A Simple and Efficient Synthesis of Fused Benzo[ b ]thiophene Derivatives

Article abstract of DOI:10.1055/a-1416-4924

A new approach to the synthesis of fused benzothiophene derivatives was developed based on iodine-promoted photocyclization of 4,5-diaryl-substituted thiophenes obtained in three steps from commercially available compounds. Comparative analysis showed that photochemical cyclization is a more efficient method for the preparation of fused benzo[ b ]thiophene derivatives, compared to oxidative coupling of 4,5-diaryl-substituted thiophenes in the presence of iron(III) chloride and palladium-catalyzed intramolecular arylation. This new approach provides an efficient synthesis of functionally substituted naphtho[2,1- b:3,4- b ′]dithiophenes, phenanthro[9,10- b ]thiophenes, benzo[1,2- b:3,4- b ′:6,5- b ′′]trithiophenes, as well as new fused heterocycles containing a pyridine ring and/or a carbazole moiety.

Full text of DOI:10.1055/a-1416-4924

SYNTHESIS
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Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart
2021, 53, 2422–2434
paper
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E. B. Ulyankin et al.
Paper
Synthesis
A Simple and Efficient Synthesis of Fused Benzo[b]thiophene
Derivatives
Evgeny B. Ulyankina,b
Anastasia S. Kostyuchenkoa,b
Sergey A. Chernenkoa,b
Mikhail O. Bystrushkina,b
Anna L. Samsonenkoa,b
Anton L. Shatsauskasa,b
Alexander S. Fisyuk*a,b
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a Department of Organic Chemistry, Omsk F. M. Dostoevsky State
University, Mira Ave. 55a, 644077 Omsk, Russian Federation
fisyuk@chemomsu.ru
b Laboratory of New Organic Materials, Omsk State Technical
University, Mira Ave. 11, 644050 Omsk, Russian Federation
Corresponding Author
Received: 28.01.2021
Accepted after revision: 08.03.2021
Published online: 08.03.2021
However, this approach has a number of disadvantages as-
sociated with a limited availability of building blocks, the
toxicity and high cost of transition metal catalysts, the use
of ligands, and the laborious product purification steps.
An alternative to this approach is the oxidative C–H/C–H
coupling,1a,13 and oxidative photocyclization.14 Despite the
large number of Ar–Ar bond formation strategies,15 the de-
velopment of methods for photochemical C–H/C–H cou-
pling for the synthesis of FBTDs are of interest because of
their greater environmental friendliness and high atom
economy, since they allow exclusion of metal catalysis, the
use of ligands, and the preliminary introduction of func-
tionalities into the starting reactants. The main problem
preventing the development of this method is the limited
availability of the starting compounds.12a,16 However, the
FBTD precursors 18a–k can be obtained in three steps
starting from commercially available compounds (Table 1).
We adopted a similar approach that has been used to syn-
thesize 2,2′-bithiophenes derivatives.17 Such substituted
2,2′-bithiophenes containing a long alkyl chain at the C(3)
position are widely used in the synthesis of donor-acceptor
organic semiconductors,5,18 materials for LEDs,19 and thin-
film transistors.20
DOI: 10.1055/a-1416-4924; Art ID: ss-2021-t0038-op
Abstract A new approach to the synthesis of fused benzothiophene
derivatives was developed based on iodine-promoted photocyclization
of 4,5-diaryl-substituted thiophenes obtained in three steps from
commercially available compounds. Comparative analysis showed that
photochemical cyclization is a more efficient method for the prepara-
tion of fused benzo[b]thiophene derivatives, compared to oxidative
coupling of 4,5-diaryl-substituted thiophenes in the presence of iron(III)
chloride and palladium-catalyzed intramolecular arylation. This new ap-
proach provides an efficient synthesis of functionally substituted naph-
tho[2,1-b:3,4-b′]dithiophenes, phenanthro[9,10-b]thiophenes, benzo-
[1,2-b:3,4-b′:6,5-b′′]trithiophenes, as well as new fused heterocycles
containing a pyridine ring and/or a carbazole moiety.
Key words heterocycles, fused-ring systems, photochemistry, cycliza-
tion, molecular electronics
Fused benzothiophene derivatives (FBTDs) are an im-
portant class of compounds.1 Interest in these heterocycles
is due to their unique electronic and photophysical proper-
ties.2 Due to the planar structure, molecular packing
through -stacking interactions and high mobility of charge
carriers, they are widely used in organic electronics3 as ma-
terials for LEDs,2c,4 thin-film transistors,2a,5 and organic
photovoltaics.6 This structural motif is a part of helicenes7
and nanographenes.8 Among these compounds, of particu-
lar interest are phenanthro[9,10-b]thiophene (1),2b,c,9 naph-
tho[2,1-b:3,4-b′]dithiophene (2),10 and benzo[1,2-b:3,4-
b′:6,5-b′′]trithiophene (3)2d,11 (Figure 1).
Ketones 16a–k were synthesized in 38–92% yield by re-
acting an aromatic or heteroaromatic precursor 4–9 with
the corresponding arylacetic acid 10–15. The resulting ke-
S
The most popular methods for their synthesis are based
on cross-coupling reactions catalyzed by transition met-
als.1,12 This approach allows one to selectively obtain and
modify complex organic molecules under mild conditions.
S
S
S
S
S
1
2
3
Figure 1 Fused benzo[b]thiophene derivatives
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

2423
E. B. Ulyankin et al.
Paper
Synthesis
tones 16a–k were converted into acrylaldehydes 17a–k
through the Vilsmeier–Haack reaction. Compounds 17a–k
were formed as mixtures of Z- and E-isomers in 64–94%
yields. Further reaction of compounds 17a–k with methyl
mercaptoacetate in basic medium led to the formation of
methyl 4,5-diarylthiophene-2-carboxylates 18a–k in yield
of 60–88% (Table 1).
Table 1 Synthesis of Compounds 16–18a
OHC
Cl
S
Ar
CO2Me
i
ii
Ar1
iii
Ar1CH2COX
Ar
Ar–H
Ar1
+
Ar
Ar1
O
4–9
10–15
16a–k
17a–k
18a–k
Entry
Substrate (Method) Product
Ar
Ar1
Yield (%)
16
17
18
I
MeO
4 + 10
(A)
1
2
a
79
45
85
60
S
S
MeO
MeO
4 + 11
(A)
b
78
80
MeO
MeO
5 + 11
(B)
3
4
5
c
60
38
92
89
94
92
88
85
63
C6H13
S
MeO
6 + 12
d
(B)
C10H21
S
4 + 13
e
(A)
S
5 + 13
(A)
6
7
8
f
84
81
86
64
65
91
84
86
85
C6H13
S
4 + 14
(A)
g
S
S
MeO
MeO
C9H19
O
I
7 + 10
h
(A)
C9H19
O
C6H13
N
MeO
MeO
8 + 11
(B)
9
10
11
i
61
68
53
78
86
77
65
80
73
C6H13
N
9 + 15
(C)
j
N
C6H13
N
9 + 14
(D)
k
S
a Reaction conditions: (i) Method A [X = OH]: (CF3CO)2O, H+; Method B [X = Cl]: SnCl4; Method C [X = OH]: Ac2O; Method D [X = Cl]: EtAlCl2, 38–92%; (ii) DMF,
POCl3, r.t. or 60–70 °C, 64–94%; (iii) HSCH2CO2Me, NaOMe, MeOH, Δ, 60–88%.
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

2424
E. B. Ulyankin et al.
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Synthesis
In order to select the optimal pathway for the synthesis
of FBTDs, we performed the intramolecular cyclization of
18a and 18b under various conditions (Scheme 1). It was
found that the ring closure in compound 18а proceeded in
the presence of 10 mol% Pd(PPh3)4 upon heating at 130 °C in
DMF for 4 hours with the formation of naphthobithiophene
19a in a yield of 42% (route 1). The oxidative coupling of
compound 18b in the presence of FeCl3 (route 2) in DCM at
room temperature resulted in the formation of 19a in a
yield of 75%. However, in this case, resinification of the re-
action mixture was observed.
The absorption bands of compounds 18a, 18b and the
cyclization product 19a lie in the region from 200 to 410
nm, overlapping in the entire range. To irradiate compounds
18, a 365 nm LED was used as a light source (Figure 2). UV
irradiation of a THF solution of compound 18а for 10 hours
at room temperature resulted in the formation of naph-
thodithiophene 19a in 86% yield (route 3). At the same
time, iodine-promoted cyclization of compound 18b in a
THF solution furnished naphthodithiophene 19a in a yield
of 91% (route 4).
The reaction progress was monitored by HPLC and TLC
methods. The reaction time was in the range of 6–60 hours,
and the yields of the target compounds reached 61–95%.
Substituted thiophenes 18a, e–i, k containing donor aro-
matic substituents reacted faster than 18c, j. Since both
compounds 18 and 19 absorb light in the 365 nm range, the
reaction proceeds more slowly as the cyclization product
accumulates. In most cases, compounds 19 were the sole
reaction products. Only in the case of FBTDs 19i and 19j
were trace amounts of isomeric by-products detected. The
structures of the new compounds were confirmed by 1H
and 13C NMR data, including COSY and NOESY correlation
spectra, IR spectroscopy, and elemental analysis.
In conclusion, a new approach to the efficient synthesis
of fused benzothiophene derivatives was developed, based
on iodine-promoted photocyclization of methyl 4,5-diar-
ylthiophene-2-carboxylates obtained in three steps from
commercially available compounds. This one provides a
simple way for the synthesis of benzothiophenes fused
with different carbo- and heterocycles. Thus a series of
naphtho[2,1-b:3,4-b']dithiophenes,
phenanthro[9,10-
The latter method was used to synthesize FBTDs 19c–k,
since it did not require preliminary preparation of iodinat-
ed precursors and gave the target compounds in high yields
(Scheme 2).
b]thiophenes, benzo[1,2-b:3,4-b′:6,5-b′′]trithiophenes, and
new fused heterocycles containing a pyridine core and/or
carbazole fragment were prepared in good yields.
MeO
MeO
MeO
OMe
MeO
OMe
365 nm, 40 W
2 (20 mol%)
hν, THF, r.t.
c = 10 mM
91% (10 h)
365 nm, 40 W
I
hν, THF, r.t.
c = 10 mM
86% (10 h)
I
4
3
10 mol% Pd(PPh3)4
KOAc, DMF
FeCl3, CH2Cl2
r.t.; c = 5 mM
75% (3 h)
S
S
S
S
S
S
18b
CO2Me
CO2Me
CO2Me
130 °C, 4 h, 42%
18a
19a
1
2
Scheme 1 Synthesis of naphtho[2,1-b:3,4-b′]dithiophene-2-carboxylate 19a
Figure 2 Absorption spectra of compounds 18a + 19a (left) and 18b + 19a (right) in THF solution (c = 4·10–6 M)
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

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E. B. Ulyankin et al.
Paper
Synthesis
Ar1
hν, 365 nm, 40 W
THF, I2 (20 mol%)
MeO2C
Ar
19a, c–k
S
18a–k
H3CO
OCH3
S
S
S
S
R
CO2Me
C10H21
CO2Me
S
S
R
CO2Me
19a (86% from 18a, 91% from 18b),
R = H, 10 h; 19c (95%), R = C6H13,15 h
19d (61%), 60 h
19e (93%), R = H; 12 h
19f (72%), R = C6H13; 14 h
MeO
OMe
MeO
OMe
S
N
C9H19O
C6H13
S
S
19i (84%), 7 h
S
CO2Me
S
CO2Me
CO2Me
C9H19O
19g (80%), 6 h
19h (85%), 8 h
N
S
C6H13
C6H13
N
N
S
CO2Me
S
CO2Me
19k (84%), 8 h
19j (78%), 20 h
Scheme 2 Synthesis of fused benzothiophene derivatives 19a,c–k
crude product was purified by column chromatography (silica gel, n-
hexane); yield: 50.68 g (74%); colorless oil.
The IR spectra were recorded on an Infralum FT-801 spectrometer in
KBr pellets for solid or in thin films for liquid compounds. HPLC was
carried out at Agilent 1200 series chromatograph with UV-VIS detec-
tor using MeCN/H2O as eluent. The 1H and 13C NMR spectra were ob-
tained in CDCl3, using a Bruker DRX 400 spectrometer (400 and 101
MHz, respectively). The 13C NMR spectra were obtained in the J-mod-
ulation mode. The elemental analyses were carried out on a Carlo
Erba 1106 CHN analyzer. The melting points were determined on the
REACH Devices RD-MP apparatus. The reaction course and purity of
the products were checked by TLC on Sorbfil UV-254 plates, which
were visualized with UV light (254, 365 nm). Photochemical experi-
ments were carried out with 2 irradiators with 4 × UV/LED chips (365
nm, 5W, Chanzon 5W) each at quartz tubes, and the reaction was
cooled by using a fan. Total power of photoreactor was 40 W. The dis-
tance from the light source to the irradiation vessel was about 3 cm.
All chemicals were of analytical grade and purchased from Sigma-Al-
drich Chemical Co. Compounds 8,21 9,22 16b, and 17b17a were synthe-
sized according to the described procedures and showed identical
spectroscopic properties.
IR (thin film): 2923, 2854, 1592, 1500, 1468, 1252, 1222, 1122, 1042,
736 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 6.88–6.92 (m, 4 H, H-3, 4, 5, 6), 4.00 (t,
3J = 6.65 Hz, 4 H, 2 × OCH2), 1.80–1.85 (m, 4 H, OCH2CH2), 1.23–1.57
[m, 24 H, CH3(CH2)6], 0.88–0.92 (m, 6 H, 2 × CH3).
13C NMR (CDCl3, 101 MHz):  = 149.3, 121.0, 114.2, 69.3, 31.9, 29.6,
29.5, 29.4, 29.3, 26.1, 22.7, 14.1.
Anal. Calcd for C24H42O2: C, 79.50; H, 11.68. Found: C, 79.55; H, 11.64.
(2-Iodo-4,5-dimethoxyphenyl)acetic Acid (10)
To a solution of 3,4-dimethoxyphenylacetic acid (11; 2.00 g, 10.2
mmol) and N-iodosuccinimide (2.43 g, 10.8 mmol) in AcOH (32 mL)
was added dropwise concd H2SO4 (1.08 mL) and the reaction mixture
was stirred 1 h at r.t. The precipitate formed was filtered, washed
with sat. aq Na2S2O3 and recrystallized from H2O/EtOH (20:1) and
dried using azeotrope water distillation with benzene in a Dean–
Stark apparatus; yield: 2.10 g (64%); pink solid; mp 156–157 °С (Lit.23
mp 161–164 °С).
1,2-Bis(nonyloxy)benzene (7)
Catechol (20.92 g, 0.19 mol) and 1-iodononane (76 mL, 0.42 mol)
were placed in a flask fitted with reflux condenser and dropping fun-
nel. The contents of the flask was heated at 90 °C with stirring, fol-
lowed by dropwise addition of a solution of KOH (35.30 g, 0.63 mol)
in EtOH (160 mL) over 2 h. The reaction mixture was refluxed for 1 h
more, cooled to r.t. and H2O (300 mL) was added. The organic layer
was washed with H2O (200 mL), dried (MgSO4), and concentrated. The
IR (KBr): 3546, 3334, 2967, 2937, 2843, 1727 (С=О), 1601, 1505, 1464,
1414, 1257, 1219, 1156, 1026, 858, 677, 600 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.24 (s, 1 H, H-3′), 6.80 (s, 1 H, H-6′),
3.85, 3.86 (s each, 3 H each, OCH3), 3.78 (s, 2 H, CH2).
13C NMR (CDCl3, 101 MHz):  = 176.6, 149.5, 149.0, 129.4, 121.9,
113.5, 89.0, 56.2, 56.1, 45.4.
Anal. Calcd for C10H11IO4: C, 37.29; H, 3.44. Found: C, 37.50; H, 3.50.
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

2426
E. B. Ulyankin et al.
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Synthesis
1,2-Diaryl-Substituted Ethanones 16a–k; General Procedures
13C NMR (CDCl3, 101 MHz):  = 189.6, 149.5, 148.8, 143.9, 133.9,
Method A (for 16a,b,e–h):24 A mixture of acid 10–11, 13, 14 (6.7
mmol), thiophene 4 (1.75 g, 20.8 mmol) or the aromatic compound 5,
7 (6.7 mmol), 85% H3PO4 (0.41 mL, 6.7 mmol), and anhyd (distilled
from P2O5) MeCN (30 mL) was stirred at 50 °C, then a solution of tri-
fluoroacetic anhydride (5.36 g, 25.5 mmol) in anhyd MeCN (10 mL)
was rapidly added. The reaction mixture was stirred at 50 °C for an
additional 3 h. Then it was cooled to r.t. and H2O was added. The
product was extracted with EtOAc (3 × 20 mL) and the combined or-
ganic layers were washed with aq NaHCO3, and dried (Na2SO4). In the
next step, the solvent was evaporated under reduced pressure, using a
rotary evaporator. The resulting crude products were purified by col-
umn chromatography (silica gel, benzene/EtOAc 20:1).
132.5, 130.4, 128.2, 121.8, 113.5, 89.2, 56.2, 56.0, 50.5.
Anal. Calcd for C14H13IO3S: C, 43.31; H, 3.38. Found: C, 43.28; H, 3.41.
2-(3,4-Dimethoxyphenyl)-1-(5-hexylthiophen-2-yl)ethan-1-one
(16c)
Method B; yield: 17.88 g (60%); red liquid.
IR (thin film): 2929, 2855, 1650 (С=О), 1514, 1453, 1263, 1237, 1142,
1028 cm–1
.
3
1H NMR (CDCl3, 400 MHz):  = 7.60 (d, J = 3.72 Hz, 1 H, H-3′), 6.78–
6.87 (m, 4 H, H-2′′, H-5′′, H-6′′, H-4′), 4.07 [s, 2 H, C(O)CH2], 3.84, 3.86
(s each, 3 H each, OCH3), 2.82 [t, 3J = 7.63 Hz, 2 H, CH3(CH2)4CH2],
1.63–1.72 [m, 2 H, CH3(CH2)3CH2], 1.25–1.38 [m, 6 H, CH3(CH2)3],
0.86–0.91 (m, 3 H, Alkyl CH3).
Method B (for 16c,d, i): A mixture of arylacetic acid 11 or 12 (86
mmol) and SOCl2 (12.40 mL, 171 mmol) in absolute benzene (15 mL)
was stirred at r.t. for 40 min and then at 55 °C for 2 h. Excess of SOCl2
and benzene were evaporated under low pressure. After that, absolute
CH2Cl2 (150 mL) and the respective aromatic compound 5–6, 8 (86
mmol) were added to the resulting chloroanhydride, and then SnCl4
(86 mmol) was added using a dropping funnel under ice-bath cooling.
The mixture was cooled for 1 h and stirred at r.r. for 2 h. Aq 2 M HCl
(20 mL) and H2O (200 mL) were slowly added to the mixture. The or-
ganic layer was separated and the aqueous layer was extracted by
CH2Cl2 (3 × 50 mL). The combined organic phases were washed with
H2O, sat. aq NaHCO3, and again H2O, dried (Na2SO4), and concentrated.
The resulting product was purified by flash chromatography over sili-
ca gel using benzene/EtOAc (20:1) as eluent.
13C NMR (CDCl3, 101 MHz):  = 190.3, 156.2, 149.0, 148.0, 141.1,
132.9, 127.1, 125.5, 121.5, 112.5, 111.3, 55.8, 45.4, 31.4, 31.2, 30.6,
28.6, 22.4, 13.9.
Anal. Calcd for C20H26O3S: C, 69.33; H, 7.56. Found: C, 69.36; H, 7.62.
1-(5-Decylthiophen-2-yl)-2-phenylethan-1-one (16d)
Method B; yield: 11.19 g (38%); brown liquid.
IR (thin film): 2924, 2851, 1667 (С=О), 1466, 1232, 1063, 936, 817,
722, 697, 586, 560 cm–1
.
3
1H NMR (CDCl3, 400 MHz):  = 7.57 (d, J = 3.72 Hz, 1 H, H-3′), 7.18–
7.33 (m, 5 H, H-2′′, 3′′, 4′′, 5′′, 6′′), 6.76 (d, 3J = 3.72 Hz, 1 H, H-4′), 4.09
[s, 2 H, C(O)CH2], 2.78 (t, 3J = 7.63 Hz, 2 H, C-5′-CH2), 1.59–1.70 (m, 2
H, C-5′-CH2CH2), 1.16–1.37 [m, 14 H, CH3(CH2)7], 0.86 (t, 3J = 6.75 Hz, 3
H, Alkyl CH3).
Method C (for 16j): A mixture of 3-pyridylacetic acid hydrochloride
(15; 4.00 g, 23 mmol) in Ac2O (15 mL) was stirred in a sealed vial at 90
°C for 1 h, then N-hexylindole (9; 6.03 g, 30 mmol) was added and the
stirring continued at 90 °C for 2 h. The mixture was cooled, H2O (100
mL) and EtOAc (50 mL) were added. The organic layer was separated,
washed with sat. aq NaHCO3 and brine, dried (Na2SO4), and concen-
trated. The resulting product was purified using flash chromatogra-
phy over silica gel using n-hexane/EtOAc (20:1) as eluent.
13C NMR (CDCl3, 101 MHz):  = 190.0, 156.3, 141.3, 134.7, 133.0,
129.3, 128.6, 126.8, 125.6, 45.9, 31.8, 31.3, 30.6, 29.5, 29.4, 29.2, 29.0,
22.6, 14.0.
Anal. Calcd for C22H30OS: C, 77.14; H, 8.83. Found: C, 77.08; H, 8.75.
Method D (for 16k): A mixture of 2-thienylacetic acid 14 (12.23 g, 86
mmol) and SOCl2 (12.40 mL, 171 mmol) in absolute benzene (15 mL)
was stirred at r.t. for 40 min and then at 55 °C for 2 h. The excess of
SOCl2 and benzene were evaporated under low pressure. After that,
absolute CH2Cl2 (150 mL) and N-hexylindole (9; 17.31 g, 86 mmol)
were added to the resulting chloroanhydride, followed by EtAlCl2 (1 M
in hexane, 86 mL, 86 mmol) using a dropping funnel under ice-bath
cooling. The mixture was cooled for 1 h and stirred at r.t. for 2 h. Aq 2
M HCl (20 mL) and H2O (200 mL) were slowly added to the mixture.
The organic layer was separated and the aqueous layer was extracted
with CH2Cl2 (3 × 50 mL). The combined organic phases were washed
with H2O, sat. aq NaHCO3, and again H2O, dried (Na2SO4), and concen-
trated. The resulting product was purified using flash chromatogra-
phy over silica gel, using benzene/EtOAc (20:1) as eluent.
2-(Naphthalen-1-yl)-1-(thiophen-2-yl)ethan-1-one (16e)25,26
Method A; yield: 1.56 g (92%); white solid; mp 71–72 °С.
IR (KBr): 3104, 2902, 1670 (С=О), 1510, 1408, 1236, 1212, 1059, 851,
785, 722, 578 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 8.02–8.08 (m, 1 H, H-8′′), 7.90–7.96 (m,
1 H, H-5′′), 7.82–7.89 (m, 2 H, H-3′, 2′′), 7.62 (dd, 3J = 5.05 Hz, 4J = 1.17
3
Hz, 1 H, H-5′), 7.45–7.58 (m, 4 H, H-3′′, 4′′, 6′′, 7′′), 7.11 (dd, J = 5.05
Hz, 3J = 3.81 Hz, 1 H, H-4′), 4.67 (s, 2 H, CH2).
13C NMR (CDCl3, 101 MHz)  = 190.2, 143.6, 133.8, 133.7, 132.4, 132.1,
130.9, 128.6, 128.2, 128.0, 127.9, 126.2, 125.6, 125.3, 123.8, 43.8.
Anal. Calcd for C16H12OS: C, 76.16; H, 4.79. Found: C, 76.19; H, 4.82.
1-(5-Hexylthiophen-2-yl)-2-(naphthalen-1-yl)ethan-1-one (16f)
Method A; yield: 1.89 g (84%); yellow solid; mp 67–68 °С.
2-(2-Iodo-4,5-dimethoxyphenyl)-1-(thiophen-2-yl)ethan-1-one
(16a)
IR (KBr): 3095, 3049, 2952, 2922, 2849, 1647 (С=О), 1450, 1225, 1061,
Method A; yield: 2.05 g (79%); light-yellow solid; mp 109–110 °С.
935, 817, 788 cm–1
.
IR (KBr): 2961, 2903, 2837, 1665 (С=О), 1596, 1509, 1411, 1257, 1215,
1H NMR (CDCl3, 400 MHz):  = 7.99–8.03 (m, 1 H, H-8′′), 7.86–7.89 (m,
1 H, H-5′′), 7.81 (dd, 3J = 6.46 Hz, 4J = 3.13 Hz, 1 H, H-2′′), 7.69 (d, 3J =
3.82 Hz, 1 H, H-3′), 7.42–7.55 (m, 4 H, H-3′′, 4′′, 6′′, 7′′), 6.82 (d, 3J =
3.82 Hz, 1 H, H-4′), 4.62 [s, 2 H, C(O)CH2], 2.84 [t, 3J = 7.63 Hz, 2 H,
CH3(CH2)4CH2], 1.66–1.74 [m, 2 H, CH3(CH2)3CH2], 1.30–1.41 [m, 6 H,
CH3(CH2)3], 0.89–0.93 (m, 3 H, Alkyl CH3).
1164, 1020, 858, 722, 579 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.85 (dd, 3J = 3.81 Hz, 4J = 1.11 Hz, 1 H,
H-3′), 7.65 (dd, 3J = 4.96 Hz, 4J = 1.11 Hz, 1 H, H-5′), 7.25 (s, 1 H, H-3′′),
7.11–7.17 (m, 1 H, H-4′), 6.81 (s, 1 H, H-6′′), 4.32 (s, 2 H, CH2), 3.81–
3.86 (m, 6 H, 2 × OCH3).
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

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Synthesis
13C NMR (CDCl3, 101 MHz):  = 190.1, 156.2, 141.2, 133.9, 132.8,
132.3, 131.3, 128.7, 128.1, 127.9, 126.3, 125.7, 125.6, 125.4, 124.0,
43.6, 31.4, 31.8, 30.7, 28.7, 22.5, 14.0.
IR (thin film): 2928, 2857, 1640 (С=О), 1523, 1465, 1383, 1211, 1183,
1133, 1060, 744, 710 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 8.61 (br s, 1 H, H-2′′), 8.50 (d, 3J = 4.11
Hz, 1 H, H-6′′), 8.38 (d, 3J = 7.43 Hz, 1 H, H-4′), 7.86 (s, 1 H, H-2′), 7.78
(d, 3J = 7.04 Hz, 1 H, H-4′′), 7.28–7.39 (m, 4 H, H-5′, 6′, 7′, 5′′), 4.13–
4.20 [m, 4 H, C(O)CH2, NCH2], 1.88 (d, 3J = 6.06 Hz, 2 H, NCH2CH2), 1.33
[br s, 6 H, CH3(CH2)3], 0.89 (br s, 3 H, CH3).
13C NMR (CDCl3, 101 MHz):  = 190.9, 149.5, 147.1, 138.0, 136.9,
134.8, 131.9, 126.5, 123.6, 123.5, 122.8, 122.6, 115.8, 109.9, 47.3,
43.35, 31.23, 29.8, 26.5, 22.4, 13.9.
Anal. Calcd for C22H24OS: C, 78.53; H, 7.19. Found: C, 78.61; H, 7.14.
1,2-Di(thiophen-2-yl)ethan-1-one (16g)
Method A; yield: 1.13 g (81%); light-yellow liquid (Lit.27 colorless oil).
IR (thin film): 3102, 1656 (С=О), 1517, 1411, 1219, 1058, 853, 694,
576 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.81 (dd, 3J = 3.81 Hz, 4J = 1.17 Hz, 1 H,
H-3′), 7.66 (dd, 3J = 4.89 Hz, 4J = 1.17 Hz, 1 H, H-5′), 7.21–7.24 (m, 1 H,
H-4′), 7.14 (dd, 3J = 4.99 Hz, 3J = 3.81 Hz, 1 H, H-4′′), 6.97–6.99 (m, 2 H,
H-3′′, 5′′), 4.40 (s, 2 H, CH2).
13C NMR (CDCl3, 101 MHz):  = 188.7, 143.1, 135.2, 134.3, 132.7,
128.2, 126.8, 126.8, 125.0, 40.1.
Anal. Calcd for C21H24N2O: C, 78.71; H, 7.55; N, 8.74. Found: C, 78.76;
H, 7.48; N, 8.71.
1-(1-Hexyl-1H-indol-3-yl)-2-(thiophen-2-yl)ethan-1-one (16k)
Method D; yield: 14.83 g (53%); yellow liquid.
IR (thin film): 2928, 2856, 1640 (С=О), 1524, 1465, 1384, 1211, 1181,
Anal. Calcd for C10H8OS2: C, 57.66; H, 3.87. Found: C, 57.71; H, 3.84.
1134, 1059, 743, 692 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 8.44 (dd, 3J = 6.65 Hz, 4J = 2.54 Hz, 1 H,
H-4′), 7.82 (s, 1 H, H-2′), 7.29–7.39 (m, 3 H, H-3′′, 6′, 7′), 7.21 (dd, 3J =
4.89 Hz, 4J = 1.57 Hz, 1 H, H-5′′), 6.95–7.01 (m, 2 H, H-4′′, 5′), 4.35 [s, 2
H, C(O)CH2], 4.16 (t, 3J = 7.09 Hz, 2 H, NCH2), 1.89 (t, 3J = 7.09 Hz, 2 H,
NCH2CH2), 1.29–1.37 [m, 6 H, CH3(CH2)3], 0.88–0.93 (m, 3 H, CH3).
13C NMR (CDCl3, 101 MHz):  = 190.8, 137.2, 136.8, 134.7, 126.8,
126.7, 126.2, 124.5, 123.4, 122.8, 122.7, 115.5, 109.8, 47.2, 40.8, 31.3,
29.8, 26.5, 22.4, 13.9.
1-[3,4-Bis(nonyloxy)phenyl]-2-(2-iodo-4,5-dimethoxyphe-
nyl)ethan-1-one (16h)
Method A; yield: 3.84 g (86%); white solid; mp 110–111 °С.
IR (KBr): 2923, 2850, 1672 (С=О), 1583, 1511, 1466, 1426, 1271, 1260,
1218, 1167, 1143, 1031, 873, 800 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.65 (dd, 3J = 8.41 Hz, 4J = 2.05 Hz, 1 H,
H-6′), 7.54 (d, 4J = 2.05 Hz, 1 H, H-2′), 7.24 (s, 1 H, H-3′′), 6.88 (d, J =
3
8.41 Hz, 1 H, H-5′), 6.74 (s, 1 H, H-6′′), 4.32 [s, 2 H, C(O)CH2], 4.04 [q,
3J = 6.46 Hz, 4 H, 2 × CH3(CH2)7CH2], 3.79, 3.84 (s each, 3 H each,
OCH3), 1.76–1.88 [m, 4 H, 2 × CH3(CH2)6CH2], 1.27–1.46 (m, 24 H, 2 ×
CH3(CH2)6], 0.81–0.94 (m, 6 H, 2 × Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 195.5, 153.7, 149.4, 148.9, 148.5,
131.2, 129.5, 123.0, 121.6, 113.2, 112.8, 111.7, 89.1, 69.3, 69.0, 56.1,
55.9, 49.6, 31.9, 29.5, 29.3, 29.2, 29.1, 29.0, 26.0, 25.9, 22.6, 14.1.
Anal. Calcd for C21H24N2O: C, 73.81; H, 7.12; N, 4.30. Found: C, 73.86;
H, 7.18; N, 4.41.
3-Chloro-2,3-diarylacrylaldehydes 17a–k; General Procedure
POCl3 (3.54 g, 23.1 mmol) was added to DMF (20 mL) at 0 °C and the
mixture was stirred for 30 min at the same temperature. In the next
step, a solution of ketone 16a–k (5.9 mmol) in DMF (5 mL) was added
dropwise. The reaction mixture was heated at 60–65 °C for 5 h or
stirred at r.t. for 12 h (for 16g, j, k). Then the solution was poured onto
crushed ice (50 g) in H2O (150 mL) and extracted with EtOAc (3 × 20
mL). The combined organic layers were washed with sat. aq NaOAc
and dried (Na2SO4). The solvent was evaporated under reduced pres-
sure and the crude product was purified by column chromatography
on silica gel using benzene/EtOAc (20:1) as eluent.
Anal. Calcd for C34H51IO5: C, 61.25; H, 7.71. Found: C, 61.22; H, 7.76.
2-(3,4-Dimethoxyphenyl)-1-(9-hexyl-9H-carbazol-3-yl)ethan-1-
one (16i)
Method B; yield: 22.53 g (61%); light-yellow solid; mp 94–95 °С
IR (KBr): 2946, 2928, 2864, 2843, 1677 (С=О), 1592, 1514, 1469, 1358,
1339, 1261, 1235, 1186, 1137, 1028, 997, 812, 755 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 8.82 (d, 4J = 1.76 Hz, 1 H, H-4′), 8.17
(dd, 3J = 8.61 Hz, 4J = 1.76 Hz, 1 H, H-2′), 8.14 (d, 3J = 7.82 Hz, 1 H, H-
5′), 7.51 (t, 3J = 7.82 Hz, 1 H, H-7′), 7.43 (d, 3J = 8.22 Hz, 1 H, H-5′′), 7.39
(E/Z)-3-Chloro-2-(2-iodo-4,5-dimethoxyphenyl)-3-(thiophen-2-
yl)acrylaldehyde [(E/Z)-17a]
3
(d, J = 7.82 Hz, 1 H, H-8′), 7.30 (t, 3J = 7.82 Hz, 1 H, H-6′), 6.87–6.91
E/Z ratio = 1:4; yield: 2.18 g (85%); yellow solid; mp 112–113 °С.
(m, 2 H, H-2′′, 6′′), 6.83 (d, 3J = 8.61 Hz, 1 H, H-1′), 4.35 [s, 2 H,
C(O)CH2], 4.29 (t, 3J = 7.29 Hz, 2 H, NCH2), 3.87 (s, 3 H, C-3′-OCH3),
3.85 (s, 3 H, C-4′-OCH3), 1.86 (dt, 2J = 14.67 Hz, 3J = 7.29 Hz, 2 H,
NCH2CH2), 1.33–1.40 [m, 2 H, CH3(CH2)2CH2], 1.26–1.33 [m, 4 H,
CH3(CH2)2], 0.86 (t, 3J = 7.04 Hz, 3 H, Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 197.2, 149.0, 147.9, 143.2, 141.1,
128.0, 127.9, 126.7, 126.4, 123.1, 122.6, 122.1, 121.5, 120.5, 119.9,
112.6, 111.4, 109.2, 108.3, 55.9, 45.0, 43.3, 31.5, 28.8, 26.9, 22.5,
13.91.
IR (KBr): 2958, 2839, 1676 (С=О), 1595, 1570, 1503, 1250, 1171, 1023,
929, 865, 841, 723 cm–1
.
1H NMR (CDCl3, 400 MHz):  (Z) = 10.53 (s, 1 H, CHO), 7.64 (dd, 3J =
4.01 Hz, 4J = 1.17 Hz, 1 H, H-3′), 7.46 (dd, 3J = 5.09, 4J = 1.17 Hz, 1 H, H-
3
3
5′), 7.34 (s, 1 H, H-3′′), 7.01 (dd, J = 5.09 Hz, J = 4.01 Hz, 1 H, H-4′),
6.60 (s, 1 H, H-6′′), 3.92 (s, 3 H, С-4′′-OCH3), 3.79 (s, 3 H, C-5′′-OCH3);
 (E) = 9.91 (s, 1 H, CHO), 7.69 (dd, 3J = 5.09 Hz, 4J = 1.17 Hz, 1 H, H-5′),
7.48 (dd, 3J = 4.01 Hz, 4J = 1.17 Hz, 1 H, H-3′), 7.31 (s, 1 H, H-3′′), 7.16
(dd, 3J = 5.09 Hz, 3J = 4.01 Hz, 1 H, H-4′), 6.66 (s, 1 H, H-6′′), 3.89 (s, 3 H,
С-4′′-OCH3), 3.86 (s, 3 H, С-5′′-OCH3).
Anal. Calcd for C28H31NO3: C, 78.29; H, 7.27; N, 3.26. Found: C, 78.38;
H, 7.35; N, 3.31.
13C NMR (CDCl3, 101 MHz):  = 190.2, 188.2, 150.6, 150.4, 149.6,
149.6, 143.6, 138.4, 137.8, 136.3, 133.4, 133.7, 133.4, 132.7, 131.4,
128.3, 127.6, 127.0, 122.1, 121.5, 113.7, 113.0, 89.4, 87.3, 56.2, 56.1.
1-(1-Hexyl-1H-indol-3-yl)-2-(pyridin-3-yl)ethan-1-one (16j)
Method C; yield: 5.01 g (68%); red liquid.
Anal. Calcd for C15H12ClIO3S: C, 41.45; H, 2.78. Found: C, 41.20; H,
2.80.
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

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Synthesis
(E/Z)-3-Chloro-2-(3,4-dimethoxyphenyl)-3-(5-hexylthiophen-2-
yl)acrylaldehyde [(E/Z)-17c]
13C NMR (CDCl3, 101 MHz):  = 191.1, 189.1, 143.4, 139.9, 138.6,
138.1, 134.1, 133.5, 133.7, 133.3, 132.7, 132.4, 131.9, 131.8, 131.7,
130.9, 129.8, 129.1, 128.8, 128.7, 128.6, 127.6, 127.5, 126.9, 126.6,
126.6, 126.3, 126.0, 126.0, 125.3, 124.6, 124.1.
E/Z ratio = 1:4; yield: 2.06 g (89%); yellow liquid.
IR (thin film): 2929, 2855, 1700 (С=О), 1514, 1463, 1259, 1141, 1027
cm–1
.
Anal. Calcd for C17H11ClOS: C, 68.34; H, 3.71. Found: C, 68.48; H, 3.83.
1H NMR (CDCl3, 400 MHz):  (Z) = 10.51 (s, 1 H, CHO), 7.35 (d, 3J = 3.91
(E/Z)-3-Chloro-3-(5-hexylthiophen-2-yl)-2-(naphthalen-1-
yl)acrylaldehyde [(E/Z)-17f]
3
3
Hz, 1 H, H-3′), 6.94 (d, J = 8.22 Hz, 1 H, H-5′′), 6.70 (dd, J = 8.22 Hz,
4J = 1.96 Hz, 1 H, H-6′′), 6.64 (d, 3J = 3.91 Hz, 1 H, H-4′), 6.62 (d, 4J =
1.96 Hz, 1 H, H-2′′), 3.81, 3.93 (s each, 3 H each, OCH3), 2.65 [t, 3J =
7.53 Hz, 2 H, CH3(CH2)4CH2], 1.53 [d, 3J = 7.53 Hz, 2 H, CH3(CH2)3CH2],
1.21–1.43 [m, 9 H, CH3(CH2)3], 0.85–0.89 (m, 3 H, Alkyl CH3);  (E) =
9.88 (s, 1 H, CHO), 7.20 (d, 3J = 3.91 Hz, 1 H, H-3′), 6.92 (d, 3J = 8.22 Hz,
1 H, H-5′′), 6.83 – 6.86 (m, 1 H, H-6′′), 6.79–6.81 (m, 2 H, H-2′′, H-4′),
3.87, 3.90 (s each, 3 H each, OCH3), 2.65 [t, 3J = 7.53 Hz, 2 H,
CH3(CH2)4CH2], 1.53 [d, 3J = 7.53 Hz, 2 H, CH3(CH2)3CH2], 1.21–1.44 [m,
9 H, CH3(CH2)3], 0.85–0.91 (m, 4 H, Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 191.3, 189.8, 154.9, 153.8, 149.8,
149.7, 149.1, 148.6, 143.2, 139.7, 136.1, 136.0, 133.8, 133.7, 133.0,
126.8, 126.2, 124.7, 124.3, 123.1, 122.8, 113.3, 113.3, 111.9, 110.9,
55.9, 55.8, 55.8, 31.4, 31.3, 31.2, 31.0, 30.4, 30.1, 28.6, 28.5, 22.4, 22.4,
13.9, 13.9.
E/Z ratio = 1:3; yield: 1.45 g (64%); yellow liquid.
IR (thin film): 2927, 2853, 1668 (С=О), 1561, 1447, 1301, 1126, 995,
818, 784 cm–1
.
1H NMR (CDCl3, 400 MHz):  (Z) = 10.72 (s, 1 H, CHO), 7.97 (d, 3J = 8.22
Hz, 1 H, H-5′′), 7.88–7.94 (m, 1 H, H-4′′), 7.62 (d, 3J = 8.61 Hz, 1 H, H-
8′′), 7.53–7.58 (m, 1 H, H-7′′), 7.46–7.50 (m, 1 H, H-2′′), 7.39–7.43 (m,
3
1 H, H-3′′), 7.30–7.33 (m, 1 H, H-6′′), 7.29 (d, J = 4.11 Hz, 1 H, H-3′),
6.55 (d, 3J
= 4.11 Hz, 1 = 7.53 Hz, 2 H,
H, H-4′), 2.51 [t, 3J
CH3(CH2)4CH2], 1.13–1.49 [m, 8 H, CH3(CH2)4], 0.83–0.88 (m, 3 H, Al-
kyl CH3);  (E) = 10.15 (s, 1 H, CHO), 7.88–7.94 (m, 3 H, H-2′′, 4′′, 5′′),
7.62 (d, 3J = 8.61 Hz, 1 H, H-8′′), 7.53–7.58 (m, 1 H, H-7′′), 7.39–7.46–
7.50 (m, 1 H, H-3′), 7.33–7.36 (m, 2 H, H-3′′, 6′′), 6.89 (d, 3J = 4.11 Hz, 1
3
H, H-4′), 2.92 [t, J = 7.63 Hz, 2 H, CH3(CH2)4CH2], 1.13–1.49 [m, 8 H,
CH3(CH2)4], 0.90–0.94 (m, 3 H, Alkyl CH3).
Anal. Calcd for C21H25ClO3S: C, 64.19; H, 6.41. Found: C, 64.46; H, 6.22.
13C NMR (CDCl3, 101 MHz):  = 191.2, 189.3, 155.4, 154.1, 143.8,
138.8, 135.7, 135.4, 134.0, 133.9, 133.9, 133.7, 132.7, 132.0, 131.9,
131.4, 130.9, 130.3, 129.7, 129.0, 128.8, 128.7, 128.5, 127.6, 126.7,
126.5, 126.2, 126.0, 125.3, 125.0, 124.7, 124.3, 124.2, 31.4, 31.3, 30.8,
30.5, 30.0, 29.7, 28.8, 28.4, 22.5, 22.4, 14.0, 14.0.
(E/Z)-3-Chloro-3-(5-decylthiophen-2-yl)-2-phenylacrylaldehyde
[(E/Z)-17d]
E/Z ratio = 2:1; yield: 1.47 g (94%); yellow liquid.
IR 2916, 2849, 1672 (С=О), 1567, 1444, 1298, 1084, 805, 710, 559 cm–1
.
Anal. Calcd for C23H23ClOS: C, 72.14; H, 6.05. Found: C, 72.03; H, 6.12.
1H NMR (CDCl3, 400 MHz):  (Z) = 10.54 (s, 1 H, CHO), 7.28–7.48 (m, 3
H, H-3′′, 4′′, 5′′), 7.26 (m, 1 H, H-3′), 7.12 (dd, 3J = 6.55 Hz, 4J = 2.84 Hz,
2 H, H-2′′, 6′′), 6.64 (d, 3J = 3.72 Hz, 1 H, H-4′), 2.65 (t, 3J = 7.63 Hz, 1 H,
C-5′-CH2), 1.64–1.80 (m, 2 H, C-5′-CH2CH2), 1.18–1.60 [m, 14 H,
CH3(CH2)7], 0.88–0.92 (m, 3 H, CH3);  (E) = 9.92 (s, 1 H, CHO), 7.28–
7.48 (m, 5 H, H-2′′, 3′′, 4′′, 5′′, 6′′), 7.24 (d, 3J = 3.72 Hz, 1 H, H-3′), 6.82
(d, 3J = 3.72 Hz, 1 H, H-4′), 2.88 (t, 3J = 7.63 Hz, 2 H, C-5 ′-CH2), 1.64–
1.80 (m, 2 H, C-5′-CH2CH2), 1.18–1.34 [m, 14 H, CH3(CH2)7], 0.88–0.92
(m, 3 H, CH3).
13C NMR (CDCl3, 101 MHz):  = 191.2, 189.6, 154.8, 153.9, 147.3,
140.0, 139.9, 136.3, 135.8, 134.5, 134.2, 133.9, 133.9, 133.4, 130.4,
129.9, 129.2, 129.0, 128.4, 128.2, 124.8, 124.5, 31.9, 31.4, 31.0, 30.5,
30.1, 29.6, 29.5, 29.5, 29.5, 29.3, 29.2, 29.1; 28.9, 22.7, 14.1.
(E/Z)-3-Chloro-2,3-di(thiophen-2-yl)acrylaldehyde [(E/Z)-17g]
E/Z ratio = 23:27; yield: 0.98 g (65%); yellow solid; mp 53–54 °С.
IR (KBr): 3106, 1680 (С=О), 1565, 1413, 1257, 1243, 851, 766, 717 cm–1
.
1H NMR (CDCl3, 400 MHz):  (E) = 10.53 (s, 1 H, CHO), 7.56 (dd, 3J =
5.09 Hz, 4J = 1.17 Hz, 1 H, H-5′), 7.48–7.52 (m, 2 H, H-3′, 5′′), 7.11–7.16
(m, 1 H, H-4′′), 7.00 (dd, 3J = 5.09 Hz, 3J = 3.91 Hz, 1 H, H-4′), 6.96 (dd,
3J = 3.62 Hz, 4J = 1.08 Hz, 1 H, H-3′′);  (Z) = 9.81 (s, 1 H, CHO), 7.67 (dd,
J = 5.09 Hz, 1.08 Hz, 1 H, H-5′′), 7.59 (dd, J = 3.91 Hz, 1.17 Hz, 1 H, H-
3′), 7.48–7.52 (m, 1 H, H-5′), 7.32 (dd, J = 3.62 Hz, 1.08 Hz, 1 H, H-3′′),
7.11–7.16 (m, 2 H, H-4′′, 4′).
13C NMR (CDCl3, 101 MHz):  = 190.2, 188.9, 144.7, 144.6, 139.1,
138.7, 133.9, 133.8, 133.7, 133.6, 133.4, 132.0, 130.5, 130.2, 129.0,
128.1, 127.8, 127.5, 126.9, 126.5.
Anal. Calcd for C23H29ClOS: C, 71.02; H, 7.51. Found: C, 70.95; H, 7.62.
(E/Z)-3-Chloro-2-(naphthalen-1-yl)-3-(thiophen-2-yl)acrylalde-
hyde [(E/Z)-17e]
Anal. Calcd for C11H7ClOS2: C, 51.86; H, 2.77. Found: C, 51.98; H, 2.81.
E/Z ratio = 1:2; yield: 1.62 g (92%); yellow solid; mp 65–66 °C.
(E/Z)-3-[3,4-Bis(nonyloxy)phenyl]-3-chloro-2-(2-iodo-4,5-dime-
thoxyphenyl)acrylaldehyde [(E/Z)-17h]
IR (KBr): 3059, 1667 (С=О), 1593, 1574, 1422, 1119, 992, 868, 825,
806, 783, 744, 709 cm–1
.
E/Z ratio = 89:11; yield: 3.83 g (91%); yellow liquid.
1H NMR (CDCl3, 400 MHz):  (Z) = 10.74 (s, 1 H, CHO), 7.98 (d, 3J = 7.84
Hz, 1 H, H-5′′), 7.87–7.94 (m, 1 H, H-4′′), 7.46–7.66 (m, 5 H, H-5′, 2′′,
3′′, 7′′, 8′′), 7.31 (dd, 3J = 7.84 Hz, 4J = 1.17 Hz, 1 H, H-6′′), 7.22 (dd, 3J =
5.09 Hz, 4J = 1.27 Hz, 1 H, H-3′), 6.83 (dd, 3J = 5.09 Hz, 3J = 3.91 Hz, 1 H,
H-4′);  (E) = 10.12 (s, 1 H, CHO), 7.87–7.94 (m, 3 H, H-2′′, 4′′, 5′′), 7.69
(dd, 3J = 5.09 Hz, 4J = 1.27 Hz, 1 H, H-5′), 7.46–7.66 (m, 2 H, H-3′, 8′′),
7.37–7.43 (m, 1 H, H-3′′, 7′′), 7.35 (dd, 3J = 7.84 Hz, 4J = 1.17 Hz, 1 H, H-
6′′), 7.18 (dd, 3J = 5.09 Hz, 3J = 3.72 Hz, 1 H, H-4′).
IR (thin film): 2923, 2853, 1674 (С=О), 1594, 1504, 1439, 1261, 1208,
1173, 1140, 1027, 777, 734 cm–1
.
1H NMR (CDCl3, 400 MHz):  (Z) = 10.51 (s, 1 H, CHO), 7.22 (s, 1 H, H-
6′′), 7.07 (dd, 3J = 8.51 Hz, 4J = 2.25 Hz, 1 H, H-6′), 6.81 (d, 4J = 2.25 Hz,
1 H, H-2′), 6.73 (d, 3J = 8.51 Hz, 1 H, H-5′), 6.40 (s, 1 H, H-3′′), 4.04–
4.10 (m, 4 H, 2 × OCH2), 3.86–3.92 (m, 6 H, 2 × OCH3), 1.83–1.90 (m, 4
H, 2 × OCH2CH2), 1.30–1.55 [m, 24 H, 2 × CH3(CH2)6], 0.88–0.92 (m, 6
H, 2 × Alkyl CH3);  (E) = 9.67 (s, 1 H, CHO), 7.32 (s, 1 H, H-6′′), 7.18
4
(dd, 3J = 8.51 Hz, 4J = 2.25 Hz, 1 H, H-6′), 7.16 (d, J = 2.25 Hz, 1 H, H-
2′), 6.93 (d, 3J = 8.51 Hz, 1 H, H-5′), 6.67 (s, 1 H, H-3′′), 4.04–4.10 (m, 4
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Synthesis
H, 2 × OCH2), 3.86, 3.92 (s each, 3 H each, OCH3), 1.83–1.90 (m, 4 H, 2
× OCH2CH2), 1.30–1.55 [m, 24 H, 2 × CH3(CH2)6], 0.88-0.92 (m, 6 H, 2 ×
Alkyl CH3).
(E/Z)-3-Chloro-3-(1-hexyl-1H-indol-3-yl)-2-(thiophen-2-yl)acryl-
aldehyde [(E/Z)-17k]
E/Z ratio = 1:4; yield: 1.69 g (77%); yellow oil.
13C NMR (CDCl3, 101 MHz):  = 188.94, 156.99, 152.18, 149.55,
149.42, 149.06, 142.78, 132.75, 127.43, 124.57, 121.33, 114.96,
112.91, 112.21, 87.45, 69.55, 69.22, 56.14, 56.04, 31.89, 29.56, 29.40,
29.37, 29.26, 29.21, 29.09, 26.01, 22.67, 14.08..
IR (thin film): 2926, 2856, 1664 (С=О), 1555, 1515, 1465, 1389, 1359,
1244, 1178, 1135, 740, 696 cm–1
.
1H NMR (CDCl3, 400 MHz):  (Z) = 9.71 (s, 1 H, CHO), 7.96 (d, 3J = 8.02
Hz, 1 H, H-4′), 7.47–7.51 (m, 2 H, H-5′, 5′′), 7.41–7.46 (m, 2 H, H-2′, 7′),
7.34–7.39 (m, 1 H, H-6′), 7.28–7.33 (m, 1 H, H-3′′), 7.16 (dd, 3J = 5.09
Hz, 3J = 3.72 Hz, 1 H, H-4′′), 4.18 (t, 3J = 7.24 Hz, 2 H, NCH2), 1.73–1.83
(m, 2 H, NCH2CH2), 1.26–1.41 [m, 6 H, CH3(CH2)3], 0.89–0.93 (m, 3 H,
CH3);  (E) = 10.54 (s, 1 H, CHO), 7.47–7.51 (m, 1 H, H-4′), 7.41–7.46
(m, 1 H, H-5′′), 7.28–7.33 (m, 1 H, H-7′), 7.21–7.25 (m, 2 H, H-2′, 5′),
7.06–7.11 (m, 1 H, H-6′), 6.92–6.95 (m, 1 H, H-3′′), 6.89–6.92 (m, 1 H,
Anal. Calcd for C35H50ClIO5: C, 58.95; H, 7.07. Found: C, 59.03; H, 7.22.
(E/Z)-3-Chloro-2-(3,4-dimethoxyphenyl)-3-(9-hexyl-9H-carbazol-
3-yl)acrylaldehyde [(E/Z)-17i]
E/Z ratio = 41:9; yield: 2.19 g (78%); yellow solid; mp 138–139 °С.
IR (KBr): 2928, 2869, 1672 (С=О), 1592, 1512, 1461, 1221, 1145, 1029,
3
H-4′′), 3.97 (t, J = 7.04 Hz, 2 H, NCH2), 1.65–1.75 (m, 2 H, NCH2CH2),
809, 751, 733 cm–1
.
1.18–1.33 [m, 6 H CH3(CH2)3], 0.81–0.85 (m, 3 H, CH3).
1H NMR (CDCl3, 400 MHz):  (Z) = 10.65 (s, 1 H, CHO), 8.25 (d, 4J = 1.66
13C NMR (CDCl3, 101 MHz):  = 190.2, 189.2, 149.1, 136.9, 136.3,
135.3, 134.3, 133.6, 131.8, 129.7, 129.3, 127.1, 127.0, 126.8, 126.7,
126.5, 126.0, 123.6, 122.8, 121.7, 121.5, 121.4, 121.1, 112.0, 110.4,
110.0, 47.1, 47.0, 31.3, 29.9, 29.7, 29.6, 26.6, 26.4, 22.4, 13.9.
Hz, 1 H, H-4′), 8.00 (d, 3J = 7.63 Hz, 1 H, H-5′), 7.45–7.58 (m, 3 H, H-5′′,
3
7′), 7.40 (d, J = 8.22 Hz, 1 H, H-2′), 7.29–7.34 (m, 1 H, H-6′), 7.12 (d,
3
3
3J = 9.39 Hz, 1 H, H-8′), 6.75 (d, J = 8.22 Hz, 1 H, H-1′), 6.67 (dd, J =
8.41 Hz, 4J = 1.86 Hz, 1 H, H-6′′), 6.57 (d, 4J = 1.86 Hz, 1 H, H-2′′), 4.23
(s, 2 H, NCH2), 3.82 (s, 3 H, C-8′′-OCH3), 3.61 (s, 3 H, C-7′′-OCH3), 1.88–
1.97 (m, 2 H, NCH2CH2), 1.26–1.48 [m, 6 H, CH3(CH2)3], 0.85–0.93 (m,
3 H, Alkyl CH3);  (E) = 9.74 (s, 1 H, CHO), 8.32 (d, 4J = 1.66 Hz, 1 H, H-
4′), 8.14 (d, 3J = 7.63 Hz, 1 H, H-5′), 7.71 (dd, 3J = 8.22 Hz, 4J = 1.66 Hz, 1
H, H-2′), 7.45–7.58 (m, 3 H, H-5′′, 6′′, 7′), 7.29–7.34 (m, 1 H, H-6′),
6.90–7.01 (m, 3 H, H-1′, 8′, 2′′), 4.35 (t, 3J = 7.24 Hz, 2 H, NCH2), 3.94,
3.95 (s each, 3 H each, OCH3), 1.88–1.97 (m, 2 H, NCH2CH2), 1.26–1.48
[m, 6 H, CH3(CH2)3], 0.85–0.93 (m, 3 H, Alkyl CH3).
Anal. Calcd for C21H22ClNOS: C, 67.82; H, 5.96; N, 3.77. Found: C,
67.75; H, 5.88; N, 3.72.
Methyl 2,3-Diarylthiophene-5-carboxylates 18a–k; General Proce-
dure
A mixture of NaOMe (270 mg, 5.0 mmol), methyl mercaptoacetate
(530 mg, 5.0 mmol), and compound 17a–k (4.1 mmol) in MeOH (20
mL) was heated under reflux for 3 h. The solvent was evaporated un-
der reduced pressure; the resulting solid residue was dissolved in H2O
(7 mL) and EtOAc (15 mL). The organic extract was washed with brine
(30 mL), dried (Na2SO4), and concentrated. The product was purified
by column chromatography on silica gel using benzene/EtOAc (20:1)
as eluent.
13C NMR (CDCl3, 101 MHz):  = 191.8, 190.7, 156.6, 152.0, 148.0,
148.7, 141.8, 141.1, 141.0, 140.9, 139.4, 128.0, 127.7, 127.7, 127.2,
127.1, 126.7, 126.3, 126.2, 123.6, 123.4, 122.8, 122.7, 122.6, 122.4,
120.7, 120.4, 119.9, 119.7, 114.1, 113.4, 110.9, 111.0, 109.2, 109.1,
108.6, 107.9, 55.9, 55.8, 55.7, 43.4, 43.2, 31.5, 31.4, 28.9, 28.8, 26.9,
26.8, 22.5, 13.9.
Methyl 3-(2-Iodo-4,5-dimethoxyphenyl)-[2,2′-bithiophene]-5-car-
boxylate (18a)
Anal. Calcd for C29H30ClNO3: C, 73.17; H, 6.35; N, 2.94. Found: C,
73.06; H, 6.65; N, 3.02.
Yield: 1.20 g (60%); yellow solid; mp 149–150 °С.
(E/Z)-3-Chloro-3-(1-hexyl-1H-indol-3-yl)-2-(pyridin-3-yl)acrylal-
dehyde [(E/Z)-17j]
IR (KBr): 3085, 2943, 2834, 1719, 1699 (С=О), 1500, 1454, 1433, 1288,
1251, 1212, 1173, 1080, 1027, 860, 706 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.60 (s, 1 H, H-4), 7.33 (s, 1 H, H-4′′),
E/Z ratio = 41:9; yield: 1.86 g (86%); red solid; mp 117–119 °С.
3
7.20 (d, 3J = 5.09 Hz, 1 H, H-5′), 7.10 (d, J = 3.52 Hz, 1 H, H-3′), 6.89–
IR (KBr): 1666 (С=О) cm–1
.
6.96 (m, 1 H, H-4′), 6.77 (s, 1 H, H-6′′), 3.91, 3.93 (s each, 3 H each,
ArOCH3), 3.79 (s, 3 H, CO2CH3).
13C NMR (CDCl3, 101 MHz):  = 162.4, 149.6, 149.5, 140.6, 140.4,
136.4, 134.9, 132.6, 129.4, 127.2, 127.1, 126.6, 121.3, 113.4, 88.7, 56.1,
56.0, 52.2.
1H NMR (CDCl3, 400 MHz):  (Z) = 10.46 (s, 1 H, CHO), 8.31–8.34 (m, 1
H, H-6′′), 8.26 (s, 1 H, H-2′′), 7.93 (s, 1 H, H-2′), 7.47 (d, 3J = 7.82 Hz, 1
H, H-4′), 7.28–7.38 (m, 2 H, H-4′′, 5′′), 7.09–7.15 (m, 1 H, H-5′), 6.95–
7.01 (m, 1 H, H-6′), 6.92 (br s, 1 H, H-7′), 3.89 (t, 3J = 7.14 Hz, 2 H,
NCH2), 1.62 (br s, 2 H, NCH2CH2), 1.13–1.25 [m, 6 H, CH3(CH2)3], 0.81
(t, 3J = 6.16 Hz, 3 H, CH3);  (E) = 9.70 (s, 1 H, CHO), 8.51–8.56 (m, 2 H,
H-2′′, 6′′), 7.83 (d, 3J = 8.02 Hz, 1 H, H-4′′), 7.61–7.66 (m, 1 H, H-4′),
7.41 (s, 1 H, H-2′), 7.28–7.38 (m, 2 H, H-5′, 5′′), 7.16–7.23 (m, 2 H, H-
6′, 7′), 4.11 (t, 3J = 7.14 Hz, 2 H, NCH2), 1.82 (d, 3J = 7.14 Hz, 2 H,
NCH2CH2), 1.13–1.25 [m, 6 H, CH3(CH2)3], 0.81 (t, 3J = 6.16 Hz, 3 H,
CH3).
Anal. Calcd for C18H15IO4S2: C, 44.45; H, 3.11. Found: C, 44.50; H, 3.02.
Methyl 3-(3,4-Dimethoxyphenyl)-[2,2′-bithiophene]-5-carboxyl-
ate (18b)
Yield: 1.18 g (80%); yellow solid; mp 116–117 °С.
IR (KBr): 3097, 2831, 1697 (С=О), 1607, 1585, 1549, 1520, 1450, 1302,
13C NMR (CDCl3, 101 MHz):  = 190.3, 189.2, 151.6, 150.8, 150.6,
148.3, 147.8, 138.4, 137.8, 137.8, 136.9, 135.0, 133.6, 133.3, 131.1,
128.3, 126.8, 123.7, 123.2, 123.0, 121.9, 121.5, 121.3, 120.8, 111.2,
110.5, 110.2, 47.1, 47.0, 31.2, 31.2, 29.8, 29.5, 26.5, 26.3, 22.4, 13.9.
844, 821, 765, 751, 722, 626, 605 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.71 (s, 1 H, H-4), 7.20 (dd, 3J = 5.09 Hz,
4
4J = 1.12 Hz, 1 H, H-5′), 7.05 (dd, 3J = 3.58 Hz, J = 1.12 Hz, 1 H, H-3′),
6.91 (dd, 3J = 5.09 Hz, 3J = 3.58 Hz, 1 H, H-4′), 6.88 (dd, 3J = 8.22 Hz, 4J =
1.76 Hz 1 H, H-6′′), 6.83 (d, 3J = 8.22 Hz 1 H, H-5′′), 6.81 (d, 4J = 1.76 Hz,
1 H, H-2′′), 3.86; 3.87 (s, 6 H, 2 × ArOCH3), 3.73 (s, 3 H, CO2CH3).
Anal. Calcd for C22H23ClN2O: C, 72.02; H, 6.32; N, 7.64. Found: C,
72.05; H, 6.27; N, 7.62.
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

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Synthesis
13C NMR (CDCl3, 101 MHz):  = 162.2, 148.7, 148.6, 139.0, 137.9,
136.0, 134.8, 130.2, 127.5, 127.3, 127.1, 126.8, 121.4, 112.2, 111.0,
55.6, 55.5, 52.0.
1H NMR (CDCl3, 400 MHz):  = 7.89–7.97 (m, 2 H, H-5′′, 4′′), 7.69–7.74
(m, 1 H, H-2′′), 7.61–7.66 (m, 1 H, H-3′′), 7.38–7.54 (m, 4 H, H-3′, 4′,
8′′, 4), 6.75 (t, 3J = 4.11 Hz, 1 H, H-6′′), 6.46–6.48 (m, 1 H, H-7′′), 3.87–
3.98 (m, 3 H, CO2CH3), 2.50–2.61 (m, 2 H, C-5′-CH2), 1.46 (br s, 2 H, C-
5′-CH2CH2), 1.15–1.39 [m, 6 H, CH3(CH2)3], 0.85 (m, 3 H, Alkyl CH3).
Anal. Calcd for C18H16O4S2: C, 59.98; H, 4.47. Found: C, 60.01; H, 4.54.
13C NMR (CDCl3, 101 MHz):  = 162.6, 148.0, 141.5, 137.6, 136.0,
133.7, 133.3, 132.4, 132.3, 129.0, 128.7, 128.3, 128.1, 126.6, 126.4,
126.0, 125.5, 125.5, 124.2, 52.2, 31.4, 31.2, 29.8, 28.6, 22.5, 14.0.
Methyl 3-(3,4-Dimethoxyphenyl)-5′-hexyl-[2,2′-bithiophene]-5-
carboxylate (18c)
Yield: 1.60 g (88%); yellow solid; mp 52–53 °С.
Anal. Calcd for C26H26O2S2: C, 71.85; H, 6.03. Found: C, 71.82; H, 6.05.
IR (KBr): 2929, 2845, 1711 (С=О), 1509, 1466, 1283, 1244, 1170, 1141,
1107, 1074, 1029, 796, 750 cm–1
.
Methyl [2,2′:3′,2′′-Terthiophene]-5′-carboxylate (18g)
Yield: 1.08 g (86%); yellow solid; mp 98–99 °С.
1H NMR (CDCl3, 400 MHz):  = 7.71 (s, 1 H, H-4), 6.93 (dd, 3J = 8.32 Hz,
4J = 1.96 Hz, 1 H, H-6′′), 6.90 (d, 3J = 3.52 Hz, 1 H, H-4′), 6.87 (d, 3J =
8.32 Hz, 1 H, H-5′′), 6.86 (d, 4J = 1.96 Hz, 1 H, H-2′′), 6.62 (d, 3J = 3.52
Hz, 1 H, H-3′), 3.90, 3.92 (s each, 3 H each, OCH3), 3.78 (s, 3 H,
CO2CH3), 2.72 [t, 3J = 7.34 Hz, 2 H, CH3(CH2)4CH2], 1.61 [t, 3J = 7.34 Hz,
2 H, CH3(CH2)3CH2], 1.25–1.38 [m, 6 H, CH3(CH2)3], 0.86–0.90 (m, 3 H,
Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 162.5, 148.8, 148.8, 148.1,0 138.9,
138.4, 136.3, 132.3, 129.7, 128.0, 127.3, 124.3, 121.6, 112.5, 111.2,
55.8, 52.1, 31.4, 31.4, 30.0, 28.6, 22.5, 14.0.
IR (KBr): 3073, 2954, 1714 (С=О), 1513, 1453, 1245, 1172, 1093, 1077,
710 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.82 (s, 1 H, H-4′), 7.35 (dd, 3J = 4.99 Hz,
4J = 1.08 Hz, 1 H, H-5), 7.32 (dd, 3J = 4.99 Hz, 4J = 1.08 Hz, 1 H, H-5′′),
7.19 (dd, 3J = 3.62 Hz, 4J = 1.08 Hz, 1 H, H-3), 7.07 (dd, 3J = 3.62 Hz, 4J =
1.08 Hz, 1 H, H-3′′), 7.01–7.05 (m, 2 H, H-4, 4′′), 3.92 (CO2CH3).
13C NMR (CDCl3, 101 MHz):  = 162.3, 138.7, 136.1, 135.8, 134.0,
132.3, 131.0, 128.5, 127.7, 127.4, 127.2, 126.2, 52.3.
Anal. Calcd for C24H28O4S2: C, 64.83; H, 6.35. Found: C, 64.87; H, 6.41.
Anal. Calcd for C14H10O2S3: C, 54.88; H, 3.29. Found: C, 54.92; H, 3.33.
Methyl 5′-Decyl-3-phenyl-[2,2′-bithiophene]-5-carboxylate (18d)
Yield: 1.60 g (85%); yellow liquid.
Methyl 5-[3,4-Bis(nonyloxy)phenyl]-4-(2-iodo-4,5-dimethoxyphe-
nyl)thiophene-2-carboxylate (18h)
IR (thin film): 2927, 2848, 1710 (С=О), 1468, 1438, 1286, 1111, 1075,
Yield: 2.67 g (85%); white solid; mp 47–48 °С.
870, 796, 777, 765, 752, 699, 558 cm–1
.
IR (KBr): 2923, 2853, 1709 (С=О), 1600, 1547, 1505, 1455, 1442, 1244,
1H NMR (CDCl3, 400 MHz):  = 7.73 (s, 1 H, H-4), 7.35–7.40 (m, 5 H,
C6H5), 6.87 (d, 3J = 3.62 Hz, 1 H, H-4′), 6.62 (d, 3J = 3.62 Hz, 1 H, H-3′),
3.91 (s, 3 H, CO2CH3), 2.72 (t, 3J = 7.53 Hz, 2 H, C-5′-CH2), 1.62 (s, 2 H,
C-5′-CH2CH2), 1.22–1.38 [m, 14 H, CH3(CH2)7], 0.88–0.93 (m, 3 H, Al-
kyl CH3).
13C NMR (CDCl3, 101 MHz):  = 162.5, 148.1, 139.4, 138.5, 136.4,
135.5, 132.2, 129.9, 129.3, 128.5, 127.8, 127.3, 124.4, 52.1, 31.9, 31.4,
30.0, 29.5, 29.5, 29.3, 29.0, 22.7, 14.1.
1215, 1139, 1031, 864, 804, 753, 699, 619 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.68–7.73 (m, 1 H, H-3), 7.07–7.28 (m,
1 H, H-2′′), 6.82–6.87 (m, 1 H, H-6′′), 6.71–6.77 (m, 2 H, H-5′′, 3′),
3
6.63–6.69 (m, 1 H, H-6′), 3.96 (t, J = 6.75 Hz, 2 H, C-3′′-OCH2), 3.86–
3.93 (m, 6 H, 2 × ArOCH3), 3.67–3.77 (m, 5 H, C-4′′-OCH2, CO2CH3),
1.65–1.85 (m, 4 H, 2 × OCH2CH2), 1.22–1.48 [m, 24 H, 2 × CH3(CH2)6],
0.85, 0.92 (s each, 3 H each, Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 162.6, 149.4, 149.3, 149.2, 149.1,
148.6, 148.6, 148.4, 147.6, 147.3, 139.9, 136.9, 136.8, 136.7, 133.9,
129.4, 129.3, 129.2, 125.8, 125.7, 121.3, 121.1, 121.1, 115.4, 114.2,
114.1, 113.7, 113.6, 113.6, 113.2, 88.1, 69.0, 68.9, 56.1, 55.9, 52.1,
31.9, 31.8, 29.5, 29.5, 29.4, 29.3, 29.2, 29.1, 29.0, 26.0, 25.9, 22.6, 14.1.
Anal. Calcd for C26H32O2S2: C, 70.87; H, 7.32. Found: C, 70.82; H, 7.30.
Methyl 3-(Naphthalen-1-yl)-[2,2′-bithiophene]-5-carboxylate
(18e)
Anal. Calcd for C38H53IO6S: C, 59.68; H, 6.99. Found: C, 59.72; H, 7.03.
Yield: 0.90 g (63%); light-yellow solid; mp 116–117 °С.
IR (KBr): 3088, 2943, 1709 (С=О), 1442, 1281, 1260, 1175, 1080, 841,
803, 782, 754, 707 cm–1
.
Methyl 4-(3,4-Dimethoxyphenyl)-5-(9-hexyl-9H-carbazol-3-
yl)thiophene-2-carboxylate (18i)
1H NMR (CDCl3, 400 MHz):  = 7.91–7.96 (m, 2 H, H-4′′, 5′′), 7.76 (s, 1
Yield: 1.41 g (65%); yellow liquid.
3
H, H-4), 7.63 (d, J = 8.41 Hz, 1 H, H-2′′), 7.38–7.55 (m, 4 H, H-3′′, 6′′,
7′′, 8′′), 7.03 (d, 3J = 4.99 Hz, 1 H, H-5′), 7.00 (d, 3J = 3.93 Hz, 1 H, H-3′),
6.80 (dd, 3J = 4.99 Hz, 3J = 3.91 Hz, 1 H, H-4′), 3.94 (s, 3 H, CH3).
IR (thin film): 2929, 1706 (С=О), 1512, 1437, 1241, 1026, 746, 730
cm–1
.
13C NMR (CDCl3, 101 MHz):  = 162.5, 140.8, 137.4, 136.8, 135.1,
133.7, 133.1, 132.3, 129.8, 128.8, 128.3, 128.1, 127.0, 126.9, 126.7,
126.5, 126.1, 125.5, 125.4, 52.2.
1H NMR (CDCl3, 400 MHz):  = 8.14 (d, 4J = 1.76 Hz, 1 H, H-4′), 8.01 (d,
3J = 7.83 Hz, 1 H, H-5′), 7.89 (s, 1 H, H-3), 7.45–7.49 (m, 1 H, H-7′),
7.38–7.41 (m, 1 H, H-5′′), 7.35 (br s, 1 H, H-2′), 7.26–7.29 (m, 1 H, 1′),
7.21–7.25 (m, 1 H, H-6′), 6.90 (dd, 3J = 8.31 Hz, 4J = 2.05 Hz, 1 H, H-6′′),
6.76–6.81 (m, 2 H, H-2′′, 8′), 4.26 (t, 3J = 7.34 Hz, 2 H, NCH2), 3.93 (s, 3
H, C-4′-OCH3), 3.86 (s, 3 H, C-3′-OCH3), 3.56 (s, 3 H, CO2CH3), 1.81–
1.88 (m, 2 H, NCH2CH2), 1.35–1.40 [m, 2 H, CH3(CH2)2CH2], 1.27–1.33
[m, 4 H, CH3(CH2)2], 0.85–0.89 (m, 3 H, Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 162.8, 148.6, 148.2, 146.6, 140.8,
140.2, 137.7, 136.1, 130.1, 128.6, 127.1, 126.0, 124.0, 123.0, 122.6,
121.3, 121.2, 120.4, 119.2, 112.4, 111.2, 108.9, 108.6, 55.8, 55.6, 52.1,
43.2, 31.49, 28.9, 26.9, 22.5, 13.9.
Anal. Calcd for C20H14O2S2: C, 68.54; H, 4.03. Found: C, 68.58; H, 4.00.
Methyl 5′-Hexyl-3-(naphthalen-1-yl)-[2,2′-bithiophene]-5-carbox-
ylate (18f)
Yield: 1.50 g (84%); yellow liquid.
IR (thin film): 2926, 2854, 1708 (С=О), 1467, 1438, 1283, 1242, 1174,
1074, 798, 779, 750 cm–1
.
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

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E. B. Ulyankin et al.
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Anal. Calcd for C32H33NO4S: C, 72.84; H, 6.30; N, 2.65. Found: C, 72.86;
H, 6.27; N, 2.69.
Method 3: In a 150 mL tube equipped with a magnetic stir bar, a solu-
tion of methyl ester 18b–g,i–k (1 mmol), I2 (51 mg, 0.2 mmol) in THF
(100 mL) was irradiated by UV/LED chips with emission maximum
365 nm (total power = 40 W) for 10–60 h (monitoring using TLC and
HPLC). After that, THF was evaporated, EtOAc (20 mL) and sat. aq
Na2S2O3 (100 mL) were added. The organic phase was washed with
H2O, dried (Na2SO4), and concentrated. An analytical sample was ad-
ditionally purified by column chromatography on silica gel using ben-
zene/EtOAc (20:1) as eluent.
Methyl 5-(1-Hexyl-1H-indol-3-yl)-4-(pyridin-3-yl)thiophene-2-
carboxylate (18j)
Yield: 1.37 g (80%); yellow liquid.
IR (thin film): 2928, 1704 (С=О), 1524, 1440, 1286, 1241, 1185, 1075,
808, 736, 709 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 8.65 (d, 4J = 1.57 Hz, 1 H, H-2′′), 8.49
Method 4: FeCl3 (2.5 mmol) was added to a solution of ester 18b (360
mg, 1 mmol) in CH2Cl2 (220 mL) by small portions under N2 atmo-
sphere at 0 °С. The reaction mixture was stirred for 2 h at 0 °С fol-
lowed by stirring at r.t. for 1 h. H2O (200 mL) was added, the organic
layer separated, washed with brine, dried, and concentrated. Pure es-
ter 19a was obtained by column chromatography (benzene/EtOAc
15:1).
3
(dd, 3J = 4.89 Hz, 1.57 Hz, 1 H, H-6′′), 7.91 (s, 1 H, H-2′), 7.63 (dd, J =
3
6.56 Hz, 4J = 1.57 Hz, 1 H, H-4′′), 7.53 (d, J = 7.55 Hz, 1 H. H-4′), 7.34
(d, 3J = 7.55 Hz, 1 H, H-7′), 7.24 (t, 3J = 7.55 Hz, 1 H, H-6′), 7.17 (dd, 3J =
6.56 Hz, 3J = 4.89 Hz, 1 H, H-5′′), 7.09 (t, 3J = 7.55 Hz, 1 H, H-5′), 6.96 (s,
1 H, H-3), 4.05 (t, 3J = 7.14 Hz, 2 H, NCH2), 3.94 (s, 3 H, CO2CH3), 1.79
(d, 3J = 6.65 Hz, 2 H, NCH2CH2), 1.28 [br s, 6 H, CH3(CH2)3], 0.88 (t, 3J =
6.46 Hz, 3 H, Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 162.6, 149.6, 148.3, 141.3, 136.3,
135.9, 135.4, 134.1, 132.4, 130.3, 128.1, 126.1, 123.2, 122.4, 120.5,
120.3, 109.8, 107.5, 52.2, 46.6, 31.3, 29.9, 26.5, 22.4, 14.0.
Methyl 5,6-Dimethoxynaphtho[2,1-b:3,4-b′]dithiophene-2-car-
boxylate (19a)
Method 1; yield: 0.15 g (42%) from 18a – Method 2; irradiation time:
10 h; yield: 0.31 g (86%) from 18a – Method 3; irradiation time: 10 h;
yield: 0.33 g (91%) from 18b – Method 4; yield: 0.27 g (75%) from
18b; yellow solid; mp 216–217 °С.
Anal. Calcd for C25H26N2O2S: C, 71.74; H, 6.26; N, 6.69. Found: C,
71.70; H, 6.27; N, 6.72.
Methyl 2′-(1-hexyl-1H-indol-3-yl)-[2,3′-bithiophene]-5′-carboxyl-
ate (18k)
IR (KBr): 3084, 2941, 2837, 1707 (С=О), 1623, 1550, 1519, 1463, 1439,
1251, 1208, 1066, 833, 743, 624 cm–1
.
Yield: 1.27 g (73%); yellow liquid.
1H NMR (CDCl3, 400 MHz):  = 8.48 (s, 1 H, H-3), 7.81 (d, 3J = 5.48 Hz, 1
H, H-8), 7.54 (m, 3 H, H-4, 7, 9), 4.08 (s, 6 H, 2 × OCH3), 4.00 (s, 3 H,
CO2CH3).
IR (thin film): 2927, 1706 (С=О), 1512, 1452, 1285, 1242, 1176, 1075,
737, 694 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.98 (s, 1 H, H-4′), 7.59 (d, 3J = 8.02 Hz,
1 H, H-4′′), 7.39 (d, 3J = 8.41 Hz, 1 H, H-7′′), 7.24–7.29 (m, 1 H, H-6′′),
7.16–7.19 (m, 2 H, H-5, 2′′), 7.11–7.15 (m, 1 H, H-5′′), 7.04 (dd, 3J =
3.62 Hz, 4J = 1.17 Hz, 1 H, H-3), 6.94 (dd, 3J = 5.09 Hz, 3J = 3.62 Hz, 1 H,
H-4), 4.12 (t, 3J = 7.04 Hz, 2 H, NCH2), 3.94 (s, 3 H, CO2CH3), 1.84 (br s,
2 H, NCH2CH2), 1.32 [d, J = 4.11 Hz, 6 H, CH3(CH2)3], 0.88–0.92 (m, 3
H, Alkyl CH3).
13C NMR (CDCl3, 101 MHz):  = 162.7, 139.8, 137.7, 136.2, 135.4,
131.2, 129.8, 128.5, 127.0, 126.7, 125.9, 125.0, 122.2, 120.4, 120.3,
109.7, 107.4, 52.1, 46.6, 31.4, 30.0, 26.5, 22.5, 14.0.
13C NMR (CDCl3, 101 MHz):  = 163.1, 149.1, 136.0, 134.5, 133.0,
130.0, 129.7, 129.0, 125.4, 122.7, 122.6, 122.5, 104.6, 104.4, 56.0, 52.5.
Anal. Calcd for C18H14O4S2: C, 60.32; H, 3.94. Found: C, 60.28; H, 3.98.
Methyl 9-Hexyl-5,6-dimethoxynaphtho[2,1-b:3,4-b′]dithiophene-
2-carboxylate (19c)
3
Method 3; irradiation time: 15 h; yield: 0.42 g (95%); yellow solid; mp
146–147 °С.
IR (KBr): 2928, 2850, 1713 (С=О), 1530, 1514, 1251, 1206, 1080, 1070,
841, 760, 629 cm–1
.
Anal. Calcd for C24H25NO2S2: C, 68.05; H, 5.95; N, 3.31. Found: C,
68.10; H, 5.87; N, 3.32.
1H NMR (CDCl3, 400 MHz):  = 7.38 (s, 1 H, H-3), 7.36 (s, 2 H, H-4, H-
7), 4.02, 4.04 (s each, 3 H each, OCH3), 3.98 (s, 3 H, CO2H3), 2.95 (t, 3J =
3
3
7.48 Hz, 2 H, C-9-CH2), 1.80 (dt, J = 14.57 Hz, J = 7.48 Hz, 2 H, C-9-
CH2CH2), 1.36–1.45 [m, 6 H, CH3(CH2)3], 0.89–0.95 (m, 3 H, Alkyl CH3).
Fused Methyl Benzo[b]thiophene-2-carboxylates 19a,c–k; General
Procedure
13C NMR (CDCl3, 101 MHz):  = 163.2, 148.7, 148.7, 146.6, 136.0,
134.4, 132.0, 129.0, 128.8, 128.2, 122.6, 122.1, 119.1, 104.4, 104.1,
55.8, 52.3, 31.5, 31.4, 30.8, 28.9, 22.5, 14.0.
Method 1: A mixture of ester 18a (486 mg, 1 mmol), Pd(PPh3)4 (116
mg, 0.1 mmol) and KOAc (196 mg, 2 mmol) in DMF (4 mL) was heated
at 130 °С under N2 atmosphere for 3 h. After cooling, the reaction
mixture was poured into H2O (6 mL) and extracted with CH2Cl2 (3 × 5
mL), dried (Na2SO4), and concentrated. Pure ester 19a was obtained
by column chromatography (benzene/EtOAc 15:1 as eluent).
Anal. Calcd for C24H26O4S2: C, 65.13; H, 5.92. Found: C, 65.28; H, 6.02.
Methyl 9-Decylnaphtho[2,1-b:3,4-b′]dithiophene-2-carboxylate
(19d)
Method 2: In a 150 mL tube equipped with a magnetic stir bar, a solu-
tion of methyl ester 18a or 18h (1 mmol) in THF (100 mL) was irradi-
ated by UV/LED chips with emission maximum 365 nm (total power =
40 W) for 10–60 h (monitoring using TLC and HPLC). After that, THF
was evaporated, EtOAc (20 mL) and sat. aq Na2S2O3 (100 mL) were
added. The organic phase was washed with H2O, dried (Na2SO4), and
concentrated. An analytical sample was additionally purified by col-
umn chromatography on silica gel using benzene/EtOAc (20:1) as elu-
ent.
Method 3; irradiation time: 60 h; yield: 0.27 g (61%); yellow solid; mp
95–96 °С.
IR (KBr): 2921, 2850, 1712 (С=О), 1528, 1491, 1433, 1252, 1075, 746,
635 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 8.63 (s, 1 H, H-3), 8.31 (dd, 3J = 6.16 Hz,
3J = 3.23 Hz, 1 H, H-4), 8.24 (d, 3J = 6.06 Hz, 1 H, H-7), 7.57–7.64 (m, 3
H, H-5, 6, 8), 3.99 (s, 3 H, CO2CH3), 3.00 (t, 3J = 7.63 Hz, 2 H, C-9-
CH2CH2), 1.82 (t, 3J = 7.43 Hz, 2 H, C-9-CH2), 1.28–1.49 [m, 14 H, C-9-
(CH2)2(CH2)7], 0.88–0.91 (m, 3 H, Alkyl CH3).
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

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E. B. Ulyankin et al.
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Synthesis
13C NMR (CDCl3, 101 MHz):  = 163.1, 147.1, 136.7, 136.2, 132.9,
129.9, 129.8, 129.3, 127.9, 127.5, 126.2, 126.1, 124.4, 124.1, 119.7,
52.4, 31.9, 31.4, 30.8, 29.6, 29.5, 29.4, 29.3, 29.1, 22.7, 14.1.
1H NMR (CDCl3, 400 MHz):  = 8.36 (s, 1 H, H-3), 7.64 (s, 1 H, H-7),
7.60 (s, 1 H, H-11), 7.41 (s, 1 H, H-4), 7.22 (s, 1 H, H-8), 4.10–4.14 (m,
4 H, OCH2), 4.09 (s, 3 H, C-6-OCH3), 4.05 (s, 3 H, C-5-OCH3), 3.99 (s, 3
H, CO2CH3), 1.91–1.99 (m, 4 H, 2 × OCH2CH2), 1.53–1.62 [m, 4 H, 2 ×
O(CH2)2CH2], 1.27–1.48 [m, 20 H, 2 × CH3(CH2)5], 0.91 (m, 6 H, 2 × Al-
kyl CH3).
13C NMR (CDCl3, 101 MHz):  = 163.2, 149.9, 149.3, 148.8, 148.7,
139.1, 132.6, 129.6, 129.2, 123.8, 122.9, 122.5, 121.5, 106.6, 106.2,
104.6, 103.9, 69.6, 68.9, 56.0, 55.9, 52.3, 31.9, 29.6, 29.5, 29.5, 29.4,
29.3, 29.2, 26.2, 26.1, 22.7, 14.1.
Anal. Calcd for C26H30O2S2: C, 71.19; H, 6.89. Found: C, 71.28; H, 6.82.
Methyl Phenanthro[2,1-b:3,4-b′]dithiophene-11-carboxylate (19e)
Method 3; irradiation time: 12 h; yield: 0.32 g (93%); light-yellow sol-
id; mp 190–191 °С.
IR (KBr): 2924, 2852, 1725 (С=О), 1519, 1434, 1261, 814, 745, 655 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 9.15 (s, 1 H, H-10), 8.92 (d, 3J = 8.41 Hz,
1 H, H-9), 8.17 (d, 3J = 8.80 Hz, 1 H, H-3), 7.96 (dd, 3J = 7.92 Hz, 4J =
1.37 Hz, 1 H, H-6), 7.89 (d, 3J = 5.38 Hz, 1 H, H-5), 7.85 (d, 3J = 8.80 Hz,
1 H, H-2), 7.69–7.74 (m, 1 H, H-8), 7.64 (dd, 3J = 7.92 Hz, 4J = 1.08 Hz, 1
H, H-7), 7.55 (d, 3J = 5.38 Hz, 1 H, H-4), 4.03 (s, 3 H, CH3).
13C NMR (CDCl3, 101 MHz):  = 163.1, 137.8, 137.0, 133.2, 132.4,
132.2, 131.9, 130.4, 130.2, 128.8, 127.5, 126.9, 126.7, 126.3, 126.0,
125.9, 124.6, 123.1, 122.7, 52.5.
Anal. Calcd for C38H52O6S: C, 71.66; H, 8.23. Found: C, 71.63; H, 8.31.
Methyl 6-Hexyl-12,13-dimethoxy-6H-thieno[2′,3′:3,4]naph-
tho[2,1-c]carbazole-2-carboxylate (19i)
Method 3; irradiation time: 7 h; yield: 0.44 g (84%); white solid; mp
167–168 °С.
IR (KBr): 2952, 2928, 2853, 1708 (С=О), 1519, 1465, 1257, 1212, 1088,
749 cm–1
.
Anal. Calcd for C20H12O2S2: C, 68.94; H, 3.47. Found: C, 69.01; H, 3.53.
1H NMR (CDCl3, 400 MHz):  = 8.68 (d, 3J = 8.12 Hz, 1 H, H-10), 8.65 (s,
1 H, H-1), 8.55 (s, 1 H, H-11), 8.06 (d, 3J = 8.61 Hz, 1 H, H-5), 7.65 (s, 1
H, H-14), 7.60 (d, 3J = 8.61 Hz, 1 H, H-4), 7.48–7.55 (m, 2 H, H-7,8),
7.23 (ddd, 3J = 8.12 Hz, 3J = 6.70 Hz, 4J = 1.57 Hz, 1 H, H-9), 4.39 (t, 3J =
7.48 Hz, 2 H, NCH2), 4.13 (s, 3 H, CO2CH3), 3.99 (s, 6 H, 2 × OCH3), 1.93
Methyl 2-Hexylphenanthro[2,1-b:3,4-b′]dithiophene-11-carboxyl-
ate (19f)
Method 3; irradiation time: 14 h; yield: 0.31 g (72%); light-yellow sol-
id; mp 98–99 °С.
3
(quint, J = 7.48 Hz, 2 H, NCH2CH2), 1.46 [br s, 2 H, N(CH2)2CH2], 1.33
IR (KBr): 2927, 2858, 1714 (С=О), 1526, 1469, 1434, 1297, 1269, 1081,
[br s, 4 H, CH3(CH2)2], 0.86–0.90 (m, 3 H, Alkyl CH3).
805, 739, 719, 658 cm–1
.
13C NMR (CDCl3, 101 MHz):  = 163.3, 149.7, 147.1, 141.2, 140.7,
140.3, 132.0, 129.7, 129.2, 127.3, 125.2, 124.4, 123.9, 123.3, 123.0,
122.7, 121.3, 118.0, 116.6, 110.3, 109.8, 109.4, 104.4, 56.0, 56.0, 52.3,
43.3, 31.5, 29.1, 27.0, 22.5, 14.0.
1H NMR (CDCl3, 400 MHz):  = 9.27 (s, 1 H, H-10), 9.04 (d, 3J = 8.61 Hz,
1 H, H-9), 8.24 (d, 3J = 8.80 Hz, 1 H, H-5), 8.00 (d, 3J = 7.63 Hz, 1 H, H-
6), 7.92 (d, 3J = 8.80 Hz, 1 H, H-4), 7.73–7.78 (m, 1 H, H-8), 7.62–7.68
(m, 2 H, H-3,7), 4.03 (s, 3 H, CO2CH3), 3.04 [t, 3J = 7.53 Hz, 2 H,
CH3(CH2)4CH2], 1.86 [t, 3J = 7.53 Hz, 2 H, CH3(CH2)3CH2], 1.30–1.53 [m,
6 H, CH3(CH2)3], 0.90–0.96 (m, 3 H, Alkyl CH3).
Anal. Calcd for C32H31NO4S: C, 73.12; H, 5.94; N, 2.66. Found: C, 73.21;
H, 6.01; N, 2.71.
13C NMR (CDCl3, 101 MHz):  = 163.3, 147.5, 138.0, 137.4, 133.4,
132.5, 131.7, 131.1, 130.5, 130.0, 128.8, 127.3, 126.9, 126.5, 126.5,
126.0, 124.9, 123.0, 119.9, 52.5, 31.6, 31.4, 31.0, 28.8, 22.6, 14.0.
Methyl 8-Hexyl-8H-pyrido[2,3-a]thieno[3,2-c]carbazole-2-carbox-
ylate (19j)
Method 3; irradiation time: 20 h; yield: 0.33 g (78%); yellow solid; mp
Anal. Calcd for C26H24O2S2: C, 72.19; H, 5.59. Found: C, 72.23; H, 5.63.
143–144 °С.
IR (KBr): 2925, 1708 (С=О), 1593, 1548, 1524, 1469, 1342, 1241, 1074,
808, 788, 750, 741, 620 cm–1
.
Methyl Benzo[1,2-b:3,4-b′:6,5-b′′]trithiophene-2-carboxylate
(19g)
1H NMR (CDCl3, 400 MHz):  = 8.82 (dd, 3J = 4.30 Hz, 4J = 1.56 Hz, 1 H,
Method 3; irradiation time: 6 h; yield: 0.24 g (80%); white solid; mp
186–187 °С.
H-6), 8.45–8.49 (m, 2 H, H-3, 4), 8.11 (d, 3J = 7.82 Hz, 1 H, H-12), 7.58
3
3
4
(d, J = 8.22 Hz, 1 H, H-9), 7.55 (dd, J = 8.22 Hz, J = 1.08 Hz, 1 H, H-
10), 7.37–7.42 (m, 2 H, H-5, 11), 5.09–5.16 (m, 2 H, NCH2), 4.00 (s, 3 H,
CO2CH3), 1.93 (t, 3J = 7.53 Hz, 2 H, NCH2CH2), 1.29–1.53 [m, 6 H,
CH3(CH2)3], 0.88–0.93 (m, 3 H, Alkyl CH3).
IR (KBr): 3110, 2954, 1711 (С=О), 1514, 1432, 1305, 1284, 1106, 1075,
847, 749, 714 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 8.32 (s, 1 H, H-3), 7.73 (m, 2 H, H-6,7),
7.59 (d, 3J = 5.38 Hz, 1 H, H-8), 7.55 (d, 3J = 5.28 Hz, 1 H, H-5), 4.00 (s, 3
H, CO2CH3).
13C NMR (CDCl3, 101 MHz):  = 163.3, 147.1, 139.8, 139.0, 136.9,
133.1, 131.5, 128.9, 128.5, 128.4, 125.1, 123.9, 121.4, 121.0, 120.4,
120.2, 114.5, 110.0, 52.3, 45.6, 31.5, 30.0, 26.6, 22.6, 14.0.
13C NMR (CDCl3, 101 MHz):  = 162.9, 134.7, 134.3, 133.2, 132.9,
131.6, 130.7, 130.5, 128.7, 126.3, 125.1, 122.9, 122.6, 52.5.
Anal. Calcd for C25H24N2O2S: C, 72.09; H, 5.81; N, 6.73. Found: C,
72.11; H, 5.78; N, 6.75.
Anal. Calcd for C14H8O2S3: C, 55.24; H, 2.65. Found: C, 55.31; H, 2.68.
Methyl 7-Hexyl-7H-dithieno[3,2-a:3′,2′-c]carbazole-2-carboxylate
(19k)
Methyl 5,6-Dimethoxy-9,10-bis(nonyloxy)phenanthro[9,10-
b]thiophene-2-carboxylate (19h)
Method 3; irradiation time: 8 h; yield: 0.36 g (84%); white solid; mp
167–168 °С.
Method 2; irradiation time: 8 h; yield: 0.44 g (85%); pink solid; mp
128–129 °С.
IR (KBr): 2922, 2853, 1710 (С=О), 1564, 1513, 1465, 1292, 1212, 1191,
IR (KBr): 2922, 2852, 1717 (С=О), 1616, 1522, 1505, 1465, 1279, 1267,
1084, 746, 737 cm–1
.
1206, 1194, 1090, 842, 741 cm–1
.
© 2021. Thieme. All rights reserved. Synthesis 2021, 53, 2422–2434

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E. B. Ulyankin et al.
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Synthesis
1H NMR (CDCl3, 400 MHz):  = 8.30 (s, 1 H, H-3), 8.12 (d, 3J = 7.83 Hz, 1
H, H-11), 7.69 (d, 3J = 5.48 Hz, 1 H, H-6), 7.44–7.52 (m, 3 H, H-5, 8, 9),
7.37–7.41 (m, 1 H, H-10), 4.42–4.47 (m, 2 H, NCH2), 4.02 (s, 3 H,
CO2CH3), 1.88 (d, 3J = 7.43 Hz, 2 H, NCH2CH2), 1.46 [br s, 2 H,
N(CH2)2CH2], 1.30–1.37 [m, 4 H, CH3(CH2)2], 0.88–0.92 (m, 3 H, Alkyl
CH3).
13C NMR (CDCl3, 101 MHz):  = 163.4, 138.9, 135.4, 134.6, 134.1,
129.4, 128.3, 126.7, 124.5, 124.1, 123.5, 121.7, 120.9, 120.8, 120.3,
112.4, 109.1, 52.3, 44.8, 31.5, 29.9, 26.7, 22.5, 13.9.
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5402. (d) Matsuoka, W.; Ito, H.; Itami, K. Angew. Chem. Int. Ed.
2017, 56, 12224. (e) Verbitskiy, E. V.; Rusinov, G. L.; Chupakhin,
O. N.; Charushin, V. N. ARKIVOC 2016, (iv), 204. (f) Saito, K.;
Chikkade, P. K.; Kanai, M.; Kuninobu, Y. Chem. Eur. J. 2015, 21, 1.
(g) Hu, T.; Xu, K.; Ye, Z.; Zhu, K.; Wu, Y.; Zhang, F. Org. Lett. 2019,
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Anal. Calcd for C24H23NO2S2: C, 68.38; H, 5.50; N, 3.32. Found: C,
68.41; H, 5.49; N, 3.30.
Conflict of Interest
The authors declare no conflict of interest.
Funding Information
(13) (a) Tian, D.; Zhou, Y.; Li, Z.; Liu, S.; Shao, J.; Yang, X.; Shao, J.;
Huang, W.; Zhao, B. ChemistrySelect 2017, 2, 8137. (b) Zhang, J.;
Li, Z.; Xing, H.; Zhang, W.; Guo, L.; Liu, Y.; Shing Wong, M.; Yu, G.
Org. Chem. Front. 2014, 1, 333. (c) Yang, S.-M.; Shie, J.-J.; Fang, J.-
M.; Nandy, S. K.; Chang, H.-Y.; Lu, S.-H.; Wang, G. J. Org. Chem.
2002, 67, 5208.
This work was supported by the Russian Science Foundation (Grant
No. 20-73-10043).
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Supporting Information
Supporting information for this article is available online at
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