Silver-Catalyzed Synthesis of Diaryl Selenides by Reaction of Diaryl Diselenides with Aryl Boronic Acids

Article abstract of DOI:10.1021/acs.joc.6b02108

We described herein our results on the silver-catalyzed synthesis of diaryl selenides via a cross-coupling reaction of diaryl diselenides with aryl boronic acids. The methodology is tolerant to electron-donor and electron-withdrawing groups at the substrates and the desired products were obtained in good to excellent yields.

Full text of DOI:10.1021/acs.joc.6b02108

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Note
Silver-catalyzed synthesis of diaryl selenides by
reaction of diaryl diselenides with aryl boronic acids
Bruna Goldani, Vanessa G. Ricordi, Natália Seus, Eder J.
Lenardao, Ricardo Frederico Schumacher, and Diego Alves
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02108 • Publication Date (Web): 12 Oct 2016
Downloaded from http://pubs.acs.org on October 14, 2016
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Silver-catalyzed synthesis of diaryl selenides by
reaction of diaryl diselenides with aryl boronic acids
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Bruna Goldani, Vanessa G. Ricordi, Natália Seus, Eder J. Lenardão,
Ricardo F. Schumacher, Diego Alves*
LASOL - CCQFA - Universidade Federal de Pelotas - UFPel - P.O. Box 354 - 96010-
900, Pelotas, RS, Brazil.
diego.alves@ufpel.edu.br
Abstract: We described herein our results on the silver-catalyzed synthesis of diaryl
selenides via a cross-coupling reaction of diaryl diselenides with aryl boronic acids. The
methodology is tolerant to electron-donor and electron-withdrawing groups at the
substrates and the desired products were obtained in good to excellent yields.
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Organoselenium compounds have been known for many years merely as
precursor to introduce unsaturated carbon-carbon bonds to organic molecules by an
intramolecular syn elimination of selenoxides.1 Although, it is still a widely used
method, since the 80’s, with the success of ebselen (Figure 1) as the first synthetic
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organoselenium compound considered as
a
promising antioxidant2 and
a
neuroprotective agent,3 many other applications into chemistry, biochemistry and
materials sciences have been found for this class of compounds.4
In this context, diaryl selenides have attracted considerable attention because of
their biological activities (e.g. anticancer, antitumor, antiviral, antimicrobial, and
antioxidant) and some biologically important molecules containing the diaryl selenide
skeleton are shown in Figure 1.5
Figure 1. Biologically important selenium compounds
This point has motivated the report of different methodologies to synthesize
these compounds, and the use of diorganyl dichalcogenides combinated to aryl
boronic acids are one of the most studied.6-8 In this sense, many transition metals,
such as indium,6 iron7 and mainly copper salts,8 have been used as catalysts for this
purpose. Alternatively, our research group recently published the reaction of
nucleophilic arylselenium species, generated in situ by the reaction of diorganyl
diselenides with hypophosphorous acid (H3PO2), with arenediazonium salts.9
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On the other hand, silver has emerged in the last years as an efficient transition
metal-catalyst used for many organic transformations, such as aza-Diels-Alder,10
asymmetric aldol11 and cyclization12 reactions. The selective interaction of silver(I) salts
with the C–C π-bond of alkynes appeared to be the more explored property for the
construction of new C-C and C-heteroatom bonds through C-H activation reaction.13
Regarding to the chalcogen chemistry, silver has become an interesting building block
for the construction of supramolecular assemblies and semiconductor devices.14
However, to the best of our knowledge, the use of silver catalyst in the synthesis of
diorganyl chalcogenides have not been reported before.
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In view of the explained above and due to our interest in the development of
versatile protocols to the synthesis of organochalcogenides, we report here our results
on the silver-catalyzed cross-coupling reaction of aryl boronic acids with diaryl
diselenides (Scheme 1).
Scheme 1.
Initially, our efforts were devoted to select a suitable catalytic system for an
efficient coupling. In this way, diphenyl diselenide 1a and 4-methoxy-phenyl boronic
acid 2a were considered as standard substrates to the silver-catalyzed cross-coupling
reaction. Thus, diphenyl diselenide 1a (0.15 mmol) and commercially available 4-
methoxy-phenyl boronic acid 2a (0.30 mmol) were reacted in the presence of different
silver (I) salts and a variety of solvents and the results are showed in Table 1.
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As a preliminary experiment 10 mol% of silver (I) acetate was used as catalyst
in 1,4-dioxane (0.5 mL) at 100 °C and under this condition, the desired (4-
methoxyphenyl)(phenyl)selenide 3a was obtained in 30 % yield after 12 h (Table 1,
entry 1). With this result in hands, as shown in Table 1, entries 2-5, several silver (I)
catalysts were tested in a the same catalytic amount (10 mol%). The best result was
obtained when AgNO3 was used, giving the desired product 3a in 93 % yield (Table 1,
entry 3). Next, we planned to verify the influence of the solvent in the reaction and
diverse solvents with different characteristics, such as toluene, DMF, DMSO, H2O,
glycerol and PEG-400 were used (Table 1, entries 6-11). However, none chemical or
environmental benefits were achieved in these experiments. It is important to mention
that when the cross-coupling reaction was performed at room temperature, only 48%
yield of the expected selenide 3a was obtained (Table 1, entry 12) and even a slight
decrease in the temperature from 100 °C to 80 °C considerably affects the reaction yield
(Table 1, entry 13). Moreover, it is worth noting that when the amount of AgNO3 was
reduced from 10 to 5 mol% or 2 mol%, a consecutive decrease in the yields of the
coupling products was observed (Table 1, entries 14 and 15).
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Finally, considering the reaction time, we believe that the best performance for
this reaction of diphenyl diselenide 1a with boronic acid 2a catalyzed by silver (I)
nitrate in 1,4-dioxane at 100 °C was obtained after a period of 6 h, when the product 3a
was isolated in 91 % yield (Table 1, entry 16).
Once the best experimental conditions to the synthesis of 3a was established
(Table 1, entry 16), we envisioned to extend the methodology to a variety of diorganyl
diselenides 1a-j, as well as, differently substituted aryl boronic acids 2a-l. Fortunately,
the method proved robust and general, with the respective diorganyl selenides 3a-u
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being obtained efficiently in good to excellent yields and the results are presented in
Table 2.
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Table 1. Optimization of the reaction conditions.a
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Silver (I) salt
(mol %)
Temp. Yield
Entry
Solvent
(°C)
100
100
100
100
100
110
110
100
90
(%)
35
40
93
NR
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20
70
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12b
13
14c
15c
16d
AgOAc (10) 1,4-dioxane
Ag2SO4 (10) 1,4-dioxane
AgNO3 (10) 1,4-dioxane
AgOTf (10) 1,4-dioxane
Ag2CO3(10) 1,4-dioxane
AgNO3 (10)
AgNO3 (10)
AgNO3 (10)
AgNO3 (10)
AgNO3 (10)
AgNO3 (10)
AgNO3 (10) 1,4-dioxane
AgNO3 (10) 1,4-dioxane
AgNO3 (5)
AgNO3 (2)
AgNO3 (10) 1,4-dioxane
DMF
DMSO
toluene
H2O
glycerol
PEG-400
50
30
90
90
r.t.
80
20
traces
48
75
1,4-dioxane
1,4-dioxane
100
100
100
75
60
91
a
The reactions were performed using diphenyl diselenide 1a
(0.15 mmol), 4-methoxy-phenyl boronic acid 2a (0.30 mmol),
silver salt and solvent (0.5 mL) during 12 h under air. b Reaction
c
d
time of 48 h. Reaction time of 24 h. Reaction time of 6 h.
NR= No Reaction.
Regarding to the aryl boronic acids 2, various functional groups directly
attached to the benzene ring at ortho- or para-position were tolerated, but it is
important to point out that electronic effects of the substituents have a somewhat
influence in the reaction yield of the corresponding diaryl selenides 3. For
example, electron-rich aryl boronic acids, having a p-methoxy (2a) or a p-methyl
group (2b), gave better yields if compared to those containing slightly electron-
withdrawing groups as bromo (2d) and chloro (2e). This influence becomes still
more evident when the boronic acid 2f, having a trifluoromethane group at the
meta-position, was used (Table 2, compare entries 1-2 with 4-6). In this way, it is
interesting to note that electronic effects are also observed when substituents at
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the ortho-position are evaluated in the aryl boronic acids 2g-j (Table 2, entries 7-
10). In contrast, the reaction appears not to be sensible to steric effects, and
comparable yields were obtained for the para- and ortho-substituted boronic acids
where the same functional group is present (Table 2, entries 1 vs 7 and 5 vs 9). 3-
Thienylboronic acid 2l was efficiently reacted with diphenyl diselenide 1a giving
the product 3l in good yield (Table 2, entry 12).
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The possibility to extend the methodology to differently substituted diaryl
diselenides 1b-i was also explored in the reaction with 4-methoxy-phenyl boronic acid
2a. The reaction worked well, affording the respective diaryl selenides 3m-t in good to
excellent yields under the same reaction conditions (Table 2, entries 13-20). It was
observed that the presence of electron-withdrawing groups at the aromatic ring of the
diselenide adversely affects the reaction compared to electron-donating ones (Table 2,
entries 13-17). Differently to the observed for the boronic acids counterpart, when
hindered diaryl diselenides 1g-h were used as substrates in the cross-coupling reaction,
lower yields of the respective products 3r-s were obtained (Table 2, entries 18 and 19).
The methodology was successfully extended to dipyridyl diselenide 1i, which
furnished the expected selenide 3t in 80% yield, showing the versatility of this reaction
also to diheteroaryl diselenides (Table 2, entry 20). Not only aromatic diselenides are
suitable substrates to the reaction; dibutyl diselenide 1j reacted with 4-methoxy-phenyl
boronic acid 2a in the presence of AgNO3 (10 mol %) to produce, after 6 h, (4-
methoxy-phenyl)(butyl) selenide 3u in 75% yield (Table 2, entry 21). This is a valuable
result which reinforces the versatility of our protocol. Considering the previously
described protocols to access diorganyl selenides from arylboronic acids and diorganyl
diselenides, which use indium, iron and copper catalysts,6-8 our methodology can be
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considered an efficient and attractive alternative, once AgNO3 is not expensive and
easily handled.
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Table 2. AgNO3-catalyzed synthesis of differently substituted diorganyl selenides.a
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Entry
1
R (1)
Ph (1a)
Ar (2)
Product 3 (Yield)
3a (91%)
3b (96%)
3c (96%)
3d (85%)
3e (83%)
3f (75%)
3g (90%)
3h (92%)
3i (82%)
3j (60%)
3k (90%)
3l (77%)
3m (86%)
3n (83%)
3o (80%)
3p (93%)
3q (72%)
3r (70%)
3s (55%)
3t (80%)
3u (75%)
4-OMeC6H4 (2a)
4-MeC6H4 (2b)
Ph (2c)
2
Ph (1a)
3
Ph (1a)
4
Ph (1a)
4-BrC6H4 (2d)
4-ClC6H4 (2e)
3-CF3C6H4 (2f)
2-OMeC6H4 (2g)
2-MeC6H4 (2h)
2-ClC6H4 (2i)
2-BrC6H4 (2j)
2-Naph (2k)
5
Ph (1a)
6
Ph (1a)
7
Ph (1a)
8
Ph (1a)
9
Ph (1a)
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21
Ph (1a)
Ph (1a)
Ph (1a)
3-Th (2l)
4-ClC6H4 (1b)
4-FC6H4 (1c)
3-CF3C6H4 (1d)
4-OMeC6H4 (1e)
4-MeC6H4 (1f)
2-MeC6H4 (1g)
Mes (1h)
2-Py (1i)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
4-OMeC6H4 (2a)
n-Bu (1j)
a The reactions were performed using diorganyl diselenide 1 (0.15 mmol), aryl boronic acid 2 (0.30 mmol), AgNO3
(10 mol%, 0.005 g) at 100 °C in 1,4-dioxane (0.5 mL) under air during 6 h.
Based on recent publications involving silver-catalyzed reactions15 and our
experiments, a plausible mechanism proposed for this Ag(I)-catalyzed C–Se coupling
reaction of aryl boronic acids 2 with diorganyl diselenides 1 is depicted in Figure 2. We
believe that, at first, the reaction of AgNO3 with diorganyl diselenide 1 leads to the
Ag(III) intermediate A. After that, aryl boronic acid 2 would attack the intermediate A
to form the corresponding product 3 and the intermediate B. Then, the obtained
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(RSe)[B(OH)2]AgIII B reacts with other equivalent of aryl boronic acid 2 leading to the
intermediate C and tetrahydroxydiboron D. Finally, intermediate C can undergo a
reductive elimination to form the desired product 3 regenerating the Ag(I) catalyst in the
catalytic cycle. The proposed mechanism indicates that this Ag(I)-catalyzed C–Se
coupling reaction is able to use both groups on diorganyl dichalcogenide 1.
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Analysis of 77Se NMR spectroscopy and HRMS spectrometry were performed to
prove the formation of the intermediate A. Diphenyl diselenide 1a and AgNO3 were
mixed in CDCl3 in a NMR tube and after 20 min at room temperature the mixture was
77
analyzed by Se NMR and the HRMS was measured in ESI(+)-MS mode (please see
the Support Information for the spectra images). A peak with m/z of 420.4080 in the
77
HRMS spectrum and the presence of two signals in the Se NMR, one at 462.93 ppm
(PhSeSePh 1a) and other at 382.56 ppm (due to Ph2Se2AgIII A) are strong indications
that support such mechanism, at least in the first step.
Figure 2. A plausible mechanism of the reaction.
In summary, we developed an alternative method for the synthesis of diaryl
selenides through the silver-catalyzed cross-coupling reaction of diaryl diselenides with
aryl boronic acids. Using a catalytic amount of silver (I) nitrate in 1,4-dioxane at 100 °C
under air atmosphere, a range of diaryl selenides was obtained from substituted diaryl
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diselenides and arylboronic acids bearing electron-withdrawing and electron-donating
groups in good to excellent yields. Studies on the determination of the identity of the
AgNO3/diorganyl diselenides intermediates are in course in our laboratory.
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Experimental Section
General Information: The reactions were monitored by TLC carried out on Merck
silica gel (60 F254) by using UV light as visualizing agent and 5% vanillin in 10% H2SO4
and heat as developing agents. Baker silica gel (particle size 0.040-0.063 mm) was used
for flash chromatography. Hydrogen nuclear magnetic resonance spectra (1H NMR)
were obtained at 400 MHz and were recorded in CDCl3 solutions. Chemical shifts are
reported in ppm, referenced to tetramethylsilane (TMS) as the external reference.
Coupling constants (J) are reported in Hertz. Abbreviations to denote the multiplicity of
a particular signal are s (singlet), d (doublet), dd (double doublet), ddd (double double
doublet), t (triplet), q (quartet), quint. (quintet), sex (sextet) and m (multiplet). Carbon-
13 nuclear magnetic resonance spectra (13C NMR) were obtained at 100 MHz. Chemical
shifts are reported in ppm, referenced to the solvent peak of CDCl3. Low-resolution
mass spectra were obtained with a mass spectrometer using electron ionisation (EI) as
an ionization method and positive charge ion detector. The starting materials (aryl- or
heteroarylboronic acids 2a-v) were purchased from a commercial supplier. Diorganyl
diselenides were synthesized according to the literature.16
General Procedure for Silver(I)-Catalyzed Synthesis of Diaryl Selenides (3): To a 5
mL round-bottomed flask equipped with a small magnetic stirring bar and under air
atmosphere containing the catalyst AgNO3 (0.005 g, 10 mol %), a solution of 0.15
mmol of the appropriate diorganyl diselenide 1 in 0.5 mL of 1,4-dioxane was added. To
this solution, the appropriate aryl boronic acid 2 (0.30 mmol) was added and the
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reaction mixture was allowed to stir at 100 °C for 6 hours. After that, the reaction
mixture was cooled to the room temperature, and was quenched using water (5 mL).
The mixture was then extracted by ethyl acetate (10 mL) and washed with water (3 x 10
mL). The combined organic layers were dried over anhydrous MgSO4 and concentrated
under vacuum to yield the crude product, which was purified by flash chromatography
on silica gel using hexane (for 3b-k) or a mixture of hexane/ethyl acetate (for 3a, 3l-r
and 3t: 95/5; for 3s: 80/20) as eluent. All the compounds were characterized and the
spectral data of compounds 3a-u are in agreement with those from literature.
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1
4-Methoxyphenyl-phenyl-selenide8g (3a): Yield: 0.073 g (91%). H NMR (CDCl3,
400 MHz): δ 7.50 (d, J = 8.8 Hz, 2H); 7.33-7.31 (m, 2H); 7.21-7.16 (m, 3H); 6.84
(d, J = 8.4 Hz, 2H); 3.79 (s, 3H). 13C{1H} NMR (CDCl3 100 MHz); δ (ppm): 159.7,
136.5, 133.2, 130.9, 129.1, 126.4, 119.9, 115.1, 55.2. MS (relative intensity) m/z:
264 (65), 262 (34), 184 (100), 153 (32), 65 (14).
4-Tolyl-phenyl-selenide8g (3b): Yield: 0.071 g (96%). 1H NMR (CDCl3, 400 MHz):
δ 7.38-7.32 (m, 4H); 7.23-7.16 (m, 3H); 7.04 (d, J = 8.5 Hz, 2H); 2.33 (s, 3H).
13C{1H} NMR (CDCl3 100 MHz); δ (ppm): 137.6, 133.8, 132.0, 130.1, 129.1, 126.8,
21.1. MS (relative intensity) m/z: 248 (70), 246 (39), 168 (100), 153 (25), 91 (63),
65 (30).
1
Diphenyl-selenide8g (3c): Yield: 0.067 g (96%). H NMR (CDCl3, 400 MHz): δ
7.46-7.44 (m, 4H); 7.24-7.21 (m, 6H). 13C{1H} NMR (CDCl3 100 MHz); δ (ppm):
132.9, 131.1, 129.3, 127.2. MS (relative intensity) m/z: 234 (30), 154 (100), 77 (20),
51 (17).
1
4-Bromophenyl-phenyl-selenide8g (3d): Yield: 0.079 g (85%). H NMR (CDCl3,
400 MHz): δ 7.46-7.44 (m, 2H); 7.34 (d, J = 8.4 Hz, 2H); 7.28-7.25 (m, 5H).
13C{1H} NMR (CDCl3 100 MHz); δ (ppm): 134.1, 133.2, 133.0, 130.4, 130.3, 129.4,
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127.6, 121.41. MS (relative intensity) m/z: 314 (68), 312 (86), 234 (84), 232 (99),
5
6
152 (100), 116 (27), 77 (58), 51 (41).
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4-Chlorophenyl-phenyl-selenide8g (3e): Yield: 0.066 g (83%). H NMR (CDCl3,
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400 MHz): δ 7.46-7.44 (m, 2H); 7.36 (d, J = 8.0 Hz, 2H); 7.28-7.26 (m, 3H); 7.21
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(d, J = 8.0 Hz, 2H). C{1H} NMR (CDCl3 100 MHz); δ (ppm): 134.1, 133.5, 133.1,
130.6, 129.5, 129.4, 127.6. MS (relative intensity) m/z: 270 (15), 268 (36), 188
(100), 152 (27), 77 (22), 51 (18).
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3-(trifluoromethyl)phenyl-phenyl-selenide17 (3f): Yield: 0.067 g (75%). H NMR
(CDCl3, 400 MHz): δ 7.67 (s, 1H); 7.53-7.44 (m, 4H); 7.31-7.26 (m, 4H). 13C{1H}
NMR (CDCl3 100 MHz); δ (ppm): 135.1, 134.0, 133.2, 131.5 (q, J = 32.2 Hz),
129.6, 129.5, 129.4, 128.4 (q, J = 3.8 Hz), 128.2, 123.7 (q, J = 272.8 Hz), 123.6 (q, J
= 3.8 Hz). MS (relative intensity) m/z: 302 (55), 222 (100), 153 (16), 77 (35), 51
(24).
2-Methoxyphenyl-phenyl-selenide8g (3g): Yield: 0.071 g (90%). 1H NMR (CDCl3,
400 MHz): δ 7.61–7.56 (m, 2H), 7.35–7.31 (m, 3H), 7.24–7.14 (m, 1H), 6.97-7.74
(m, 3H), 3.88 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3); δ (ppm): 156.9, 135.2,
131.2, 129.4, 128.6, 127.9, 127.8, 122.0, 121.6, 110.6, 55.9. MS (relative intensity)
m/z: 264 (65), 262 (33), 184 (100), 169 (40), 141 (33), 77 (32).
2-Tolyl-phenyl-selenide8g (3h): Yield: 0.068 g (92%). 1H NMR (CDCl3, 400 MHz):
δ 7.40-7.38 (m, 2H); 7.35-7.32 (m, 1H); 7.27-7.17 (m, 5H); 7.08-7.04 (m, 1H); 2.40
(s, 3H). 13C{1H} NMR (CDCl3 100 MHz); δ (ppm): 139.8, 133.6, 132.7, 131.7,
130.7, 130.2, 129.3, 127.7, 127.1, 126.7, 22.3. MS (relative intensity) m/z: 248 (72),
246 (37), 168 (100), 153 (20), 91 (57), 65 (32).
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2-Chlorophenyl-phenyl-selenide8g (3i): Yield: 0.065 g (82%). H NMR (CDCl3,
400 MHz): δ 7.65-7.58 (m, 2H); 7.41-7.23 (m, 4H); 7.15-6.98 (m, 2H), 6.91 (dd, J =
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7.6, 1.9 Hz, 1H). 13C{1H} NMR (CDCl3 100 MHz); δ (ppm): 135.9, 133.9, 131.6,
131.0, 129.7, 129.4, 128.7, 128.2, 127.4, 127.3. MS (relative intensity) m/z: 270
(19), 268 (41), 188 (100), 152 (32), 77 (19), 51 (19).
2-Bromophenyl-phenyl-selenide18 (3j): Yield: 0.056 g (60%). H NMR (CDCl3,
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400 MHz): δ 7.66–7.62 (m, 2 H), 7.52–7.38 (m, 4 H), 7.07–7.00 (m, 2 H), 6.88–6.83
(m, 1 H). 13C{1H} NMR (CDCl3 100 MHz); δ (ppm): 136.4, 136.2, 132.7, 130.4,
129.8, 128.9, 128.4, 127.8, 127.3, 123.4. MS (relative intensity) m/z: 312 (61), 232
(58), 207 (27), 156 (22), 152 (100), 77 (50).
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2-Naphthyl-phenyl-selenide19 (3k): Yield: 0.076 g (90%). H NMR (CDCl3, 400
MHz): δ 7.98–7.97 (m, 1 H), 7.80-7.69 (m, 3 H), 7.53–7.43 (m, 5 H), 7.27–7.24 (m,
13
3 H). C{1H} NMR (100 MHz, CDCl3); δ (ppm): 133.9, 132.8, 132.3, 132.0, 131.2,
130.4, 129.3, 128.7, 128.4, 127.7, 127.4, 127.3, 126.5, 126.2. MS (relative intensity)
m/z: 284 (24), 204 (100), 126 (11), 115 (19), 77 (11).
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3-thienyl-phenyl-selenide20 (3l): Yield: 0.056 g (77%). H NMR (CDCl3, 400
MHz): δ 7.32 (dd, J = 3.0, 1.0 Hz, 1H), 7.28-7.23 (m, 3H), 7.16-7.10 (m, 3H), 7.01
13
(dd, J = 4.9, 1.0 Hz, 1H). C{1H} NMR (CDCl3 100 MHz); δ (ppm): 132.7, 132.2,
131.0, 129.2 (2C), 126.8, 126.7, 122.7. MS (relative intensity) m/z: 240 (45), 236
(11), 160 (100), 128 (12), 115 (22), 77 (22), 51 (22).
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4-Chlorophenyl-4-methoxylphenyl-selenide8g (3m): Yield: 0.076 g (86%). H
NMR (CDCl3, 400 MHz): δ 7.47 (d, J = 8.8 Hz, 2H); 7.21 (d, J = 8.8 Hz, 2H); 7.14
(d, J = 8.8 Hz, 2H); 6.83 (d, J = 8.8 Hz, 2H), 3.77 (s, 3H). 13C{1H} NMR (CDCl3
100 MHz); δ (ppm): 159.9, 136.6, 132.4, 132.0, 131.5, 129.1, 119.4, 115.2, 55.2. MS
(relative intensity) m/z: 298 (35), 296 (17), 218 (100), 203 (40), 175 (27), 63 (12).
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4-Fluorophenyl-4-methoxylphenyl-selenide9 (3n): Yield: 0.069 g (83%). H NMR
(CDCl3, 400 MHz): δ 7.46 (d, J = 8.9 Hz, 2H), 7.36-7.33 (m, 2H), 6.92 (t, J = 8.8
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Hz, 2H), 6.83 (d, J = 8.9 Hz, 2H), 3.79 (s, 3H). C{1H} NMR (CDCl3 100 MHz); δ
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(ppm):162.1 (d, J = 246 Hz), 159.7, 135.8, 133.6 (d, J = 7.7 Hz), 127.2 (d, J = 3 Hz),
120.6, 116.3 (d, J = 21 Hz), 115.2, 55.3. MS (relative intensity) m/z: 281 (28), 202
(100), 187 (50), 155 (33), 77 (4).
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3-(Trifluoromethyl)phenyl-4-methoxylphenyl-selenide21 (3o): Yield: 0.079 g
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(80%). H NMR (CDCl3, 400 MHz): δ 7.55-7.50 (m, 3H), 7.42-7.23 (m, 3H), 6.88
13
(d, J = 8.8 Hz, 2H), 3.80 (s, 3H). C{1H} NMR (CDCl3 100 MHz); δ (ppm): 160.3,
137.3, 135.1, 133.4, 131.4 (q, J = 32.2 Hz), 129.4, 126.7 (q, J = 3.8 Hz), 123.8 (q, J
= 272.8 Hz), 123.0 (q, J = 3.8 Hz), 118.5, 115.5, 55.3. MS (relative intensity) m/z:
332 (39), 252 (100), 237 (30), 209 (23), 63 (10).
Bis-4-methoxylphenyl-selenide22 (3p): Yield: 0.081 g (93%). 1H NMR (CDCl3, 400
MHz): δ 7.26 (d, J = 8.9 Hz, 4H), 6.65 (d, J = 8.9 Hz, 2H), 3.59 (s, 6H). 13C{1H}
NMR (CDCl3 100 MHz); δ (ppm): 159.1, 134.4, 121.9, 114.8, 55.1. MS (relative
intensity) m/z: 294 (71), 214 (100), 186 (42), 65 (17).
4-Tolyl-4-methoxylphenyl-selenide8g (3q): Yield: 0.059 g (72%). 1H NMR (CDCl3,
400 MHz): δ 7.43 (d, J = 8.8 Hz, 2H); 7.26 (d, J = 8.0 Hz, 2H); 7.00 (d, J = 8.0 Hz,
13
2H); 6.79 (d, J = 8.8 Hz, 2H); 3.72 (s, 3H); 2.25 (s, 3H). C{1H} NMR (CDCl3 100
MHz); δ (ppm): 159.4, 136.5, 135.6, 131.7, 129.9, 128.8, 120.8, 114.9, 55.1, 20.9.
MS (relative intensity) m/z: 278 (65), 198 (100), 183 (43), 170 (33), 91 (32), 65 (22).
2-Tolyl-4-methoxylphenyl-selenide8g (3r): Yield: 0.058 g (70%). 1H NMR (CDCl3,
400 MHz): δ 7.44 (d, J = 8.8 Hz, 2H), 7.14-7.06 (m, 3H), 6.99-6.95 (m, 1H), 6.83 (d,
J = 8.8 Hz, 2H), 3.75 (s, 3H), 2.36 (s, 3H). 13C{1H} NMR (CDCl3 100 MHz); δ
(ppm): 159.7, 137.8, 136.5, 133.8, 130.7, 129.9, 126.5, 119.2, 115.2, 55.2, 21.8. MS
(relative intensity) m/z: 278 (71), 198 (100), 183 (37), 170 (30), 91 (26), 65 (24).
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2,4,6-(trimethyl)phenyl-4-methoxylphenyl-selenide (3s): Yield: 0.050 g (55%). H
NMR (CDCl3, 400 MHz): δ 6.95 (d, J = 8.8 Hz, 2H), 6.83 (s, 2H), 6.59 (d, J = 8.8 Hz,
2H), 3.58 (s, 3H), 2.33 (s, 6H), 2.16 (s, 3H). 13C{1H} NMR (CDCl3 100 MHz); δ (ppm):
158.0, 143.2, 138.6, 130.6, 128.7, 127.8, 123.1, 114.8, 55.1, 24.2, 20.9. MS (relative
intensity) m/z: 306 (100), 226 (54), 211 (22), 197 (78), 183 (18), 119 (25), 105 (12), 91
(40), 77 (25), 63 (8).
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2-pyridine-4-methoxylphenyl-selenide23 (3t): Yield: 0.063 g (80%). H NMR
(CDCl3, 400 MHz): δ 8.41 (ddd, J = 4.9, 1.9, 0.8 Hz, 1H); 7.63 (d, J = 8.9 Hz, 2H);
13
7.36 (ddd, J = 7.5, 4.9, 1.9 Hz, 1H); 7.01-6.88 (m, 4H), 3.83 (s, 3H). C{1H} NMR
(CDCl3 100 MHz); δ (ppm): 160.3, 159.8, 149.6, 138.2, 136.5, 123.3, 120.0, 117.6,
115.3, 55.2. MS (relative intensity) m/z: 265 (68), 264 (100), 262 (63), 249 (21), 185
(25), 142 (15), 78 (59), 51 (32).
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Butyl-4-methoxylphenyl-selenide6a (3u): Yield: 0.054 g (75%). H NMR (CDCl3 400
MHz): δ 7.45 (d, J = 8.8 Hz, 2H); 6.80 (d, J = 8.8 Hz, 2H); 3.78 (s, 3H); 2.81 (t, J = 7.6
Hz, 2H); 1.63 (quint, J = 7.6 Hz, 2H); 1.40 (sex, J = 7.6 Hz, 2H); 0.89 (t, J = 7.6 Hz,
3H). C{1H} NMR (CDCl3 100 MHz): δ 159.1, 135.4, 120.2, 114.6, 55.2, 32.3, 28.7,
13
22.8, 13.5. MS (relative intensity) m/z: 244 (32), 188 (39), 108 (100), 77 (6), 57 (7).
Acknowledgment. We thank the CNPq, CAPES, FAPERGS (PRONEM) and FINEP
for the financial support. CNPq is also acknowledged for the fellowship for E. J. L. and
D. A..
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Supporting Information: Copy of H and C{1H} NMR spectra of all compounds
were presented on supporting information.
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ACS Paragon Plus Environment