Synthesis of the 1-Bromotricyclo[4.1.0.02,7]heptane Adduct with 2-Bromoethanesulfonyl Bromide and Its Transformations

Article abstract of DOI:10.1134/S107042802003015X

Abstract: The addition of 2-bromoethanesulfonyl bromide to1-bromotricyclo[4.1.0.0^2,7]heptane at theC¹–C⁷ centralbicyclobutane bond follows a radical mechanism to give 1:1 adduct with abicyclo[3.1.1]heptane structure. Treatment of the adduct with triethylamineleads to the formation of vinyl sulfone as a result of 1,2-dehydrobromination,and its reaction with 2 equiv of sodium methoxide involves 1,2- and1,3-dehydrobromination to afford7-bromo-1-(ethenesulfonyl)tricyclo[4.1.0.0^2,7]heptane.The latter is capable of reacting with sodium methoxide and sodiummethanesulfonate to form nucleophilic addition products.

Full text of DOI:10.1134/S107042802003015X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 3, pp. 458–464. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 3, pp. 456–463.
Synthesis of the 1-Bromotricyclo[4.1.0.02,7]heptane
Adduct with 2-Bromoethanesulfonyl Bromide
and Its Transformations
S. G. Kostryukova,* and Yu. Yu. Masterovaa
a Ogarev Mordovian National Research State University, Saransk, 430005 Russia
*e-mail: kostryukov_sg@mail.ru
Received November 21, 2019; revised January 18, 2020; accepted January 20, 2020
Abstract—The addition of 2-bromoethanesulfonyl bromide to 1-bromotricyclo[4.1.0.02,7]heptane at the C1–C7
central bicyclobutane bond follows a radical mechanism to give 1:1 adduct with a bicyclo[3.1.1]heptane
structure. Treatment of the adduct with triethylamine leads to the formation of vinyl sulfone as a result of
1,2-dehydrobromination, and its reaction with 2 equiv of sodium methoxide involves 1,2- and 1,3-dehydro-
bromination to afford 7-bromo-1-(ethenesulfonyl)tricyclo[4.1.0.02,7]heptane. The latter is capable of reacting
with sodium methoxide and sodium methanesulfonate to form nucleophilic addition products.
Keywords: 2-bromoethanesulfonyl bromide, 1-bromotricyclo[4.1.0.02,7]heptane, radical addition, bicyclo-
[3.1.1]heptane, dehydrobromination, vinyl sulfone
DOI: 10.1134/S107042802003015X
It is known [1–4] that bromomethanesulfonyl
bromide reacts with alkenes to give α,β′-dibromo sul-
fones which undergo dehydrobromination and desul-
fonation by the action of bases with the formation of
conjugated dienes. Bromomethanesulfonyl bromide
reacts with 1-bromotricyclo[4.1.0.02,7]heptane (1) in
a similar way [5] to produce a bicyclo[3.1.1]heptane
(norpinane) derivative with syn orientation of the
bromomethanesulfonyl group. Treatment of the adduct
with sodium hydroxide in aqueous dioxane leads to the
formation of 2-bromo-1-(bromomethanesulfonyl)tri-
cyclo[4.1.0.02,7]heptane as a result of 1,3-dehydro-
bromination (Scheme 1).
with benzenesulfonyl bromide [7] and benzenesulfonyl
and methanesulfonyl thiocyanates [8]. Therefore, reac-
tions of 1-bromotricycloheptane 1 with other sulfonat-
ing agents are of great interest as they could give rise to
new sulfones of the tricyclo- and bicycloheptane series.
With the goal of extending the series of available
haloalkanesulfonyl halides, in this work we have
synthesized 2-bromoethanesulfonyl bromide (2) and
studied its reaction with tricycloheptane 1. We have
found no published data on the synthesis of sulfonyl
bromide 2, and it was prepared according to the proce-
dure proposed previously for the synthesis of iodo-
methanesulfonyl bromide [4]. For this purpose, by
reacting excess 1,2-dibromoethane with sodium sulfite
we obtained sodium 2-bromoethane-1-sulfonate [9],
and the latter was treated with phosphorus(V) bromide
(Scheme 2).
Due to the presence of a bromine atom, 1-bromotri-
cyclo[4.1.0.02,7]heptane (1) possesses a significant
synthetic potential. For example, the adduct of 1 and
hydrogen sulfide was converted to bis(tricyclo-
[4.1.0.02,7]heptan-1-yl) sulfoxide and the corresponding
sulfone [6]. 6-Norpinanones and 6-norpinanethiones
were obtained by alkaline treatment of the adducts of 1
The reaction of 1-bromotricyclo[4.1.0.02,7]heptane
(1) with sulfonyl bromide 2 was carried out by mixing
the reactants at 0°C in anhydrous methylene chloride in
Scheme 1.
BrCH2SO2Br
NaOH, dioxane, Δ
Br
SO2CH2Br
Br
Br
SO2CH2Br
Br
1
458

SYNTHESIS OF THE 1-BROMOTRICYCLO[4.1.0.02,7]HEPTANE ADDUCT
459
Scheme 2.
Na2SO3
PBr5
Br
SO3Na
SO2Br
Br
Br
Br
2
Scheme 3.
3
4
2
1
BrCH2CH2SO2Br (2)
CH2Cl2
5
1
Br
SO2CH2CH2Br
6
7
Br
3
the presence of anhydrous sodium carbonate, followed
by keeping the mixture at room temperature on ex-
posure to scattered sunlight for 10 h; the consumption
of 2 was monitored by TLC. The corresponding 1:1
adduct, 6,6-dibromo-7-(2-bromoethanesulfonyl)bicy-
clo[3.1.1]heptane (3) was isolated in a high yield
(Scheme 3) by crystallization and was characterized
(2) adds to tricycloheptane 1 exclusively at the central
C1–C7 bond. On the basis of our previous considera-
tions [7, 8, 10, 11], these reactions should be assumed
to follow a radical mechanism (Scheme 4). As in other
cases [5], the reaction is initiated by the endo attack of
sulfonyl radical on the sterically more accessible
unsubstituted C7 atom of 1-bromotricyclo[4.1.0.02,7]-
heptane (1) with high regioselectivity. The subsequent
bromine transfer to bicyclo[3.1.1]heptyl intermediate
A involves predominantly the exo position, which
however does not matter for the bromo-substituted
substrate, since in any case the same product 3 is
formed.
1
by IR and H and 13C NMR spectra and elemental
analysis.
The bicyclo[3.1.1]heptane structure of 3 was con-
firmed by the presence in its 13C NMR spectrum of
five signals for seven carbon atoms of the norpinane
skeleton in expected positions and with expected
intensities. The configuration of C7 was assigned by
analysis of the position and multiplicity of the 7-H
Due to the presence of a 2-bromoethanesulfonyl
substituent, compound 3 can be subjected to various
transformations by the action of nucleophiles and
bases. The reaction of 3 with an equimolar amount of
triethylamine in benzene gave vinyl sulfone 4 as
a result of 1,2-dehydrobromination. The same product
was formed in the reaction of 3 with an equimolar
amount of sodium methoxide in methanol at 0°C, but
in this case the reaction was accompanied by the
formation of tricycloheptane 5 (Scheme 5). According
1
signal in the H NMR spectrum with account taken of
known correlations [5–8, 10, 11]. In particular, the 7-H
signal appeared as a triplet, which suggests its anti
orientation with respect to the trimethylene bridge. The
sulfonyl group characteristically gave rise to strong
absorption bands in the IR spectrum at ~1130 and
~1330 cm–1 [12].
Thus, like bromomethanesulfonyl bromide [5],
arenesulfonyl halides [7, 10, 11], and some other sul-
fonyl derivatives [8], 2-bromoethanesulfonyl bromide
1
to the H NMR data, the ratio 4/5 was 65:35. When
the reaction was carried out with 2 equiv of sodium
Scheme 4.
1
SO2CH2CH2Br
hν
·
·
·
SO2CH2CH2Br
2
Br
+
Br
A
3
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 3 2020

KOSTRYUKOV, MASTEROVA
460
Scheme 5.
MeONa (1 equiv)
MeOH, 0°C
Et3N (1 equiv), PhH
3
4
+
Br
SO2CH=CH2
Br
SO2CH2CH2Br
Br
4
5
Scheme 6.
MeONa (2 equiv)
MeOH, 0°C
3
Br
SO2CH=CH2
6
methoxide at 0°C, the only product was ethenesulfonyl-
tricycloheptane 6 (Scheme 6).
oxide and sodium methanethiolate added exclusively to
the vinylsulfonyl fragment to give compounds 7 and 8
with the C1–C7 bond remaining intact (Scheme 7). The
bicyclobutane moiety did not change in the reactions
with 2 equiv of nucleophile. Only in the reaction with
3 equiv of MeONa or MeSNa under more severe
conditions (heating at 90°C in a sealed ampule) we
isolated products of addition to both C=C and C1–C7
bonds, bicycloheptanes 9 and 10. Compounds 9 and 10
were also obtained from tricycloheptanes 7 and 8 under
similar conditions (Scheme 7).
Compound 6 is an interesting system containing
a bicyclobutane moiety and C=C double bond, and it
can be used as a model structure to study the relative
reactivity of the bicyclobutane system and multiple
bond toward nucleophiles. As shown previously [13],
there is no linear correlation between the reactivities of
bicyclobutane derivatives and analogous vinylic com-
pounds. Olefinic systems containing an ester, sulfonyl,
or cyano group proved to be more reactive than bicy-
clobutane derivatives with similar substituents [13].
The formation of compounds 9 and 10 can be
illustrated by Scheme 8. Initial nucleophilic attack on
C7 gives carbanion A which loses bromide ion to
generate highly reactive zwitterionic intermediate B,
and the latter is converted to bicycloheptane 9 and 10
via addition of the second nucleophile molecule. The
formation of zwitterion B is indirectly supported by the
fact that the reaction with 1 equiv of nucleophile would
produce tricycloheptane C, whereas only compound 9
or 10 was detected in the reaction mixture.
We examined reactions of tricycloheptane 6 with
sodium methoxide and sodium methanethiolate.
An equimolar amount of the nucleophile was used with
a view to determining whether the bicyclobutane or
exocyclic C=C bond would be more reactive toward
nucleophilic addition. The progress of reactions was
monitored by TLC, and the product structure was
1
determined on the basis of their H and 13C NMR
spectra. Under the given conditions, both sodium meth-
Scheme 7.
MeXNa (1 equiv)
MeOH, 20°C
MeXNa (2 equiv)
MeOH, 90°C
9, 10
Br
SO2CH2CH2XMe
7, 8
6
MeXNa (3 equiv)
MeOH, 90°C
MeX
SO2CH2CH2XMe
XMe
9, 10
7, 9, X = O; 8, 10, X = S.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 3 2020

SYNTHESIS OF THE 1-BROMOTRICYCLO[4.1.0.02,7]HEPTANE ADDUCT
461
Scheme 8.
Nu
Nu–
Slow
Br
SO2CH2CH2Nu
SO2CH2CH2Nu
Br
A
Nu
SO2CH2CH2Nu
–Br–
C
Nu
SO2CH2CH2Nu
NuH
Fast
9, 10
B
All sulfones 4–10 were isolated in the pure state and
were characterized by 1H and 13C NMR and IR spectra,
as well as elemental analyses.
2-Bromoethane-1-sulfonyl bromide (2).
A 500-mL round-bottom flask equipped with a reflux
condenser was charged with 21.1 g (0.1 mol) of sodium
2-bromoethane-1-sulfonate, 51.7 g (0.12 mol) of phos-
phorus(V) bromide, and 150 mL of anhydrous methy-
lene chloride. The mixture was refluxed for 6 h and
cooled to 0°C, and ~250 g of crushed ice was added to
the mixture. When the added ice melted, the organic
phase was separated and dried over CaCl2, the solvent
was distilled under reduced pressure (10–20 mm Hg),
and the residue was distilled in a vacuum (≤1 mm Hg)
to collect a fraction boiling at 80–90°C. Repeated
vacuum distillation gave 17 g (68%) of 2 with bp 88–
89°C (0.5 mm Hg). IR spectrum, ν, cm–1: 2950 w,
Thus, 2-bromoethane-1-sulfonyl bromide is an ef-
ficient reagent for introducing a 2-bromoethanesulfonyl
fragment. Its reaction with 1-bromotricyclo[4.1.0.02,7]-
heptane gives only one product which can be converted
to vinylsulfonyl-substituted bicycloheptane and tri-
cycloheptane derivatives. 7-Bromo-1-(ethenesulfonyl)-
tricyclo[4.1.0.02,7]heptane reacts with nucleophiles to
give products of addition to both exocyclic C=C bond
and bicyclobutane C1–C7 bond.
EXPERIMENTAL
1
1364 s (SO2, asym.), 1153 v.s (SO2, sym.). H NMR
spectrum, δ, ppm: 3.75 t (2H, J = 8.0 Hz), 4.18 t (2H,
J = 7.9 Hz). 13C NMR spectrum, δC, ppm: 21.7 (C2),
48.7 (C1). Found, %: C 9.59; H 1.58. C2H4Br2O2S.
Calculated, %: C 9.54; H 1.60.
1
The H and 13C NMR spectra were recorded from
solutions in CDCl3 on a Jeol JNM-ECX400 spectrom-
eter at 400 and 100 MHz, respectively, using the
residual proton and carbon signals of the solvent as
reference (CHCl3, δ 7.26 ppm; CDCl3, δC 77.16 ppm).
The IR spectra were recorded on an InfraLYuM FT-02
spectrometer from samples prepared as KBr disks.
Elemental analysis was carried out with a Vario
MICRO CHNS analyzer. Analytical TLC was per-
formed on Silufol UV-254 plates using light petroleum
ether–diethyl ether (1:1) as eluent; spots were visual-
ized by treatment with iodine vapor or under UV light.
The products were isolated by dry-column flash chro-
matography on silica gel using hexane–diethyl ether
(3:1 to 1:1) as eluent. The melting points were meas-
ured in sealed glass capillary tubes using an MP-50
melting point analyzer.
Reaction of tricycloheptane 1 with 2-bromo-
ethane-1-sulfonyl bromide (2). A mixture of 1.73 g
(10 mmol) of tricycloheptane 1 in 15 mL of anhydrous
methylene chloride and 0.5 g of anhydrous sodium
carbonate was cooled to 0°C, and 2.52 g (10 mmol) of
sulfonyl bromide 2 was added. The mixture was kept
for 1 h at 0°C and for 10 h at room temperature,
following the disappearance of 2 by TLC monitoring.
After completion of the reaction, the solvent was
removed under reduced pressure, and the residue was
1
analyzed by TLC and H NMR and purified by
recrystallization.
6,6-Dibromo-7-syn-(2-bromoethanesulfonyl)bi-
cyclo[3.1.1]heptane (3). Yield 3.31 g (79%), mp 119–
120°C (from CH2Cl2–hexane). IR spectrum, ν, cm–1:
2951 m, 1450 m, 1304 s (SO2, asym.), 1288 s, 1134 v.s
(SO2, sym.), 1030 m, 740 s, 686 s. 1H NMR spectrum,
1-Bromotricyclo[4.1.0.02,7]heptane (1) [14] and
sodium 2-bromoethane-1-sulfonate [9] were prepared
according to reported procedures.
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KOSTRYUKOV, MASTEROVA
462
7-Bromo-1-(2-bromoethanesulfonyl)tricyclo-
[4.1.0.02,7]heptane (5). Yield 36 mg (21%), mp 59–
60°C (from Et2O–hexane). IR spectrum, ν, cm–1:
3040 w, 2945 m, 1485 m, 1450 m, 1331 s (SO2, asym.),
1210 m, 1140 v.s (SO2, sym.), 1120 m, 755 s, 661 m.
1H NMR spectrum, δ, ppm: 1.21–1.48 m (2H, 4-H),
1.50–1.64 m (4H, 3-H, 5-H), 3.29 br.s (2H, 2-H, 6-H),
3.12 t (2H, CH2Br, J = 7.5 Hz), 3.34 t (2H, CH2SO2,
J = 7.5 Hz). 13C NMR spectrum, δC, ppm: 20.6
(C3, C5), 23.7 (CH2Br), 24.2 (C4), 31.9 (C7), 35.6 (C1),
49.1 (C2, C6), 57.6 (CH2SO2). Found, %: C 31.41;
H 3.50. C9H12Br2O2S. Calculated, %: C 31.42; H 3.52.
δ, ppm: 0.86–0.99 m (1H, 3-endo-H), 1.03–1.14 m
(1H, 3-exo-H), 1.43–1.55 m (2H, 2-endo-H, 4-endo-H),
1.58–1.70 m (2H, 2-exo-H, 4-exo-H), 2.57 br.d (2H,
1-H, 5-H), 2.72 t (2H, CH2Br, J = 7.5 Hz), 2.88 t (2H,
CH2SO2, J = 7.5 Hz), 3.56 t (1H, 7-anti-H, J = 5.0 Hz).
13C NMR spectrum, δC, ppm: 11.8 (C3), 20.7 (CH2Br),
25.8 (C2, C4), 57.1 (C6), 57.3 (C1, C5), 57.6 (CH2SO2),
65.8 (C7). Found, %: C 25.46; H 3.10. C9H13Br3O2S.
Calculated, %: C 25.44; H 3.08.
Reaction of bicycloheptane (3) with triethyl-
amine. A solution of 0.069 mL (0.5 mmol) of triethyl-
amine in 2.0 mL of anhydrous benzene was added to
a solution of 212 mg (0.5 mmol) of compound 3 in
5 mL of anhydrous benzene. The mixture was stirred
for 1 h at 0°C, and the precipitate of triethylamine
hydrobromide was filtered off and washed with 10 mL
of benzene. The filtrate was combined with the
washings, washed with water (2×5 mL), and dried over
MgSO4. The solvent was distilled off on a rotary
evaporator, and the crystalline residue was analyzed by
1H and 13C NMR and purified by recrystallization.
Reaction of bicycloheptane 3 with 2 equiv of
sodium methoxide. Compound 3, 212 mg (0.5 mmol),
was dissolved in 10 mL of anhydrous methanol, 2 mL
of a 0.5 M solution of sodium methoxide in methanol
was added, and the mixture was stirred for 1 h at 0°C.
The solvent was removed under reduced pressure, the
residue was dissolved in 15 mL of methylene chloride,
and the solution was washed with water (2×5 mL)
and dried over MgSO4. The solvent was distilled off on
a rotary evaporator, and the crystalline residue was
6,6-Dibromo-7-syn-(ethenesulfonyl)bicyclo-
[3.1.1]heptane (4). Yield 139 mg (81%), mp 94–95°C
(from Et2O–hexane). IR spectrum, ν, cm–1: 3092 m,
2951 m, 1648 m (C=C), 1448 m, 1310 s (SO2, asym.),
1295 s, 1139 v.s (SO2, sym.), 1031 m, 745 s, 690 s.
1H NMR spectrum, δ, ppm: 0.91–1.02 m (1H,
3-endo-H), 1.10–1.20 m (1H, 3-exo-H), 1.55–1.67 m
(2H, 2-endo-H, 4-endo-H), 1.76–1.88 m (2H, 2-exo-H,
4-exo-H), 2.91 br.d (2H, 1-H, 5-H), 3.59 t (1H,
7-anti-H, J = 5.6 Hz), 6.19 d.d (1H, CH2=, J = 10.5,
1.7 Hz), 6.51 d.d (1H, CH2=, J = 17.1, 1.7 Hz),
6.78 d.d (1H, SO2CH=, J = 17.1, 10.7 Hz). 13C NMR
spectrum, δC, ppm: 12.5 (C3), 23.5 (C2, C4), 47.8 (C1,
C5), 58.3 (C7), 57.5 (C6), 130.5 (CH2=), 137.2
(=CHSO2). Found, %: C 31.41; H 3.50. C9H12Br2O2S.
Calculated, %: C 31.42; H 3.52.
1
analyzed by H and 13C NMR and purified by
recrystallization.
7-Bromo-1-(ethenesulfonyl)tricyclo[4.1.0.02,7]-
heptane (6). Yield 85 mg (65%), mp 47–48°C (from
Et2O–hexane). IR spectrum, ν, cm–1: 3090 w, 2944 m,
1642 m (C=C), 1484 m, 1445 m, 1335 s (SO2, asym.),
1208 m, 1142 v.s (SO2, sym.), 1118 m, 750 s, 663 m.
1H NMR spectrum, δ, ppm: 1.18–1.39 m (2H, 4-H),
1.45–1.60 m (4H, 3-H, 5-H), 3.21 br.s (2H, 2-H, 6-H),
6.11 d.d (1H, CH2=, J = 10.5, 1.7 Hz), 6.46 d.d (1H,
CH2=, J = 17.1, 1.7 Hz), 6.65 d.d (1H, SO2CH=, J =
17.1, 10.7 Hz). 13C NMR spectrum, δC, ppm: 21.1 (C3,
C5), 24.2 (C4), 31.5 (C7), 35.8 (C1), 49.0 (C2, C6),
130.3 (CH2=), 136.8 (=CHSO2). Found, %: C 41.10;
H 4.24. C9H11BrO2S. Calculated, %: C 41.08; H 4.21.
Reaction of bicycloheptane 3 with an equimolar
amount of sodium methoxide. Compound 3, 212 mg
(0.5 mmol), was dissolved in 10 mL of anhydrous
methanol, 1 mL of a 0.5 M solution of sodium
methoxide was added, and the mixture was stirred for
1 h at 0°C. The solvent was removed under reduced
pressure, the residue was dissolved in 15 mL of
methylene chloride, and the solution was washed with
water (2×5 mL) and dried over MgSO4. The solvent
was distilled off on a rotary evaporator, and the residue
Reaction of tricycloheptane 6 with an equimolar
amount of sodium methoxide or sodium methane-
thiolate (general procedure). Compound 6, 263 mg
(1 mmol), was dissolved in 10 mL of anhydrous metha-
nol, 2 mL of a 0.5 M solution of sodium methoxide or
sodium methanethiolate in methanol was added, and
the mixture was stirred for 5 h at 20°C. The solvent
was removed under reduced pressure, the residue was
dissolved in 15 mL of methylene chloride, and the
solution was washed with water (2×5 mL) and dried
over MgSO4. The solvent was distilled off on a rotary
evaporator, and the crystalline residue was analyzed by
1H and 13C NMR and purified by flash chromatography
on silica gel.
1
13
was analyzed by H and C NMR. The products were
isolated by flash chromatography on silica gel.
6,6-Dibromo-7-syn-(ethenesulfonyl)bicyclo-
[3.1.1]heptane (4). Yield 78 mg (45%).
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SYNTHESIS OF THE 1-BROMOTRICYCLO[4.1.0.02,7]HEPTANE ADDUCT
463
5.6 Hz). 13C NMR spectrum, δC, ppm: 14.3 (C3), 23.1
(C2, C4), 40.8 (C1, C5), 53.4 (CH2SO2), 55.9 (CH3O),
56.5 (CH3O), 66.1 (C7), 58.8 (CH3O), 59.7 (CH2O),
73.2 (C6). Found, %: C 53.22; H 8.11. C11H20O4S.
Calculated, %: C 53.20; H 8.12.
7-Bromo-1-(2-methoxyethane-1-sulfonyl)tri-
cyclo[4.1.0.02,7]heptane (7). Yield 221 mg (75%),
mp 53–54°C (from Et2O–hexane). IR spectrum, ν,
cm–1: 3035 w, 2944 m, 1481 m, 1439 m, 1330 s (SO2,
asym.), 1212 m, 1141 v.s (SO2, sym.), 1109 m, 753 s,
1
660 m. H NMR spectrum, δ, ppm: 1.23–1.49 m (2H,
6,6-Bis(methylsulfanyl)-7-syn-[2-(methylsul-
fanyl)ethane-1-sulfonyl]bicyclo[3.1.1]heptane (10).
Yield 274 mg (84%), mp 134–135°C (from CH2Cl2–
hexane). IR spectrum, ν, cm–1: 3095 m, 2951 m,
1454 m, 1330 s (SO2, asym.), 1261 m, 1211 m,
1132 v.s (SO2, sym.), 1138 s, 1091 s, 1061 m, 880 m,
740 s, 651 m. 1H NMR spectrum, δ, ppm: 1.19–1.34 m
(1H, 3-endo-H), 1.55–1.66 m (1H, 3-exo-H), 1.75–
1.85 m (2H, 2-endo-H, 4-endo-H), 1.95–2.10 m (2H,
2-exo-H, 4-exo-H), 2.95 br.s (2H, 1-H, 5-H), 2.01 s
(3H, CH3S), 2.15 s (3H, CH3S), 2.21 s (3H, CH3S),
2.70 t (2H, CH2S, J = 7.5 Hz), 3.19 t (2H, CH2SO2, J =
7.5 Hz), 3.35 t (1H, 7-anti-H, J = 5.8 Hz). 13C NMR
spectrum, δC, ppm: 11.9 (C3), 13.0 (CH3S), 13.9
(CH3S), 14.8 (CH3S), 22.1 (C2, C4), 39.8 (C1, C5), 42.6
(CH2S), 51.2 (CH2SO2), 65.1 (C7), 63.0 (C6).
Found, %: C 44.16; H 6.77. C12H22O2S4. Calculat-
ed, %: C 44.14; H 6.79.
4-H), 1.65–1.87 m (4H, 3-H, 5-H), 2.91 br.s (2H, 2-H,
6-H), 3.18 s (3H, CH3O), 3.37 t (2H, CH2SO2, J =
5.8 Hz), 3.78 t (2H, CH2O, J = 5.8 Hz). 13C NMR
spectrum, δC, ppm: 22.6 (C3, C5), 24.3 (C4), 32.2 (C7),
36.3 (C1), 50.2 (C2, C6), 56.0 (CH3O), 58.6 (CH2SO2),
65. 5 (CH2O). Found, %: C 41. 71; H 5. 14.
C10H15BrO3S. Calculated, %: C 40.69; H 5.12.
7-Bromo-1-[2-(methylsulfanyl)ethane-1-sul-
fonyl]tricyclo[4.1.0.02,7]heptane (8). Yield 235 mg
(76%), mp 71–72°C (from Et2O–hexane). IR spectrum,
ν, cm–1: 3040 w, 2951 m, 1481 m, 1439 m, 1334 s
(SO2, asym.), 1215 m, 1142 v.s (SO2, sym.), 1105 m,
753 s, 660 m. 1H NMR spectrum, δ, ppm: 1.16–1.41 m
(2H, 4-H), 1.52–1.72 m (4H, 3-H, 5-H), 2.53 br.s (2H,
2-H, 6-H), 2.12 s (3H, CH3S), 3.61 t (2H, CH2SO2, J =
6.5 Hz), 2.98 t (2H, CH2S, J = 6.5 Hz). 13C NMR
spectrum, δC, ppm: 16.0 (CH3S), 19.3 (C3, C5), 23.5
(C4), 26.1 (C7), 28.5 (CH2S), 35.2 (C1), 38.0 (C2, C6),
58.7 (CH2SO2). Found, %: C 38.60; H 4.87.
C10H15BrO2S2. Calculated, %: C 38.59; H 4.86.
Reaction of tricycloheptanes 7 and 8 with 2 equiv
of sodium methoxide or sodium methanethiolate
(general procedure). Compound 7 or 8, 0.5 mmol, was
dissolved in 10 mL of anhydrous methanol, 2 mL of
a 0.5 M solution of sodium methoxide or sodium
methanethiolate in methanol was added, and the
mixture was heated in a sealed ampule at 90°C for 5 h.
The ampule was cooled and opened, the solvent was
removed under reduced pressure, the residue was
dissolved in 15 mL of methylene chloride, and the
solution was washed with water (2×5 mL) and dried
over MgSO4. The solvent was distilled off on a rotary
evaporator, and the crystalline residue was analyzed
by 1H and 13C NMR.
Reaction of tricycloheptane 6 with 3 equiv of
sodium methoxide or sodium methanethiolate
(general procedure). Compound 6, 263 mg (1 mmol),
was dissolved in 10 mL of anhydrous methanol, 6 mL
of a 0.5 M solution of sodium methoxide or sodium
methanethiolate in methanol was added, and the
mixture was heated in a sealed ampule at 90°C for 5 h.
The ampule was cooled and opened, the solvent was
removed under reduced pressure, the residue was
dissolved in 15 mL of methylene chloride, and the
solution was washed with water (2×5 mL) and dried
over MgSO4. The solvent was distilled off on a rotary
evaporator, and the crystalline residue was analyzed by
1H and 13C NMR and purified by recrystallization.
CONFLICT OF INTEREST
The authors declare the absence of conflict of interest.
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cm–1: 3093 m, 2949 m, 1453 m, 1334 s (SO2, asym.),
1267 m, 1210 m, 1133 v.s (SO2, sym.), 1110 s, 1095 s,
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