Catalysis by L-lysine: A green method for the condensation of aromatic aldehydes with acidic methylene compounds in water at room temperature

Article abstract of DOI:10.1002/cjoc.201090373

The condensation of aromatic aldehydes with acidic methylene compounds such as ethyl benzoylacetate, 2,4-pentanedione and dimedone proceeded efficiently in pure water in the presence of L-lysine at room temperature. Interestingly, there are two different

Full text of DOI:10.1002/cjoc.201090373

FULL PAPER
Catalysis by L-Lysine: A Green Method for the Condensation of
Aromatic Aldehydes with Acidic Methylene Compounds in
Water at Room Temperature
Zhang, Yan(张岩)
Sun, Cuizhi(孙翠枝)
Liang, Jun(梁军)
Shang, Zhicai*(商志才)
Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, China
The condensation of aromatic aldehydes with acidic methylene compounds such as ethyl benzoylacetate,
2,4-pentanedione and dimedone proceeded efficiently in pure water in the presence of L-lysine at room temperature.
Interestingly, there are two different reaction mechanisms taking place under the same green catalyst system. This
provides a green and mild synthetic method for the preparation of these two classes of compounds.
Keywords condensation, aldehyde, L-lysine, xanthenedione, green chemistry
Introduction
pounds. Knoevenagel condensation is one of the impor-
tant reactions of organic chemistry and its synthetic util-
ity has special place of significance in organic synthesis,
for it is largely employed to form C—C bonds for the
synthesis of unsaturated compounds. For example,
α,β-enones are synthetically important organic mole-
cules, which are generally used as substrates for Diels-
Alder reactions, Michael addition and Morita-Baylis-
Hillman reactions.3 Knoevenagel condensations are usu-
ally carried out in the presence of base,4 Lewis acid,5
surfactants,6 zeolites,7 grinding,8 metal ions9 and alkali
metal modified NbMCM-41 have also been employed to
catalyze this reaction.10 However, these methods suffer
from many limitations such as harsh reaction conditions,
the use of harmful organic solvents, requirement of high
temperatures, and in some reactions the catalysts can not
be reused. Similarly, the use of ionic liquids11 paves a
new path for the condensation. Yet, the application of
ionic liquids in the industrial syntheses of fine chemicals
is still problematic because of the relatively high cost of
these solvents. Xanthenediones, a group of synthetically
and biologically important compounds, constitute a
structural unit in a number of natural products and have
been used as versatile synthons due to the inherent reac-
tivity of the inbuilt pyran ring. Obviously, xan-
thenediones can be simply obtained by dehydration cy-
clization from their ring-opening derivatives 4. Recently,
several reports have been put forward in which xan-
thenedione derivatives were obtained through condensa-
tion of aldehyde and 5,5-dimethyl-1,3-cyclohexanedione
(dimedone) under various conditions.12 Similarly, taking
their limitations into account, to develope novel and
practical methods for the preparation of xanthenedione
and its derivatives is still necessary. To the best of our
knowledge, there is no report of the application of lysine
In recent years, there has been an increased demand
for “clean” and environmentally friendly reactions in
chemistry, which is essential to the sustainable devel-
opment of our society. Especially in organic chemistry,
synthesis is mainly carried out in the presence of cata-
lyst in the solution phase. Nowadays catalysis has to
face new challenges, including the ability to meet sus-
tainability criteria, and once it is translated into chemical
words, it means the implementation of the twelve green
chemistry principles.1 Organo-catalysis became a new
research area in synthetic chemistry several years ago,
which is one of the most important contents for green
chemistry. Driven by environmental concerns, there are
great interest and need for cheap and readily available,
recyclable and reusable nonmetallic small-molecule
catalysts that promote reactions to expand the scope of
organocatalysis, which obviously is an environmentally
benign approach to fine chemical synthesis, especially
large scale reactions. Organic solvents are still the main
choice in modern organic synthesis. But these solvents
are often problematic because of their toxicity, flamma-
bility, or environmental hazards. Fortunately, in recent
years, there has been increased recognition that organic
reactions carried out in aqueous media may offer ad-
vantages over those occurring in organic solvents.2 So
switching from organic solvents to water as reaction
medium is a challenging and attractive task for synthetic
chemists. We concentrate our attention on using water
instead of organic solvent in chemical processes.
In our recent studies, we have found that the basic
amino acids L-lysine in pure water is an efficient and
reusable green catalyst system for condensations of
aromatic aldehydes with many acidic methylene com-
*
E-mail: shangzc@zju.edu.cn; Fax: 0086-0571-87951895
Received March 20, 2010; revised May 14, 2010; accepted August 11, 2010.
Chin. J. Chem. 2010, 28, 2255— 2259
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Zhang et al.
FULL PAPER
for these condensations. In this paper, we will report
that L-lysine dissolved in water is an efficient catalyst
system for these two types of condensation reaction as
shown in Scheme 1.
lacetate is more likely to carry out Knoevenagel reaction
in water than 2,4-pentanedione in the presence of
L-lysine. The electron-deficient aldehydes proceeded
much better and faster than the electron-rich ones.
On the basis of these observations, we then extended
the reactions of aldehydes to other dicarbonyl compound.
Dimedone (2c) was investigated. Surprisingly, contrary to
our expectation, the initial Knoevenagel products 5 are not
formed, only 4 is obtained in excellent yield (Table 2),
Scheme 1 The condensation of aromatic aldehydes with acidic
methylene compounds
which is in contrast to other reported examples.13,14
That’s to say, there are two very different reaction
mechanisms taking place in the same reaction condi-
tions.
Table 2 The results on the reaction of aromatic aldehydes 1
with dimedone (2c) in water at room temperature catalyzed by
L-lysine
Entry
11
Ar
Time/h
Product
4a
Yielda/%
4-NO2C6H4
4-CNC6H4
4-BrC6H4
3-BrC6H4
4-ClC6H4
C6H5
5
5
6
6
6
7
9
9
95
12
4b
92
13
4c
91
14
4d
92
15
4e
90
16
4f
89
17
4-CH3C6H4
4-CH3OC6H4
4g
90
18
4h
88
a Isolated yields after column chromatography.
Results and discussion
This result prompted us to reflect on the different
mechanisms of the two type condensations (Scheme 2
and Scheme 3), especially the latter. Some people think
that the initial Knoevenagel product is an intermediate,
then the Michael addition carries out to form 4.6,12c We
also think so, but it is hard to explain why 3 does not
occur Michael addition even if 2a—2b are excessive.
As we know, L-lysine, a cheap basic amino acid, can
easily dissolve in water. But it can hardly dissolve in
organic solvents, such as ether, ethyl acetate and even
acetone. Therefore, it is easy to get the product from the
reaction system by extraction. We first applied this
green catalyst system in the reaction of aromatic alde-
hydes 1 with acidic methylene compounds 2a—2b as
shown in Table 1. The results show that ethyl benzoy-
Conclusions
Table 1 The results for the Knoevenagel condensation between
aromatic aldehydes 1 and dicarbonyl compounds 2a— 2b in water
Dicarbonyl
In conclusion, we have developed a clean, inexpen-
sive, efficient and reusable methodology to carry out
two types of condensations between aromatic aldehydes
and dicarbonyl compounds in water. The catalyst of
L-lysine was found to be a mild and effective catalyst.
Efforts are underway to elucidate the mechanistic details
of the condensation and disclose its scope and limitations.
Entry
Ar
Time/h Product Yielda/%
compound
1
2
3
4
5
6
7
8
9
2-NO2C6H4
3-NO2C6H4
4-NO2C6H4
4-CNC6H4
4-CH3OC6H4
3-BrC6H4
2a
2a
2a
2a
2a
2b
2b
2b
2b
2b
28
30
30
30
34
50
48
50
54
54
3a
3b
3c
3d
3e
3f
82 (11)b
82
80
79
Experimental
68
In a typical experimental procedure, a mixture of an
aldehyde 1 (1 mmol), acidic methylene compound 2a—
2b (1 mmol) or 2c (2 mmol), and L-lysine (20 mol%) in
4 mL of water was stirred in a 10 mL, round-bottomed
flask at ambient temperature. The reaction was followed
and monitored by TLC. When the reaction was com-
pleted, ethyl acetate or dichloromethane (5 mL×3) was
added into the flask to extract the product. Then the re-
action mixture was partitioned between aqueous and
61
4-NO2C6H4
4-ClC6H4
3g
3h
3i
64
60
4-CH3C6H4
58
10 4-CH3OC6H4
3j
62
a
b
Isolated yields after column chromatography; reactions per-
formed with no addition of L-lysine.
2256
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© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 2255— 2259

Catalysis by L-Lysine: A Green Method for the Condensation of Aromatic Aldehydes
Scheme 2 Mechanism of the Knoevenagel condensation reac-
tion
The physical and spectra data of the compounds are
as follows.
The process of reactions was monitored by TLC on
1
silica. H NMR and 13C NMR spectra were recorded
with TMS as internal standard using a Bruker AMX-500
MHz spectrometer at 500 and 125 MHz, respectively.
IR spectra were measured with a Nicolet Nexus FTIR
670 spectrophotometer. Low-resolution MS analyses
were measured on a Bruke Esquire 3000 spectrometer
using ESI (electrospray ionization) technique.
Ethyl 2-benzoyl-3-(2-nitrophenyl)acrylate (3a)
White solid; m.p. 106—108 ℃; Rf＝0.43 V(EtOAc)∶
1
V(petroleum)＝1∶5; H NMR (CDCl3, 500 MHz) δ:
8.32 (s, 1H), 8.04 (d, J＝7.93 Hz, 1H), 7.83 (t, J＝7.34
Hz, 2H), 7.45—7.47 (m, 2H), 7.40 (t, J＝7.51 Hz, 2H),
7.33 (t, J＝7.72 Hz, 2H), 4.28 (q, J＝7.11 Hz, 2H), 1.24
(t, J＝7.11 Hz, 3H); 13C NMR (CDCl3, 125 MHz) δ:
193.9, 164.3, 147.4, 140.0, 136.5, 134.3, 134.1, 134.0,
131.6, 130.3, 130.1, 129.2, 128.9, 125.1, 62.0, 14.2; IR
(KBr) ν: 2985, 1716, 1668, 1601, 1560, 1525, 1344,
Scheme 3 Proposed reaction steps that take place in the con-
densation between the aromatic aldehydes and dimedone
－1
1253, 123＋3, 1201, 801, 727 cm ; MS (ESI) m/z: 325.9
([M＋H]) .
Ethyl 2-benzoyl-3-(3-nitrophenyl)acrylate (3b)
White solid; m.p. 94—96 ℃; Rf＝0.40 V(EtOAc)∶
1
V(petroleum)＝1∶5; H NMR (CDCl3, 500 MHz) δ:
8.22 (s, 1H), 8.11 (q, J＝6.7 Hz, 1H), 7.98 (s, 1H), 7.94
(d, J＝7.3 Hz, 2H), 7.66 (d, J＝7.8 Hz, 1H), 7.57 (d, J＝
7.4 Hz, 1H), 7.41—7.47 (m, 3H), 4.26 (q, J＝7.2 Hz,
2H), 1.20 (t, J＝7.1 Hz, 3H); IR (KBr) ν: 3084, 1712,
1663, 1619, －1595, 1528, 1450, 1353, 1251, 12＋05, 1096,
1
809, 737 cm ; MS (ESI) m/z: 325.9 ([M＋H]) .
Ethyl 2-benzoyl-3-(4-nitrophenyl)acrylate (3c)
White solid; m.p. 100—102 ℃; Rf＝0.36 V(EtOAc)∶
1
organic phase. The organic layer was separated and
concentrated, then the residue was purified by column
chromatography eluting with petroleum/ethyl acetate or
ethyl acetate/dichloromethane to give the condensation
product. We also investigated the reusability of this
catalyst system. After the reaction was completed, the
product was extracted out by filling in ethyl acetate or
dichloromethane. Amazingly, the aqueous solution
could be reused without any loss of its activity even af-
ter five runs (Table 3).
V(petroleum)＝1∶6; H NMR (CDCl3, 500 MHz) δ:
8.09 (d, J＝8.8 Hz, 2H), 7.98 (s, 1H), 7.92 (q, J＝8.0 Hz,
2H), 7.58 (d, J＝7.4 Hz, 1H), 7.52 (t, J＝1.7 Hz, 2H),
7.45 (t, J＝7.8 Hz, 2H), 4.26 (q, J＝7.1 Hz, 2H), 1.19 (t,
J＝7.2 Hz, 3H); 13C NMR (CDCl3, 125 MHz) δ: 194.0,
164.4, 148.4, 139.6, 139.3, 135.9, 135.7, 134.6, 130.8,
129.3, 128.9, 124.1, 62.3, 14.2; IR (KBr) ν: 1723, 1673,
1596, 1519, 1449, 1346, 1250, 1231＋, 1197, 851, 692
－1
cm ; MS (ESI) m/z: 348.2 ([M＋Na]) .
Ethyl 2-benzoyl-3-(4-cyanophenyl)acrylate (3d)
Pale-yellow oil; Rf＝0.26 V(EtOAc)∶V(petroleum)＝
1∶4; 1H NMR (CDCl3, 500 MHz) δ: 7.91 (q, J＝6.3 Hz,
3H), 7.59 (t, J＝7.5 Hz, 1H), 7.52 (d, J＝8.4 Hz, 2H),
7.44—7.47 (m, 4H), 4.24 (q, J＝7.1 Hz, 2H), 1.18 (t, J＝
7.1 Hz, 3H); 13C NMR (CDCl3, 125 MHz) δ: 194.7,
164.5, 140.1, 137.4, 135.9, 135.0, 134.5, 133.1, 132.6,
130.4, 130.1, 129.2, 118.2, 62.2, 14.1; IR (KBr) ν: 2985,
2230, 1721, 1673, 1627, －1596, 1581, 1501, 1449, 1368,
Table 3 Recycling experiments with L-lysinea
1
125＋2, 1016, 832, 689 cm ; MS (ESI) m/z: 305.9 ([M＋
H]) .
Run
1
2
3
4
5
Yieldb/%
92
90
91
89
89
Ethyl 2-benzoyl-3-(4-methoxyphenyl)acrylate (3e)
Yellow oil; Rf＝0.51 V(EtOAc)∶V(petroleum)＝1∶4;
1H NMR (CDCl3, 500 MHz) δ: 7.96 (t, J＝7.3 Hz, 2H),
7.90 (s, 1H), 7.55 (s, 1H), 7.43 (t, J＝7.9 Hz, 2H), 7.31
(d, J＝8.8 Hz, 2H), 6.75 (d, J＝8.8 Hz, 2H), 4.20 (q, J＝
a Reactions performed with p-cyanobenzaldehyde (1 mmol), di-
medone (2 mmol), and L-lysine (20 mol%) in pure water (4 mL)
and stirred for 5 h at r.t. b Isolated yields after column chromatog-
raphy.
Chin. J. Chem. 2010, 28, 2255— 2259
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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2257

Zhang et al.
FULL PAPER
7.1 Hz, 2H), 3.74 (s, 3H), 1.16 (t, J＝7.1 Hz, 3H); IR
5-dimethylcyclohex-2-enone) (4c) Yellow solid; m.p.
172—174 ℃; Rf＝0.45 V(EtOAc)∶V(petroleum)＝
1∶5; 1H NMR (CDCl3, 500 MHz) δ: 11.86 (s, 1H, OH),
7.37 (d, J＝8.6 Hz, 2H), 6.95 (d, J＝8.0 Hz, 2H), 5.45 (s,
1H), 2.33—2.44 (m, 8H), 1.21 (s, 6H), 1.10 (s, 6H); 13C
NMR (CDCl3, 125 MHz) δ: 190.9, 189.6, 137.5, 131.5,
128.8, 119.9, 115.5, 47.3, 46.7, 32.7, 31.7, 29.8, 27.7;
IR (KBr) ν: 3420, 2958, 1594, 1486, 1468, 1450, 1373,
(KBr) ν: 2979, 1716, 1673, 1601, 1513, 1449, 1306,
1251, 1175, 1027, 831, 690 cm .
－1
3-(3-Bromobenzylidene)pentane-2,4-dione
(3f)
Yellow oil; Rf＝0.52 V(EtOAc)∶V(petroleum)＝1∶4;
1H NMR (CDCl3, 500 MHz) δ: 7.54 (q, J＝1.8 Hz, 2H),
7.40 (s, 1H), 7.32 (s, 1H), 7.27 (d, J＝8.1 Hz, 1H), 2.42
(s, 3H), 2.29 (s, 3H); 13C NMR (CDCl3, 125 MHz) δ:
205.0, 196.4, 144.1, 138.0, 135.2, 133.6, 132.7, 130.7,
128.0, 123.3, 31.8, 26.8; IR (KBr) ν: 2997, 2919, 1711,
1662, 1618, 1561,－1473, 1419, 1381, 1278, 1241, 1179,
－1
1304, 126＋5, 1167, 898, 825 cm ; MS (ESI) m/z: 448.8
([M＋H]) .
2,2'-[(3-Bromophenyl)methylene]bis(3-hydroxy-5,
5-dimethylcyclohex-2-enone) (4d) Pink solid; m.p.
184—186 ℃; Rf＝0.50 V(EtOAc)∶V(petroleum)＝1∶
＋
(3g)
1
1075, 785, 686 cm ; MS (ESI) m/z: 291.0 ([M＋Na]) .
3-(4-Nitrobenzylidene)pentane-2,4-dione
1
Yellow oil; Rf＝0.47 V(EtOAc)∶V (petroleum)＝1∶4;
1H NMR (CDCl3, 500 MHz) δ: 8.25 (d, J＝8.7 Hz, 2H),
7.57 (d, J＝8.7 Hz, 2H), 7.51 (s, 1H), 2.47 (s, 3H), 2.30
(s, 3H); IR (KBr) ν: 3105, 3069, 1712, 1661, 1597, 1520,
4; H NMR (CDCl3, 500 MHz) δ: 11.88 (broad signal,
OH), 7.29 (t, J＝7.8 Hz, 1H), 7.23 (s, 1H), 7.13 (t, J＝7.8
Hz, 1H), 7.01 (d, J＝7.8 Hz, 1H), 5.49 (s, 1H), 2.29—
2.48 (m, 8H), 1.22 (s, 6H), 1.09 (s, 6H); 13C NMR
(CDCl3, 125 MHz) δ: 190.9, 189.7, 141.0, 130.4, 129.9,
129.2, 125.7, 122.7, 115.3, 47.3, 46.7, 32.9, 31.7, 29.8,
27.6; IR (KBr) ν: 3447, 2955, 2869, 1597, 1471, 141＋9,
－1
1418, 1347, 1237, 1175, 862, 752, 691 ㎝ .
3-(4-Chlorobenzylidene)pentane-2,4-dione
(3h)
White solid; m.p. 75—76 ℃; Rf＝0.51 V(EtOAc)∶
1
－1
V(petroleum)＝1∶5; H NMR (CDCl3, 500 MHz) δ:
1377, 788, 725 －cm ; MS (ESI) m/z: 447.2 ([M＋H]) ,
7.41 (s, 1H), 7.36 (d, J＝8.7 Hz, 2H), 7.33 (d, J＝8.7 Hz,
2H), 2.41 (s, 3H), 2.28 (s, 3H); IR (KBr) ν: 2997, 1710,
1659, 1616, 1590, 1490, 1421, 1384, 1356, 1309, 1282,
446.8 ([M－H]) .
2,2'-[(4-Chlorophenyl)methylene]bis(3-hydroxy-
5,5-dimethylcyclohex-2-enone) (4e) White solid; m.p.
139—141 ℃; Rf＝0.46 V(EtOAc)∶V(petroleum)＝
1∶4; 1H NMR (CDCl3, 500 MHz) δ: 11.86 (s, 1H, OH),
7.22 (d, J＝8.6 Hz, 2H), 7.01 (d, J＝8.4 Hz, 2H), 5.47 (s,
1H), 2.29—2.48 (m, 8H), 1.21 (s, 6H), 1.10 (s, 6H); IR
(KBr) ν: 3435, 2958, 2872, 1595, 1490, 1468, 1374,
－1
1242, 1175, 1093, 1012, 823 cm .
3-(4-Methylbenzylidene)pentane-2,4-dione
(3i)
Pale-yellow oil; Rf＝0.51 V(EtOAc)∶V(petroleum)＝
1∶4; 1H NMR (CDCl3, 500 MHz) δ: 7.46 (s, 1H), 7.29
(d, J＝8.2 Hz, 2H), 7.20 (d, J＝8.0 Hz, 2H), 2.41 (s,
3H), 2.38 (s, 3H), 2.30 (s, 3H); IR (KBr) ν: 2919, 1709,
1658, 1605, 1507, 1419, 1386, 1350, 1246, 1173, 813
－1
1304, 1253, 830 cm .
2,2'-(Phenylmethylene)bis(3-hydroxy-5,5-dimethyl-
cyclohex-2-enone) (4f) White solid; m.p. 190—192
℃; Rf ＝0.50 V(EtOAc)∶V(petroleum)＝1∶4; 1H
NMR (CDCl3, 500 MHz) δ: 11.89 (s, 1H, OH), 7.26 (q,
J＝7.6 Hz, 2H), 7.17 (d, J＝7.0 Hz, 1H), 7.09 (d, J＝8.1
Hz, 2H), 5.54 (s, 1H), 2.29—2.48 (m, 8H), 1.23 (s, 6H),
1.10 (s, 6H); IR (KBr) ν: 3450, 2962, 2872, 1594, 1492,
－1
cm .
3-(4-Methoxybenzylidene)pentane-2,4-dione (3j)
Pale-yellow oil; Rf＝0.38 V(EtOAc)∶V(petroleum)＝
1∶4; 1H NMR (CDCl3, 500 MHz) δ: 7.43 (s, 1H), 7.36
(d, J＝8.8 Hz, 2H), 6.91 (d, J＝7.0 Hz, 2H), 3.85 (s,
3H), 2.41 (s, 3H), 2.32 (s, 3H); 13C NMR (CDCl3, 125
MHz) δ: 206.4, 196.7, 162.0, 141.0, 140.0, 132.1, 125.6,
114.8, 55.7, 31.9, 26.6; IR (KBr) ν: 2925, 2835, 1709,
1654, 1－600, 1570, 1513, 1423, 1307, 1260, 1172, 1028,
－1
1448, 1375, 1302, 1251, 1164, 845, 777, 695 cm .
2,2'-(p-Tolylmethylene)bis(3-hydroxy-5,5-dimethyl-
cyclohex-2-enone) (4g) Yellow solid; m.p. 126—128
℃; Rf ＝0.52 V(EtOAc)∶V(petroleum)＝1∶4; 1H
NMR (CDCl3, 500 MHz) δ: 11.90 (broad signal, OH),
7.07 (d, J＝8.0 Hz, 2H), 6.97 (d, J＝7.8 Hz, 2H), 5.50 (s,
1H), 2.29—2.47 (m, 11H), 1.22 (s, 6H), 1.09 (s, 6H); IR
(KBr) ν: 2958, 2871, 1714, 1596, 1511, 1450, 1372,
1
830 cm .
2,2'-[(4-Nitrophenyl)methylene]bis(3-hydroxy-5,5-
dimethylcyclohex-2-enone) (4a) Yellow solid; m.p.
169—171 ℃; Rf＝0.23 V(EtOAc)∶V(petroleum)＝
1
1∶4; H NMR (CDCl3, 500 MHz) δ: 11.94 (broad sig-
－1
nal, OH), 8.12 (d, J＝8.4 Hz, 2H), 7.25 (d, J＝7.8 Hz,
2H), 5.56 (s, 1H), 2.31—2.46 (m, 8H), 1.11 (s, 6H),
1.06 (s, 6H); IR (KBr) ν: 3435, 2958, 1594, 1513, 1468,
1305, 1041, 813 cm .
2,2'-[(4-Methoxyphenyl)methylene]bis(3-hydroxy-
5,5-dimethylcyclohex-2-enone) (4h) White solid; m.p.
142—144 ℃; Rf＝0.43 V(EtOAc)∶V(petroleum)＝
1∶4; 1H NMR (CDCl3, 500 MHz) δ: 11.91 (s, 1H, OH),
6.99 (d, J＝8.4 Hz, 2H), 6.81 (d, J＝8.7 Hz, 2H), 5.48 (s,
1H), 3.77 (s, 3H), 2.29—2.47 (m, 8H), 1.22 (s, 3H),
1.09 (s, 3H); IR (KBr) ν: 3452, 2959, 1593, 1509, 1467,
－1
1451, 1375, 1345, 1252, 1167, 1154, 1044, 852 cm .
4-[Bis(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-
yl)methyl]benzonitrile (4b) Pale-yellow solid; m.p.
164—166 ℃; Rf＝0.56 V(EtOAc)∶V(petroleum)＝
1
1∶4; H NMR (CDCl3, 500 MHz) δ: 11.86 (broad sig-
－1
nal, OH), 7.56 (d, J＝8.3 Hz, 2H), 7.19 (d, J＝8.1 Hz,
2H), 5.52 (s, 1H), 2.31—2.46 (m, 8H), 1.22 (s, 6H),
1.11 (s, 6H); IR (KBr) ν: 3484, 2964, 2887, 2225, 1594,
1452, 1417, 1375, 1305, 1248, 1179, 1034, 830 cm .
References
－1
1501, 1447, 1375, 1306, 1253, 1120, 842 cm .
1
Anastas, P.; Warner, J. Green Chemistry: Theory and Prac-
2,2'-[(4-Bromophenyl)methylene]bis(3-hydroxy-5,
2258
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 2255— 2259

Catalysis by L-Lysine: A Green Method for the Condensation of Aromatic Aldehydes
tice, Oxford University Press, New York, 1998.
(a) Narayan, S.; Muldoon, J.; Finn, M. G.; Fokin, V. V.;
Kolb, H. C.; Sharpless, K. B. Angew. Chem., Int. Ed. 2005,
44, 3275.
(b) Chen, X.; She, J.; Shang, Z.-C.; Wu, J.; Zhang, P. Z.
Synthesis 2008, 3478.
(c) Li, C.-J. Chem. Rev. 2005, 105, 3095.
(d) Shiraishi, Y.; Tsukamoto, D.; Hirai, T. Org. Lett. 2008,
10, 3117.
(e) Azizi, N.; Torkian, L.; Saidi, M. R. J. Mol. Catal. A:
Chem. 2007, 275, 109.
(a) Morita, K.; Suzuki, Z.; Hirose, H. Bull. Chem. Soc. Jpn.
1968, 41, 2815.
(b) Shi, M.; Chen, L.-H. Chem. Commun. 2003, 1310.
(a) Dubey, V. S.; Ingle, V. N. J. Indian Chem. Soc. 1989, 66,
174.
(b) Climent, M. J.; Corma, A.; Domínguez, I.; Iborra, S. J.
Catal. 2007, 246, 136.
(c) Cao, Y.-Q.; Dai, Z.; Zhang, R.; Chen, B.-H. Synth.
Commun. 2004, 34, 2965.
2008, 49, 2555.
Ren, Z.-J.; Cao, W.-G.; Tong, W.-Q.; Jing, X.-P. Synth.
Commun. 2002, 32, 1947.
Wang, Q.-L.; Ma, Y.-D.; Zuo, B.-J. Synth. Commun. 1997,
27, 4107.
Wu, D.-Y.; Ren, Z.-J. Synth. Commun. 2005, 35, 3157.
Attanasi, O.; Filippone, P.; Mei, A. Synth. Commun. 1983,
13, 1203.
2
6
7
8
9
10 Zienkiewicz, Z.; Casilda, V. C.; Sobczak, I.; Ziolek, M.;
Aranda, R. M.; Peinado, A. J. Catal. Today 2009, 142, 303.
11 Su, C.; Chen, Z.-C.; Zheng, Q.-G. Synthesis 2003, 555.
12 (a) Fan, X.-S.; Li, Y.-Z.; Zhang, X.-Y.; Hu, X.-Y.; Wang,
J.-J. Chin. Chem. Lett. 2005, 16, 897.
3
4
(b) Rong, L.-C.; Li, X.-Y.; Wang, H.-Y.; Shi, D.-Q.; Tu,
S.-J.; Zhuang, Q.-Y. Synth. Commun. 2006, 36, 2345.
(c) Kantevari, S.; Bantu, R.; Nagarapu, L. J. Mol. Catal. A:
Chem. 2007, 269, 53.
(d) Kaupp, G.; Naimi, M. R.; Schmeyers, J. Tetrahedron
2003, 59, 3753.
(e) Shi, D.-Q.; Zhang, Q.-Y.; Chen, J.; Wang, X.-S.; Tu,
S.-J.; Hu, H.-W. Chin. J. Org. Chem. 2003, 23, 694 (in
Chinese).
(d) Siebenhaar, B.; Casagrande, B.; Studer, M.; Blaser, H. U.
Can. J. Chem. 2001, 79, 566.
5
(a) Prajapati, D.; Sandhu, J.-S. Chem. Lett. 1992, 1945.
(b) Bao, W.-L.; Zhang, Y.-M.; Wang, J.-G. Synth. Commun.
1996, 26, 3025.
(c) Bartoli, G.; Bosco, M.; Carlone, A.; Dalpozzo, R.;
Galzerano, P.; Melchiorre, P.; Sambri, L. Tetrahedron Lett.
13 (f) Shi, D.-Q.; Lu, Z.-S.; Gao, Y.; Feng, Y.-J.; Zhou, L.-H.;
Dai, G.-Y. Chin. J. Org. Chem. 1998, 18, 82 (in Chinese).
14 Goswami, P.; Das, B. Tetrahedron Lett. 2009, 50, 897.
15 Deb, M. L.; Bhuyan, P. J. Tetrahedron Lett. 2005, 46, 6453.
(E1003201 Cheng, B.; Zheng, G.)
Chin. J. Chem. 2010, 28, 2255— 2259
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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