Clean synthesis of 2-arylideneindan-1,3-diones in water

Article abstract of DOI:10.1007/s11164-011-0442-4

A high-yield synthesis of 2-arylideneindan-1,3-diones in water was achieved by the Knoevenagel condensation of indan-1,3-dione with aromatic aldehydes at ambient temperature avoiding the addition of any catalyst. The procedure is simple, efficient, as wel

Full text of DOI:10.1007/s11164-011-0442-4

Res Chem Intermed (2012) 38:1063–1068
DOI 10.1007/s11164-011-0442-4
Clean synthesis of 2-arylideneindan-1,3-diones in water
•
Peng Hui Yang Qun Zheng Zhang Wei Sun
•
Received: 19 October 2011 / Accepted: 9 November 2011 / Published online: 29 November 2011
Ó Springer Science+Business Media B.V. 2011
Abstract A high-yield synthesis of 2-arylideneindan-1,3-diones in water was
achieved by the Knoevenagel condensation of indan-1,3-dione with aromatic
aldehydes at ambient temperature avoiding the addition of any catalyst. The pro-
cedure is simple, efficient, as well as environmentally friendly.
Keywords Arylideneindan-1,3-diones Á Synthesis Á Catalyst free
Introduction
Green chemistry has become common knowledge as people are more aware of
environmental protection. Green chemistry encourages the design of products and
processes that minimize the use and generation of hazardous substances. Traditional
organic reactions used organic solvents extensively, causing serious pollution.
Water is an ideal substitute for organic solvents because it is cheap, readily
available, is not inflammable, and is nontoxic. Research of reactions in water has
become a hot spot since the 1980s as Breslow pointed out that hydrophobic effects
can strongly enhance the rate of several organic reactions [1, 2].
2-arylideneindan-1,3-diones are important intermediates for the synthesis of
various kinds of biologically active compounds [3–5] and thus are of tremendous
industrial interest. On the other hand, they show important activities as anticoag-
ulants [6] and cytotoxics [7]. According to the literature, these compounds were
usually synthesized by the Knoevenagel condensation of indan-1,3-dione with
aromatic aldehyde in organic solvents as ethanol, toluene, acetic acid employing an
P. H. Yang (&) Á Q. Z. Zhang
College of Chemistry and Chemical Engineering, Xi’an Shiyou University, Xi’an 710065, China
e-mail: yaph2001@iccas.ac.cn
W. Sun
College of Chemistry and Chemical Materials, Northwest University, Xi’an 710069, China
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acid or base catalyst as piperidine [8], sodium acetate, concentrated sulfuric acid [6],
gaseous HCl [9] or p-toluenesulfonic acid. The yield varied from moderate to high.
In 2005, a solvent-free synthesis of 2-arylideneindan-1,3-diones in the presence of
magnesium oxide or silica gel under grinding was reported [10].
In continuation of our interests in organic reactions in water, we would like to
report for the first time a novel method for the synthesis of 2-arylideneindan-1,
3-diones in water avoiding the addition of any catalyst (Scheme 1).
Results and discussion
When we studied the chemistry of 2-arylideneindan-1,3-diones, we found that
4-hydroxylbenzaldehyde condensed readily with indan-1,3-dione in water in the
absence of any catalyst to give 2-(4-hydroxybenzylidene)indan-1,3-dione in high
yield occasionally. We thought it might be a new general method to synthesize
2-arylideneindan-1,3-diones. As far as we know, there are no reports about the
synthesis of 2-arylideneindan-1,3-diones in water at ambient temperature under
catalyst-free conditions. At first, we compared the method with traditional methods
in organic solvents. So the same reaction, using 4-hydroxybenzaldehyde and indan-
1,3-dione as starting materials in different solvents in the presence or absence of
catalyst was preformed. The results are shown in Table 1.
It can be seen from Table 1 that the clean synthesis of 2-(4-hydroxybenzylid-
ene)indan-1,3-dione in water is more efficient than the traditional methods and
produced high-yield products. The efficiency of the method might be ascribed to the
enforced hydrophobic interaction between the substrates. To investigate the
generality of this process, the reactions of various aromatic aldehydes with indan-
1,3-dione were performed in water. The results are given in Table 2.
Table 2 shows that simple aromatic aldehydes condensed readily with indan-1,
3-dione in water to give 2-arylideneindan-1,3-diones. However, the substitution
pattern made a great difference to the reaction. The reaction with aromatic
aldehydes carrying electron-withdrawing groups usually went well and gave almost
quantitative yields; those carrying electron-donating groups such as methoxy group
gave relative poorer yields. It should be noted that the reaction with hydroxyl
aromatic aldehydes usually gave high-yield products.
The proposed mechanism of the reaction is shown in Scheme 2. Water facilitated
the deprotonation of indan-1,3-dione to form indan-1,3-dione carbanion. The latter
O
O
O
O
Scheme 1 Synthesis of
2-arylideneindan-1,3-diones
Ar
H2O
ArCHO
1
2
3
Ar = 4-NO2C6H4, 2-NO2C6H4, 4-ClC6H4, 4-HOC6H4, 2-HOC6H4,
3-HOC6H4, 3,4-(HO)2C6H3, 4-CH3OC6H4, etc.
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Clean synthesis of 2-arylideneindan-1,3-diones
1065
Table 1 Comparison
of different methods
Product Solvent Catalyst
Reaction condition Yield (%)
3d
3d
3d
H2O
None
r.t. 14 h, 80 °C 3 h 85.2
EtOH
Morpholine Reflux 12 h
23.2
Toluene PTSA
Reflux 20 h
83.2
Table 2 Synthesis of
arylideneindan-1,3-diones
in water
Entry
Ar
Product
Yield (%)
1
2
3
4
5
6
7
8
9
4-NO2C6H4
2-NO2C6H4
4-ClC6H4
3a
3b
3c
3d
3e
3f
97.5
92.5
95.5
85.2
94.4
96.0
88.7
66.7
85.3a
4-HOC6H4
2-HOC6H4
3-HOC6H4
3,4-(HO)2C6H3
4-CH3OC6H4
2-furyl
3g
3h
3i
a
Stirred at r.t. for 14 h, then
at 60 °C for 4 h
Cl
O
O
O
O
O
H
O
H2O
H3O
H
H
2
O
O
1
Cl
Cl
O
O
OH
-H2O
H3O
O
O
Cl
3
Scheme 2 Proposed mechanism for the formation of 2-arylideneindan-1,3-diones 3
attacked the carbonyl group of the aromatic aldehydes and was followed by
dehydration to afford the 2-arylideneindan-1,3-diones.
Conclusions
In summary, we have developed a novel method for preparing 2-arylideneindan-1,
3-diones in water at ambient temperature avoiding the addition of any catalyst. The
procedure is simple, efficient, and environmentally friendly.
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P. H. Yang et al.
Experimental
Melting points were uncorrected and determined on WRS-1A digital melting-point
apparatus. IR spectra were measured in KBr on an EQUINOX-55 spectrometer.
1HNMR spectra were recorded at a INOVA-400 using TMS as internal reference.
All reagents and solvents were obtained from commercial sources and were used
without purification.
General procedure for preparing 2-arylideneindan-1,3-diones
The suspension of 1.1 mmol of aldehyde (for solid aldehyde, it must be finely
powdered) in 18 mL of water was rapidly stirred at r.t. for 15 min. Then 1.0 mmol
of finely powdered indan-1,3-dione was added in one portion. The mixture was
stirred at this temperature for 14–16 h, then heated in an oil bath maintained at
80 °C for 3–4 h. The reaction mixture was cooled and then filtered. The filter cake
was washed with EtOH and dried to give the pure product.
2-(4-nitro)benzylideneindan-1,3-dione (3a)
Mp 234–236 °C, lit [11]. 228 °C; 1HNMR(CDCl3)d: 8.55(td, 2H, J = 8.8 Hz,
2.0 Hz, Ar–H), 8.33(td, 2H, J = 9.6 Hz, 2.8 Hz, Ar–H), 8.06(dd, 2H, J = 5.6 Hz,
3.2 Hz, Ar–H), 7.86–7.90 (m, 3H, CH=, Ar–H); IR (KBr) 1732, 1694, 1625, 1589,
1349, 747 cm-1
.
2-(2-nitro)benzylideneindan-1,3-dione (3b)
Mp 192–194 °C, lit [7]. 180 °C; 1HNMR(DMSO)d: 8.27(dd, 1H, J = 8.0 Hz,
0.8 Hz, Ar–H), 8.25(s, 1H, Ar–H), 8.06–8.08(m, 1H, Ar–H), 7.98–8.03(m, 2H,
Ar–H), 7.93–7.97(m, 2H, AR–H), 7.84–7.88(m, 1H, Ar–H), 7.76-7.81(m, 1H,
CH=); IR (KBr) 1732, 1693, 1638, 1520, 1341, 738 cm-1
.
2-(4-chloro)benzylideneindan-1,3-dione (3c)
Mp 180–182 °C, lit [12]. mp176–177 °C; 1HNMR (CDCl3)d: 8.42(td, 2H,
J = 6.8 Hz, 1.6 Hz, Ar–H), 8.00–8.03(m, 2H, Ar–H), 7.82–7.84(m, 3H, Ar–H),
7.48(td, 2H, J = 8.4 Hz, 2.0 Hz, Ar–H, CH=); IR (KBr) 1728, 1688, 1578, 830,
735 cm-1
.
2-(4-hydroxy)benzylideneindan-1,3-dione (3d)
1
Mp 241–243 °C, lit [12]. mp 233–234 °C; HNMR(DMSO) d: 10.88(s, 1H, OH),
8.55(d, 2H, J = 12.0 Hz, Ar–H), 7.90–7.96(m, 4H, Ar–H), 7.76 (s, 1H, CH=),
6.95(d, 2H, J = 9.2 Hz, Ar–H); IR (KBr) 3306, 1723, 1670, 1584, 1443, 832,
732 cm-1
.
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Clean synthesis of 2-arylideneindan-1,3-diones
1067
2-(2-hydroxy)benzylideneindan-1,3-dione (3e)
1
Mp 193–195 °C, lit [13]. mp 194–196 °C; HNMR(DMSO)d: 10.87(s, 1H, OH),
8.89(dd, 1H, J = 7.2 Hz, 0.4 Hz, Ar–H), 8.33(s, 1H, Ar–H), 7.93–8.00(m, 4H,
Ar–H), 7.45–7.50(m, 1H, Ar–H), 7.01(d, 1H, J = 8.4 Hz, Ar–H), 6.96(t, 1H,
J = 7.6 Hz, CH=); IR (KBr) 1719, 1665, 1582, 1389, 1348, 991, 734 cm-1
.
2-(3-hydroxy)benzylideneindan-1,3-dione (3f)
1
Mp 226–228 °C, lit [12]. mp 219–222 °C; HNMR(DMSO)d: 9.85(s, 1H, OH),
8.05(t, 1H, J = 1.6 Hz, Ar–H), 7.95–8.02(m, 4H, Ar–H), 7.85(d, 1H, J = 7.6 Hz,
Ar–H), 7.76(s, 1H, Ar–H), 7.38(t, 1H, J = 8.0 Hz, Ar–H), 7.05(dd, 1H, J = 8.0 Hz,
2.4 Hz, CH=); IR (KBr) 3237, 1720, 1667, 1591, 1453, 1230, 741 cm-1
.
2-(3,4-dihydroxy)benzylideneindan-1,3-dione (3g)
1
Mp 263–265 °C, lit [14]. mp 262–264 °C; HNMR(DMSO)d: 10.50(s, 1H, OH),
9.58(s, 1H, OH), 8.35(d, 1H, J = 2.0 Hz, Ar–H), 7.90–7.97(m, 4H, Ar–H), 7.86(dd,
1H, J = 8.8 Hz, 2.0 Hz, Ar–H), 7.67(s, 1H, Ar–H), 6.91(d, 1H, CH=); IR (KBr)
3464, 3233, 1721, 1663, 1591, 1245, 732 cm-1
.
2-(4-methoxy)benzylideneindan-1,3-dione (3h)
1
Mp 162–164 °C, lit [8]. mp 165 °C; HNMR(CDCl3)d: 8.55(d, 2H, J = 7.2 Hz,
Ar–H), 7.97–8.01(m, 2H, Ar–H), 7.86 (s, 1H, CH=), 7.78–7.80(m, 2H, Ar–H),
7.02(d, 2H, J = 9.2 Hz, Ar–H), 3.92(s, 3H, OCH3); IR (KBr) 1718, 1684,1581,
1560, 1179, 1023 cm-1
.
2-(2-furyl)benzylideneindan-1,3-dione (3i)
Mp 209–211 °C, lit [6]. mp 209–211 °C; 1HNMR(CDCl3)d: 8.59(d, 1H,
J = 3.6 Hz, Ar–H), 7.96–7.99(m, 2H, Ar–H), 7.77–7.81(m, 3H, Ar–H), 7.76
(s, 1H, Ar–H), 6.72–6.73(m, 1H, CH=); IR (KBr) 1722, 1691, 1608, 1467, 1353,
773, 736 cm-1
.
Acknowledgments This study was supported by the Natural Science Foundation of Education Bureau
of Shaanxi Province, China (2010JK782) and Foundation of Xi’an Shiyou University (Z08012).
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