Reaction of phenyl and 4-methylphenyl phenylethynyl sulfones with methyl acetoacetate

Article abstract of DOI:10.1134/S1070428013090029

Stereoselective anti-addition of methyl acetoacetate at the triple C≡C bond of phenyl- and 4-methylphenyl phenylethynyl sulfones in the presence of sodium hydride yields the corresponding Michael adduct containing an impurity of arylsulfonylacetophenone.

Full text of DOI:10.1134/S1070428013090029

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 9, pp. 1257–1263. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.A. Vasin, I.Yu. Bolusheva, V.V. Razin, N.V. Somov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 9,
pp. 1275–1281.
Reaction of Phenyl and 4-Methylphenyl Phenylethynyl Sulfones
with Methyl Acetoacetate
a
a
b
c
V. A. Vasin , I. Yu. Bolusheva , V. V. Razin , and N. V. Somov
a
Ogarev Mordovian State University, ul. Bol’shevistskaya 68, Saransk, 430005 Russia
e-mail: vasin@mrsu.ru
b
St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
c
Lobachevskii State University of Nizhni Novgorod, pr. Gagarina 23, Nizhni Novgorod, 603950 Russia
Received February 15, 2013
Abstract—Stereoselective anti-addition of methyl acetoacetate at the triple C≡C bond of phenyl- and
-methylphenyl phenylethynyl sulfones in the presence of sodium hydride yields the corresponding Michael
4
adduct containing an impurity of arylsulfonylacetophenone. In the reaction with 4-methylphenyl phenylethynyl
sulfone, methyl (Z)-2-acetyl-4-(4-methylphenylsulfonyl)-3-phenylbut-3-enoate was also obtained.
DOI: 10.1134/S1070428013090029
We previously showed [1] that nucleophilic ad-
dition of dimethyl malonate or malononitrile to the
activated triple C≡C bond of phenylethynyl sulfones Ia
and Ib yields sulfonyl-substituted ethylidenemalonic
acid derivatives IIa–IId instead of the expected
Michael adducts. This reaction path was rationalized
assuming 1,3-proton transfer in initially formed vinylic
carbanion A to give allylic anion A′ and subsequent
protonation of the latter at the α-position with respect
to the sulfonyl group upon treatment of the reaction
mixture with water (Scheme 1).
4-methylphenyl phenylethynyl sulfones Ib and Ic with
methyl acetoacetate. The reactions were carried out
with equimolar amounts of the reactants in THF at
50°C (reaction time 20 h) using 1.5 equiv of sodium
hydride to generate CH acid anion. The behavior of
methyl acetoacetate toward phenylethynyl sulfones Ib
and Ic essentially differed from the behavior of di-
methyl malonate and malononitrile. In all cases, the
major product was the corresponding Michael adduct
(IIIb or IIIc), whereas ethylidene derivative II was
isolated in a poor yield (7%) only in the reaction with
sulfone Ib (Scheme 2). No analogous derivative was
detected in the reaction with Ic. In addition, the forma-
tion of arylsulfonylacetophenone (IVb or IVc) was
Scheme 1.
Ph
CH W , NaH
W
W
1
2
2
SO R
2
observed. According to the H NMR data, the product
Ph
SO R
2
ratio was IIIb/IVb/II 4.7 : 1.6 : 1.0 and IIIc/IVc
H
5
.7:1.0.
Ia, Ib
A
Individual compounds II–IV were isolated by col-
Ph
Ph
+
umn chromatography on silica gel and/or by crystal-
lization. Previously reported sulfonyl ketones IVb and
IVc were identified by comparing their properties with
published data. The structure of compounds II and III
H /H O
W
SO R
2
W
SO R
2
2
W
H
W
A'
IIa–IId
1
13
was proved by analysis of their IR, H and C NMR,
Ia, IIa, IIb, R = Me; Ib, IIc, IId, R = 4-MeC
6 4
H ;
and mass spectra. The IR spectra of II and III con-
II, W = CO Me (a, b), CN (c, d).
2
–
1
tained strong absorption bands at 1150 and 1310 cm
With a view to elucidate regioselectivity of reac-
tions of phenylethynyl sulfones with CH acids, in the
present work we examined reactions of phenyl and
which are typical of sulfonyl group. The molecular ion
peaks in the mass spectra of II and III had low
intensity, and the base peak in the mass spectrum of II
1
257

1
258
VASIN et al.
Scheme 2.
O
Ph
OMe Ph
O
MeC(O)CH C(O)OMe
2
NaH
SO C H Me-4
SO Ar
2
2
6
4
Ph
SO Ar
+
+
Ph
2
Me
O
H
C(O)OMe
SO Ar
2
O
Me
Ib, Ic
II
IIIb, IIIc
IVb, IVc
6 4
Ar = 4-MeC H (b), Ph (c).
was that with m/z 217; it corresponds to elimination of
the tosyl group from the molecular ion. The fragmenta-
tion patterns of the molecular ions of IIIb and IIIc
were similar: the most abundant ions were those result-
ing from loss of arylsulfonyl group and arenesulfinic
acid, m/z 217 and 216, respectively.
protons in the spectrum of II were assigned using
1
13
H– C HMBC correlation technique.
1
13
In keeping with the H and C NMR data, adducts
IIIb and IIIc in solution are completely enolized. This
follows from the presence of a downfield broadened
1
signal at δ 12.95 ppm in the H NMR spectrum (OH)
1
3
1
13
and a signal at δ 171.1 ppm in the C NMR spectrum
As might be expected, the H and C NMR spectra
of II resembled those of known model compound [1].
The Z configuration of the double C=C bond in II was
C
(
=C–OH); the ester carbonyl carbon atom resonates at
δC ~175 ppm. The formation of intramolecular hydro-
1
1
gen bond in the β-keto ester fragment is additionally
determined on the basis of the H– H NOESY data,
according to which protons in the methylene group
were coupled with ortho-protons in the phenyl (cross-
peaks a) and tolyl fragments (cross-peaks b; Fig. 1). In
addition, ortho-protons in the phenyl group displayed
coupling with methyl protons in the acetyl group (cross
peaks c) indicating cis orientation of the corresponding
fragments with respect to the double C=C bond. Cross-
peaks d reflected interactions between meta-protons
and para-methyl group in the tolyl ring. Signals from
confirmed by the presence of fairly strong carbonyl
–
1
absorption bands at 1651–1656 cm and enolic OH
–
1
bands at 3056–3063 cm in the IR spectrum [2].
The configuration of molecules IIIb and IIIc was
also determined using two-dimensional NMR tech-
1
1
niques. The H– H NOESY spectra revealed interac-
tion between ortho-protons in the benzene ring and
proton at the double bond, which implies trans orienta-
tion of the phenyl and arylsulfonyl substituents with
OMe
CH
2
6 4
MeC H
MeCO
δ, ppm
7
7
7
7
7
7
.3
.4
.5
.6
.7
.8
o-H in
C H
6 4
d
d
H
H
a
c
H
a
Me
6 5
C H
O
S
c
H
O
b
Me
C(O)OMe
O
6 4
C H
b
5
.0
4.5
4.0
3.5
3.0
2.5
2.0 δ, ppm
1
1
Fig. 1. A fragment of the H– H NOESY spectrum of methyl (Z)-2-acetyl-4-(4-methylphenylsulfonyl)-3-phenylbut-2-enoate (II).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

REACTION OF PHENYL AND 4-METHYLPHENYL PHENYLETHYNYL SULFONES
1259
d
c
a
H
H
H
O
S
Me
H
b
H
O
Me
OMe
O
O
H
OMe
MeC
6
H
4
MeCO
δ, ppm
1
.0
MeCO
b
2
3
4
5
6
7
8
.0
.0
.0
.0
.0
.0
.0
6 4
MeC H
c
OMe
a
CH=
d
a
C
C
6
6
H
H
5
d
4
8
.0
7.0
6.0
5.0
4.0
3.0
2.0
δ, ppm
1
1
Fig. 2. H– H NOESY spectrum of methyl (2Z,3Z)-2-(1-hydroxyethylidene)-4-(4-methylphenylsulfonyl)-3-phenylbut-3-enoate
IIIb). Signal from the enolic hydroxy proton is not shown.
(
respect to the double C=C bond. This interaction gives
rise to cross-peaks a in the NOESY spectrum of IIIb
shown in Fig. 2. Cross-peaks b reflect coupling of
ortho-protons in the phenyl group with methyl protons
of the enol fragment, cross-peaks c correspond to inter-
action between protons of the 4-methyl group and
meta-protons in the tolyl substituent, and cross-peaks d
arise from interaction of magnetically nonequivalent
ortho- and meta-protons in the tolyl group.
diene fragment is nonplanar, and the plane of the
enolized methyl acetoacetate fragment is almost ortho-
8
9
10
gonal to the plane of the styryl fragment (C –C –C ).
9
17
Due to restricted rotation about the C –C bond, mole-
cules IIIb in crystal occur as a mixture of equal
amounts of conformers A and B. Least-squares refine-
ment of populations of non-hydrogen atoms revealed
6
A
19A
6B
19B
that the O (C ) and O (C ) positions are occupied
by 50% of oxygen and 50% of carbon atoms and that
2
0A
20B
The structure of compound IIIb was studied in
detail by X-ray analysis of its single crystal (Fig. 3,
Table 1). The X-ray diffraction data unambiguously
confirmed the enol structure of IIIb and trans arrange-
ment of the phenyl and tosyl groups with respect to the
the C and C positions are occupied each by only
50% of carbon atoms which are characterized by high
thermal vibration parameters and anomalous inter-
atomic distances (average of ordinary and multiple
bonds; Tables 1, 2). The positions of the carbonyl
oxygen atom of one conformer coincide with the posi-
8
9
8
9
17
18
16
double C =C bond. The C –C –C –C (C ) buta-1,3-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

1
260
VASIN et al.
responsible for the formation of the corresponding
1
3
C
1
2
C
Michael adduct as the major product, while its isomer
II is formed as minor one, unlike analogous addition
reactions with dimethyl malonate and malononitrile.
1
5
1
1
C
O
C
2
8
C
C
1
0
C
1
9
S
7
C
3
C
4
C
1
4
C
Side formation of arylsulfonylacetophenones IVb
and IVc may be attributed to some contribution of con-
current O-alkylation of methyl acetoacetate anion with
activated acetylene through carbanion C and divinyl
ether D which undergoes hydrolysis upon treatment
of the reaction mixture with water. We plan to extend
the set of CH acids to be involved in reactions with
ethynyl sulfones.
C
11
C
6
B
19B
O (C
)
1
7
2
5
C
O
C
6
A
19A
2
0B
6
O (C
)
C
C
1
8
C
2
0A
16
C
C
4
O
3
O
Fig. 3. Structure of the molecule of methyl (2Z,3Z)-2-(1-hy-
droxyethylidene)-4-(4-methylphenylsulfonyl)-3-phenylbut-
EXPERIMENTAL
1
13
3
-enoate (IIIb) according to the X-ray diffraction data.
The H and C NMR spectra were measured from
Hydrogen atoms are not shown.
solutions in CDCl on a Jeol JNM-ECX400 spectrom-
3
eter at 400 and 100 MHz, respectively, using the
residual proton and carbon signals of the solvent as
reverence. The IR spectra were recorded in KBr on
an InfraLYuM FT-02 spectrometer with Fourier trans-
form. The elemental compositions were determined on
a Vario MICRO CHNS analyzer. The mass spectra
tions of the enol oxygen atom of the other conformer;
likewise, the positions of the carbonyl carbon atoms of
different conformers coincide with the positions of the
carbon atoms linked to the enolic hydroxy group. The
other structural parameters of conformers A and B are
completely identical, and the corresponding divergence
factor has an acceptable value.
(
electron impact, 70 eV) were obtained on a KONIK
RBK-HRGC5000B-MSQ12 system. Analytical thin-
layer chromatography was performed using Silufol
UV-254 plates and light petroleum ether–ethyl acetate
Thus the addition of methyl acetoacetate to phenyl-
ethynyl sulfones Ib and Ic is strictly regioselective in
keeping with the orientating effect of the electron-
withdrawing sulfonyl substituent and is exclusively
anti-stereoselective. The reaction involves interme-
diate formation of vinylic carbanion B as a result of
C-alkylation of methyl acetoacetate carbanion with
activated acetylene; the subsequent isomerization of B
into more stable conjugated anion B′ and protonation
of the latter yields compounds II and IIIb or IIIc
(
3:1) as eluent; spots were developed by treatment
with iodine vapor. Silica gel L 40/60 μm was used for
column chromatography (eluent light petroleum ether–
ethyl acetate, 5:1). Initial phenylethynyl sulfones Ib
[
3] and Ic [4] were synthesized according to known
methods.
Reaction of phenylethynyl sulfones Ib and Ic
with methyl acetoacetate (general procedure). So-
dium hydride, 0.25 g (6.2 mmol; a 60% suspension in
mineral oil), was washed with hexane to remove
(
Scheme 3). We believe that just enhanced stability of
the enol structure of the methyl acetoacetate residue is
Scheme 3.
O
Ph
Me
Ph
+
H /H O
MeO
O
2
IIIb, IIIc
SO Ar
SO Ar
2
2
O
Me
Ph
O
OMe
O
O
B
B'
Ib, Ic
+
Me
OMe
Me
Me
Ph
+
+
H /H O
H /H O
O
2
O
2
IVb, IVc
C(O)OMe
SO Ar
C(O)OMe
SO Ar
2
2
C
D
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

REACTION OF PHENYL AND 4-METHYLPHENYL PHENYLETHYNYL SULFONES
1261
Table 1. Coordinates, populations, and equivalent temperature factors of non-hydrogen atoms in the molecule of methyl
(
2Z,3Z)-2-(1-hydroxyethylidenr)-4-(4-methylphenylsulfonyl)-3-phenylbut-3-enoate (IIIb)
2
Atom
x
y
z
Population
Ueq, Å
1
C
1.1617(6)
1.2986(6)
1.2683(6)
1.4187(8)
1.1007(7)
0.9623(5)
0.9929(4)
0.8136(4)
0.7396(3)
0.7490(3)
0.6957(6)
0.8078(6)
0.8194(7)
0.7065(7)
0.7714(4)
0.4700(3)
0.6511(3)
0.7459(3)
0.8731(3)
0.6591(3)
0.3881(3)
0.6776(3)
0.3874(4)
0.3874(4)
0.2191(9)
0.9162(4)
0.9162(4)
01.0091(10)
000.81893(11)
0.2457(4)
0.3412(5)
0.4148(2)
0.3924(3)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
1.000(0)
0.498(3)
0.498(3)
0.498(3)
0.502(3)
0.502(3)
0.502(3)
1.000(0)
00.0986(12)
00.1107(13)
00.1047(12)
00.1481(18)
00.1022(12)
00.0885(10)
0.0774(8)
2
C
3
C
0.4571(4)
0.3621(2)
4
C
0.5599(6)
0.3379(4)
5
C
0.4763(4)
0.3549(2)
6
C
0.3829(4)
0.3744(2)
7
C
0.2663(3)
000.40509(18)
000.34002(19)
000.23675(16)
000.16759(16)
0.0599(2)
8
C
–0.0228(3)–
–0.0709(2)–
–0.2146(2)–
–0.2578(3)–
–0.3108(3)–
–0.4426(4)–
–0.3908(4)–
–0.4821(3)–
0.0089(3)
0.0758(8)
9
C
0.0519(5)
1
0
C
C
C
C
C
C
C
C
C
O
O
O
O
O
0.0480(5)
11
00.1050(13)
00.1099(13)
00.1366(19)
00.1175(14)
0.0889(9)
1
1
1
1
1
1
1
2
3
4
5
6
7
8
0.2084(3)
0.1414(3)
–0.0055(3)–
0.0361(3)
000.18497(19)
000.18597(16)
000.13684(17)
000.53724(14)
000.41591(16)
000.14625(17)
000.09473(15)
0.2216(2)
0.0629(6)
0.0197(2)
0.0546(5)
0.1112(2)
0.0556(5)
1
2
3
4
6
0.1316(3)
0.0985(7)
0.1893(2)
0.0973(7)
0.0871(2)
0.0883(6)
000.19301(19)
–0.0932(3)–
–0.0932(3)–
–0.1215(9)–
0.1080(3)
0.0806(6)
A
00.1065(12)
00.1065(12)
0.103(2)0
1
9A
0A
C
C
O
0.2216(2)
2
0.2158(6)
6
B
0.1339(2)
00.0927(10)
00.0927(10)
00.0859(18)
0.0818(3)
1
9B
0B
C
C
0.1080(3)
0.1339(2)
2
0.1887(7)
0.0901(5)
1
S
00.14499(8)
00.43311(5)
mineral oil; the solvent was separated by decanting,
and its residue was removed under reduced pressure.
The flask was then filled with argon, 5 ml of anhy-
drous THF was added, and a solution of 0.53 g
pressure. In the reaction with Ib, the residue was
1.16 g of a viscous oily material which was subjected
to column chromatography on silica gel to isolate
0.52 g (34%) of IIIb, 0.12 g (10%) of IVb, and 0.10 g
(7%) of II. In the reaction with Ic, the residue was
1.18 g of a semicrystalline material which was washed
with diethyl ether. From the ether washings we isolated
(
4.5 mmol) of methyl acetoacetate in 10 ml of THF
was added dropwise over a period of 15 min at 20°C.
The mixture was stirred for 1.5 h, a solution of
0
.42 g (32%) of IIIc as a colorless crystalline sub-
4
.1 mmol of sulfone Ib or Ic in 10 ml of THF was
stance; the oily residue, 0.70 g, was subjected to
column chromatography on silica gel to isolate 0.13 g
added, and the mixture was stirred for 20 h at 50°C,
diluted with 250 ml of water, neutralized with dilute
(
12%) of IVc.
(
1:1) hydrochloric acid, and extracted with methylene
chloride (4× 30 ml). The extract was washed with
Methyl (Z)-2-acetyl-4-(4-methylphenylsulfonyl)-
water, dried over CaCl , and evaporated under reduced
3-phenylbut-2-enoate (II). mp 105–106°C (from
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

1
262
VASIN et al.
Table 2. Selected bond lengths in the molecule of methyl
7.04 s (1H, =CH), 7.33–7.43 m (5H, Harom), 7.54 t (2H,
Harom, J = 7.1 Hz), 7.61 t (1H, Harom, J = 7.1 Hz),
(
2Z,3Z)-2-(1-hydroxyethylidene)-4-(4-methylphenylsul-
fonyl)-3-phenylbut-3-enoate (IIIb)
7
.85 d (2H, Harom, J = 8.2 Hz), 12.95 br.s (1H, OH).
C NMR spectrum, δ , ppm: 19.7 (CH ), 51.6
1
3
C
3
Bond
d, Å
Bond
d, Å
(
OCH ), 97.4 (=CH), 126.8 (2C), 128.0 (2C), 128.9
3
8
9
17
18
C –C
1.331(3)
1.481(3)
1.500(3)
1.400(3)
1.282(3)
1.321(4)
C –C
1.392(3)
1.278(3)
1.346(4)
1.282(7)
1.266(6)
(
4C), 130.6, 130.8, 133.2, 137.1, 141.1, 148.3 (Carom
,
9
10
17
18
4
C –C
C –O
C=C), 171.0 (C–OH), 174.9 (C=O, easter). Mass
+
9
18
6B
C –C
C –O
spectrum, m/z (Irel, %): 358 (1) [M] , 218 (15), 217
1
6
17
3
20A
6A
(96) [M – SO Ph], 216 (100) [M – PhSO H], 215 (17),
2
2
C –C
C
C
–O
1
6
20B
6B
185 (21), 184 (19), 157 (12), 129 (12), 115 (28), 77
C –O
–O
(
17). Found, %: C 63.64; H 4.91; S 8.89. C H O S.
16
6A
19 18 5
C –O
Calculated, %: C 63.67; H 5.06; S 8.95.
2
-(4-Methylphenylsulfonyl)-1-phenylethanone
–
1
acetone–hexane). IR spectrum, ν, cm : 2994 w,
(
IVb). mp 107–108°C (from acetone–hexane);
published data: mp 108–109°C [5], 109–110°C [6].
IR spectrum, ν, cm : 1678 v.s, 1597 s, 1447 s,
319 v.s, 1273 v.s, 1150 v.s, 1084 s, 995 s, 749 s,
1
1
1
725 v.s, 1686 s, 1597 m, 1323 s, 1316 s, 1150 s,
084 m, 714 m, 529 m. H NMR spectrum, δ, ppm:
.93 s (3H, COCH ), 2.44 s (3H, C H CH ), 3.75 s
3H, OCH ), 4.85 s (2H, CH ), 7.33 d (2H, Harom, J =
.0 Hz), 7.37 br.s (5H, Harom), 7.78 d (2H, Harom, J =
.0 Hz). C NMR spectrum, δ , ppm: 21.6 (C H CH ),
1.0 (COCH ), 52.5 (OCH ), 59.8 (CH ); 128.3 (2C),
28.5 (2C), 128.8 (2C), 129.6, 129.8 (2C), 136.4,
37.7, 139.0, 140.4, 144.9 (Carom); 164.8 (C=O, ester),
01.7 (C=O). Mass spectrum, m/z (I , %): 372 (4)
M] , 218 (15), 217 (100) [M – Ts], 216 (64), 215 (17),
57 (15), 129 (19), 115 (54), 91 (81), 90 (18), 65 (27).
Found, %: C 64.44; H 5.51; S 8.69. C H O S. Cal-
1
–1
3
6
4
3
1
7
(
1
3
2
41 s, 683 s, 590 s, 536 s, 502 s. H NMR spectrum, δ,
8
8
3
1
1
2
1
3
ppm: 2.43 s (3H, CH
J = 8.2 Hz); 7.35–7.39 m (1H), 7.47 t (2H, J = 7.5 Hz),
.62 t (1H, J = 7.5 Hz), 7.76 d (2H, J = 7.5 Hz), 7.93 d
2H, J = 8.2 Hz) (Harom). C NMR spectrum, δ , ppm:
1.7 (CH ), 63.5 (CH ); 128.5 (2C), 128.8 (2C), 129.3
3 2
), 4.72 s (2H, CH ), 7.33 d (2H,
3 2
C
6
4
3
3
3
2
7
(
2
1
3
C
rel
+
(2C), 129.8 (2C), 134.3, 135.6, 135.7, 145.3 (Carom);
88.1 (C=O). Found, %: C 65.64; H 5.15; S 11.79.
C H O S. Calculated, %: C 65.67; H 5.14; S 11.69.
[
1
1
1
5
14
3
2
0
20
5
1
-Phenyl-2-(phenylsulfonyl)ethanone (IVc).
culated, %: C 64.50; H 5.41; S 8.61.
mp 90–91°C (from acetone–hexane); published data:
mp 92–93°C [5], 94–95°C [6], 90–91°C (from CCl )
7]. IR spectrum, ν, cm : 2998 w, 1674 v.s, 1454 m,
447 m, 1319 v.s, 1308 v.s, 1281 m, 1157 v.s, 752 s,
87 m, 536 m, 517 m. H NMR spectrum, δ, ppm:
.74 s (2H, CH ); 7.47 t (2H, J = 7.6 Hz), 7.54 t (2H,
J = 7.6 Hz), 7.58–7.68 m (2H), 7.86–7.96 m (4H)
Harom). C NMR spectrum, δ , ppm: 63.4 (CH );
Methyl (2Z,3Z)-2-(1-hydroxyethylidene)-4-(4-
methylphenylsulfonyl)-3-phenylbut-3-enoate (IIIb).
mp 109–110°C (from acetone–hexane). IR spectrum,
ν, cm : 3056 w, 1651 m, 1644 m, 1624 m, 1593 m,
443 m, 1347 m, 1312 s, 1254 v.s, 1146 v.s, 1084 m,
56 m, 552 s. H NMR spectrum, δ, ppm: 1.64 s (3H,
CH ), 2.42 s (3H, C H CH ), 3.40 s (3H, OCH ),
.02 s (1H, =CH), 7.30 d (2H, Harom, J = 8.0 Hz), 7.34–
.41 m (5H, Harom), 7.72 d (2H, Harom, J = 8.0 Hz),
4
–
1
[
–
1
1
6
4
1
1
7
1
2
3
6
4
3
3
1
3
(
1
1
7
7
1
C 2
28.6 (2C), 128.8 (2C), 129.2 (2C), 129.3 (2C), 134.2,
34.4, 135.7, 138.7 (Carom); 187.9 (C=O). Found, %:
C 64.64; H 4.59; S 12.39. C H O S. Calculated, %:
1
3
2.95 s (1H, OH). C NMR spectrum, δ , ppm: 19.7
C
(
CH ), 22.6 (C H CH ), 51.6 (OCH ), 97.4 (=CH);
26.8 (2C), 128.0 (2C), 128.9 (2C), 129.5 (2C), 130.5,
31.1, 137.2, 138.3, 144.1, 147.8 (Carom, C=C); 171.1
14 12
3
3
6
4
3
3
C 64.60; H 4.65; S 12.32.
1
1
X-Ray diffraction data for compound IIIb. Total
of 13167 reflection intensities were measured at
93(2) K from a 0.4×0.2×0.1-mm transparent pris-
matic single crystal of IIIb on an Oxford Diffraction
Xcalibur Gemini S automatic four-circle diffractometer
(graphite monochromator, Sapphire III CCD detector,
(
%
C–OH), 174.8 (C=O, ester). Mass spectrum, m/z (I ,
rel
+
): 372 (1) [M] , 218 (15), 217 (100) [M – Ts], 216
99) [M – TsH], 215 (17), 185 (21), 184 (19), 157 (13),
29 (13), 91 (32). Found, %: C 64.53; H 5.50; S 8.67.
C H O S. Calculated, %: C 64.50; H 5.41; S 8.61.
2
(
1
2
0
20
5
Methyl (2Z,3Z)-2-(1-hydroxyethylidene)-3-phe-
nyl-4-(phenylsulfonyl)but-3-enoate (IIIc). mp 118–
MoK irradiation, λ = 0.71073 Å, ω-scanning, 2θ
=
α
max
52.74°, hkl ranges –9 ≤ h ≤ 9, –12 ≤ k ≤ 12, –16 ≤ l ≤
16). Averaging of equivalent reflections left 3834 in-
dependent reflections (Rint = 0.0166), 3086 of which
were characterized by I > 2σ(I). The unit cell param-
eters were determined, and reflection intensities were
–
1
119°C (from acetone–hexane). IR spectrum, ν, cm :
3
063 m, 1662 s, 1605 s, 1443 s, 1304 s, 1234 v.s,
1
1142 v.s, 1084 s, 756 v.s, 687 m, 555 s. H NMR spec-
trum, δ, ppm: 1.63 s (3H, CH ), 3.39 s (3H, OCH ),
3
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

REACTION OF PHENYL AND 4-METHYLPHENYL PHENYLETHYNYL SULFONES
measured, using CrysAlisPro software package [8].
REFERENCES
1263
A correction for absorption was applied empirically
using SCALE3 ABSPACK algorithm [9]. Triclinic
crystal system with the following unit cell parameters:
a = 7.8383(4), b = 9.9537(4), c = 13.1052(3) Å; α =
1. Vasin, V.A., Bolusheva, I.Yu., Masterova, Yu.Yu., and
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Affolter, C., Eds., Berlin: Springer, 2000, 3rd ed.
1
9
0
06.408(3), β = 95.347(3), γ = 101.918(4)°; V =
3
3
47.10(7) Å ; M 182.68; Z = 4; d = 1.281 g/cm ; μ =
calc
–
1
–
.197 mm ; F(000) = 378; space group P1. The struc-
3. Truce, W.E. and Wolf, G.C., J. Org. Chem., 1971,
vol. 36, p. 1727.
ture was solved by the direct method and was refined
2
against F by the least-squares procedure in full-matrix
4. Amiel, Y., J. Org. Chem., 1974, vol. 39, p. 3867.
anisotropic approximation for non-hydrogen atoms
using SHELX-97 [10] and WinGX [11]; number of
variables 245, goodness of fit 1.049; residual electron
5. Xie, Y.-Y. and Chen, Zh.-Ch., Synth. Commun., 2001,
vol. 31, p. 3145.
6. Sun, X., Wang, L., and Zhang, Y., Synth. Commun.,
–
3
density –0.23 and –0.309 ēÅ . The final divergence
1998, vol. 28, p. 1785.
factors were R = 0.0618 [for reflections with I >
7. Thomsen, M.W., Handwerker, B.M., Katz, S.A., and
1
2
σ(I)] and wR = 0.1757 (for all independent reflec-
Belser, R.B., J. Org. Chem., 1988, vol. 53, p. 906.
2
tions). The positions of hydrogen atoms were deter-
mined on the basis of geometry considerations and
were refined according to the riding model [U(H) =
8
. CrysAlis171.NET. version 1.171.36.21, release 14-08-
2012, Oxford Diffraction.
9
. Clark, R.C. and Reid, J.S., Acta Crystallogr., Sect. A,
1
1
.5U (C) for methyl hydrogen atoms, U(H) =
1995, vol. 51, p. 887.
eq
.2U (C) for other hydrogen atoms]. A weight scheme
eq
10. Sheldrick, G.M., Programs SHELXS97 (Crystal Struc-
ture Solution) and SHELXL97 (Crystal Structure Refine-
ment), Göttingen, Germany: University of Göttingen,
1997.
2
2
2
w = 1/[σ (F ) + (0.0822P) + 0.3791P] was applied,
where P = (F + 2F )/3. The coordinates of non-hydro-
gen atoms and their populations and equivalent tem-
perature factors are given in Table 1, and selected bond
lengths are presented in Table 2.
o
2
o
2
s
11. Farrugia, L.J., J. Appl. Crystallogr., 1999, vol. 32,
p. 837.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013