Synthesis of previously unknown 3,3′-linearly linked sulfur- and selenium-containing bispyrazoles by reactions of 3-alkenyl-5-chloropyrazoles with bischalcogenols

Article abstract of DOI:10.1134/S1070428013050175

By reactions of 3-alkenyl-5-chloropyrazoles with appropriate dichalcogenols the fi rst specimens were obtained of previously unknown 3,3'-linearly linked bispyrazoles containing in the alkyl chain of the linker two heteroatoms, sulfur or selenium. 3-Vinyl-5-chloropyrazoles react with 1,3-propanedithiol, 2-hydroxy-1,3-propanedithiol, and 2-hydroxy-1,3-propanediselenol under UV irradiation and heating at 60 C over 8 h affording products of the addition against Markovnikoff rule. The radical addition of 1,3-propanedithiol to 3-isopropenyl-5-chloropyrazole required a longer time, 15 h.

Full text of DOI:10.1134/S1070428013050175

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 5, pp. 734−738. © Pleiades Publishing, Ltd., 2013.
Original English Text © E.V. Rudyakova, D.O. Samultsev, E.P. Levanova, G.G. Levkovskaya, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49,
No. 5, pp. 751−755.
Synthesis of Previously Unknown 3,3'-Linearly Linked
Sulfur- and Selenium-Containing Bispyrazoles by Reactions
of 3-Alkenyl-5-chloropyrazoles
with Bischalcogenols
E. V. Rudyakova, D. O. Samultsev, E. P. Levanova, and G. G. Levkovskaya
Faworsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, Irkutsk, 664033 Russia
e-mail: ggl@irioch.irk.ru
Received July 12, 2012
Abstract—By reactions of 3-alkenyl-5-chloropyrazoles with appropriate dichalcogenols the first specimens
were obtained of previously unknown 3,3'-linearly linked bispyrazoles containing in the alkyl chain of the linker
two heteroatoms, sulfur or selenium. 3-Vinyl-5-chloropyrazoles react with 1,3-propanedithiol, 2-hydroxy-1,3-
propanedithiol, and 2-hydroxy-1,3-propanediselenol under UV irradiation and heating at 60°С over 8 h affording
products of the addition against Markovnikoff rule. The radical addition of 1,3-propanedithiol to 3-isopropenyl-
5-chloropyrazole required a longer time, 15 h.
DOI: 10.1134/S1070428013050175
The pyrazole ring is present in the structure of many A number of 3(5)-methyl(ethyl)-substituted alkanediyl-
modern pharmaceuticals possessing analgesic, antiphlo- 1,4-methylenephenyl-, 1,4'-diphenyleneoxy(sulfido)
gistic, antibacterial etc. action [1–3]. Pyrazole derivatives pyrazoles joined at the positions 5,5' (3,3') and prepared
are used as insectoacaricides [4], dyes, luminophores, from appropriate bis(1,3-diketones) and hydrazine hy-
and ligands [1–3]. Still greater scientific and practical drate was described [20].
interest is attracted by organic compounds containing in
their structure two and more pyrazole rings, first of all
due to the opportunity to use them for the preparation of
polynuclear complexes, coordination polymers possess-
ing a number of valuable properties [5–20]. Multitopic
pyrazole-containing ligands are also applied as sorbents
and are widely used as semiproducts in the synthesis of
substances possessing biological and catalytic activity,
they participate in the self-assembly processes of supra-
molecular ensembles, etc.
We have developed a targeted synthesis of 3,3'-joined
bispyrazoles underlain by the heterocyclization of bi-
functional halovinyl ketones [21], but this approach is
impeded by the poor choice of available bisketones.
The search for new synthons for the preparation of
pyrazole derivatives [1–3], in particular, bispyrazoles, is
fairly active nowadays. The development of the chem-
istry of alkenylpyrazoles provides wide opportunities
for manufacturing various members of the pyrazole
series, among them linked bispyrazoles, polynuclear and
fused heterocyclic structures. We recently synthesized
3-haloalkyl-5-chloropyrazole and developed a procedure
of preparation therefrom earlier undescribed 3-alkenyl-
5-chloropyrazoles [22], multi-purpose building blocks
Polypyrazole-containing ligands are insufficiently
understood due to their inavailability, and the search for
new approaches to the synthesis of this class compounds
develops up till now [5–20].
The most widely spread and well known are the ensem- for the targeted synthesis of new pyrazole derivatives,
bles where the pyrazole ring is linked through the pyrrole biologically active substances and materials for the
nitrogen atom [5–16]. The 4,4'-pyrazole systems obtained high technology. The chemical reactions of the known
in the reaction of pyrazoles with polyelectrophiles, e.g., alkenylpyrazoles are poorly investigated, except for the
with aldehydes and ketones [17–19], are rather common. polymerization [23], complex formation [24], thiylation
734

SYNTHESIS OF PREVIOUSLY UNKNOWN 3,3'-LINEARLY LINKED...
735
of N-vinylpyrazoles [25], cycloaddition [26], and ami-
doalkylation [27]. The chemical properties of the most
difficultly available 3-alkenylpyrazoles [22] are virtually
unknown [27]. All above shows that further research in
the field of the chemistry of 3-alkenylpyrazoles is timely
and necessary.
[28]. 1-Vinylpyrazoles, both unsubstituted in the ring
and having one or two methyl groups in the positions
of 3,5 of the ring react with thiols along the ionic (S,
SO2, BF3·Et2O, p-toluenesulfonic acid) as well as free
radical mechanisms giving respectively the products of
α- β-addition [25]. At heating from 20 to 80°С and using
the initiators of the radical processes [photoirradiation
(lamp DRT 300), AIBN (0.5–1 wt%)] the reaction can
be considerably accelerated retaining its direction. The
reaction time decreases from 24 h to 10 min. The reactions
of 1-vinylpyrazoles with thiols under the ionic conditions
are not regioselective even in the presence of radical
inhibitors (benzoquinone, hydroquinone, sulfur) and are
accompanied with the formation of β-adducts [24].
In this study we have developed an original synthe-
sis of linearly linked 3,3'-bispyrazoles containing in the
linker heteroatoms S and Se proceeding from the reaction
of 3-alkenylpyrazoles with dithiols and diselenols. The
thiylation of multiple bonds of 1-vinylazoles (pyrroles,
imidazoles) is carried out by ionic and radical reac-
tions and leads to the formation of α-adducts in keeping
with Markovnikoff rule and of β-adducts respectively
S
S
R2
UV, 8 h, 60oC
HSR2SH
C6H6
2
Cl
+
N
N
N
Cl
Cl
N
N
N
R1
R1
R1
Iа, Ib
IIа, IIb
R1 = Bn, R2 = CH2CH2CH2 (a); R1 = Me, R2 = CH2CH(OH)CH2 (b).
The reactions of 3-alkenylpyrazoles with chalcogenols
were not investigated before our study [29] because of
the virtual inaccessibility of these azoles. We studied
the reactions of 3-alkenyl-5-chloropyrazoles Ia–Ic with
dichalcogenols propane-1,3-dithiol, 2-hydroxypropane-
1,3-dithiol, and 2-hydroxypropane-1,3-diselenol. The
addition of dithiols to pyrazoles I in the presence of p-
toluenesulfonic acid or CF3COOH, a specific and mild
selective catalyst of the electrophilic addition to a vinyl
group [30], did not occur. The reaction was accompanied
with slight tarring.
The radical thiylation of 3-vinyl-5-chloropyrazoles
Ia, Ib proceeded regioselectively against Markovnikoff
rule providing 3,3'-[propane-1,3-diylbis(sulfanylethane-
2,1-diyl)]bis(5-chloropyrazoles) IIa, IIb in 93% yield at
simultaneous heating and UV irradiation of the reagents
mixture in benzene.
The reactions were carried out at the molar ratio
alkenylpyrazole–dithiol 2:1 at 60°С in the course of 6–8
h. The reaction progress was monitored by intermittent
sampling the reaction mixture and analyzing the samples
by GLC. The reaction was performed till complete con-
version of 3-vinylpyrazoles.
At heating the reagents without catalysts the dithiols
addition proceeded slowly (addition products yield
≤10% in 24 h at 20–25°С and 20% in 12 h at 60°С). The
vinylazole conversion at heating of reagents is somewhat
higher (40%) than without heating (15%), because of a
side reaction of vinylpyrazole thermal polymerization.
The reaction of 1-benzyl-3-isopropenyl-5-chloro-
pyrazole (Ic) with 1,3-propanedithiol under common
conditions required a longer time (15 h), and the taget
anti-Markovnikoff product III formed in a lower yield
(77%) than in the reaction of this thiol with vinylpyrazole
S
S
2
UV, 8 h, 60oC
C6H6
+
HS
SH
N
N
N
Cl
Cl
Cl
N
N
N
Bn
Ic
Bn
Bn
III
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013

RUDYAKOVA et al.
736
Ia. This result is apparently due to the steric effect of the
EXPERIMENTAL
methyl group.
IR spectra of compounds synthesized were recorded
from thin films on a Fourier spectrophotometer
Varian-3100 equipped with an adapter for frustrated total
The introduction of a selenium atom into the structure
of the 3,3’-linearly linked bispyrazoles which is of obvi-
ous theoretical and practical interest we have performed
reacting vinylpyrazole Ib with 2-hydroxypropane-1,3-
diselenol under analogous conditions. The yield of
bispyrazole IV was lower (82%) than that of its sulfur
analog IIb due to the instability of the diselenol [31].
1
internal reflection (ATR). Н, 13С NMR spectra were
registered from solutions in CDCl3 on a spectrometer
Bruker DPX-400 (operating frequencies 400.13 and
101.61 MHz respectively), internal reference HMDS.
The chemical shifts of 1Н, 13С are reported with respect to
TMS with an accuracy of 0.01 and 0.02 ppm respectively.
Spin-spin coupling constants were determined with an
accuracy of 0.1 Hz.
In the studied processes we did not found any
monoaddition products or the addition involving the
hydroxy group in the reactions of vinylpyrazole Ib with
2-hydroxypropane-1,3-dichalcogenols. Also the side
oligomeric products did not form in notable amounts.
UV irradiation was performed using a DRT-240 lamp
(λ 240–320 nm) of the power 240 W.
Previously unknown bispyrazoles II–IV isolated in
individual state were colorless or slightly colored viscous
fluids, which did not crystallize after chromatographic
purification. Their structure was proved by IR and NMR
spectra, the composition was confirmed by elemental
analysis. The signals in the 1Н and 13С NMR spectra of
compounds II–IV and their intensities are consistent with
the assumed structures.
1Н NMR spectra of bispyrazoles II–IV lack the signals
of the protons of alkenyl groups in the position 3 of the
pyrazole ring characteristic of the initial pyrazoles [22].
In the IR spectra absorption bands are observed character-
istic of bonds С4–H, С=N, and С=С of the pyrazole rings
and the bands belonging to alkyl groups. The absorption
of the НO group in the spectra of compounds IIb, IV
appears as a broad band in the region 3320 cm–1.
The monitoring of the reaction progress and the analy-
sis of the formed liquid compounds were carried out on a
chromatograph LKhM 80-MD-2 (column 2000 × 3 mm,
liquid phase DC-550, 5%, on a carrier Chromaton N-AW-
HMDS, ramp at a rate 12 deg/min, carrier gas helium).
Pyrazoles Ia–Ic were synthesized by procedures [22].
Dithiols were obtained by reductive cleavage of the S–S
bonds of thiocols in the system hydrazine hydrate–KOH
[32]. 2-Hydroxypropane-1,3-diselenol was obtained as
described in [31].
Compounds IIа, IIb, III, IV. General procedure. A
mixture of 0.001 mol of dichalcogenol and 0.002 mol of
3-alkenyl-5-chloropyrazole Iа–Ic in 5 ml of benzene was
subjected simultaneously to UV irradiation and heating at
60°С; samples were taken intermittently and subjected to
GLC. On the completion of the reaction the solvent was
removed at a reduced pressure. The reaction product was
washed with cold hexane and dried in a vacuum.
In the 1Н NMR spectrum of the selenium-containing
compound IV all signals of alkyl fragments linking the
pyrazole ring are shifted downfield with respect to the
spectrum of its sulfur analog IIb, whereas in the 13С NMR
spectra the reverse pattern is observed.
3,3'-[Propane-1,3-diylbis(sulfandiylethane-2,1-
diyl)]bis(1-benzyl-5-chloro-1Н-pyrazole) (IIa) was
obtained from 0.24 g (0.002 mol) of 1-benzyl-3-vinyl-5-
chloropyrazole (Iа) and 0.11 g (0.001 mol) of propane-
1,3-dithiol. Time of irradiation 8 h. Yield 0.51 g (94%).
IR spectrum, ν, cm–1: 3128 (=CHPyr), 3088, 3064,
3031, 3006 (=CHPh), 2921, 2850 (CHAlk), 1605, 1514
Thus by reactions of 3-vinyl-5-chloropyrazoles with
propane-1,3-dithiols and 2-hydroxypropane-1,3-diselenol
the first specimens were obtained of previously unknown
3,3'-linearly linked bispyrazoles containing each in the
alkyl chain of the linker two heteroatoms of sulfur or
selenium. The simplicity of the experiment, the high
preparative yield of the new pyrazole family combining
in their structur two biogenic fragments, an azole ring
and a chalcogen atom, in the case of isopropenylpyrazole,
additional chiral center, show the promising aspect of
the developed approach for designing new polydentate
ligands and semiproducts for the synthesis of new drugs
and pesticides.
1
(C=N, С=С). Н NMR spectrum, δ, ppm: 1.76 br.m
(2H, SCH2СН2СН2S), 2.51 br.m (4H, SCH2СН2СН2S),
2.72 br.t (4H, СН2СН2S), 2.80 br.t (4H, СН2СН2S), 5.19 s
(4H, NCH2), 6.03 s (2H, НPyr), 7.11 m (10H, C6H5).
13С NMR spectrum, δ, ppm: 28.81 (SCH2СН2СН2S),
30.42 (СН2SСН2), 31.06 (СН2СН2S), 52.08 (NCH2),
103.55 (С4), 126.74 (Cp), 127.34 (С5), 127.45 (Cm),
128.22 (Co), 135.74 (Ci), 150.92 (С3). Found, %: С 59.24;
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013

SYNTHESIS OF PREVIOUSLY UNKNOWN 3,3'-LINEARLY LINKED...
737
H 5.45; Cl 13.81; N 10.15; S 11.35. C27H30Cl2N4S2.
Calculated, %: C 59.44; H 5.54; Cl 13.00; N 10.27;
S 11.75.
spectrum, δ, ppm: 28.27 [SeCH2СН(OН)], 29.96
(СН2СН2Se), 30.32 (СН2СН2Se), 35.80 (NMe), 70.28
[SeCH2СН(OН)], 103.41 (С4), 126.78 (C5), 150.78 (С3).
Found, %: С 35.45; H 4.45; Cl 13.86; N 11.23; Se 31.75.
C15H22Cl2N4OSe2. Calculated, %: C 35.81; H 4.41;
Cl 14.09; N 11.13; Se 31.38
1,3-Bis{[2-(1-methyl-5-chloro-1Н-pyrazol-3-yl)-
ethyl]sulfanyl}propan-2-ol (IIb) was obtained from
0.28 g (0.002 mol) of 1-methyl-3-vinyl-5-chloropyrazole
(Ib) and 0.13 g (0.001 mol) of 1,3-disulfanylpropan-
2-ol. Time of irradiation 8 h. Yield 0.38 g (93%). IR
spectrum, ν, cm–1: 3131 (=CHPyr), 2943, 2918 (CHAlk),
ACKNOWLEDGMENTS
1
1607, 1512 (C=N, С=С). Н NMR spectrum, δ, ppm:
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant
no. 11-03-00461_а).
2.57 d.d (2H, СН2СН, 2J 7.5, 3J 6.8 Hz), 2.69 d.d (2H,
СН2СН, 3J 6.8 Hz), 2.79 br.s (8H, СН2СН2S), 2.82 q (1H,
3
СН, J 6.8 Hz), 3.76 s (6H, NCH3), 5.99 s (2H, НPyr).
13С NMR spectrum, δ, ppm: 28.83 [SCH2СН(OН)], 31.45
(СН2СН2S), 35.79 (СН2СН2S), 37.95 (NСН3), 70.27
[SCH2СН(OН)], 103.35 (С4), 125.92 (C5), 150.35 (С3).
Found, %: С 44.42; H 5.32; Cl 17.31; N 13.95; S 15.44.
C15H22Cl2N4OS2. Calculated, %: C 44.00; H 5.42;
Cl 17.32; N 13.69; S 15.66.
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СН2СН2Sе), 2.96 br.s (4H, SeСН2СН), 3.31 br.s (1H,
СН), 3.76 с (3H, NCH3), 6.01 с (2H, НPyr). 13С NMR
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