One-Pot Synthesis of 3-Halo-2-organochalcogenylbenzo[b]chalcogenophenes from 1-(2,2-Dibromovinyl)-2-organochalcogenylbenzenes

Article abstract of DOI:10.1002/adsc.202001586

A transition-metal-free one-pot synthesis of 3-halo-2-organochalcogenylbenzo[b]chalcogenophenes has been developed using 1-(2-organochalcogenylethynyl)-2-butylchalcogenylbenzenes generated in situ from 1-(2,2-dibromovinyl)-2-organochalcogenylbenzenes and

Full text of DOI:10.1002/adsc.202001586

FULL PAPER
DOI: 10.1002/adsc.202001586
One-Pot Synthesis of 3-Halo-2-organochalcogenylbenzo[b]
chalcogenophenes from 1-(2,2-Dibromovinyl)-2-
organochalcogenylbenzenes
a
a
a
a
Eduardo Q. Luz, Gabriel L. Silvério, Diego Seckler, David B. Lima,
b
a
a
Francielli S. Santana, Ronilson V. Barbosa, Caroline R. Montes D’Oca, and
Daniel S. Rampon *
a,
a
Laboratory of Polymers and Catalysis (LaPoCa), Department of Chemistry, Federal University of Paraná-UFPR, P. O. Box
1
9061, Curitiba, PR, 81531-980, Brazil
Phone: (+55) 413361-3175
E-mail: danielrampon@quimica.ufpr.br
Department of Chemistry, Federal University of Paraná-UFPR, P. O. Box 19061, Curitiba, PR, 81531-980, Brazil
b
Manuscript received: December 21, 2020; Revised manuscript received: March 9, 2021;
Version of record online: ■■■, ■■■■
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202001586
Abstract: A transition-metal-free one-pot synthesis of 3-halo-2-organochalcogenylbenzo[b]chalcogenophenes
has been developed using 1-(2-organochalcogenylethynyl)-2-butylchalcogenylbenzenes generated in situ from
1
2
-(2,2-dibromovinyl)-2-organochalcogenylbenzenes and diorganoyl dichalcogenides. By this method, several
,3-disubstituted benzo[b]chalcogenophenes were prepared in yields of 48–93%. The mechanistic investigation
suggests that the formation of chalcogenoacetylenes containing an adjacent chalcogen atom in the first step of
this one-pot procedure involves acetylide anions formed from 1-(2,2-dibromovinyl)-2-organochalcogenylben-
zenes and mild bases.
Keywords: chalcogenoacetylenes; benzo[b]chalcogenophenes; one-pot; 1-(2,2-dibromovinyl)-2-organochalcoge-
nylbenzenes
[
11]
Introduction
electrophile-promoted nucleophilic cyclizations, in-
[12]
tramolecular nucleophilic additions
and radical
[13]
[14]
Chalcogenophene derivatives are important structural cyclizations, intramolecular condensations, transi-
[1]
[15]
ring systems in materials science,
medicinal tion-metal-catalyzed reactions, and hypervalent io-
[2]
[3]
[2a,4] [16]
chemistry, electrochemistry, agrochemistry,
and dine-mediated cyclizations. Despite these advances,
organic synthesis. In particular, the π-extended benzo current methods usually employ a number of separated
b]chalcogenophene derivatives have attracted great steps which are both time- and cost-consuming. This is
[5]
[
attention due to their improved properties as materials especially important when the degree of substitution of
for optoelectronic devices such as organic field-effect the heteroarene is high, as in 2,3-disubstituted benzo
[
6]
[7]
transistors (OFETs), organic photovoltaics (OPVs),
[b]chalcogenophenes.
[8]
organic light-emitting diodes (OLEDs), liquid-crystal
In this regard, chalcogenoacetylenes are very useful
[9]
[10]
displays (LCDs), and optical sensors. In addition, intermediates (Scheme 1), since through electrophile-
these organic frameworks show diverse potential promoted nucleophilic cyclization of an adjacent
applications in drug discovery, and nowadays several chalcogen atom several 3-halo-2-organochalcogenyl-
of these chalcogen-heterocycles are available on the benzo[b]chalcogenophenes can be prepared and further
[2]
market. Therefore, the straightforward synthesis of functionalized by cross-coupling reactions for the
[11,17]
this class of compounds is of great interest in synthesis of more complex molecules.
chemistry. However, the preparation of these key chalcogenoa-
There is a variety of synthetic methodologies for cetylene intermediates requires purification steps or
synthesis of benzo[b]chalcogenophenes, including harsh reaction conditions before cyclization
Adv. Synth. Catal. 2021, 363, 1–10
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We also carried out several control experiments in
order to gain insights into the reaction mechanism in
the first chalcogenoacetylene formation step.
Results and Discussion
Initial optimization efforts were focused on the
formation of the key intermediate 1-(2-phenylsulfanyl-
ethynyl)-2-butylselenanylbenzene (3a) from 1a and
diphenyl disulfide (2a; Table 1). Interestingly, we
observed that 3a was produced in 19% yield when
only t-BuOLi was employed, which in fact typifies a
new transition-metal-free methodology for the syn-
thesis of thioacetylenes (Table 1, entry 1) from 1,1-
dibromoalkenes and diorganoyl disulfides. Under these
conditions, the terminal alkyne butyl(2-ethynylphenyl)
Table 1. Optimization studies for the synthesis of 3a.
Scheme 1. Synthesis of 3-halo-2-organochalcogenylbenzo[b]
chalcogenophenes.
[
a]
#
Base
equiv.)
Solvent
Temp.
t.
[h]
3a
[%]
[
b]
[17]
(
[°C]
(
Scheme 1a). On the other hand, 1,1-dibromoalkenes
containing an adjacent heteroatom have emerged as an
interesting possibility, along with thiols in basic media
[c]
[c]
1
2
3
4
5
6
7
8
9
1
t-BuOLi (4)
t-BuOLi (3)
t-BuONa (3)
t-BuOK (3)
K PO (3)
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
110
110
110
110
110
110
110
110
110
120
140
100
110
110
110
110
110
110
110
110
110
110
12
12
12
12
12
12
12
12
12
12
12
12
1.0
0.5
0.25
0.5
0.5
0.5
0.5
0.5
0.5
0.5
19
83
58
45
70
15
63
89
51
65
42
26
93
95
70
14
5
[17b]
[
[
[
c]
c]
c]
for the synthesis of chalcogenoacetylenes;
however,
there are still purification steps involved, and the
handling of thiols is not easy.
Inspired by these pioneering works, we observed
that the easily handled diorganoyl disulfides could be
alternative and complementary reagents for the syn-
3
4
Na CO (3)
2
3
K
CO
2
(3)
3
Cs CO (3)
2
3
Cs CO (2)
thesis
of
3-halo-2-organochalcogenylbenzo[b]
2
3
[
c]
c]
0
Cs CO (3)
2
3
chalcogenophenes from 1-(2,2-dibromovinyl)-2-orga-
nochalcogenylbenzenes using a sequential one-pot
metal-free two-step procedure (Scheme 1c). The mech-
anism of 1-(2-organochalcogenylethynyl)-2-butylchal-
cogenylbenzenes formation in the first step puzzled us,
since ordinarily it requires a nucleophilic organosulfur
[
1
1
Cs CO (3)
2
3
12
13
14
15
16
17
Cs CO (3)
2
3
Cs CO (3)
2
3
Cs CO (3)
2
3
Cs CO (3)
2
3
Cs CO (3)
2
3
[17b,18]
or organoselenium species,
and yet only cesium
Cs CO (3)
NMP
Toluene
EtOH
DMSO
DMSO
DMSO
2
3
carbonate was employed along with the diorganoyl 18
dichalcogenide. Therefore, a mechanistic investigation 19
of this reaction is indispensable. Additionally, the key 20
Cs CO (3)
–
–
47
64
42
2
3
Cs CO (3)
2
2
2
3
3
3
[
[
[
d]
e]
f]
Cs
Cs
CO
CO
(3)
(3)
1
-(2-organochalcogenylethynyl)-2-butylchalcogenyl-
21
2
2
Cs CO (3)
2 3
benzenes intermediate could be converted in high yield
to the expected products in the same pot without
isolation, which is a noteworthy finding in the syn-
thesis of this class of relevant compounds.
[a]
Reaction conditions: 1 a (1.0 equiv., 0.28 mmol), 2 a
1.0 equiv., 0.14 mmol), base (equiv.), DMSO (2.0 mL), air
atmosphere.
(
[
b]
c]
As part of our continuous endeavor to develop
efficient methods for the construction of organochalco-
Isolated yields.
[
The terminal alkyne butyl(2-ethynylphenyl)selane (4a) was
detected by GC-MS as side product in the experiment.
Under argon atmosphere.
[19]
gen compounds, herein we describe the first one-pot
synthesis of 3-halo-2-organochalcogenylbenzo[b]
chalcogenophenes from the appropriate 1-(2,2-dibro-
movinyl)-2-organochalcogenylbenzenes (Scheme 1c).
[d]
[e]
[f]
Under O atmosphere.
2
2
a (0.5 equiv., 0.07 mmol).
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selane (4a) was observed as side product along with
[20]
the starting materials 1a and 2a. In fact, the product
a was obtained in 83% yield by performing the
3
reaction with 3.0 equivalents of base (Table 1, entry 2),
but other tert-butoxides did not improve the yield
further (Table 1, entries 3 and 4). Additionally, in the
presence of a weaker base such as K PO the yield of
3
4
3
a was 70% (Table 1, entry 5), and only traces of 4a
were detected by GC-MS analysis of the crude reaction
mixture.
Scheme 2. One-pot two step synthesis fo 5a.
On the other hand, we found that 3.0 equivalents of
K CO completely suppressed the formation of the side
2
3
product 4a, but the expected 3a was obtained in only lower amounts of I (Scheme 2c and 2d) decreased the
2
moderate yield (Table 1, entry 7). The use of Na CO3 yield of 5a.
2
furnished 3a in low yield, also with no side products
Table 1, entry 6); however, under the same reaction found, we explored further the scope and limitations of
conditions the base Cs CO cleanly provided 89% the one-pot synthesis of 3-halo-2-organochalcogenyl-
Once the optimum conditions for both steps were
(
2
3
yield of 3a (Table 1, entry 8). Further optimization benzo[b]chalcogenophenes using several diorganoyl
revealed that lower amounts of Cs CO3 (Table 1, dichalcogenides (2 and 6) and 1-(2,2-dibromovinyl)-2-
2
entry 9) or temperatures either higher or lower than organochalcogenylbenzenes (1a, 1b and 1c; Tables 2–
1
10°C resulted in substantial reductions in the yield of 4). The reaction times of the first and second steps (T1
3
a (Table 1, entries 10–12). Fortunately, the reaction and T2) were monitored by TLC. In general, the first
yield remained high, even after only 0.5 h (Table 1, step required a short reaction time when diaryl
entries 13 and 14), but shorter time gave the product disulfides were employed (2a–g; Table 2), and no clear
3
a in 70% yield (Table 1, entry 15). Other solvents, electronic effects were encountered from substituents
such as DMF (N,N-dimethylformamide) and NMP (N- on the S-aryl group. A slight longer T1 time was
Methyl-2-pyrrolidone), led to lower yields (Table 1, observed only when the phenyl rings on the diaryl
entries 16 and 17), and the reaction did not occur at all disulfides were substituted with either electron-donat-
in toluene or ethanol (Table 1, entries 18 and 19). ing or electron-withdrawing groups, although the
When the reaction was carried out under an argon reaction with dibutyl disulfide (2h) clearly took longer
atmosphere, only 47% of the product 3a was obtained, T1 and T2 times to afford a moderate yield of 5h. The
which indicates that an oxidizing medium is necessary T2 times were also longer in the in situ I -promoted
2
for the reaction (Table 1, entry 20). Although, when nucleophilic cyclizations of 3c–g; that is, when its S-
the reaction was developed under molecular oxygen aryl groups were substituted with electron-donating or
atmosphere the yield of 3a was 64%, which indicates electron-withdrawing groups, good to excellent yields
that an excess of O was not beneficial to the reaction of 5c–g were obtained. On the other hand, the
2
yield (Table 1, entry 21). Additionally, when the compounds 5a and 5b were achieved in 93% and 89%
reaction was developed with 0.5 equiv. of 2a, only yields, respectively, after a T1 time of 1.0 h.
4
2% yield of 3a was obtained (Table 1, entry 22).
Considering the excellent yield of 3a achieved in a genylbenzo[b]chalcogenophenes was based on NMR
short reaction time under simple reaction conditions analysis and confirmed by single-crystal X-ray diffrac-
Structural characterization of the 3-halo-2-chalco-
(
Table 1, entry 14), we envisioned that the molecular tion of 5e (Table 2), which proved the 5-endo-dig
[21]
complexity could be further increased through an one- cyclization in the second step of the one-pot process.
pot electrophile-promoted intramolecular nucleophilic Further diversity in the general structure 5 was
cyclization by the simple addition of I as electrophile introduced by the use of 1-(2,2-dibromovinyl)-2-
2
(Scheme 2). In this way, after an experiment under the butylthiobenzene (1b), which after longer T1 and T2
optimized reaction conditions (Table 1, entry 14), the reaction times afforded 5i in 79% yield. Despite the
system was cooled to room temperature and a solution efficient production of the intermediate 3j after a T1
of 1.5 equivalents of I in dichloromethane was added time of 2.5 h (observed by GC-MS analysis), the
2
[11,17]
to the system.
The progress of the second step of product 5j was not detected even after a longer time at
this one-pot process was monitored by thin-layer higher temperature in the second step. These results
[
11k]
chromatography (TLC), which indicated the total indicated that the lower nucleophilicity of oxygen
[
11k,17a]
conversion of 3a after only 1.0 h, thereby providing added to the steric hindrance from the butyl chain
3% yield of the expected product 5a (Scheme 2a). significantly suppressed the second step of the one-pot
After rapid screening of the second-step conditions, we reaction.
9
observed that shorter reaction times (Scheme 2b) or
The reaction also preceded efficiently with di-
versely substituted diorganoyl diselenides (6a–g)
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Table 2. Scope of the one-pot procedure to prepare the
compounds 5a–j.
Table 3. Scope of the one-pot procedure to prepare the
compounds 8a–h.
[
a]
Reaction conditions: 1 (0.25 mmol, 1.0 equiv.), 6
0.125 mmol, 1.0 equiv.), Cs CO (0.75 mmol, 3.0 equiv.),
(
2
3
DMSO (2.0 mL), air atmosphere, I (1.5 equiv., 0.37 mmol),
2
DCM (2.0 mL).
[b]
4
5°C at second step.
Table 4. NBS as electrophilic source in the second step of the
one-pot procedure (5k–m, 8i–k).
[a]
Reaction conditions: 1 (0.25 mmol, 1.0 equiv.), (0.125 mmol,
.0 equiv.), Cs CO (0.75 mmol, 3.0 equiv.), DMSO
1
2
3
(
2.0 mL), air atmohphere, I (1.5 equiv., 0.37 mmol), DCM
2
(
1
4
2.0 mL).
.0 equiv. of 2h.
5°C at second step.
[
b]
c]
[
(Table 3). In general, the yields of the corresponding 3-
iodo-2-organoselenylbenzo[b]chalcogenophenes (8a–
g) were slightly lower than for 5a–i, and similar times
of reactions were reported. The T1 time was also
shorter with diaryl diselenides (6a–e), and again no
clear electronic effects were observed from substitu-
ents on the Se-aryl group. The T1 time was longer
with dibutyl diselenide (6f), as well the T2 time in the
second step with the in situ-produced 7f. The observed
T2 times of reactions were also longer when the Se-
aryl groups on 7a–e were substituted with electron-
donating or electron-withdrawing groups. The one-pot
procedure for the synthesis of benzo[b]thiophenes also
[a]
Reaction conditions: 1a–c (0.25 mmol, 1.0 equiv.), 2a or 6a
(
0.125 mmol, 1.0 equiv.), Cs CO3 (0.75 mmol, 3.0 equiv.),
2
DMSO (2.0 mL), air atmosphere, NBS (2.5 equiv.,
0.62 mmol), DCM (2.0 mL).
45°C at second step.
[b]
took longer T1 and T2 times, and the compound 8g 2.5 h of the first step of the one-pot procedure, as
was obtained in good yield. The compound 8h could detected by GC-MS analysis.
not be produced by this one-pot reaction from 1c, but
The use of NBS in the second step of this one-pot
the intermediate 7h was produced efficiently after procedure was also investigated with the 1-(2,2-
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dibromovinyl)-2-organochalcogenylbenzenes (1a, 1b (Scheme 3b). The role of the base in the following
and 1c) and diphenyl dichalcogenides 2a and 6a steps was also confirmed by a reaction employing 3aa
(Table 4). When these reactions were performed with a and 2a under the standard conditions of time and
higher amount of a stronger electrophile, even the temperature, where only the starting materials were
benzo[b]furans (5m, 8k) were obtained in moderate detected (Scheme 3c). The intermediate 3a was ob-
yields. The benzo[b]thiophenes (5l, 8j) and benzo[b] tained in 74% isolated yield only after the addition of
selenophenes (5k, 8i) were also prepared in good 2.0 equivalents of Cs CO .
2
3
yields in up to 2.0 h of reaction at the second step.
Furthermore, the reaction was conducted in the
In order to clarify the intriguing reaction mecha- presence of radical scavengers such as TEMPO
nism of the first step of the one-pot procedure, several (2,2,6,6-tetramethylpiperidin-1-oxyl), BHT (2,6-di-
experiments were carried out (Scheme 3). Firstly, the tert-butyl-4-methylphenol) or HQ (hydroquinone)
reaction between the 1-(2,2-dibromovinyl)-2-butylsela- under the standard conditions, and the product 3a was
nylbenzene (1a) and diphenyl disulfide (2a) under obtained in 85%, 89% and 91% yields, respectively
1
standard conditions was followed by GC-MS, H and (Scheme 3d). These data suggests that a radical path-
1
3
1
C{ H} NMR spectroscopy (see figures S1–S4, way is not involved in the reaction.
supporting information). The formation of the respec- On the basis of our results and the knowledge that
tive 1-bromoalkyne 3aa from a quick base-mediated 1-bromoalkynes could be a source of acetylide anions
[22]
elimination of 1a was detected by GC-MS after 0.08 h in the presence of mild organic or inorganic bases,
a
(5.0 min) of reaction, and trace amounts of the terminal plausible mechanism for the first step of this one-pot
alkyne 4a were observed after 0.25 h (15 min) of methodology is proposed in Scheme 4. The reaction
reaction. The formation of 3aa was also detected by initiates through a fast base-promoted elimination of
1
3
1
C{ H} NMR spectroscopy after 0.08 h (5.0 min) of the
1-(2,2-dibromovinyl)-2-organochalcogenylben-
reaction, where we observed two characteristic signals zenes (1) to generate the respective 1-bromoalkyne
[23]
at 78.48 ppm and 57.79 ppm, related to both carbons (A). Subsequently, the umpolung of the key inter-
of the triple bond on the 1-bromoalkyne 3aa. The role mediate A by Cs CO results in the cesium acetylide
2
3
[22]
of 3aa as reaction intermediate was supported by an anion (B), which follows a nucleophilic substitution
experiment using this compound as starting material (S 2) at the XÀ X bond of the diorganoyl dichalcoge-
N
[24]
with 2.0 equivalents of Cs CO (Scheme 3a), which nide (2 or 6) to produce the expected product (3 or
2
3
provided 89% isolated yield of 3a.
7) and an organochalcogenolate anion (C). After this,
On the other hand, when the standard conditions the diorganoyl dichalcogenide (2 or 6) could be
were applied to the terminal alkyne 4a, only the regenerated through oxidation of the organochalcoge-
[25]
starting materials were obtained after 0.5 h at 110°C nol (D) with O2, which is in accordance with the air-
atmosphere-dependence of this method (Table 1, en-
try 20). Nevertheless, the oxidation of organochalcoge-
[26]
nol (D) by DMSO cannot be ruled out.
Finally,
probably through an acid-base reaction and reduction
[27]
by DMSO, the cesium hypobromite is quenched in
the system.
Conclusion
In summary, we have developed a rapid and efficient
transition-metal-free method for the synthesis of
chalcogenoacetylenes from 1,1-dibromoalkenes. Con-
ceptually, this reaction offers a new approach to
trapping diorganoyl dichalcogenides with acetylide
anions formed in situ from 1,1-dibromoalkenes and
mild bases. The conditions of this reaction allowed us
to develop a one-pot procedure for the synthesis of 3-
halo-2-organochalcogenylbenzo[b]chalcogenophenes
through an electrophile-promoted nucleophilic cycliza-
tion. By using this strategy, we have rapidly achieved
the one-pot synthesis of several 2,3-disubstituted
benzo[b]chalcogenophenes in moderate to excellent
yields.
Scheme 3. Control experiments.
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Scheme 4. Proposed reaction steps for the first step of the one-pot methodology.
Experimental Section
atoms were located in difference maps and were refined
isotropically and freely. Scattering factors for neutral atoms
Unless otherwise stated, all reagents were purchased from
commercial suppliers and used without further purification. The
reaction solvents DMSO (dimethyl sulfoxide), DMF (N,N-
dimethylformamide), NMP (N-methyl-2-pyrrolidone), DCM
[31]
were taken from reference. Computer programs used in this
analysis have been noted above, and were run through
[32]
WinGX and figures that refer to the compound 5e were made
[32]
using program ORTEP; refinement details can be found in
(dichloromethane), toluene and ethanol and were dried, purified
the support information. High resolution mass spectra (HMRS)
were recorded in positive ion mode (APCI) using a Bruker
micrOTOF-QIII spectrometer.
and degassed by classical methods. Solvents used in liquid-
liquid extraction and as eluents for chromatographic purification
were distilled before use. The reactions were monitored by thin-
layer chromatography (TLC) using silica gel 60 F254 aluminum
sheets, and the visualization of the spots was by UV light General procedure for the one-pot synthesis of
254 nm) or stained with iodine. Column chromatography was 3-iodo-2-(organochalcogenyl)benzo[b]
(
1
13
performed on silica gel (230–400 mesh). H NMR and
C
chalcogenophenes (5a–5i, 8a–8g)
NMR were recorded on a 400 MHz Bruker Nuclear Ascend 400
spectrometer and the chemical shifts (δ) reported in parts per
million (ppm) relative to TMS as internal standard in spectra
To a Schlenk tube containing the appropriate 1-(2,2-dibromo-
vinyl)-2-butylchalcogenylbenzene
.0 equiv.), the dioganyl dichalcogenide (2a–h) or (6a–f)
0.125 mmol, 1.0 equiv.) was added in dry DMSO (2.0 mL).
After this, Cs CO (0.244 g, 0.75 mmol, 3.0 equiv.) was added.
(1a–c)
(0.25 mmol,
1
(
made in CDCl . Coupling constants (J) are reported in hertz.
3
Abbreviations to denote the multiplicity of a particular signal
on the NMR spectra are described as s (singlet), d (doublet), dt
2
3
The reaction system was heated at 110°C for the reaction time
(doublet of triplets), ddd (doublet of doublet of doublets), t
(triplet), td (triplet of doublets), q (quartet), quint (quintet), sext
(sextet), m (multiplet, complex pattern) and br (broad signal).
(T1) described on the Tables 2, 3 and 4. After this, the reaction
was cooled to room temperature and 1.5 equivalents of I were
2
dissolved in 2 ml of DCM were slowly added (2.0 min). The
reaction was stirred at room temperature for the reaction times
Melting point (mp) values were measured on a Mettler Toledo
MP90 Melting Point System. Low-resolution mass spectra were
obtained with a Shimadzu GC-MS-QP2010 Plus mass spec-
trometer. The single-crystal X-ray diffraction analyses of 5e
(T2) described on the Tables 2, 3 and 4. After this, the reaction
solution was diluted in water (20 mL) and the excess I was
2
removed by washing the reaction with saturated sodium
thiosulfate solution (10 mL). Then, mixture was washed with
ethyl acetate (3x 10 mL). The organic phase was dried over
(which was obtained by slow evaporation in DMF) were
performed at room temperature (rt) on a Bruker D8 Venture
diffractometer equipped with a Photon 100 CMOS detector,
MoÀ Kα radiation (λ=0.71073 Å) and graphite monochromator.
magnesium sulfate (MgSO ) and concentrated under reduced
4
[28]
pressure. The products were further purified by flash chroma-
tography using hexane as eluent.
The data were processed using the APEX3 program.
The
structures were determined by the direct method routines in the
[29]
SHELXS program and refined by full-matrix least-squares
[17b]
3
-iodo-2-(phenylsulfanyl)benzo[b]benzoselenophene (5a):
2
[30]
methods, on F ’s, in SHELXL. The non-hydrogen atoms were
1
Yield: 0,096 g (93%); yellow oil. H NMR (CDCl , 400 MHz) δ
3
refined with anisotropic thermal parameters. All hydrogen
(ppm)=7.75 (dd, J=8.2 and 1.4 Hz, 1H); 7.62 (dd, J=8.4 and
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1
1
1
1
1
2
.3 Hz, 1H); 7.50–7.48 (m, 2 H); 7,37 (ddd, J=8.2, 7.2 and
Wang, Z. Pan, J. A. Chen, Angew. Chem. Int. Ed. 2016,
55, 6428–6432; Angew. Chem. 2016, 128, 6538–6542.
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.3 Hz, 1H); 7.34–7.31 (m, 3H); 7,22 (ddd, J=8.4, 7.2 and
13
1
.4 Hz, 1H). C{ H} NMR (CDCl , 100 MHz) δ (ppm)=
3
43.4, 141.3, 139.8, 134.6, 131.7, 129.4, 128.4, 128.0, 125.7,
25.6, 124.9, 89.2. MS (Rel. Int.) m/z: 416 (88.7), 288 (86.1),
08 (100), 77 (22.6).
1
38, 1002–1033; b) A. B. A. Mahmoud, G. Kirsch, E.
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General procedure for the one-pot synthesis of
-bromo-2-(organochalcogenyl)benzo[b]
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chalcogenophenes (5k–5m, 8i–8k)
To a Schlenk tube containing the appropriate 1-(2,2-dibromo-
vinyl)-2-butylchalcogenylbenzene
.0 equiv.), the dioganyl dichalcogenide (2a) or (6a)
0,125 mmol, 1.0 equiv.) was added in dry DMSO (2.0 mL).
After this, Cs CO (0.244 g, 0.75 mmol, 3.0 equiv.) was added.
(1a–c)
(0.25 mmol,
1
(
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The reaction system was heated at 110°C for the reaction time
(T1) described on the Tables 2, 3 and 4. After this, the reaction
2
was cooled to room temperature and 2.5 equivalents of N-
bromosuccinimide were dissolved in 2 ml of DCM were slowly
added (2.0 min). The reaction was stirred at room temperature
for the reaction times (T2) described on the Tables 2, 3 and 4.
After this, the reaction solution was diluted in water (20 mL)
and washed with a saturated sodium thiosulfate solution
[
[
3
5
ihara, M. Kanai, K. Yoshida, N. kakysawa, D. Hashi-
zume, M. Uchiyama, S. Yasuike, Tetrahedron 2016, 72,
(
1
(
10 mL). Then, mixture was washed with ethyl acetate (3x
0 mL). The organic phase was dried over magnesium sulfate
MgSO ) and concentrated under reduced pressure. The prod-
8
085–8090; c) G. Leonel, D. F. Back, G. Zeni, Adv.
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4
ucts were further purified by flash chromatography using
hexane as eluent.
[
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[
17b]
3
-bromo-2-(phenylsulfanyl)benzo[b]selenophene
(5k):
1
Yield: 0,072 g (78%); yellow oil. H NMR (CDCl , 400 MHz) δ
ppm)=7.82 (dd, J=8.1 and 1.0 Hz, 1H); 7.82 (dd, J=8.0 and
.1 Hz, 1H); 7.54–7.50 (m, 2H); 7.44 (ddd, J=8.1, 7.2 and
.0 Hz, 1H); 7.39–7.28 (m, 4H). C{ H} NMR (CDCl ,
00 MHz) δ (ppm)=140.3, 140.2, 134.6, 132.0, 131.5, 129.4,
28.4, 125.7, 125.6, 125.5, 125.1, 113.1. MS (Rel. Int.) m/z:
67 (78.3), 288 (92.5), 207 (100), 77 (25.8).
3
(
2
2321; c) Z. Yi, S. Wang, L. Liu, Adv. Mater. 2015, 27,
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1
1
1
3
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3589–3606; d) M. R. Reddya, H. Kimb, C. Kimb, S.
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3
Acknowledgements
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior e Brasil
CAPES) – Finance Code 001, CNPq Process: 400400/2016-2,
(
Fundação Araucaria and UFPR.
[7] a) R. S. Ashraf, I. Meager, M. Nikolka, M. Kirkus, M.
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He, Z. He, H.-B. Wu, W. Yang, B. Zhang, Y. Cao, ACS
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Adv. Synth. Catal. 2021, 363, 1–10
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FULL PAPER
One-Pot Synthesis of 3-Halo-2-organochalcogenylbenzo[b]
chalcogenophenes from 1-(2,2-Dibromovinyl)-2-organochal-
cogenylbenzenes
Adv. Synth. Catal. 2021, 363, 1–10
E. Q. Luz, G. L. Silvério, D. Seckler, D. B. Lima, F. S.
Santana, R. V. Barbosa, C. R. Montes D’Oca, D. S. Rampon*