Synthesis of 1-indanones via intramolecular cyclodehydration of 3-arylpropionic acids catalyzed by heteropoly acid as heterogeneous catalyst

Article abstract of DOI:10.1080/00397910701392293

Intramolecular cyclodehydration of 3-arylpropionic acids catalyzed by heteropoly acids was investigated for the first time. Several 3-arylpropionic acids were refluxed and dehydrated in chlorobenzene in the presence of 0.2 equivalent of heteropoly acids, and 1-indanones were obtained in good yield. At the same time, intermolecular Friedel-Crafts acylation were observed in this experiment. Copyright Taylor & Francis Group, LLC.

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Synthesis of 1‐Indanones via Intramolecular
Cyclodehydration of 3‐Arylpropionic
Acids Catalyzed by Heteropoly Acid as
Heterogeneous Catalyst
Kun Lan a & Zi‐Xing Shan a
a Department of Chemistry , Wuhan University , Wuhan, China
Published online: 03 Jul 2007.
To cite this article: Kun Lan & Zi‐Xing Shan (2007) Synthesis of 1‐Indanones via Intramolecular
Cyclodehydration of 3‐Arylpropionic Acids Catalyzed by Heteropoly Acid as Heterogeneous Catalyst, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:13,
2171-2177, DOI: 10.1080/00397910701392293
To link to this article: http://dx.doi.org/10.1080/00397910701392293
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Synthetic Communicationsw, 37: 2171–2177, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701392293
Synthesis of 1-Indanones via Intramolecular
Cyclodehydration of 3-Arylpropionic Acids
Catalyzed by Heteropoly Acid as
Heterogeneous Catalyst
Kun Lan and Zi-Xing Shan
Department of Chemistry, Wuhan University, Wuhan, China
Abstract: Intramolecular cyclodehydration of 3-arylpropionic acids catalyzed by
heteropoly acids was investigated for the first time. Several 3-arylpropionic acids
were refluxed and dehydrated in chlorobenzene in the presence of 0.2 equivalent of
heteropoly acids, and 1-indanones were obtained in good yield. At the same time, inter-
molecular Friedel–Crafts acylation were observed in this experiment.
Keywords: 3-arylpropionic acid, Friedel–Crafts acylation, heteropoly acids
INTRODUCTION
1-Indanones are very important intermediates used in pharmaceuticals,[1]
ligands of catalysts,[2] and discotic liquid crystals.[3] Among various
methods for the synthesis of 1-indanones, the intramolecular Friedel–Crafts
cyclization reaction of 3-arylpropionic acids or 3-arylpropionyl chlorides is
one of the most general and useful methods.[4–7] The direct cyclodehydration
of 3-arylpropionic acids is beneficial to the environment in that it creates less
toxic and corrosive by-products than other methods. However, direct cycliza-
tion has been performed by using an excess of protonic acids (H2SO4,[8] HF,[9]
polyphosphoric acid,[10] trifluoromethanesulfonic acid[11]) or Lewis acids
(AlCl3,[12] AlCl3-NaCl,[13] P2O3Cl4[14]). In these methods, producing a mass
of acidic wasted water after the reaction is inevitable.
Received September 20, 2006
Address correspondence to Zi-Xing Shan, Department of Chemistry, Wuhan
University, Wuhan, China. E-mail: zxshan@whu.edu.cn
2171

2172
K. Lan and Z.-X. Shan
In view of increasing environmental problems, the application of hetero-
geneous catalysis has become attractive.[15] In the east decades, using solid
acid as heterogeneous catalyst has received much attention in organic
synthesis.[16] In comparison with liquid mineral acids, solid acids can be
easily separated from the reaction mixture by simple filtration, with high
recovery. This advantage directly leads to decreasing equipment cauterization
and environment pollution. Recently it was reported that a Y-faujasite-type
zeolite[17] was an effective catalyst for dehydrative cyclization to form
tricyclic ketones containing an indanone structure, although it was not very
effective for the synthesis of simple indanones.
Among various solid acids, HPAs (heteropoly acids)[18,19] have unique
physical–chemical properties. Their acidity is significantly higher than that
of traditional mineral acids. Furthermore, HPAs are capable of protonating
and activating the substrate; in some cases, HPAs are more effective than the
usual inorganic acid and the traditional acid catalyst. Therefore, they are
widely used as homogeneous and heterogeneous acid catalysts for the
synthesis reaction.[20] However, the intramolecular cyclodehydration reaction
of an aromatic compound catalyzed by HPAs have been seldom reported.
In our previous research,[21] 1,10-spirobiindanes were synthesized in high
yield via intramolecular cyclodehydration of 1,5-diaryl-3-pentanones
catalyzed by heteropoly acid as heterogeneous catalyst, so this method was
further investigated with other intramolecular cyclodehydrations. In this com-
munication, we report that a series of 1-indanones was synthesized from
3-arylpropionic acids via intramolecular cyclodehydration catalyzed by het-
eropoly acids as heterogeneous catalyst.
RESULTS AND DISCUSSION
Using heteropoly acids as heterogeneous catalyst, dehydrations of several
3-arylpropionic acids in arenes were done as shown in Scheme 1.
As a reaction model, cyclodehydration of 3-phenylpropionic acid
catalyzed by HPAs was investigated under different reaction conditions, and
the results are summarized in Table 1. The three kinds of HPAs
(H3PW12O40, H3PMo12O, and H4SiW12O40) used in the experiments show
different catalytic activity toward the cyclodehydration (Entries 1–3), and
H4SiW12O40 is the best catalyst for the reaction (Entry 1) when
H3PMo12O40 (Entry 3) is shown without catalytic activity.
As far as the amount of the catalyst used is concerned, 0.2 equivalent of
the catalyst offers the desired product in the highest yield, and more catalyst
will not improve the yield further. Reaction medium considerably influences
the conversion and selectivity of the cyclodehydration product. When
chlorobenzene was used, the reaction was achieved in the highest conversion
(93–95%, Entries 7, 9); however, the selectivity is lower in chlorobenzene
(76%) than in toluene (93%) and in xylene (78%). Higher reflux temperature

Synthesis of 1-Indanones
2173
Scheme 1. Dehydration of 3-arylpropionic acids catalyzed by heteropoly acids.
R1 ¼ 4-Me, 3-OMe, 2-Cl, 4-Cl; R2 ¼ 4-Me, 2,5-dimethyl.
was perhaps beneficial to the conversion of 3-arylpropionic acids and aroused
other competitive reactions at the same time.
Several 3-arylpropionic acids were refluxed and dehydrated in the
presence of 0.2 equivalent of H4SiW12O40, and the result is summarized in
Table 2.
Some interesting phenomenon in this reaction should be pointed out.
When chlorophenylpropionic acids (1d and 1e) were refluxed in toluene or
p-xylene (Entries 5, 6, 8, and 9), an intermolecular Friedel–Crafts reaction
was achieved instead of intramolecular cyclodehydration and compounds
3d1, 3d2 or 3e1, 3e2 were gained. When chlorophenylpropionic acids (1d
and 1e) were refluxed in chlorobenzene (Entries 4 and 7), chloroindanones
(2d and 2e) were gained. It followed the classic Brown selectivity relationship
theory in the Friedel–Crafts acylation reaction.[22,23] The phenyl ring with an
electron-withdrawing substituent is less reactive than the phenyl ring with an
electron-donating substituent in Friedel–Crafts acylation. In this experiment,
Table 1. Preparation of 1-indanone (2a) via dehydration of 3-phenylpropionic acids
(1a) in different conditions
Entry
Cat. (eq.)
Solvent
Conv. (%) Select. (%) Yield (%)a
1
2
3
4
5
6
7
8
9
H4SiW12O40 (0.2) Toluene
H3PW12O40 (0.2) Toluene
H3PMo12O40 (0.2) Toluene
H4SiW12O40 (0.2) Benzene
H4SiW12O40 (0.2) Toluene
H4SiW12O40 (0.2) p-Xylene
H4SiW12O40 (0.2) Chlorobenzene
H4SiW12O40 (0.1) Chlorobenzene
H4SiW12O40 (0.3) Chlorobenzene
46
27
0
93
90
0
43
24
0
0
0
0
42
74
93
53
95
87
78
76
88
72
37
58
71
47
68
aIsolated yield. Yield (%) ¼ conversion ꢀ selectivity.

Table 2. Dehydration of 3-arylpropionic acids catalyzed by H4SiW12O40
3-Arylprpionic acids
Entry
1
Solvent
Product
Conv. (%)
93
Select. (%)
76
Yield (%)a
72
Chlorobenzene
2
3
4
5
Chlorobenzene
Chlorobenzene
Chlorobenzene
Toluene
85
87
82
37
62
57
78
90
53
50
64
33
6
p-Xylene
68
74
50
7
8
Chlorobenzene
Toluene
84
31
75
88
63
27
9
p-Xylene
60
67
40
aIsolated yield. Yield (%) ¼ conversion ꢀ selectivity.

Synthesis of 1-Indanones
2175
the nucleophilicity of chlorophenylpropionic acid is lower than arene solvent
(toluene or xylene) because of the electron-withdrawing character of the Cl
group. These should cause such intermolecular reactions.
In conclusion, intramolecular cyclodehydration of 3-arylpropionic acids
was achieved in the presence of heteropoly acids. A series of 1-indanones
was gained in good yield when corresponding 3-arylpropionic acids and
H4SiW12O40 were refluxed and dehydrated in the chlorobenzene. By the
way, intermolecular Friedel–Crafts acylation were observed in this exper-
iment. These will help us to further comprehend the characters of heteropoly
acids and Friedel–Crafts acylation.
EXPERIMENTAL
IR spectra were recorded on a Testscan Shimadzu FTIR 8000 in KBr.
1H NMR and 13C NMR spectra were performed on a Varian Mercury VS
300. Elemental analyses were carried out on a Vario EL III (German) instru-
ment. Melting points were determined on a VEB Wagetechnik Rapio
PHMK05 instrument and are uncorrected.
General Experimental Procedure for Dehydration of
3-Arylpropionic Acids
3-Arylpropionic acids (10 mmol), heteropoly acids (1–3 mmol) and 30 mL of
arene as solvent were charged in a 50-mL flask with a water segregator and
reflux condensator, followed by reflux and dehydration until no water was
separated (about 6–12 h). It was cooled, filtered, and washed with CHCl3
and ethyl acetate. The organic phases were combined, then eluted through a
pad of Celite.R The product was purified by recrystallization or column
chromatography on the SiO2.
Data
1
6-Methylindanone (2b): mp 335–337 K. H NMR (300 MHz, CDCl3): d
2.40 (s, 3H), 2.69 (t, J ¼ 6 Hz, 2H), 3.10 (t, J ¼ 6 Hz, 2H), 7.35–7.42
(m, 2H), 7.56 (s, 3H); IR (KBr, cm21): n 1704, 1613, 1455, 1378, 802.
5-Methoxyindanone (2c): mp 385–387 K. 1H NMR (300 MHz, CDCl3): d 2.67
(t, J ¼ 6 Hz, 2H), 3.09 (t, J ¼ 6 Hz, 2H), 3.88 (s, 3H), 6.86–6.91 (m, 2H), 7.68
(d, J ¼ 4.5 Hz, 1H). IR (KBr, cm21): n, 1696, 1602, 1254, 1096, 841.
6-Chloroindanone (2d): mp 353–355 K. 1H NMR (300 MHz, CDCl3):
d 2.75 (t, J ¼ 6 Hz, 2H), 3.14 (t, J ¼ 6 Hz, 2H), 7.42 (d, J ¼ 8 Hz, 1H),
7.54 (d, J ¼ 8 Hz, 2H), 7.71 (s, 1H). IR (KBr, cm21): n, 1708, 1601,
1260, 779.

2176
K. Lan and Z.-X. Shan
4-Chloroindanone (2c): mp 367–369 K 1H NMR (300 MHz, CDCl3): d2.74
(t, J ¼ 6 Hz, 2H), 3.14 (t, J ¼ 6 Hz, 2H), 7.35 (t, J ¼ 8 Hz, 2H), 7.59
(d, J ¼ 4.1 Hz, 2H), 7.67 (d, J ¼ 4.1 Hz, 2H). IR (KBr, cm21): n, 1700,
1613, 1472, 753.
3-(4-Chlorophenyl)-1-(4-methylphenyl)-1-propanone (3d1): mp 359–
1
361 K. H NMR (300 MHz, CDCl3): d 2.42 (s, 3H), 3.04 (t, J ¼ 8 Hz, 2H),
3.27 (t, J ¼ 8 Hz, 2H), 7.19 (d, J ¼ 8 Hz, 2H), 7.25–7.31 (m, 4H), 7.85
(d, J ¼ 8 Hz, 2H); IR (KBr, cm21): n, 1713, 1612, 1440, 833.
3-(4-chlorophenyl)-1-(2,5-dimethylphenyl)-1-propanone (3d2): mp 363–
365 K. 1H NMR (300 MHz, CDCl3): d 2.33 (s, 3H), 2.41 (s, 3H), 3.00
(t, J ¼ 7.2 Hz, 2H), 3.18 (t, J ¼ 7.2 Hz, 2H), 7.09–7.23 (m, 6H), 7.37
(s, 1H). 13C NMR (75 MHz, CDCl3): d 21.1, 29.8, 30.6, 43.2, 125.8, 128.8,
129.2, 130.1, 132.1, 132.3, 135.2, 135.4, 137.9, 140.0, 203.3. IR (KBr, in
film, cm21): n 1678, 1492, 1089, 808. Anal. calcd for C17H17ClO: C, 74.86;
H, 6.28. Found: C, 74.74; H, 6.06.
3-(2-Chlorophenyl)-1-(4-methylphenyl)-1-propanone (3e1): colorless oil,
1H NMR (300 MHz, CDCl3): d 2.41 (s, 3H), 3.17 (t, J ¼ 8 Hz, 2H), 3.29
(t, J ¼ 8 Hz, 2H), 7.15–7.37 (m, 6H), 7.87 (d, J ¼ 7.2 Hz, 2H); IR (KBr,
cm21): n, 1681, 1606, 1474, 751.
3-(2-Chlorophenyl)-1-(2,5-dimethylphenyl)-1-propanone (3e2): colorless
oil, 1H NMR (300 MHz, CDCl3): d 2.32 (s, 3H), 2.44 (s, 3H), 3.14
(t, J ¼ 7 Hz, 2H), 3.21 (t, J ¼ 7 Hz, 2H), 7.09–7.17 (m, 4H), 7.24–7.35
(m, 2H), 7.42 (s, 1H). 13C NMR (75 MHz, CDCl3): d 18.0, 20.8, 28.5, 41.1,
127.3, 128.0, 129.5, 129.9, 131.1, 132.2, 132.4, 134.3, 135.5, 136.1, 137.9,
139.2, 203.7. IR (KBr, in film, cm21): n 1683, 1050, 754. Anal. calcd. for
C17H17ClO: C, 74.86; H, 6.28. Found: C, 74.69, H, 6.14.
ACKNOWLEDGMENT
This study was financially supported in part by the National Natural Science
Foundation of China (20372053 and 29972033).
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