Solvent-free synthesis of 2-arylideneindan-1,3-diones in the presence of magnesium oxide or silica gel under grinding

Article abstract of DOI:10.1080/00397910500282968

The solvent-free synthesis of 2-arylideneindan-1,3-diones can be achieved in the presence of MgO or silica gel under grinding. This process is simple, efficient, and environmentally benign. Copyright Taylor & Francis, Inc.

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Solvent‐Free Synthesis of
2‐Arylideneindan‐1,3‐diones in the Presence
of Magnesium Oxide or Silica Gel Under
Grinding
Danyi Wu a , Zhongjiao Ren a , Weiguo Cao a b & Weiqi Tong a
a Department of Chemistry, Shanghai University, Shanghai, China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, Shanghai, China
Version of record first published: 20 Aug 2006.
To cite this article: Danyi Wu , Zhongjiao Ren , Weiguo Cao & Weiqi Tong (2005): Solvent‐Free Synthesis
of 2‐Arylideneindan‐1,3‐diones in the Presence of Magnesium Oxide or Silica Gel Under Grinding, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 35:24,
3157-3162
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Synthetic Communicationsw, 35: 3157–3162, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500282968
Solvent-Free Synthesis of 2-Arylideneindan-
1,3-diones in the Presence of Magnesium
Oxide or Silica Gel Under Grinding
Danyi Wu and Zhongjiao Ren
Department of Chemistry, Shanghai University, Shanghai, China
Weiguo Cao
Department of Chemistry, Shanghai University, Shanghai, China and
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, Shanghai, China
Weiqi Tong
Department of Chemistry, Shanghai University, Shanghai, China
Abstract: The solvent-free synthesis of 2-arylideneindan-1,3-diones can be achieved
in the presence of MgO or silica gel under grinding. This process is simple, efficient,
and environmentally benign.
Keywords: Arylideneindan-1,3-dione, Knoevenagel condensation, magnesium oxide,
silica gel, solvent-free reaction
Over the past several years, chemists have been aware of the environmental
implications of their chemistry. Nowadays they are trying to develop new
synthetic methods, reaction conditions, and uses, of chemicals that reduce
risks to humans and the environment. Organic solvents are high on the list
of damaging chemicals because they are employed in huge amounts and are
usually volatile liquids that are difficult to contain. In recent years the
dramatic increases in the investigation of the solvent-free reactions under
Received in Japan December 9, 2004
Address correspondence to Zhongjiao Ren, Department of Chemistry, Shanghai
University, Shanghai 200444, China. Fax: þ86-21-6613-4856; E-mail:
renrui198229@hotmail.com
3157

3158
D. Wu et al.
Scheme 1. 1a, 3a: X ¼ H; 1b, 3b: X ¼ 4-CH3O; 1c, 3c: X ¼ 4-CH3; 1d, 3d: X ¼
4-NO2; 1e, 3e: X ¼ 4-Cl; 1f, 3f: X ¼ 3-Cl; 1g, 3g: X ¼ 2-Cl; 1h, 3h: X ¼ 2-4-(Cl)2.
grinding have been seen, such as the Grignard reaction,[1] Knoevenagel conden-
sation,[2] Aldol condensation,[3] Dieckmann condensation,[4] Reformatsky
reaction,[5] reduction,[6] and other reactions.[7] The advantages of these
processes are higher efficiency, milder conditions, easier workup, and environ-
mental acceptability.[8] We strive to employ the environmentally acceptable
methods in our research.
In conjunction with our program of stereoselective synthesis of cyclo-
propane, we needed 2-arylideneindan-1,3-diones as starting material.
According to the literature, these compounds were prepared through
Knoevenagel condensation of aromatic aldehydes with indan-1,3-dione in
the presence of piperidine in organic solvent.[9] In recent years, the use of
heterogeneous inorganic reagents in the different areas of organic synthesis
[10]
has received considerable attention.
We have also reported the solvent-
free reaction in the presence of CaO.[11] In continuation of our interests in
solvent-free reactions with inorganic reagents, here we report a process of
preparing 2-arylideneindan-1,3-diones in the presence of magnesium oxide
or silica gel under grinding (Scheme 1).
For Knoevenagel condensation, the base or acid catalyst is essential.
Initially, some oxides, such as MgO, CaO, Al2O3, B2O3, and silica gel, were
examined, which are nontoxic, cheap, and easily available. In the model exper-
iment, a mixture of 4-chlorobenzaldehyde (1e) (1 equiv), indan-1,3-dione (2)
(1 equiv), and oxide (3 equiv) was ground at room temperature. The end of
reaction was determined by TLC. The results are summarized in Table 1.
Table 1. Condensation reaction with oxides
Reaction time
(min)
Yield
(%)
Entry
Oxide
MgO
1
2
3
4
5
20
10
15
—
20
92
67
70
—
95
CaO
Al2Oa3
B2O3
Silica gel
aAl2O3 is neutral.

2-Arylideneindan-1,3-diones
3159
In the presence of MgO or silica gel, the desired product (3e) was
obtained in excellent yields (entry 1 and 5 in the Table 1). In the reactions
with CaO or Al2O3, the product (3e) was given in moderate yields (entry 2
and 3 in the Table 1). No product (3e) was detected in the presence of B2O3.
To investigate the generality of this process, the reactions of various
aromatic aldehydes with indan-1,3-dione were performed in the presence of
magnesium oxide or silica gel. The results are given in Table 2.
In the presence of silica gel, the indan-1,3-dione and the aromatic
aldehydes bearing either electron-withdrawing or electron-donating groups
are successfully condensed to afford the products (3a–3h) in high to
excellent yields. For MgO, the products (3a–h) are also obtained in
moderate to excellent yields under the same conditions, but the yields of
products (3d–h) from aromatic aldehydes with electron-withdrawing groups
are higher than ones of products (3a–c) from aromatic aldehydes with
electron-donating groups. The structures of products (3a–h) are determined
by 1H NMR, IR, and elemental analysis.
For comparison with traditional methods, the same reaction, using 4-chloro-
benzaldehyde and indan-1,3-dione as starting materials and piperidine as the
base in boiling ethanol, was preformed. The results are shown in Table 3.
It is worth noting that, in general, the efficiency of heterogenous reactions
are often lower than that of homogenous reactions, because of the poor sol-
ubility of inorganic compounds in organic solvents. This drawback hampers
their wide application in organic synthesis. Our papers, both previously
Table 2. Synthesis of arylideneinda-1,3-diones in the presence of
magnesium or silica gel
Reaction time
(min)
Yield
(%)
Product
Oxide
MgO
MgO
3a
3b
3c
3d
3e
3f
15
50
30
20
20
15
20
30
20
45
30
15
20
15
25
25
65
75
72
94
92
87
84
98
85
96
77
90
95
91
80
84
MgO
MgO
MgO
MgO
3g
3h
3a
3b
3c
3d
3e
3f
MgO
MgO
Silica gel
Silica gel
Silica gel
Silica gel
Silica gel
Silica gel
Silica gel
Silica gel
3g
3h

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D. Wu et al.
Table 3. Comparison of catalyst
Reaction
condition
Reaction time Yield
(min)
Product Catalyst
(%)
3e
3e
3e
Piperidine
MgO
Silica gel
Reflux
Grinding
Grinding
260
20
87
92
95
20
reported[2,11,12] and described here, show that the heterogenous reactions
under grinding are more efficient than the homogenous reaction in solvent,
thus the grinding method may be one of the methods solving the shortcoming
of heterogenous reactions.
In summary, we have achieved an improved process for preparing
2-arylideneindan-1,3-dione in the presence of MgO or silica gel under
grinding. It is simple, efficient, economical, and environmentally benign.
EXPERIMENTAL
All reagents and solvents were obtained from commercial sources and were
used without purification. Al2O3 is neutral and silica gel is for thin-layer
chromatography. Melting points are uncorrected. Melting points were deter-
mined on WRS-1 digital melting-point apparatus made by Shanghai
Physical Instrument Factory (SPOIF), China. IR spectra were measured in
KBr on a PE-580B spectrometer. 1H NMR spectra were recorded at a
Bruker AM-300, using CDCl3 as solvent and TMS as internal reference.
Elemental analyses were measured on a Foss Heraeus CHN-O-RAPID
element analysis instrument.
General Procedure for Preparing 2-Arylideneinda-1,3-dione
Method 1. A mixture of aldehyde (1 mmol), indan-1,3-dione (0.146 g,
1 mmol), and MgO (0.121 g, 3 mmol) is ground at room temperature with
the glass mortar and pestle. The reaction is monitored by TLC. The crude
reaction mixture is neutralized with 5% HCl. The precipitate is collected by
suction filtration and washed with carbon tetrachloride and water. The pro-
duct is recrystallized from a mixture of ethanol and water and dried under
room temperature.
Method 2. A mixture of aldehyde (1 mmol), indan-1,3-dione (0.146 g,
1 mmol) and silica gel (0.18 g, 3 mmol) is ground at room temperature with
the glass mortar and pestle. The reaction is monitored by TLC. The product
is extracted by ethyl acetate and the solvent is evaporated under reduced
pressure to give crude product.

2-Arylideneindan-1,3-diones
Data
3161
2-Benzylideneinda-1.3-dione (3a). Mp 151–1528C, lit.[13] mp 149–1508C;
1H NMR (300 MHz, CDCl3) d 7.58–7.60 (q, 3H, Ar-H), 7.83–7.87 (m, 3H,
Ar-H, 55CH), 7.90–7.94 (m, 2H, Ar-H), 8.11–8.14 (q, 2H, Ar-H); IR
(KBr) 3064, 1726, 1686, 1588 cm21
.
2-(4-Methoxy)benzylideneinda-1,3-dione (3b). Mp 156–1578C, lit.[13]
1
mp 155–1568C; H NMR (300 MHz, CDCl3) d 3.92 (s, 3H, OCH3), 7.20
(d, J ¼ 9.9 Hz, 2H, Ar-H), 7.78–7.80 (m, 2H, Ar-H), 7.86 (s, 1H, 55CH),
7.97–8.01 (m, 2H, Ar-H), 8.56 (d, J ¼ 9.9 Hz, 2H, Ar-H); IR (KBr) 3073,
1718, 1680, 1580, 1510 cm21
.
2-(4-Methyl)benzylideneinda-1,3-dione (3c). Mp 150–1518C, lit.[14] mp
154–1558C; 1H NMR (300 MHz, CDCl3) d 2.45 (s, 3H, CH3), 7.33
(d, J ¼ 8.0 Hz, 2H, Ar-H), 7.79–7.82 (m, 2H, Ar-H), 7.89 (s, 1H, 55CH),
7.99–8.03 (m, 2H, Ar-H), 8.40 (d, J ¼ 8.2 Hz, 2H, Ar-H); IR (KBr) 3063,
1725, 1682, 1588, 1510 cm21
.
1
2-(4-Nitro)benzylideneinda-1,3-dione (3d). Mp 199–2008C, H NMR
(300 MHz, CDCl3) d 7.50 (d, J ¼ 9.3 Hz, 2H, Ar-H), 7.82–7.86 (m, 3H,
Ar-H, 55CH), 8.01–8.04 (m, 2H), 8.43 (d, J ¼ 9.2 Hz, 2H, Ar-H); IR (KBr)
3085, 1745, 1705, 1594, 1509 cm21. Calcd. for C16H9NO4: C, 68.82; H,
3.25; N, 5.02; found: C, 69.04; H, 3.09; N, 5.24.
2-(4-Chloro)benzylideneinda-1,3-dione (3e). Mp 173–1748C, lit.[13] mp
1
176–1778C; H NMR (300 MHz, CDCl3) d 7.52 (d, J ¼ 8.2 Hz, 2H, Ar-H),
7.81–7.84 (m, 2H, Ar-H), 7.92 (s, 1H, 55CH), 8.01–8.05 (m, 2H), 8.47
.
(d, J ¼ 8.2 Hz, 2H, Ar-H); IR (KBr) 3092, 1726, 1707, 1690, 1589, 1487 cm21
1
2-(3-Chloro)benzylideneinda-1,3-dione (3f). Mp 167–1688C; H NMR
(300 MHz, CDCl3) d 7.42–7.55 (m, 2H, Ar-H), 7.82–7.87 (m, 3H, Ar-H,
55CH), 8.01–8.06 (m, 2H), 8.24–8.27 (q, 1H, Ar-H), 8.56–8.57 (t, 1H, Ar-
H); IR (KBr) 3091, 1731, 1687, 1612, 1589, 1480 cm21. Calcd. for
C16H9ClO2: C, 71.52; H, 3.38; found: C, 71.73; H, 3.14.
1
2-(2-Chloro)benzylideneinda-1,3-dione (3g). Mp 132–1338C; H NMR
(300 MHz, CDCl3) d 7.26–7.52 (m, 2H, Ar-H), 7.81–7.87 (m, 3H, Ar-H,
55CH), 8.00–8.06 (m, 2H, Ar-H), 8.35 (s, 1H), 8.63–8.66 (dd, 1H, Ar-H);
IR (KBr) 3085, 1734, 1691, 1625, 1587, 1466 cm21. Calcd. for C16H9ClO2:
C, 71.52; H, 3.38; found: C, 71.19; H, 3.21.
2-(2,4-Dichloro)benzylideneinda-1,3-dione (3h). Mp 194–1958C; 1H
NMR (300 MHz, CDCl3) d 7.37–7.40 (dd, 1H, Ar-H), 7.51–7.52 (d, 1H,
Ar-H), 7.82–7.88 (m, 3H, Ar-H, 55CH), 7.98–8.08 (m, 2H, Ar-H), 8.69–
8.72 (d, 1H, Ar-H); IR (KBr) 3070, 1729, 1692, 1620, 1579, 1468 cm21
Calcd. for C16H8Cl2O2: C, 63.34; H, 2.66; found: C, 63.17; H, 2.89.
.
ACKNOWLEDGMENT
Thanks are due to the National Natural Science Foundation of China for
financial support.

3162
D. Wu et al.
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