Potassium tert-butoxide-mediated synthesis of unsymmetrical diaryl ethers, sulfides and selenides from aryl bromides

Article abstract of DOI:10.1016/j.tet.2013.04.113

Potassium tert-butoxide mediated carbon-chalcogen C-E (E=O, S and Se) coupling reaction has been studied from aryl bromide and phenol/aryl disulfide/diselenide substrates. A series of unsymmetrical diaryl chalcogenides were accessed from aryl bromide and diaryl dichalcogenide precursors by using 2.5 equiv of potassium tert-butoxide in DMSO at 80 C. Unsymmetrical diaryl ethers were also obtained by using phenol precursors at 40-45 C. Aryl bromides with methyl, trifluoromethyl, methoxy and nitro substituents showed compatibility in the carbon-chalcogen bond forming reaction. 4-Methoxy, methyl, trifluoromethyl substituted bromobenzene substrates gave two regioisomers: 3-substituted and 4-substituted diaryl chalcogenides when reacted with phenols/diaryl disulfides/diselenides. Formation of two regioisomeric diaryl chalcogenides in the reaction mixture suggests that potassium tert-butoxide reacts with bromobenzene to produce benzyne intermediate, which subsequently reacts with diaryl dichalcogenides and finally give a regioisomeric mixture of 4-substituted and 3-substituted diaryl chalcogenides.

Full text of DOI:10.1016/j.tet.2013.04.113

Accepted Manuscript
Potassium tert-Butoxide-Mediated Synthesis of Unsymmetrical Diaryl Ethers,
Sulfides, and Selenides from Aryl Bromides
Amit Kumar, Bhagat Singh Bhakuni, Ch. Durga Prasad, Shailesh Kumar, Sangit
Kumar
PII:
S0040-4020(13)00673-X
10.1016/j.tet.2013.04.113
TET 24313
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 20 January 2013
Revised Date: 22 April 2013
Accepted Date: 25 April 2013
Please cite this article as: Kumar A, Bhakuni BS, Prasad CD, Kumar S, Kumar S, Potassium tert-
Butoxide-Mediated Synthesis of Unsymmetrical Diaryl Ethers, Sulfides, and Selenides from Aryl
Bromides, Tetrahedron (2013), doi: 10.1016/j.tet.2013.04.113.
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ACCEPTED MANUSCRIPT
Potassium tert-Butoxide-Mediated Synthesis of
Unsymmetrical Diaryl Ethers, Sulfides, and Selenides
from Aryl Bromides
Amit Kumar, Bhagat Singh Bhakuni, Ch. Durga Prasad, Shailesh Kumar, Sangit
Kumar*
Department of Chemistry, Indian Institute of Science Education and Research (IISER)
Bhopal, MP 462 023, India
E-mail: sangitkumar@iiserb.ac.in
Abstract
Potassium tert-butoxide mediated carbon-chalcogen C-E (E = O, S, and Se) coupling reaction
has been studied from aryl bromide and phenol/ aryl disulfide/ diselenide substrates. A series
of unsymmetrical diaryl chalcogenides were accessed from aryl bromide and diaryl
o
dichalcogenide precursors by using 2.5 equiv of potassium tert-butoxide in DMSO at 80 C.
o
Unsymmetrical diaryl ethers were also obtained by using phenol precursors at 40-45 C. Aryl
bromides with methyl, trifluoromethyl, methoxy, and nitro substituents showed compatibility
in the carbon-chalcogen bond forming reaction. 4-Methoxy, methyl, trifluoromethyl
substituted bromobenzene substrates gave two regio-isomers: 3-substituted and 4-substituted
1

ACCEPTED MANUSCRIPT
diaryl chalcogenides when reacted with phenols/ diaryl disulfides/ diselenides. Formation of
two regioisomeric diaryl chalcogenides in the reaction mixture suggests that potassium tert-
butoxide reacts with bromobenzene to produce benzyne intermediate which subsequently
reacts with diaryl dichalcogenides and finally give a regioisomeric mixture of 4-substituted
and 3-substituted diaryl chalcogenides.
Introduction
Diaryl chalcogenides are an important class of organic compounds which play a
1
-3
significant role in biological, polymer, and material sciences. As a consequence, many
approaches have been developed for the synthesis of unsymmetrical diaryl chalcogenides.
Transition metal catalyzed intermolecular reaction of phenol, diaryl disulfide, and -diselenide
with aryl halide is an attractive method for the formation of carbon-chalcogen bond.
Palladium, nickel, copper, gold, and iron together with ligands are known to catalyse carbon–
4
-6
chalcogen bond forming reaction. Many advances such as reaction in aqueous solvent, low
catalyst loading and compatibility with various substrates have been made in this area.
Efforts are also being made to develop transition metal free approaches for the
7
-9
formation of carbon-chalcogen (C-E; E = O, S, Se) bond. Recently, potassium tert-
butoxide mediated carbon-carbon and carbon-heteroatom coupling reactions have been
1
0
reported for the synthesis of various organic molecules. Out of these the synthesis of diaryl
selenides/ sulfides is of particular interest. Although, potassium tert-butoxide mediated
8b
synthesis of unsymmetrical diaryl ethers has been described during our investigation on the
synthesis of diaryl chalcogenides, however, synthesis of unsymmetrical diaryl sulfides and
selenides using potassium tert-butoxide has not been reported. Moreover, the synthesis of
o
8b
diaryl ethers was achieved from respective phenol precursors at 120 C. Selenium
analogues (ArSeH) of phenols are not readily available. Although, aryl thiols (ArSH) are
2

ACCEPTED MANUSCRIPT
commercially available, they possess foul smell. Diaryl disulfides are easily accessible sulfur
substrates and also easy to handle due to their low foul smell. Similarly, diaryl diselenides are
the only key substrates for the synthesis of unsymmetrical diaryl selenides. Therefore, a
method which utilizes diaryl dichalcogenides would be beneficial for the synthesis
unsymmetrical diaryl selenides. Hence it is worth studying the reaction of diaryl disulfides
and diselenides with aryl halides in the potassium tert-butoxide mediated reaction. In
1
1a-c,e-g
continuation of our work on organochalcogen chemistry
and potassium tert-butoxide
11d
mediated coupling reaction,
herein, we present a potassium tert-butoxide mediated
synthesis of diaryl sulfides and selenides using diaryl disulfide and diselenide precursors,
respectively. Also, the synthesis of diaryl ethers was achieved from phenols and bromoarenes
o
at 40-45 C using highly pure DMSO.
Results and discussion
Bromobenzene and diphenyl disulfide were chosen as the substrates for the screening
t
of various reaction conditions in the KO Bu-mediated reaction (Table 1). As studied earlier
by us, we employed five equiv of potassium tert-butoxide and 20 mol % of 1,10-
11d
phenanthroline or 0.2 equiv of AIBN in solvents such as benzene, toluene, and mesitylene.
3

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a
Table 1: Optimization of reaction conditions
o
Entry
Base
CO
Solvent
DMSO
DMSO
DMF
T ( C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
K
2
3
rt
12
4
nil
10
nil
13
56
18
K CO3
2
80
80
80
80
rt
NaOH
4
Cs
2
CO
3
DMSO
DMSO
DMSO
DMSO
Benzene
Mesitylene
DMF
4
KOH
8
t
KO Bu
24
2
t
b
KO Bu
80
110
110
80
80
80
80
89/ 87
t
KO Bu
24
24
2
traces
traces
65
t
KO Bu
t
1
1
1
0
1
2
3
KO Bu
t
KO Bu
MeCN
DMSO
DMSO
2
nil
NaH
2
nil
1
K
3
PO
4
2
10
a
Reactions were carried out at 1 mmol scale using 1.0 mmol of bromobenzene, 0.5 mmol of
t
diphenyl disulfide, and 1.25 mmol of KO Bu in 1 mL of solvent otherwise stated and isolated
yield of 1 was based on the diphenyl disulfide used in the reaction. rt = 40-45 C. Yield of
diaryl sulfide 1 was obtained using KO Bu of 99.99% purity. Anhydrous DMSO with sure
o
b
t
seal septa is important for high yield of the sulfide 1.
Unfortunately, traces of product, diaryl sulfide 1 were observed under these conditions
(entries 8 and 9, Table 1). Yield of diaryl sulfide 1 increased substantially in the solvents
DMF and DMSO (entries 1-7, 10, 12-13, Table 1). It was observed that the addition of 1,10-
4

ACCEPTED MANUSCRIPT
phenanthroline ligand or radical initiator was ineffective in the formation of diaryl sulfide 1
as the isolated yield remained the same in their presence. Moreover, 2.5 equiv of potassium
tert-butoxide is enough for the complete conversion of substrate. It is worthy to note that the
reaction time is considerably shorter (6 to 8 h) than the copper catalyzed (8-30 h) coupling
5
a,f
reactions.
2 3 2 3 3 4
Various other bases K CO , NaOH, Cs CO , KOH, NaH, and K PO were also
screened for the C-S coupling reaction (entries 1-5, 12 and 13, Table 1). None of the base was
noticed to be effective for the promotion of C-S coupling reaction and poor yield of C-S
coupled product 1 was observed. Next, iodo and chloro benzenes were studied as substrates
in the C-S coupling reaction. Iodo benzene gave slightly better yield (95%) than the
corresponding bromo substrate (89%) when reacted with diphenyl disulfide. Chlorobenzene
reacted sluggishly with diphenyl disulfide and poor yield of product 1 was obtained (Scheme
1
, vide infra).
Scheme 1. Synthesis of diaryl sulfides and selenides using various diaryl disulfides and
diselenides
After screening a series of reaction conditions, we used potassium tert-butoxide, aryl bromide
and DMSO to further study the scope and limitation of this method. The results are
5

ACCEPTED MANUSCRIPT
summarized in Scheme 1. First, we studied substituted diphenyl disulfides in the potassium
tert-butoxide mediated C-S coupling reaction. Para-methoxy and methylphenyl disulfides
reacted smoothly with bromobenzene and yielded unsymmetrical diaryl sulfides 2 and 3 in 82
and 87% yield, respectively (Scheme 1). Interestingly, 2-aminophenyl disulfide having acidic
NH proton also coupled with bromobenzene chemo-selectively to give 2-aminophenyl
2
phenyl sulfide 4 in 76% yield. Similarly, diphenyl selenide 5 was obtained in 3.5-4.5 h in 93,
9
0, and 18% yield from iodo, bromo, and chlorobenzene, respectively. However, the reaction
was noticed to be slightly slower as compared to the sulfur analogue 1.
6

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Table 2. Synthesis of diaryl sulfides and selenides from substituted bromoarenes
a
Entry Aryl bromide
1
Product (a)
Product (b)
Yield (%)
b
3/6b (1:0.9) (79)
b
2
3
2/7b E =S (1:1) (81)
8a/8b E = Se
b
(
0.7:0.3) (81)
c
--
4
5
9 E = S (56)
10 E = Se (52)
b
6
7
11a/11b (1:1) E = S
(76)
b
1
2a/12b (1:1) E= Se
(87)
c
8
9
--
13 E = S (90)
14 E = Se (86)
c
--
d
c
1
0
--
15 (79)
c
1
1
1
2
--
16 E = S (82)
17 E = Se (79)
c
--
c
1
1
3
4
--
18 E = S (60)
19 E= Se (57)
c
--
7

ACCEPTED MANUSCRIPT
a
b
Isolated yields are based on the diaryldisulfide used in the reaction Ratio of regioisomers
1
c
d
was determined by H NMR. Formation of isomer b was not observed.
Bis (4-
methoxyphenyl) disulfide was used.
After studying, substituted diaryl disulfides and diphenyl diselenide, we explored substituted
bromobenzenes in the potassium tert-butoxide mediated C-S coupling reaction and the results
are presented in Table 2. 4-Methylbromobenzene reacted completely with diphenyl disulfide
in 2.5 h, however, a regioisomeric mixture of 3- and 4-methylphenyl phenyl sulfides 3 and 6b
was observed in the ration of 1:0.9. Similar observation was made with 4-methoxy
bromobenzene (entries 2 Table 2), which afforded a mixture of diaryl sulfides (2 and 7b).
Similar to electron rich substituted bromobenzenes, 1-bromo-naphthalene reacted with
diphenyl disulfide in potassium tert-butoxide mediated C-S coupling reaction and gave a
regioisomeric mixture of 1-naphthyl and 2-naphthyl phenyl sulfides (11a and 11b). We
attempted to optimize the formation of one regioisomer by varying the reaction temperature
o
and by adding additives. Lowering the reaction temperature to 40-45 C failed to provide any
product despite the prolonged (24 h) stirring of reaction mixture. Similarly, addition of
radical initiator AIBN to the reaction mixture did not improve the regioselectivity. Additives
such as L-proline, 1,10-phenanthrolene, N,N’-dimethylethyldiamine (DMEDA) were also
failed to provide selective formation of one regioisomer.
Interestingly, trifluoromethyl and nitro substituted bromobenzenes gave only one
regioisomeric product in the potassium tert-butoxide mediated C-S coupling reaction (entries
4
, 8, 10, 11 and 13, Table 2). Also, ortho and para substituted nitrobromobenzenes gave
quantitative yield of ortho and para-nitrophenyl phenyl sulfides 13, 15 and 16, respectively.
Moreover, methyl substituted bromobenzene together with nitro group gave regioselectively
only one isomer 18 in the C-S coupling reaction. Reaction of substituted bromobenzenes was
also studied with diphenyl diselenide. Indeed similar results were obtained as noticed for
8

ACCEPTED MANUSCRIPT
sulfur analogues (entries 3, 5, 7, 9, 12, and 14; Table 2). Diphenyl diselenide provided
slightly better regioselectivity (0.7:0.3) as compared to sulfur analogue (1:1) when reacted
with 4-methoxybromobenzene (entries 2 and 3; Table 2). However, dipehenyl diselenide
gave selenides 12a/12b in poor regioselectivity ration (1:1) when reacted with 1-
bromonaphthalene.
9

ACCEPTED MANUSCRIPT
Table 3. Coupling of substituted phenol with bromobenzene
a
Entry
1
Phenol
Product
Yield (%)
20 (96)
2
21 (62)
3
4
5
22 (58)
23 (65)
24 (76)
6
7
25 (79)
26 (82)
8
9
27 (76)
28 (64)
1
1
0
1
29 (83)
30 (84)
a
Isolated yields of ethers are based on the respective phenols used in the reaction.
1
0

ACCEPTED MANUSCRIPT
We next turned our attention to the potassium tert-butoxide mediated carbon-oxygen
coupling reaction using bromobenzene and substituted phenol for the synthesis of
unsymmetrical diaryl ethers. Unsymmetrical diaryl ethers are of paramount importance and
as a result several methodologies have been developed for the synthesis of diaryl
7
,8,12,13
t
ethers.
Yang and Xu et al. have reported KO Bu mediated C-O and C-N coupling
t
o
8b
reactions using two equiv of KO Bu at 120 C (vide supra). Potassium hydroxide has also
been reported as a super base for Ullmann type of carbon-heteroatom coupling reaction.
Nonetheless, high amount of potassium hydroxide (250 mol %) and/ or high temperature
o
7i,j
(
120-135 C) were required for smooth formation of the diaryl ethers.
To see the
compatibility of C-O bond formation in the potassium tert-butoxide mediated coupling
reaction and also to compare the reactivity with heavy chalcogen (sulfur and selenium)
analogues, we studied the synthesis of unsymmetrical diaryl ether. A series of substituted
phenols underwent coupling reaction with bromobenzene and produced diaryl ethers 20-30 in
5
8-96% yield (Table 3). In contrast to diaryl sulfides and selenides, synthesis of
o
unsymmetrical diaryl ethers was achieved at 40 -45 C. However, longer reaction time is
necessary to achieve the complete conversion of the substrates into diaryl ethers. It seems that
the high purity of DMSO solvent and slight excess of potassium tert-butoxide may be
responsible for milder reaction conditions for the carbon-oxygen bond formation. Under our
reaction conditions, a series of unsymmetrical diaryl ethers 20-30 with substituents such as
methyl, bromo, fluoro, tert-butyl, cyano, and methoxy have been accessed in good to
o
excellent yield at 40-45 C.
1
1

ACCEPTED MANUSCRIPT
Scheme 2. Synthesis of naphthyl ether 30 and C-C coupled naphtha-2-ols 31 and 32
α-, β-Naphthols also reacted with bromo benzene in the potassium tert-butoxide mediated
coupling reaction and produced β and α-naphthyl phenyl ethers 29-30 in 84 and 83% yields,
respectively. In case of α-naphthol substrates, intermolecular carbon-carbon coupled products
3
1 and 32 were also observed (Scheme 2). Synthesis of biaryls having various functional
10a-n
groups has been reported using potassium tert-butoxide reagent.
However, intermolecular
carbon-carbon coupling in phenols has not been described using potassium tert-butoxide.
Here phenyl naphthalenols 31 and 32 are produced in 15 and 20% yields respectively.
1
2

ACCEPTED MANUSCRIPT
Table 4. Coupling of aryl alcohol with substituted bromobenzene
a
Entry Bromoarene Product (a)
1
Product (b)
Yield (%)
33 (72)
b
--
b
2
34 (80)
--
c
3
35a/35b (1:1)
59)
(
c
4
36a/36b (5:3)
53)
(
c
5
37a/37b (5:3)
56)
(
c
6
37b/38 (5:3)
57)
(
a
b
Isolated yields of ethers are based on the respective phenols used in the reaction. Phenol
c
was used. β-Naphthol was used
1
3

ACCEPTED MANUSCRIPT
After studying various substituted phenols in the potassium tert-butoxide mediated carbon-
oxygen coupling reaction, we explored substituted bromobenzenes. Nitro-substituted
bromobenzenes gave only one product regioselectively and quantitative yields (72 and 80%)
of nitro-substituted diphenyl ethers 33 and 34 were obtained (Table 4). Reaction of
substituted
bromobenzenes
such
as
4-methoxy-bromobenzene,
1-Bromo-4-
(trifluoromethyl)benzene, 1-bromo-4-chlorobenzene, 1-bromo-2-methylbenzene, and 1-
bromo-4-methylbenzene gave a mixture of regioisomeric products together with side
products when reacted with the phenol. Purification of products was noticed to be difficult
despite applying mild reaction conditions when substituted bromobenzenes were used in the
C-O coupling reaction with phenol. However, substituted bromobenzens reacted smoothly
with β-naphthol and produced a mixture of products and the formation of other side products
was not observed (entries 3-6, Table 4).
t
Mechanism: Recently, a radical mechanism for the KO Bu mediated carbon-carbon coupling
reaction has been suggested by us and others in which carbon-halogen and carbon-hydrogen
10,11d
bonds are involved.
In the present C-E coupling reaction, it is very unlikely that reaction
proceeds via radical pathway. Instead, reaction proceeds by another pathway in which
benzyne intermediate forms in the potassium tert-butoxide mediated reaction and is very
8b
similar to previously reported mechanism by Yang and Xu et al. The formation of two
regioisomers from para substituted bromobenzene could be well correlated by the formation
of benzyne intermediate (Scheme 3).
1
4

ACCEPTED MANUSCRIPT
t
Scheme 3. Proposed reaction pathway for KO Bu mediated C-E coupling
It seems that diaryl disulfide/ diselenide is equivalent to phenol in the potassium tert-butoxide
mediated C-E coupling reaction as both substrates gave respective thioether and selenoether
8b
when reacted with bromobenzene.
It is worth comparing the reactivities of diphenyl disulfide, diselenide, and phenol in
the potassium tert-butoxide carbon-chalcogen coupling reaction. Diphenyl disulfide and
o
diselenide reacted with bromobenzene at 80 C (Scheme 1, Table 2) whereas phenols reacted
o
at 40-45 C. Coupling of disulfide and diselenide with bromobenzene was not completed at
o
t
4
2
0-45 C even in the presence of excess of KO Bu. Also increase in reaction time from 4 to
4 h failed to provide the satisfactory yield of diaryl sulfide and selenide. Although,
difference between the reactivities of disulfide and diselenide is not substantial with respect
to reaction time, however, disulfide reacts slightly in short time as compared to diselenide.
t
It may be worth comparing the reactivity of KO Bu with other bases. Other bases such
2 3 2 3 3 4
as K CO , Cs CO , and K PO were noticed to be ineffective in the C-S coupling reaction.
Also sodium and potassium-hydroxides produced less yield of C-S coupled product which
could be due to the formation of trace amount of water by the reaction of KOH and
8
b
bromobenzene. This is well explained by Xu et al. Another reason could be more solubility
8
b
of potassium tert-butoxide in DMSO. Another possibility in which methylsulfinylmethyl
1
5

ACCEPTED MANUSCRIPT
-
t
14
anion (CH
3
S(O)CH
2
) was formed by the reaction of KO Bu with DMSO.
t
Methylsulfinylmethyl anion (pKa = 35.1) is a stronger base than the KO Bu (32.2). This
could be another reason for the high reactivity of potassium tert-butoxide in DMSO for the
formation of carbon-chalcogen bond. Thus, the better solubility of potassium tert-butoxide in
DMSO, absence of trace of H O, and generation of methylsulfinyl anion could make this base
2
superior over the other bases in C-E coupling reactions.
Conclusion
In summary, we have shown that potassium tert-butoxide can be used for the
synthesis of unsymmetrical diaryl sulfides and selenides by using diaryl disulfides and
o
bromobenzene at 80 C. A series of unsymmetrical diaryl sulfides and selenides have been
synthesized in 2-4 h without adding any transition metal and or ligand in the reaction. Also
o
the synthesis of unsymmetrical diaryl ethers has been achieved at 40-45 C in 4-6 h. It seems
that reaction proceeds via the formation of benzyne intermediate from bromobenzene as the
reaction gives two regioisomers when studied with substituted bromobenzene. Coupling of
benzyne with in-situ formed phenolate, thiolate, and selenolate would lead to the formation
carbon-chalcogen bond.
General Methods
Dimethyl formamide and dimethyl sulfoxide with seal septa were used as received from
Aldrich. Potassium tert-butoxide (98% purity) was purchased from SPECTROCHEM Pvt.
o
Ltd. used as purchased and stored under desiccator. Room temperature refers to 40-45 C.
Reactions were conducted in 10 mL round bottom flask with glass stopper. Silica gel (100-
2
00 mesh size) was used for column chromatography. TLC analysis of reaction mixtures was
1
13
13
performed using silica gel plates. H NMR (400 MHz), C NMR (100 MHz), C DEPT-135
1
6

ACCEPTED MANUSCRIPT
77
(
100 MHz), and Se NMR (76 MHz) spectra were recorded on a FT NMR spectrometer and
referenced to solvent DMSO or CDCl peak.
A typical procedure for C-S/ Se coupling: DMSO (1 mL) was added to a single neck flask
3
(10 mL) containing stirrer bar. To this flask, diphenyl disulfide (109 mg, 0.5 mmol) and
t
bromobenzene (157 mg, 1.0 mmol). After this, KO Bu (140 mg, 1.25 mmol) was added
o
portion wise and resulted reaction mixture was stirred at 40-45 C for 15 min and then heated
at 80 °C. Progress of reaction was monitored by TLC. Upon completion of the reaction (2-4
h), the mixture was cooled to room temperature, poured into water, and extracted four times
with 20 mL of ethyl acetate. The combined organic layers were dried over Na SO , and
2
4
filtered. The solvent was removed in vacuo and the residue was purified by column
chromatography (silica gel, eluent: hexane/ethyl acetate) to afford the coupling product.
5
f
1
f
Diphenylsulfane (1): R 0.60 (100% hexane), colourless oil, yield 0.16 g (89%); H NMR
(400 MHz, CDCl
3
) δ 7.49 (d, J = 7.6 Hz, 4 H), 7.4 (t, J = 7.4 Hz, 4H), 7.35 (t, J = 7.2 Hz,
1
3
-1
2
1
H); C NMR (100 MHz, CDCl
3
) δ 136.0, 131.2, 129.3, 127.2; IR (film) ț cm 3051, 1579,
467, 1242, 1023, 740; GC/MS (EI): rt = 6.38 min, m/z = 186.
5
a
4
f
-Methoxyphenyl(phenyl)sulfane (2): R 0.43 (100% hexane), colourless oil, yield 0.17 g
1
(
82%); H NMR (400 MHz, CDCl
3
) δ 7.44 – 7.38 (m, 2H), 7.22 (t, J = 7.3 Hz, 2H), 7.17 –
13
7
3
.11 (m, 3H), 6.88 (sextet, J = 1.9 Hz, 2H), 3.81 (s, 3H); C NMR (100 MHz, CDCl ) δ
-
1
1
1
59.8, 138.6, 135.4, 128.9, 128.2, 125.8, 124.3, 115.0, 55.38; IR (film) ț cm 3030, 2948,
592, 1592, 1493, 1288, 1031, 827, 739, 690; GC/MS (EI): rt = 7.48 min, m/z = 216.
5
a
1
Phenyl(p-tolyl)sulfane (3): R
f
0.61 (100% hexane), colourless oil, yield 0.17 g (87%); H
NMR (400 MHz, CDCl ) δ 7.31 (d, J = 8.1 Hz, 2H), 7.28 (s, 2H), 7.26 (d, J = 1.7 Hz, 2H),
3
1
3
7
3
.22 – 7.17 (m, 1H), 7.14 (d, J = 8.0 Hz, 2H), 2.35 (s, 3H); C NMR (100 MHz, CDCl ) δ
1
7

ACCEPTED MANUSCRIPT
-1
1
2
37.6, 137.2, 132.3, 131.3, 130.1, 129.8, 129.1, 126.4, 21.2; IR (film) ț cm 3059, 3021,
922, 1582, 1492, 1083, 809, 739, 690; GC/MS (EI): rt = 6.86 min, m/z = 200.
1
5
2
0
-
-(Phenylthio)aniline (4): R 0.60 (9.5:0.5 hexane: ethyl acetate), dark yellow-green, yield
f
1
.17 (76%); H NMR (400 MHz, CDCl
3
) δ 7.48 (dd, J = 7.7, 1.4 Hz, 1H), 7.25(m, 3H), 7,16
1
3
7.11 (m, 3H), 6.85 - 6.78 (m, 2H), 4.16 (s, 3H); C NMR (100 MHz, CDCl ) δ 148.4,
3
-
1
1
3
37.4, 136.7, 131.1, 129.0, 126.6, 125.5, 190.0, 115.6, 114.8; IR (film) ț cm 3465, 3367,
055, 2919, 1607, 1477, 739; HRMS (APCI) m/z 202.0685, calcd for C12
H
11S + H: 202.0679.
5
f
1
Diphenylselane (5): R
400 MHz, CDCl
f
0.54 (100% hexane), colourless oil, yield 0.21 g (90%); H NMR
13
(
3
) δ 7.47 -7.45 (m, 4H), 7.27 7.24 (m, 6H); C NMR (100 MHz, CDCl
3
) δ
) δ 416.3; IR (film) ț cm 3052,
937, 2834, 1590, 1476, 1246, 1033, 828, 739, 689; GC/MS (EI): rt = 6.66 min, m/z = 234.
77
-1
1
2
33.0, 131.1, 129.3, 127.3; Se NMR (76 MHz, CDCl
3
5
f
16
Phenyl(p-tolyl)sulfane (3) and Phenyl(m-tolyl)sulfane (6b):
R
f
0.32 (100% hexane),
1
colourless oil, yield 0.16 g (79%); H NMR (400 MHz, CDCl
3
) δ 7.34-7.22 (m 11H), 7.21-
13
7
.11 (m, 6H), 7.06 (d, J = 7.1 Hz, 1H), 2.34 (s, 3H), 2.31 (s, 3H); C NMR (100 MHz,
CDCl ) δ 139.1, 137.6, 137.2, 136.2, 135.3, 132.3, 131.9, 131.3, 130.8, 130.1, 129.8, 129.2,
3
-1
1
1
29.1, 128.4, 128.1, 127.6, 126.9, 126.4, 21.3, 21.2; IR (film) ț cm 3057, 2921, 1582, 1491,
439, 1082, 739, 689; GC/MS (EI): rt = 6.78, 6.87 min, m/z = 200.
5
a
17
(
4-Methoxyphenyl)(phenyl)sulfane (2) and (3-Methoxyphenyl)(phenyl)sulfane (7b):
1
R
f
0.27 (100% hexane), colourless oil, yield 0.17 g (81%); H NMR (400 MHz, CDCl
3
) δ
7
.44-7.38 (m, 4H), 7.32 (t, J = 7.5 Hz, 2H), 7.28-7.13 (m, 7H), 6.94-6.90 (m, 4H), 6.79 (dd, J
13
=
3
8.3, 1.9Hz, 1H), 3.82(s, 3H), 3.76 (s, 3H); C NMR (100 MHz, CDCl ) δ 160.1, 159.9,
1
38.7, 137.3, 135.4, 135.3, 131.5, 130.0, 129.3, 129.0, 128.3, 127.3, 125.8, 124.4, 123.0,
1
8

ACCEPTED MANUSCRIPT
-1
1
16.0, 115.1, 112.8, 55.4, 55.3; IR (film) ț cm 3052, 2937, 2834, 1590, 1476, 1246, 1033,
8
28, 739, 689; GC/MS (EI): rt = 7.36, 7.50 min, m/z = 216.
5
e
18
4
-Methoxyphenyl)(phenyl)selane (8a) and 3-methoxyphenyl)(phenyl)selane (8b):
1
Ratio of 8a/8b = 2/1, R
f
0.35 (100% hexane), yellow oil, yield 0.21 g (81%); H NMR (400
MHz, CDCl ) δ 7.56-7.52 (m, 3H), 7.38 – 7.36 (m, 1H), 7.33-7.30 (m, 3H), 7.27- 7.20 (m,
3
3
H), 7.07 (dt, J = 7.7, 1.2 Hz, 1H), 7.04 (t, J = 2.2 Hz, 1H), 6.91 – 6.88 (m, 1H), 6.85-6.82
13
(
m, 1H), 3.84 (s, 1.5 H), 3.78 (s, 3H); C NMR (100 MHz, CDCl
3
) δ 160.0, 159.8, 136.6,
1
1
33.3, 132.3, 131.5, 130.9, 130.8, 130.1, 129.4, 129.2, 127.5, 126.5, 125.0, 120.0, 118.0,
77
-1
15.2, 113.2, 55.3, 55.2; Se NMR(76 MHz, CDCl
3
) δ 420.3, 398.9; IR (film) ț cm 3057,
3
2
000, 2936, 1587, 1475, 1246, 1039, 826, 736, 688; GC/MS (EI): rt = 7.60, 7.74 min, m/z =
64.
1
9
Phenyl(3,5-(di-trifluoromethyl)phenyl)sulfane (9):
R
f
0.30 (100% hexane), colourless
) δ 7.64 (s, 1H), 7.58 (s, 2H), 7.50 (m,
) δ 141.7, 133.8, 133.5, 133.4, 133.1, 132.8,
32.4, 132.1, 132.0(m), 131.8, 131.2, 130.0, 129.3, 127.8(m), 127.1, 124.4, 123.8, 123.4,
1
liquid, yield 0.18 g (56%); H NMR (400 MHz, CDCl
3
1
3
2
1
H), 7.43 (m, 3H); C NMR (100 MHz, CDCl
3
-1
1
21.6, 121.2(m), 121.1(m), 119.6(m), 118.9; IR (film) ț cm 3080, 1793, 1616, 1599, , 1477,
1
3
352, 1278, 1180, 1139, 885, 749; HRMS (APCI) m/z 322.0245, calcd for C H F S:
14
8 6
22.0231.
1
9
Phenyl(3,5-(di-trifluoromethyl)phenyl)selane (10):
R
f
0.4 (100% hexane), colourless
) δ 7.73 (s, 2H), 7.68 (s, 1H), 7.60 –
) δ 135.9, 135.0(t), 132.7,
32.4, 132.1, 131.7, 130.6(m), 130.1, 129.2, 127.7, 127.0, 124.3, 121.6, 120.4(m), 118.9;
1
liquid, yield 0.19 g (52%); H NMR (400 MHz, CDCl
3
1
3
7
1
.57 (m, 2H), 7.43 – 7.35 (m, 3H); C NMR (100 MHz, CDCl
3
-1
7
7Se NMR (76 MHz, CDCl ) 438.8; IR (film) ț cm 3077, 2927, 2855, 1801, 1617, 1595,
3
1
9

ACCEPTED MANUSCRIPT
1
578, 1477, 1440, 1349, 1278, 1178, 1140, 885, 741; HRMS (APCI) m/z 369.9690, calcd for
14 8 6
C H F Se: 369.9682.
5
a,f
Naphthalen-2-yl(phenyl)sulfane (11a) and naphthalen-1-yl(phenyl)sulfane (11b): R
f
1
0
8
.38 (100% hexane), yellowish oil, yield 0.18 g (76%); H NMR (400 MHz, CDCl
3
) δ 8.47-
1
3
.45 (m, 1H), 7.93-7.72 (m, 7H), 7.57-7.54 (m, 8H), 7.37-7.17 (m, 8H); C NMR (100 MHz,
CDCl ) δ 137.0, 136.0, 134.3, 133.9, 133.7, 133.1, 132.7, 132.4, 131.3, 131.1, 130.0, 129.4,
3
1
1
1
29.3, 129.2, 129.1, 129.0, 128.9, 128.7, 127.9, 127.5, 127.2, 127.1, 126.7, 126.5, 126.3,
-1
26.2, 125.9, 125.7; IR (film) ț cm 3055, 1579, 1476, 1256, 1023, 740; GC/MS (EI): rt =
1.42, 11.4 min, m/z = 236.
5
a,f,20
Naphthalen-2-yl(phenyl)selane (12a) and naphthalen-1-yl(phenyl)selane (12b):
R
f
1
0
8
.56 (100% hexane), colourless liquid, yield 0.24 g (87%); H NMR (400 MHz, CDCl
3
) δ
.45-8.43 (m, 1H), 8.07 (s, 1H), 7.91-7.89 (m, 2H), 7.85 (d, J = 6.4Hz, 2H), 7.78 (d, J = 7.9
Hz, 2H), 7.61-7.56 (m, 5H), 7.53-7.51 (m, 2H), 7.45-7.40 (m, 3H), 7.33 (t, J = 3.0Hz, 2H),
1
3
7
1
.25 (t, J = 3.2 Hz, 4H); δ C NMR (100 MHz, CDCl ) δ 134.3, 134.2, 134.1, 134.0, 133.0,
3
32.5, 132.2, 131.9, 131.8, 131.4, 130.6, 129.6, 129.5, 129.4, 129.3, 128.9, 128.7, 128.6,
-1
1
1
27.9, 127.8, 127.6, 127.5, 127.1, 126.9, 126.7, 126.5, 126.4, 126.2; IR (film) ț cm 3050,
579, 1486, 1196, 1033, 742. GC/MS (EI): rt = 9.45, 9.72 min, m/z = 283.9.
5
a
2
-Nitrophenyl)(phenyl)sulfane (13):
R
f
0.50(100% hexane); yellow solid, yield 0.21 g
1
(
90%); H NMR (400 MHz, CDCl
3
) δ 8.20 (dd, J = 8.3, 1.3 Hz, 1H), 7.58 – 7.56 (m 2H),
1
3
7
.50-7.44(m, 3H), 7.32 (m, 1H), 7.19 (m, 1H), 6.85 (dd, J = 8.2, 0.9 Hz, 1H),; C NMR (100
MHz, CDCl ) δ 145.0, 139.5, 135.9, 133.4, 131.0, 130.1, 130.0, 128.3, 125.7, 125.0; IR
3
-1
(
film) ț cm 3061, 1926, 1591, 1567, 1337, 733; GC/MS (EI): rt = 8.38 min, m/z = 231.
2
0

ACCEPTED MANUSCRIPT
5
a
2
-Nitrophenyl)(phenyl)selane (14):
f
R 0.34 (8:2 hexane : ethyl acetate); yellow solid,
1
Yield 0.24 g (86%); H NMR (400 MHz, CDCl ) δ 8.29 (d, J = 7.9 Hz, 1H), 7.69 (d, J = 6.8
3
1
3
Hz, 2H), 7.52 7.43 (m, 3H), 7.31-7.23 (m, 2H), 6.98 (d, J = 7.6Hz, 1H). C NMR (100 MHz,
77
3
CDCl ) δ 145.6, 137.4, 135.9, 133.7, 130.3, 130.1, 129.9, 128.2, 126.1, 125.8. Se NMR(76
-1
MHz, CDCl ) δ 485.6; IR (film) ț cm 3061, 2926, 1591, 1516, 1475, 1337, 1250, 733;
3
GC/MS (EI): rt = 8.84 min, m/z = 278.9.
2
1
4
-Methoxyphenyl)(2-nitrophenyl)sulfane (15): R 0.40 (8:2 hexane : ethyl acetate);
f
1
yellow solid, yield 0.20 g (79%); H NMR (400 MHz, CDCl
3
) δ 8.19 (dd, J = 8.2, 1.2 Hz,
1
H), 7.49-7.45 (m, 2H), 7.33-7.29(m, 1H), 7.18-7.14 (m, 1H), 6.98 (d, J = 8.7 Hz, 2H), 6.81
1
3
(
3
dd, J = 8.2, 1 Hz, 1H), 3.85 (s, 3H); C NMR (100 MHz, CDCl ) δ 161.2, 144.6, 140.7,
-1
1
1
37.7, 133.4, 127.9, 125.7, 124.7, 121.2, 115.8, 55.5; IR (film) ț cm 3020, 2927, 2854,
592, 1455, 1204, 1036; GC/MS (EI): rt = 10.22 min, m/z = 260.9.
5
a
4
-Nitrophenyl)(phenyl)sulfane (16): R
f
0.52 (9.5:0.5 hexane : ethyl acetate); yellow oil,
) δ 8.04 (d, J = 8.9 Hz, 2H), 7.54-7.51 (m,
1
yield 0.19 g (82%); H NMR (400 MHz, CDCl
3
1
3
2
1
1
3
H), 7.46-7.43(m, 3H), 7.16 (d, J = 9.0 Hz, 2H), C NMR (100 MHz, CDCl ) δ 148.5,
-1
45.4, 134.8, 130.5, 130.1, 129.7, 126.7, 124.0. IR (film) ț cm 3063, 2915, 1574, 1515,
475, 1083, 852, 740, HRMS-APCI m/z: 232.0427 (calculated for C H NO S: 232.0430).
1
2
9
2
5a
4
-Nitrophenyl)(phenyl)selane (17):
f
R 0.50 (9.5:0.5 hexane : ethyl acetate), yellow oil,
1
yield 0.22 g (79%); H NMR (400 MHz, CDCl ) δ 7.99 (d, J = 8.9 Hz, 2H), 7.62-7.60 (m,
3
1
3
2
1
H), 7.45-7.35 (m, 3H), 7.32 (d, J = 8.8 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 146.2,
77
44.0, 135.9(t), 130.1, 129.7(t), 129.4, 127.2, 124.0; Se NMR(76 MHz, CDCl
3
) δ 440.5; IR
2
1

ACCEPTED MANUSCRIPT
-1
(
film) ț cm 3060, 2923, 1595, 1574, 1060, 850, 737, 691; HRMS-APCI m/z: 279.9872
8
0
(calculated for C12
H
9
NO
2
Se: 279.9854).
1
5
2
-Nitro-4-methyl-phenyl(phenyl)sulfane (18): R 0.48 (9.5:0.5 hexane : ethyl acetate),
f
1
yellow oil, yield 0.14 g (60%); H NMR (400 MHz, CDCl
3
) δ 8.01(s, 1H), 7.56-7.54 (m, 2H),
13
7
.45-7.43 (m, 3H), 7.13 (dd, J = 8.4, 1.4, 1H), 6.75 (d, J = 8.4Hz, 1H), 2.34 (s, 3H);
C
3
NMR (100 MHz, CDCl ) δ 145.2, 135.8, 135.7, 135.5, 134.5, 131.5, 130.0, 129.7, 128.5,
-1
1
8
25.8, 20.4; IR (film) ț cm 3054, 2914, 1518, 1329, 1290, 1199, 751; GC/MS (EI): rt =
.96 min, m/z = 244.9
2
-Nitro-4-methyl-phenyl(phenyl)selane (19): R
f
0.46 (9.5:0.5 hexane: ethyl acetate), yellow
) δ 8.12 (s, 1H), 7.69-6.67 (m, 2H), 7.50-
1
oil, yield 0.16g (57%); H NMR (400 MHz, CDCl
3
13
7
.41 (m, 3H), 7.11 (dd, J = 8.3, 1.4 Hz, 1H), 6.85(d, J = 8.3 Hz, 1H), 2.34 (s, 3H); C NMR
(
100 MHz, CDCl ) δ 145.5, 137.4, 136.2, 134.9, 132.1, 130.1, 130.0, 129.7, 128.4, 126.1,
3
7
7
-1
2
1
0.5; Se NMR(76 MHz, CDCl
3
) δ 478.5; IR (film) ț cm 3059, 2918, 1518, 1340, 1199,
80
024, 739; HRMS-APCI m/z: 292.9950 (calculated for C13
H
11NO
2
Se: 292.9938).
A general procedure for C-O coupling: Phenol (94 mg, 1 mmol) and bromobenzene (314
mg, 2.0 mmol) were added to a single necked flask containing DMSO (1 mL) and resulted
reaction mixture was stirrer for 5 min. After this potassium tert-butoxide (280 mg, 2.5 mmol)
o
was added portion wise and stirring continued for 6-8 h at 40-45 C. The progress of reaction
was monitored by TLC. Upon completion of the reaction, mixture poured into water, and
extracted four times with 20 mL of ethyl acetate. The combined organic layer was dried over
2 4
Na SO , and filtered. The solvent was removed in vacuo and the residue was purified by
column chromatography (silica gel, eluent: hexane/ ethyl acetate) to afford the coupling
product.
2
2

ACCEPTED MANUSCRIPT
1
3g
1
Oxydibenzene (20):
f
R 0.62 (100% hexane), colourless liquid, yield 0.16 g (96%); H
13
NMR (400 MHz, CDCl ) δ 7.42-7.37 (m, 4H), 7.18-7.14 (m, 2H), 7.09-7.06 (m 4H);
C
3
-1
NMR (100 MHz, CDCl
3
) δ 157.3, 129.8, 123.2, 118.9; IR (film) ț cm 3042, 2960, 1586,
1
490, 1012; GC/MS (EI): rt = 5.51 min, m/z = 170.1.
2
2
1
-Bromo-2-phenoxybenzene (21): R
f
0.39 (100% hexane), white solid, yield 0.15 g (62%);
1
H NMR (400 MHz, CDCl
3
) δ 7.66 (dd, J =7.9 Hz, 1.6 Hz, 1H), 7.39-7.34 (m, 2H), 7.31-
13
7
.27 (m, 1H), 7.16-7.12 (m, 1H), 7.05 (dd, J = 7.5 Hz, 1.5Hz, 1H), 7.03-6.98 (m, 3H); C
3
NMR (100 MHz, CDCl ) δ 156.9, 153.7, 133.8, 129.8, 128.7, 125.0, 123.4, 120.6, 118.1,
-1
1
2
14.9; IR (film) ț cm 2964, 1577, 1261, 1029, 797; GC/MS (EI): rt = 6.66 min, m/z =
47.9, 249.9.
2
3
1
f
-Bromo-4-phenoxybenzene (22): R 0.39 (100% hexane), colourless, yield 0.14 g (58%);
1
H NMR (400 MHz, CDCl ) δ 7.33-7.30 (m, 2H), 7.26-7.21 (m, 2H), 7.04-7.00 (m, 1H),
3
1
3
6
1
.90-6.88 (m, 2H), 6.79-7.76 (m, 2H); C NMR (100 MHz, CDCl
3
) δ 156.7, 156.4, 132.7,
-1
29.9, 123.7, 120.4, 119.0, 115.6; IR (film) ț cm 3067, 2925, 1578, 1481, 1236, 752;
GC/MS (EI): rt = 6.79 min, m/z = 248, 250.
1
3g
1
-Fluoro-4-phenoxybenzene (23):
R
f
0.38 (100% hexane), colourless dense oil, yield
1
0
.12g (65%); H NMR (400 MHz, CDCl
3
) δ 7.40-7.35 (m, 2H), 7.16-7.11 (m, 1H), 7.10-7.00
1
3
(
m, 6H); C NMR (100 MHz, CDCl ) δ 160.0, 157.7, 157.6, 153.0, 152.9, 129.8, 123.1,
3
-1
1
20.6, 120.5, 118.3, 116.4, 116.2; IR (film) ț cm 3060, 2925, 1571, 1481, 1236, 755;
GC/MS (EI): rt = 5.47 min, m/z = 188.1.
2
4
1
-Methyl-2-phenoxybenzene (24):
R
f
0.40 (100% hexane), colourless liquid, yield 0.14g
1
(
76%); H NMR (400 MHz, CDCl
3
) δ 7.39-7.28 (m, 3H), 7.22-7.18 (m, 1H), 7.127.06 (m,
2
3

ACCEPTED MANUSCRIPT
1
3
2
1
1
3
H), 6.95-6.93 (m, 3H), 2.28 (s, 3H); C NMR (100 MHz, CDCl ) δ 157.9,154.5, 131.4,
-1
30.0, 129.7, 127.1, 124.0, 122.3, 119.8, 117.3, 16.2; IR (film) ț cm 3039
,
2925, 1583,
488, 1239, 874; GC/MS (EI): rt = 5.96 min, m/z = 184.1.
2
5
o
1
-Methyl-3-phenoxybenzene (25):
R
f
0.37 (100% hexane), mp = 20 C, colorless liquid
o
1
which is solid at 0 C, yield 0.14 g (79%); H NMR (400 MHz, CDCl ) δ 7.41-7.36 (m, 2H),
3
7
6
.26 (t, J = 7.5 Hz, 1H), 7.16-7.13 (m, 1H), 7.08-7.05 (m, 2H), 6.97 (d, J = 7.6 Hz, 1H),
13
3
.90-6.86 (m, 2H), 2.83 (s, 3H); C NMR (100 MHz, CDCl ) δ 157.4, 157.2, 139.9, 129.7,
-1
1
1
29.5, 124.1, 123.1, 119.6, 118.9, 115.9, 21.4; IR (film) ț cm 3039, 2920, 1584, 1487,
256, 1216, 936; GC/MS (EI): rt = 5.94 min, m/z = 184.2.
1
3g
1
-(tert-Butyl)-4-phenoxybenzene (26):
f
R 0.56 (100% hexane), white solid, yield 0.18 g
1
(
82%); H NMR (400 MHz, CDCl
3
) δ 7.42-7.35 (m, 4H), 7.15-7.11 (m, 1H), 7.08-7.05 (m,
13
2
3
H), 7.02-6.99 (m, 2H), 1.38 (s, 9H); C NMR (100 MHz, CDCl ) δ 157.6, 154.8, 146.1,
-1
1
1
29.7, 126.6, 122.9, 118.7, 118.5, 34.3, 31.5; IR (film) ț cm 3040, 2963, 1905, 1589, 1488,
238, 1170, 753; GC/MS (EI): rt = 6.92 min, m/z = 226.2.
1
3
3g
1
-Methoxy-4-phenoxybenzene (27):
R
f
0.46 (100% hexane), colourless liquid, yield 0.15
1
g (76%); H NMR (400 MHz, CDCl
) δ 7.35-7.28 (m, 2H), 7.07 (t, J = 7.5 Hz, 1H), 7.02-
1
3
6
1
1
3
.96 (m, 4H), 6.93-6.89 (m, 2H), 3.83 (s, 3H); C NMR (100 MHz, CDCl ) δ 158.5,155.9,
-1
50.1, 129.6, 122.4, 120.8, 117.6, 114.9, 55.7; IR (film) ț cm 3040, 2952, 1590, 1505,
489, 1225, 1186, 841; GC/MS (EI): rt = 6.55 min, m/z = 200.1.
1
3t
1
4
-Phenoxybenzonitrile (28):
f
R 0.40 (100% hexane), white solid, yield 0.12 g (64%); H
NMR (400 MHz, DMSO-d ) δ 7.91 (d, J = 8.6 Hz, 2H), 7.44 (t, J = 8.0 Hz, 2H), 7.29 (bs,
6
1
3
1
H), 7.21 (t, J = 7.2 Hz, 1H), 7.05 (dd, J = 29.6, 8.6 Hz, 3H); C NMR (100 MHz, DMSO-
2
4

ACCEPTED MANUSCRIPT
-1
d6) δ 167.6, 159.9, 156.1, 130.7, 130.1, 129.5, 124.7, 119.9, 117.7; IR (film) ț cm 3028,
2
974, 2250, 1580, 1470, 1253, 753; GC/MS (EI): rt = 6.99 min, m/z = 195.
2
6
2
-Phenoxynaphthalene (29): R 0.48 (9:2 hexane: ethyl acetate), white solid, yield 0.18 g
f
1
(
83%); H NMR (400 MHz, CDCl
3
) δ 7.74-7.71 (m, 2H), 7.60 (d, J = 8.2Hz, 1H), 7.36 (dd, J
=
6.8 Hz, 1.3 Hz, 1H), 7.32 (dd, J = 4.8 Hz, 1.5 Hz, 1H), 7.30-7.28 (m, 1H), 7.27-7.24 (m,
1
6
H), 7.22 (d, J = 2.4 Hz, 1H), 7.17 (dd, J = 8.9 Hz, 2.5 Hz, 1H), 7.06-7.02 (m, 1H), 6.99-
1
3
3
.97 (m, 2H); C NMR (100 MHz, CDCl ) δ 157.2, 155.1, 134.5, 130.2, 129.9, 129.8, 127.7,
-1
1
1
27.2, 126.5, 124.7, 123.5, 120.0, 119.2, 114.1; IR (film) ț cm 3050, 1588, 1488, 1249,
222, 807; GC/MS (EI): rt = 8.01 min, m/z = 220.1.
2
6
1
-Phenoxynaphthalene (30): R 0.46 (9:2 hexane: ethyl acetate), white solid, yield 0.18 g
f
1
(
83%); H NMR (400 MHz, CDCl
3
) δ 8.24 (d, J = 7.9 Hz, 1H), 8.91 (d, J = 7.9 Hz, 1H), 7.66
(d, J = 8.3 Hz, 1H), 7.58-7.50 (m, 2H), 7.43-736 (m, 3H), 7.16-7.13 (m, 1H), 7.08 (dd, J =
13
8
3
.7 Hz, 1 Hz, 2H), 6.99 (d J = 7.5Hz, 1H); C NMR (100 MHz, CDCl ) δ 157.9,153.0,
1
35.0, 129.8, 127.8, 126.9, 126.6, 125.9, 125.8, 123.4, 123.1, 122.1, 118.6, 113.5; IR (film) ț
-
cm 1 3055, 2925, 1594, 1574, 1488, 1392, 1210, 772; GC/MS (EI): rt = 8.81 min, m/z =
2
20.1.
2
7
2
-Phenylnaphthalen-1-ol (31): R 0.37 (100% hexane), colourless liquid, yield 30 mg
f
1
(
15%); H NMR (400 MHz, CDCl
3
) δ 8.32 (t, J = 4.9 Hz, 1H), 7.87-7.84(m, 1H), 7.58 (d, J
=
4.3 Hz, 4H), 7.55- 7.53 (m, 2H), 7.51 (s, 1H), 7.47 (m 1H), 7.39 (d, J = 8.4 Hz, 1H), 5.87
1
3
(
3
bs, 1H); C NMR (100 MHz, CDCl ) δ 147.8, 137.4, 134.2, 129.6,129.4, 127.9, 127.6,
-
1
1
1
27.5, 126.5, 125.6, 124.3, 122.3, 122.4, 120.2; IR (film) ț cm 3560, 3055, 2925, 1594,
574, 1488, 1392, 1234, 1080, 772; GC/MS (EI): rt = 8.81 min, m/z = 220.1.
2
5

ACCEPTED MANUSCRIPT
28
4
f
-Methoxy-2-phenylnaphthalen-1-ol (32): R 0.39 (100% hexane), colourless solid, yield
1
4
0 mg (20%); H NMR (400 MHz, CDCl ) δ 8.32 (m, 2H), 7.56 – 7.51 (m,6H), 7.44 – 7.41
3
1
3
(
m, 1H), 6.69 (s, 1H), 5.46 (bs, 1H) 3.96 (s, 3H); C NMR (100 MHz, CDCl
3
) δ 149.4,
1
5
41.5, 137.9, 129.6, 129.4, 127.9, 126.2, 125.9, 126.8, 125.2, 122.2, 121.8, 120.2, 106.6,
-1
5.8; IR (film) ț cm 3410, 3068, 2925, 1664, 1597, 1305, 1249, 759; GC/MS (EI): rt = 9.16
min, m/z = 249.9.
2
9
1
-Nitro-2-phenoxybenzene (33): R 0.43 (100% hexane), yellow solid, yield 0.15 g (72%);
f
1
H NMR (400 MHz, CDCl
3
) δ 7.93 (dd, J = 8.2, 1.6 Hz, 1H), 7.50-7.46 (m, 1H), 7.37 (t, J =
1
3
8
.4Hz, 2H), 7.19 – 7.16 (m, 2H), 7.02 (d, J = 7.8 Hz, 2H), 7.00 (d, J = 8.4 Hz, 1H); C
3
NMR (100 MHz, CDCl ) δ 155.8, 150.8, 134.1, 130.1, 125.7, 124.6, 123.11, 120.5, 119.3,
-1
1
11.8; IR (film) ț cm 2918, 2852, 1588, 1346, 742; GC/MS (EI): rt = 7.28 min, m/z = 215.
1
3g,t
1
-Nitro-4-phenoxybenzene (34):
R
f
0.42 (100% hexane), yellow solid, yield 0.17 g,
1
(
80%); H NMR (400 MHz, CDCl
3
) δ 8.19 – 8.15 (m, 2H), 7.44-7.40 (m, 2H), 7.24 (t, J =
1
3
7
1
1
3
.5 Hz, 1H), 7.1 (d, J = 7.6 Hz, 2H), 7.01 – 6.97 (m, 2H); C NMR (100 MHz, CDCl ) δ
-1
63.4, 154.7, 142.6, 130.3, 125.9, 125.4, 120.5, 117.1; IR (film) ț cm 2956, 2910, 1566,
408, 846; GC/MS (EI): rt = 7.57 min, m/z = 215.
2
-(4-(Trifluoromethyl)phenoxy)naphthalene
(35a)
and
2-(3-
(trifluoromethyl)phenoxy)naphthalene (35b). R
f
0.23 (100% hexane), liquid, yield 0.17 g
1
(
59%); H NMR (400 MHz, CDCl ) δ 7.89 – 7.84 (m, 4H), 7.76 – 7.73 (m, 2H), 7.59 (d, J =
3
8
7
1
.6 Hz, 2H), 7.51 – 7.42 (m, 6H), 7.37 (m, 2H), 7.31(s, 1H), 7.26 (d, J = 2.3Hz, 1H), 7.24 –
1
3
.20 (m, 2H), 7.10 (d, J = 8.5 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 160.5, 157.9, 153.9,
53.5, 134.4, 134.3, 130.8, 130.6, 130.3, 127.8 (d), 127.3 (d), 127.2 (d), 126.8 (d), 125.3 (d),
-1
1
21.8, 120.2, 120.0, 119.8 (d), 118.1, 115.9, 115.5(m), 115.2; IR (film) ț cm 3059, 1616,
2
6

ACCEPTED MANUSCRIPT
1
596, 1325, 1124, 964, 840; HRMS (GC): rt = 4.387 min, m/z = 288.0767 (calculated for
17 11 3
C H F O = 288.0769)
2
0
7
7
1
1
-(4-Chlorophenoxy)naphthalene (36a) and 2-(3-chlorophenoxy)naphthalene (36b). R
f
1
.27 (100% hexane), liquid, yield 0.13 g (53%); H NMR (400 MHz, CDCl
3
) δ 7.86 –
.82(m, 4H), 7.72(t, J = 9.1Hz, 2H), 7.43 (m, 4H), 7.37 (d, J = 2.1Hz, 1H), 7.33 – 7.30 (3H),
.26 – 7.22 (m, 3H), 7.10 (m, 1H), 7.05 (t, J = 2.0Hz, 1H), 7.00 (m, 2H), 6.95 (dd, J = 8.3,
13
.6Hz, 1H); C NMR (100 MHz, CDCl
3
) δ 158.3, 155.9, 154.7, 154.1, 135.2, 134.3, 130.6,
30.5, 130.3, 130.2, 130.1, 129.8, 128.5, 127.8, 127.7, 127.3, 127.2, 126.7, 125.1, 125.0,
-
1
1
1
23.4, 120.3, 120.1, 119.8, 119.0, 116.9, 115.1, 114.3; IR (film) ț cm 3058, 1633, 1586,
485, 1248, 963, 810; HRMS (GC): rt =6.673 min, m/z = 254.0494 (calculated for C16
2254.0496).
H11ClO
=
2
-(o-Tolyloxy)naphthalene (37a) and 2-(m-tolyloxy)naphthalene (37b). R 0.30 (100%
f
1
hexane), liquid, yield 0.13 g (56%); H NMR (400 MHz, CDCl
3
) δ 7.81(m, 3H), 7.70 (d, J =
8
6
3
1
.6Hz, 1H), 7.64 (d, J = 8.3Hz, 1H), 7.47 – 7.35 (m, 3H), 7.31- 7.19 (m, 5H), 7.13 (d, J =
.3Hz, 1H), 7.10 (d, J = 2.1Hz, 1H), 7.00 – 6.95 (m, 2H), 6.88 (m, 1H), 2.34 (s, 2H), 2.27 (s,
1
3
H); C NMR (100 MHz, CDCl
3
) δ 157.2, 155.9, 155.2, 154.3, 140.0, 134.4, 131.6, 130.2,
30.1, 129.8, 129.7, 129.5, 127.8, 127.7, 127.3, 127.1, 127.0, 126.5(d), 124.6, 124.3, 124.2,
-
1
1
1
20.2, 120.1, 119.8, 119.1, 116.2, 114.1, 111.7, 21.4, 16.2; IR (film) ț cm 3056, 1633,
584, 1488, 1252, 1229, 963, 748; HRMS (GC): rt = 6.22 min, m/z = 234.1041 (calculated
for C17
H
14O = 234.1045).
3
0
2
-(m-Tolyloxy)naphthalene (37b) and 2-(p-tolyloxy)naphthalene (38).
R
f
0.27 (100%
) δ 7.85 – 7.81 (m, 3H),
.70(t, J = 8.1Hz, 2H), 7.47 – 7.37 (m, 3H), 7.33 (m, 1H), 7.26 (m, 4H), 7.18 (d, J = 8.1Hz,
1
hexane), liquid, yield 0.13 g (57%); H NMR (400 MHz, CDCl
3
7
1
13
H), 7.01 – 6.96(m, 2H), 6.90 (m, 2H), 2.37 (s, 2H), 2.35 (s, 3H); C NMR (100 MHz,
2
7

ACCEPTED MANUSCRIPT
CDCl
3
) δ 157.2, 155.2, 154.7, 140.1, 134.4, 133.8, 133.2, 130.4, 130.2, 129.8(d), 129.5,
1
2
27.7(d), 127.1(d), 126.5(d), 124.6, 124.5, 124.3, 120.1, 119.8(d), 119.4, 116.2, 114.1, 113.3,
-1
1.4, 20.8; IR (film) ț cm 3056, 1585, 1505, 1254, 1169, 963, 748; HRMS (GC): rt = 6.369
min, m/z:=234.1043 (calculated for C17H14O = 234.1047).
References
(1) (a) Mugesh, G.; Singh, H. B. Chem. Soc. Rev. 2000, 29, 347. (b) Ley, S. V.; Thomas, A.
W. Angew. Chem. Int. Ed. 2003, 42, 5400. (c) Evano, G.; Blanchard, N.; Toumi, M. Chem.
Rev. 2008, 108, 3054. (d) Wirth, T. Organoselenium Chemistry: Synthesis and Reactions;
Wiley-VCH, Weiheim, Germany, 2012, pp 1-65 and 321-356.
(2) For application in biology: (a) Engman, L.; Stern, D.; Frisell, H.; Vessman, K.; Berglund,
M.; Ek, B.; Andersson, C.-M. Bioorg. Med. Chem. 1995, 3, 1255. (b) Malmström, J.;
Jonsson, M.; Cotgreave, I. A.; Hammarström, L.; Sjödin, M.; Engman, L. J. Am. Chem. Soc.
2
001, 123, 3434–3440. (c) Shanks, D.; Al-Maharik, N.; Malmström, J.; Engman, L.;
Eriksson, P.; Stenberg, B.; Reitberger, T. Polym. Degrad. Stab. 2003, 81, 261. (d) Kumar, S.;
Singh, H. B.; Wolmershauser, G. Organometallics 2006, 25, 382. (e) Amorati, R.; Pedulli, G.
F.; Valgimigli, L.; Johansson, H.; Engman, L. Org. Lett. 2010, 12, 2326–2329. (f) Kumar, S.;
Johansson, H.; Kanda, T.; Engman, L.; Müller, T.; Bergenudd, H.; Jonsson, M.; Pedulli, G.
F.; Amorati, R.; Valgimigli, L. J. Org. Chem. 2010, 75, 716–725.
(3) For application in the synthesis of organic compounds: (a) Ericsson, C.; Engman, L. Org.
Lett. 2001, 3, 3459–3462. (b) Besev, M.; Engman, L. Org. Lett. 2002, 4, 3023-3025. (c)
Berlin, S.; Ericsson, C.; Engman, L. Org. Lett. 2002, 4, 3-6. (d) Berlin, B.; Ericsson, C.;
Engman, L. J. Org. Chem. 2003, 68, 8386–8396. (e) Srivastava, P.; Engman, L. Tetrahedron
Lett. 2010, 51, 1149-1151.
2
8

ACCEPTED MANUSCRIPT
4
) Reviews on transition metal catalyzed C-E coupling reactions: Beletskaya, I. P.; Ananikov,
V. P Chem. Rev., 2011, 111, 1596.
5) (a) Taniguchi N.; Onami, T. J. Org. Chem. 2004, 69, 915. (b) Taniguchi, N. J. Org.
Chem. 2004, 69, 6904. (c) Taniguchi, N. Synlett 2005, 1185. (d) Taniguchi, N. J. Org. Chem.
006, 71, 7874. (e) Taniguchi, N. J. Org. Chem. 2007, 72, 1241. (f) Kumar S.; Engman, L. J.
(
2
Org. Chem. 2006, 71, 5400. (g) Jiang, Y.; Qin, Y.; Xie, S.; Zhang, X.; Dong, J.; Ma, D. Org.
Lett. 2009, 70 11, 5250. (h) Gan, J.; Ma, D. Org. Lett. 2009, 11, 2788. (i) Taniguchi, N.
Tetrahedron 2009, 65, 2782. (j) Ma, D.; Xie, S.; Xue, P.; Zhang, J.; Dong X.; Jiang, Y.
Angew. Chem. Int. Ed. 2009, 48, 4222. (k) Ma, D.; Geng, Q.; Zhang, Y.; Jiang, H. Angew.
Chem. Int. Ed. 2010, 49, 1291. (l) Taniguchi, N. Eur. J. Org. Chem. 2010, 2670. (m) Shi, L.;
Liu, X.; Zhang, H.; Jiang, Y.; Ma, D. J. Org. Chem. 2011, 76, 4200. (n) Ma, D.; Lu, X.; Shi,
L.; Zhang, H.; Jiang, Y.; Liu, X. Angew. Chem. Int. Ed. 2011, 50, 1118. (o) Taniguchi, N.
Synlett 2011, 1308. (o) Li, J.; Zhang, Y.; Jiang, Y.; Ma, D. Tetrahedron Lett. 2012, 53, 2511.
(p) Taniguchi, N. Tetrahedron, 2012, 68, 10510-10515.
6
. (a) Migita, T.; Shimizu, T.; Shiobara, J.; Kato, Y.; Kosugi, M. Bull. Chem. Soc. Jpn. 1980,
3, 1385. (b) Cristau, H. J.; Chabaud, B.; Christol, C. H. Synthesis 1981, 892. (c) Cristau, H.
5
J.; Chabaud, B.; Labaudiniere, R.; Christol, H. 1985, 4, 657. (d) Nishiyama, Y.; Tokunaga,
K.; Sonoda, N. Org. Lett. 1999, 1, 1725. (e) Beletskaya, I. P.; Sigeev, A. S.; Peregudov, A.
S.; Petrovskii, P. V. J. Organomet. Chem. 2000, 605, 96. (f) Beletskaya, I. P.; Sigeev, A. S.;
Peregudov, A. S.; Petrovskii, P. V. Russ. J. Org. Chem. 2001, 37, 1463. (g) Beletskaya, I. P.;
Sigeev, A. S.; Peregudov, A. S.; Petrovskii, P. V. Tetrahedron Lett. 2003, 44, 7039. (h) Itoh,
T.; Mase, T. Org. Lett. 2004, 6, 4587. (i) Fernández- Rodriges, M. A.; Shen, Q.; Hartwig, J.
F. J. Am. Chem. Soc. 2006, 128, 2180.
7
. Selected examples of metal-free O-arylations: (a) Kingsbury, C. A. J. Org. Chem. 1964,
9, 3262. (b) Cadogan, J. I. G.; Hall, J. K. A.; Sharp, J. T. J. Chem. Soc. C 1967, 1860. (c)
2
2
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