Dioxothietanylation of heterocycles 2*. Imidazoles and benzimidazoles

Article abstract of DOI:10.1007/s10593-019-02543-0

[Figure not available: see fulltext.] 1-(1,1-Dioxidothietan-3-yl)-1H-imidazoles and 1-(1,1-dioxidothietan-3-yl)-1H-benzimidazoles were synthesized in the reaction of 3,5-dibromo-1-(1,1-dioxidothietan-3-yl)-1H-1,2,4-triazole with the sodium salts of imidaz

Full text of DOI:10.1007/s10593-019-02543-0

DOI 10.1007/s10593-019-02543-0
Chemistry of Heterocyclic Compounds 2019, 55(9), 823–826
Dioxothietanylation of heterocycles
2
*. Imidazoles and benzimidazoles
1
1
1
Nadezhda N. Makarova *, Elena E. Klen , Ferkat А. Khaliullin
1
Bashkir State Medical University,
3
Lenina St., Ufa 450008, Russia; е-mail: nnm16@yandex.ru
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
Submitted January 25, 2019
Accepted after revision June 14, 2019
2
019, 55(9), 823–826
1
3
-(1,1-Dioxidothietan-3-yl)-1H-imidazoles and 1-(1,1-dioxidothietan-3-yl)-1H-benzimidazoles were synthesized in the reaction of
,5-dibromo-1-(1,1-dioxidothietan-3-yl)-1H-1,2,4-triazole with the sodium salts of imidazoles and benzimidazoles. The reaction involves
addition of azoles to thiete 1,1-dioxide formed in situ, which acts as a Michael acceptor. The effect of pK
a
values of imidazoles and
benzimidazoles on their reactivity is shown.
Keywords: benzimidazole, imidazole, thietane 1,1-dioxide, 1,2,4-triazole, aza-Michael reaction, dioxothietanylation.
One of the common methods for the synthesis of
compounds containing the 1,1-dioxidothietane ring is the
in its nucleophilicity contribute to the retro-Michael reaction
with the formation of thiete 1,1-dioxide and 3,5-dibromo-
1H-1,2,4-triazole (pK
5.17).7
2
oxidation of the corresponding thietanes. This method
a
requires preliminary introduction of a thietane ring into the
initial molecule and has a number of drawbacks. For
example, the thietanylation of compounds is often
accompanied by the formation of polymers and leads to
The reaction of 3,5-dibromo-1-(1,1-dioxidothietan-3-yl)-
1H-1,2,4-triazole (1) with substituted imidazoles was
carried out by heating under reflux sodium salts of imid-
azoles 2a–d, obtained in situ from corresponding imid-
azoles 3a–d, in t-BuOH. The choice of t-BuOH as the
solvent was due to its low ability to compete with nucleo-
philes as a Michael donor because of steric hindrance. As a
result, 1-(1,1-dioxidothietan-3-yl)-1H-imidazoles 4a–d were
isolated in moderate yields. The proposed reaction mechanism
involves the generation of thiete 1,1-dioxide (5), which is
involved in the aza-Michael reaction (Scheme 1).
3
low yields of thietanyl derivatives, and the oxidation of the
latter leads to the formation of byproducts, which
negatively affects the purity and reduces the yields of the
target thietane 1,1-dioxides.
Previously, we developed a new method for the
4
5
synthesis of 3-alkoxy- and 3-aryloxythietane 1,1-dioxides
and 3,5-disubstituted 1-(1,1-dioxidothietan-3-yl)-1H-1,2,4-
6
triazoles, based on the use of 3,5-dibromo-1-(1,1-dioxido-
It has been established that imidazoles with NH acidity
thietan-3-yl)-1H-1,2,4-triazole as the dioxothietanylating
in the pK
a
range 9.30–15.1 (imidazole (3a) pK 14.4,
a
agent. In continuation of these studies, the reactions of this
2-methylimidazole (3b) pK 15.1, 4(5)-nitroimidazole (3c)
a
1
,2,4-triazole with imidazoles and benzimidazoles
pK
a
9.30, and 2-methyl-4(5)-nitroimidazole (3d) pK 9.75)
a
7
containing electron-withdrawing (Cl, Br, I, NO
2
, СО
2
Me,
enter the reaction. The use of asymmetric 4(5)-nitro- and
SO Me) and electron-donating (Ph, Me, CH Ph, SAlk)
2
2
2-methyl-4(5)-nitroimidazoles 3c,d can lead to the
1
13
substituents and significantly differing in nucleophilicity
and acidity were studied. An increase in the acidity of the
azole forming the dioxothietanylating agent and a decrease
formation of two isomers (Fig. 1). The H– C HMBC and
1 15
HSQC spectra of compounds 4c,d, as well as the H– N
HMBC spectrum of compound 4c, indicate that only
4
-nitroimidazoles 4c,d are formed in the studied reaction,
For Communication 1, see1.
which is consistent with published data.
8
*
0
009-3122/19/55(9)-0823©2019 Springer Science+Business Media, LLC
823

Chemistry of Heterocyclic Compounds 2019, 55(9), 823–826
Scheme 1
NH
O
O
S
R2
R1
N
O
S
O
3
a d
O
O
t-BuONa
NNa
1
2
1
. Na, t-BuOH
a R = R = H
S
N
N N
N
+
1
2
R2
R1
b R = Me, R = H
N
2
2. t-BuOH, , 2 h
R2
R1
5
1
2
Br
Br
N
c R = H, R = NO
2
a–d
46–52%
1
2
4
a–d
d R = Me, R = NO
2
1
15
With the aid of a H– N HMBC experiment for
compound 4c, a correlation was found between the signals
of the protons H-2,5 of the imidazole ring and protons of
apparently due to steric hindrances introduced by
substituents at positions 4 and 5 of the imidazole ring.
A similar reaction of 3,5-dibromo-1-(1,1-dioxidothietan-
3-yl)-1H-1,2,4-triazole (1) with sodium salts of benz-
imidazoles 5a–f, obtained in situ from the corresponding
benzimidazoles 6a–f, was carried out in t-BuOH (for
compounds 7a,b,d,e) or in PhH (for compounds 7c,f) with
the formation of 1-(1,1-dioxidothietan-3-yl)-1H-benz-
imidazoles 7a–f with 30–85% yields (Scheme 2).
the 2,4-CH group of the 1,1-dioxidothietane ring with the
2
signals of the imidazole N-1,3 atoms (Fig. 1). The most
informative are the cross peaks H-2/N-1, H-2/N-3, and
H-5/N-1. The absence in the spectrum of the cross peak
H-4/N-3 indicates the formation of 1-(1,1-dioxidothietan-
3
-yl)-4-nitro-1H-imidazole (4c). According to published
9 1
data, in the H NMR spectra of 1,4-disubstituted
imidazoles, the value of the spin-spin coupling constant
Scheme 2
(
1
SSCC) JH-2,H-5 is usually 1.1–1.5 Hz and in the spectra of
,5-disubstituted imidazoles, the values of JH-2,H-4 are in the
range of 0.9–1.0 Hz. The SSCC values of 1.4 and 1.5 Hz
obtained for the protons of the product of the reaction of
4
1
(5)-nitroimidazole (3c) with 1-(1,1-dioxidothietan-3-yl)-
H-1,2,4-triazole 1 also confirm the proposed structure of
1
13
compound 4c. The H– C HMBC spectra of compounds
4
c,d showed a correlation of the signals of the H-2.5
protons of the imidazole ring with the signals of the C-3
atoms of the 1,1-dioxidothietane ring and imidazole C-2,4
signals (Fig. 2).
It was found that benzimidazoles with NH acidity in the
In the case of 2,4,5-tribromoimidazole (рK
а
6.9) and
pK
a
range of 9.60–13.80 (benzimidazole (6a) pK 12.86,
a
1
0
2
,4,5-triiodimidazole (рK
а
8.0), both possessing high
2-chlorobenzimidazole (6b) pK
azole (6c) pK 13.18, 2-benzylbenzimidazole (6d) pK
2-(methylsulfanyl)benzimidazole (6e) pK
a
9.60, 2-methylbenzimid-
12.7,
11.8, 2-(ethyl-
11.67 ) take part in the
reaction. In the case of 2-(methylsulfonyl)benzimidazole
pK
6.59),11 the corresponding product could not be
obtained. Also, 2-isopropoxybenzimidazole (pK 13.28)
acidity and low nucleophilicity, N-dioxothietanylation
a
a
7
products are not formed. Dimethyl 4,5-imidazole
a
1
1
11
dicarboxylate (рK
а
9.26) and 4,5-diphenylimidazole (рK
а
sulfanyl)benzimidazole (6f) pK
a
1
2.80)7 were also inactive in this reaction. This is
(
a
a
and 2-(N-benzylamino)benzimidazole (pK
15.44)1 did not
1
a
enter the reaction, which is apparently explained by steric
barriers introduced by substituents at position 2 of
benzimidazole.
The IR spectra of compounds 4b–d and 7b–f contain
intense absorption bands of stretching vibrations of the
S=O bonds of the sulfonyl group in the ranges 1313–1346
Figure 1. Major correlations in 1H– N HMBC spectrum for
15
–1
and 1134–1147 cm , which confirms the presence of the
compound 4с and the expected correlations for 1-(1,1-dioxidothietan-
1
,1-dioxidothietane ring. Compound 7b does not lower the
3-yl)-5-nitro-1H-imidazole.
melting temperature of the sample when mixed with the
12
compound obtained by the known method, and their IR
1
spectra perfectly match. In the H NMR spectra of com-
pounds 4b–d and 7b–f, proton signals of the 2,4-CH and
2
3-CH groups of the 1,1-dioxidothietane ring are observed
in the ranges of 4.47–5.04 and 5.12–5.85 ppm, respectively.
Signals of the aromatic protons in the downfield region
confirm the presence of azole rings. The 13C NMR spectra
of compounds 4b–d and 7b–f contain the signals of the
C-2,4 and C-3 atoms of the 1,1-dioxidothietane ring in the
ranges of 70.2–72.0 and 35.1–39.2 ppm, respectively.
1
13
Figure 2. Major correlations in H– C HMBC spectra for
compounds 4с,d.
8
24

Chemistry of Heterocyclic Compounds 2019, 55(9), 823–826
To conclude, an effective method for a one-step
36.2 (CH); 72.0 (2CH ); 116.8 (С Ar); 127.6 (С Ar); 145.1
2
synthesis of 1-(1,1-dioxidothietan-3-yl)-1H-imidazoles and
(С Ar). Found, %: С 45.09; Н 5.48; N 15.09. С
Calculated, %: С 45.15; Н 5.41; N 15.04.
7
Н
10
N
2
O S.
2
1
-(1,1-dioxidothietan-3-yl)-1H-benzimidazoles based on
the reactions of 3,5-dibromo-1-(1,1-dioxidothietan-3-yl)-
H-1,2,4-triazole with the sodium salts of imidazoles and
benzimidazoles. It was established that imidazoles and
benzimidazoles with NH acidity in the рK ranges of 9.30–
5.1 and 9.60–13.80, respectively, enter the reaction.
1-(1,1-Dioxidothietan-3-yl)-4-nitro-1H-imidazole (4c).
1
After filtration, the precipitate was washed with Me
2
CO
(15 ml). Yield 0.30 g (46%), white powder, mp 235–237°С
–
1
а
(EtOH). IR spectrum, ν, cm : 1549 (NO
С=С), 1388, 1346 (S=O), 1224, 1146 (S=O). H NMR
spectrum, δ, ppm (J, Hz): 4.76–4.90 (4Н, m, 2,4-CH );
.34–5.41 (1Н, m, 3-CH); 8.08 (1Н, d, J = 1.4, Н-2); 8.60
2
), 1495 (С=N,
1
1
2
Experimental
5
13
IR spectra were registered on an Infralum FT-02 FT-IR
(1Н, d, J = 1.5, Н-5). C NMR spectrum, δ, ppm: 39.2
1
13
spectrometer in KBr pellets. H and C NMR spectra (500
(CH); 71.0 (2CH ); 120.4 (С-5); 136.9 (С-2); 147.2 (С-4).
2
1
13
and 125 MHz, respectively), Н– C HMBC and HSQC
Found, %: С 33.23; Н 3.31; N 19.54. С
Calculated, %: С 33.18; Н 3.25; N 19.35.
6
Н
7
N
3
O S.
4
1
15
(
compounds 4c,d) and H– N HMBC (compound 4с)
spectra were acquired on Bruker Avance 500
. The residual solvent signals
a
1-(1,1-Dioxidothietan-3-yl)-2-methyl-4-nitro-1H-imid-
spectrometer in DMSO-d
6
azole (4d). Yield 0.36 g (52%), white powder, mp 188–
1
13
–1
(
2.50 ppm for Н nuclei, 39.5 ppm for C nuclei) or TMS
190°С (EtOH). IR spectrum, ν, cm : 1533 (NO
2
), 1495
(
for compound 4с) were used as internal standard.
(С=N, С=С), 1394, 1317 (S=O), 1222, 1147 (S=O).
1
3
1
С NMR spectra were additionally registered in DEPT
H NMR spectrum, δ, ppm: 2.35 (3Н, s, СН
(4Н, m, 2,4-CH ); 5.22–5.29 (1Н, m, 3-CH); 8.61 (1Н, s,
Н-5). 13C NMR spectrum, δ, ppm: 13.5 (СH
); 38.1 (CH);
); 120.1 (С-5); 146.0 (С-2); 146.2 (С-4). Found,
3
); 4.77–4.88
mode. Mass spectra were recorded on an Agilent 5973А
2
GC/MSD mass spectrometer, 6890B series, EI ionization
3
(
70 eV), scan range 15–600 Da, scan rate 2.5 scan/s.
71.2 (2CH
2
Temperature program of the chromatography column:
starting temperature 80°С, 2 min isotherm, ramp to 260°С
at 20°С/min, injector temperature 250°С. Elemental
analysis was performed on a Hekatech Euro3000 Elemental
analyzer. Melting points were determined on a Stuart
SMP30 apparatus. Monitoring of the reaction progress and
assessment of the purity of synthesized compounds were
done by TLC on Sorbfil P-А-UV plates, visualization with
UV or in an iodine chamber.
%: С 36.26; Н 3.84; N 18.11. С
С 36.36; Н 3.92; N 18.17.
7
Н
9
N
3
O S. Calculated, %:
4
2-Chloro-1-(1,1-dioxidothietan-3-yl)-1H-benzimidazole
(7b). Yield 0.45 g (58%), white powder, mp 187–189°С
–1
(n-BuOH). IR spectrum, ν, cm : 1479 (С=N, С=С), 1327
1
(S=O), 1222, 1143 (S=O). H NMR spectrum, δ, ppm
(J, Hz): 4.84–5.04 (4Н, m, 2,4-CH ); 5.75–5.85 (1Н, m,
2
3-CH); 7.27–7.43 (2Н, m, H-5,6); 7.66 (1Н, d, J = 8.0,
13
H-7); 7.91 (1Н, d, J = 8.2, H-4). C NMR spectrum,
3
,5-Dibromo-1-(1,1-dioxidothietan-3-yl)-1H-1,2,4-tri-
δ, ppm: 36.0 (CH); 70.6 (2CH ); 111.6 (С Ar); 119.8
2
4
azole (1) was synthesized according to a literature method.
(С Ar); 123.5 (С Ar); 124.0 (С Ar); 133.6 (С Ar); 140.6
(С Ar); 141.8 (С Ar). Mass spectrum, m/z (Irel, %): 258
Synthesis according to the proposed method and analytical
+
+
data for 1-(1,1-dioxidothietan-3-yl)-1H-imidazole (4a) and
[М] (12), 256 [М] (32), 180 (33), 178 (100). Found, %:
1
-(1,1-dioxidothietan-3-yl)-1H-benzimidazole (7a) were
С 46.70; Н 3.48; N 11.11. С10
С 46.79; Н 3.53; N 10.91.
Н
9
СlN
2
O S. Calculated, %:
2
13
published earlier.
Synthesis of 1-(1,1-dioxidothietan-3-yl)-1H-imid-
azoles 4b–d and 1-(1,1-dioxidothietan-3-yl)-1H-benz-
imidazoles 7b,d,e (General method). Metallic Na (76 mg,
2-Benzyl-1-(1,1-dioxidothietan-3-yl)-1H-benzimidazole
(7d). After filtration, the precipitate was washed with
n-BuOH (20 ml). Yield 0.30 g (32%), white powder,
–1
3
.3 mmol) was added to t-BuOH (30 ml), and the mixture
mp 195–197°С (EtOH). IR spectrum, ν, cm : 1458 (С=N,
1
was heated under reflux until effervescence ceased. Then
azole 3b–d or 6b,d,e (3 mmol) and 3,5-dibromo-1-(1,1-di-
oxidothietan-3-yl)-1H-1,2,4-triazole (1) (0.99 g, 3 mmol)
were added. The reaction mixture was heated under reflux
for 2 h (for compounds 4b–d, 7d,e) or 3 h (for compound
С=С), 1332 (S=O), 1213, 1134 (S=O). H NMR spectrum,
δ, ppm (J, Hz): 4.31 (2Н, s, СН Ph); 4.48–4.56 (2Н, m)
2
and 4.83–4.91 (2Н, m, 2,4-CH
2
); 5.67–5.76 (1Н, m, 3-CH);
7.20–7.34 (7Н, m, H-5,6, H Ph); 7.65 (1Н, d, J = 7.9, H-7);
13
7.84 (1Н, d, J = 8.0, H-4). C NMR spectrum, δ, ppm:
33.6 (CH Ph); 35.2 (CH); 70.2 (2CH ); 111.4 (С Ar); 120.1
7
b). The solvent was evaporated under reduced pressure,
2
2
and H
2
O (15 ml) was added to the residue. The precipitate
(С Ar); 122.6 (С Ar); 123.0 (С Ar); 127.2 (С Ph); 129.0
(2С Ph); 129.1 (2С Ph); 132.7 (С Ar); 137.1 (С Ph); 143.5
(С Ar); 154.8 (С Ar). Found, %: С 65.11; Н 5.23; N 8.91.
was filtered off, dried at 60°C, and recrystallized from a
suitable solvent.
1-(1,1-Dioxidothietan-3-yl)-2-methyl-1H-imidazole (4b).
С
17
Н
16
N
2
O S. Calculated, %: С 65.36; Н 5.16; N 8.97.
2
After evaporation of the solvent, the residue was washed
with CHCl (20 ml). Yield 0.27 g (49%), white powder,
mp 188–190°С (PhH–hexane, 1:5). IR spectrum, ν, cm :
430 (С=N, С=С), 1313 (S=O), 1225, 1144 (S=O).
1-(1,1-Dioxidothietan-3-yl)-2-(methylsulfanyl)-1H-benz-
3
imidazole (7e). Yield 0.66 g (82%), white powder, mp 201–
–1
–1
202°С (i-BuOH). IR spectrum, ν, cm : 1447 (С=N, С=С),
1
1
1323 (S=O), 1275, 1142 (S=O). H NMR spectrum, δ, ppm
1
H NMR spectrum, δ, ppm (J, Hz): 2.27 (3Н, s, СН
3
);
); 5.12–
.20 (1Н, m, 3-CH); 6.80 (1Н, d, J = 1.0, Н-4); 7.40 (1Н,
(J, Hz): 2.83 (3Н, s, СН
3
); 4.84–5.00 (4Н, m, 2,4-CH );
2
4
5
.47–4.55 (2Н, m) and 4.76–4.84 (2Н, m, 2,4-CH
2
5.52–5.62 (1Н, m, 3-CH); 7.18–7.29 (2Н, m, H-5,6); 7.60
13
(1Н, d, J = 7.7, H-7); 7.82 (1Н, d, J = 7.8, H-4). C NMR
spectrum, δ, ppm: 15.4 (CH ); 35.7 (CH); 70.3 (2CH );
13
d, J = 1.1, Н-5). C NMR spectrum, δ, ppm: 13.4 (СН
3
);
3
2
8
25

Chemistry of Heterocyclic Compounds 2019, 55(9), 823–826
1
1
10.9 (С Ar); 118.8 (С Ar); 122.5 (С Ar); 122.6 (С Ar);
Ar); 134.2 (С Ar); 144.0 (С Ar); 152.4 (С Ar). Found, %:
34.5 (С Ar); 144.0 (С Ar); 153.4 (С Ar). Mass spectrum,
С 51.11; Н 4.92; N 9.98. С12
С 51.04; Н 5.00; N 9.92.
Н
14
N
2
O
2
S . Calculated, %:
2
+
+
m/z (Irel, %): 268 [М] (100), 253 [M–CH
3
] (18), 189 (99),
1
75 (50), 171 (52), 157 (50), 131 (34). Found, %: С 49.47;
1
13
13
Н 4.50; N 10.32. С11
Н
12
N
2 2
O S
2
. Calculated, %: С 49.23;
Supplementary information file containing Н and
С
1
Н 4.51; N 10.44.
NMR spectra for compounds 4b–d and 7b–f, Н– С
HMBC and HSQC 2D NMR spectra for compounds 4c,d,
and Н– N HMBC spectrum for compound 4с, as well as
mass spectra for compounds 7b,c,e is available at the
journal website at http://link.springer.com/journal/10593.
Synthesis of 1-(1,1-dioxidothietan-3-yl)-1H-benz-
imidazoles 7c,f (General method). Metallic Na (76 mg,
1
15
3
.3 mmol) was added to anhydrous EtOH (20 ml), and the
mixture was heated under reflux until effervescence ceased.
Benzimidazole 6с,f, (3 mmol) was then added, and the
mixture was heated under reflux for 5 min. The solvent was
evaporated under reduced pressure. Then PhH (30 ml) and
References
1
. Klen, E. E.; Makarova, N. N.; Khaliullin, F. A. Chem.
Heterocycl. Compd. 2013, 48, 1473. [Khim. Geterotsikl.
Soedin. 2012, 1583.]
3
,5-dibromo-1-(1,1-dioxidothietan-3-yl)-1H-1,2,4-triazole (1)
0.99 g, 3 mmol) were added to the residue. The reaction
mixture was heated under reflux for 2 h. The solvent was
(
2. Block, E. In Comprehensive Heterocyclic Chemistry;
Katritzky, A. R.; Rees, C. W., Eds.; Elsevier: New York,
evaporated under reduced pressure, and H
O (20 ml) was
added to the residue. The precipitate was filtered off, dried
at 60°C, and recrystallized from EtOH.
2
1
984, Vol. 7, p. 403.
3
4
5
. Chemistry of thiiranes [in Russian]; Fokin, А. V.;
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(
7с). Yield 0.21 g (30%), white powder, mp 227–228°С.
–1
IR spectrum, ν, cm : 1466 (С=N, С=С), 1327 (S=O),
1
1
229, 1135 (S=O). H NMR spectrum, δ, ppm (J, Hz): 2.59
3Н, s, СН ); 4.75–5.00 (4Н, m, 2,4-CH ); 5.58–5.70 (1Н,
m, 3-CH); 7.15–7.30 (2Н, m, H-5,6); 7.58 (1Н, d, J = 7.8,
(
3
2
6. Klen, E. E.; Makarova, N. N.; Khaliullin, F. A. Chem.
Heterocycl. Compd. 2013, 48, 1473. [Khim. Geterotsikl.
Soedin. 2012, 1583.]
1
3
H-7); 7.80 (1Н, d, J = 7.9, H-4). C NMR spectrum,
δ, ppm: 14.7 (CH ); 35.1 (CH); 70.3 (2CH ); 111.0 (С Ar);
3
2
7
. Catalan, J.; Abboud, J. L. M.; Elguero, J. In Advances in
Heterocyclic Chemistry; Katritzky, A. R., Ed.; Elsevier: New
York, 1987, Vol. 41, p. 187.
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1
1
2
20.0 (С Ar); 122.3 (С Ar); 122.6 (С Ar); 132.9 (С Ar);
43.4 (С Ar); 153.0 (С Ar). Mass spectrum, m/z (Irel, %):
+
36 [М] (36), 158 (100), 157 (27). Found, %: С 55.98;
8
Н 5.01; N 11.73. С11
Н 5.12; N 11.86.
Н
12
N
2
O S. Calculated, %: С 55.92;
2
1-(1,1-Dioxidothietan-3-yl)-2-(ethylsulfanyl)-1H-benz-
9. Matthews, H. R.; Rapoport, H. J. Am. Chem. Soc. 1973, 95,
297.
2
imidazole (7f). Yield 0.72 g (85%), white powder, mp 134–
–
1
1
0. Lombardino, J. G. J. Heterocycl. Chem. 1973, 10, 697.
1
35°С. IR spectrum, ν, cm : 1450 (С=N, С=С), 1319
1
11. ACD/Structure Elucidator, Version 2018.1; Advanced
(
(
S=O), 1276, 1143 (S=O). H NMR spectrum, δ, ppm
J, Hz): 1.38 (3Н, t, J = 7.3, SCH СН ); 3.32 (2Н, q,
СН ); 4.84–4.99 (4Н, m, 2,4-CH ); 5.54–5.62
1Н, m, 3-CH); 7.19–7.27 (2Н, m, H-5,6); 7.61 (1Н, d,
Chemistry Development, Inc.: Toronto, 2019.
2
3
1
1
2. Khaliullin, F. A.; Kataev, V. A.; Zaks, A. S.; Terekhova, N. M.;
Strokin, Yu. V. Pharm. Chem. J. 1993, 27, 192. [Khim. Farm.
Zh. 1993, 27(3), 25.]
3. Klen, E. E.; Makarova, N. N.; Khaliullin, F. A. Chem.
Heterocycl. Compd. 2011, 47, 519. [Khim. Geterotsikl.
Soedin. 2011, 625.]
J = 7.3, SCH
2
3
2
(
1
3
J = 7.8, H-7); 7.83 (1Н, d, J = 7.7, H-4). C NMR
spectrum, δ, ppm: 15.3 (SCH СН ); 27.3 (SCH СН ); 35.6
CH); 70.3 (2CH ); 111.0 (С Ar); 118.9 (С Ar); 122.6 (2С
2
3
2
3
(
2
8
26