Carbomylative Suzuki-Miyaura coupling of arylboronic acids with aryl iodides catalyzed by the MCM-41-supported bidentate phosphane palladium(II) complex

Article abstract of DOI:10.1002/ejoc.200801253

The first heterogeneous carbonylative Suzuki-Miyaura cross-coupling reaction of arylboronic acids with aryl iodides under an atmospheric pressure of carbon monoxide has been achieved in anisole at, 80 °C in the presence of a catalytic amount of an MCM-41-supported bidentate phosphane palladium(II) complex (MCM-41-2P-Pd^II), yielding unsymmetrical biaryl ketones in good-to-high yields. This polymeric palladium catalyst exhibited higher activity and selectivity than fPdCl₂(PPh₃)₂] and can be reused at least 10 times without any decrease in activity. Wiley-VCH Verlag GmbH & Co, KGaA.

Full text of DOI:10.1002/ejoc.200801253

FULL PAPER
DOI: 10.1002/ejoc.200801253
Carbonylative Suzuki–Miyaura Coupling of Arylboronic Acids with Aryl
Iodides Catalyzed by the MCM-41-Supported Bidentate Phosphane
Palladium(II) Complex
Mingzhong Cai,*[a] Guomin Zheng,[a] Lingfang Zha,[a] and Jian Peng[a]
Keywords: Carbonylation / Cross coupling / Supported catalysts / Palladium / Ketones
The first heterogeneous carbonylative Suzuki–Miyaura
cross-coupling reaction of arylboronic acids with aryl iodides
under an atmospheric pressure of carbon monoxide has been
achieved in anisole at 80 °C in the presence of a catalytic
amount of an MCM-41-supported bidentate phosphane pal-
cal biaryl ketones in good-to-high yields. This polymeric pal-
ladium catalyst exhibited higher activity and selectivity than
[PdCl2(PPh3)2] and can be reused at least 10 times without
any decrease in activity.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ladium(II) complex (MCM-41-2P-PdII), yielding unsymmetri- Germany, 2009)
Very recently, an N-heterocyclic carbene palladium complex
Introduction
catalyzed carbonylative Suzuki reaction has also been de-
scribed.[9] However, carbonylative Suzuki reactions gen-
erally proceed in the presence of a homogeneous palladium
catalyst such as [PdCl2(PPh3)2], [Pd(OAc)2], and an N-het-
erocyclic carbene palladium complex, which makes the re-
covery of the metal tedious if not impossible and might
result in unacceptable palladium contamination of the
product. The high cost of transition-metal catalysts coupled
with the toxic effects associated with many transition metals
have led to increased interest in immobilizing catalysts onto
a support. This class of supported reagents can facilitate
both the isolation and recycling of the catalysts by simple
filtration, thus providing an environmentally cleaner pro-
cess.[10] So far, polymer-supported palladium catalysts have
successfully been used in, for example, the Heck reaction,[11]
the Suzuki reaction,[12] the Sonogashira reaction,[13] and the
Stille reaction.[14] However, to the best of our knowledge,
there has been no general study of carbonylative Suzuki–
Miyaura coupling reactions catalyzed by a polymer-sup-
ported palladium complex described to date.
Recent developments of the mesoporous material MCM-
41 have provided a possible new candidate for a solid sup-
port for immobilization of homogeneous catalysts.[15]
MCM-41 has a regular pore diameter of around 5 nm and
a specific surface area of Ͼ700 m2 g–1.[16] Its large pore size
allows passage of large molecules such as organic reactants
and metal complexes through the pores to the surface of
the channel.[17] It is generally believed that a heterogeneous
catalyst with a high surface area results in high catalytic
activity. Considering the facts that the MCM-41 support
has an extremely high surface area and the catalytic palla-
dium species is anchored on the inner surface of the meso-
pore of the MCM-41 support, we expect that an MCM-41-
Aryl ketones are important building blocks for a large
number of natural products and pharmaceutical com-
pounds, and many methods for their preparation have been
reported.[1] One general approach is the Friedel–Crafts acyl-
ation of substituted aromatic rings.[2] The crucial disadvan-
tage of traditional Friedel–Crafts acylation reactions is the
use of more than a stoichiometric amount of aluminium
trichloride, which is incompatible with many functional
groups and generates a large amount of waste. Further-
more, the formation of ortho and para isomers with untun-
able regioselectivity results in separation problems and
makes aryl ketones with meta substituents difficult to ac-
cess. The transition-metal-catalyzed three-component cross-
coupling reaction between arylmetal reagents, carbon mon-
oxide, and aryl electrophiles has provided a straightforward
and convenient route to the synthesis of unsymmetrical bi-
aryl ketones. Various arylmetal reagents, including magne-
sium,[3] aluminium,[4] silicon,[5] and tin compounds,[6] have
been reported to undergo carbonylative coupling, but the
application of the protocol to aryl electrophiles with elec-
tron-withdrawing groups is severely limited due to a side-
reaction that gives a direct coupling product without car-
bon monoxide insertion. Miyaura and co-workers reported
the palladium-catalyzed carbonylative cross-coupling reac-
tion of arylboronic acids with aryl halides, providing a new
route to the synthesis of biaryl ketones.[7] Zeni and co-
workers reported the palladium-catalyzed carbonylative
cross-coupling of 2-iodoselenophene and boronic acids.[8]
[a] Department of Chemistry, Jiangxi Normal University,
Nanchang 330022, P. R. China
Fax: +86-791-8120388
E-mail: caimzhong@163.com
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M. Cai, G. Zheng, L. Zha, J. Peng
FULL PAPER
supported palladium catalyst will exhibit high activity and Table 1. Carbonylative coupling of phenylboronic acid with 4-
iodoacetophenone under different conditions.[a]
good reusability. To date, only a few palladium complexes
on a functionalized MCM-41 support have been prepared
and successfully used in organic reactions.[18] Recently, we
reported the synthesis of the MCM-41-supported bidentate
phosphane palladium(0) complex (abbreviated as MCM-
41-2P-Pd0) and found that this complex is a highly active
and recyclable catalyst for the Sonogashira reaction of aryl
halides.[13e] In this paper we wish to report that the carbon-
ylative Suzuki–Miyaura cross-coupling reaction of aryl-
boronic acids with aryl iodides under an atmospheric pres-
sure of carbon monoxide can be easily achieved in the pres-
ence of a catalytic amount of MCM-41-supported bidentate
phosphane palladium(II) complex (MCM-41-2P-PdII) to
yield unsymmetrical biaryl ketones in good-to-high yields.
Entry Solvent
Base
Catalyst amount Temp. [°C],
% Yield[b]
[mol-%]
Time [h]
A
B
1
2
3
4
5
6
anisole K2CO3
anisole K2CO3
anisole K2CO3
dioxane K2CO3
o-xylene K2CO3
toluene K2CO3
2
2
2
2
2
2
2
2
2
2
4
1
60, 24
80, 5
100, 4
80, 5
80, 5
80, 5
80, 24
80, 5
80, 5
80, 9
80, 3
80, 9
0
0
8
85
84
83
80
65
16
83
64
48
84
83
10
10
11
14
0
7
DMF
K2CO3
8
9
10
11
12
anisole Na2CO3
anisole Cs2CO3
anisole K3PO4
anisole K2CO3
anisole K2CO3
9
21
23
8
Results and Discussion
9
The MCM-41-supported bidentate phosphane palla-
dium(II) complex (MCM-41-2P-PdII) was prepared by fol-
lowing our previous procedure.[13e] The phosphane and pal-
ladium contents were 1.12 and 0.51 mmol/g, respectively.
Initially, to determine the optimum conditions, the carbon-
ylative cross-coupling reaction of phenylboronic acid
[a] Reaction conditions: phenylboronic acid (1.1 mmol), 4-iodoace-
tophenone (1.0 mmol), CO (1 atm), base (3 mmol), and solvent
(6 mL). [b] Isolated yields.
(1.1 equiv.) with 4-iodoacetophenone was examined under the base in the presence of a catalytic amount of MCM-41-
an atmospheric pressure of carbon monoxide. The results 2P-PdII under an atmospheric pressure of carbon monoxide
are summarized in Table 1. Of the temperatures evaluated (Scheme 1). The experimental results are summarized in
(60, 80, and 100 °C), 80 °C gave the best result and no reac- Table 2 and show that the carbonylative Suzuki–Miyaura
tion occurred at 60 °C. The carbonylative coupling reaction cross-coupling reaction of phenylboronic acid with a variety
worked well in less polar solvents such as anisole, dioxane, of aryl iodides proceeded smoothly under mild conditions
o-xylene, or toluene, with anisole proving the best choice, to give the corresponding carbonylative coupling products
however, the carbonylative coupling product was obtained 3a–l in good-to-high yields. The presence of a strong elec-
in low yield in polar solvents such as DMF, presumably tron-withdrawing substituent such as NO2 is known to pro-
due to another side-reaction leading to 4-acetylbenzoic acid mote the direct coupling reaction to produce the biaryl. For
(Table 1, entry 7).[19] Bases affected the selectivity of the re- example, the carbonylative coupling reaction of triphenyl-
action. Cs2CO3 and K3PO4, which have been utilized in Su- alane with 4-iodonitrobenzene has been reported to provide
zuki–Miyaura coupling reactions of organoboron com- a 41% yield of 4-nitrobenzophenone and a 55% yield of 4-
pounds,[20] had a strong tendency to produce the direct nitrobiphenyl,[4] and an analogous reaction with tributyltin
coupling product, 4-acetylbiphenyl (21–23%; entries 9 and hydride resulted in only a 9% yield of 4-nitrobenzaldehyde
10). K2CO3 (3 equiv.) suspended in anisole is the most ef- accompanied by an 84% yield of nitrobenzene.[21] This
ficient, yielding 4-acetylbenzophenone in 85% yield, which, polymeric palladium catalyst exhibits higher activity and
however, was still accompanied by 4-acetylbiphenyl (8%; selectivity than [PdCl2(PPh3)2]. For example, the carbon-
entry 2). Increasing the amount of palladium catalyst could ylative coupling reaction of 4-iodonitrobenzene with phen-
shorten the reaction time, but did not increase the yield of ylboronic acid in the presence of 2 mol-% of MCM-41-2P-
4-acetylbenzophenone (entry 11). Low palladium concen- PdII in anisole at 80 °C for 5 h gave an 88% yield of the
trations usually led to a longer reaction time, which is con- carbonylative coupling product 3d along with only a 9%
sistent with our experimental results (entry 12). Taken to- yield of 4-nitrobiphenyl (entry 4). The same reaction in the
gether, a good result was obtained when the carbonylative presence of 3 mol-% of [PdCl2(PPh3)2] in anisole at 80 °C
coupling reaction was carried out with 2 mol-% of MCM- for 5 h gave 3d in 50% yield and 4-nitrobiphenyl in 35%
41-2P-PdII with K2CO3 as the base in anisole at 80 °C (en- yield.[7b] The reactions of the sterically hindered 2-iodo-
try 2).
anisole and 1-iodonaphthalene with phenylboronic acid
To examine the scope for this carbonylative cross-coup- also proceeded to afford the corresponding carbonylative
ling reaction, various arylboronic acids were coupled with coupling products 3e and 3l in good yields, respectively (en-
a variety of aryl iodides in anisole at 80 °C using K2CO3 as tries 5 and 12). The carbonylative coupling of heteroaryl
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Suzuki–Miyaura Coupling of Arylboronic Acids with Aryl Iodides
iodides such as 2-iodothiophene with phenylboronic acid coupling reaction of aryl bromides with arylboronic acids
gave the corresponding heteroaryl ketone 3k in 76% yield in anisole at 80 or 100 °C afforded only traces of carbon-
(entry 11).
ylative coupling products after 24 h. On the other hand, the
carbonylation of 4-bromoiodobenzene selectively occurred
at the C–I bond, that is, no diketones were formed (en-
tries 10, 16, and 21).
To determine whether the catalysis was due to the MCM-
41-2P-PdII complex or to a homogeneous palladium com-
plex that comes off the support during the reaction and
then returns to the support at the end, we performed the
hot filtration test.[22] We focused on the carbonylative coup-
ling reaction of 4-iodonitrobenzene with phenylboronic
acid. We filtered off the MCM-41-2P-PdII complex after a
reaction time of 1 h and allowed the filtrate to react further.
The catalyst filtration was performed at the reaction tem-
perature (80 °C) to avoid possible re-coordination or pre-
cipitation of soluble palladium upon cooling. We found that
no further reaction was observed after this hot filtration.
This result suggests that the palladium catalyst remains on
the support at elevated temperatures during the reaction.
The heterogeneous carbonylative Suzuki–Miyaura cross-
coupling of arylboronic acid with aryl iodide may proceed
through a catalytic cycle analogous to that proposed for
other metal reagents (cycle A in Scheme 2).[3–6] Oxidative
addition of ArI (1) to the MCM-41-2P-Pd0 complex pro-
vides the MCM-41-bound arylpalladium(II) complex (5),
which is followed by migratory insertion of carbon mon-
oxide to give the MCM-41-bound acylpalladium(II) com-
plex (6). Subsequent transmetalation between 6 and aryl-
boronic acid (2) with the aid of K2CO3 and reductive elimi-
nation of biaryl ketone (3) from intermediate 7 regenerates
the MCM-41-2P-Pd0 complex. As 5 is a common interme-
diate for both the carbonylation (cycle A) and the direct
coupling reaction, which gives biaryls (cycle B), large
amounts of biaryls (4) are often formed when the insertion
reaction of carbon monoxide into intermediate 5 is slower
than the transmetalation reaction between 5 and aryl-
boronic acid (2).
Scheme 1. Synthesis of unsymmetrical biaryl ketones.
Table 2. Synthesis of unsymmetrical biaryl ketones.[a]
Entry
Ar
Ar1
Product % Yield[b]
1
2
3
4
5
6
7
8
4-CH3COC6H4
4-CH3OC6H4
4-CH3C6H4
4-O2NC6H4
2-CH3OC6H4
3-CH3C6H4
3-NCC6H4
4-H2NC6H4
4-CH3OCOC6H4 Ph
4-BrC6H4
2-thienyl
1-naphthyl
4-O2NC6H4
4-CH3OC6H4
4-CH3COC6H4
4-BrC6H4
4-CH3OCOC6H4 4-CH3C6H4
Ph
4-CH3OC6H4
4-CH3C6H4
4-BrC6H4
4-CH3OCOC6H4 4-ClC6H4
2-thienyl
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3a
3b
3c
3d
3e
3f
3g
3h
3i
85
86
90
88
67
81
84
86
87
86
76
70
85
83
87
84
86
84
86
84
79
85
80
74
82
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Ph
Ph
Ph
3j
3k
3l
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
3m
3n
3o
3p
3q
3r
3s
3t
3u
3v
3w
3x
3y
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
The MCM-41-2P-PdII catalyst can be easily recovered by
simple filtration. We also investigated the possibility of re-
using the catalyst through the carbonylative coupling reac-
tion of 4-methyliodobenzene with phenylboronic acid. In
general, continuous recycling of resin-supported palladium
catalysts is difficult owing to leaching of the palladium spe-
cies from the polymer supports, which often reduces their
1-naphthyl
3-NCC6H4
[a] The reaction was carried out with arylboronic acid (1.1 mmol),
aryl iodide (1.0 mmol), CO (1 atm), K2CO3 (3 mmol), and palla-
dium catalyst (2 mol-%) in anisole (6 mL) at 80 °C for 5 h. [b] Iso-
lated yields.
The carbonylative Suzuki–Miyaura cross-coupling reac- activity within five recycles. However, when the reaction of
tion of substituted phenylboronic acids such as 4-methyl- 4-methyliodobenzene with phenylboronic acid was per-
phenylboronic acid and 4-chlorophenylboronic acid with a formed even with 2 mol-% of MCM-41-2P-PdII, the catalyst
variety of aryl iodides also proceeded smoothly under the could be recycled 10 times without any loss of activity. The
same conditions to give the corresponding unsymmetrical reaction promoted by the catalyst on its tenth cycle gave 3c
biaryl ketones in good-to-high yields (entries 13–25). The in 88% yield (Table 3, entry 2). The average yield of 3c from
method provides a quite general route to the synthesis of 10 consecutive reactions with the same catalyst was 89%
unsymmetrical biaryl ketones with various functionalities. (entry 3). The palladium content of the catalyst was deter-
These results prompted us to investigate the reaction of aryl mined to be 0.50 mmol/g after 10 consecutive runs, thus,
bromides, but the carbonylative coupling reaction did not only 2% of palladium had been lost from the MCM-41 sup-
occur under the conditions optimized for the iodides. Even port. The high stability and excellent reusability of the cata-
though NaI or KI (3 equiv.) was used as the additive, as lyst result from the chelating action of the bidentate phos-
reported by Miyaura and co-workers,[7b] the carbonylative phane ligand on palladium and the mesoporous structure
Eur. J. Org. Chem. 2009, 1585–1591
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M. Cai, G. Zheng, L. Zha, J. Peng
FULL PAPER
Scheme 2. Catalytic cycle.
of the MCM-41 support. The result is important from a
practical point of view. The high catalytic activity, excellent
reusability, and the easy accessibility of the MCM-41-2P-
PdII catalyst make them a highly attractive supported palla-
dium catalyst for the parallel solution-phase synthesis of
diverse libraries of compounds.
Experimental Section
General: All chemicals were of reagent grade and used as pur-
chased. All solvents were dried and distilled before use. The prod-
ucts were purified by flash chromatography on silica gel. A mixture
of EtOAc and hexane was generally used as the eluent. All carbon-
ylative coupling products were characterized by comparison of
their spectra and physical data with authentic samples. IR spectra
were recorded with a Perkin–Elmer 683 instrument. 1H and 13C
NMR spectra were recorded with a Bruker AC-P400 (400 and
100 MHz, respectively) spectrometer in CDCl3 as solvent. TMS
was used as the internal standard. Melting points are uncorrected.
Microanalyses were measured by using a Yanaco MT-3 CHN mi-
croelemental analyzer.
Table 3. Carbonylative Suzuki–Miyaura coupling reaction of 4-
methyliodobenzene with phenylboronic acid catalyzed by recycled
catalyst.
General Procedure for the Carbonylative Suzuki–Miyaura Cross-
Coupling Reaction: A 50 mL round-bottomed flask equipped with
a gas inlet tube, a reflux condenser, and a magnetic stirring bar was
charged with MCM-41-2P-PdII (39 mg, 0.02 mmol Pd), aryl iodide
(1.0 mmol), arylboronic acid (1.1 mmol), and K2CO3 (3 mmol).
The flask was flushed with carbon monoxide and anisole (6 mL)
was then added. After stirring at 80 °C for 5 h under CO (1 atm),
the reaction mixture was cooled to room temperature and diluted
with diethyl ether (50 mL). The palladium catalyst was separated
from the mixture by filtration, washed with distilled water
(3ϫ10 mL), ethanol (2ϫ10 mL), and ether (2ϫ10 mL), and re-
used in the next run. The ethereal solution was washed with water
(3ϫ20 mL) and dried with anhydrous magnesium sulfate and con-
centrated under reduced pressure. The residue was purified by flash
column chromatography on silica gel (hexane/ethyl acetate, 10:1).
Entry Catalyst cycle
% Yield
(isolated product)
TON
1
2
3
1st
10th
90
88
45
44
1st to 10th consecutive av. 89
total of 445
4-Acetylbenzophenone (3a): Yield 0.191 g, 85%. White solid, m.p.
83–84 °C (ref.[23] 83–84 °C). 1H NMR (400 MHz, CDCl3): δ =
8.07–8.05 (m, 2 H), 7.88–7.86 (m, 2 H), 7.82–7.80 (m, 2 H), 7.65–
7.49 (m, 3 H), 2.68 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 197.57, 195.98, 141.31, 139.54, 136.89, 133.03, 130.12, 130.06,
Conclusions
We have described the first heterogeneous carbonylative
Suzuki–Miyaura cross-coupling reaction catalyzed by an
MCM-41-supported bidentate phosphane palladium(II)
complex. This polymeric palladium catalyst exhibits higher
activity and selectivity than [PdCl2(PPh3)2] and can be re-
used 10 times without any decrease in activity. The carbon-
ylative Suzuki–Miyaura coupling reaction of aryl iodides
with arylboronic acids catalyzed by the MCM-41-2P-PdII
complex under an atmospheric pressure of carbon mon-
oxide provides a better and practical procedure for the syn-
thesis of unsymmetrical biaryl ketones.
128.50, 128.18, 26.94 ppm. IR (KBr): ν = 1693, 1661, 1579, 931,
˜
699 cm–1. C15H12O2 (224.26): calcd. C 80.34, H 5.39; found C
80.13, H 5.45.
4-Methoxybenzophenone (3b): Yield 0.182 g, 86%. White solid, m.p.
59–60 °C (ref.[24] 61–62 °C). 1H NMR (400 MHz, CDCl3): δ =
7.85–7.82 (m, 2 H), 7.76–7.74 (m, 2 H), 7.58–7.45 (m, 3 H), 6.98–
6.95 (m, 2 H), 3.88 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 195.64, 163.24, 138.27, 132.60, 131.94, 130.13, 129.76, 128.21,
113.57, 55.52 ppm. IR (KBr): ν = 1651, 1599, 1508, 1172, 1029,
˜
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Suzuki–Miyaura Coupling of Arylboronic Acids with Aryl Iodides
701 cm–1. C14H12O2 (212.25): calcd. C 79.22, H 5.70; found C
78.95, H 5.49.
7.78–7.76 (m, 2 H), 7.69–7.67 (m, 2 H), 7.64–7.59 (m, 3 H), 7.49
(t, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.67,
137.17, 136.31, 132.71, 131.63, 131.59, 129.96, 128.43, 127.54 ppm.
4-Methylbenzophenone (3c): Yield 0.176 g, 90%. White solid, m.p.
56–57 °C (ref.[24] 57–58 °C). 1H NMR (400 MHz, CDCl3): δ =
7.79–7.77 (m, 2 H), 7.72 (d, J = 8.0 Hz, 2 H), 7.58–7.54 (m, 1 H),
7.48–7.44 (m, 2 H), 7.28–7.25 (m, 2 H), 2.43 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 196.52, 143.26, 137.96, 134.89,
IR (KBr): ν = 1650, 1585, 1285, 725, 696 cm–1. C H BrO (261.22):
˜
13
9
calcd. C 59.77, H 3.47; found C 59.49, H 3.28.
2-Benzoylthiophene (3k): Yield 0.143 g, 76%. White solid, m.p. 54–
55 °C (ref.[29] 56–57 °C). 1H NMR (400 MHz, CDCl3): δ = 7.89–
7.85 (m, 2 H), 7.72–7.71 (m, 1 H), 7.64–7.63 (m, 1 H), 7.61–7.56
(m, 1 H), 7.51–7.47 (m, 2 H), 7.18–7.14 (m, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 188.28, 143.63, 138.14, 134.93, 134.29,
132.19, 130.33, 129.95, 129.00, 128.23, 21.68 ppm. IR (KBr): ν =
˜
1657, 1606, 1578, 1277, 700 cm–1. C14H12O (196.25): calcd. C 85.68,
H 6.16; found C 85.43, H 5.89.
132.31, 129.19, 128.45, 128.03 ppm. IR (KBr): ν = 1634, 1598,
˜
4-Nitrobenzophenone (3d): Yield 0.201 g, 88%. Yellow solid, m.p.
136–137 °C (ref.[24] 138–139 °C). 1H NMR (400 MHz, CDCl3): δ =
8.35 (d, J = 8.8 Hz, 2 H), 7.95 (d, J = 8.4 Hz, 2 H), 7.82–7.80 (m,
2 H), 7.66–7.51 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 194.84, 149.82, 142.88, 136.27, 133.51, 130.73, 130.12, 128.71,
1577, 1514, 1286, 842, 716 cm–1. C11H8OS (188.25): calcd. C 70.18,
H 4.28; found C 69.94, H 4.02.
1-Benzoylnaphthalene (3l):[29] Yield 0.162 g, 70%. Oil. 1H NMR
(400 MHz, CDCl3): δ = 8.10–8.08 (m, 1 H), 7.98 (d, J = 8.4 Hz, 1
H), 7.92–7.84 (m, 3 H), 7.59–7.42 (m, 7 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 198.06, 138.34, 136.37, 133.75, 133.28,
131.31, 130.99, 130.45, 128.49, 128.45, 127.82, 127.30, 126.50,
123.57 ppm. IR (KBr): ν = 1652, 1595, 1515, 1358, 707 cm–1.
˜
C13H9NO3 (227.22): calcd. C 68.72, H 3.99, N 6.16; found C 68.50,
H 3.74, N 5.89.
2-Methoxybenzophenone (3e):[25] Yield 0.142 g, 67%. Oil. 1H NMR
(400 MHz, CDCl3): δ = 7.82–7.80 (m, 2 H), 7.56–7.52 (m, 1 H),
7.49–7.40 (m, 3 H), 7.37–7.35 (m, 1 H), 7.06–6.98 (m, 2 H), 3.71
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 196.50, 157.36,
137.81, 132.95, 131.91, 129.84, 129.59, 128.85, 128.24, 120.50,
125.72, 124.38 ppm. IR (neat): ν = 1659, 1596, 1578, 1282, 1249,
˜
775, 697 cm–1. C17H12O (232.28): calcd. C 87.91, H 5.21; found C
87.64, H 5.29.
4-Methyl-4Ј-nitrobenzophenone (3m): Yield 0.205 g, 85%. Yellow
solid, m.p. 120–122 °C (ref.[30] 120–121 °C). 1H NMR (400 MHz,
CDCl3): δ = 8.34–8.32 (m, 2 H), 7.93–7.90 (m, 2 H), 7.71 (d, J =
8.4 Hz, 2 H), 7.32 (d, J = 8.0 Hz, 2 H), 2.47 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 194.53, 149.67, 144.60, 143.33,
111.47, 55.61 ppm. IR (neat): ν = 1667, 1599, 1581, 1244, 1023,
˜
702 cm–1. C14H12O2 (212.25): calcd. C 79.22, H 5.70; found C
79.35, H 5.88.
3-Methylbenzophenone (3f):[26] Yield 0.159 g, 81%. Oil. 1H NMR
(400 MHz, CDCl3): δ = 7.81–7.79 (m, 2 H), 7.63 (s, 1 H), 7.60–
7.56 (m, 2 H), 7.47 (t, J = 7.6 Hz, 2 H), 7.41–7.33 (m, 2 H), 2.42
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 196.96, 138.14,
137.74, 137.61, 133.19, 132.33, 130.45, 130.03, 128.23, 128.08,
133.63, 130.57, 130.34, 129.40, 123.50, 21.77 ppm. IR (KBr): ν =
˜
1652, 1600, 1520, 1353, 1315, 732 cm–1. C14H11NO3 (241.24): calcd.
C 69.70, H 4.60, N 5.80; found C 69.42, H 4.37, N 5.54.
4-Methoxy-4Ј-methylbenzophenone (3n): Yield 0.188 g, 83%. White
solid, m.p. 88–89 °C (ref.[29] 85–87 °C). 1H NMR (400 MHz,
CDCl3): δ = 7.83–7.81 (m, 2 H), 7.69 (d, J = 8.0 Hz, 2 H), 7.28 (d,
J = 8.4 Hz, 2 H), 6.98–6.96 (m, 2 H), 3.90 (s, 3 H), 2.45 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.39, 163.04, 142.63,
135.51, 132.45, 130.49, 130.02, 128.89, 113.49, 55.50, 21.64 ppm.
127.36, 21.36 ppm. IR (neat): ν = 1660, 1598, 1281, 720 cm–1.
˜
C14H12O (196.25): calcd. C 85.68, H 6.16; found C 85.50, H 6.32.
3-Cyanobenzophenone (3g): Yield 0.174 g, 84%. White solid, m.p.
91–92 °C (ref.[27] 90–91 °C). 1H NMR (400 MHz, CDCl3): δ = 8.07
(s, 1 H), 8.06–8.04 (m, 1 H), 7.89–7.87 (m, 1 H), 7.79–7.77 (m, 2
H), 7.67–7.62 (m, 2 H), 7.53 (t, J = 7.8 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 194.44, 138.60, 136.31, 135.38, 133.88,
133.48, 133.32, 130.02, 129.43, 128.70, 117.98, 112.83 ppm. IR
IR (KBr): ν = 1646, 1598, 1505, 1262, 1170, 849, 761 cm–1.
˜
C15H14O2 (226.28): calcd. C 79.62, H 6.24; found C 79.39, H 6.28.
4-Acetyl-4Ј-methylbenzophenone (3o): Yield 0.207 g, 87%. White
solid, m.p. 109–111 °C (ref.[31] 111–112 °C). 1H NMR (400 MHz,
CDCl3): δ = 8.05 (d, J = 8.4 Hz, 2 H), 7.84 (d, J = 8.4 Hz, 2 H),
7.72 (d, J = 8.0 Hz, 2 H), 7.30 (d, J = 8.0 Hz, 2 H), 2.67 (s, 3 H),
2.45 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 197.59,
195.70, 143.98, 141.75, 139.37, 134.23, 130.34, 129.92, 129.19,
(KBr): ν = 3076, 2232, 1663, 1597, 1280, 724 cm–1. C H NO
˜
14
9
(207.23): calcd. C 81.14, H 4.38, N 6.76; found C 80.87, H 4.21, N
6.54.
4-Aminobenzophenone (3h): Yield 0.169 g, 86%. White solid, m.p.
120–121 °C (ref.[24] 121–123 °C). 1H NMR (400 MHz, CDCl3): δ =
7.74–7.71 (m, 4 H), 7.56–7.43 (m, 3 H), 6.68 (d, J = 8.8 Hz, 2 H),
4.17 (br., 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.36,
150.91, 138.86, 132.97, 131.43, 129.54, 128.08, 127.47, 113.65 ppm.
128.13, 26.91, 21.73 ppm. IR (KBr): ν = 1689, 1651, 1604, 1286,
˜
858, 757 cm–1. C16H14O2 (238.29): calcd. C 80.65, H 5.92; found C
80.38, H 5.71.
IR (KBr): ν = 3340, 3226, 1640, 1629, 1591, 1275, 687 cm–1.
˜
4-Bromo-4Ј-methylbenzophenone (3p): Yield 0.231 g, 84%. White
solid, m.p. 139–140 °C (ref.[29] 123–125 °C). 1H NMR (400 MHz,
CDCl3): δ = 7.70–7.61 (m, 6 H), 7.29 (d, J = 8.0 Hz, 2 H), 2.45 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.36, 143.57, 136.69,
134.49, 131.54, 131.46, 130.18, 129.11, 127.18, 21.67 ppm. IR
C13H11NO (197.23): calcd. C 79.17, H 5.62, N 7.10; found C 78.95,
H 5.44, N 6.92.
4-Methoxycarbonylbenzophenone (3i): Yield 0.209 g, 87%. White
solid, m.p. 108–109 °C (ref.[28] 106 °C). 1H NMR (400 MHz,
CDCl3): δ = 8.14 (d, J = 8.4 Hz, 2 H), 7.83 (d, J = 8.4 Hz, 2 H),
7.80–7.78 (m, 2 H), 7.62–7.58 (m, 1 H), 7.49 (t, J = 7.6 Hz, 2 H),
3.95 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.89,
166.21, 141.24, 136.88, 133.16, 132.94, 130.07, 129.75, 129.47,
(KBr): ν = 1645, 1605, 1586, 1288, 748 cm–1. C H BrO (275.24):
˜
14 11
calcd. C 61.09, H 4.03; found C 60.82, H 3.90.
4-Methoxycarbonyl-4Ј-methylbenzophenone (3q): Yield 0.218 g,
1
86%. White solid, m.p. 125–126 °C (ref.[32] 127–128 °C). H NMR
128.45, 52.43 ppm. IR (KBr): ν = 1717, 1647, 1596, 1276, 1107,
˜
(400 MHz, CDCl3): δ = 8.16–8.13 (m, 2 H), 7.83–7.81 (m, 2 H),
7.72 (d, J = 8.4 Hz, 2 H), 7.30 (d, J = 8.0 Hz, 2 H), 3.97 (s, 3 H),
2.46 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.83,
166.40, 143.94, 141.73, 134.26, 132.99, 130.36, 129.68, 129.47,
713 cm–1. C15H12O3 (240.26): calcd. C 74.99, H 5.03; found C
74.76, H 4.87.
4-Bromobenzophenone (3j): Yield 0.224 g, 86%. White solid, m.p.
78–79 °C (ref.[29] 77–79 °C). 1H NMR (400 MHz, CDCl3): δ =
129.18, 52.49, 21.74 ppm. IR (KBr): ν = 1717, 1646, 1606, 1276,
˜
Eur. J. Org. Chem. 2009, 1585–1591
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1589

M. Cai, G. Zheng, L. Zha, J. Peng
FULL PAPER
1110, 736 cm–1. C16H14O3 (254.29): calcd. C 75.57, H 5.55; found
193.15, 139.92, 138.29, 135.54, 134.60, 133.68, 133.28, 131.37,
C 75.32, H 5.40.
129.52, 129.08, 117.79, 113.05 ppm. IR (KBr): ν = 2235, 1659,
˜
1587, 1297, 1091, 850, 752 cm–1. C14H8ClNO (241.72): calcd. C
69.57, H 3.34, N 5.79; found C 69.33, H 3.15, N 5.57.
4-Chlorobenzophenone (3r): Yield 0.182 g, 84%. White solid, m.p.
73–74 °C (ref.[29] 74–76 °C). 1H NMR (400 MHz, CDCl3): δ =
7.78–7.74 (m, 4 H), 7.62–7.58 (m, 1 H), 7.50–7.45 (m, 4 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 195.46, 138.90, 137.26, 135.89,
Acknowledgments
132.64, 131.46, 129.93, 128.64, 128.41 ppm. IR (KBr): ν = 1651,
˜
1597, 1586, 1285, 728, 696 cm–1. C13H9ClO (216.71): calcd. C
72.05, H 4.19; found C 71.87, H 4.03.
We thank the National Natural Science Foundation of China (Pro-
ject No. 20462002) and the Natural Science Foundation of Jiangxi
Province in China (2007GZW0172) for financial support.
4-Chloro-4Ј-methoxybenzophenone (3s): Yield 0.212 g, 86%. White
solid, m.p. 125–126 °C (ref.[29] 116–118 °C). 1H NMR (400 MHz,
CDCl3): δ = 7.81–7.78 (m, 2 H), 7.71–7.69 (m, 2 H), 7.46–7.43 (m,
2 H), 6.98–6.95 (m, 2 H), 3.89 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 194.23, 163.40, 138.26, 136.58, 132.44, 131.15, 129.81,
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128.52, 113.69, 55.52 ppm. IR (KBr): ν = 1640, 1605, 1508, 1256,
˜
1030, 853, 760 cm–1. C14H11ClO2 (246.74): calcd. C 68.15, H 4.49;
found C 67.87, H 4.58.
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4-Chloro-4Ј-methylbenzophenone (3t): Yield 0.194 g, 84%. White
solid, m.p. 127–129 °C (ref.[29] 123–125 °C). 1H NMR (400 MHz,
CDCl3): δ = 7.75 (d, J = 8.4 Hz, 2 H), 7.71 (d, J = 8.0 Hz, 2 H),
7.47 (d, J = 8.4 Hz, 2 H), 7.31 (d, J = 8.0 Hz, 2 H), 2.46 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 195.22, 143.53, 138.60,
136.25, 134.56, 131.34, 130.17, 129.10, 128.56, 21.66 ppm. IR
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˜
14 11
1217–1219.
(230.74): calcd. C 72.88, H 4.81; found C 72.63, H 4.70.
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lid, m.p. 146–148 °C (ref.[33] 147–148 °C). 1H NMR (400 MHz,
CDCl3): δ = 7.73 (d, J = 8.4 Hz, 2 H), 7.64 (s, 4 H), 7.47 (d, J =
8.8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 194.38,
139.21, 135.97, 135.46, 131.76, 131.41, 131.32, 128.79, 127.78 ppm.
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˜
13
8
(295.71): calcd. C 52.80, H 2.73; found C 52.54, H 2.61.
4-Chloro-4Ј-methoxycarbonylbenzophenone (3v):[34] Yield 0.233 g,
85%. White solid, m.p. 168–169 °C). 1H NMR (400 MHz, CDCl3):
δ = 8.15 (d, J = 8.4 Hz, 2 H), 7.81 (d, J = 8.4 Hz, 2 H), 7.75 (d, J
= 8.4 Hz, 2 H), 7.48 (d, J = 8.4 Hz, 2 H), 3.97 (s, 3 H) ppm. 13C
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135.24, 133.45, 131.47, 129.64, 129.61, 128.84, 52.49 ppm. IR
(KBr): ν = 1732, 1651, 1588, 1283, 1111, 738 cm–1. C H ClO
˜
15 11
3
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(274.75): calcd. C 65.57, H 4.04; found C 65.72, H 4.28.
2-(4-Chlorobenzoyl)thiophene (3w): Yield 0.178 g, 80%. White solid,
1
m.p. 99–100 °C (ref.[29] 93–95 °C). H NMR (400 MHz, CDCl3): δ
= 7.83–7.80 (m, 2 H), 7.75–7.74 (m, 1 H), 7.63–7.62 (m, 1 H),
7.49–7.46 (m, 2 H), 7.18–7.16 (m, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 186.97, 143.20, 138.71, 136.38, 134.85, 134.62, 130.62,
128.79, 128.13 ppm. IR (KBr): ν = 1632, 1588, 1414, 1304, 853,
˜
722 cm–1. C11H7ClOS (222.74): calcd. C 59.32, H 3.17; found C
59.53, H 3.39.
1-(4-Chlorobenzoyl)naphthalene (3x):[29] Yield 0.197 g, 74%. Oil. 1H
NMR (400 MHz, CDCl3): δ = 8.12–7.91 (m, 3 H), 7.82–7.80 (m, 2
H), 7.57–7.41 (m, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
196.62, 139.74, 136.71, 135.87, 133.79, 131.77, 131.58, 130.90,
128.84, 128.53, 127.82, 127.45, 126.63, 125.60, 124.39 ppm. IR
(neat): ν = 1661, 1586, 1508, 1284, 1251, 800, 778 cm–1. C H ClO
˜
17 11
(266.77): calcd. C 76.54, H 4.16; found C 76.31, H 3.88.
4-Chloro-3Ј-cyanobenzophenone (3y): Yield 0.198 g, 82%. White so-
lid, m.p. 139–140 °C (ref.[35] 144–147 °C). 1H NMR (400 MHz,
CDCl3): δ = 8.05 (s, 1 H), 8.00 (d, J = 7.6 Hz, 1 H), 7.88 (d, J =
7.6 Hz, 1 H), 7.74 (d, J = 8.0 Hz, 2 H), 7.67–7.63 (m, 1 H), 7.51
(d, J = 8.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
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Eur. J. Org. Chem. 2009, 1585–1591

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Received: December 17, 2008
Published Online: February 18, 2009
Eur. J. Org. Chem. 2009, 1585–1591
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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