Reactions of some alken-1-yl and cycloalken-1-yl bromomethyl sulfones with dimethyl malonate and malononitrile

Article abstract of DOI:10.1134/S1070428012090047

Bromomethyl cyclopent-1-enyl sulfone and bromomethyl cyclohex-1-enyl sulfone reacted with dimethyl malonate and malononitrile sodium salts in THF at 20-50°C to give products of Michael-induced Ramberg-Baecklund reaction, functionalized derivatives of meth

Full text of DOI:10.1134/S1070428012090047

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 9, pp. 1173–1179. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.A. Vasin, I.Yu. Bolusheva, V.V. Razin, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 9, pp. 1176–1181.
Reactions of Some Alken-1-yl and Cycloalken-1-yl Bromomethyl
Sulfones with Dimethyl Malonate and Malononitrile
V. A. Vasina, I. Yu. Bolushevaa, and V. V. Razinb
a Ogarev Mordovian State University, ul. Bolshevistskaya 68, Saransk, 430005 Russia
e-mail: vasin@mrsu.ru
b St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
Received January 23, 2012
Abstract—Bromomethyl cyclopent-1-enyl sulfone and bromomethyl cyclohex-1-enyl sulfone reacted with
dimethyl malonate and malononitrile sodium salts in THF at 20–50°C to give products of Michael-induced
Ramberg–Bäcklund reaction, functionalized derivatives of methylidenecyclopentane and methylidenecyclo-
hexane. Reactions of bromomethyl hex-1-en-1-yl sulfone and bromomethyl hept-1-en-1-yl sulfones with the
same sodium enolates followed the Michael-induced ring closure pattern with formation of tetrahydrothiophene
1,1-dioxide derivatives containing allylmalonic acid derivatives as impurities. Factors responsible for the
different reaction pathways of cyclic and acyclic bromomethyl sulfones are discussed.
DOI: 10.1134/S1070428012090047
We previously showed that bromomethyl (E)-styryl
sulfone reacts with a hard base (nucleophile), sodium
methoxide, according to the Michael-induced Ram-
berg–Bäcklund (MIRB) pattern with formation of allyl
derivative [1] and that its reaction with soft bases
(nucleophiles), such as sodium salts of malononitrile
and malonic, cyanoacetic, and acetoacetic acid esters,
leads to tetrahydrotiophene 1,1-dioxide derivatives via
Michael-induced ring closure (MIRC) [2] (Scheme 1).
[3] (Scheme 2). Reactions of these sulfones with soft
nucleophiles were not reported in the literature.
Scheme 2.
O
O
O
t-BuOK
S
Br
R
S
VRB
R
O
CH2
R
–SO2
In the present work we examined reactions of
Scheme 1.
unsaturated cyclic and acyclic bromomethyl sulfones
I–IV with sodium enolates derived from dimethyl
malonate and malononitrile with a view to reveal
factors responsible for chemoselectivity of reactions
initiated by Michael addition.* Initial unsaturated sul-
fones I–IV were prepared in two steps including UV-
initiated addition of bromomethanesulfonyl bromide to
the corresponding cycloalkene or terminal alkene in
methylene chloride at 20°C and dehydrobromination
of adducts V–VIII by the action of sodium carbonate
in aqueous dioxane at 50°C.
Ph
MeONa
H2C
MIRB
OMe
Ph
Br
S
W
W'
O
O
Ph
NaCHWW'
MIRC
S
O
O
W, W′ = CN, CO2Me; Ac, CO2Me.
Unlike bromomethyl (E)-styryl sulfone, bromo-
methyl (E)-alk-1-en-1-yl sulfones having activated
hydrogen atoms in the γ-position with respect to the
sulfonyl group react with hard nucleophiles (alkali
metal alkoxides) to give products of vinylogous
Ramberg–Bäclund (VRB) reaction, conjugated dienes
The addition of bromomethanesulfonyl bromide to
cyclic alkenes I and II was trans-stereoselective,
which is consistent with published data [5–8], and the
dehydrobromination of V–VIII was strictly regioselec-
* For preliminary communication, see [1].
1173

VASIN et al.
1174
Br
( )n
Me
S
Br
Br
( )n
Me
S
Br
S
( )n
Br
O
O
O
O
S
Br
( )n
O
O
O
O
I, II
III, IV
V, VI
VII, VIII
I, III, V, VII, n = 1; II, IV, VI, VIII, n = 2.
tive. Adducts V–VIII and their dehydrobromination
products I–IV were isolated by column chromatog-
raphy on silica gel and/or recrystallization. The struc-
ture of I–VIII was determined by IR spectroscopy,
1H and 13C NMR, and mass spectrometry. In particular,
E configuration of the double bond in unsaturated
sulfones I and II followed from the vicinal coupling
constant for the olefinic protons (3J = 15 Hz) [9].
separate singlets from diastereotopic CO2Me groups.
In the C NMR spectra of IXa, IXb, Xa, and Xb two
13
downfield signals with strongly different intensities
reliably characterized 1,1-disubstituted ethylene frag-
ment; in addition, separate carbon signals from dia-
stereotopic groups W were observed. Likewise, in the
13C NMR spectra of allylic derivatives XIIa, XIIb,
XIVa, and XIVb we identified diastereotopic groups
W, as well as vinyl groups and CH carbon atom linked
to W. Cyclic sulfones XIa, XIb, XIIIa, and XIIIb
Cycloalkenyl and alkenyl sulfones I–IV were
brought into reactions with CH acid sodium salts
(taken in a slight excess) at 20–50°C under dry argon
by stirring over a period of 20–30 h. From cyclopen-
tenyl and cyclohexenyl sulfones I and II we obtained
MIRB reaction products IXa, IXb, Xa, and Xb in 20–
34% yield. Acyclic unsaturated sulfones III and IV
reacted with dimethyl malonate and malononitrile
sodium salts to give mixtures of cyclic sulfones XIa,
XIb, XIIIa, and XIIIb and allylmalonic acid deriva-
tives XIIa, XIIb, XIVa, and XIVb, the former prevail-
ing (according to the 1H NMR data, the ratio was ~4:1
and 3:1, respectively). The yield in the MIRC reaction
was 24–32%, and in the MIRB reaction, 8–23%.
1
characteristically showed in the H NMR spectra two
doublets at δ 3.6–3.9 ppm from diastereotopic protons
2
on C2 with a geminal coupling constant J of ~14 Hz.
Like other compounds considered above, the 13C NMR
spectra of XIa, XIb, XIIIa, and XIIIb contained
separate signals of diastereotopic groups W and were
very consistent with the assumed structures.
Thus our experimental results revealed differences
in the behavior of cyclic (I, II) and acyclic (III, IV)
unsaturated bromomethyl sulfones toward dimethyl
malonate and malononitrile sodium salts. We believe
that these differences are related to specific structure of
carbanionic intermediates, which determines their sta-
bility and reactivity. Michael addition to cycloalkenyl
sulfones initially gives carbanion A which is capable
of undergoing reversible isomerization into thermo-
dynamically more stable (due to better delocalization
of negative charge over two electron-withdrawing
groups W) carbanions B and C (Scheme 3).
W
W
R
CHW2
CH2
R
CH2
W
S
( )n
W
O
O
IXa, IXb, Xa, Xb
XIa, XIb, XIIIa, XIIIb
XIIa, XIIb, XIVa, XIVb
IX, n = 1; X, n = 2; W = CO2Me (a), CN (b); XI, XII, R =
C4H9; XIII, XIV, R = C5H11.
Obviously, for steric reasons, 1,5-cyclization prod-
uct E can be formed only from carbanion B with cis
orientation of the substituents. Carbanion B is less
stable than its trans isomer C, so that its concentration
in the reaction mixture may be insignificant. There-
fore, the main reaction direction is 1,3-elimination
from carbanion A, leading to episulfone D which loses
SO2 molecule with formation of methylidene deriva-
tive IX or X.
Compounds IX–XIV were isolated by column
chromatography on silica gel, and their structure was
1
13
determined on the basis of their IR, H and C NMR,
and mass spectra (GC–MS). For example, compounds
XI and XIII displayed in the IR spectra characteristic
absorption bands due to stretching vibrations of the
sulfonyl group at ~1130 (νs) and ~1310 cm–1 (νas). The
1H NMR spectra of methylidene derivatives IXa and
IXb contained two poorly resolved downfield dou-
blets, whereas compounds Xa and Xb were charac-
terized by two broadened singlets from olefinic pro-
tons. In addition, compounds IXa and Xa gave rise to
Carbanions generated from open-chain unsaturated
sulfones III and IV are stabilized by two electron-
withdrawing substituents. In this case, there are no
such rigorous steric limitations to 1,5-cyclization, and
tetrahydrothiophene 1,1-dioxide derivatives XI and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

REACTIONS OF SOME ALKEN-1-YL AND CYCLOALKEN-1-YL BROMOMETHYL
1175
Scheme 3.
CHW2
S
CHW2
CW2
Br
Br
Br
S
S
O
( )n
( )n
( )n
O
O
O
O
O
C
A
B
–Br–
–Br–
W
W
CHW2
IXa, IXb, Xa, Xb
( )n
S
–SO2
( )n
S
O
O
O
O
D
E
XIII are formed as the major products. The com-
position of the equilibrium carbanion mixture is likely
to be affected by the nature of electron-withdrawing
group W. In particular, this is indicated by consider-
ably higher yield of 1,5-cyclization product in the reac-
tion of III and IV with malononitrile as compared to
dimethyl malonate. In addition, the reaction mixtures
obtained from sulfones I and II and malononitrile
contained small impurities (5–8%; according to the
Bromomethanesulfonyl bromide was prepared
according to the procedure described in [3]; its purity
was 97%.
Reactions of cyclopentene, cyclohexene, hex-1-
ene, and hept-1-ene with bromomethanesulfonyl
bromide (general procedure). Cold (0°C) solutions of
20 mmol of the corresponding alkene in 10 ml of anhy-
drous methylene chloride and of 5 g (21 mmol) of
bromomethanesulfonyl bromide in 10 ml of the same
solvent were mixed, 0.2 g of anhydrous sodium car-
bonate was added,** and the the mixture was irra-
diated with UV light in a tightly capped quartz test-
tube at 20°C over a period of 28–30 h. The solvent was
distilled off under reduced pressure, and the solid resi-
due (in the reactions with acyclic alkenes) was washed
with diethyl ether (3×2 ml), dried in air, and recrys-
tallized from appropriate solvent. The oily residue
obtained from cyclic alkenes was subjected to column
chromatography on silica gel.
1
GLC and H NMR data) which may be identified as
the corresponding MIRC reaction products.
Undoubtedly, concurrent pathways in the reactions
of cyclic and acyclic unsaturated bromomethyl sul-
fones with CH acids require additional study.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded from
solutions in CDCl3 on a Bruker AMX-400 spectrom-
eter at 400.1 and 100.6 MHz, respectively; the chem-
ical shifts were determined relative to the residual
proton signal and carbon signal of the solvent. The IR
spectra were measured from thin films or KBr pellets
on an InfraLYuM FT-02 spectrometer with Fourier
transform. The elemental compositions were deter-
mined on a Vario MICRO CHN analyzer. Analytical
thin-layer chromatography was performed on Silufol
UV-254 plates using light petroleum ether–ethyl
acetate (3:1) as eluent; spots were visualized by treat-
ment with iodine vapor. Silica gel L40/60 μm was used
for column chromatography (eluent light petroleum
ether–ethyl acetate, 7:1). Photochemical reactions
were carried out under irradiation with a DRT-400
mercury lamp.
trans-1-Bromo-2-(bromomethylsulfonyl)cyclo-
pentane (V). Yield 60%, mp 45–46°C (from diethyl
ether–pentane). IR spectrum, ν, cm–1: 3036 m, 2967 m,
1304 v.s, 1269 m, 1246 m, 1138 v.s, 575 m, 494 m.
1H NMR spectrum, δ, ppm: 1.83–1.95 m (1H), 1.96–
2.07 m (1H), 2.11–2.34 m (3H), and 2.35–2.47 m (1H)
[(CH2)3]; 4.14–4.23 m (1H, CHSO2), 4.48 q (2H,
BrCH2SO2, AB, ΔνAB = 40.3, JAB = 12.0 Hz), 4.57–
4.63 m (1H, CHBr). 13C NMR spectrum, δC, ppm:
23.8, 25.5, 38.6, 41.2, 46.3, 67.3. Found, %: C 23.50;
H 3.38. C6H10Br2O2S. Calculated, %: C 23.55; H 3.29.
trans-1-Bromo-2-(bromomethylsulfonyl)cyclo-
hexane (VI). Yield 67%, Rf 0.62, mp 59–60°C (from
** The reaction with cyclohexene may start spontaneously and be
accompanied by strong exothermic effect.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

VASIN et al.
1176
diethyl ether–hexane). IR spectrum, ν, cm–1: 3032 w,
2948 m, 2928 w, 2863 w, 1447 m, 1327 m, 1312 s,
1134 s, 1127 v.s, 1100 m, 845 m. 1H NMR spectrum, δ,
ppm: 1.35–1.55 m (2H), 1.64–1.84 m (2H), 1.87–
2.05 m (2H), and 2.37–2.61 m (2H) [(CH2)4]; 3.77–
3.90 m (1H, CHSO2), 4.36–4.47 m (1H, CHBr), 4.51 d
and 4.92 d (1H each, BrCH2SO2, Ј = 11.6 Hz).
13C NMR spectrum, δC, ppm: 23.7, 24.8, 25.1, 37.0,
43.9, 47.8, 62.9. Found, %: C 26.10; H 3.68.
C7H12Br2O2S. Calculated, %: C 26.27; H 3.78.
1-(Bromomethylsulfonyl)cyclopentene (I). Yield
76%, Rf 0.42, mp 44–45°C (from diethyl ether–pen-
tane). IR spectrum, ν, cm–1: 3036 m, 2959 m, 1613 m,
1373 w, 1308 v.s, 1142 v.s, 1069 w, 745 m, 594 m,
505 s. 1H NMR spectrum, δ, ppm: 2.15 quint (2H, 4-H,
J = 7.6 Hz), 2.62–2.68 m and 2.69–2.75 m (2H each,
3-H, 5-H), 4.34 s (2H, CH2Br), 6.92–6.94 m (1H,
=CH). 13C NMR spectrum, δC, ppm: 23.7, 31.7, 33.1,
41.8, 139.5, 149.6. Found, %: C 32.10; H 3.68.
C6H8BrO2S. Calculated, %: C 32.16; H 3.60.
2-Bromohexyl bromomethyl sulfone (VII). Yield
85%, mp 48–49°C (from diethyl ether–hexane). IR
spectrum, ν, cm–1: 3032 m, 2959 s, 2928 s, 1300 v.s,
1154 s, 1134 s, 930 m, 876 m, 586 m, 494 s. 1H NMR
spectrum, δ, ppm: 0.93 t (3H, CH3, J = 7.2 Hz), 1.29–
1.62 m (4H) and 1.86–2.06 m (2H) [(CH2)3], 3.55 d.d
(1H, J = 5.3, 15.2 Hz) and 4.00 d.d (1H, J = 7.7,
15.2 Hz) (CH2SO2), 4.38–4.45 m (overlapped by the
doublet at δ 4.42 ppm, 1H, CHBr), 4.42 d and 4.63 d
(1H each, SO2CH2Br, J = 11.9 Hz). 13C NMR spec-
trum, δC, ppm: 13.7, 21.7, 29.0, 38.1, 42.9, 45.0, 57.6.
Found, %: C 25.98; H 4.47. C7H14Br2O2S. Calculated,
%: C 26.11; H 4.38.
1-(Bromomethylsulfonyl)cyclohexene (II). Yield
81%, Rf 0.45, mp 55–56°C (from diethyl ether–hex-
ane). IR spectrum, ν, cm–1: 3036 m, 2959 m, 2936 m,
1640 m, 1439 m, 1308 s, 1300 s, 1142 v.s, 764 m,
1
606 m, 594 m, 521 m. H NMR spectrum, δ, ppm:
1.62–1.74 m (2H), 1.76–1.88 m (2H), and 2.32–2.41 m
(4H) [(CH2)4]; 4.32 s (2H, CH2Br), 7.08 br.s (1H,
13
=CH). C NMR spectrum, δC, ppm: 20.6, 21.8, 23.8,
25.7, 40.8, 134.9, 144.5. Found, %: C 35.10; H 4.68.
C7H11BrO2S. Calculated, %: C 35.16; H 4.64.
Bromomethyl (E)-hex-1-en-1-yl sulfone (III).
Yield 81%, oily substance. IR spectrum, ν, cm–1:
2959 m, 2932 m, 2874 w, 1636 m, 1323 s, 1142 v.s,
1
2-Bromoheptyl bromomethyl sulfone (VIII).
Yield 77%, mp 50–51°C (from diethyl ether–hexane).
IR spectrum, ν, cm–1: 3032 m, 2955 m, 2928 m,
1466 w, 1300 v.s, 1157 m, 1130 m, 887 w, 582 w,
857 m, 667 w. H NMR spectrum, δ, ppm: 0.89 t (3H,
CH3, J = 7.3 Hz); 1.29–1.38 m, 1.43–1.50 m, and
2.29–2.34 m [2H each, (CH2)3]; 4.31 s (2H, CH2Br),
6.37 d.t (1H, 1-H, J = 1.6, 15.2 Hz), 7.04 d.t (1H, 2-H,
1
13
482 w. H NMR spectrum, δ, ppm: 0.91 t (3H, CH3,
J = 6.9, 15.2 Hz). C NMR spectrum, δC, ppm: 13.6,
J = 6.9 Hz); 1.29–1.41 m (4H), 1.44–1.54 m (1H),
1.54–1.65 m (1H), and 1.89–2.07 m (2H) [CH2)4];
3.54 d.d.d (1H, J = 1.3, 5.3, 15.3 Hz) and 4.02 d.d (1H,
J = 7.7, 15.3 Hz) (SO2CH2), 4.38–4.47 m (1H, CHBr),
4.40 d.d (1H, J = 1.3, 11.9 Hz) and 4.64 d (1H, J =
22.0, 29.4, 31.4, 43.2, 124.5, 153.8. Found, %:
C 34.88; H 5.38. C7H13BrO2S. Calculated, %: C 34.87;
H 5.43.
Bromomethyl (E)-hept-1-en-1-yl sulfone (IV).
Yield 83%, oily substance. IR spectrum, ν, cm–1:
2955 m, 2932 m, 2859 s, 1628 m, 1323 s, 1142 v.s,
13
11.9 Hz) (SO2CH2Br). C NMR spectrum, δC, ppm:
13.9, 22.4, 26.7, 30.8, 38.5, 42.9, 45.0, 57.7. Found,
%: C 28.43; H 4.68. C8H16Br2O2S. Calculated, %:
C 28.59; H 4.80.
1
864 m, 667 w. H NMR spectrum, δ, ppm: 0.86–
0.94 m (3H, CH3); 1.28–1.37 m (4H) and 1.47–1.57 m
(2H) [(CH2)3]; 2.35 q.d (2H, 3-H, J = 1.5, 7.1 Hz),
4.33 s (2H, CH2Br), 6.37 d.t (1H, 1-H, J = 1.5,
15.2 Hz), 7.05 d.t (1H, 2-H, J = 6.8, 15.2 Hz). 13C NMR
spectrum, δC, ppm: 13.8, 22.2, 27.1, 31.0, 31.7, 43.2,
124.5, 153.9. Found, %: C 37.58; H 6.08. C8H15BrO2S.
Calculated, %: C 37.66; H 5.93.
Dehydrobromination of adducts V–VIII (general
procedure). A solution of 2.54 g (24.0 mmol) of
sodium carbonate in 15 ml of water was added to a so-
lution of 20.0 mmol of compound V–VIII in 15 ml of
dioxane, and the mixture was stirred at 50°C for 20 h
(VII, VIII) or 50 h (V, VI) and diluted with 150 ml of
water. Compounds I and II gradually precipitated and
were filtered off, dried in air, and recrystallized. Com-
pounds III and IV containing ~5% of the correspond-
ing Z isomer (according to the GLC and 1H NMR data)
were extracted into chloroform (3×30 ml), the com-
bined extracts were washed with water, dried over
MgSO4, and evaporated, and the residue was purified
by column chromatography on silica gel.
Reactions of compounds I–IV with dimethyl
malonate and malononitrile (general procedure).
A 60% suspension of sodium hydride in mineral oil,
0.34 g (8.4 mmol), was washed with hexane. Most
solvent was removed by decanting, and its residue was
removed under reduced pressure. The remaining so-
dium hydride was de-evacuated with argon, and 5 ml
of THF was added. A solution of 6.3 mmol of dimethyl
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REACTIONS OF SOME ALKEN-1-YL AND CYCLOALKEN-1-YL BROMOMETHYL
1177
malonate or malononitrile in 10 ml of THF was added
dropwise over a period of 15 min under stirring at
20°C, and the mixture was stirred for 1 h at 20°C.
A solution of 4.2 mmol of compound I–IV in 10 ml of
THF was added, and the mixture was stirred for 28–
30 h at 20°C, diluted with 300 ml of water, neutralized
with dilute (1:1) hydrochloric acid, and extracted with
chloroform (3×15 ml). The combined extracts were
washed with water, dried over MgSO4, and evaporated
under reduced pressure (water-jet pump), and the resi-
cm–1: 2940 v.s, 2932 s, 2867 m, 2257 w, 1651 m,
1451 m, 1327 m, 1316 m, 1134 m, 903 m. H NMR
1
spectrum, δ, ppm: 1.23–1.65 m (5H), 1.85–1.99 m
(2H), and 2.08–2.17 m (1H) [(CH2)4]; 2.50–2.58 m
(1H, CH), 3.80 d [1H, CH(CN)2, J = 6.6 Hz], 4.61 s
and 4.83 s (1H each, =CH2). 13C NMR spectrum, δC,
ppm: 23.9, 25.8, 27.2, 30.8, 34.5, 44.1 109.8, 111.8,
112.3, 144.5. Found, %: C 74.84; H 7.61; N 17.36.
C10H12N2. Calculated, %: C 74.97; H 7.55; N 17.48.
Dimethyl 4-butyl-1,1-dioxotetrahydro-3H-1λ6-
thiophene 3,3-dicarboxylate (XIa). Yield 32%,
mp 66–67°C (from ethyl acetate–hexane). IR spec-
trum, ν, cm–1: 2966 m, 2935 m, 1747 s, 1732 s,
1315 v.s, 1273 s, 1261 s, 1219 s, 1146 s, 1126 v.s,
1
due was analyzed by H NMR and purified by column
chromatography on silica gel.
Dimethyl 2-(2-methylidenecyclopentyl)malonate
(IXa). Yield 19%, bp 88°C (1 mm), Rf 0.58. IR spec-
trum, ν, cm–1: 2951 m, 1759 v.s, 1740 s, 1740 s, 1655 w,
1435 m, 1273 m, 1196 m, 1161 m, 1022 w, 891 w.
1H NMR spectrum, δ, ppm: 1.51–1.66 m (2H), 1.67–
1.76 m (1H), 1.83–1.93 m (1H), and 2.29–2.36 m (2H)
[(CH2)3]; 3.05–3.13 m (1H, CH), 3.69 s and 3.70 s (3H
each, OMe), 3.50 d [1H, CH(CO2Me)2, J = 8.6 Hz],
4.73 d and 4.88 d (1H each, =CH2, J 1.8 Hz). 13C NMR
spectrum, δC, ppm: 23.7, 30.3, 32.8, 43.2, 52.1, 52.2,
55.0, 106.4, 152.6, 168.7, 169.0. Found, %: C 62.40;
H 7.45. C11H16O4. Calculated, %: C 62.25; H 7.60.
1
1061 m. H NMR spectrum, δ, ppm: 0.89 t (3H, CH3,
J = 6.6 Hz); 1.22–1.44 m (5H) and 1.58–1.68 m (1H)
[(CH2)3]; 3.03–3.13 m (2H) and 3.35 d.d.d (1H, J =
1.0, 10.8, 16.9 Hz) (4-H, 5-H), 3.56 d.d (1H, J = 1.0,
14.1 Hz) and 3.82 d (1H, J = 14.1 Hz) (2-H), 3.80 s
13
(6H, OCH3). C NMR spectrum, δC, ppm: 13.7, 22.1,
29.3, 30.0, 41.2, 53.3, 53.6, 54.5, 56.5, 60.0, 168.1,
168.5. Mass spectrum, m/z (Irel, %): 264 (0.06), 263
(0.5), 145 (100), 113 (68.9). Found, %: C 49.38;
H 7.01. C12H20O6S. Calculated, %: C 49.30; H 6.90.
4-Butyl-1,1-dioxotetrahydro-3H-1λ6-thiophene-
3,3-dicarbonitrile (XIb). Yield 24%, Rf 0.35, mp 84–
85°C (from ethyl acetate–hexane). IR spectrum, ν,
cm–1: 3029 m, 2967 m, 2944 m, 2257 w, 1331 v.s,
2-(2-Methylidenecyclopentyl)malononitrile
(IXb). Yield 20%, bp 110°C (2 mm), Rf 0.5. IR spec-
trum, ν, cm–1: 2971 s, 2948 m, 2936 m, 2253 w,
1655 w, 1435 m, 1273 m, 1196 m, 1161 m, 1022 w,
1
1
891 w. H NMR spectrum, δ, ppm: 1.63–1.83 m (2H),
1316 s, 1269 m, 1142 s. H NMR spectrum, δ, ppm:
1.86–1.98 m (1H), 2.18–2.29 m (1H), and 2.43–
2.50 (2H) [(CH2)3]; 2.99–3.08 m (1H, CH), 3.88 d [1H,
CH(CN)2, J = 5.6 Hz], 5.13 d and 5.25 d (1H each,
=CH2, J = 2.1 Hz). 13C NMR spectrum, δC, ppm: 23.8,
27.2, 30.9, 33.1, 43.9, 110.0, 112.0, 112.4, 148.8.
Found, %: C 73.74; H 6.85; N 19.06. C9H10N2. Cal-
culated, %: C 73.94; H 6.89; N 19.16.
0.97 t (3H, CH3, J = 7.1 Hz); 1.39–1.49 m (4H), 1.72–
1.84 (1H), and 1.98–2.09 m (1H) [(CH2)3]; 2.91–
3.01 m (1H, 4-H), 3.08 t (1H, J = 13.2 Hz) and
3.58 d.d (1H, J = 6.6, 13.2 Hz) (5-H), 3.70 d and
3.94 d (1H each, 2-H, J = 14.1 Hz). 13C NMR spec-
trum, δC, ppm: 13.6, 22.2, 29.3, 30.2, 37.0, 45.0, 53.8,
58.7, 111.3, 112.3. Mass spectrum, m/z (Irel, %): 226
(0.08) [M]+·, 161 (25.5), 147 (27.6), 134 (53.6), 133
(33.7), 120 (13.6), 119 (31.5), 107 (12.2), 106 (15.1),
105 (10.1), 94 (29.0), 93 (11.3), 84 (10.9), 83 (75.8),
82 (16.5), 81 (19.0), 80 (13.4), 79 (39.6), 69 (32.7), 57
(12.2), 56 (49.4), 55 (100), 54 (12.9), 53 (14.2), 52
(11.2), 43 (31.6), 42 (24.6), 41 (66.0). Found, %:
C 53.28; H 6.20; N 12.44. C10H14N2O2S. Calculated,
%: C 53.08; H 6.24; N 12.38.
Dimethyl 2-(2-methylidenecyclohexyl)malonate
(Xa). Yield 30%, bp 102°C (1 mm). IR spectrum, ν,
cm–1: 2936 s, 1763 s, 1755 s, 1748 s, 1740 s, 1732 v.s,
1651 w, 1435 m, 1319 m, 1277 m, 1235 s, 1157 s,
1
1146 m, 895 w. H NMR spectrum, δ, ppm: 1.41–
1.68 m (6H), 2.05–2.14 m (1H), and 2.17–2.26 (1H)
[(CH2)4]; 2.92–3.01 m (1H, CH), 3.66 s and 3.73 s (3H
each, OMe), 3.71 d [1H, CH(CO2Me)2, J = 9.6 Hz],
4.57 br.s and 4.68 br.s (1H each, =CH2). 13C NMR
spectrum, δC, ppm: 23.2, 28.2, 30.8, 34.0, 43.3, 52.3,
52.4, 54.0, 108.1, 148.9, 168.8, 168.9. Found, %:
C 63.74; H 8.15. C12H18O4. Calculated, %: C 63.70;
H 8.02.
Dimethyl 2-(hept-1-en-3-yl)malonate (XIIa).
Yield 8%, bp 82°C (1 mm). IR spectrum, ν, cm–1:
2955 m, 2931 m, 1755 s, 1740 v.s, 1643 w, 1435 m,
1
1265 m, 1242 m, 1146 m. H NMR spectrum, δ, ppm:
0.86 t (3H, CH3, J = 6.7 Hz), 1.16–1.36 m (5H) and
1.37–1.48 m (1H) [(CH2)3], 2.70–2.79 m (1H, CH),
3.36 d [1H, CH(CO2Me)2, J = 8.9 Hz], 3.67 s and
2-(2-Methylidenecyclohexyl)malononitrile (Xb).
Yield 34%, bp 124°C (1 mm), Rf 0.70. IR spectrum, ν,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 9 2012

VASIN et al.
1178
3.72 s (3H each, OCH3), 5.03–5.11 m (2H, =CH2),
5.56–5.67 m (1H, =CH). 13C NMR spectrum, δC, ppm:
13.9, 22.3, 29.1, 31.9, 44.1, 52.1, 52.3, 56.8, 117.3,
138.1, 168.5, 168.7. Mass spectrum, m/z (Irel, %): 228
(0.17) [M]+·, 197 (10.1), 172 (10.2), 171 (100), 170
(10.9), 169 (93.0), 168 (12.1), 165 (31.2), 164 (12.5),
140 (11.3), 139 (86.2), 137 (16.8), 136 (11.2), 133
(33.6), 132 (75.1), 127 (14.1), 126 (59.7), 113 (52.4),
111 (21.3), 108 (13.6), 101 (28.8), 100 (34.9), 97
(20.9), 96 (22.5), 95 (17.4), 94 (12.3), 82 (11.4), 81
(47.9), 79 (15.6), 71 (12.3), 69 (20.7), 67 (24.9), 59
(23.5), 55 (45.6), 41 (27.4). Found, %: C 63.30;
H 8.88. C12H20O4. Calculated, %: C 63.14; H 8.83.
3.08 t (1H, J = 13.2 Hz) and 3.58 d.d (1H, J = 6.3,
13.2 Hz) (5-H), 3.70 d and 3.93 d (1H each, 2-H, J =
14.0 Hz). 13C NMR spectrum, δC, ppm: 13.8, 22.2,
26.9, 30.5, 31.1, 37.0, 45.1, 53.8, 58.7, 111.2, 112.3.
Mass spectrum, m/z (Irel, %): 239 (0.39) [M – 1]+·, 175
(20.1), 161 (36.5), 148 (33.8),147 (47.4), 134 (35.2),
133 (65.9), 132 (11.2), 120 (20.2), 119 (32.8), 108
(18.3), 107 (18.4), 106 (19.7), 97 (34.3), 96 (22.0),
95 (23.8), 94 (44.8), 93 (14.1), 83 (19.3), 82 (34.1),
81 (43.7), 80 (16.4), 79 (48.5), 70 (15.9), 69 (32.4),
68 (14.7), 67 (23.7), 57 (18.5), 56 (25.9), 55 (100),
54 (16.8), 53 (16.2), 52 (10.2), 43 (49.7), 42 (21.7),
41 (82.3). Found, %: C 54.80; H 6.78; N 11.51.
C11H16N2O2S. Calculated, %: C 54.98; H 6.71; N 11.66.
2-(Hept-1-en-3-yl)malononitrile (XIIb). Yield
23%, Rf 0.66, bp 112°C (1 mm). IR spectrum, ν, cm–1:
3086 w, 2963 v.s, 2936 v.s, 2863 m, 2257 w, 1644 w,
1466 m, 1423 m, 992 m, 934 m. 1H NMR spectrum, δ,
ppm: 0.93 t (3H, CH3, J = 6.8 Hz), 1.23–1.43 m (4H)
and 1.54–1.75 m (2H) [(CH2)3], 2.58–2.68 m (1H,
CH), 3.74 d [1H, CH(CN)2, J = 5.4 Hz], 5.33–5.43 m
Dimethyl 2-(oct-1-en-3-yl)malonate (XIVa). Yield
11%, Rf 0.63, bp 96°C (1 mm). IR spectrum, ν, cm–1:
2958 s, 2931 m, 2858 m, 1763 s, 1740 v.s, 1646 w,
1435 m, 1261 s, 1142 s, 1018 m. 1H NMR spectrum, δ,
ppm: 0.86 t (3H, CH3, J = 6.9 Hz), 1.15–1.36 m (7H)
and 1.38–1.47 m (1H) [(CH2)4], 2.71–2.81 m (1H,
CH), 3.38 d [1H, CH(CO2Me)2, J = 9.1 Hz], 3.68 s and
3.71 s (3H each, OCH3), 5.04–5.11 m (2H, =CH2),
5.57–5.67 m (1H, =CH). 13C NMR spectrum, δC, ppm:
14.0, 22.4, 26.6, 31.5, 32.2, 44.2, 52.2, 52.3, 56.9,
117.3, 138.1, 168.6, 168.7. Mass spectrum, m/z
(Irel, %): 242 (0.09) [M]+·, 183 (78.4), 179 (24.4), 172
(10.5), 171 (100), 151 (10.8), 140 (11.3), 139 (72.5),
133 (38.8), 132 (63.1), 127 (11.3), 126 (39.3) 123
(11.0), 113 (46.6), 112 (17.9), 111 (19.6), 110 (20.3),
109 (12.1), 108 (14.9), 101 (21.5), 100 (25.3), 95
(14.5), 82 (10.9), 81 (40.3), 79 (12.7), 69 (33.2), 68
(11.8), 67 (20.4), 59 (17.2), 55 (22.3), 54 (11.3), 53
(17.7), 43 (12.0), 41 (24.5). Found, %: C 64.30;
H 9.18. C13H22O4. Calculated, %: C 64.44; H 9.15.
13
(2H, =CH2), 5.63–5.74 m (1H, =CH). C NMR spec-
trum, δ, ppm: 13.7, 22.1, 28.5, 28.7, 31.2, 44.9, 111.6,
111.9, 121.2, 134.1. Mass spectrum, m/z (Irel, %): 162
(0.05) [M]+·, 106 (12.6), 97 (15.0), 80 (11.5), 79 (19.0),
67 (14.1), 57 (30.9), 56 (69.5), 55 (100), 53 (11.1), 41
(47.1). Found, %: C 74.20; H 8.78; N 17.31. C10H14N2.
Calculated, %: C 74.03; H 8.70; N 17.27.
Dimethyl 1,1-dioxo-4-pentyltetrahydro-3H-1λ6-
thiophene-3,3-dicarboxylate (XIIIa). Yield 28%,
Rf 0.31, mp 50–51°C (from diethyl ether–hexane). IR
spectrum, ν, cm–1: 2958 m, 2931 m, 1743 s, 1724 v.s,
1304 v.s, 1281 s, 1265 s, 1215 m, 1134 s, 1068 m.
1H NMR spectrum, δ, ppm: 0.88 t (3H, CH3, J =
6.9 Hz), 1.22–1.44 m (7H) and 1.57–1.68 m (1H)
[(CH2)4], 3.03–3.13 m (2H) and 3.31–3.40 m (1H)
4-H, 5-H, 3.56 d and 3.83 d (1H each, 2-H, J =
2-(Oct-1-en-3-yl)malononitrile (XIVb). Yield
16%, oily substance, Rf 0.62, bp 125°C (1 mm). IR
spectrum, ν, cm–1: 3086 w, 2959 s, 2932 v.s, 2863 s,
2257 w, 1644 w, 1458 m, 1424 m, 992 m, 934 m.
1H NMR spectrum, δ, ppm: 0.90 t (3H, CH3, J =
6.7 Hz), 1.22–1.41 m (6H) and 1.54–1.74 m (2H)
[(CH2)4], 2.58–2.69 m (1H, CH), 3.74 d [1H,
CH(CN)2, J = 5.4 Hz], 5.33–5.42 m (2H, =CH2), 5.63–
5.74 m (1H, =CH). 13C NMR spectrum, δC, ppm: 13.8,
22.3, 26.2, 28.5, 31.1, 31.5, 45.0, 111.6, 111.9, 121.2,
134.1. Mass spectrum, m/z (Irel, %): 176 (0.19) [M]+,
147 (12.0), 120 (17.9), 107 (10.8), 94 (12.1), 81 (18.8),
80 (15.7), 79 (17.2), 71 (18.0), 70 (81.4), 69 (100), 67
(19.3), 56 (12.7), 55 (72.2), 54 (13.1), 53 (12.6), 43
(71.0), 42 (22.7), 41 (52.7). Found, %: C 75.03;
H 9.28; N 15.71. C11H16N2. Calculated, %: C 74.96;
H 9.15; N 15.89.
13
14.3 Hz), 3.80 s (6H, OCH3). C NMR spectrum, δC,
ppm: 13.8, 22.3, 27.6, 29.6, 31.2, 41.3, 53.3, 53.6,
54.55 (C5); 56.5, 60.0, 168.2, 168.5. Mass spectrum,
m/z (Irel, %): 278 (0.04), 277 (0.36), 145 (100), 113
(58.7). Found, %: C 50.83; H 7.28. C13H22O6S. Cal-
culated, %: C 50.96; H 7.24.
1,1-Dioxo-4-pentyltetrahydro-3H-1λ6-thiophene-
3,3-dicarbonitrile (XIIIb). Yield 27%, Rf 0.39,
mp 93–94°C (from ethyl acetate–hexane). IR spec-
trum, ν, cm–1: 3024 m, 2962 m, 2931 m, 2256 v.w,
1323 v.s, 1300 m, 1269 m, 1138 s, 1130 v.s, 933 w.
1H NMR spectrum, δ, ppm: 0.93 t (3H, CH3, J =
6.9 Hz); 1.32–1.52 m (6H), 1.73–1.84 m (1H), and
1.98–2.08 m (1H) [(CH2)4]; 2.91–3.01 m (1H, 4-H),
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REACTIONS OF SOME ALKEN-1-YL AND CYCLOALKEN-1-YL BROMOMETHYL
1179
5. Liu, L.K., Chi, Y., and Jen, K-Y., J. Org. Chem., 1980,
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