Synthesis of New (Arylsulfanyl)maleimide Derivatives

Article abstract of DOI:10.1134/S1070428019120066

Previously unknown 2-(arylsulfanyl)-3-hydroxymaleimide and 2-(arylsulfanyl)-3-chloromaleimide derivatives have been synthesized, and several synthetic approaches to 2-(arylamino)-3-(arylsulfanyl)-maleimides have been tested. The reactivities of 2-chloro-3-(4-methylphenylsulfanyl)maleimide and 2,3-bis(4-methylphenylsulfanyl)maleimide toward nitrogen and sulfur nucleophiles have been studied, and products of substitution of one or two arylsulfanyl groups have been obtained.

Full text of DOI:10.1134/S1070428019120066

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 12, pp. 1847–1852. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 12, pp. 1850–1856.
Synthesis of New (Arylsulfanyl)maleimide Derivatives
a
a
a
A. A. Panov ,* A. Yu. Simonov , and A. M. Korolev
a
Gauze Research Institute of New Antibiotics, Moscow, 119021 Russia
e-mail: 7745243@mail.ru
*
Received May 20, 2019; revised October 18, 2019; accepted October 24, 2019
Abstract—Previously unknown 2-(arylsulfanyl)-3-hydroxymaleimide and 2-(arylsulfanyl)-3-chloromaleimide
derivatives have been synthesized, and several synthetic approaches to 2-(arylamino)-3-(arylsulfanyl)-
maleimides have been tested. The reactivities of 2-chloro-3-(4-methylphenylsulfanyl)maleimide and 2,3-bis(4-
methylphenylsulfanyl)maleimide toward nitrogen and sulfur nucleophiles have been studied, and products of
substitution of one or two arylsulfanyl groups have been obtained.
Keywords: maleimides, (arylsulfanyl)maleimides, antibacterial agents, (arylamino)maleimides.
DOI: 10.1134/S1070428019120066
Maleimide derivatives are used not only as polymers
1, 2] or fluorescent dyes [3] but also as biologically
involved substitution of one bromine atom with the
formation of 2-(arylamino)-3-bromomaleimides 4a and
4b. It should be noted that some 2-(arylamino)-3-bromo-
maleimides reacted with amines, such as butylamine,
piperidine, and morpholine to give the corresponding
diamino derivatives [10]. However, the reactivity of 4a
and 4b was relatively low, and the bromine atom therein
was replaced only by the action of benzenethiols to
produce compounds 5a–5c (Scheme 2).
[
active compounds. In particular, some antitumor agents
4] and protein kinase inhibitors [5] are derivatives of
[
maleimide. A 2,3-bis(arylsulfanyl)maleimide fragment
was used to modify the antibiotic teicoplanin with the
goalofextendingitsspectrumofaction[6].Antibacterial
and antifungal activities of N-alkyl-2-(arylsulfanyl)-
maleimides have also been reported [7]. We previously
synthesized a series of bis(phenylsulfanyl)maleimides
which showed antimicrobial activity [8, 9]. In this work
we synthesized a series of new related compounds.
We succeeded in obtaining mono(arylsulfanyl)
derivatives 7 and 8 using a modified Faul’s procedure
[11, 12]. The condensation of 2-(4-methylphenylsul-
fanyl)acetamide (6) with diethyl oxalate afforded
hydroxymaleimide 7, and treatment of the latter with
oxalyl chloride in THF produced chloro derivative 8
New symmetrical bis(arylsulfanyl)maleimides 3a
and 3b were synthesized by reaction of dibromo-
maleimide 1a or N-methyldibromomaleimide 1b with
(Scheme 3) [13]. No desired products were obtained
4
-methylbenzenethiol in the presence of triethylamine
with the use of other reagents such as phosphoryl
chloride or thionyl chloride.
(Scheme1)[9]. Onlytracesof2-bromo-3-(arylsulfanyl)-
maleimides2weredetected,presumablyduetotheirhigh
reactivity. 2-(Arylamino)-3-(arylsulfanyl)maleimides
Like 2-(arylamino)-3-hydroxymaleimides [12],
compound 7 reacted with aniline and dihydroindole
to give products 9 and 10 as a result of substitution of
the hydroxy group (Scheme 4). However, no similar
5
3
a–5c may be regarded as the closest analogs of 3a and
b. The reaction of 1a with substituted anilines in the
presence of ethyl(diisopropyl)amine (DIPEA) initially
Scheme 1.
O
O
O
Br
Br
Br
ArS
ArS
3
ArSH, THF, Et N
N
R
N
R
+
N
R
ArS
O
O
O
1a, 1b
2
3a (85%), 3b (77%)
1
, R = H (a), Me (b); 3, R = H (a, 85%), Me (b, 77%); Ar = 4-MeC H .
6 4
1
847

1848
PANOV et al.
Scheme 2.
R1
R2
R3
SH
O
O
H
O
1
4
-R C
THF,DIPEA
2–45%
6 4 2
H NH
Br
Br
N
HN
S
R2
THF, DIPEA
NH
NH
NH
2
R1
18–30%
Br
4a, 4b
R3
O
O
O
1a
5a–5e
1
1
2
3
1
2
3
1
2
3
4
, R = F (a), Cl (b); 5, R = F, R = R = H (a), R = Cl, R = R = H (b), R = Cl, R = R = MeO (c).
reaction occurred with benzenethiol. On the other hand,
the reaction of 8 with 4-methoxybenzenethiol in THF
in the presence of triethylamine led to the formation
of symmetrically substituted maleimide 11 rather than
the expected unsymmetrical derivative (Scheme 5).
Presumably, the reaction involved replacement of both
chlorine atom and phenylsulfanyl group. The same
product was obtained by heating compound 3a in
dioxane with a large excess of 4-methoxybenzenethiol
in the presence of triethylamine.
In fact, mass spectral analysis of the reaction mixture
obtained under similar conditions from chloromaleimide
8 and an equimolar amount of benzenethiol revealed
the presence of three bis(arylsulfanyl)maleimides
Scheme 3.
O
O
O
(
(
1) (COOEt)
2) HCl
2
, KOBu-t, THF
S
S
S
(COCl)
2
, THF
NH
2
NH
NH
67%
81%
Me
Me
Me
HO
Cl
O
O
6
7
8
Scheme 4.
NH
2
H
N
Cl
O
O
AcOH, reflux
6%
7
Cl
Me
2
S
HN
9
H
N
O
O
N
H
AcOH, reflux
7
Me
S
N
34%
10
Scheme 5.
OMe
OMe
H
N
HS
O
O
HS
Et N, dioxane
Et
3
N, Et
2
O
3
8
3a
OMe
MeO
34%
S
S
11
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

SYNTHESIS OF NEW (ARYLSULFANYL)MALEIMIDE DERIVATIVES
1849
Scheme 6.
H
H
N
H
N
PhSH, Et
min
3
N, Et
2
O
N
O
O
O
O
O
O
5
8
+
+
Me
Me
Me
S
SPh
S
S
PhS
SPh
12a
12b
12c
Scheme 7.
NH
2
R
N
,
100°C
O
O
Me
3a, 3b
Me
Me
S
HN
3a, 13b
1
1
3, R = H (a), Me (b).
1
2a–12c (m/z 327, 342, and 314, respectively; Fig. 1,
Analytical TLC was performed on Silica gel F254
plates (Merck), and Silica gel 60 (Merck) was used
for column chromatography. Extracts were dried
over anhydrous sodium sulfate and were evaporated
under reduced pressure. The purity of the isolated
compounds was checked by HPLC on a Shimadzu
LC10 instrument equipped with a Gemini 110A-C18
column (4.6×250 mm, grain size 5 μm; Phenomenex,
USA) and a Shimadzu SPD-10A UV-Vis detector
Scheme 6). Presumably, bis(arylsulfanyl)maleimides,
especially unsymmetrical ones, are quite reactive
toward nucleophiles. This was confirmed by the trans-
formation of 3a and 3b into 2-(4-methylanilino)-3-
(
4-methylphenylsulfanyl)maleimides 13a and 13b,
respectively, on heating with excess p-toluidine at
00°C (Scheme 7).
1
EXPERIMENTAL
4
3
2
1
0
+
MS, 0.1–0.2 min, Deconvoluted
The melting points were measured with a Buchi
SMP-20 melting point apparatus and are uncorrected.
The H and C NMR spectra were recorded on a Varian
VXR-400spectrometerat400and100MHz,respectively,
1
+ (A)
1
13
328.0477
1+ (B)
42.0606
3
1
+ (D)
using DMSO-d as solvent and tetramethylsilane as
6
369.3819
1+ (G)
81.0606
1
+ (K)
standard. The high-resolution mass spectra (electrospray
ionization) were obtained on a Bruker Daltonics
MicrOTOF-Q II instrument (Germany); samples were
introduced as solutions in methanol or acetonitrile
3
4
03.0434
320
340
360
380
400 m/z
m/zI
I
I, %
(
c = 0.1 mg/mL) directly into the ion source using
3
14.0321
7656
21283
15259
4279
11047
3968
8401
9696
4348
3717
36.0
a syringe pump (flow rate 3 μL/min); capillary
voltage –4.5 and +4 kV for negative and positive ions,
respectively; nebulizer gas (nitrogen) pressure 0.4 bar
328.0477
100.0
71.7
20.1
51.9
18.6
39.5
45.6
20.4
17.5
3
3
3
3
3
42.0606
45.0712
50.0257
59.0881
64.0425
(
5.8 psi), drying gas flow rate 4.0 L/min; ion source
temperature 180°C; the mass analyzer was calibrated
using a 1% ESI calibration solution (Sigma–Aldrich,
Switzerland) in 95% aqueous acetonitrile; the accuracy
was 0.43 ppm in the a.m.u. range from 118.086255 to
2
721.894829; LC/MS grade solvents with a purity of
369.3819
higher than 98% were used. The electron impact mass
spectra were recorded on a Finnigan SAQ 710 mass
spectrometer (UK) with direct sample admission into
the ion source (70 eV, ion source temperature 150°C).
3
3
81.0604
85.3795
Fig. 1. Mass spectrum of product mixture 12a–12c.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

1850
PANOV et al.
(
Japan); detection at the wavelengths corresponding to
128.96, 135.68, 141.30, 167.16, 168.38. Mass spectrum:
+
absorption maxima; eluent 0.2% ammonium formate
in acetonitrile (pH 4.5). Reagents and solvents were
commercial products.
m/z 300.9296 [M + H] . C H BrClN O . Calculated:
1
0
6
2
2
M + H 300.9374.
3
-(4-Fluoroanilino)-4-(phenylsulfanyl)-1H-pyr-
Compound 6 was synthesized as described in [14].
Compounds 3a and 3b were synthesized according to
the procedure reported in [9].
role-2,5-dione (5a). Compound 4a, 150 mg
(0.53 mmol), was dissolved in 5 mL of DMF, 0.2 mL
(1.81 mmol) of benzenethiol and 0.3 mL (1.72 mmol)
of DIPEA were added, and the mixture was stirred for
3
,4-Bis[(4-methylphenyl)sulfanyl]-1H-pyrrole-
1
2 h at 50°C. The mixture was poured into a mixture of
2
,5-dione (3a). Yield 290 mg (85%), yellow crystals,
1
water and ethyl acetate, the organic layer was separated,
and the aqueous layer was extracted with 20 mL of ethyl
acetate. The extracts were evaporated with addition of
toluene to remove traces of water. The residue was
purified by column chromatography using petroleum
ether–ethyl acetate (5:1) as eluent. Yield 50 mg (30%),
yellow crystals, mp 203–204°C (from EtOAc). HPLC:
mp 104–106°C. H NMR spectrum, δ, ppm: 2.27 s
(
8
2
6H, CH ), 7.09 d (4H, J = 8.1 Hz), 7.16 d (4H, J =
3
1
3
.1 Hz), 11.28 s (1H, NH). C NMR spectrum, δ , ppm:
C
0.65, 125.97, 129.64, 131.08, 136.37, 137.71, 167.42.
+
Mass spectrum: m/z 342.0622 [M + H] . C H NO S .
1
8
15
2 2
Calculated: M + H 342.0617.
1
-Methyl-3,4-bis[(4-methylphenyl)sulfanyl]-1H-
1
τ = 8.4 min, 96.6%. H NMR spectrum, δ, ppm: 7.54–
pyrrole-2,5-dione (3b). Yield 273 mg (77%), yellow
6
.66 m (9H), 9.88 s (1H), 10.92 s (1H). 13C NMR
1
crystals, mp 114–115°C. H NMR spectrum, δ, ppm:
spectrum, δ , ppm: 114.5, 114.73, 125.53, 126.32,
C
2
8
.26 s (6H, CH ), 2.84 s (3H, NCH ), 7.08 d (4H, J =
.1 Hz), 7.15 d (4H, J = 8.1 Hz). C NMR spectrum,
3 3
1
1
26.78, 129.13, 132.85, 136.34, 146.66, 158.9, 161.31,
67.73, 171.96. Mass spectrum: m/z 313.0616 [M – H] .
1
3
–
δC, ppm: 21.12, 24.90, 126.33, 130.11, 131.58,
36.32, 138.27, 166.81. Mass spectrum: m/z 356.0778
C H FN O S. Calculated: M – H 313.0453.
1
6
11
2
2
1
+
3
-(4-Chloroanilino)-4-(phenylsulfanyl)-1H-
[M + H] . C H NO S . Calculated: M + H 356.0773.
19 17 2 2
pyrrole-2,5-dione (5b) was synthesized as described
above for 5a. Yield 31 mg (18%), yellow crystals,
3
-Bromo-4-(4-fluoroanilino)-1H-pyrrole-2,5-
dione (4a). Dibromomaleimide 1a, 2.0 g (7.84 mmol),
was dissolved in 15 mL of anhydrous DMF, and 0.9 mL
1
mp 205–207°C. HPLC: τ = 10.9 min, 96.5%. H NMR
spectrum, δ, ppm: 6.84 d (2H, J = 8.6 Hz), 6.95 d (2H,
J = 8.0 Hz), 7.07–7.16 m (5H), 9.94 s (1H, NH), 10.97 s
(
9.51 mmol) of 4-fluoroaniline and 2 mL (11.5 mmol)
of DIPEA were added. The mixture was stirred for
4 h at 50°C and poured into a mixture of water and
1
3
(
1H, NH). C NMR spectrum, δ , ppm: 125.66, 125.97,
C
2
1
1
26.53, 127.75, 129.11, 129.53, 135.48, 135.74, 145.74,
67.79, 171.81. Mass spectrum: m/z 329.0364 [M – H] .
ethyl acetate. The organic layer was separated, washed
with dilute aqueous HCl, and evaporated under reduced
pressure, and the residue was purified by column
chromatography using petroleum ether–ethyl acetate
–
C H ClN O S. Calculated: M – H 329.0157.
1
6
11
2
2
3-(4-Chloroanilino)-4-(3,4-dimethoxyphenyl-
(
5 : 1) as eluent. Yield 503 mg (22%), pale yellow
crystals, mp 208–210°C; HPLC: τ = 11.09 min, 96%.
sulfanyl)-1H-pyrrole-2,5-dione (5c) was synthesized
as described above for 5a. Yield 62 mg (30%), yellow
crystals, mp 176–181°C (from EtOAc). H NMR spec-
1
1
H NMR spectrum, δ, ppm: 7.15–7.23 m (4H), 9.60 s
1
13
(
1H, 4-NH), 10.96 s (1H, N H). C NMR spectrum,
δC, ppm: 80.39, 114.83 d (J = 22.8 Hz), 126.64 d
J = 8.5 Hz), 132.89, 141.73, 159.63 d (J = 242.0 Hz),
trum, δ, ppm: 3.60 s (1H), 3.65 s (1H), 6.28 s (1H),
6.36 d (1H, J = 8.2 Hz), 6.69 d (1H, J = 8.4 Hz), 6.91 d
(1H, J = 8.7 Hz), 7.19 d (1H, J = 8.7 Hz), 10.55 s (1H,
(
+
13
1
67.04, 168.4. Mass spectrum: m/z 284.9703 [M + H] .
NH). C NMR spectrum, δ, ppm: 55.73, 56.13, 111.68,
C H BrFN O . Calculated: M + H 284.9669.
112.79, 120.43, 125.39, 125.70, 127.76, 128.95, 135.58,
10
6
2
2
1
35.61, 143.75, 147.86, 149.13, 168.08, 171.95. Mass
3
-Bromo-4-(4-chloroanilino)-1H-pyrrole-2,5-
dione (4b) was synthesized in a similar way from
.0 g (7.84 mmol) of 1b and 1.1 g (8.66 mmol)
of 4-chloroaniline in 20 mL of DMF. Yield 1.16 g
45% based on 4-chloroaniline), pale yellow crystals,
spectrum: m/z 391.0577. C H ClN O S. Calculated:
M + H 391.0514.
1
8
15
2
4
2
3-Hydroxy-4-(4-methylphenylsulfanyl)-1H-
pyrrole-2,5-dione (7). 2-(4-Methylphenylsulfanyl)-
acetamide (6), 1.03 g (5.7 mmol), was dissolved in
25 mL of anhydrous DMF, 0.83 g (5.6 mmol) of diethyl
oxalate was added, and 2.5 g (22.3 mmol, 3.9 equiv) of
potassium tert-butoxide was then added in one portion.
(
1
mp 230–235°C (decomp., from EtOAc). H NMR
spectrum, δ, ppm: 7.17 d (2H, J = 8.6 Hz), 7.38 d (2H,
J = 8.6 Hz), 9.68 s (1H, 4-NH), 11.01 s (1H, N H).
C NMR spectrum, δ , ppm: 82.67, 125.81, 128.07,
1
13
C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

SYNTHESIS OF NEW (ARYLSULFANYL)MALEIMIDE DERIVATIVES
1851
The mixture turned yellow and warmed up. After 24 h,
the mixture was treated with 50 mL of 25% aqueous
HCl, kept for 10 min, and extracted with ethyl acetate
reduced pressure, and the residue was purified by
column chromatography using petroleum ether–ethyl
acetate (5:1) as eluent. Yield 73 mg (34%), light beige
1
(2×20 mL). The combined extracts were evaporated,
crystals, mp 163–164°C. H NMR spectrum, δ, ppm:
and the residue was purified by column chromatography
2.15 s (3H, CH ), 2.82 t (2H, CH ), 4.20 t (2H, CH ),
3
2
2
using ethyl acetate–ethanol (10:1) as eluent. Yield
6.84–6.93 m (6H, Harom), 7.04 t (2H, Harom), 11.01 br.s
1
3
9
12 mg (67%), yellow crystals, mp 175–180°C.
(1H, NH). C NMR spectrum, δ , ppm: 20.87, 29.20,
C
1
H NMR spectrum, δ, ppm: 2.18 s (3H, CH ), 6.89 d
53.91, 100.91, 116.12, 123.30, 124.52, 126.24, 127.39
(2C), 129.70 (2C), 131.33, 133.13, 135.43, 141.91,
144.12, 167.70, 170.61. Mass spectrum: m/z 337.1008
3
(
2H, J = 8.1 Hz), 6.97 d (2H, J = 8.1 Hz), 9.66 s
13
(1H, NH). C NMR spectrum, δ , ppm: 20.87, 80.48,
C
+
1
25.17, 129.43, 133.09, 138.26, 169.84, 174.65, 175.62.
[M + H] . C H N O S. Calculated: M + H 337.1005.
1
9
16
2
2
–
Mass spectrum: m/z 234.0168 [M – H] . C H NO S.
1
1
9
3
3,4-Bis[(4-methoxyphenyl)sulfanyl]-1H-pyrrole-
,5-dione (11). Maleimide 8, 80 mg (0.316 mmol), was
Calculated: M – H 234.0230.
2
3
-Chloro-4-(4-methylphenylsulfanyl)-1H-pyr-
dissolved in 10 mL of diethyl ether, and a solution of
150 mg (1.22 mmol) of 4-methoxybenzenethiol and
0.2 mL (1.43 mmol) of triethylamine in 5 mL of diethyl
ether was added in portions over a period of 30 min.
The mixture was heated to the boiling point and was
refluxed for 1 h until the reaction was complete (TLC).
The mixture was evaporated, and the residue was
purified by column chromatography using petroleum
ether–ethyl acetate (3:1) as eluent. Yield 40 mg (34%).
role-2,5-dione (8). Maleimide 7, 82 mg (0.39 mmol),
was dissolved in 5 mL of DMF, and 0.1 mL (1.16 mmol)
of oxalyl chloride was added dropwise with stirring.
After 2 h (complete conversion according to the TLC
data), the mixture was poured into 15 mL of water and
extracted with ethyl acetate (20 mL). The organic layer
was separated and evaporated, and the residue was
purified by column chromatography using petroleum
ether–ethyl acetate (5:1) as eluent. Yield 80 mg (81%),
mp 169–171°C. H NMR spectrum, δ, ppm: 2.30 s
3H, CH ), 7.21 d (2H, J = 7.8 Hz), 7.44 d (2H, J =
.8 Hz), 11.50 s (1H, NH). C NMR spectrum, δ , ppm:
1.21, 123.48, 130.35, 130.53, 133.83, 137.42, 139.70,
1
H NMR spectrum, δ, ppm: 3.74 s (6H, OCH ),
3
1
6.87 d (4H, J = 8.8 Hz), 7.26 d (4H, J = 8.8 Hz),
1
3
(
11.17 br.s (1H, NH). C NMR spectrum, δ , ppm:
3
C
1
3
7
2
1
55.30, 114.70, 119.64, 133.58, 136.13, 159.58, 167.51.
C
+
Mass spectrum: m/z 374.0552 [M + H] . C H NO S .
1
8
15
4 2
–
65.73, 167.10. Mass spectrum: m/z 251.9931 [M – H] .
Calculated: M + H 374.0515.
C H ClNO S. Calculated: M – H 251.9892.
11
8
2
3-(4-Methylanilino)-4-[(4-methylphenyl)sul-
fanyl]-1H-pyrrole-2,5-dione (13a). Maleimide 3a,
341 mg (1 mmol), was dissolved on heating in 3 mL of
p-toluidine, and the mixture was stirred for 2 h at 100°C.
The mixture was poured into water (20 mL), acidified
with aqueous HCl, and extracted with ethyl acetate. The
extract was evaporated under reduced pressure, and
the residue was purified by column chromatography
using petroleum ether–ethyl acetate (3:1) as eluent.
3
-(4-Chloroanilino)-4-(4-methylphenylsulfanyl)-
H-pyrrole-2,5-dione (9). Maleimide 7, 117 mg
0.5 mmol), was dissolved in 10 mL of acetic acid,
0 mg (0.55 mmol) of 4-chloroaniline was added, and
1
(
7
the mixture was refluxed for 3 h with stirring. The
mixture was evaporated under reduced pressure, and the
residue was purified by column chromatography using
petroleum ether–ethyl acetate (3:1) as eluent. Yield
1
1
4
6 mg (26%), mp 224–225°C (from EtOAc). H NMR
Yield 150 mg (46%). H NMR spectrum, δ, ppm: 2.19 s
spectrum, δ, ppm: 2.18 s (3H, CH ), 6.73 d (2H, J =
(3H), 2.22 s (3H), 6.80 d (2H, J = 8.1 Hz), 6.95 m (2H),
3
1
3
8
9
.0 Hz), 6.90–6.97 m (4H), 7.16 d (2H, J = 8.6 Hz),
.86 s (1H, NH), 10.93 s (1H, NH). C NMR spectrum,
9.83 br.s (1H), 10.75 br.s (1H). C NMR spectrum,
δC, ppm: 20.39, 20.50, 88.48, 124.21, 126.31, 128.04,
129.30, 132.80, 133.78, 134.41, 134.51, 146.42,
167.32, 171.43. Mass spectrum: m/z 325.1037
1
3
δC, ppm: 20.89, 91.30, 125.93, 126.95, 127.79, 129.47,
1
1
29.77, 132.12, 135.19, 135.61, 145.45, 167.84,
71.81. Mass spectrum: m/z 345.0440 [M + H] .
+
+
[M + H] . C H N O S. Calculated: M + H 325.1005.
1
8
16
2
2
C H ClN O S. Calculated: M + H 345.0459.
17
13
2
2
N-Methyl-3-(4-methylanilino)-4-[(4-methyl-
phenyl)sulfanyl]-1H-pyrrole-2,5-dione (13b) was
synthesized as described above for 13a. Yield 128 mg
3
-(2,3-Dihydro-1H-indol-1-yl)-4-(4-methyl-
phenylsulfanyl)-1H-pyrrole-2,5-dione (10). Male-
imide 7, 150 mg (0.64 mmol), was dissolved in 10 mL
of acetic acid, 100 mg (0.84 mmol) of 2,3-dihydro-1H-
indole was added, and the mixture was refluxed for
1
(38%). H NMR spectrum, δ, ppm: 2.19 s (3H), 2.22 s
(3H), 2.93 s (3H), 6.82 d (2H, J = 7.0 Hz), 6.95 m (6H),
1
3
9.98 s (1H, NH). C NMR spectrum, δ , ppm: 20.45,
C
1
h with stirring. The mixture was evaporated under
20.55, 24.09, 87.19, 124.31, 126.27, 128.09, 129.35,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 12 2019

1852
PANOV et al.
1
32.85, 133.77, 134.45, 134.72, 146.56, 166.26, 170.66.
6. Szűcs, Z., Bereczki, I., Csávás, M., Rőth, E., Borbás, A.,
Batta, G., Ostorházi, E., Szatmári, R., and Herczegh, P.,
J. Antibiot., 2017, vol. 70, p. 664.
+
Mass spectrum: m/z 339.1185 [M + H] . C H N O S.
Calculated: M + H 339.1162.
1
9
18
2
2
https://doi.org/10.1038/ja.2017.2
FUNDING
7. Igarashi, Y. and Watanabe, S., J. Ind. Microbiol., 1992,
vol. 9, p. 91.
This study was performed under financial support by the
Russian Science Foundation (project no. 16-15-10300P).
8. Lakatosh, S.A., Trenin, A.S., Simonov, A.Yu.,
Lavrenov, S.N., Bychkova, O.P., and Tsvigun, E.A.,
Antibiot. Khimioter., 2017, vol. 62, p. 3.
CONFLICT OF INTERESTS
The authors declare the absence of conflict of interests.
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