Ligand-free, atom-efficient Suzuki-Miyaura type cross-coupling reactions at room temperature

Article abstract of DOI:10.1016/j.tet.2010.07.022

The atom-efficient cross-coupling reaction of sodium tetraarylborates with aryl iodides and bromides was reported. The reaction can be performed directly using a catalytic system composed of palladium chloride, sodium carbonate and methanol (PdCl₂/Na₂CO₃/MeOH) under heat-free conditions at room temperature in an open air conditions. The reactions carried out in an atom-efficient way as 4 equiv of aryl halides coupled effectively with 1 equiv of sodium tetraarylborates to furnish 4 equiv of the corresponding functionalized biaryls in good to excellent yields.

Full text of DOI:10.1016/j.tet.2010.07.022

Tetrahedron 66 (2010) 7633e7641
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Ligand-free, atom-efficient SuzukieMiyaura type cross-coupling reactions
at room temperature
,
b
,
a
Wen-Jun Zhou a, Ke-Hu Wang a, Jin-Xian Wang a , Zhi-Rong Gao
*
a Institute of Chemistry, Department of Chemistry, Northwest Normal University, 967 Anning Road (E), Lanzhou 730070, PR China
b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 12 May 2010
Received in revised form 6 July 2010
Accepted 13 July 2010
Available online 21 July 2010
The atom-efficient cross-coupling reaction of sodium tetraarylborates with aryl iodides and bromides
was reported. The reaction can be performed directly using a catalytic system composed of palladium
chloride, sodium carbonate and methanol (PdCl2/Na2CO3/MeOH) under heat-free conditions at room
temperature in an open air conditions. The reactions carried out in an atom-efficient way as 4 equiv of
aryl halides coupled effectively with 1 equiv of sodium tetraarylborates to furnish 4 equiv of the corre-
sponding functionalized biaryls in good to excellent yields.
Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction
reactions were conducted at room temperature, such as BayliseHill-
man reaction,10 Aldol reaction,11 Michael addition reaction,12 asym-
The palladium-catalyzed SuzukieMiyaura cross-coupling re-
action is one of the most versatile and utilized reactions for the
selective construction of carbonecarbon bonds,1 which has found
extensive use in the synthesis of pharmaceutical mediates,2 poly-
mers,3 and agrochemicals.4 Among the approaches described in the
literature, numerous efforts have been devoted to the development
of ligand-promoted catalytic systems,5 and great successes have
been achieved. However, most of theses ligands are not only sen-
sitive to air oxidation and therefore require careful and air-free
handling, but also comparatively difficult to prepare or rather ex-
pensive.6 To circumvent this issue, the development of efficient
ligand-free catalytic systems7 consisting of economical catalysts
was still a highly desirable goal.
metric hydrogenation,13 and cross-coupling reaction,14 and so on.
Although great success has been achieved, however, the atom-effi-
cient cross-coupling of sodium tetraarylborates at room temperature
has not so far been reported. In continuation of our studies on the
scope of transitions metals catalyzed organic transformations,15 in
this paper, we report our recent results for the study of the atom-ef-
ficient, palladium-catalyzed ligand-free cross-coupling reaction of
sodium tetraarylborates with aryl iodides and aryl bromides at room
temperature in an open air conditions. We have reinvestigated the
procedure with respect to five key variables: (1) atom-efficient (as
4 equiv of aryl halides coupled effectively with 1 equiv of sodium
tetraarylborates), (2) ligand-free conditions, (3) short reaction time,
(4) low reaction temperature, and (5) simple operate processes.
As a new type of borate source, sodium tetraphenylborate is
a stable and commercially available reagent for the organic syn-
thesis.8 Up to now, only a few reactions involving sodium tetra-
phenylborate for CeC bond formation have been reported.9
Furthermore, these known reactivity of sodium tetraphenylborate
with electrophonic reagents always suffer from disadvantages, such
as atom efficiency, high reaction temperature, long reaction times,
and harsh reaction conditions. Hence, to expand the scope and
reactivity of sodium tetraphenylborate, development of new, and
efficient catalytic protocols is in demand.
2. Results and discussion
During our investigation for preparing the biaryl compounds by
employing this reaction, surprisingly, we found that the reaction
can be run in air without using any ligand. Under this mild condi-
tion, we examined the effect of bases using sodium tetraphe-
nylborate and bromobenzene as substrates in the presence of
palladium chloride in methanol. The uses of organic base, such as
triethylamine, gave the corresponding cross-coupling product in
the yield of 64% (Table 1, entry 1). Comparison of inorganic bases
utilized showed that sodium bases were more suitable than the
potassium ones. For example, the reaction proceeded in high yield
within short time in the presence of Na2CO3, NaOAc, NaOH or
NaHCO3 while it was less satisfactory in the case of K2CO3, KHCO3,
Nowadays, considering the simple operate processes, tremendous
interest has been focused on the room-temperature reactions. Many
* Corresponding author. Tel.: þ86 931 7970567; fax: þ86 931 7768159; e-mail
address: wangjx@nwnu.edu.cn (J.-X. Wang).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.07.022

7634
W.-J. Zhou et al. / Tetrahedron 66 (2010) 7633e7641
KOH or K3PO4, (Table 1, entries 2e9). Further study with varying
Na2CO3 base equivalents produced mixed conversions revealing
that 3.0 equiv of base is necessary to obtain high yield of the cross-
coupling product (Table 1, entries 9e13).
gathered that Ni and Co pieces were not effective for the reaction
even after prolonged the stirring time (Table 3, entries 1e5). Also,
Pd/C which is one of the most common heterogeneous catalysts is
not an effective catalyst for the present coupling reaction (Table 3,
entry 6). When PdCl2(PPh3)2 or Pd (PPh3)4 was used, the coupling
proceed smoothly and moderate yields of biphenyl was obtained
(Table 3, entries 8 and 9). Strikingly, the cross-coupling reaction
carried out in the presence of NaCO3 in MeOH with palladium
chloride catalyst at room temperature provided the highest cross-
coupling conversion. Furthermore, it is noteworthy that the present
protocol is highly efficient as 4 equiv of bromobenzene reacted with
1 equiv of sodium tetraphenylborate cleanly to provide the desire
cross-coupling products with high yield in short reaction time.
Table 1
Effect of bases on the coupling of bromobenzene with Ph4BNaa
Entry
Base [mmol]
Time [h]
Yieldb [%]
1
2
3
4
5
6
7
8
Et3N (3.0)
KOH (3.0)
KF (3.0)
12
12
24
24
24
12
12
12
3
3
3
3
3
64
21
18
<5
<5
65
75
82
93
70
82
91
92
K3PO4 (3.0)
K2CO3 (3.0)
NaOH (3.0)
NaHCO3 (3.0)
NaOAc (3.0)
Na2CO3 (3.0)
Na2CO3 (1.5)
Na2CO3 (2.0)
Na2CO3 (2.5)
Na2CO3 (3.5)
Table 3
Comparative experiments with simple catalystsa
9
10
11
12
13
Entry
Catalyst
Time [h]
Yieldb [%]
1
2
3
4
5
6
7
8
9
NiCl2$5H2O
NiCl2(PPh3)2
Ni(acac)2
CoBr2$2H2O
CoCl(PPh3)3
Pd/C
PdCl2
PdCl2(PPh3)2
Pd (PPh3)4
60
60
60
60
60
12
3
<5
<5
<5
<5
<5
8
93
36
50
a
Reaction conditions: bromobenzene (1.0 mmol), Ph4BNa (0.25 mmol), base,
PdCl2 (0.03 mmol), and MeOH (3 mL) stirring at room temperature for the appro-
priate time.
b
Isolated yield.
The choice of solvent was also important for the present
method. Dimethyl sulfoxide (DMSO), dichloromethane (CH2Cl2),
and polyethylene glycol (PEG 400) were not effective in the present
coupling reaction (Table 2, entries 1e3). Acetonitrile (MeCN), tet-
rahydrofuran (THF), and ethyl acetate gave quite poor results (Table
2, entries 4e6). Some other aprotic polar solvents, such as N,
N,-dimethylformamide (DMF), dioxane, and acetone, which are
commonly used in Pd-catalyzed coupling reactions, gave the cor-
responding cross-coupling product in moderate yields (Table 2,
entries 7e9). Alcoholic solvents, especially MeOH and EtOH gave
satisfactory results (Table 2, entries 12 and 13).
12
12
a
Reaction conditions: bromobenzene (1.0 mmol), Ph4BNa (0.25 mmol), Na2CO3
(3.0 mmol), catalyst (0.03 mmol), and solvents (3 mL) stirring at room temperature
for the appropriate time.
b
Isolated yield.
Encouraged by these results, the cross-coupling scope and
generality of a variety of aryl bromides with different sodium tet-
raarylborates was investigated using the optimized conditions and
the results are given in Table 4.
As shown in Table 4, aryl bromides with electron-deficient or
electron-rich groups showed good to excellent reactivity and fur-
nished the products in short reaction times. It can be seen that
bromobenzene and 1-bromo-4-nitrobenzene can be reacted effi-
ciently with different sodium tetraarylborates and furnished the
desire functionalized biphenyls in high yields (Table 4, entries 1e8).
Furthermore, the reactions of variety of aryl bromides substituted
with both electron-deficient (such as acetyl, cyano, fluoro, and nitro)
and electron-withdrawing group (such as methyl, methoxyl,
ethoxyl, amidine, andacetamido) groups produced goodtoexcellent
isolated yields of the functionalized biaryls with sodium tetraphe-
nylborate (Table 4, entries 9e18), and the electron-rich substrates
show lower reactivity (Table 4, entries 15e18). The reaction of
1-bromonaphthalene and 2-bromonaphthalene were remarkable
furnishing the corresponding coupling products in excellent yields
(Table 4, entries 19 and20). Furthermore, the reaction of heterocyclic
bromides with sodium tetraphenylborate also provided the cross-
coupling products (Table 4, entries 21e23). It is worth noting that
the catalytic system was tolerant to a broad range of functional
groups, and aryl bromides with hydroxyl, amidine, carboxylic acid
groups underwent the coupling reaction in high yields without any
protection.
Table 2
Effect of solvents on the coupling of bromobenzene with Ph4BNaa
Entry
Solvents [3 mL]
Time [h]
Yieldb [%]
1
2
3
4
5
6
7
8
DMSO
16
12
24
16
12
12
12
12
24
12
12
3
5
5
CH2Cl2
PEG 400
MeCN
THF
Ethyl acetate
DMF
Acetone
Dioxane
i-PrOH
n-BuOH
MeOH
<5
18
28
32
54
58
60
48
48
93
89
9
10
11
12
13
EtOH
6
a
Reaction conditions: bromobenzene (1.0 mmol), Ph4BNa (0.25 mmol), Na2CO3
(3.0 mmol), PdCl2 (0.03 mmol). and solvents (3 mL) stirring at room temperature for
the appropriate time.
b
Isolated yield.
During our further research, we found that the reactivity of
substituted aryl iodides with sodium tetraarylborates were faster
and efficient furnishing excellent yields of the cross-coupled
biphenyls in a short reaction time (less than 1 h) catalyzed by PdCl2
in MeOH. As shown in Table 5, the reaction of various aryl iodides
with both electron-withdrawing and electron-donating substitute
We next examined the simple catalyst activity of Ni, Co, and Pd
particles. Among them, PdCl2 was the most efficient catalyst for the
present atom-efficient room temperature SuzukieMiyaura cross-
coupling reactions (Table 3, entry 7). From Table 3, it can be

W.-J. Zhou et al. / Tetrahedron 66 (2010) 7633e7641
7635
Table 4
Pd-catalyzed cross-coupling of aryl bromides with sodium tetraarylboratea
Entry
1
R1
H
R2
H
Products
Time [h]
3
Yieldb [%]
93
90
86
84
94
92
85
86
2
3
4
5
6
7
8
4-Cl
H
5
5
5
2
3
3
3
4-CH3
4-OCH3
H
H
H
4-NO2
4-NO2
4-NO2
4-NO2
4-Cl
4-CH3
4-OCH3
9
H
2-Cl
2
91
10
11
12
13
14
15
16
17
18
H
H
H
H
H
H
H
H
H
4-CN
0.5
0.5
0.5
0.5
0.5
6
93
93
92
91
93
80
87
89
88
4-COCH3
4-F
4-CHO
4-COOCH3
4-NH2
4-OCH3
4-OC2H5
4-CH3
3
3
3
(continued on next page)

7636
Table 4 (continued)
W.-J. Zhou et al. / Tetrahedron 66 (2010) 7633e7641
Entry
R1
R2
Products
Time [h]
Yieldb [%]
19
H
2-Naphthyl
3
90
20
H
H
1-Naphthyl
3
91
81
21
22
0.5
H
H
0.5
0.5
84
86
23
a
Reaction conditions: aryl bromides (1.0 mmol), Ar4BNa (0.25 mmol), Na2CO3 (3.0 mmol), PdCl2 (0.03 mmol), and MeOlH (3 mL) stirring at room temperature for the
appropriate time.
b
Isolated yield.
Table 5
Pd-catalyzed cross-coupling of aryl iodides with sodium tetraarylboratea
Entry
1
R1
H
R2
H
Products
Time [min]
15
Yieldb [%]
99
2
3
4
5
6
7
4-CH3
4-OCH3
H
H
15
15
10
10
10
20
97
97
99
98
98
97
H
4-NO2
4-NO2
4-NO2
4-NO2
4-Cl
4-F
4-CH3
8
4-OCH3
4-NO2
20
97

W.-J. Zhou et al. / Tetrahedron 66 (2010) 7633e7641
7637
Table 5 (continued)
Entry
R1
H
R2
Products
Time [min]
10
Yieldb [%]
9
3-NO2
98
96
96
96
95
96
94
92
92
98
96
96
10
11
12
13
14
15
16
17
18
19
20
4-Cl
3-NO2
3-NO2
3-NO2
3-NO2
2-Cl
15
15
20
20
10
20
20
30
10
20
20
4-F
4-CH3
4-OCH3
H
4-F
2-Cl
4-CH3
4-OCH3
H
2-Cl
2-Cl
3-Me
3-Me
3-Me
4-CH3
4-OCH3
21
22
H
4-OMe
4-OMe
10
20
99
97
4-Cl
23
4-F
4-OMe
20
96
(continued on next page)

7638
Table 5 (continued)
W.-J. Zhou et al. / Tetrahedron 66 (2010) 7633e7641
Entry
R1
R2
Products
Time [min]
20
Yieldb [%]
97
24
4-Me
4-OMe
25
4-OMe
4-OMe
20
96
a
Reaction conditions: aryl iodides (1.0 mmol), Ar4BNa (0.25 mmol), Na2CO3 (3.0 mmol), PdCl2 (0.01 mmol), and MeOH (3 mL) stirring at room temperature for the ap-
propriate time.
b
Isolated yield.
groups furnished excellent yields of the functionalized biphenyls.
Notably, the cross-coupling reactivity with aryl iodides was found
to be efficient even with a lower palladium catalyst loading
(1 mmol %) when compared to the corresponding reactivity with
aryl bromides.
Further study indicated that aryl chlorides can also react with
sodium tetraphenylborate under PdCl2/Na2CO3/MeOH conditions.
However, the yields of biaryls were very poor even prolonged the
reaction time (Scheme 1).
4.2. Typical experimental procedure for the atom-efficient
SuzukieMiyaura cross-coupling reaction
A mixture of aryl halides (1 mmol), sodium tetraphenylborate
(0.25 mmol), Na2CO3 (3 mmol), PdCl2 (0.03 mmol for aryl bro-
mides, 0.01 mmol for aryl iodides), and MeOH (3 mL) was stirred at
room temperature in an open air for the indicated time until
complete consumption of starting material as monitored by TLC.
Then the mixture was diluted with H2O (10 mL) and extracted with
Et2O (4ꢀ10 mL). The combined organic layers were washed with
brine (10 mL), dried over MgSO4, and concentrated in vacuo. The
residue was purified by flash column chromatography on silica gel
(petroleum ether/EtOAc, 60:1) to give the corresponding biaryl
compound.
4.3. Typical experimental procedure for the synthesis of
16
NaBAr4
Slow addition of a solution of (0.09 mol) of aryl bromides in Et2O
(150 mL) to Mg turnings (0.11 mol) in Et2O (150 mL), followed by
refluxing for 30 min, gave a dark gray solution of the aryl Grignard
reagent. Upon addition of NaBF4 (0.15 mol), the heterogeneous re-
action mixture was stirred for 48 h, during which time the solution
became brown and a fine precipitate formed. The reaction mixture
was then added to Na2CO3 (38 g) in water (1 L), stirred for 20 min,
and then filtered. The mixture was extracted with Et2O (4ꢀ100 mL)
and the combined organic layer was dried over Na2SO4 and con-
centrated in vacuo. The residue was recrystallized from petroleum
ether.
Scheme 1. Palladium-catalyzed cross-coupling of aryl chlorides with sodium
tetraphenylborate.
3. Conclusion
In conclusion, we have developed an atom-efficient, ligand-free
palladium-catalyzed atom-efficient SuzukieMiyaura cross-cou-
pling reaction under mild conditions in short reaction times. Sodium
tetraarylborate underwent the coupling reaction with various aryl
bromides or aryl iodides in good to excellent isolated yields at room
temperature in an open air atmosphere condition. It is noteworthy
that the present protocolcan be performed in a highlyatom-efficient
way as 4 equiv of aryl halides reacted with 1 equiv of sodium tet-
raphenylborate at room temperature.
4.4. Spectral data
4.4.1. Biphenyl. Mp (ꢁC): 69e70,17 71.18 IR ( /cmꢂ1): 3032, 1943,
n
1596, 1568,1479, 1008, 984, 729; 1H NMR (400 MHz, CDCl3):
d¼7.59
4. Experimental
4.1. General
(d, J¼7.2 Hz, 4H), 7.44 (t, J¼8.0 Hz, 4H), 7.36e7.32 (m, 2H); 13C NMR
(100 MHz, CDCl3):
100), 76 (50).
d
¼141.2, 128.7, 127.2, 127.1. MS m/z (%): 154 (Mþ,
1H NMR spectra were recorded on a Brucker AM 400 MHz and
Brucker AC-E 200 MHz spectrometers in CDCl3 with TMS as an
internal standard. 13C NMR spectra were obtained on a Brucker AM-
400 operating at 100 MHz or a Brucker AC-E 200 operating at
50 MHz. IR spectra were recorded on an Alpha Centauri FI-IR
spectrometer. Mass spectra were recorded on a HP 5988A and GC/
MS/DS instruments. Elemental analyses were carried out on Carlo
Erba-1106 instruments. Purification of products was performed via
flash chromatography with 200e400 mesh silica gel (15:1 petro-
leum/diethyl ether). All substrates and reagents were obtained
commercially which were prepared by standard procedures.
4.4.2. 4-Methylbiphenyl. MP (ꢁC): 46e47,17 46e48.19 IR (
3038, 2932, 1607, 1568, 1444, 1130, 1006, 822; 1H NMR (400 MHz,
CDCl3):
¼7.57 (d, J¼8.0 Hz, 2H), 7.49 (d, J¼7.6 Hz, 2H), 7.42 (t,
J¼7.6 Hz, 2H), 7.33e7.30 (m, 1H), 7.24 (d, J¼8.0 Hz, 2H), 2.39 (s, 3H);
13C NMR (100 MHz, CD3COCD3):
¼141.5, 138.6, 137.4, 130.0, 129.3,
127.5, 127.2, 127.1, 20.7. MS m/z (%): 168 (Mþ, 100), 152 (24).
n
/cmꢂ1):
d
d
4.4.3. 3-Methylbiphenyl. Oil,20 IR ( /cmꢂ1): 3030, 2920, 1696, 1601,
n
1480, 1072, 1033, 752, 697; 1H NMR (400 MHz, CDCl3):
d
¼7.59e7.56 (m, 2H), 7.45e7.38 (m, 4H), 7.35e7.31 (m, 2H), 7.16 (t,
J¼7.6 Hz, 1H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3):
¼141.3,
d

W.-J. Zhou et al. / Tetrahedron 66 (2010) 7633e7641
7639
141.2, 138.3, 128.7, 128.6, 128.0, 127.2, 124.3, 21.5. MS m/z (%): 168
d
¼7.69 (q, J¼8.8 Hz, 4H), 7.59e7.55 (m, 1H), 7.49e7.40 (m, 4H); 13
C
(Mþ, 100), 153 (35), 76 (44).
NMR (100 MHz, CDCl3):
d
¼145.5, 139.0, 132.5, 129.0, 128.6, 127.6,
127.1, 118.9, 110.8. MS m/z (%): 179 (Mþ, 100), 151 (14), 76 (23).
4.4.4. 4-Methoxybiphenyl. Mp (ꢁC) 87e88,17 85e87.19 IR ( /cmꢂ1):
n
3034, 2908, 1604, 1592, 1486, 918, 823, 756; 1H NMR (400 MHz,
4.4.14. Biphenyl-4-amine. Mp (ꢁC) 45e47.27 IR (
n
/cmꢂ1): 3422, 3203,
CDCl3):
d
¼7.56e7.51 (m, 4H), 7.41 (t, J¼7.6 Hz, 2H), 7.30 (t, J¼7.6 Hz,
3026, 2926, 1624, 1482, 1259, 834; 1H NMR (400 MHz, CDCl3):
1H), 6.98 (d, J¼7.2 Hz, 2H), 3.85 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
¼7.55e7.52 (m, 2H), 7.43e7.36 (m, 4H), 7.26 (t, J¼8.4 Hz,1H), 6.75 (d,
d
¼159.1, 140.8, 133.7, 128.7, 128.1, 126.7, 126.6, 114.2, 55.3. MS m/z
J¼8.0 Hz, 2H), 3.71 (s, 2H); 13C NMR (100 MHz, CDCl3):
¼145.8, 141.1,
d
(%): 184 (Mþ, 100), 169 (MþꢂCH3, 48).
131.6, 128.7, 126.4, 126.3, 115.4. MS m/z (%): 169 (Mþ, 100), 141 (7).
4.4.5. 4-Nitrobiphenyl. Mp (ꢁC): 112e114,17 114.18 IR
(n
/cmꢂ1):
4.4.15. Methyl
115.5e116.5.29 IR (
1002, 697; 1H NMR (400 MHz, CDCl3):
7.66e7.59 (m, 4H), 7.47e7.36 (m, 3H), 3.92 (s, 3H); 13C NMR
biphenyl-4-carboxylate. Mp
/cmꢂ1): 3030, 2945, 1938, 1716, 1603, 1111,
¼8.10 (d, J¼8.4 Hz, 2H),
(ꢁC)
115e116,17
3063, 1601, 1570, 1525, 1357, 1074, 853, 740; 1H NMR (400 MHz,
n
CDCl3):
d
¼8.30 (d, J¼8.0 Hz, 2H), 7.74 (d, J¼8.0 Hz, 2H), 7.63 (d,
d
J¼7.6 Hz, 2H), 7.52e7.45 (m, 3H); 13C NMR (100 MHz, CDCl3):
d¼147.6, 47.0, 138.7, 129.1, 128.9, 127.8, 127.4, 124.1. MS m/z (%): 199
(100 MHz, CDCl3):
d¼167.0, 145.6, 139.9, 130.1, 128.9, 128.3, 128.1,
(Mþ, 100), 152 (85), 151 (30).
127.2, 127.0, 52.1. MS m/z (%): 212 (Mþ, 57), 181 (100), 152 (75), 76
(24).
4.4.6. 3-Nitrobiphenyl. Mp (ꢁC): 60e61, 62.18 IR ( /cmꢂ1): 3082,
n
2924, 1625, 1569, 1351, 1064, 853, 748; 1H NMR (400 MHz, CDCl3):
4.4.16. 5-Phenyl-2-furoic acid. Mp (ꢁC) 153e154,17 152e155.30 IR (
cmꢂ1): 3033, 2897, 1678, 1525, 1475, 1452, 1025, 917; 1H NMR
n/
d
¼8.45 (s, 1H), 8.20 (d, J¼8.0 Hz, 1H), 7.91 (d, J¼8.0 Hz, 1H),
7.65e7.59 (m, 3H), 7.52e7.26 (m, 3H); 13C NMR (100 MHz, CDCl3):
¼148.7,142.8,138.6,133.0,129.7,129.1,128.5,127.1,122.0,121.9. MS
m/z (%): 199 (Mþ, 80), 152 (100), 153 (52).
(400 MHz, CDCl3):
d
¼11.52 (s, 1H), 7.81 (d, J¼7.2 Hz, 2H), 7.45e7.35
d
(m, 4H), 6.79 (d, J¼3.6 Hz, 1H); 13C NMR (100 MHz, CD3COCD3):
d
¼159.2, 157.6, 144.7, 130.2, 129.5, 129.4, 125.1, 120.4, 107.8. MS m/z
(%): 188 (Mþ, 100), 115 (42).
4.4.7. 1-Phenylnaphthalene. Oil.17,18 IR ( /cmꢂ1): 3056, 1592, 1494,
n
1395, 802, 779, 761, 617; 1H NMR (400 MHz, CDCl3):
d¼7.90 (d,
4.4.17. 5-Acetyl-2-phenylthiophene. Mp (ꢁC) 114e115,17 115.31 IR (
n/
J¼8.0 Hz, 2H), 7.85 (d, J¼8.0 Hz, 1H), 7.54e7.40 (m, 9H); 13C NMR
cmꢂ1): 3026, 1649, 1447, 1361, 1278, 924, 809; 1H NMR (400 MHz,
(100 MHz, CDCl3):
d¼140.7, 140.2, 133.8, 131.6, 130.1, 128.4, 128.2,
CDCl3):
d
¼7.66e7.58 (m, 2H), 7.43e7.26 (m, 5H), 2.56 (s, 3H); 13C
127.6, 127.2, 126.9, 126.0, 125.7, 125.4. MS m/z (%): 204 (Mþ, 100).
NMR (100 MHz, CDCl3):
d
¼190.6, 152.7, 143.0, 133.4, 133.2, 129.1,
129.0, 126.2, 123.8, 26.5. MS m/z (%): 202 (Mþ, 58), 187 (100), 115
4.4.8. 2-Phenylnaphthalene. Mp (ꢁC) 96e97,17 95e96.43 IR ( /cmꢂ1):
n
(50).
3053, 1947, 1597, 1494, 1453, 1130, 893, 860; 1H NMR (400 MHz,
CDCl3):
¼8.03 (s, 1H), 7.92e7.85 (m, 3H), 7.73 (t, J¼8.0 Hz, 3H),
7.51e7.46 (m, 4H), 7.39e7.23 (m, 1H); 13C NMR (100 MHz, CDCl3):
¼141.0, 138.5, 133.6, 132.6, 128.8, 128.4, 128.2, 127.6, 127.4, 127.3,
126.3, 125.9, 125.8, 125.6. MS m/z (%): 204 (Mþ, 100).
d
4.4.18. Methyl 5-phenylfuran-2-carboxylate. Mp (ꢁC): 58e60.17 IR
(n
/cmꢂ1): 3025, 2952, 1717, 1145, 988, 695; 1H NMR (400 MHz,
d
CDCl3):
d
¼7.78 (d, J¼7.6 Hz, 2H), 7.43e7.32 (m, 3H), 7.24 (d,
J¼7.2 Hz, 1H), 6.73 (d, J¼7.6 Hz, 1H), 3.91 (s, 3H); 13C NMR
(100 MHz, CDCl3):
d¼159.2, 157.5, 143.5, 129.4, 128.9, 128.8, 124.8,
4.4.9. 2-Chloridebiphenyl. Oil,21 IR (
n
/cmꢂ1): 3059, 2924, 1642,
106.8, 51.8. MS m/z(%): 202 (Mþ, 100), 171 (80), 115 (99).
1462, 1420, 750, 697; 1H NMR (400 MHz, CDCl3):
d
¼7.48e7.38 (m,
6H), 7.36e7.26 (m, 3H); 13C NMR (100 MHz, CDCl3):
d
¼140.5, 139.4,
4.4.19. 4-Fluoro-biphenyl. Mp (ꢁC): 73e73.5,36 73e74, IR ( /cmꢂ1):
n
132.5, 131.4, 129.9, 129.4, 128.5, 128.0, 127.6, 126.8. MS m/z (%): 188
3051, 2936, 1892, 1622, 1523, 1228, 1159, 835, 756; 1H NMR
(Mþ, 100), 152 (60).
(400 MHz, CDCl3):
d
¼7.59 (d, J¼8.0 Hz, 1H), 7.55e7.52 (m, 2H),
7.46e7.41 (m, 3H), 7.34 (t, J¼7.6 Hz, 3H), 7.12 (t, J¼8.4 Hz, 2H); 13C
4.4.10. 4-Acetylbiphenyl. Mp (ꢁC) 120e121,17 121.18 IR (
3032, 2998, 1678, 1599, 1400, 1359, 837, 687; 1H NMR (400 MHz,
CDCl3):
¼8.03 (d, J¼8.0 Hz, 2H), 7.68 (d, J¼8.0 Hz, 2H), 7.62 (d,
J¼7.6 Hz, 2H), 7.47 (t, J¼7.6 Hz, 2H), 7.41 (d, J¼7.6 Hz,1H), 2.65 (s, 3H);
13C NMR (100 MHz, CDCl3):
¼197.7, 145.7, 139.8, 135.8, 128.9, 128.8,
128.2, 127.2, 127.1, 26.7. MS m/z (%): 196 (Mþ, 42), 181 (100), 152 (59).
n
/cmꢂ1):
NMR (100 MHz, CDCl3):
d
¼162.4 (d, J¼244.6 Hz, 1C), 141.2, 140.2,
137.3, 128.8, 128.6, 128.5, 127.2, 127.1, 115.6 (d, J¼21.4 Hz, 1C). MS m/
d
z (%): 172 (Mþ, 100).
d
4.4.20. 4-Methyl-40-nitrobiphenyl. Mp (ꢁC) 140-141.34 IR (
n
/cmꢂ1):
3052, 2932, 2847, 1637, 1599, 1513, 1340, 1104, 822, 749; 1H NMR
(400 MHz, CDCl3):
d
¼8.29 (d, J¼9.2 Hz, 2H), 7.72 (d, J¼8.8 Hz, 2H),
4.4.11. 4-Ethoxybiphenyl. Mp (ꢁC)69e71.25 IR ( /cmꢂ1): 3034, 2927,
n
7.53 (d, J¼8.4 Hz, 2H), 7.31 (d, J¼8.8 Hz, 2H), 2.43 (s, 3H); 13C NMR
1601, 1483, 1450, 1249, 1047, 760; 1H NMR (400 MHz, CDCl3):
(100 MHz, CDCl3):
d
¼147.6, 146.8, 139.1, 135.8, 129.9, 127.5, 127.2,
d
¼7.56e7.50 (m, 4H), 7.41 (t, J¼8.0 Hz, 2H), 7.31e7.28 (m, 1H), 6.96
124.1, 21.2. MS m/z (%): 213 (Mþ, 100), 165 (38), 152 (48).
(d, J¼8.8 Hz, 2H), 4.07 (q, J¼7.2 Hz, 2H), 1.44 (t, J¼7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3):
d
¼158.5, 140.8, 133.6, 128.7, 128.1, 126.7,
4.4.21. 4-Methoxy-40-nitrobiphenyl. Mp (ꢁC) 106-108.35 IR
(n/
126.6, 114.7, 63.5, 14.9. MS m/z (%): 198 (Mþ, 68), 170 (100).
cmꢂ1): 3066, 2926, 1598, 1509, 1342, 1248, 1181, 1103, 1012, 826,
752; 1H NMR (400 MHz, CDCl3):
J¼8.8 Hz, 2H), 7.58 (d, J¼7.6 Hz, 2H), 7.02 (d, J¼6.4 Hz, 2H), 3.88 (s,
d¼8.27 (d, J¼9.2 Hz, 2H), 7.69 (d,
4.4.12. 4-Carboxaldehydebiphenyl. Mp (ꢁC)57e58,17 57e59.18 IR (
n
/
cmꢂ1): 3356, 3027, 2835, 1695, 1600, 1170, 1001, 832; 1H NMR
3H); 13C NMR (100 MHz, CDCl3):
d¼160.4, 147.2, 146.5, 131.0, 128.5,
(400 MHz, CDCl3):
d
¼10.06 (s, 1H), 7.95 (d, J¼8.0 Hz, 2H), 7.75 (d,
127.0, 124.1, 114.6, 55.4. MS m/z (%): 229 (Mþ, 100), 199 (27), 139
J¼8.4 Hz, 2H), 7.64 (d, J¼6.8 Hz, 2H), 7.50e7.42 (m, 3H); 13C NMR
(68).
(100 MHz, CDCl3):
d
¼191.9, 147.2, 139.7, 135.2, 130.2, 129.0, 128.4,
127.7, 127.3. MS m/z (%): 181 (Mþ, 100), 152 (68), 76 (46).
4.4.22. 4-Chloro-40-nitrobiphenyl. Mp (ꢁC): 112e113.37 IR (
n
/cmꢂ1):
3072, 2931, 1595, 1510, 1476, 1342, 1092, 1004, 854, 817, 749; 1H
4.4.13. 4-Cyanobiphenyl. Mp (ꢁC): 85e86,17 86e87.26 IR (
n
/cmꢂ1):
NMR (400 MHz, CDCl3):
d¼8.30 (d, J¼7.6 Hz, 2H), 7.71 (d, J¼7.2 Hz,
2227, 1606, 1485, 1526, 1354, 1068, 768; 1H NMR (400 MHz, CDCl3):
2H), 7.56 (d, J¼7.6 Hz, 2H), 7.47 (d, J¼8.4 Hz, 2H); 13C NMR

7640
W.-J. Zhou et al. / Tetrahedron 66 (2010) 7633e7641
(100 MHz, CDCl3):
d
¼147.2, 146.3, 137.2, 135.3, 129.4, 128.6, 127.7,
(d, J¼8.8 Hz, 2H), 3.84 (s, 3H); 13C NMR (100 MHz, CDCl3):
¼159.4,
d
124.2. MS m/z (%): 233 (Mþ, 68), 202 (41), 152 (100).
139.3, 132.7, 132.5, 128.8, 128.0, 127.9, 114.3, 55.3. MS m/z (%): 246
(Mþ, 84), 231 (100), 202 (89).
4.4.23. 4-Fluoro-40-nitrobiphenyl. Mp (ꢁC): 125e126,38 127e128. IR
(
n
/cmꢂ1): 3076, 2844, 1597, 1515, 1481, 1346, 1232, 1107, 833, 752;
4.4.32. 3,40-Dimethylbiphenyl. Oil,23 IR (
n
/cmꢂ1): 3024, 2920, 1902,
1H NMR (400 MHz, CDCl3):
d¼8.30 (d, J¼8.0 Hz, 2H), 7.70 (d,
1606, 1483, 1451, 1039, 821, 779; 1H NMR (400 MHz, CDCl3):
d
¼7.48
J¼8.8 Hz, 2H), 7.62e7.58 (m, 2H), 7.19 (t, J¼8.4 Hz, 2H); 13C NMR
(d, J¼8.4 Hz, 1H), 7.38 (d, J¼8.4 Hz, 2H), 7.31 (t, J¼7.6 Hz, 1H), 7.23 (d,
(100 MHz, CDCl3):
d
¼164.6, 162.1, 147.0, 146.5, 134.9, 129.1 (d,
J¼7.6 Hz, 2H), 7.14 (d, J¼7.6 Hz, 2H), 2.41 (s, 3H), 2.39 (s, 3H); 13C NMR
J¼8.4 Hz, 1C), 127.6, 124.2, 116.2 (d, J¼22.1 Hz, 1C). MS m/z (%): 217
(100 MHz, CD3COCD3):
d
¼141.1,138.4,138.2,136.9,129.4,128.6,127.8,
(Mþ, 95), 187 (56), 170 (100).
127.7, 127.0, 124.1, 21.5, 21.1. MS m/z (%): 182 (Mþ, 100), 165 (43).
4.4.24. 4-Methyl-30-nitrobiphenyl. Mp (ꢁC): 75.5e76.5,31 79e80. IR
4.4.33. 4-Methoxy-30-methylbiphenyl. Mp (ꢁC): 51e52.24 IR
(n/
(n
/cmꢂ1): 3085, 2922, 1512, 1346, 1087, 804, 738; 1H NMR
cmꢂ1): 3032, 2951, 1605, 1514, 1498, 1249, 1184, 1028, 833, 785; 1H
(400 MHz, CDCl3):
d
¼8.43 (t, J¼2.0 Hz, 1H), 8.17 (d, J¼8.0 Hz, 1H),
NMR (400 MHz, CDCl3):
7.30 (t, J¼7.6 Hz, 1H), 7.12 (d, J¼7.6 Hz, 1H), 6.98e6.94 (m, 2H), 3.84
(s, 3H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3):
138.3, 138.7, 128.6, 128.1, 127.5, 127.4, 123.8, 114.1, 55.3, 21.5. MS m/z
(%): 198 (Mþ, 100), 183 (MþꢂCH3, 49), 155 (40).
d
¼7.54e7.46 (m, 2H), 7.35 (d, J¼9.2 Hz, 2H),
7.90 (d, J¼8.0 Hz, 1H), 7.59 (t, J¼8.0 Hz, 1H), 7.53 (d, J¼8.4 Hz, 2H),
7.30 (d, J¼8.4 Hz, 2H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
¼159.0, 140.8,
d
¼142.8, 138.5, 135.7, 132.8, 129.8, 129.6, 126.9, 121.7, 121.6, 109.7,
21.1. MS m/z (%): 213 (Mþ, 100), 165 (52).
4.4.25. 4-Methoxy-30-nitrobiphenyl. Mp (ꢁC) 70e71.39 IR (
n
/cmꢂ1):
4.4.34. 4-Methoxy-40-methylbiphenyl. Mp (ꢁC) 110e111,28 110e112.
3081, 2962, 1607, 1512, 1457, 1348, 1246, 1021, 830, 805, 741; 1H
IR (
(400 MHz, CDCl3):
7.22 (d, J¼8.0 Hz, 2H), 6.96 (d, J¼8.4 Hz, 2H), 3.84 (s, 3H), 2.38 (s,
3H); 13C NMR (100 MHz, CDCl3):
¼158.9, 137.9, 136.3, 133.7, 129.4,
127.9, 126.6, 114.1, 55.3, 21.0. MS m/z (%): 198 (Mþ, 100), 183 (58).
n
/cmꢂ1): 3019, 2953, 1607, 1493, 1248, 1180, 1037, 807; 1H NMR
NMR (400 MHz, CDCl3):
d
¼8.40 (s, 1H), 8.14 (d, J¼8.4 Hz, 1H), 7.86
d¼7.51 (d, J¼8.8 Hz, 2H), 7.44 (d, J¼8.4 Hz, 2H),
(d, J¼8.4 Hz, 1H), 7.59e7.55 (m, 3H), 7.01 (d, J¼8.4 Hz, 2H), 3.87 (s,
3H); 13C NMR (100 MHz, CDCl3):
d¼160.0, 148.7, 142.4, 132.5, 131.0,
d
129.6, 128.2, 121.2, 114.5, 55.4. MS m/z (%): 229 (Mþ, 100), 214 (10),
149 (23).
4.4.35. 4,40-Dimethoxybiphenyl. Mp (ꢁC) 178e180.32 IR ( /cmꢂ1):
n
4.4.26. 4-Chloro-30-nitrobiphenyl. Mp (ꢁC) 90e92.40 IR (
3081, 2861, 1521, 1495, 1351, 1084, 1005, 822, 735; 1H NMR
(400 MHz, CDCl3):
¼8.42 (t, J¼2.0 Hz, 1H), 8.22 (d, J¼8.0 Hz, 1H),
n
/cmꢂ1):
2954, 2912, 1605, 1499, 1257, 1246, 1179, 1038, 1010, 821; 1H NMR
(400 MHz, CDCl3):
¼6.95 (d, J¼8.0 Hz, 4H), 7.47 (d, J¼8.4 Hz, 4H),
d
d
3.84 (s, 6H); 13C NMR (100 MHz, CDCl3):
d
¼158.7, 133.4, 127.7, 114.1,
7.88 (d, J¼8.0 Hz, 1H), 7.63 (t, J¼4.0 Hz, 1H), 7.56 (d, J¼8.4 Hz, 2H),
55.3. MS m/z (%): 214 (Mþ, 100), 199 (MþꢂCH3, 87), 171 (24).
4.4.36. 4-Fluoro-40-methoxybiphenyl. Mp (ꢁC) 90e91,33 92e93. IR
7.47 (d, J¼8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3):
¼148.8, 141.6,
d
137.1, 134.8, 132.8, 129.9, 129.4, 128.4, 122.3, 121.8. MS m/z (%): 233
(Mþ, 64), 152 (100).
(n
/cmꢂ1): 3013, 2966, 1893, 1602, 1495, 1289, 1234, 1035, 825; 1H
NMR (400 MHz, CDCl3):
d
¼7.50e7.44 (m, 4H), 7.09 (t, J¼8.8 Hz, 2H),
4.4.27. 4-Fluoro-30-nitrobiphenyl. Mp (ꢁC) 89e90.41 IR (
n
/cmꢂ1):
6.96 (d, J¼8.8 Hz, 2H), 3.82 (s, 3H); 13C NMR (100 MHz, CDCl3):
3042, 1622, 1552, 1466, 1423, 1152, 880, 693; 1H NMR (400 MHz,
d
¼163.3, 160.9, 159.1, 136.9, 132.8, 128.1 (d, J¼7.6 Hz, 1C), 128.0,
CDCl3):
d
¼8.41 (t, J¼2.0 Hz, 1H), 8.20 (d, J¼8.0 Hz, 1H), 8.87 (d,
115.5 (d, J¼21.4 Hz, 1C), 114.2, 55.3. MS m/z (%): 202 (Mþ, 100), 187
(MþꢂCH3, 57), 159 (66), 133 (47).
J¼8.0 Hz, 1H), 7.63e7.21 (m, 3H), 7.19 (t, J¼4.8 Hz, 2H); 13C NMR
(100 MHz, CDCl3):
128.9 (d, J¼9.4 Hz, 1C), 122.0, 121.8, 116.1 (d, J¼21.3 Hz, 1C). MS m/z
d
¼164.3, 161.9, 148.7, 141.8, 134.8, 132.9, 129.8,
Acknowledgements
(%): 217 (Mþ, 96), 170 (100).
The work was supported by the Natural Science Foundation of
China (Grant 20272047, 20572086), the Gansu Natural Science
Foundation of China (0308RJZA-100) and Key Laboratory of Eco-
Environment-Related Polymer Material (Northwest Normal Uni-
versity), Ministry of the Education of China.
4.4.28. 2-Chloro-40-methylbiphenyl. Oil,22 IR ( /cmꢂ1): 3025, 1922,
n
1514, 1467, 1071, 1034, 817, 754; 1H NMR (400 MHz, CDCl3):
d¼7.45
(d, J¼8.0 Hz, 1H), 7.35e7.23 (m, 7H), 2.41 (s, 3H); 13C NMR
(100 MHz, CDCl3):
d
¼140.5, 137.4, 136.5, 132.5, 131.4, 129.9, 129.3,
128.8, 128.3, 126.8, 21.2. MS m/z (%): 202 (Mþ, 100), 165 (82).
References and notes
4.4.29. 2-Chloro-40-methoxybiphenyl. Oil,21 IR /cmꢂ1): 3060,
(n
2954, 2836, 1611, 1515, 1466, 1248, 1178, 1036, 832, 758; 1H NMR
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d
¼7.47e7.44 (m, 1H), 7.40e7.38 (m, 2H),
7.34e7.26 (m, 3H), 6.97 (d, J¼7.2 Hz, 2H); 13C NMR (100 MHz,
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n
1892, 1602, 1513, 1468, 1228, 1159, 835, 756; 1H NMR (400 MHz,
CDCl3):
d
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¼163.6, 161.1,
d
139.5, 135.4, 132.5, 131.3, 131.2 (d, J¼8.4 Hz, 1C), 130.0, 128.7, 126.9,
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IR (
(400 MHz, CDCl3):
n
/cmꢂ1): 2960, 1605, 1483, 1286, 1255, 1036, 812, 733; 1H NMR
d
¼7.49e7.45 (m, 4H), 7.36 (d, J¼8.4 Hz, 2H), 6.97

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