Reactions of styryl and phenylethynyl sulfones with some CH-acids

Article abstract of DOI:10.1134/S1070428011080033

Reactions of methyl and p-tolyl phenylethynyl sulfones with enolated of dimethyl malonate and malononitrile lead to the formation of sulfonyl-substituted derivatives of ethylidenemalonic acid. Methyl (E)-β- styryl sulfone reacts with sodium enolates of di

Full text of DOI:10.1134/S1070428011080033

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 8, pp. 1139−1141. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.A. Vasin, I.Yu. Bolusheva, Yu.Yu. Masterova, V.V. Razin, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 8,
pp. 1124−1126.
Reactions of Styryl and Phenylethynyl Sulfones
with Some CH-Acids
V. A. Vasina, I. Yu. Bolushevaa, Yu. Yu. Masterovaa, and V. V. Razinb
aOgarev Mordovia State University, Saransk, 430005 Russia
e-mail: vasin@mrsu.ru
bSt. Petersburg State University, St. Petersburg, Russia
Received January 17, 2011
Abstract—Reactions of methyl and p-tolyl phenylethynyl sulfones with enolated of dimethyl malonate and
malononitrile lead to the formation of sulfonyl-substituted derivatives of ethylidenemalonic acid. Methyl (E)-β-
styryl sulfone reacts with sodium enolates of dimethyl malonate, malononitrile, and methyl cyanoacetate to give
common Michael adducts.
DOI: 10.1134/S1070428011080033
It is known that α,β-unsaturated sulfones are good
Michael acceptors [1, 2]. For instance, β-(phenylsulfonyl)
styrene reacted with sodium malonate and sodium malo-
nonitrile affording common Michael adducts [3, 4], and
(methylsulfonyl)- and (phenylsulfonyl)ethenes in reac-
tions with enolates of diethyl malonate, ethyl acetoacetate,
ethylcyanoacetate, phenylacetonitrile, and nitroalkanes
provide Michael adducts of the composition 2 : 1 [5–7].
In some cases the Michael addition is accompanied with
the 1,3-elimination of sulfinic acid leading to the forma-
tion of a cyclopropane derivative like in the reaction of
β-(methylsulfonyl)- and β-(phenylsulfonyl)styrenes with
the phenylacetonitrile enolate [4]. The information on
reactions of ethynyl sulfones with CH-acids is scarce.
However it is known that the (phenylsulfonyl)ethyne
reacts with enolates of diethyl butylmalonate to give a
common Michael adduct [8].
From compound III after treating the reaction mix-
tures with water the expected Michael adducts IVа–IVc
were isolated.
Ph
Ph
W'
CH2WW'
NaH
MeSO2
MeSO2
W
IVa_IVc
III
W = W' = CO2Me (a), CN (b); W = CO2Me, W' = CN (c).
The reactions of ethynyl sulfones I, II with sodium
malonate and sodium malononitrile afforded sulfonyl-
substituted ethylidenemalonic acids Va, Vb, VIa, VIb.
Ph
In this study we investigated the reactions of two
ethynyl sulfones, 1-methylsulfonyl- and 1-p-tolylsulfonyl-
2-phenylethynes (I, II) with dimethyl sodium malonate
and sodium malononitrile. For comparison we also car-
ried out the reactions of the same enolates and also of
the methylcyanoacetate enolate with β-(methylsulfonyl)
styrene (III). These reactions were performed in THF at
20–50°С using a slight excess of the reagent. The enolates
were generated by treating the corresponding CH-acid
with sodium hydride.
CH2W2
W
RSO2
RSO2
Ph
NaH
W
Va, Vb, VIa, VIb
I, II
R = Me (I, V), p-Tol (II, VI); W = CO2Me (а), CN (b).
Compounds IV–VI were isolated in the individual
state by recrystallization in sufficient yields. Their struc-
ture was established from 1Н, 13С NMR, and IR spectra.
1139

VASIN et al.
1140
The 1Н and 13С NMR spectra confirm the presence in each
compound IV–VI of diastereotopic W groups and diaste-
reotopic protons of the СН2 fragment in compounds IV.
The reaction of compound III with methyl cyanoacetate
might result in the mixture of diastereomeric adducts
IVc, but only one of them of unidentified configuration
was obtained.
over 10 h at 50°С in the case of dimethyl malonate and 18 h
at 20°С in event of malononitrile, afterwards it was diluted
with water (250 ml) and netralized with dilute (1 : 1) HCl.
The solid reaction product was filtered off, washed with water
on the filter, dried in air, and rystallized from the mixture
benzene–hexane.
Dimethyl 2-[2-(methylsulfonyl)-1-phenylethylidene]
malonate (Va). Yield 33%, mp 83–84°С. IR spectrum, v,
cm–1: 1740 s, 1732 v.s, 1725 v.s, 1717 s, 1435 m, 1316 s,
1235 s, 1130 m, 1096 m, 702 w. 1Н NMR spectrum, δ, ppm:
2.86 s (3Н, SO2Mе), 3.50 s (3Н), 3.83 s (3Н, ОMе), 4.83 s
(2Н, СН2), 7.28–7.35 m (2Нarom), 7.37–7.43 m (3Нarom).
13С NMR spectrum, δ, ppm: 41.9 (SO2Mе), 52.4 (ОMе), 52.8
(ОMе), 59.0 (СН2), 127.4 (2С), 128.7 (2С), 129.7, 130.8, 137.8,
145.9 (Сarom, Сolefin.), 163.8, 165.8 (С=О). Found, %: С 53.91;
Н 5.22. C14H16O6S. Calculated, %: С 53.84; Н 5.16.
SO2R
Ph
Ph
SO2R
H3O
V, VI
W
W
H
W
W
B
A
The formation of derivatives of ethylidenemalonicacid
V, VI in the reactions involving ethynyl sulfones I, II is
apparently due to the isomerization of the initially formed
vinyl carbanion А into more stable allyl type anion B
through the 1,3-proton shift from the CHW2 fragment of
the high СН-acidity. At quenching the reaction mixtures
with water the protonation of B carbanion occurs at the
harder reaction center, cf. [9].
2-[2-(Methylsulfonyl)-1-phenylethylidene]
malononitrile (Vb). Yield 28%, mp 120–121°С. Spectral
characteristics coincide with those published in [9].
Dimethyl 2-[2-(p-tosyl)-1-phenylethylidene]malonate
(VIa).Yield 69%, mp 122–123°С. IRspectrum, v, cm–1: 1740
s, 1732 v.s, 1319 m, 1258 m, 1227 s, 1142 m, 548 m. 1НNMR
spectrum, δ, ppm: 2.40 s (3Н, Mе), 3.47 s (3Н, ОMе), 3.71 s
(3Н, ОMе), 4.93 s (2Н, СН2) 7.27 d (2Н, J 8.1 Hz), 7.30 br.s
(5Н), 7.72 d (2Нarom, J 8.1 Hz). 13СNMR spectrum,δ,ppm:
21.5 (Me), 52.3 (ОMе), 52.5 (ОMе), 59.8 (СН2), 127.5 (2С), 128.4
(4С), 129.2, 129.6 (2С), 136.3, 138.1, 144.5, 144.7 (Сarom, Сolefin.);
163.6, 166.0 (С=О). Found, %: С 61.91; Н 5.23. C20H20O6S.
Calculated, %: С 61.84; Н 5.19.
Examples of similar reactions of CH-acids with some
acetylene activated with the other acceptor moieties have
been published [10–12].
EXPERIMENTAL
1H and 13C NMR spectra were registered on a spec-
trometer Bruker АMX-400 (400.1 and 100.6 MHz re-
spectively) from solutions of compounds in CDCl3. IR
spectra were recorded on a Fourier spectrophotometer
InfraLYuM FT-02 from pellets with KBr. The purity of
compounds was checked by analytic TLC on Silufol UV-
254 plates, eluent hexane–diethyl ether, 2 : 1; develop-
ment in iodine vapor.
2-[2-(п-Tosyl)-1-phenylethylidene]malononitrile
(VIb). Yield 55%, mp 86.5–87.5°С. IR spectrum, v, cm–1:
2234 w, 1327 v.s, 1307 m, 1150 s, 1088 m, 741 m, 714 m,
694 m, 563 m, 528 m, 505 m. 1Н NMR spectrum, δ, ppm:
2.43 s (3Н, Mе), 4.67 s (2Н, СН2), 7.30 d (2Н, J 8.0 Hz),
13
7.42–7.57 m (5Н), 7.66 d (2Нarom, J 8.0 Hz). С NMR
Reaction of ethynyl sulfones I, II with dimethyl
malonate and malononitrile. General procedure. The
60% dispersion of NaH in mineral oil (0.15 g, 3.8 mmol) was
washed with hexane. The solvent was decanted, the residual
solvent was evaporated in a vacuum.To the evacuated reactor
argon was added till atmospheric pressure, 5 ml of THF was
charged. The solution of 3.4 mmol of dimethyl malonate
or malononitrile in 5 ml of THF was added dropwise while
stirring within 10 min at 20°С under an argon atmosphere.
The reaction mixture was stirred for 1.5 h, then at stirring and
external cooling with running water to the reaction mixture
was slowly added a solution of 3.1 mmol of ethynyl sulfone
I [13] or II [14] in 10 ml of THF. The mixture was stirred
spectrum δ, ppm: 21.7 (Mе), 63.1 (СН2), 89.7, 163.9
(Сolefin.), 111.8, 112.0 (CN), 128.3 (4С), 129.2 (2С),
130.2 (2С), 132.8, 133.1, 134.8, 146.2 (Сarom). Found,
%: С 67.11; Н 4.44; N 8.59. C18H14N2O2S. Calculated,
%: С 67.06; Н 4.38; N 8.69.
Reaction of ethenyl sulfone III with dimethyl
malonate, malononitrile, and methyl cyanoacetate.
General procedure. From 6.1 mmol of dimethyl malonate,
malononitrile, or methyl cyanoacetate and 8.3mmol of 60%
dispersion of NaH in mineral oil the solution was prepared
of sodium enolate in 10 ml of THF as described above.
Then the solution of 5.5 mmol of ethenyl sulfone III [9] in
10 ml of THF was added. The mixture was stirred for 10 h at
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

REACTIONS OF STYRYL AND PHENYLETHYNYL SULFONES
1141
50°Сin the case of dimethyl malonate and 20 h at 20°Сin the
case of malononitrile and methyl cyanoacetate. Afterwards
the reaction mixture was worked up as described above.
(3Н, ОMе), 4.12–4.19 m (1Н, СНPh), 4.48 d (1H, CHCN,
J5.3 Hz), 7.39 br.s (5H, Ph). 13СNMR spectrum,δ,ppm:39.0,
42.0, 43.4, 53.5, 56.7, 114.7 (CN), 128.0 (2С), 129.1, 129.2
(2С), 135.8 (Сarom), 164.4 (С=О). Found, %: С55.41; Н5.66;
N 5.07. C13H15NO4S. Calculated, %:С55.50; Н5.37; N 4.98.
Dimethyl 2-[2-(methylsulfonyl)-1-phenylethyl]
malonate (IVa). Yield 22%, mp 120–121°С (benzene–
hexane). IR spectrum, v, cm–1: 2955 s, 2932 s, 1748 v.s,
1732 s, 1431 w, 1300 s, 1254 s, 1154 s, 1123 s, 710 m, 517 s.
1Н NMR spectrum, δ, ppm: 2.40 s (3Н, SО2Mе), 3.54 s
(3Н, ОMе), 3.76 s (3Н, ОMе), 3.54–3.65 m (2Н, CH2SО2),
3.83 d (1Н, СНСО2Mе, J 8.8 Hz), 4.04 t.d (1Н, СНPh, J 3.5,
9.0 Hz), 7.25–7.44 m (5 Нarom). 13С NMR spectrum, δ, ppm:
40.5, 41.7, 52.6, 52.9, 56.6, 58.0, 128.3, 128.4 (2C), 129.0 (2С),
137.6(Сarom), 167.2, 167.8(С=О).Found, %: С53.54; Н5.81.
C14H18O6S. Calculated, %: С 53.49; Н 5.77.
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1265 m, 1142 v.s, 968 m, 787 m, 702 m, 502 m. 1Н NMR
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hexane). IR spectrum, v, cm–1: 2932 w, 2253 w, 1752 m,
1740 s, 1296 v.s, 1254 s, 1142 s, 934 m, 764 w, 513 w.
1Н NMR spectrum, δ, ppm: 2.77 s (3Н, SO2Mе), 3.56 d.d
(1Н, J5.8, 14.4 Hz), 3.69 d.d (1Н, СН2, J8.3, 14.4 Hz), 3.67 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011