Synthesis 5-(pyrazolin-3-ylmethylidene)-2-thiohydantoins and 2-alkylsulfanyl-5-(pyrazolin-3-ylmethylidene)-3,5-dihydro-4H-imidazol-4-ones

Article abstract of DOI:10.1007/s11172-017-1764-1

A reaction of 3-allyl- and 3-phenylthiohydantoins with 1,5-diphenyl- and 1-phenyl-substituted 3-formyl-2-pyrazolines was used to obtain a series of 5-(pyrazolin-3-ylmethylidene)-2-thioxotetrahydro-4H-imidazol-4-ones, the subsequent alkylation of which with methyl iodide or ethyl chloroacetate gave the corresponding 2-alkylthio-5-(pyrazolin-3-ylmethylidene)-3,5-dihydro-4H-imidazol-4-ones in the yields from 30 to 77%. The oxidation of (5Z)-3-phenyl-5-[(1,5-diphenylpyrazolin-3-yl)methylidene]-2-methylsulfanyl-4,5-dihydroimidazol-4-one with lead tetraacetate led to the corresponding pyrazole in 48% yield.

Full text of DOI:10.1007/s11172-017-1764-1

Russian Chemical Bulletin, International Edition, Vol. 66, No. 3, pp. 506—510, March, 2017
506
Synthesis 5ꢀ(pyrazolinꢀ3ꢀylmethylidene)ꢀ2ꢀthiohydantoins
and 2ꢀalkylsulfanylꢀ5ꢀ(pyrazolinꢀ3ꢀylmethylidene)ꢀ3,5ꢀdihydroꢀ
4Hꢀimidazolꢀ4ꢀones
N. I. Vorozhtsov,a L. A. Sviridova,a O. S. Grigorkevich,a D. D. Korablina,b
E. K. Beloglazkina,a A. G. Majouga,a and N. V. Zyka
aM. V. Lomonosov Moscow State University, Department of Chemistry,
Build. 3, 1 Leninskie Gory, 119991 Moscow, Russian Federation.
Eꢀmail: bel@org.chem.msu.ru
bM. V. Lomonosov Moscow State University, Department of Fundamental Medicine,
Build. 1, 27 Lomonosovsky prosp., 119991 Moscow, Russian Federation
A reaction of 3ꢀallylꢀ and 3ꢀphenylthiohydantoins with 1,5ꢀdiphenylꢀ and 1ꢀphenylꢀsubstiꢀ
tuted 3ꢀformylꢀ2ꢀpyrazolines was used to obtain a series of 5ꢀ(pyrazolinꢀ3ꢀylmethylidene)ꢀ2ꢀ
thioxotetrahydroꢀ4Hꢀimidazolꢀ4ꢀones, the subsequent alkylation of which with methyl iodide
or ethyl chloroacetate gave the corresponding 2ꢀalkylthioꢀ5ꢀ(pyrazolinꢀ3ꢀylmethylidene)ꢀ3,5ꢀ
dihydroꢀ4Hꢀimidazolꢀ4ꢀones in the yields from 30 to 77%. The oxidation of (5Z)ꢀ3ꢀphenylꢀ5ꢀ
[(1,5ꢀdiphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ2ꢀmethylsulfanylꢀ4,5ꢀdihydroimidazolꢀ4ꢀone with
lead tetraacetate led to the corresponding pyrazole in 48% yield.
Key words: thiohydantoins, 2ꢀalkylthioimidazolꢀ4ꢀones, pyrazolines, pyrazoles.
2ꢀThioxotetrahydroꢀ4Hꢀimidazolꢀ4ꢀones (thiohydanꢀ
tal section) by the addition of the corresponding pyrazoꢀ
line to a cooled solution of the Vilsmeier reagent. This
procedure allowed us to avoid side reactions of the pyrazoꢀ
line ring opening and the formylation of the benzene ring
and to obtain reproducible yields of target aldehydes. Note
that though compounds 2a,b were described earlier, we for
toins) and their derivatives attract attention of researchers
already during more than a hundred of years,1,2 which is
explained by their biphilic reactivity and a wide range of
pharmacological activity: anticonvulsant, antibacterial,
antiviral, antihypertensive, antidiabetic.3—7 Starting from
1950 (see Ref. 8) and to the present time,7—11 the reacꢀ
tions leading to the preparation of thiohydantoin cycles
are widely used for analytical purposes in determination of
polypeptide structures by Edman degradation. Complexes
based on 2ꢀthiohydantoins and their derivatives with tranꢀ
sition metals can serve as efficient models of the active
centers of some metalloenzymes12 and act as the catalysts
of redox reactions, for example, the epoxidation reacꢀ
tion13—18 and reduction of nitrite anion.19
In continuation of our studies of 5ꢀhetarylmethylideneꢀ
substituted 2ꢀthioxoimidazolꢀ4ꢀones and their Sꢀalkylated
derivatives,12—32 in the present work we used 3ꢀallylꢀ and
3ꢀphenylꢀ2ꢀthiohydantoins 1a,b and 3ꢀformylꢀ4,5ꢀdiꢀ
hydroꢀ1Hꢀpyrazoles (3ꢀformylꢀ2ꢀpyrazolines) 2a,b in a twoꢀ
step sequence of reactions with the intermediate formaꢀ
tion of 5ꢀ(pyrazolinꢀ3ꢀylmethylidene)ꢀ2ꢀthioxotetrahyꢀ
droꢀ4Hꢀimidazolꢀ4ꢀones 3a—d to synthesize new organic
ligand of the series of 5ꢀhetarylꢀsubstituted 2ꢀalkylthiodiꢀ
hydroimidazolones, namely, 2ꢀalkylthioꢀ5ꢀ(pyrazolinꢀ3ꢀ
ylmethylidene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀones 4 and 5.
The starting formylꢀ2ꢀpyrazolines 2a,b were syntheꢀ
sized according to a modified procedure (see Experimenꢀ
1
the first time characterized them by H NMR spectroꢀ
scopy data. Thus, the 1H NMR spectrum of compound 2a
exhibits characteristic multiplets for the protons HC(4) of
the pyrazoline ring in the region of δ 3.02—3.05 and
3.64—3.66, a multiplet for the pyrazoline proton HC(5) at
δ 5.50—5.52, as well as multiplets for the aromatic proꢀ
tons at δ 6.96—7.85 and a singlet at δ 9.89 corresponding
to the proton of the aldehyde group.
The literature describes two methods for the preparaꢀ
tion of 5ꢀarylideneꢀsubstituted thiohydantoins from the
corresponding 5ꢀunsubstituted 2ꢀthioxotetrahydroꢀ4Hꢀ
imidazolꢀ4ꢀones: the condensation of 2ꢀthiohydantoin and
an aldehyde in the presence of an equimolar amount
of anhydrous sodium acetate in acetic acid33 and a simiꢀ
lar condensation in the alcoholic solution of KOH.34
In the case of 3ꢀallylthiohydantoin 1a, acetic acid was
shown to be the optimal for carrying out the reaction
(Scheme 1). In the case of the condensation of 3ꢀphenylꢀ
thiohydantoin 1b with pyrazolines 2a and 2b, the preparaꢀ
tive yields of the products were obtained when the conꢀ
densation was carried out in 2% ethanolic solution of KOH
(Scheme 1).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0506—0510, March, 2017.
1066ꢀ5285/17/6603ꢀ0506 © 2017 Springer Science+Business Media, Inc.

Pyrazolinylmethylenethiohydantoins
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 3, March, 2017
507
Scheme 1
region of δ 6.13—6.45. This agrees with the literature data
on the higher thermodynamic stability of Zꢀisomers of the
corresponding 5ꢀarylideneꢀsubstituted derivatives.35—38
In the literature, there is a description of the reaction
of a mild oxidation of pyrazolines to pyrazoles upon treatꢀ
ment with lead tetraacetate.39 Using compound 4c as an
example, we showed a possibility of such oxidation of
5ꢀpyrazolylmethylideneꢀsubstituted 2ꢀalkylthioimidazolꢀ
4ꢀones. The reaction proceeded selectively and involved
only the pyrazoline fragment of the starting compound
(Scheme 3).
Starting
compounds
R
R´
Ph
H
Reagents
and conditions
AcONa,
AcOH/H2O
AcONa
AcOH/H2O
KOH,
EtOH
Product Yield
Scheme 3
3
a
(%)
85
1a
1a
1b
1b
2a
2b
2a
2b
All
All
Ph
Ph
b
c
d
28
97
10
Ph
H
KOH,
EtOH
The pyrazolinylmethylenethiohydantoins 3 were inꢀ
volved in the alkylation reaction with methyl iodide or
ethyl chloroacetate in a 2% solution of KOH in ethanol
with the formation of the corresponding Sꢀalkylated deꢀ
rivatives 4 and 5 (Scheme 2).
In conclusion, we have developed preparatively conveꢀ
nient methods for the preparation of new 5ꢀpyrazolinꢀ3ꢀ
ylmethylideneꢀsubstituted 2ꢀthiohydantoins and 2ꢀalkylꢀ
thioimidazolꢀ4ꢀones. The compounds obtained are of inꢀ
terest for the study in the complexation reactions and for
the screening biological activity.
Scheme 2
Experimental
Reaction progress was monitored by thinꢀlayer chromatoꢀ
graphy (TLC) on preꢀcoated plates with silica gel (Silufol).
1H NMR spectra were recorded on a Bruker Evancꢀ400 spectroꢀ
meter at 25 °C in deuterochloroform and dimethyl sulfoxideꢀd6.
IR spectra were recorded on a URꢀ20 spectrometer in Nujol and
on an IR200 Fourierꢀtransform spectrometer (TermoNicolet,
USA) with a resolution of 4 cm–1. Chemical ionization mass
spectra were recorded on a Shimadzu LCMS 2010A instrument
at atmospheric pressure in the positive ion mode.
3ꢀAllylꢀ2ꢀthiohydantoin (1a) and 3ꢀphenylꢀ2ꢀthiohydantoin
(1b) were obtained according to the known procedures.40,41
3ꢀFormylꢀ1,5ꢀdiphenylꢀ2ꢀpyrazoline (2a) and 3ꢀformylꢀ1ꢀ
phenylꢀ2ꢀpyrazoline (2b) were obtained according to a modified*
procedure.42
3ꢀFormylꢀ1,5ꢀdiphenylꢀ2ꢀpyrazoline (2a). The reagent POCl3
(0.841 mL, 0.009 mol) was added dropwise to dimethylformaꢀ
mide (0.696 mL, 0.009 mol) at 0 °C. The mixture was stirred at
0 °C for 20 min. Then, a solution of 1,5ꢀdiphenylpyrazoline (1 g)
in DMF (2 mL) was added to the complex obtained. The mixture
Product
4a
4b
4c
5a
R
R´
Ph
H
Ph
Ph
H
Yield (%)
53
All
All
Ph
All
All
52
77
30
48
5b
All the 5ꢀpyrazolinylmethylidene derivatives 3a—d
were isolated as the only geometrical isomers with
a Zꢀconfiguration of the exocyclic C=C bond, that was
confirmed by the presence in the H NMR spectrum of
each of them of the only signal for the vinyl proton in the
1
* Attempted scaling led to a decrease in the yield of the target
formylpyrazolines.

508
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 3, March, 2017
Vorozhtsov et al.
was heated for 2 h at 95—100 °C. Upon completion, the mixture
was quenched by the addition of ice and potassium carbonate to
рH 8. A dark brown resin was extracted with benzene and dried
with sodium sulfate, the drying agent was filtered off, the soluꢀ
tion was allowed to stand over SiO2 (40/100; 10 g per 250 mL of
the solution) for 12 h, SiO2 was filtered off, and the solution was
concentrated on a rotary evaporator. Compound 2a (0.81 g, 72%)
was obtained as a brown oil crystallizing on standing. M.p. 109 °C
(Ref. 42: 105—106 °C). 1H NMR (CDCl3), δ: 3.04 (dd, 1 H,
C(4)H, J1 = 17.8 Hz, J2 = 6.6 Hz); 3.66 (dd, 1 H, C(4)H´,
J1 = 17.7 Hz, J2 = 13.2 Hz); 5.52 (dd, 1 H, C(5)H, J1 = 13.3 Hz,
J2 = 6.6 Hz); 6.96—7.38 (m, 10 H, Harom); 9.89 (s, 1 H, 3ꢀCHO).
3ꢀFormylꢀ1ꢀphenylꢀ2ꢀpyrazoline (2b). The reagent POCl3
(2.56 mL, 0.028 mol) was added dropwise to dimethylformaꢀ
mide (2.12 mL, 0.028 mol) at room temperature. The mixture
was stirred for 30 min, then a solution of 1ꢀphenylꢀ2ꢀpyrazoline
(2 g) in DMF (2 mL) was added. The mixture was heated for 30 min
at 95—100 °C, cooled, poured onto ice, and allowed to stand for
2 days. A precipitate formed was filtered and dried in air to
obtain compound 2a (1.6 g, 67%), m.p. 51 °C (Ref. 42: 51 °C).
(5Z)ꢀ3ꢀAllylꢀ5ꢀ[(1,5ꢀdiphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ2ꢀ
thioxotetrahydroꢀ4Hꢀimidazolꢀ4ꢀone (3a). Thiohydantoin 1a
(1.07 g, 0.00686 mol) and anhydrous sodium acetate (1.69 g,
0.02 mol) in acetic acid (27 mL) were added to formylpyrazoline
2a (1.55 g, 0.0137 mol). The mixture was heated with stirring for
4 h, then diluted with a small amount of water. A precipitate
formed was filtered on a Buchner funnel, recrystallized from
ethanol, and dried in air to obtain compound 3a (2.26 g, 85%) as
a red powder, m.p. 141—142 °C. 1H NMR (DMSOꢀd6), δ: 3.43
(m, 1 H, C(4)H); 3.83 (dd, 1 H, C(4)H´, J1 = 17.8 Hz, J2 = 12.6 Hz);
4.38 (d, 2 H, CH2—CH=, J = 4.6 Hz); 5.12 (m, 2 H, CH2=);
5.67 (dd, 1 H, J1 = 12.7 Hz, C(5)H, J2 = 5.3 Hz); 5.81 (m, 1 H,
CH2—CH=); 6.43 (s, 1 H, CH=); 6.80—7.35 (m, 10 H, Harom);
11.79 (s, 1 H, NH). IR, ν/cm–1: 1740 (C=O), 3220 (NH). Found (%):
C, 68.45; H, 5.53; N, 13.83. C22H20N4OS. Calculated (%):
C, 68.02; H, 5.19; N, 14.42.
C(4)H´, J1 = 17.0 Hz, J2 = 13.1 Hz); 5.41 (dd, 1 H, C(5)H,
J1 = 12.6 Hz, J2 = 6.4 Hz); 6.23 (s, 1 H, CH=); 6.94 (t, 1 H,
Harom, J = 7.2 Hz); 7.06 (d, 2 H, Harom, J = 7.8 Hz); 7.25—7.56
(m, 12 H, Harom); 10.24 (s, 1 H, NH). Found (%): C, 65.68; H,
4.80; N, 16.18. C25H20N4OS. Calculated (%): C, 65.50; H, 4.63;
N, 16.18.
(5Z)ꢀ3ꢀPhenylꢀ5ꢀ[(1ꢀphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ2ꢀ
thioxotetrahydroꢀ4Hꢀimidazolꢀ4ꢀone (3d) was obtained similarly
to compound 3c from thiohydantoin 1b (0.88 g, 0.0046 mol) and
formylpyrazoline 2b (0.8 g, 0.0046 mol). A precipitate formed
was purified by flashꢀchromatography on SiO2 (5/40), eluent
a mixture of benzene—ethyl acetate, 20 : 1 to obtain compound 3d
(0.15 g, 10%) as a dark red powder, m.p. 160 °C. 1H NMR
(DMSOꢀd6), δ: 3.39 (m, 2 H, C(4)H2); 4.03 (t, 2 H, C(5)H2,
J =11.1 Hz); 6.45 (s, 1 H, CH=); 6.92 (t, 1 H, Harom, J = 7.3 Hz);
7.19 (d, 2 H, Harom, J = 7.7 Hz); 7.31—7.39 (m, 3 H, Harom);
7.47—7.54 (m, 4 H, Harom); 11.95 (s, 1 H, NH). Found (%):
C, 65.38; H, 4.60; N, 16.27. C19H16N4OS. Calculated (%): C, 65.50;
H, 4.63; N, 16.08.
Alkylation of compounds 3a—d (general procedure). Comꢀ
pounds 3a—d (1 equiv.) was dissolved in a 20% ethanolic soluꢀ
tion of KOH (1 equiv.). After the complete dissolution, an alkyl
halide (1.2 equiv.) added, and the mixture was stirred until
a precipitate was formed, monitoring the reaction progress by TLC.
A precipitate formed was filtered and recrystallized from EtOH.
(5Z)ꢀ3ꢀAllylꢀ5ꢀ[(1,5ꢀdiphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ2ꢀ
methylsulfanylꢀ4,5ꢀdihydroꢀ3Hꢀimidazolꢀ4ꢀone (4a). Compound
4a (0.11 g, 53%) was obtained from compound 3a (0.5 g,
0.0013 mol) and methyl iodide (0.09 mL, 0.00143 mol) as a red
powder, m.p. 187 °C. 1H NMR (DMSOꢀd6), δ: 2.56 (s, 3 H,
CH3); 3.35 (m, 1 H, C(4)H); 4.00 (dd, 1 H, C(4)H´, J1 = 18.2 Hz,
J2 = 12.6 Hz); 4.15 (d, 2 H, CH2—CH=, J = 5.0 Hz); 5.08
(d, 1 H, CH2=, J =18.2 Hz); 5.17 (d, 1 H, CH2=, J = 11.2 Hz);
5.69 (dd, 1 H, C(5)H, J1 =12.7 Hz, J2 = 5.4 Hz); 5.81 (m, 1 H,
CH2—CH=); 6.80 (s, 1 H, CH=); 7.06—7.36 (m, 10 H, Harom).
Found (%): C, 68.82; H, 6.35; N, 13.81. C24H26N4OS. Calcuꢀ
lated (%): C, 68.87; H, 6.26; N, 13.39.
(5Z)ꢀ3ꢀAllylꢀ5ꢀ[(1ꢀphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ2ꢀmeꢀ
thylsulfanylꢀ4,5ꢀdihydroꢀ3Hꢀimidazolꢀ4ꢀone (4b). Compound 4b
(0.11 g, 52%) was obtained from compound 3b (0.2 g, 0.00064 mol)
and methyl iodide (0.044 mL, 0.0007 mol) as an orange powder,
m.p. 169 °C. 1H NMR (DMSOꢀd6), δ: 2.66 (s, 3 H, CH3); 3.48
(m, 2 H, C(4)H2); 4.03 (m, 2 H, C(5)H2); 4.17 (d, 2 H, CH2,
J = 6.0 Hz); 5.09 (d, 1 H, CH2=, J = 17.2 Hz); 5.19 (d, 1 H, CH2=,
J = 9.2 Hz); 5.81 (m, 1 H, CH2—CH=); 6.74 (s, 1 H, CH=);
6.81 (t, 1 H, Harom, J = 6.8 Hz); 7.14 (d, 2 H, Harom, J = 9.7 Hz);
7.31 (m, 2 H, Harom). Found (%): C, 62.52; H, 5.92; N, 16.00.
C17H18N4OS. Calculated (%): C, 62.55; H, 5.56; N, 17.16.
(5Z)ꢀ3ꢀPhenylꢀ5ꢀ[(1,5ꢀdiphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ
2ꢀmethylsulfanylꢀ4,5ꢀdihydroimidazolꢀ4ꢀone (4c). Compound 4c
(0.2 g, 77%) was obtained from compound 3c (0.25 g, 0.0006 mol)
and methyl iodide (0.037 mL, 0.0006 mol) as an orange powder,
m.p. 175 °C. 1H NMR (CDCl3), δ: 2.57 (s, 3 H, CH3); 3.53 (dd,
1 H, J1 = 6.2 Hz, J2 = 18.0 Hz); 4.12 (dd, 1 H, C(4)H´,
J1 = 12.0 Hz, J2 = 18.0 Hz); 5.42 (dd, 1 H, C(5)H, J1 = 6.2 Hz,
J2 = 12.0 Hz); 6.28 (s, 1 H, CH=); 6.87 (t, 1 H, Harom, J = 7.2 Hz);
7.05—7.58 (m, 14 H, Harom). Found (%): C, 71.12; H, 5.20;
N, 12.55. C26H22N4OS. Calculated (%): C, 71.21; H, 5.06; N, 12.78.
Ethyl (5Z)ꢀ(3ꢀallylꢀ5ꢀ[(1,5ꢀdiphenylpyrazolinꢀ3ꢀyl)methylꢀ
idene]ꢀ4ꢀoxoꢀ4,5ꢀdihydroimidazolꢀ2ꢀyl)thioacetate (5a). Comꢀ
pound 5a (0.13 g, 30%) was obtained from compound 3a (0.35 g,
(5Z)ꢀ3ꢀAllylꢀ5ꢀ[(1ꢀphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ2ꢀthiꢀ
oxotetrahydroꢀ4Hꢀimidazolꢀ4ꢀone (3b) was obtained similarly to
compound 3a from formylpyrazoline 2b (0.8 g, 0.0046 mol) and
thiohydantoin 1a (0.7176 g, 0.0046 mol). A precipitate formed
was purified by flashꢀchromatography on SiO2 (5/40), eluent
a mixture of benzene—ethyl acetate, 20 : 1. Compound 3b (0.4 g,
28%) was obtained as an orange powder, m.p. 145 °C. 1H NMR
(DMSOꢀd6) δ: 3.36 (m, 2 H, C(4)H2); 4.00 (t, 2 H, C(5)H2,
J = 11.3 Hz); 4.41 (d, 2 H, CH2—CH=, J = 5.4 Hz); 5.12 (m, 2 H,
CH2=); 5.85 (m, 1 H, CH2—CH=); 6.41 (s, 1 H, CH=);
6.91—7.34 (m, 5 H, Harom); 11.83 (s, 1 H, NH). IR, ν/cm–1
:
1745 (CO), 3218 (NH). Found (%): C, 61.36; H, 5.41; N, 17.63.
C16H16N4OS. Calculated (%): C, 61.52; H, 5.16; N, 17.93.
(5Z)ꢀ3ꢀPhenylꢀ5ꢀ[(1,5ꢀdiphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ
2ꢀthioxotetrahydroꢀ4Hꢀimidazolꢀ4ꢀone (3c). Thiohydantoin 1b
(3.84 g, 0.02 mol) was dissolved in a 2% ethanolic solution of
KOH (60 mL) with vigorous stirring. After the complete dissoluꢀ
tion of 2ꢀthiohydantoin, formylpyrazoline 2a (4.42 g, 0.02 mol)
was added in portions to the solution. The mixture was stirred for
12 h, a precipitate was filtered and dissolved in water. Then, this
solution was neutralized with dilute hydrochloric acid with vigꢀ
orous stirring to рH = 7. A precipitate formed was filtered and
recrystallized from EtOH to obtain compound 3c (8.2 g, 97%) as
1
a dark red powder, m.p. 191 °C. H NMR (DMSOꢀd6), δ: 3.05
(dd, 1 H, C(4)H, J1 = 17.3 Hz, J2 = 6.2 Hz); 3.76 (dd, 1 H,

Pyrazolinylmethylenethiohydantoins
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 3, March, 2017
509
0.0009 mol) and ethyl chloroacetate (0.1 mL, 0.00099 mol) as
a red powder, m.p. 163 °C. 1H NMR (DMSOꢀd6), δ: 0.98 (t, 3 H,
CH3, J = 7.1 Hz); 3.24 (dd, 1 H, C(4)H, J1 = 18.5 Hz, J2 = 5.8 Hz);
3.71 (m, 1 H, C(4)H´); 3.90 (m, 2 H, OCH2); 4.07 (s, 2 H,
CH2S); 4.18 (d, 2 H, CH2—CH=); 5.11 (d, 1 H, CH2=, J= 17.0 Hz);
5.20 (d, 1 H, CH2=, J = 10.5 Hz); 5.71 (dd, 1 H, C(5)H,
J1 = 12.4 Hz, J2 = 5.9 Hz); 5.82 (m, 1 H, CH2—CH=); 6.82 (s, 1 H,
CH=); 7.08—7.37 (m, 10 H, Harom). Found (%): C, 65.98;
H, 5.30; N, 11.75. C26H26N4O3S. Calculated (%): C, 65.80;
H, 5.52; N, 11.81.
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Moiseeva, N. V. Zyk, Mendeleev Commun., 2014, 24, 37.
20. E. K. Beloglazkina, A. G. Majouga, I. V. Yudin, N. V. Zyk,
A. A. Moiseeva, K. P. Butin, Russ. Chem. Bull., 2005,
54, 2163.
21. E. K. Beloglazkina, S. Z. Vatsadze, A. G. Majouga, N. A.
Frolova, R. B. Romashkina, N. V. Zyk, A. A. Moiseeva,
K. P. Butin, Russ. Chem. Bull., 2005, 54, 2771.
22. E. K. Beloglazkina, A. G. Majouga, I. V. Yudin, N. A. Frolꢀ
ova, N. V. Zyk, V. D. Dolzhikova, A. A. Moiseeva, R. D.
Rakhimov, K. P. Butin, Russ. Chem. Bull., 2006, 55, 1015.
23. E. K. Beloglazkina, A. G. Majouga, A. A. Moiseeva, M. G.
Tsepkov, N. V. Zyk, Russ. Chem. Bull., 2007, 56, 351.
24. A. G. Majouga, E. K. Beloglazkina, O. V. Shilova, A. A.
Moiseeva, N. V. Zyk, Russ. Chem. Bull., 2009, 58, 1392.
25. A. V. Yudina, A. G. Majouga, E. K. Beloglazkina, I. V.
Yudin, I. A. Rodin, N. V. Zyk, Russ. Chem. Bull., 2011,
60, 2120.
Ethyl (5Z)ꢀ(3ꢀallylꢀ5ꢀ[(1ꢀphenylpyrazolinꢀ3ꢀyl)methylidene]ꢀ
4ꢀoxoꢀ4,5ꢀdihydroimidazolꢀ2ꢀyl)thioacetate (5b). Compound 5b
(0.12 g, 48%) was obtained from compound 3b (0.2 g, 0.00064 mol)
and ethyl chloroacetate (0.074 mL, 0.0007 mol) as a red powder,
m.p. 139 °C. 1H NMR (DMSOꢀd6), δ: 1.21 (t, 3 H, CH3,
J = 7.1 Hz); 3.38 (m, 2 H, C(4)H2); 4.05 (m, 2 H, C(5)H2);
4.13—4.20 (m, 6 H, OCH2CH3, CH2S, CH2—CH=); 5.12
(d, 1 H, CH2=, J = 18.2 Hz); 5.22 (d, 1 H, CH2=, J = 10.4 Hz);
5.83 (m, 1 H, CH2—CH=); 6.75 (s, 1 H, HC=); 6.92 (t, 1 H,
Harom, J = 7.3 Hz), 7.15 (d, 2 H, Harom, J = 7.8 Hz); 7.32 (t, 2 H,
Harom, J = 7.9 Hz). Found (%): C, 60.28; H, 6.56; N, 14.00.
C20H22N4O3S. Calculated (%): C, 60.85; H, 6.32; N, 13.52.
(5Z)ꢀ3ꢀPhenylꢀ5ꢀ[(1,5ꢀdiphenylpyrazolꢀ3ꢀyl)methylidene]ꢀ2ꢀ
methylsulfanylꢀ4,5ꢀdihydroimidazolꢀ4ꢀone (6). Lead tetraacetate
(0.2 g, 0.011 mol) was added to a solution of compound 4c (0.2 g,
0.0007 mol) in acetic acid (3 mL) and the mixture was stirred
until the starting pyrazoline disappeared (TLC monitoring). The
reaction mixture was poured into water, extracted with chloroꢀ
form, and dried with Na2SO4. The solvent was evaporated at
reduced pressure, the residue was recrystallized from EtOH to
obtain compound 6 (0.19 g, 63%) as a light yellow powder.
1H NMR (CDCl3), δ: 2.74 (s, 3 H, CH3); 7.28 (s, 1 H, HC=);
7.30—7.60 (m, 16 H, Harom, C(4)H). Found (%): C, 71.56;
H, 4.89; N, 12.72. C26H20N4OS. Calculated (%): C, 71.54;
H, 4.62; N, 12.83.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 16ꢀ03ꢀ00921).
26. E. A. Manzhelii, E. K. Beloglazkina, A. G. Majouga, N. V.
Zyk, Russ. Chem. Bull., 2013, 62, 2631.
27. E. K. Beloglazkina, A. G. Majouga, R. B. Romashkina, A. A.
Moiseeva, N. V. Zyk, Polyhedron, 2007, 26, 797.
28. A. G. Majouga, A. V. Udina, E. K. Beloglazkina, D. A.
Skvortsov, M. I. Zvereva, O. A. Dontsova, N. V. Zyk, N. S.
Zefirov, Tetrahedron Lett., 2012, 53, 51.
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Received April 27, 2016;
in revised form August 31, 2016