Self-condensation of N-substituted (4H-thieno[3,2-b]-pyrrol-5-yl)methanols into bis(thienopyrrolyl)methanes

Article abstract of DOI:10.1016/j.mencom.2018.03.028

N-Substituted (4H-thieno[3,2-b]pyrrol-5-yl)methanols were obtained by alkylation of methyl 4H-thieno[3,2-b]pyrrole-5-carboxylate followed by reduction with LiAlH₄. These compounds on contact with Amberlyst 15 (H-form) in CH₂Cl_2<

Full text of DOI:10.1016/j.mencom.2018.03.028

Mendeleev
Communications
Mendeleev Commun., 2018, 28, 192–194
Self-condensation of N-substituted (4H-thieno[3,2-b]-
pyrrol-5-yl)methanols into bis(thienopyrrolyl)methanes
a
b
a
Seda A. Torosyan, Vadim V. Zagitov, Fanuza A. Gimalova,
b
a
Raisa Z. Biglova and Mansur S. Miftakhov*
a
b
Ufa Institute of Chemistry, Russian Academy of Sciences, 450054 Ufa, Russian Federation.
E-mail: bioreg@anrb.ru
Department of Chemistry, Bashkir State University, 450074 Ufa, Russian Federation
DOI: 10.1016/j.mencom.2018.03.028
N-Substituted (4H-thieno[3,2-b]pyrrol-5-yl)methanols were
obtained by alkylation of methyl 4H-thieno[3,2-b]pyrrole-
S
S
S
Amberlyst 15
CH2Cl2
CH2OH
5
-carboxylate followed by reduction with LiAlH . These com-
N
N
4
N
pounds on contact with Amberlyst 15 (H-form) in CH Cl
2
2
R
R
R
undergo self-condensation to produce bis(4H-thieno[3,2-b]-
R = Me, allyl, propargyl, CH2Ph
pyrrol-5-yl)methanes.
4
H-Thieno[3,2-b]pyrrole-5-carboxylic derivatives1,2 are of interest
tion. In addition, bis(thienopyrrolyl)methanes 4 seem promising
in creation of cross-conjugation involving their methylene fragment.
On the way to methanes 4, reactions of alcohol 3a in SiO2–
CH Cl and TsOH–benzene systems were studied at room tem-
3–8
in search for bioactive thienopyrrole compounds, as well as
base matrices in preparation of p-condensed systems for opto-
electronics.
9–12
In this study, we performed N-alkylation of methyl
2
2
4H-thieno[3,2-b]pyrrole-5-carboxylate 1 with iodomethane, allyl,
perature and on heating. In all cases, the reactions were sluggish
propargyl or benzyl bromides and obtained the corresponding
and conversion of alcohol 3a was never complete even after
N-derivatives 2a–d, which were further reduced (LiAlH ) into
the corresponding alcohols 3a–d (Scheme 1). We anticipated
several hours. Meanwhile, in the Amberlyst 15 (H-form)–CH Cl2
system, alcohol 3a was fully converted into a new product whose
4
2
†
of using alcohols 3 to access more complex structures of
bis(thienopyrrolyl)methane type 4 by means of self-condensa-
tion reaction. Choice of alcohols 3 for this purpose was based
S
S
6a
3a
NaH, THF
then RHal
6
LiAlH4
THF
2
CO2Me
5
2
CO Me
3
N
N
13(a),(b)
on known precedents of acid
or ion-exchange Montmoril-
H
13(c)
R
lonite resin
catalyzed syntheses of pyrromethanes (dipyrrolyl-
1
2
a–d
methanes) from monomeric acetoxymethylpyrroles and 5-unsub-
stituted pyrroles. Bis(thienopyrrolyl)methanes14 are the valuable
S
S
S
Amberlyst 15
CH2Cl2, 20 °C
CH2OH
1
5
intermediates in the synthesis of porphyrins via pyrromethenes.
N
N
N
1
3(a),(c)
The data on self-condensation of such compounds are scarce
R
a–d
R
R
and relate to pyrroles with NH group.1
2,13(c),14(e),16
In the case of
3
4a–d
N-substituted pyrroles, the possibilities of acid-catalyzed 3®4 route
are not obvious and hence they require experimental confirma-
a R = Me
c R = HC CCH2
d R = CH Ph
b R = H C=CHCH
2
2
2
†
The IR spectra were recorded from thin films on a Shimadzu IR
Scheme 1
1
13
Prestige-21 spectrometer. The H and C NMR spectra were recorded
on Bruker AM-300 (300.13 and 75.47 MHz, respectively) and Bruker
Avance-500 instruments (500.13 and 125.77 MHz, respectively) using
tetramethylsilane as internal standard. The mass spectra (EI, 70 eV) were
obtained on Thermo Finnigan MAT 95XP and Shimadzu LCMS-2010EV
mass spectrometers (sample solutions in chloroform–acetonitrile were
injected by a syringe at a flow rate of 0.1 ml min , eluent acetonitrile–
water, 95:5) in the register mode of positive ions with the ionizing potential
of needle electrode 4.5 kV, temperature of capillary interface 250°C, voltage
Methyl 4-methyl-4H-thieno[3,2-b]pyrrole-5-carboxylate 2a.18 A solution
of pyrrole 1 (0.20 g, 1.10 mmol) in anhydrous THF (2 ml) was added
to a stirred suspension of NaH (55.0 mg, 2.29 mmol) (pre-rinsed with
anhydrous hexane from a 55% dispersion in mineral oil) in anhydrous
THF (10 ml) under an argon atmosphere, and the mixture was stirred for
0 min. Then a solution of iodomethane (0.14 ml, 2.19 mmol) in THF
5 ml) was added dropwise, and the mixture was stirred at 40°C until the
–1
3
(
starting pyrrole was consumed (TLC control). The mixture was cooled
3
–1
of capillary interface 5 V, flow rate of atomizing gas (nitrogen) 1.5 dm min
for chemical ionization at atmospheric pressure). The reaction course
and quenched with saturated NH Cl solution, the product was extracted
4
(
with CH Cl (3×20 ml). The solvent was evaporated, the residue was
2
2
was monitored by TLC on ‘Sorbphil’ plates with visualization of com-
pounds in the ethanol solution of anisaldehyde acidified with sulfuric
acid with subsequent heating at 120–150°C. The products were isolated
by column chromatography on silica gel (30–60 g of adsorbent per 1 g of
compound); freshly distilled solvents were used as eluents.
Methyl 4H-thieno[3,2-b]pyrrole-5-carboxylate 1 was obtained according
to published procedure,1 the spectral characteristics conformed to those
given in literature.
purified by column chromatography on SiO2 (light petroleum–ethyl
acetate, 5:1) to give 0.17 g (79%) of compound 2a as slightly yellow
–1
crystals, mp 62–63°C. IR (n/cm ): 1710, 1695, 1532, 1464, 1445, 1378,
1
1369, 1235, 1209, 1179, 1095, 1075, 962, 728. H NMR (500 MHz,
CDCl ) d: 3.86 (s, 3H, OMe), 4.06 (s, 3H, NMe), 6.95 (d, 1H, H-3,
3
1
3
J 5.4 Hz), 7.18 (s, 1H, H-6), 7.34 (d, 1H, H-2, J 5.4 Hz). C NMR
(125 MHz, CDCl ) d: 51.3 (NMe, OMe), 109.0 (C ), 110.0 (C ), 114.8
(C ), 121.9 (C ), 129.13 (C ), 138.0 (C ), 164.6 (CO Me).
,2
6
3
3
6a
5
2
3a
2
©
2018 Mendeleev Communications. Published by ELSEVIER B.V.
–
192 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2018, 28, 192–194
spectra were in accordance with structure 4a (see Scheme 1).
S
Clay-SO3H
– H2O
3
In the same manner, alcohols 3b–d underwent self-condensation
CH2
3
into bis(thienopyrrolyl)methanes 4b–d.‡
N
To our knowledge, symmetric bis(thienopyrrolyl)methanes of
type 4 are not documented. The most close precedent is condensa-
tion of aldehyde 5 with C(5)-unsubstituted pyrroles leading to
unsymmetrical (thienopyrrolyl)methanes used for the preparation
of BODIPY complexes.16 At the same time, syntheses of more
simple dipyrromethanes 6 are well developed [see, e.g., refs.
R
A
OH
S
S
4
–
CH2O
N
N
+
–
H
1
4(d),17].
R
R
B
R
Scheme 2
S
CHO
N
N
The tentative mechanism of the self-condensation is outlined in
Scheme 2. Alcohol 3 on contact with highly acidic Amberlyst 15
is converted into carbocation A which would regioselectively
attack C(2) site of the second molecule of 3. The thus formed
adduct B with secondary carbocation centre is supposed to
N
H
H
H
6
5
R = H, Alk, Ar, etc.
Methyl 4-allyl-4H-thieno[3,2-b]pyrrole-5-carboxylate 2b was prepared
analogously from pyrrole 1 (0.06 g, 0.33 mmol), NaH (9.5 mg, 0.39 mmol
)
and allyl bromide (79.9 mg, 0.66 mmol) using Bu NI (6 mg) as the phase
transfer catalyst. The purification by column chromatography on SiO2
4
(
4-Allyl-4H-thieno[3,2-b]pyrrol-5-yl)methanol 3b was prepared similarly
from 2b (60 mg, 0.27 mmol) and LiAlH (12 mg, 0.32 mmol). Purification
by column chromatography on SiO (light petroleum–EtOAc, 5:1) gave
.38 g (72%) of compound 3b as an oil. IR (n/cm ): 2948, 1703, 1699,
532, 1464, 1441, 1395, 1303, 1256, 1216, 1175, 1103, 759, 719. H NMR
300 MHz, CDCl ) d: 1.82 (br.s, 1H, OH), 4.65 (s, 2H, OCH ), 4.75
d, 2H, NCH , J 4.8 Hz), 4.99 (d, 1H, =CH , J 17.1 Hz), 5.16 (d, 1H,
CH , J 10.1 Hz), 5.99 (ddd, 1H, =CH, J 5.1, 10.2, 5.3 Hz), 6.38 (s, 1H,
H-6), 6.89 (d, 1H, H-3, J 5.1 Hz), 7.09 (d, 1H, H-2, J 5.3 Hz). C NMR
4
(
light petroleum–ethyl acetate, 5:1) gave 0.70 g (95%) of 2b as an oily
–1
2
substance. IR (n/cm ): 2948, 1703, 1699, 1532, 1464, 1441, 1395, 1303,
1
–1
0
1
(
(
=
1
256, 1216, 1175, 1103, 759, 719. H NMR (500 MHz, CDCl ) d: 3.86
3
1
(
s, 3H, OMe), 4.98 (dd, 1H, =CH , J 17.1 and 1.1 Hz), 5.13 (dd, 1H,
2
3
2
=
CH , J 10.4 and 1.1 Hz), 5.15 (m, 2H, NCH ), 6.01 (m, 1H, =CH,
2 2
2
2
J 17.0, 1.5, 10.4 and 5.3 Hz), 6.92 (d, 1H, H-3, J 5.5 Hz), 7.21 (s, 1H,
1
3
2
H-6), 7.33 (d, 1H, H-2, J 5.3 Hz). C NMR (125 MHz, CDCl ) d: 49.4
3
13
6
3
6a
(
1
(
CH ), 51.3 (OMe), 109.5 (C ), 110.4 (=CH ), 116.3 (C ), 122.2 (C ),
25.9 (C ), 129.3 (C ), 133.9 (=CH), 145.1 (C ), 161.9 (CO Me). HRMS
ESI), m/z: 221.0505 [M] (calc. for C H NO S, m/z: 221.0510).
2
2
6
5
2
3a
(125 MHz, CDCl3) d: 48.0 (NCH2), 57.5 (OCH2), 101.2 (C ), 110.5
(=CH2), 116.6 (C ), 121.9 (C ), 122.0 (C ), 123.7 (C ), 134.1 (=CH),
41.5 (C ). Found (%): C, 62.48; H, 5.49; N, 7.46; S, 16.98. Calc. for
2
3
6a
5
2
+
11
11
2
3a
1
Methyl 4-(prop-2-yn-1-yl)-4H-thieno[3,2-b]pyrrole-5-carboxylate 2c
was prepared in a similar manner from pyrrole 1 (0.37 g, 2.04 mmol) and
0% solution of propargyl bromide (0.45 ml, 4.10 mmol) in toluene.
C H NOS (%): C, 62.15; H, 5.74; N, 7.25; S, 16.59.
10
11
{
4-(Prop-2-yn-1-yl)-4H-thieno[3,2-b]pyrrol-5-yl}methanol 3c was
prepared analogously from 2c (60 mg, 0.27 mmol) and LiAlH4 (12.4 mg,
.33 mmol). Yield 81% (42 mg). Light yellow crystals, mp 66–68°C.
8
–1
Bright yellow crystals, mp 83–86°C. Yield 0.42 g (94%). IR (n/cm ):
0
3
1
2
106, 3265, 2953, 1692, 1534, 1492, 1464, 1438, 1394, 1377, 1306, 1261,
–1
1
IR (n/cm ): 3312, 3270, 3203, 2950, 1462, 1400, 1438, 1377, 1364,
330, 1295, 1013, 782, 721, 682, 655. H NMR (500 MHz, acetone-d )
d: 2.79 (s, 1H, OH), 2.87 (t, 1H, ºCH, J 2.3 Hz), 4.73 (s, 2H, OCH2),
5.06 (d, 2H, CH2, J 2.3 Hz), 6.33 (s, 1H, H-6), 7.12 (d, 1H, H-3, J 5.3 Hz),
7.15 (d, 2H, H-2, J 5.3 Hz). 13C NMR (125 MHz, acetone-d6) d: 34.4
(CH ), 56.4 (OCH ), 73.1 (ºCH), 78.9 (ºC), 100.5 (C ), 110.7 (C ),
22.1 (C ), 122.8 (C ), 125.9 (C ), 144.1 (C ). Found (%): C, 62.46;
220, 1181, 1171, 1111, 776, 732, 659. H NMR (500 MHz, CDCl ) d:
3
1
1
6
.32 (t, 1H, ºCH, J 2.3 Hz), 3.88 (s, 3H, OMe), 5.38 (d, 2H, NCH2,
J 2.4 Hz), 7.09 (d, 1H, H-3, J 5.2 Hz), 7.22 (s, 1H, H-6), 7.38 (d, 1H, H-2,
J 5.2 Hz). 13C NMR (125 MHz, CDCl ) d: 36.1 (CH ), 51.5 (OMe), 72.5
3
2
6
3
6a
5
(
(
(
ºCH), 78.4 (ºC), 110.1 (C ), 110.5 (C ), 122.6 (C ), 125.5 (C ), 129.7
C ), 145.3 (C ), 162.3 (CO Me). HRMS (ESI), m/z: 219.0349 [M]
6
3
2
3a
+
2 2
2
6a
2
5
3a
1
calc. for C H NO S, m/z: 219.0354).
11
9
2
H, 4.49; N, 7.46; S, 16.49. Calc. for C H NOS (%): C, 62.80; H, 4.74;
Methyl 4-benzyl-4H-thieno[3,2-b]pyrrole-5-carboxylate 2d was prepared
similarly from pyrrole 1 (0.06 g, 0.33 mmol) and benzyl bromide (0.084 g,
.66 mmol). Yellowish crystals, mp 81–83°C. Yield 80 mg (92%). IR
10
9
N, 7.32; S, 16.77.
4-Benzyl-4H-thieno[3,2-b]pyrrol-5-yl)methanol 3d was prepared
similarly from 2d (60 mg, 0.22 mmol) and LiAlH (10.0 mg, 0.27 mmol).
(
0
–
1
(n/cm ): 2950, 1703, 1532, 1490, 1464, 1441, 1395, 1303, 1257, 1216,
4
–1
1
Yield 34.0 mg (64%), oil. IR (n/cm ): 3537, 2931, 2873, 1526, 1476,
452, 1405, 1375, 1356, 1336, 1294, 1241, 1218, 1137, 1080, 1048, 995,
35, 826, 801, 776, 743, 592. H NMR (500 MHz, acetone-d ) d: 2.90 (s,
1H, OH), 4.64 (s, 2H, OCH ), 5.44 (s, 2H, NCH ), 6.38 (s, 1H, H-6),
6.87 (d, 1H, H-3, J 5.2 Hz), 7.06 (d, 1H, H-2, J 5.3 Hz), 7.16 (d, 2H, Ph,
J 7.2 Hz), 7.23–7.29 (m, 3H, Ph). C NMR (125 MHz, acetone-d ) d:
48.7 (CH ), 56.5 (OCH ), 100.2 (C ), 110.8 (C ), 122.5 (C ), 122.6 (C ),
2 2
26.6 (C ), 127.1 (C ), 128.5 (C ), 128.5 (C ), 138.6 (C ), 138.4 (C ).
MS (EI), m/z (%): 244 [MH] (5), 226 [M–OH] (100). Found (%) C, 68.89;
H, 5.47; N, 5.44; S, 13.44. Calc. for C H NOS (%): C, 69.10; H, 5.39;
N, 5.76; S, 13.18.
Bis(4-methyl-4H-thieno[3,2-b]pyrrol-5-yl)methane 4a. Amberlyst 15
1
175, 1103, 1085, 991, 918, 781, 759, 719, 666. H NMR (500 MHz,
1
9
CDCl ) d: 3.83 (s, 3H, OMe), 5.76 (s, 2H, NCH ), 6.86 (d, 1H, H-3,
3
2
1
J 5.4 Hz), 7.13 (d, 2H, Ph, J 7.4 Hz), 7.25 (s, 1H, H-6), 7.23–7.28 (m, 3H,
6
1
3
Ph), 7.32 (d, 1H, H-2, J 5.7 Hz). C NMR (125 MHz, CDCl ) d: 50.4
2
2
3
6
3
6a
5
(
(
CH ), 51.3 (OMe), 109.8 (C ), 110.6 (C ), 122.4 (C ), 126.1 (C ), 126.6
C ), 127.3 (C ), 128.6 (C ), 129.4 (C ), 137.9 (C ), 145.4 (C ),
61.9 (CO Me). HRMS (ESI), m/z: 271.0662 [M] (calc. for C H NO S,
2
13
2
3a
6
Ar
Ar
Ar
Ar
6
3
6a
2
+
1
2
15 13
2
5
3a
1
m/z: 271.0667).
4-Methyl-4H-thieno[3,2-b]pyrrol-5-yl)methanol 3a. A solution of
Ar
Ar
Ar
+
Ar
+
(
ester 2a (70 mg, 0.36 mmol) in anhydrous THF (5 ml) was added to a
14 15
stirred suspension of LiAlH (40.0 mg, 1.05 mmol) in anhydrous THF
4
‡
(10 ml) under an argon atmosphere. The mixture was stirred until the
starting ester was consumed (TLC control), then quenched with saturated
(0.15 g) was added to a stirred solution of 3a (0.14 g, 0.84 mmol) in
CH2Cl2 (10 ml), the reaction mixture was stirred until the starting alcohol
was consumed (5–6 h, TLC control). Amberlyst was filtered off, the
CH2Cl2 filtrate was concentrated, and the residue was purified by column
chromatography on silica gel (EtOAc–light petroleum, 1:5) to isolate
solution of NH Cl, THF was evaporated and the product was extracted
4
with CH Cl (3×20 ml). The combined extracts were washed with brine,
2
2
dried over MgSO , and the solvent was evaporated. The residue was
4
purified by column chromatography on silica gel (EtOAc–light petroleum,
–
1
–1
1
3
9
:5) to isolate 38.0 mg (63%) of white powder, mp 71–73°C. IR (n/cm ):
70.0 mg (58%) of product 4a as an oil. IR (n/cm ): 3097, 3083, 2953,
527, 3230, 2727, 1530, 1377, 1366, 1337, 1295, 1241, 1135, 1078, 987,
75, 823, 763, 713, 654. H NMR (500 MHz, CDCl ) d: 2.86 (s, 1H,
2853, 1662, 1537, 1471, 1438, 1382, 1334, 1291, 1133, 1083, 845, 765,
1
1
725. H NMR (300 MHz, CDCl3) d: 3.68 (s, 6H, NMe), 4.13 (s, 2H, CH2),
3
OH), 3.79 (s, 3H, NMe), 4.64 (d, 2H, OCH , J 5.5 Hz), 6.27 (s, 1H,
6.14 (s, 2H, H-6), 6.90 (d, 2H, H-3, J 5.3 Hz), 7.03 (d, 2H, H-2, J 5.2 Hz).
2
13
13
6'
H-6), 7.02 (d, 1H, H-3, J 5.3 Hz), 7.11 (d, 1H, H-2, J 5.2 Hz). C NMR
C NMR (75 MHz, CDCl ) d: 26.2 (CH ), 32.2 (NMe), 100.1 (C ),
3 2
6
3
3'
6a'
2'
5'
3a'
(
1
125 MHz, CDCl ) d: 31.3 (NMe), 56.3 (OCH ), 99.6 (C ), 110.2 (C ),
109.9 (C ), 121.6 (C ), 121.9 (C ), 134.7 (C ), 140.1 (C ). MS (EI),
m/z (%): 287 [MH] (100). Found (%): C, 63.16; H, 4.66; N, 9.49;
3
2
6a
5
2
3a
+
20.7 (C ), 121.3 (C ), 122.2 (C ), 138.4 (C ). MS (EI), m/z (%): 168
+
+
[M+H] (10), 150 [M–OH] (100).
S, 22.76. Calc. for C H N S (%): C, 62.90; H, 4.93; N, 9.78; S, 22.39.
15
14
2 2
–
193 –

Mendeleev Commun., 2018, 28, 192–194
release formaldehyde molecule and proton affording final stable
bis(thienopyrrolyl)methane 4.
3 K.-C. Ching, Y.-W. Kam, A. Merits, L. F. P. Ng and C. L. L. Chai,
J. Med. Chem., 2015, 58, 9196.
4
5
K.-C. Ching, T. N. Q. Tran, S. N. Amrun, Y.-W. Kam, L. F. P. Ng and
C. L. L. Chai, J. Med. Chem., 2017, 60, 3165.
In total, the herein obtained bis(4H-thieno[3,2-b]pyrrol-5-yl)-
methanes 4 seem promising as new scaffolds in search for new
bioactive compounds and design of new cross-conjugated struc-
tures. The mechanistic aspects of the chemical transformations
can also be of interest.
L. Sartori, C. Mercurio, F. Amigoni, A. Cappa, G. Fagá, R. Fattori,
E. Legnaghi, G. Ciossani,A. Mattevi, G. Meroni, L. Moretti,V. Cecatiello,
S. Pasqualato, A. Romussi, F. Thaler, P. Trifiró, M. Villa, S. Vultaggio,
O. A. Botrugno, P. Dessanti, S. Minucci, E. Zagarrí, D. Carettoni,
L. Iuzzolino, M. Varasi and P. Vianello, J. Med. Chem., 2017, 60, 1673.
D. Ashok, P. S. Goud, D. Shravani, J. Rajaiah, M. Sarasija and K. Bhaskar,
Indian J. Heterocycl. Chem., 2010, 20, 81.
A. P. Ilyin, I. G. Dmitrieva, V. A. Kustova, A. V. Manaev and A. V.
Ivachtchenko, J. Comb. Chem., 2007, 9, 96.
J. A. Sindac, B. D.Yestrepsky, S. J. Barraza, K. L. Bolduc, P. K. Blakely,
R. F. Keep, D. N. Irani, D. J. Miller and S. D. Larsen, J. Med. Chem.,
6
7
8
References
1
2
H. Hemetsberger and D. Knittel, Monatsh. Chem., 1972, 103, 194.
V. N. Yarovenko, S. L. Semenov, I. V. Zavarzin, A. V. Ignatenko and
M. M. Krayushkin, Russ. Chem. Bull., Int. Ed., 2003, 52, 451 (Izv.
Akad. Nauk, Ser. Khim., 2003, 431).
2
012, 55, 3535.
9
E. V. Verbitskiy, P. A. Slepukhin, M. S. Valova, E. M. Cheprakova,
A. V. Schepochkin, G. L. Rusinov and V. N. Charushin, Eur. J. Org.
Chem., 2014, 8133.
Bis(4-allyl-4H-thieno[3,2-b]pyrrol-5-yl)methane 4b was prepared
similarly from alcohol 3b, reaction time 8 h, oil, yield 55%. IR (n/cm ):
–1
3
1
099, 3081, 3009, 2982, 2954, 2919, 2867, 1517, 1476, 1442, 1395, 1345,
1
10 M. M. Krayushkin, V. N. Yarovenko, S. L. Semenov, I. V. Zavarzin,
337, 1298, 1285, 1082, 988, 921, 798, 773, 648. H NMR (300 MHz,
A. V. Ignatenko, A. Yu. Martynkin and B. M. Uzhinov, Org. Lett., 2002,
CDCl ) d: 4.07 (s, 2H, CH ), 4.60 (dd, 2H, NCH , J 1.6, 3.4 Hz), 4.61 (d,
3
2
2
4
, 3879.
2
2
2
7
4
H, NCH , J 1.6, 3.4 Hz), 4.92 (dd, 2H, =CH , J 1.2, 17.1 Hz), 5.13 (dd,
2
2
1
1 C. Jones, D. Boudinet, Y. Xia, M. Denti, A. Das, A. Facchetti and
T. G. Driver, Chem. Eur. J., 2014, 5938.
2 X.-D. Jiang, H. Zhang, Y. Zhang and W. Zhao, Tetrahedron, 2012, 68,
9795.
13 (a) D. H. Burns, Y. H. Li, D. C. Shi and T. M. Caldwell, J. Org. Chem.,
2002, 67, 4536; (b) S. E. Bari, J. Iturraspe and B. Frydman, Tetrahedron,
1995, 51, 2255; (c) A. H. Jackson, R. K. Pandey, K. R. Nagaraja Rao
and E. Roberts, Tetrahedron Lett., 1985, 26, 793.
H, =CH , J 1.2, 10.2 Hz), 5.88 (m, 2H, =CH, J 5.1, 10.1 Hz), 6.15 (s,
2
H, H-6'), 6.85 (d, 1H, H-3', J 5.3 Hz), 6.87 (d, 1H, H-3', J 5.2 Hz),
1
1
3
.01 (d, 2H, H-2', J 5.3 Hz). C NMR (75 MHz, CDCl ) d: 26.0 (CH ),
3
2
6'
3'
6a'
7.9 (NCH ), 100.5 (C ), 110.3 (C ), 116.5 (=CH ), 122.2 (C ), 122.0
2
2
2'
5'
3a'
(
[
C ), 133.7 (=CH), 134.5 (C ), 140.5 (C ). HRMS (ESI), m/z: 338.0906
+
M] (calc. for C H N S , m/z: 338.0911). Found (%): C, 67.81; H, 5.47;
19
18
2 2
N, 8.43; S, 18.66. Calc. for C H N S (%): C, 67.42; H, 5.36; N, 8.28;
19
18
2 2
S, 18.95.
14 (a) C.-H. Lee and J. S. Lindsey, Tetrahedron, 1994, 50, 11427; (b) K. Singh
,
S. Sharma andA. Sharma, Synth. Commun., 2011, 41, 3491; (c) T. K. Chan
,
Bis{4-(prop-2-yn-1-yl)-4H-thieno[3,2-b]pyrrol-5-yl}methane 4c was
prepared analogously from alcohol 3c, reaction time 8 h, oil, yield 43%.
IR (n/cm ): 3285, 3259, 3106, 3081, 2954, 2923, 2850, 2125, 1661,
S. K. Jana, M. Rajeswara Rao, M. S. Shaikh and M. Ravikanth, Inorg.
Chim. Acta, 2012, 383, 257; (d) T. E. Wood andA. Thomson, Chem. Rev.,
–
1
2
007, 107, 1831; (e) E. A. Mikhalitsyna, V. S. Tyurin, S. E. Nefedov,
1
1
2
647, 1531, 1517, 1472, 1436, 1394, 1334, 1296, 1248, 1133, 1086, 1055,
042, 910, 773, 715, 653. H NMR (300 MHz, acetone-d ) d: 2.33 (s,
H, ºCH), 4.32 (s, 2H, CH ), 4.75 (d, 4H, NCH , J 2.5 Hz), 6.23 (s, 2H,
S. A. Syrbu, A. S. Semeikin, O. I. Koifman and I. P. Beletskaya, Eur.
J. Inorg. Chem., 2012, 5979.
1
6
2
2
1
1
5 (a) T. D. Lash, Chem. Eur. J., 1996, 2, 1197; (b) Z. Fang and B. Liu,
Tetrahedron Lett., 2008, 49, 2311; (c) L. T. Nguen, M. O. Senge and
K. M. Smith, J. Org. Chem., 1996, 61, 998.
1
3
H-6'), 6.98 (d, 2H, H-2', J 5.3 Hz), 7.06 (d, 2H, H-3', J 5.3 Hz). C NMR
(125 MHz, acetone-d ) d: 34.4 (CH ), 56.4 (NCH ), 73.1 (ºCH), 78.9
6 2 2
6'
3'
6a'
2'
5'
(
1
ºC), 101.4 (C ), 110.1 (C ), 121.5 (C ), 122.8 (C ), 133.8 (C ),
6 L. Wu and K. Burgess, Chem. Commun., 2008, 4933.
40.3 (C3 ). HRMS (ESI), m/z: 334.0593 [M] (calc. for C H N S ,
a'
+
1
9
14
2 2
17 (a) J. S. Lindsey, Acc. Chem. Res., 2010, 43, 300; (b) A. Sharma and
S. Obrai, Der Chemica Sinica, 2015, 6, 57; (c) W. Zhao and E. M. Carreira,
Chem. Eur. J., 2006, 12, 7254; (d) N. A. M. Pereira and T. M. V. D.
Pinhole Melo, Org. Prep. Proced. Int., 2014, 46, 183.
m/z: 334.0598). Found (%): C, 68.60; H, 4.53; N, 8.47; S, 19.56. Calc. for
C H N S (%): C, 68.23; H, 4.22; N, 8.38; S, 19.17.
19
14
2 2
Bis(4-benzyl-4H-thieno[3,2-b]pyrrol-5-yl)methane 4d was prepared in
a similar manner from alcohol 3d, reaction time 9–10 h, oil, yield 62%.
1
8 S. Lotz, M. Landman, H. Goerls, C. Crause, H. Nienaber and A. Olivier,
1
Z. Naturforsch., B: Chem. Sci., 2007, 62, 419.
H NMR (500 MHz, CDCl ) d: 3.92 (s, 2H, CH ), 5.13 (s, 4H, NCH ),
3
2
2
6
.19 (s, 2H, H-6), 6.77 (d, 2H, H-3, J 5.3 Hz), 6.99 (d, 2H, H-2, J 5.2 Hz),
13
6
.89 (m, 4H, Ph), 7.21 (m, 6H, Ph). C NMR (75 MHz, CDCl ) d: 37.6
3
3'
6'
2'
6a'
(CH ), 48.5 (NCH ), 99.1 (C ), 110.0 (C ), 121.0 (C ), 121.9 (C ),
2 2
1
25.6 (C ), 126.0 (C ), 127.1 (C ), 128.0 (C ), 128.1 (C ), 128.5
Ar Ar Ar Ar Ar
5'
3a'
(C ), 134.2 (C ), 137.5 (C ), 139.9 (C ), 141.5 (C ). HRMS (ESI),
Ar Ar Ar
+
m/z: 438.1219 [M] (calc. for C H N S , m/z: 438.1224). Found (%):
27
22
2 2
C, 73.59; H, 5.13; N, 6.54; S, 14.98. Calc. for C H N S (%): C, 73.94;
27
22
2 2
H, 5.06; N, 6.39; S, 14.62.
Received: 16th August 2017; Com. 17/5335
–
194 –