Synthesis of 3,3-diphenyl-3H-pyrazoles applying vinyl sulfones as chemical equivalents of acetylenes in reaction of 1,3-dipolar cycloaddition to diphenyldiazomethane

Article abstract of DOI:10.1134/S1070428015080138

Vinyl phenyl sulfone, methyl (E)-3-(phenylsulfonyl)- and methyl (E)-3-(p-tosyl)acrylates, (E)-3-(phenylsulfonyl)- and (E)-3-(p-tosyl)acrylonitriles react in ethyl ether at 20°C with diphenyldiazomethane leading to the formation of the corresponding 5,5-di

Full text of DOI:10.1134/S1070428015080138

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 8, pp. 1144–1154. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.A. Vasin, V.V. Razin, E.V. Bezrukova, D.Yu. Korovin, P.S. Petrov, N.V. Somov, 2015, published in Zhurnal Organicheskoi Khimii,
2
015, Vol. 51, No. 8, pp. 1163–1173.
Synthesis of 3,3-Diphenyl-3H-pyrazoles Applying
Vinyl Sulfones as Chemical Equivalents of Acetylenes
in Reaction of 1,3-Dipolar Cycloaddition
to Diphenyldiazomethane
a
b
a
a
V. A. Vasin , V. V. Razin , E. V. Bezrukova , D. Yu. Korovin ,
a
c
P. S. Petrov , and N. V. Somov
a
Ogarev Mordovian State University, Bolshevistskaya ul. 68, Saransk, 430005 Russia
e-mail: vasin@mrsu.ru
b
St. Petersburg State University, St. Petersburg, Russia
c
Lobachevskii Nizhny Novgorod State University, Nizhny Novgorod, Russia
Received May 21, 2015
Abstract—Vinyl phenyl sulfone, methyl (Е)-3-(phenylsulfonyl)- and methyl (Е)-3-(p-tosyl)acrylates,
Е)-3-(phenylsulfonyl)- and (Е)-3-(p-tosyl)acrylonitriles react in ethyl ether at 20°С with diphenyl-
(
diazomethane leading to the formation of the corresponding 5,5-diphenyl-3-(arylsulfonyl)-
2
Δ -pyrazolines. Products containing a methoxycarbonyl or cyano group at treating with DBU in
dichloromethane at 0°С suffer a dehydrosulfonation and are converted into 4-substituted 3,3-diphenyl-3Н-
2
pyrazoles. The oxidation of the mentioned Δ -pyrazolines with activated manganese dioxide in
benzene at 20°С leads to the formation of 4-methoxycarbonyl- and 4-cyano-substituted 5-arylsulfonyl-
3
,3-diphenyl-3Н-pyrazoles respectively. The reactions of α-bromovinyl phenyl sulfones and
α-bromovinyl methyl sulfones with diphenyldiazomethane afforded the corresponding 3-bromo-
1
5
,5-diphenyl-3-sulfonyl-Δ -pyrazolines. The first among them at 20°С suffered spontaneous elimination
of molecular nitrogen and converted into 1-bromo-2,2-diphenyl-1-(phenylsulfonyl)cyclopropane whose
1
structure was established by X-ray diffraction analysis. The action of DBU on another Δ -pyrazoline
1
resulted in the formation of the product of the Ramberg–Bäcklund reaction, 5-methylene-3,3-diphenyl-Δ -
pyrazoline together with the product of hydrodebromination–isomerization, 5,5-diphenyl-3-(methylsulfonyl)-
2
Δ -pyrazoline.
DOI: 10.1134/S1070428015080138
Some vinyl sulfones are known to be suitable
Numerous examples are also known of the
utilization of vinyl sulfones as synthetic equivalents of
acetylenes dipolarophiles in the reactions of concerted
[3 + 2]-cycloaddition [6–8]. In particular, by the
azomethine ylides cycloaddition to vinyl sulfones
sulfonyl-substituted pyrrolidines were synthesized that
at the treatment with bases (DBU, TMEDA, etc.)
eliminated the arenesulfinic acid converting into
dihydropyrroles. At the same time, in some cases
managed to create dihydropyrroles that can not be
obtained by cycloaddition reaction to the acetylenic
dipolarophiles. Cycloadducts formed at azomethine
ylides cycloaddition to sulfone А as a result of desul-
fonation underwent aromatization in pyrrole deriva-
tives [9–12]. Pyrroles were also formed in a one-pot
synthetic equivalents of acetylene dienophiles in
Diels–Alder reactions [1–5]. For instance, vinyl
sulfones А–C were used as dienophiles in the reaction
of concerted [4+2]-cycloaddition to cyclopentadie-
ne, and the obtained cycloadducts were subjected in
the first case to desulfonation, in the second case to
dehydrosulfonation, and in the third case to
dehydrochlorination resulting in norbornadiene
[
2], 2-cyanonorbornadiene [5], and 2,3-di(phenylsul-
fonyl)norbornadiene [4]. Thus the mentioned
vinyl sulfones behaved in these Diels–Alder
reactions as synthetic equivalents of acetylene
proper, cyanoacetylene, and di(phenylsulfonyl)-
acetylene respectively.
1
144

SYNTHESIS OF 3,3-DIPHENYL-3H-PYRAZOLES APPLYING VINYL SULFONES
1145
process involving the azomethine ylides cycloaddition
to bromovinyl sulfone D and the elimination of
benzenesulfinic and hydrobromic acid under the
treatment with DBU [13]. In these syntheses of
substituted pyrroles vinyl sulfones А and D played the
role of synthetic equivalents of acetylene. Similarly
vinyl sulfone E was used as the equivalent of methyl
propiolate in the 1,3-dipolar cycloaddition to
pyrazolidinium ylides, and the yield of the target
bicyclic pyrazolidinone turned out to be considerably
higher than in its synthesis applying directly the
acetylene dipolarophile [14]. The same procedure was
utilized in the preparation of 3-aroyl-1Н-pyrazole by
the reaction of diazomethane in the presence of
triethylamine with vinyl sulfone F playing the role of
the synthetic equivalent of aroylacetylene [15].
preparation of 3,3-disubstituted 3Н-pyrazole by the
cycloaddition of 2-diazopropane to (Е)-1,2-di(aryl-
sulfonyl)ethene used as a synthetic equivalent of aryl-
sulfonylacetylene [19]. Yet the desired 3Н-pyrazole G
proved to be “elusive” and under the reaction
conditions converted into bispyrazoline H.
E
E
E
Me CN
2
2
E
N
N
H
E
H
E
H
N
N
Me CN
2
2
N
N
_EH
N
N
G
H
2
E = SO Ar.
PhO2S
NC
Cl
SO Ph
SO
2
Ph PhO
2
S
SO
2
Ph
Another approach to the synthesis of 3,3-
disubstituted 3Н-pyrazoles was attempted in [20]
applying the oxidative dehydrogenation of the corres-
ponding pyrazoline derivative which in its turn was
obtained by the cycloaddition of 2-diazopropane to
activated ethylenes, lacking, however, vinyl sulfones.
2
A
B
C
MeO C
ArOC
2
Br
SO Ph
SO
Ph
SO Ar'
2
2
2
D
E
F
R2
R1
R2
R1
MnO2
In this paper, we applied to the synthesis of
derivatives of 3,3-diphenyl-3Н-pyrazole underlain by
the diphenyldi-azomethane cycloaddition to vinyl
sulfones 1a–1c, 2b, 2c, 3, and 4 followed by the
elimination of sulfinic or hydrobromic acids.
N
N
N
N
H
1
2
2 2 2
R = NO , COMe, CO Me, CN; R = Ph, CO Me, CN.
Br
This approach we extended to the synthesis of
R
sulfonyl-substituted 3,3-diphenyl-3Н-pyrazoles.
SO Ar
SO
3, 4
R'
2
2
Reactions of vinyl sulfones 1 and 2 with a slight
excess of diphenyldiazomethane were carried out in
anhydrous ethyl ether at 20°С within 20–60 h, and
each reaction in 69–77% yield afforded a single
1
a_1c, 2b, 2c
R = H (a), CO
2
Me (b), CN (c); Ar = Ph (1), p-Tol (2);
R' = Me (3), Ph (4).
2
product, Δ -pyrazolines 5 and 6.
Our interest in this class of compounds was
connected with our desire to extend the investigations
of the van Alphen–Hüttel rearrangement [16, 17] to
new objects aiming to reveal its general laws and to
provide their better understanding. The main
traditional preparation method for 3,3-disubstituted
a_1c, 2b, 2c
1
+
Ph CN
2 2
R
SO Ar
R
SO Ar
2
2
Et O
2
Ph
Ph
Ph
Ph
N
N
N
N
H
3
Н-pyrazoles is the 1,3-dipolar cycloaddition of the
disubstituted diazomethane to acetylene dipolarophile
18]. However the application of this method has some
_
I
5a 5c, 6b, 6c
Ar = Ph (5), p-Tol (6).
[
limitation thus promoting the search for new
approaches to building up such systems. The only
known synthesis attempt was described of the
2
Δ -Pyrazolines 5a–5c, 6b, and 6c were isolated in a
crystalline state, and the presence of the appropriate
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

1
146
VASIN et al.
5
4
functional groups in the compounds was confirmed by
the elemental analysis, IR, Н and С NMR spectra. In
tion between the quaternary atom С and the atom Н .
The method Н2ВС which reveals only the СН-
correlations through two bonds may be used
additionally for the refining of the structure. This
method is totally complementary to the HMBC
method, but it does not indicate the correlations of the
quaternary carbon atoms. A fragment of Н2ВС
spectrum is shown in Fig. 2. In the spectrum two
cross-peaks b' and c' are present corresponding to the
1
13
particular, the presence of the NH group is shown in
1
the Н NMR spectra by a broadened singlet at ~6.6–
7
.0 ppm, and in the IR spectra, by the absorption band
–
1
in the region 3325–3417 cm [21]. The observed re-
gioselectivity of diphenyldiazomethane cycloaddition
to vinyl sulfone 1a appears to be evident, and therefore
the structure of Δ -pyrazoline 5а is doubtless. The
structure of Δ -pyrazolines 5b, 5c, 6b, and 6c required
2
2
4
4
3
couplings Н –CN and Н –С respectively that provides
a possibility to choose the structure 6с.
additional confirmation. We applied to the study of the
structure 6с the method of long-range (multi-bond)
The provided proof of the structure of pyrazoline 6с
makes it possible to extend the assignment of the
structure not only to compound 5с, but also to
compounds 5b and 6b. The additional confirmation of
the structure of pyrazoline 5b is described further.
1
13
correlations Н– С НMВС and Н2ВС [22]. A fragment
of the НMВС spectrum of this compound is presented
1
4
in Fig. 1. In the Н NMR spectrum atom Н appears as
a signal at 5.79 ppm. This peak has three correlations
5
in the НMВС spectrum with carbon signals at 82.16 (С ),
2
Finally, the assumed structure of all Δ -pyrazolines 5
3
1
15.17 (CN), and 141.45 (С ) ppm, noted as a, b, and c
and 6 is confirmed by the presence of the signal at
respectively. The other cross-peaks correspond to the
correlations in the aromatic fragments and are of no
interest. It should be noted that this НMВС experiment
does not provide an unambiguous answer of the
13
~
149 ppm in the С NMR spectra that belongs to the
3
atom С linked to the sulfo group.
Therefore the regioselectivity of the cycloaddition
of diphenyldiazomethane to vinyl sulfones 1b, 1c, 2b,
and 2c turned out to be under a strict control of the
sulfo group. We believe that the main cause of this
control is the steric factor: The cyano and
methoxycarbonyl groups are less bulky than the
arylsulfonyl substituent.
2
structure of Δ -pyrazoline 6с since it does not make it
2
possible to distinguish the coupling constants J and
H–C
3
JH–C and decide between the structures 6с and 6с'.
A significant feature of НMВС spectrum should be
stressed: The cross-peak а corresponds to the correla-
b
c
c'
b'
a
a
b
H4
H4
H4
c
3
Tos-p
Tos-p
CN
3
3
NC
NC
p-Tos
Ph
Ph
5
5
5
N
N
N
Ph
N
Ph
N
N
H
Ph
Ph
H
H
6c
6c
6c'
4
4
H
H
5
5
a
C
C
b
CN
b'
c'
CN
3
c
3
C
C
7
.5
7.0
6.5
6.0
δ, ppm
7.5
7.0
6.5
6.0 δ, ppm
Fig. 1. Fragment of НMВС spectrum of 5,5-diphenyl-3-p-
tosyl-Δ -pyrazoline-4-carbonitrile 6c.
Fig. 2. Fragment of Н2ВС spectrum of 5,5-diphenyl-3-p-
tosyl-Δ -pyrazoline-4-carbonitrile 6c.
2
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

SYNTHESIS OF 3,3-DIPHENYL-3H-PYRAZOLES APPLYING VINYL SULFONES
1147
proton
transfer
_
R
SO Ph
2
Ph
Ph
N
R
R
SO Ph
N
2
_PhSO_2
DBU
5
b, 5c
_
Ph
Ph
_H+
Ph
Ph
H
N
N
R
N
N
Ph
Ph
8b, 8c
_PhSO_2
N
N
2
The formation of Δ -pyrazolines in analogous
reactions of diazo compounds cycloaddition to
activated alkenes is known to be a secondary process:
of its known [23] regioisomer, 3,3-diphenyl-5-
methoxycarbonyl-3Н-pyrazol 8b', cycloadduct of
methyl propiolate to diphenyldiazomethane. We
proved it by reproducing the synthesis of the latter.
This synthesis proved both the structure of compound
8b and of its precursor, pyrazoline 5b.
1
The primarily formed Δ -pyrazoline I suffers a
prototropic rearrangement. This rearrangement of
compound 5a is likely to be reversible since at boiling
in benzene for 12 h it completely converts into
cyclopropane 7 via biradical J as a result of nitrogen
After that we carried out the dehydrogenation of
pyrazolines 5b, 5c, and 6c by oxidation with activated
manganese dioxide [20, 24]. The reaction was
performed at 20°С while stirring the reagents solutions
in a mixture benzene–dichloromethane, 1 : 1, for 20 h
1
elimination; the latter process is possible only with Δ -
pyrazoline. At the same time compound 6c proved to
be stable against boiling in benzene for 50 h. The
structure of cyclopropane 7 is confirmed by spectral
characteristics.
in the presence of 12-fold molar excess of MnO . We
2
obtained from compound 5b 3Н-pyrazole 9b with the
admixture of 4Н-pyrazole 11b. Compounds 5c and 6c
were completely converted into 3Н-pyrazoles 9c and
SO Ph
2
Ph
Ph
SO Ph
2
5
a
I
_N
Ph
2
10c. Pyrazoline 5a was not oxidized with MnO as had
2
Ph
been observed before [20] for related (but not sulfonyl-
containing) 2-pyrazolines with the unsubstituted
position 4.
J
7
Further we turned to the study of the
MeO C
2
R
SO
Ar
2
SO Ph
2
2
dehydrosulfonation of Δ -pyrazoline 5b and 5c in
order to prepare the corresponding 3Н-pyrazoles. At
their treatment with the 1,5-fold DBU excess in
dichloromethane at 0°С compounds 8b and 8c formed
in 61–72% yields. In contrast, Δ -pyrazoline 5a at this
treatment remains unchanged.
Ph
MnO2
5b, 5c, 6c
Ph
Ph
+
N
N
Ph
N
N
9
b, 9c, 10c
11b
2
Ar = Ph (9), p-Tol (10).
The possible mechanism includes a deprotonation
stage. Then in the arising anion a proton transfer is
probable from the adjacent acid site followed by the
elimination of the phenylsulfinate anion. An
alternative route is also possible: A carbene formation
with a subsequent 1,2-hydride shift. The first route is
supported as we presume by the stability under the
chosen conditions against the dehydrosulfonation of
pyrazoline 5a lacking an additional activating group.
3
Н-Pyrazoles 9c and 10c were isolated in the
crystalline state. We failed to isolate compound 9b,
and it was characterized in the presence of 4Н-
pyrazole 11b using Н NMR spectra applying the
1
DOSY-experiment. The structure of pyrazoles 9c, 10c,
1
13
and 11b was confirmed by IR, Н and С NMR
spectra taking into account the data for related
compounds [25, 26]. 4Н-Pyrazole 11b is the product of
the thermal van Alphen–Hüttel rearrangements of 3Н-
pyrazole 9b. The rearrangement can be clearly observed
already at room temperature and is completed within
10 min at boiling in toluene.
The structure of 3Н-pyrazoles 8b and 8c is
1
13
confirmed by the IR, Н and С NMR spectra. In their
1
5
Н NMR spectra the singlet signal of Н at ~8.1 ppm is
characteristic. The spectral characteristics of 3Н-
pyrazole 8b essentially differ from the characteristics
The successful synthesis of 3Н-pyrazoles 9b, 9c,
and 10c allows regarding vinyl sulfones 5b, 5c, and 6b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

1
148
VASIN et al.
Br
N
Br
SO R'
Br
Et O
SO R'
2
2
Δ
_N
2
3
, 4
+
Ph CN
2
Ph
Ph
2
0oC
SO R'
2
2
2
Ph
N
Ph
Ph
Ph
1
2, 13
K
14, 15
R' = Me (12, 14), Ph (13, 15).
1
8
at room temperature. Pyrazoline 12 is more stable
against heating, but both pyrazolines 12 and 13 at short
boiling (10–20 min) in toluene afforded in a high yield
cyclopropanes 14 and 15 respectively. The nitrogen
elimination occurs obviously through the intermediate
biradicals K. The structure of compounds 12–15 was
established with the help of Н and С spectroscopy,
mass spectrometry, and was confirmed by the
elemental analysis data. Besides compound 14 was
subjected to XRD analysis (Fig. 3).
C
20
1
C
Br
19
C
1
1
17
C
15
C
6
C
C
1
6
1
2
C
7
C
C
1
3
10
C
2
1
C
C
1
9
1
1
13
C
1
O
C
8
S
C
2
C
5
2
C
O
3
C
4
C
1
4
C
Our attempt to carry out dehydrobromination of
pyrazoline 13 by treating with DBU in CH Cl at 0–
Fig. 3. Perspective view of the molecule of 1-bromo-2,2-
diphenyl-1-(phenylsulfonyl)cyclopropane 14 according to
XRD data.
2
2
20°С aiming at the preparation of the corresponding
Н-pyrazole derivative failed: Only cyclopropane 15
3
was obtained.
as convenient chemical equivalents of difficultly
accessible and unstable esters and nitriles of sulfonyl-
substituted acetylenecarboxylic acid.
1
Δ -Pyrazoline 12 at treating with DBU in CH Cl at
2
2
0
–20°С gave a mixture of two compounds 16 and 17
1
in a ratio 0.6 : 1. 5-Methylene-Δ -pyrazoline 16 is a
product of Ramberg–Bäcklund reaction [27] that includes
the 1,3-dehydrobromination giving episulfone L and
the thermal decomposition of the latter with sulfur
dioxide elimination (cf. [28]). 5,5-Diphenyl-3-(methyl-
sulfonyl)-Δ -pyrazoline 17 forms involving a base in
the halophilic hydrodebromination reaction through
the intermediate Δ -pyrazoline M.
Finally, we investigated the possibility to synthe-
size 3Н-pyrazoles applying bromovinyl sulfones 3 and
4
as synthetic equivalents of sulfonylacetylene. To this end
by the reactions between these compounds and diphenyl-
1
2
diazomethane we obtained Δ -pyrazolines 12 and 13.
The pyrazolines were isolated in a crystalline state
1
1
13
and characterized by IR, Н and С NMR spectra. The
regiochemistry of the cycloaddition is here undoubt-
less. Δ -Pyrazoline 13 turned out to be thermally unstable
compound, whose notable nitrogen elimination with
the formation of cyclopropane 15 was observed already
The structure of compounds 16 and 17 isolated in
1
an individual state by flash-chromatography on silica
1
13
gel was confirmed by IR, Н and С NMR spectra.
2
Besides Δ -pyrazoline 17 was prepared by an authentic
SO2
SO Me
2
Ph
Ph
N
Ph
Ph
N
_HBr
_SO2
N
N
Ph
Ph
19
Δ
1
6
DBU
L
1
2
SO Me
SO Me
2
2
Diphenyldiazomethane
H+
Ph
Ph
Ph
Ph
N
N
_Br+
SO Me
2
N
H
N
1
8
M
17
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

SYNTHESIS OF 3,3-DIPHENYL-3H-PYRAZOLES APPLYING VINYL SULFONES
1149
synthesis in a reaction of vinyl methyl sulfone 18 with
diphenyldiazomethane. In the formation of methylene-
pyrazoline 16 vinyl sulfone 12 acts as a synthetic
equivalent of unsubstituted allene.
diazomethane [37] were obtained by published
methods. Methyl (Е)-3-(phenylsulfonyl)acrylate 1b,
mp 95–96°C (98–99°C [38], 97°C [39]), methyl (Е)-3-
(p-tosyl)acrylate 2b, mp 116–117°C (117°C [39]), and
(
Е)-3-(phenylsulfonyl)acrylonitrile 1c, mp 103°C
Pyrazoline 17, like its analog 5а, was not oxidized
(
103–104°C [37]) were prepared by arylsulfo-
by activated MnO into the corresponding 3Н-pyrazole.
2
iodination–dehydroiodination of methyl acrylate and
acrylonitrile by procedure [34].
On the other hand, pyrazoline 17 proved to be prone to
thermal nitrogen elimination as its analog 5а: as a
result of the reaction cyclopropane 19 was obtained.
Reactions of compounds (1а–1c, 2b, and 2c) with
diphenyldiazomethane. To a solution of 8 mmol of
vinyl sulfone 1а–1c, 2b, and 2c in 35 mL of anhydrous
ethyl ether was added a solution of 1.55 g (8 mmol) of
diphenyldiazomethane in the same volume of this
solvent. The reaction mixture was kept at 20°С in a
tightly stoppered flask away from light for 20–60 h till
the disappearance of the red-purple color of the initial
EXPERIMENTAL
1
13
H and C NMR spectra were registered on a
spectrometer ECX-400 JEOL (399.8 and 100.5 MHz
respectively) from solutions of compounds in CDCl3.
The correlation НMВС (Δ 62.5 ms) and Н2ВС (T 22 ms)
spectra were taken in DMSO-d6 using thermal
stabilization at 30°С and a low-pass J-filter of III order
2
diazo compound. The precipitated crystals of Δ -
pyrazoline 5a–5c, 6b, and 6c were filtered off and
washed with ethyl ether.
1
in the range 120 < J < 160 Hz applying pulse field
gradient. Matrix size 819, 256, points number 1024,
2
5
,5-Diphenyl-3-(phenylsulfonyl)-Δ -pyrazoline
1
28, relaxation delay 2.54 s. Compound 9b in the
(
5a). Yield 77%. Light-yellow crystals, mp 146–147°С.
IR spectrum, ν, cm : 3325 s (NH), 1547 m, 1447 s,
396 m, 1319 s (asymm. SO ), 1180 m, 1146 v.s
symm. SO ), 1076 m, 760 m, 721 s, 687 s, 606 v.s,
63 m, 532 m. Н NMR spectrum, δ, ppm: 3.58 s (2H,
H ), 6.60 br.s (1H, NH), 7.11–7.17 m (4Harom), 7.24–
.31 m (6Harom), 7.55 t (2Harom, J 7.8 Hz), 7.65 t
1Harom, J 7.3 Hz), 7.97 d (2H , J 7.9 Hz). С NMR
spectrum, δ, ppm: 43.8 (C ), 77.5 (C ), 126.1 (4Carom),
127.8 (2Carom), 128.3 (2Carom), 128.4 (4Carom), 129.3
mixture with 4Н-pyrazole 11b, 1.6 : 1, was charac-
–1
1
terized applying the diffusion-ordered H NMR
1
(
5
2
spectroscopy (DOSY) [29, 30] using a bipolar pulse
sequence BPP LED [31] at 298 K. The amplitude of
field gradient was varied from 20 to 280 mT/m
2
1
4
(
logarithmic function of base 2) for 10 points. The data
acquisition was performed with parameters Δ 70 ms, δ
ms, T 50 ms, relaxation delay 7 s, data array 8 × 1024
7
(
13
arom
1
4
5
e
points. The results were processed by the procedure
–
10
–8
2
SPLMOD [32] (10 –10
components including CDCl3).
m /s, 15 points,
(
(
2Carom), 134.0 (2Carom), 138.6 w (2Сarom), 143.9 w
1Сarom), 149.2 (С ). Found, %: С 69.76; Н 4.94; N
3
3
IR spectra were recorded on
a
Fourier
7.76; S 8.86. С Н N O S. Calculated, %: С 69.59; Н
21 18 2 2
spectrophotometer InfraLYuM FT-02 from pellets
with KBr. Elemental analyses were carried out on a
СНNS-analyzer VarioMICRO. Mass spectra were taken
using the system KONIK RBK-HRGC5000B-MSQ12,
EI, 70 eV. Analytic TLC was performed on Sorbfil
plates, eluent light petroleum ether–acetone, 4 : 1,
development in iodine vapor. The flash-
chromatography on a dry column was carried out
applying silica gel L 5/40, eluent light petroleum
ether–ethyl acetate 4–1 : 1. Melting points of
compounds were measured in sealed glass capillaries
using melting point analyzer MP-50 (Mettler Toledo,
Switzerland).
5.01; N 7.73; S 8.85.
2
Methyl 5,5-diphenyl-3-(phenylsulfonyl)-Δ -
pyrazoline-4-carboxylate (5b). Yield 69%. Light-
yellow crystals, mp 206–207°С. IR spectrum, ν, cm :
–1
3
341 m (NH), 1732 v.s (C=O), 1555 w, 1493 w, 1446
m, 1319 s (asymm. SO ), 1269 m, 1138 m (symm.
2
1
SO ), 1080 w, 856 w, 752 m, 687 m, 606 m, 536 m. Н
2
NMR spectrum, δ, ppm: 2.97 s (3H, OCH ), 4.86 s
3
4
(
1H, H ), 6.64 s (1H, NH), 7.07–7.13 m (2Harom), 7.23–
7
.33 m (8Harom), 7.53–7.59 m (2Harom), 7.63–7.67 m
13
(
1Harom), 7.99–8.02 m (2H ). С NMR spectrum, δ,
arom
4
5
ppm: 52.0 (OCH ), 58.6 (C ), 81.3 (C ), 125.7 (2Carom),
3
1
27.9 (2Carom), 128.1 (2Carom), 128.2 (1Сarom), 128.5
Vinyl phenyl sulfone 1a [33], (Е)-3-(p-tosyl)
acrylonitrile 2c [34], α-bromovinyl sulfones 3 [35], 4
(2Carom), 128.6 (1Сarom), 129.0 (2Carom), 129.2 (2Carom),
134.0 (1Сarom), 138.7 w (1Сarom), 139.0 w (1Сarom),
143.5 w (1Сarom), 147.0 (С ), 166.8 (C=O). Found, %:
3
[36], vinyl methyl sulfone 18 [35], and diphenyl-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

1
150
VASIN et al.
4
5
С 65.77; Н 4.74; N 6.69; S 7.68. С Н N O S.
21.8 (СН ), 45.0 (C ), 81.7 (C ), 112.8 (CN), 125.8
2
3
20
2
4
3
Calculated, %: С 65.70; Н 4.79; N 6.66; S 7.62.
(2Carom), 127.3 (2Carom), 128.6 (2Carom), 128.8 (2Сarom),
2
129.0 (1Carom), 129.2 (3Carom), 130.2 (2Carom), 135.2
5
,5-Diphenyl-3-(phenylsulfonyl)-Δ -pyrazoline-4-
(
1Сarom), 138.6 w (1Сarom), 141.1 w (1Сarom), 142.9 w
carbonitrile (5c). Yield 72%. Light-yellow crystals,
5
–
1
(1Сarom), 145.9 (С ). Found, %: С 68.76; Н 4.49; N
0.46; S 7.96. С Н N O S. Calculated, %: С 68.81;
mp 195–196°С. IR spectrum, ν, cm : 3417 w (NH),
927 w, 1489 w, 1462 m, 1442 w, 1303 v.s (asymm.
SO ), 1172 m, 1145 m (symm. SO ), 1099 m, 945 w,
1
2
3
19
3
2
2
Н 4.77; N 10.47; S 7.99.
2
2
1
8
37 w, 767 m, 702 m, 625 w, 544 m, 517 m. Н NMR
1-Phenylsulfonyl-2,2-diphenylcyclopropane (7).
4
2
spectrum, δ, ppm: 4.96 s (1H, H ), 7.03 s (1H, NH),
.15–7.22 m (4Harom), 7.28–7.34 m (3Harom), 7.36–7.40
m (3Harom), 7.59 t (2Harom, J 7.9 Hz), 7.69 t (1Нarom, J
400 mg (1.1 mmol) of Δ -pyrazoline 5a was boiled in
7
6 mL of anhydrous benzene for 12 h. After the
removal of the solvent on the rotary evaporator the
solid residue was crystallized. Yield 235 mg (64%),
13
7
.3 Hz), 8.07 d (2Н , J 7.5 Hz). С NMR spectrum,
arom
5
4
–1
δ, ppm: 45.1 (C ), 81.8 (C ), 112.8 (CN), 125.8
2Carom), 127.3 (2Carom), 128.6 (1Carom), 128.8 (2Сarom),
29.1 (1Carom), 129.3 (4Carom), 129.5 (2Carom), 134.6 w
1Сarom), 138.5 w (1Сarom), 138.6 w (1Сarom), 141.1 w
1Сarom), 142.8 (С ). Found, %: С 68.27; Н 4.40; N
mp 119–120°С (benzene). IR spectrum, ν, cm : 3056
(
1
(
(
1
w, 3036 w, 1497 m, 1447 s, 1308 v.s (asymm. SO2),
1289 m, 1154 v.s, 1146 v.s (symm. SO ), 1088 m, 768
2
1
s, 745 s, 706 s, 698 s, 586 s, 571 m, 540 m. Н NMR
3
3
spectrum, δ, ppm: 1.78 d.d (1Н, Н , J 5.6, 8.7 Hz),
3
1
0.96; S 8.16. С Н N O S. Calculated, %: С 68.20;
2.50 d.d (1Н, Н , J 5.8, 8.7 Hz), 3.25 d.d (1Н, Н , J
5.6, 5.8 Hz), 7.17–7.25 m (8Нarom), 7.32–7.35 m (2Нarom),
7.47 t (2Нarom, J 7.6 Hz), 7.59 t (1Нarom, J 7.3 Hz), 7.69
2
2
17
3
2
Н 4.42; N 10.85; S 8.27.
2
Methyl-5,5-diphenyl-3-p-tosyl-Δ -pyrazoline-4-
carboxylate (6b). Yield 66%. Light-yellow crystals,
1
3
d (2Н , J 7.3 Hz). С NMR spectrum, δ, ppm: 18.7
arom
3
2
1
–
1
(С ), 40.6 (С ), 45.5 (С ), 127.1 (1Сarom), 127.4
1Сarom), 127.6 (2Сarom), 127.8 (2Сarom), 128.1 (2Сarom),
28.7 (2Сarom), 129.0 (2Сarom), 129.9 (2Сarom), 133.2
1Сarom), 136.9 w (1Сarom), 140.9 w (1Сarom), 143.7 w
(1Сarom). Found, %: С 75.46; Н 3.41; S 9.48.
mp 104–105°С. IR spectrum, ν, cm : 3314 m (NH),
009 w, 2952 w, 1740 v.s (C=O), 1327 s (asymm.
SO ), 1304 m, 1250 m, 1150 m (symm. SO ), 1119 m,
076 m, 1022 m, 749 m, 706 m, 664 m, 594 m, 544 m.
Н NMR spectrum, δ, ppm: 2.44 s (3Н, СН ), 3.00 s
(
1
(
3
2
2
1
1
3
4
С
21
Н
18
O
2
S. Calculated, %: С 75.42; Н 3.47; S 9.59.
(
7
3Н, ОСН ), 4.25 s (1Н, Н ), 7.10 d (2Нarom, J 7.5 Hz),
.14–7.21 m (1Нarom), 7.25–7.30 m (7Нarom, NH), 7.35
3
2
Dehydrosulfonation of Δ -pyrazolines (5b and
d (2Нarom, J 8.1 Hz), 7.75–7.83 m (1Нarom), 7.87 d
5c). General procedure. To a solution of 1.29 mmol
of compound 5b and 5c in 20 mL of anhydrous CH Cl
1
3
(
(
(
(
(
2Нarom, J 8.1 Hz). С NMR spectrum, δ, ppm: 21.7
2
2
3
4
СН ), 51.9 (ОСН ), 58.5 (С ), 81.1 (С ), 125.7
at stirring in inert atmosphere while cooling to 0°С
was added dropwise 1.55 mmol of DBU. The reaction
mixture was stirred at the same temperature for 1.5 h
(TLC monitoring). Then the mixture was filtered
through a silica gel bed (1 cm). The solvent was
evaporated in a vacuum of the water-jet pump. The
reaction product was isolated from the residue by
flash-chromatography.
3
3
2Сarom), 127.9 (2Сarom), 128.08 (2Сarom), 128.14
1Сarom), 128.55 (Сarom), 128.60 (2Сarom), 128.9
2Сarom), 129.8 (2Сarom), 135.9 (1Сarom), 138.7 (1Сarom),
5
1
43.6 w (1Сarom), 145.1 w (1Сarom), 147.3 (С ), 166.9
(С=О). Found, %: С 66.36; Н 5.24; N 6.56; S 7.28.
С Н N O S. Calculated, %: С 66.34; Н 5.10; N 6.45;
2
4
22
2
4
S 7.38.
,5-Diphenyl-3-p-tosyl-Δ -pyrazoline-4-carbonit-
rile (6c). Yield 56%. Light-yellow crystals, mp 159–
2
5
Methyl 3,3-diphenyl-3Н-pyrazole-4-carboxylate
–
1
(8b). Yield 72%, yellow oil. IR spectrum, ν, cm :
3060 w, 2952 w, 1725 v.s (С=О), 1493 m, 1447 m,
–
1
1
2
60°С. IR spectrum, ν, cm : 3345 m (NH), 2952 m,
1
253 w (CN), 1593 m, 1559 s, 1493 m, 1447 m, 1385
1239 s, 1127 m, 1011 m, 772 m, 749 m, 698 s. Н
m, 1335 s (asymm. SO ), 1296 m, 1188 s, 1161 v.s
NMR spectrum, δ, ppm: 3.78 s (3Н, ОСН ), 7.19–7.23
2
3
5
13
(
symm. SO ), 1076 m, 1019 m, 999 m, 872 m, 845 m,
m (4Нarom), 7.31–7.35 m (6Нarom), 8.12 s (1Н, Н ). С
2
3
8
22 m, 768 s, 702 s, 668 s, 652 s, 583 v.s, 556 s, 521
NMR spectrum, δ, ppm: 52.4 (ОСН ), 106.2 (С ),
3
1
5
v.s, 490 s. Н NMR spectrum, δ, ppm: 2.44 s (3Н,
СН ), 4.93 s (1H, H ), 7.00 s (1H, NH), 7.17–7.21 m
128.5 (8Сarom), 128.6 (С ), 134.3 w (2Сarom), 148.0
(2Сarom), 148.2 (С ), 161.7 (С=О). Found, %: С 73.28;
4
4
3
(
7
4Harom), 7.28–7.33 m (3H ), 7.36–7.38 m (5Harom),
.93 d (2Harom, J 8.2 Hz). С NMR spectrum, δ, ppm:
Н 5.91; N 10.12. С Н N O . Calculated, %: С 73.37;
Н 5.07; N 10.07.
arom
17 14
2
2
1
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

SYNTHESIS OF 3,3-DIPHENYL-3H-PYRAZOLES APPLYING VINYL SULFONES
1151
3
,3-Diphenyl-3Н-pyrazole-4-carbonitrile (8c).
1088 m, 756 v.s, 733 s, 687 s, 660 m, 648 m, 590 s,
556 m. Н NMR spectrum, δ, ppm: 7.19 d (4Нarom, J
1
Yield 61%, colorless crystals, mp 66–67°C. IR
spectrum, ν, cm : 3063 w, 2230 w (CN), 1489 m,
447 s, 926 m, 764 m, 756 s, 698 v.s, 660 m. Н NMR
spectrum, δ, ppm: 7.28–7.32 m (4Нarom), 7.33–7.36 m
6Нarom), 8.05 s (1Н, Н ). С NMR spectrum, δ, ppm:
08.4 (С ), 112.6 (CN), 127.5 (4Сarom), 129.1 (4Сarom),
–
1
7.9 Hz), 7.34–7.43 m (6Нarom), 7.66 t (2Нarom, J 7.5 Hz),
1
13
1
7.78 t (1Нarom, J 7.2 Hz), 8.22 d (2Н , J 8.1 Hz). С
arom
3
NMR spectrum, δ, ppm: 110.3 (С ), 111.4 (CN), 127.6
5
13
(
1
1
(4Carom), 129.3 (2Carom), 129.6 (4Carom), 130.0 (2Carom),
3
130.1 w (2Carom), 132.1 w. (1C ), 132.3 (1Carom),
arom
5
4
5
29.3 (2С ), 130.4 (С ), 133.7 w (2Сarom), 149.4
135.7 w (2Carom), 136.9 (С ), 158.8 (С ). Found, %: С
68.51; Н 3.91; N 10.93; S 8.26. С Н N O S.
arom
4
(
С ). Found, %: С 78.38; Н 4.61; N 17.20. С Н N .
16
11
3
22 15
3
2
Calculated, %: С 78.35; Н 4.52; N 17.13.
Calculated, %: С 68.56; Н 3.92; N 10.90; S 8.32.
Methyl-3,3-diphenyl-3Н-pyrazole-5-carboxylate
8'b). A solution of 0.5 g (6 mmol) of methyl
3,3-Diphenyl-5-p-tosyl-3Н-pyrazole-4-carbonit-
rile (10c). Yield 76%, bright yellow crystals, mp 57–
58°C. IR spectrum, ν, cm : 2215 w (CN), 1593 m,
(
–
1
propiolate in 50 mL of anhydrous ethyl ether was
mixed with 1.27 g (6.5 mmol) of diphenyldiazome-
thane, and the mixture was kept for 1 h at 20°С.
Precipitated crystals were filtered off and dried in air.
Yield 0.9 g (54%), mp 139–140°С (decomp.). IR
1447 m, 1354 s (asymm. SO ), 1157 v.s (symm. SO ),
2
2
1
1084 m, 710 s, 695 m, 664 m, 590 s, 536 m. Н NMR
spectrum, δ, ppm: 2.48 s (3Н, СН ), 7.19 d (4Нarom, J
3
7.8 Hz), 7.34–7.41 m (6Н ), 7.44 d (2Нarom, J 8.1 Hz),
arom
–
1
13
spectrum, ν, cm : 3093 m, 1740 v.s (С=О), 1450 m,
8.09 d (2Нarom, J 8.1 Hz). С NMR spectrum, δ, ppm:
1
3
1
3
300 s, 1099 m, 698 s. Н NMR spectrum, δ, ppm:
21.9 (СН ), 110.3 (С ), 111.2 (CN), 127.6 (4Carom),
3
.99 s (3Н, ОСН ), 7.27–7.36 m (10Нarom), 8.22 s (1Н,
Н ). С NMR spectrum, δ, ppm: 55.8 (ОСН ), 107.3
С ), 127.9 (4С ), 128.9 (2Сarom), 129.1 (4Сarom),
35.2 (С ), 147.7 (С ), 151.9 (2Сarom), 161.2 (С=О).
129.4 (2Carom), 129.5 (4Carom), 130.0 (2Carom), 130.6
3
4
13
4
3
(2Carom), 131.5 w (1C ), 132.3 (2Carom), 133.8 (С ),
arom
3
5
(
147.4 (1Carom), 159.5 (С ). Found, %: С 69.18; Н 4.31;
arom
4
5
1
N 10.53; S 8.06. С Н N O S. Calculated, %: С
23
17
3
2
Found, %: С 73.38; Н 5.21; N 10.01. С Н N O .
69.16; Н 4.29; N 10.52; S 8.03.
1
7
14
2
2
Calculated, %: С 73.37; Н 5.07; N 10.07.
Methyl-3,4-diphenyl-5-(phenylsulfonyl)-4Н-py-
razole-4-carboxylate (11b). A solution of 0.21 g
2
Oxidative dehydrogenation of Δ -pyrazolines
(
1
5b, 5c, and 6c). General procedure. To a solution of
.5 mmol of Δ -pyrazoline 5b, 5c, and 6c in a mixture
(
0
0.5 mmol) of a mixture of compounds 9b and 11b,
.9 : 1, in 10 mL of anhydrous toluene was boiled in an
2
of 20 mL of anhydrous benzene and 20 mL of dry
CH Cl was added 1.63 g (18.7 mmol) of activated
argon atmosphere for 10 min. The solvent was
removed on a rotary evaporator to get 0.18 g (88%) of
4Н-pyrazole 11b. Colorless crystals, mp 35–36°C. IR
2
2
MnO [31]. The mixture was stirred at 20°С for 20 h,
2
–
1
then it was filtered. The filtrate was evaporated on a
rotary evaporator, and the residue was analyzed by
NMR spectroscopy. From pyrazoline 5b we obtained a
mixture of 3Н- and 4Н-pyrazoles 9b and 11b in a ratio
spectrum, ν, cm : 3067 w, 1752 v.s (С=О), 1509 m,
493 m, 1443 m, 1343 s (asymm. SO ), 1231 s, 1200
1
2
m, 1184 m, 1153 s (symm. SO ), 1080 m, 756 m, 725
2
1
s, 687 s, 610 s, 571 m, 529 m. Н NMR spectrum, δ,
1
.6 : 1 in an overall yield 67%, which we did not
ppm: 3.80 s (3Н, ОСН ), 7.23–7.28 m (4Нarom), 7.31–
3
succeed to separate. In the reaction products of cyano-
substituted derivatives 5c and 6c only 3Н-pyrazoles 9с
and 10с were present.
7
.37 m (5Нarom), 7.46 t (1Нarom, J 7.3 Hz), 7.52 t (1Нarom
,
J 8.2 Hz), 7.59 d (2Нarom, J 7.2 Hz), 7.92 d (2Нarom, J
1
3
8
(
.2 Hz). С NMR spectrum, δ, ppm: 54.0 (ОMе), 78.0
4
С ), 126.9 w (1Carom), 128.3 (2Carom), 128.47 (2Carom),
Methyl 3,3-diphenyl-5-(phenylsulfonyl)-3Н-py-
1
1
1
28.54 w. (1Carom), 128.8 (2Carom), 128.9 (2Carom),
29.2 (2Carom), 129.4 (1Carom), 129.9 (2Carom), 133.0
razole-4-carboxylate (9b). Н NMR spectrum (from
DOSY-experiment), δ, ppm: 3.84 s (3Н, ОСН ), 7.12 d
3
(
(
1Carom), 134.2 (1C ), 138.5 w (1Carom), 164.4
С=О), 174.7 (С ), 177.4 (С ). Found, %: С 66.11; Н
(4Нarom, J 7.1 Hz), 7.28–7.41 m (6Нarom), 7.61 t
(2Нarom, J 7.8 Hz), 7.71 t (1Нarom, J 7.3 Hz), 8.16 d
(2Нarom, J 7.4 Hz).
arom
3
5
4
6
.21; N 6.62; S 7.60. С Н N O S. Calculated, %: С
6.02; Н 4.34; N 6.69; S 7.66.
23 18 2 4
3
,3-Diphenyl-5-(phenylsulfonyl)-3Н-pyrazole-4-
carbonitrile (9c). Yield 58%, bright yellow crystals,
Reaction of α-bromovinylsulfones (3 and 4) with
diphenyldiazomethane. To a solution of 8.10 mmol
of sulfone 3 or 4 in 25 mL of anhydrous ethyl ether
–
1
mp 103–104°C. IR spectrum, ν, cm : 2248 w (CN),
447 m, 1354 s (asymm. SO ), 1157 s (symm. SO ),
1
2
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

1
152
VASIN et al.
1446 s, 1311 v.s (asymm. SO ), 1157 s (symm. SO ),
was added a solution of 1.73 g (8.92 mmol) of diphe-
nyldiazomethane in 10 mL of the same solvent. The
reaction mixture was kept at 20°С in a place protected
from light for 8 h. The precipitated colorless crystals
were filtered off and washed on the filter with 10 mL
of ethyl ether.
2
2
1146 s, 1080 m, 787 s, 741 m, 702 s. 690 s, 579 s, 540
1
m. Н NMR spectrum, δ, ppm: 2.21 d (1Н, СН , J
2
6.8 Hz), 3.04 d (1Н, СН , J 6.8 Hz), 7.20–7.26 m
2
(2Нarom), 7.29–7.35 m (4Нarom), 7.47–7.49 m (2Нarom),
7.53–7.57 m (2Нarom), 7.63–7.68 m (2Нarom), 7.90–7.93
1
3
1
m (2Нarom). С NMR spectrum, δ, ppm: 28.7 (СН
4
2
),
7.0 (С ), 54.6 (С ), 127.63, 127.66, 128.6, 128.9,
129.0, 129.1, 129.9, 134.0, 138.79, 138.84, 142.5. Mass
3
-Bromo-5,5-diphenyl-3-(methylsulfonyl)-Δ -
pyrazoline (12). Yield 83%, mp 115–116°С
decomp.). IR spectrum, ν, cm : 1447 m, 1327 v.s
2
1
–
1
(
(
7
+•
spectrum, m/z (I , %): 412 (0.1) [M] , 269 (23), 270
rel
asymm. SO ), 1312 s, 1150 v.s (symm. SO ), 768 m,
48 m, 702 m, 525 m. Н NMR spectrum, δ, ppm: 3.16
d (1Н, СН , J 15.6 Hz), 3.30 d (1Н, СН , J 15.6 Hz),
.52 s (3Н, СН ). С NMR spectrum, δ, ppm: 36.8
СН ), 39.1 (С ), 104.0 (С ), 104.2 (С ), 126.7 (2Сarom),
26.8 (2Сarom), 128.2 (1Сarom), 128.4 (1Сarom), 128.83
2
2
1
(23), 271 (26), 272 (20), 191 (100) [M – SO
89 (27), 190 (67), 192 (28), 165 (20), 115 (10), 77
(21), 51 (18). Found, %: С 60.97; Н 4.22; S 7.85.
S. Calculated, %: С 61.02; Н 4.15; S 7.76.
Mcalc 413.33.
2
Ph – Br],
1
2
2
1
3
3
(
1
3
4
5
3
С Н17BrO
21 2
3
(
(
2Сarom), 128.85 (2Сarom), 139.4 w (1Сarom), 141.9 w
1Сarom). Found, %: С 50.58; Н 3.92; N 7.31; S 8.50.
X-ray diffraction analysis of cyclopropane (15).
For the XRD experiment a transparent prism-like single
crystal was selected of the size 0.32 × 0.14 × 0.12 mm.
The array of diffraction reflections (overall 9884
reflections) was obtained on automatic four-circle
diffractometer Oxford Diffraction Xcalibur Gemini S
at 293(2) K (graphite monochromator, CCD detector
С Н N O S. Calculated, %: С 50.67; Н 3.99; N 7.39;
1
6
15
2
2
S 8.45.
-Bromo-5,5-diphenyl-3-(phenylsulfonyl)-Δ -py-
razoline (13). Yield 56%, mp 117–118°С (decomp.).
IR spectrum, ν, cm : 1451 m, 1327 s (asymm. SO ),
1
6
1
3
–
1
2
Sapphire III, MoK -radiation, λ 0.71073 Å, ω-scanning,
312 m, 1154 v.s (symm. SO ), 760 m, 745 m, 706 m,
α
2
1
θmax 30.51°, indices range –8 ≤ h ≤ 8, –19 ≤ k ≤ 19,
31 ≤ l ≤ 31). After averaging the equivalent
91 m, 590 m, 563 m, 540 s. Н NMR spectrum, δ,
–
ppm: 3.27 d (1Н, СН , J 15.6 Hz), 3.39 d (1Н, СН , J
1
2
2
reflections we obtained 5641 (R 0.0521) independent
5.6 Hz), 7.19 d (2Нarom, J 9.6 Hz), 7.27–7.37 m
int
reflections, 4690 reflections with I > 2σ(I). The
processing of the diffraction reflections and the
estimation of the unit cell parameters of the crystal was
carried out applying CrysAlisPro program (Agilent
Technologies, 2012) [40]. The primary fragment of the
atomic structure of compound 15 was found by the
direct method using SHELX-97 [41] and WinGX [42]
software; the remaining nonhydrogen atoms were
determined from the analysis of the difference
synthesis of the electron density. The positions of
hydrogen atoms in the structure of compound 15 were
calculated geometrically and refined in the rider model
(
6
8Нarom), 7.61 t (2Нarom, J 7.5 Hz), 7.74 t (1Нarom, J
13
.3 Hz), 8.13 d (2Нarom, J 8.5 Hz). С NMR spectrum,
3
5
δ, ppm: 41.2 (СН ), 103.5 and 105.9 (С and С ),
1
1
2
26.8, 126.9, 128.3, 128.4, 128.9, 129.0, 129.1, 131.8,
33.3, 135.3, 139.7, 142.3. Found, %: С 57.19; Н 3.90;
N 6.28; S 7.16. С Н BrN O S. Calculated, %: С
21
17
2
2
5
7.15; Н 3.88; N 6.35; S 7.26.
-Bromo-2,2-diphenyl-1-(methylsulfonyl)-cyclo-
propane (14). Yield 89%. Colorless crystals, mp 168°C
1
–
1
(
decomp.). IR spectrum, ν, cm : 1312 v.s (asymm. SO ),
2
1
1
154 s (symm. SO ). 795 m, 532 m, 494 m. Н NMR
2
spectrum, δ, ppm: 2.24 d (1Н, СН , J 6.9 Hz), 2.89 d
(
2
[
U(H) = 1.2U (C)]. The positions of hydrogen atoms
eq
1Н, СН , J 6.9 Hz), 3.18 s (3Н, СН ), 7.23–7.41 m
2
3
were found from the difference synthesis of the electron
density and were refined in the general refining cycle
without limitations. The extinction was accounted for
empirically using the algorithm SCALE3 ABSPACK
(
6Нarom), 7.55 d (2Нarom, J 8.3 Hz), 7.57 d (2Нarom, J
1
3
8
.3 Hz). С NMR spectrum, δ, ppm: 27.2 (СН ), 40.4
2
2
1
(
(
(
(
СН ), 46.5 (С ), 53.2 (С ), 127.5 (1Сarom), 127.6
3
1Сarom), 128.3 (2Сarom), 128.52 (2Сarom), 128.55
2Сarom), 128.9 (2Сarom), 138.3 w (1Сarom), 141.9 w
1Сarom). Found, %: С 54.78; Н 4.42; S 9.15.
[40]. Crystals of compound 15 monoclinic, a 6.17670
(
1
2
10), b 13.4687(2), c 22.3646(4) Å, β 94.896(2)°, V
3
3
853.77(5) Å , M 236.18, Z 4, d
1.481 g/cm , μ
calc
С Н BrO S. Calculated, %: С 54.86; Н 4.32; S 9.13.
–1
1
6
15
2
.341 mm , F(000) 840, space group P 1 21/c 1. The
1
-Bromo-2,2-diphenyl-1-(phenylsulfonyl)cyclo-
number of independent refined parameters 234, GOOF
propane (15). Yield 59%. Colorless crystals, mp 223–
1.077. the scatter of the residual electron density
–0.681 and 1.012 e·Å . The final divergense factors:
–1
–3
2
24°С (CH Cl –petroleum ether). IR spectrum, ν, cm :
2
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015

SYNTHESIS OF 3,3-DIPHENYL-3H-PYRAZOLES APPLYING VINYL SULFONES
1153
2
R1 0.0521 [for I > 2σ(I)], wR2 0.0889 (for all
conditions of the experiment with Δ -pyrazoline 5а.
Yield 55%, colorless crystals, mp 97–98°С. IR
2
independent reflections). Weighing scheme w = 1/[σ
2
o
2
2
o
2
с
–1
(
F ) + (0.0335P) + 1.0621P], where P = (F + 2F )/3.
spectrum, ν, cm : 3055 w, 3005 w, 1497 m, 146 m,
The data of the XRD study of compound 15 are
deposited in the Cambridge Crystallographic Data
Center (CCDC no. 1028707).
1323 m, 1296 v.s, 1138 v.s, 945 m, 779 m, 752 m, 706
1
s, 698 m, 528 m. Н NMR spectrum, δ, ppm: 1.82 d.d
3
3
(1Н, Н , J 5.6, 8.8 Hz), 2.48 t (1Н, Н , J 5.6 Hz), 3.86
1
1
s (3Н, СН
3
), 3.24 d.d (1Н, Н , J 5.6, 8.8 Hz), 7.22–
Reaction of Δ -pyrazoline (12) with DBU. To a
1
3
7
.36 m (8Нarom), 7.48–7.51 m (2Н ). С NMR
spectrum, δ, ppm: 18.0 (С ), 40.0 (С ), 42.4 (СН ),
3.9 (С ), 127.4 (1Сarom), 127.7 (1Сarom), 128.1
arom
solution of 0.5 g (1.3 mmol) of compound 12 in 20 mL
3
2
3
of anhydrous CH Cl was added dropwise while
2
2
1
4
stirring at 0°C 0.221 g (1.45 mmol) of DBU in 5 mL of
the same solvent. The mixture was stirred at 20°C for
(
(
2Сarom), 128.5 (2Сarom), 128.9 (2Сarom), 137.1 w
1Сarom), 143.6 w (1Сarom). Found, %: С 70.67; Н 5.82;
6
(
h, then it was filtered through a bed of silica gel
1 cm). On removing the solvent in a vacuum of the
water-jet pump we obtained a mixture of compounds
S 11.65. С Н O S. Calculated, %: С 70.56; Н 5.92; S
1
6
16
2
1
1.77.
1
1
6 and 17 in a ratio 0.6 : 1 (according to Н NMR
The work was partially carried out according to the
data). The mixture was separated by flash-chroma-
tography on silica gel.
task №2014/134 for the State works in the field of
scientific activity in the frame of the State contract.
Project code 2312.
1
5
-Methylene-3,3-diphenyl-Δ -pyrazoline (16).
–
1
Yield 12%, mp 86°С. IR spectrum, ν, cm : 1493 s,
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1
447 s, 903 m, 768 s, 752 s, 698 v.s, 637 s. Н NMR
4
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.
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3
(
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8
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7
. Llamas, T., Arrayás, R.G., and Carretero, J.C.,
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2
1
3
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28.1 (2Сarom), 129.0 (4Сarom), 144.2 w (2Сarom), 149.7
3
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9
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S 10.67.
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6
16
2
2
1
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identical to the product of hydrodebromination–
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2
1
1
1
1
-Methylsulfonyl-2,2-diphenylcyclopropane (19).
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