New example of Ramberg-Boecklund reaction initiated by Michael addition

Full text of DOI:10.1134/S1070428010050271

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 5, pp. 758−759. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.A. Vasin, I.Yu. Bolusheva, V.V. Razin, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 5, pp. 760−
761.
SHORT
COMMUNICATIONS
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New Example of Ramberg–Bocklund Reaction
Initiated by Michael Addition
V. A. Vasina, I. Yu. Bolushevaa, and V. V. Razinb
aOgarev Mordovskii State University, Saransk, 430005, Russia
e-mail: vasin@mrsu.ru
bSt. Petersburg State University, St. Petersburg
Received September 7, 2009
DOI: 10.1134/S1070428010050271
Only isolated cases were reported [1–4] on the
The structure of compound II was confirmed by IR,
1H and 13C NMR spectra. In particular, in the 1H NMR
spectrum two diastereotopic methoxycarbonyl groups
were found with the signals at 3.65 and 3.71 ppm that in
the 13C NMR spectrum gave rise to the signals at 52.3,
52.4 (OMe) and 168.7, 168.9 (C=O) ppm. The same
groups appeared in the IR spectrum as four strong
stretching vibrations bands νC=O at 1732, 1740, 1748, and
1755 cm–1.
synthesis of functionalized olefins from α-haloalkyl vinyl
..
sulfones through Ramberg–Bocklund reaction initiated
by Michael addition. The limitations of this reaction
evidently depend both on the structure of the initial
substrate and on the nature of the used reagent. For
instance, it was established in [5] that the treatment with
potassium tert-butylate, a strong base but a weak nucleo-
phile, of α-haloalkyl vinyl sulfones containing an allyl
hydrogen atom promoted the so-called vinylogic Ram-
(1) BrCH2SO2Br
(2) Na2CO3
..
berg–Bocklund reaction leading to the formation of con-
jugated dienes. For instance, by this procedure nona-1,3-
diene was obtained in 72% yield proceeding from
1-(bromomethylsulfonyl)oct-1-ene. We showed in [6] that
the treatment with the typical Michael reagents, enolates
of CH-acids, of bromomethyl β-styryl sulfone led to the
cyclization initiated by Michael addition giving tetra-
hydrothiophene S,S-dioxide derivative.
SO2CH2Br
I
CH(CO2Me)2
CH2(CO2Me)2
NaH, THF
CH2
II
We report here that at treating 1-(bromomethyl-
sulfonyl)cyclohex-1-ene (I) with sodium dimethyl
malonate (20°C, 17 h) from the three mentioned possible
We are planning to establish in future whether this
new example of the Ramberg–Bocklund reaction that
we have discovered is of a general character in the series
of 1- bromomethylsulfonylcycloalkenes.
..
reaction routes proceeds the one consisting in the
..
Ramberg–Bocklund reaction initiated by Michael addition:
1-(Bromomethylsulfonyl)cyclohex-1-ene (I)
.
The functionalized derivative of methylenecyclohexane
II is obtained.
Yield 54%, mp 55–56°C (hexane–ether, 3:1). IR spec-
trum, ν, cm–1: 3036 m, 2959 m, 2936 m, 1640 m, 1308 s,
Unsaturated sulfone I was obtained in a two-stage
process involving the addition of BrCH2SO2Br to cyclo-
hexene (CH2Cl2, 10°C, 24 h, no special initiation was
required) and the dehydrobromination of the adduct in
a water-dioxane solution of Na2CO3 at heating (50°C,
30 h).
1
1300 s, 1142 v.s, 764 m, 606 m, 594 m, 521 m. H NMR
spectrum, δ, ppm: 1.62–1.74 m (2H), 1.76–1.88 m (2H),
2.32–2.41 m (4H), methylene protons of the ring; 4.32 s
(2H, SO2CH2), 7.08 br.s (1H, CH=). 13C NMR spectrum,
δ, ppm: 20.6, 21.8, 23.8, 25.7; 40.9 (SO2CH2); 134.9 and
144.5 (C=C). Found, %: C 35.10; H 4.68. C7H11BrO2S.
758

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NEW EXAMPLE OF RAMBERG–BOCKLUND REACTION
759
Calculated, %: C 35.16; H 4.64.
(400.1 and 100.6 MHz respectively) from solutions of
compounds in CDCl3. Elemental analyses were carrier
out on a CHN-analyzer HP-185B.
Dimethyl (2-methylenecyclohexyl)malonate (II).
Yield 26%, oily substance. IR spectrum, ν, cm–1: 2936 s,
1763 s, 1748 s, 1740 s, 1732 v.s, 1435 m, 1319 m, 1277 m,
1
REFERENCES
1235 C, 1157 C, 1146 m. H NMR spectrum, δ, ppm:
1.45–1.69 m (6H), 2.05–2.13 m (1H) and 2.17–2.26 m
(1H), methylene protons of the ring; 2.92–3.01 m (1H,
CHC=), 3.66 s and 3.73 s (6H, 2CO2Me), 3.71 d [1H,
CH(CO2Me)2, J 8.3 Hz], 4.57 s and 4.68 s (2H, CH2=).
13C NMR spectrum, δ, ppm: 23.2, 28.2, 30.8 and 34.0
(4 CH2), 43.3 (CHC=), 52.4 and 52.5 (2 OMe), 54.1
[CH(CO2Me)2], 108.1 (CH2=), 148.9 (C=), 168.8 and
168.9 (2C=O). Found, %: C 63.74; H 8.15. C12H18O4.
Calculated, %: C 63.70; H 8.02.
1. Chen, T.B.R.A., Burger, J.J., and deWaard, E.R., Tetrahedron
Lett., 1977, p. 4527.
2. Burger, J.J., Chen, T.B.R.A., de Waard, E.R., and Huis-
man, H.O., Tetrahedron., 1981, vol. 37, p. 417.
3. Evans, P. and Taylor, R. J. K., Synlett., 1997, p. 1043.
4. Vasin, V.A., Bolusheva, I.Yu., and Razin, V.V., Sulfur Lett.,
2003, vol. 26, p. 101.
5. Block, E., Aslam, M., Eswarakrishnan, V., Gebreyes, K.,
Hutchin-son, J., Iyer, R., Laffitte, J.-A., and Wall,A., J. Am.
Chem. Soc., 1986, vol. 108, p. 4568.
IR spectra were recorded on a Fourier spectro-
photometer InfraLYuM FT-02. 1H and 13C NMR spectra
were registered on a spectrometer Bruker AΜX-400
6. Vasin, V.A., Bolusheva, I.Yu., and Razin, V.V., Khim.
Geterotsikl. Soedin., 2008, p. 539.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 5 2010