[HSO3-pmim][CH3SO3] as an efficient catalyst for the synthesis of xanthenedione derivatives

Article abstract of DOI:10.14233/ajchem.2013.14368

Xanthenedione derivatives were prepared through the condensation reaction of aromatic aldehydes with 5,5-dimethyl-1,3-cyclohexanedione promoted by 1-methyl-3-(3-sulfopropyl)imidazolium methyl sulphate, the reaction time was 20-40 min with the yields betwe

Full text of DOI:10.14233/ajchem.2013.14368

Asian Journal of Chemistry; Vol. 25, No. 12 (2013), 6985-6986
http://dx.doi.org/10.14233/ajchem.2013.14368
NOTE
[
HSO -pmim][CH SO ] as an Efficient Catalyst for the
3 3 3
Synthesis of Xanthenedione Derivatives
1
1,2
1,2
1
1,*
CHENG FENG , MENG-XING LIU , HAI-TAO ZHANG , CHUN WANG and JING-JUN MA
1
Hebei Key Laboratory of Bioinorganic Chemistry, College of Sciences, Agricultural University of Hebei, Baoding 071001, P.R. China
Graduate School, Agricultural University of Hebei, Baoding 071001, P.R. China
2
*
Corresponding author: Fax: +86 312 7528292; Tel: +86 312 7528291; E-mail: mjjwjpmartin@sina.com
(
Received: 27 July 2012; Accepted: 10 June 2013)
AJC-13617
Xanthenedione derivatives were prepared through the condensation reaction of aromatic aldehydes with 5,5-dimethyl-1,3-cyclohexanedione
promoted by 1-methyl-3-(3-sulfopropyl)imidazolium methyl sulphate, the reaction time was 20-40 min with the yields between 83.0-
95.1 %. It is shown that the proposed method is fast, high efficient and environmentally benign.
Key Words: 1-Methyl-3-(3-sulfopropyl)imidazolium methyl sulphate, Xanthenedione derivatives, Synthesis.
Xanthenedione derivatives have attracted considerable
1
attention owing to their unique biological activity and they
attached to the organic cation. These structural variations offer
flexibility to the chemist to devise the most idealized solvent
9
and catalyst, catering for the needs of a particular process .
were valuable intermediates because of the inherent activity
2
of the inbuilt pyran ring . The conventional synthetic methods
In continuing our endeavor in green synthesis and using
ionic liquids as a recyclable reaction medium to enhance rates
10
and selectivity , we report herein a mild and efficient protocol
of xanthenedione derivatives were carried out in organic
3
solvent . As an improvement, the condensation reaction of
aromatic aldehydes with 5,5-dimethyl-1,3-cyclohexanedione
were proceeded in water for 6 h using NH SO
for the preparation of xanthenedione and their derivatives by
(1-methyl-3-(3-sulfopropyl)-imidazolium methyl sulphate
2
3
H and SDS as
4
catalyst . Microwave irradiation has also been used to promoted
3 3 3
([HSO -pmim][CH SO ])) as an efficient catalyst (Scheme-
5
6
the condensation reaction . Recently, Fan et al. reported that
I).
the synthesis of xanthenedione derivatives could be proceeded
6
O
O
O
Ar
O
in ionic liquid [bmim]BF
4
catalyzed by Lewis acid InCl
3
and
7
O , respectively, the reaction time was between 4 to
RTILs
FeCl ·6H
3
2
ArCHO
2
H3C
H3C
CH3
CH3
1
0 h. However, some of these methods have not been entirely
H3C
CH3
O
satisfactory, associating with disadvantages such as longer
reaction time, using volatile and toxic organic solvent, using
catalyst that can not be recycled and so on.
1
2
3
Scheme-I
Room temperature ionic liquids (RTILs) have received
increasingly attention as potential "greener" alternatives to
volatile organic solvent and they have been investigated
extensively as a solvent or catalyst for many important
organic reactions because of their special properties such as
their negligible vapor pressure, tunable polarity, high thermal
stability, good solvating ability, ease of recyclability and their
Melting points were recorded on an Electrothermal
1
(Shanghai XRC-1) apparatus and are uncorrected. H NMR
13
(300 MHz) and C NMR (50 MHz) spectra were determined
with BrukerAVANCE 300 spectrometer (CDCl -d ) using TMS
as internal standard. Mass spectra were recorded on a Finnigan
3
6
-1
Mat 8230MSr operating 70 eV. IR spectra (cm ) were measured
3
with a Braic WQF-510 spectrometer. [HSO -pmim][CH SO ]
8
potential to enhance reaction rates and selectivity . They have
3
3
11
also been referred as "designer solvents," as their properties
can be altered by the fine-tuning of parameters such as the
choice of organic cation, inorganic anion and alkyl chain
was synthesized according to the literature .
Effects of reaction temperature on the yields of the product
were also studied by processing the condensation reaction at

6
986 Feng et al.
Asian J. Chem.
room temperature, 80 ºC and 95-100 ºC, respectively (Entries
,8,9). The results shown that the higher of the reaction tempe-
rature, the reaction could proceed more efficiently.
significant decrease even after five runs. The results were
shown in Table-2.
3
General procedure: A mixture of aromatic aldehydes 1
TABLE-2
STUDIES ON THE REUSE OF THE [HSO -pmim]
(
1 mmol), 5,5-dimethy-1,3-cyclohexanedione (2) (2 mmol),
HSO -pmim][CH SO ] (1 mL) were stirred at 95-100 ºC for
3
[CH SO ]FOR THE PREPARATION OF 3b
3 3
[
3
3
3
Round
1
2
3
4
5
a certain period of time as required to complete the reaction
monitored by TLC), the products was separated by fitering
Yield (%)
95
95
92
90
89
(
and washing with water, the obtained solid were recrystal-
lized from 80 % ethanol. Then the desired products 3,3,6,6-
tetramethyl-9-aryl-1,8-dioxo-1,2,3,4,5,6,7,8-octahydroxanthene
Conclusion
The present synthetic method is a simple, efficient and
green synthesis of 3,3,6,6-tetramethyl-9-aryl-1,8-dioxo-1,2,3,
(
3a-l) were obtained.
A variety of substituted aromatic aldehydes were subjected
4
,5,6,7,8-octahydroxanthene derivatives. The method offers
marked improvements with regard to operational simplicity,
reaction time, general applicability, high yields of products
and greenness of procedure, avoiding hazardous organic solvents
and toxic catalysts, so it provides a practical alternative to the
existing procedures. The appication of the task-specific ionic
liquids for other reactions is in progress.
to the condensation reaction to study the substituted effects
on the reactivity of them. The results were summarized in
Table-1. For most of the substrates, the reaction could be
completed in 20-40 min with high yields, whether the subs-
trates having electron-donating groups or with electron-with-
drawing groups, however, when the aromatic aldehydes with
a bigger ortho-position substituent, such as 2-nitrobenzenal-
dehyde and 2,4-dinitrobenzenaldehyde, the reaction could not
take place owing to the steric factors. 9-Arthenone and aceto-
phenone also could not reacted with compound 2 under the
above conditions.
ACKNOWLEDGEMENTS
This project was sponsored by the Nature Development
Foundation of Hebei Province (B2011204051), the Develo-
pment Foundation of the Department of Education of Hebei
Province (2010137) and the Research Development Founda-
tion of the Agricultural University of Hebei.
TABLE-1
SYNTHESIS OF XANTHENEDIONE
DERIVATIVES IN [HSO -pmim][CH SO ]
3
3
3
REFERENCES
Time
o
m.p. (lit) ( C)
Yield
(%)
Entry
Ar
NC
1
.
J.P. Poupelin, G. Saint-Rut, O. Foussard-Blanpin, G. Narcisse, G.
(
min)
35
20
20
25
20
30
25
25
20
40
30
25
3
6
6
6
6
Uchida-Ernouf and R. Lacroix, Eur. J. Med. Chem., 13, 67 (1978).
2. C. O'Callaghan and T.B.H.N. McMurry, J. Chem. Res. (s), 214 (1995)
3a
4-(CH
4-ClC
2- ClC
4-HOC
4-CH OC
3,4-(OCH O)C
3
)
2
6
H
4
220-221 (220-222)
236-238 (237-239)
226-227 (225-227)
247-248 (246-248)
243-245 (242-244)
89.7
95.1
94.1
93.5
93.6
93.9
91.9
92.2
88.7
83.0
91.0
92.8
3b
H
6 4
3
4
.
.
E.C. Horning and M.G. Horning, J. Org. Chem., 11, 95 (1946).
T.S. Jin, J.S. Zhang, A.Q. Wang and F.S. Zhang, Chin. J. Org. Chem.,
3c
H
6 4
3d
H
6 4
2
5, 335 (2005).
5. S.J. Tu, Y. Gao, X.H. Liu, S.F. Tang and X.J. Qiu, Chin. J. Org. Chem.,
21, 1164 (2001).
3e
3
6
H
4
3
3f
2
6
H
3
220-221 (218.5-220)
6
200-202 (199-201)
3g
C
6
H
5
6. X.Y. Hu, X.S. Fan and X.Y. Zhang, Chin. Chem. Lett., 16, 293 (2005).
7. X.S. Fan, Y.Z. Li, X.Y. Zhang, X.Y. Hu and J.J. Wang, Chin. J. Org.
Chem., 25, 1482 (2005).
6
3h
4-BrC
4-CH
3-NO
CH=CH
4-HO-3-CH OC
6
H
4
238-240 (234-236)
6
3i
3
C
6
H
4
210-211 (210-212)
6
8. (a) T. Welton, Chem. Rev., 99, 2071 (1999); (b) J. Dupont, R.F. de
Souza and P.A. Z. Suarez, Chem. Rev., 102, 3667 (2002); (c) N. Jain,
A. Kumar, S. Chauhan and S.M.S. Chauhan, Tetrahedron, 61, 1015
3j
2
C
6
H
4
153-154 (145-147)
4
3k
C
6
H
5
175-177 (175-177)
3
3l
3
6
H
3
227-228 (226-228)
(
2005); (d) S. Chowdhury, R.S. Mohan and J.L. Scott, Tetrahedron,
3, 2363 (2007).
6
9
.
(a) S.G. Lee, Chem. Commun., 10, 1049 (2006); (b) B.C. Ranu and S.
Banerjee, Org. Lett., 7, 3049 (2005); (c) A.L. Zhu, T. Jiang, D. Wang,
B.X. Han, L. Liu, J. Huang, J.C. Zhang and D.H. Sun, Green Chem., 7,
The reusability and recycling of [HSO
3
3 3
-pmim][CH SO ]
was also investingated. For the condensation reaction of
-chlorobenzaldehyde and 5,5-dimethyl cyclohexanedone,
the product was separated by directly fitering from the
reaction mixture the remainder of the ionic liquid [HSO
pmim][CH SO ] was extracted with diethyl ether for elimi-
nation of unreacted reactant and then dired under vacuum at
0 ºC for 2 h to eliminate any water, the recycled [HSO
pmim][CH SO ] was reused for subsequent reaction. The cata-
lytic activity of [HSO -pmim][CH SO ] did not show any
4
514 (2005).
10. (a) J.J. Ma, X. Zhou, X.H. Zang, C. Wang, Z. Wang, J.C. Li and Q. Li,
Aust. J. Chem., 60, 146 (2007); (b) J.J. Ma, S.T. Gao, Z. Li, R.X. Tang,
H.Y. Liu, C. Wang and Y. Gao, Chin. J. Org. Chem., 28, 339 (2008);
3
-
3
3
(c) J.J. Ma, X.H. Zang, X. Zhou, C. Wang, J.C. Li and Q. Li, Indian J.
Chem., 46B, 2045 (2007); (d) C. Wang, J.J. Ma, X. Zhou, X.H. Zang,
Z. Wang, Y.J. Gao and P.L. Cui, Synth. Commun., 35, 2759 (2005).
1. L. Zhang, M. Xian, Y.C. He, L.Z. Li, J.M. Yang, S.T. Yu and X. Xu,
Bioresour. Technol., 100, 4368 (2009).
9
3
-
1
3
3
3
3
3