150°C (2 mm Hg) was subjected to column
chromatography on silica gel (eluent petrolrum ether) and
separated in two fractions. The first fraction contained
compound X as the main component [1H NMR spectrum,
d, ppm: 6.59 d.d (1H, H2), 6.30 d.d (1H, H3), 4.35 t (1H,
H5), 3.30 s (1H, H4), 3.15 m (1H, H1), 2.89 d.d (1H, H6),
2.29 d (1H, H7'), 1.66 m (1H, H7'')] and a small amount
of exo-5-bromo-exo-6-(trichloromethyl)bicyclo[2.2.1]-
hept-2-ene (12% according to GLC and 1H NMR data:
in the 1H NMR spectrum characteristic signals of protons
at a double bond appeared at 6.27 and 6.19 ppm). The
second fraction contained the diastereomers XIc and XIIc
mixture in a ratio 69:31 (according to GLC and 1H NMR
data). 1H NMR spectrum, d, ppm (XIc): 3.96 s (1H, H5),
2.83 s (1H, H3), 2.57 s (1H, H4), 2.37 d (1H, H7'), 2.06 d
(1H, H7''), 1.84–1.55 m (3H, H1 + H2 + H6); (XIIc):
4.03 s (1H, H5), 3.65 s (1H, H3), 2.51 s (1H, H4), 2.37 d
(1H, H7'), 1.84–1.55 m (3H, H1 + H2 + H6), 1.46 s (1H,
H7'').
4.07 m (0.06H, HCCl), 2.72 m (0.12H, HCCCl2CN +
H1), 2.62 m (1.88H, HCCCl2CN + H1), 2.50 m (0.06H,
H4), 2,47 m (0.94H, H4), 2.2–1.33 m (6H). Mass
spectrum, m/z (Irel, %): 204 (0.17), 202 (0.22), 168 (0.2),
166 (0.48), 121 (0.38), 119 (0.97), 117 (1).
endo-2-Bromo-exo-3-(trichloromethyl)bicyclo-
[2.2.1]heptane (VIIIg) and exo-2-bromo-exo-3-(tri-
chloromethyl)bicyclo[2.2.1]heptane (IXe) were
obtained by adding bromo-trichloromethane to norbornene
in the presence of CuBr at 90°C within 20 h by the
procedure similar to that used in preparation of the mixture
of isomers VIIIc and IXb. Yield of compounds VIIIg
and IXe 90%, isomers ratio 1:0.14. 1H NMR spectrum,
d, ppm: 4.28 m (0.86H, HCBr), 4.21 m (0.14H, HCBr),
2.96 d (0.14H, HCCCl3), 2.63 s (1H, H1), 2.56 s (1H,
H4), 2.15 m (2H), 1.7–1.65 m (2H), 1.63–1.4 (2H). The
assignment of char-acteristic signals in the spectrum was
performed using the data on the spectrum of compound
VIIIg [21].
Chloroform and tetrachloromethane addition to
nor-bornene in the presence of CuBr. In an ampule
of 30 ml capacity was charged 0.4 g of norbornene, 6 ml
of a chlorine-containing reagent, excess of CuBr (with
respect to norbornene, 0.66 g), and 10 ml of acetonitrile.
A weak argon flow was passed for 15 min through the
solution to remove the dissolved oxygen, the ampule was
sealed and heated at 90°C. On completion of the reaction
the ampule was opened, the solvent was evaporated, and
the residue was passed through a column packed with
silica gel (eluent tetrachloromethane). The solvent was
evaporated, and the residue was analyzed with the use
of 1H NMR and mass spectra. The chloroform addition
(reaction time 9 h) led to the formation of 63.5% of
chlorine-containing adduct VIIIb and a mixture of
bromine-containing adducts endo-2-bromo-exo-3-
(dichloromethyl)bicyclo-[2.2.1]heptane (VIIIf) and exo-
2-bromo-exo-3-(di-chloromethyl)bicyclo[2.2.1]heptane
(IXd) in a ratio 1:1.5. The ratio of isomers VIIIf and
IXd was 1:0.25. 1H NMR spectrum, d, ppm: 5.74 m (0.4H,
CHCl2), 5.58 m (0.6H, CHCl2), 4.20 m (0.47H, HCBr),
4.17 m (0.4H HCCl), 4.01 m (0.13H, HCBr), 2.58–1.3
m (9H). Mass spectrum, m/z (Irel, %): 260 (0.45), 258
(0.81), 256 (0.54), 225 (0.27), 223 (0.9), 221 (0.72), 187
(1), 185 (1).
exo-3-(Trichloromethyl)-exo-5-chlorotricyclo-
[2.2.1.02.6]heptane (XIb) and exo-3-(trichloro-
methyl)-endo-5-chlorotricyclo[2.2.1.02.6]heptane
(XIIb) were obtained by a modified method [22]. Into
an ampule of 20 ml capacity was charged a solution of
3.2 ml (31.5 mmol) of diene III and 0.5 g (2 mmol) of
benzoyl peroxide in 10 ml (104 mmol) of tetrachloro-
methane; a weak argon flow was passed for 15 min
through the solution to remove the dissolved oxygen, then
the ampule was sealed and heated for 15 h at 66°C. The
ampule was opened, the unreacted tetrachloromethane
was distilled off, and the residue was distilled in a vacuum
collecting the fraction boiling at 133°C (10 mm Hg). The
fraction consisted of a mixture of diastereomers XIb and
XIIb in a ratio 65:35 (according to GLC and 1H NMR
In the reaction with tetrachloromethane the overall
yield of chlorine-containing compound VIIIc and the
mixture of bromide derivatives VIIIg and IXe was 60%,
the ratio of chlorine to bromine derivatives was 1:3.4;
the ratio of isomers VIIIg to IXe was 1:0.15.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

APPLICATION OF COPPER(I) HALIDES
1127
1
octene (I) by the procedure described for compounds
XIb and XIIb.Yield 13%, bp 95°C (1.5 mm Hg). 1H NMR
spectrum, d, ppm: 4.26 m (1H, HCCl), 2.53 m (1H,
HCCCl2CN), 2.3–1.4 m (12H, CH2). Found, %: C 47.20;
H 5.50; N 5.47. C10H14Cl3N. Calculated, %: C 47.17;
H 5.54; N 5.50.
data). Yield 6.4 g (83%). H NMR spectrum, d, ppm:
(XIb), 3.91 s (1H, H5), 2.82 s (1H, H3), 2.55 s (1H, H4),
2.37 d (1H, H7'), 2.02 d (1H, H7''), 1.80–1.65 m (3H,
H1 + H2 + H6); (XIIb): 4.0 s (1H, H5), 3.61 s (1H, H3),
2.49 s (1H, H4), 2.37 d (1H, H7 '), 1.80–1.65 m (3H, H1 +
H2 + H6), 1.45 s (1H, H7'').
2-(Trichloromethyl)-6-chlorobicyclo[3.3.0]octane
(XVI) was obtained by the addition of tetrachloromethane
to diene V initiated by the benzoyl peroxide in the same
way as described for the synthesis of compound VIIIa.
1H NMR spectrum, d, ppm: 4.15 s (1H, HCCl), 2.87 m
(3H, HCCCl3, H1,H5), 2.76–1.8 m (8H). The spectrum
2-(Trichloromethyl)-1-chlorocyclooctane (XIIIa).
In an ampule of 60 ml capacity was charged 2.28 g of
copper(I) chloride, 14 ml of tetrachloromethane, 3 ml of
cis-cyclooctene (I), and 26.5 ml of acetonitrile. A weak
argon flow was passed for 15 min through the solution to
remove the dissolved oxygen, then the ampule was sealed
and heated for 8.5 h at 95°C. The ampule was opened,
the acetonitrile was distilled off, the residue was treated
with tetrachloromethane, the solution obtained was passed
through a bed of silica gel 2 cm thick, the tetrachloro-
methane was distilled off, the residue was distilled in a
vacuum collecting the fraction boiling within 135–140°C
(12 mm Hg). The reaction product obtained was a mixture
of cis- and trans-isomers in a ratio 43:57 (according to
1
is similar to the H NMR spectrum of compound XVI
published in [9].
Tetrachloromethane addition to cycloocta-1,5-
diene (V) in the presence of CuCl. In an ampule of
35 ml capacity was charged 1 ml of diene V, 10 ml of
tetrachloromethane, 0.05 g (5 mol%) of CuCl, and 15 ml
of acetonitrile. A weak argon flow was passed for
15 min through the solution to remove the dissolved
oxygen, then the ampule was sealed and heated for 30 h
at 120°C. The ampule was opened, the solution was
evaporated, and the residue was subjected to column
chromatography on silica gel (eluent tetrachloromethane).
On removing the solvent the residue was distilled in
a vacuum, bp 112°C (8 mm Hg). The overall yield of
compound XVI and 5-(trichloromethyl)-6-chlorocyclo-
oct-1-ene (XVIIa) (diastereomers mixture) was 52.1%.
1H NMR spectrum contained a set of signals correspond-
ing to compound XVI, and also to the mixture of isomers
1
1H NMR data; the H NMR spectrum was in a full
1
agreement with the published data [8]). H NMR
spectrum, d, ppm: 4.94 m [0.428H, HCCl (cis-XIIIa)],
4.61 m [0.572H, HCCl (trans-XIIIa)], 2.95 m [0.428H,
HCCCl3 (cis-XIIIa)], 2.83 m [0.572H, HCCCl3 (trans-
XIIIa)], 2.3–1.2 m [12H, CH2 (cis-XIIIa + trans-
XIIIa)].
(2-Chlorocyclooctyl)dichloroacetonitrile (XIIIb)
was obtained by adding trichloroacetonitrile to cis-
cyclooctene (I) in the presence of 5 mol% of copper(I)
chloride at 95°C by the procedure described for the
synthesis of compound XIIIa. Reaction time 19 h. Yield
57.6%, bp 115°C (2.5 mm Hg). Yield 57.6%. 1H NMR
spectrum, d, ppm: 4.71 br.t (0.32H, HCCl, cis-isomer),
4.41m (0.68H, HCCl, trans-isomer), 2.78 m (1H,
HCCCl2CN, both isomers), 2.3–1.2m (12H, CH2, both
isomers). Mass spectrum, m/z (Irel, %): 258 (0.45), 256
(1.26), 254 (1.26), 222 (2.26), 220 (12.6), 218 (19.5), 184
(8.79), 182 (28.1), 154 (9.44), 146 (21.8), 109 (100).
Found, %: C 47.32; H 5.67; N 5.62. C10H14Cl3N.
Calculated, %: C 47.18; H 5.54; N 5.50.
1
XVIIa. H NMR spectrum, d, ppm: 5.95–5.90 m (1H,
HC=C), 5.71–5.62 m (1H, HC=C), 4.98 m (0.8H, HCCl,
main isomer), 4.51 m (0.2H, HCCl, minor isomer),
3.28 m (0.2H, HCCCl3, minor isomer), 2.83 m (0.8H,
HCCCl3, main isomer), 2.72–1.82 (8H).
Synthesis of chlorocycloalkyl aryl sulfones by the
addition of arenesulfonyl chlorides to alkenes in the
presence of copper(I) chloride. General procedure.
In an ampule of 60 ml capacity was charged 1.5–3 mmol
of copper(I) chloride, 20–30 mmol of arenesulfonyl
chloride, 20–30 mmol of cycloalkene, and 30–35 ml of
acetonitrile. A weak argon flow was passed for 15 min
through the solution to remove the dissolved oxygen, the
ampule was sealed and heated at 80°C. Then the ampule
was opened, the acetonitrile was distilled off, the residue
was treated with chloroform, the solution obtained was
passed through a bed of silica gel 0.5 cm thick, the chloro-
form was distilled off, and the residue was recrystallized
from ethanol or a mixture ethanol–chloroform.
4-(Trichlormethyl)-1-chlorocyclooctane (XIVa)
was prepared by the procedure described for compounds
XIb and XIIb. mp 63.5–64°C (publ: mp 64–65.5°C [8]).
1H NMR spectrum, d, ppm: 4.23 br.s (1H, HCCl), 2.7
br.s (1H, HCCCl3), 2.6–1.4 m (12H, CH2) is well
consistent with the data published in [8].
(4-Chlorocyclooctyl)dichloroacetonitrile (XIVb)
was obtained by adding trichloroacetonitrile to cis-cyclo-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

DNEPROVSKII et al.
1128
trans-2-Chlorocyclohexyl phenyl sulfone (VII)
(0.50). Found, %: C 60.55; H 6.54. C15H19ClO2S.
Calculated, %: C 60.29; H 6.41.
was obtained by the reaction of benzenesulfonyl chloride
with cyclohexene, reaction time 50 h, mp 81–82°C (publ.:
Synthesis of bromocycloalkyl aryl sulfones by the
addition of arenesulfonyl chlorides to alkenes in the
presence of copper(I) bromide. Standard procedure.
In an ampule of 60 ml capacity was charged 10.1 g
(70.4 mmol) of copper(I) bromide, 20 mmol of
arenesulfonyl chloride, 22 mmol of cycloalkene, and 45–
50 ml of acetonitrile. A weak argon flow was passed for
15 min through the solution to remove the dissolved
oxygen, the ampule was sealed and heated for 14 h at
80°C. Then the ampule was opened, the acetonitrile was
distilled off, the residue was treated with chloroform, the
solution obtained was passed through a bed of silica gel
0.5 cm thick, the chloroform was distilled off, and the
residue was recrystallized from ethanol.
1
mp 82.0–82.8°C [23]). H NMR spectrum, d, ppm:
3,5
7.94 d (2H, HP2h,6), 7.67 d (1H, HP4h ), 7.60 d (2H, H ),
Ph
4.39 br.s (1H, HCCl), 3.34 br.d (1H, HCSO2), 2.4–1.4 m
(8H, CH2).
endo-3-Chlorobicyclo[2.2.1]hept-exo-2-yl
4-methylphenyl sulfone (VIIIe) was obtained by the
reaction of p-toluenesulfonyl chloride with norbornene
at 97°C, reaction time 19 hYield 70%. 1H NMR spectrum,
d, ppm: 7.78 d (2H, HHP2h,6), 7.37 d (2H, HA3r), 4.42 m
(1H, H3), 2.90–2.85 m (2H, H2 + H4), 2.53 br.s (1H, H1),
2.46 s (3H, CH3), 2.05–1.28 (6H, H5 + H6 + H7). Found,
%: C 59.20; H 6.10. C14H17ClO2S. Calculated, %: C 59.04;
H 6.02.
exo-5-Chlorotricyclo[2.2.1.02,6]hept-exo-3-yl 4-
methylphenyl sulfone (XIa) was obtained by the reac-
tion of p-toluenesulfonyl chloride with norbornadiene,
reaction time 10 h. Compound XIa formed alongside
compound XIIa at the addition of p-toluenesulfonyl
chloride to norbornadiene; the isomers are easily separated
by recrystallization from ethanol Compound XIa is less
exo-3-Bromotricyclo[2.2.1.02,6]hept-exo-5-yl
(4-methylphenyl sulfone (XId) was obtained together
with endo-3-bromotricyclo[2.2.1.02,6]hept-exo-5-yl
4-methylphenyl sulfone (XIId) by the reaction of
p-toluenesulfonyl chloride with norbornadiene. Isomers
XId and XIId were separated in the same way as com-
pounds XIa and XIIa. Compound XId: mp 154–156°C
(from ethanol). 1H NMR spectrum, d, ppm: 7.78 d (2H,
1
soluble, mp 154–156°C (from ethanol). H NMR
3,5
spectrum, d, ppm: 7.78 d (2H, HA2,r6), 7.39 d (2H, H ),
Ar
2,6
3,5
3.79 s (1H, H5), 3.06 s (1H, H3), 2.47 s (3H, CH3),
2.45 d (1H, H7 '), 2.36 s (1H, H4), 2.04 d (1H, H7 ''), 1.80–
1.63 m (3H, H1 + H2 + H6). Found, %: C 59.55; H 5.27.
C14H15ClO2S. Calculated, %: C 59.46; H 5.35.
H
), 7.39 d (2H, H ), 3.81 s (1H, H5), 3.07 s (1H, H3),
Ar
Ar
2.48 s (3H, CH3), 2.46 d (1H, H7'), 2.39 C (1H, H4), 2.08
d (1H, H7''), 1.81–1.66 m (3H, H1 + H2 + H6).
The signal at 3.79 ppm observed in the spectrum
corresponds to ClCH5 in compound XIa. The intensity
ratio of the signals BrCH5 and ClCH5 is 83:17. Mass
spectrum, m/z (Irel, %): 247 (26.3), 189 (11.6), 187 (11.8),
173 (28.9), 171 (30.3), 145 (2.42), 143 (6.53), 140 (8.94),
139 (12.0), 129 (3.87), 127 (11.0), 108 (6.77), 107 (6.04),
105 (2.90), 92 (44.7), 91 (100). The elemental analysis
(found, %: C 52.60; H 4.74) corresponds to the content
in the product obtained of 85% C14H15BrO2S and 15%
C14H15ClO2S.
Compound XIId: mp 146–150°C (from ethanol). 1H
NMR spectrum, d, ppm: 7.83 d (2H, HA2,r6), 7.39 d (2H,
HA3,r5), 4.00 s (1H, H5), 3.83 s (1H, H3), 2.54–2.39 m (5H,
CH3 + H7' + H4), 1.80–1.68 m (3H, H1 + H2 + H6),
1.51 d (1H, H7''). The overall yield of compounds XId
and XIId is 47%.
endo-5-Chlorotricyclo[2.2.1.02,6]hept-exo-3-yl 4-
methylphenyl sulfone (XIIa), mp 146–150°C (from
ethanol). 1H NMR spectrum, d, ppm: 7.83 d (2H, H ),
2,6
Ar
3,5
7.39 d (2H, H ), 3.99 s (1H, H5), 3.78 C (1H, H3),
Ar
2.52 d (1H, H7'), 2.48 s (3H, CH3), 2.41 s (1H, H4), 1.80–
1.66 m (3H, H1 + H2 + H6), 1.51 d (1H, H7''). Found, %:
C 59.38; H 5.29. C14H15ClO2S. Calculated, %: C 59.46;
H 5.35. Overall yield of compounds XIa and XIIa 48.8%.
4-Methylphenyl 6-chlorocyclooct-1-en-5-yl
sulfone (XVIIb) (a mixture of cis- and trans-isomers)
was obtained by the reaction of p-toluenesulfonyl chloride
with diene V. Reaction time 24 h. The overall yield of
diastereomeric reaction products 22%, mp 62–63°C (from
1
ethyl acetate–petroleum ether mixture). H NMR
2,6
3,5
spectrum, d, ppm: 7.78 m (2H, H ), 7.36 m (2H,
H
),
Ar
Ar
5.86 (1H, HC=C), 5.58 m (1H, HC=C), 5.12 s (0.9H,
HCCl, main isomer), 4.6 m (0.1H, HCCl, minor isomer),
3.79 m (0.1H, HCSO2, minor isomer), 3.43 m (0.9H,
HCSO2, main isomer), 2.62–1.59 m (11H). Mass
spectrum, m/z (Irel, %): 300 (0.13), 289 (0.41), 263 (0.41),
262 (1), 158 (0.06), 157 (0.69), 107 (0.64), 106 (0.38), 91
exo-3-Bromotricyclo[2.2.1.02,6]hept-exo-5-yl
4-fluorophenyl sulfone (XIf) was obtained together with
endo-3-bromotricyclo[2.2.1.02,6]hept-exo-5-yl 4-
fluorophenyl sulfone (XIIf) by the addition of p-fluoro-
benzenesulfonyl chloride to norbornadiene.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

APPLICATION OF COPPER(I) HALIDES
1129
Compound XIf: mp 128°C (from ethanol). 1H NMR
Compound XIIIc. 1H NMR spectrum, d, ppm: 4.78 m
(0.54H, HCBr, cis-isomer), 4.56 m (0.46H, HCBr, trans-
isomer), 2.90 m (0.54H, HCCCl2CN, cis-isomer),
2.67 m (0.46H, HCCCl2CN, trans-isomer), 2.4–1.4 m
(12H, CH2, both isomers).
3,5
spectrum, d, ppm: 7.93 m (2H, HA2,r6), 7.28 m (2H, H ),
Ar
3.83 C (1H, H5), 3.08 s (1H, H3), 2.45 m (2H, H7' + H4),
2.10 d (1H, H7''), 1.82–1.65 m (3H, H1 + H2 + H6). The
signal at 3.81 ppm observed in the spectrum corresponds
to ClCH5 in compound XIe. The intensity ratio of the
signals BrCH5 and ClCH5 is 74:26. Mass spectrum, m/z
(Irel, %): 251 (7.99), 189 (1.74), 187 (1.74), 173 (20.1),
171 (21.5), 145 (1.04), 143 (6.25), 129 (2.64), 127 (7.99),
95 (12.5), 92 (33.3), 91 (100).
Intramolecular cyclization of ester VI. The reaction
was carried out in the presence of CuCl and CuBr in
acetonitrile in sealed ampules at various temperature. The
analysis of the reaction products was performed by GLC
and 1H NMR spectroscopy. In the presence of CuCl we
obtained in a 43% yield 3,3-dichloro-4-(chloromethyl)-
The elemental analysis (found, %: C 49.19; H 3.81)
corresponds to the content in the product obtained of 72%
C13H12BrFO2S and 28% C13H12ClFO2S. The overall
yield of compounds XIf and XIIf is 38.5%.
1
tetrahydrofuran-2-one (XVIIIa). H NMR spectrum,
d, ppm: 4.68 m (1H, OCH), 4.24 m (1H, OCH), 4.01 m
(1H, ClCH), 3.75 m (1H, ClCH), 3.55 m (1H, CH). The
1H NMR spectrum obtained is in agreement with the
published data [24]. In the process catalyzed by CuBr
according to GLC data a mixture of two components
formed whose ratio depended on the reaction conditions.
6-Bromocyclooct-1-en-5-yl 4-methylphenyl
sulfone (XVIIc) (a mixture of cis- and trans-isomers)
was obtained by the reaction of p-toluenesulfonyl chloride
with diene V. Reaction time 24 h. The overall yield of
diastereomeric reaction products 19.5%, mp 67–68°C
(from ethyl acetate–petroleum ether mixture). 1H NMR
1
In the H NMR spectrum is also observed a signal at
4.20 ppm corresponding to one of the protons in the OCH2
moiety of 4-(bromomethyl)-3,3-dichlorotetrahydro-
furan-2-one (XVIIIb). Mass spectrum of the mixture of
compounds XVIIIa and XVIIIb, m/z (Irel, %): 252 (0.08),
248 (0.19), 246 (0.12), 171 (0.08), 169 (0.34), 167 (0.26),
157 (0.07), 155 (0.31), 153 (0.24), 125 (0.16), 123 (0.1),
111 (0.06), 109 (0.11), 105 (0.32), 103 (1), 87 (0.95). The
presence of the bromine-containing XVIIIb is confirmed
by the mass spectrum of the mixture: the isotope
composition of the molecular ion corresponds to the
presence of two chlorine and one bromine atoms. Besides
the isotope composition of the fragment ions (m/z 167,
169, 171; 153, 155, 157) is consistent with the presence
in each of them of one chlorine and one bromine atom
[25].
2,6
3,5
spectrum, d, ppm: 7.78 m (2H, ), 7.36 m (2H, ),
5.90 m (1H, HC=C), 5.59 m (1H, HC=C), 5.18 m (0.A7rH,
HCBr, main isomer), 5.11 m (0.3H, HCBr, minor isomer),
3.47 m (0.3H, HCSO2, minor isomer), 3.33 m (0.7H,
HCSO2, main isomer), 2.62–1.59 m (11H). Mass
spectrum, m/z (Irel, %): 344 (0.23), 343 (0.34), 341 (0.34),
300 (0.67), 289 (1). Found, %: C 52.57; H 5.60.
C15H19BrO2S. Calculated, %: C 52.48; H 5.54.
Ar
(2-Bromocyclooctyl)dichloroacetonitrile (XIIIc)
was obtained in a mixture with compound XIIIb as
follows: in an ampule of 60 ml capacity was charged
6.62 g (46.1 mmol) of copper(I) bromide, 3 ml (23.1 mmol)
of cis-cyclooctene, 5 ml (49.7 mmol) of trichloroaceto-
nitrile, and 40 ml of acetonitrile. A weak argon flow was
passed for 15 min through the solution to remove the
dissolved oxygen, the ampule was sealed and heated for
4.5 h at 95°C. Then the ampule was opened, the
acetonitrile was distilled off, the residue was treated with
tetrachloromethane, the solution obtained was passed
through a bed of silica gel 0.5 cm thick, the solvent was
distilled off, and the residue was distilled in a vacuum
collecting the fraction boiling within 95–105°C (1 mm
Hg). The ratio of compounds XIIIb and XIIIc in the
reaction product was estimated from the data of GLC
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