Br?nsted acidic imidazolium salts containing perfluoroalkyl tails catalyzed one-pot synthesis of 1,8-dioxo-decahydroacridines in water

Article abstract of DOI:10.1016/j.jfluchem.2009.02.014

One-pot three-component synthesis of 1,8-dioxo-9,10-diaryl-decahydroacridines in water was efficiently realized in the presence of the Br?nsted acidic imidazolium salts containing perfluoroalkyl tails in good yields. The method provided several advantages such as low catalyst loading; recycle of the catalyst and simple work procedure.

Full text of DOI:10.1016/j.jfluchem.2009.02.014

Journal of Fluorine Chemistry 130 (2009) 522–527
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Brønsted acidic imidazolium salts containing perfluoroalkyl tails catalyzed
one-pot synthesis of 1,8-dioxo-decahydroacridines in water
*
Wei Shen, Li-Min Wang , He Tian, Jun Tang, Jian-jun Yu
Laboratory for Advanced Materials & Institute of Fine Chemicals, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, People’s Republic of China
A R T I C L E I N F O
A B S T R A C T
Article history:
One-pot three-component synthesis of 1,8-dioxo-9,10-diaryl-decahydroacridines in water was
efficiently realized in the presence of the Brønsted acidic imidazolium salts containing perfluoroalkyl
tails in good yields. The method provided several advantages such as low catalyst loading; recycle of the
catalyst and simple work procedure.
Received 25 January 2009
Received in revised form 19 February 2009
Accepted 22 February 2009
Available online 9 March 2009
ß 2009 Elsevier B.V. All rights reserved.
Keywords:
Decahydroacridine
Brønsted acid
Imidazolium salts
Perfluoroalkyl tail
1. Introduction
imidazolium salts containing perfluoroalkyl tails (6a and 6b) as
a Brønsted acid–surfactant combined catalyst for the synthesis of
Because of the great potential of room temperature imidazo-
lium salts as environmentally benign media for catalytic processes
[1], much attention has currently been focused on the organic
reactions catalyzed with or in imidazolium salts, and many organic
reactions, especially in the reactions promoted with acid–base
catalysts, were performed in imidazolium salts with high
performances [2]. An attractive feature of imidazolium salts is
that their solubility, depending on the choice of cations and anions,
can be tuned readily so that they can phase separate from organic
as well as aqueous media [3]. Recently, the synthesis of ‘‘task-
specific’’ imidazolium salts with special functions according to the
requirement of a specific reaction have become an attractive field
[4,5]. Task-specific imidazolium salts are a unique subclass of
imidazolium salts which possess a potential spectrum of utility
extending far beyond that likely for more conventional IL. By virtue
of the incorporated functional groups, these unique salts can act
not only as solvents but also as catalysts and reagents in an array of
synthetic, separations and electrochemical applications.
1,8-dioxo-decahydroacridine derivatives in water (Scheme 1). 1,8-
Dioxo-9,10-diaryl-decahydroacridines and their derivatives are
polyfunctionalized 1,4-dihydropyridine derivatives. Reportedly,
the conventional synthesis of 1,4-dihydropyridine derivatives was
performed in organic solvent such as HOAc [6], CH3CN [7] and DMF
[8]. There is only one literature about synthesis of those
compounds in water [9], but the substrate amine was specialized
in p-toluidine. Our group had reported the synthesis of
b-amino
carbonyl compounds [10] and homoallylic alcohols and amines
[11] in sole water as solvent. Consequently, there is scope for
further research toward simple work procedure, low catalyst
loading, and expand of substrate for the synthesis of 1,8-dioxo-
decahydroacridine.
2. Results and discussion
2.1. Synthesis of compound 6
Meanwhile, it is obvious that water is the most inexpensive and
environmentally benign solvent. In light of the advantages of water
and imidazolium salts respectively, we envisioned combination of
these two advantages together by developing a task-specific
imidazolium salts as organocatalyst used in water as solvent.
Herein, we have developed a new type of Brønsted acidic
The synthesis of the Brønsted acidic imidazolium salts 6a was
outlined in Scheme 2. First, 3-perfluorooctyl-1-propanol 2 was
synthesized according to Qing’s method [12] from the correspond-
ing perfluoroalkyl iodide C8F17I. Compound 2 was then treated
with KI in the presence of P2O5 and 85% H3PO4 to afford 3-
perfluorooctyl-1-iodopropane 3 as described in the literature [13].
The next step proceeded by the conjunction of compound 3 with
imidazole in the presence of NaOH to provide compound 4a in 73%
yield. The zwitterionic-type compound 5a was obtained by one
step reaction of compound 4a and 1,3-propanesultone in dried
* Corresponding author. Tel.: +86 21 64253881; fax: +86 21 64253881.
E-mail address: wanglimin@ecust.edu.cn (L.-M. Wang).
0022-1139/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2009.02.014

W. Shen et al. / Journal of Fluorine Chemistry 130 (2009) 522–527
523
Table 1
Screening of Brønsted acid catalyst for synthesis of 7a in water.
Scheme 1.
acetone. Finally, acidification of compound 5 with p-toluenesul-
fonic acid (PTSA) in refluxing ethanol gave the final product 6a.
The synthesis of double fluorotailed acidic imidazolium salts 6b
was more or less the same as 6a (Scheme 3). 2,20-Biimidazole is an
intriguing biaryl molecule which is prepared from glyoxal and
ammonium acetate according to the literature elsewhere [14].
Alkylation of 2,20-biimidazole with 3-perfluorooctyl-1-iodopro-
pane occurred at N-1 and N-10 to form 1,10-di(1H,1H,2H,2H,3H,3H-
perfluoroundecyl)-2,20-biimidazole 4b in modest yields. Then
under the nucleophlic attack of 4b, 1,3-propanesultone underwent
ring-opening reaction to afford zwitterion 5b. Then, acidification of
compound 5b with p-toluenesulfonic acid (PTSA) in refluxing
ethanol gave the final product 6b.
Entry
Cat.
Amount (mol%)
Time (h)
Yield (%)a
1
PTSA
2
6
6
6
6
6
4
4
4
4
4
4
18
2
SDS + PTSA
2 + 2
2
29
3
C11H23COOH
Trace
31
4
C7F15COOH
2
5
DBSA
6a
2
41
6
1
53
7
6a
2
71
8
6b
1
73
9
6b
1.5
2
86
10
11
6b
87
84,81,82b
6b
1.5
Washing 6a and 6b with toluene or diethyl ether results in no
extraction of free PTSA (soluble in either liquid). This behavior was
consistent with the donor acid being fully incorporated into the IL
a
Isolated yields.
b
Catalytic system was reused for three times.
Scheme 2.
Scheme 3.

524
W. Shen et al. / Journal of Fluorine Chemistry 130 (2009) 522–527
Table 2
Synthesis of different 1,8-dioxo-9,10-diaryl-decahydroacridines in the presence of 6b in watera
.
Entry
R1
R2
Product
Yield (%)b
Mp (8C)
Lit. (8C)
1
H
4-CH3
4-CH3
4-CH3
4-CH3
4-CH3
4-CH3
4-CH3
4-CH3O
4-CH3O
4-CH3O
4-CH3O
H
7a
7b
7c
7d
7e
7f
86
87
84
86
83
91
81
79
87
90
85
85
86
85
260–262
292–294
281–283
269–271
309–311
283–284
250–252
215–217
238–241
210–211
251–252
203–205
–
262–263 [9]
296–297 [15]
282–283 [9]
273–274 [9]
315–317 [9]
285–286 [9]
251–253 [15]
2
4-CH3
4-CH3O
4-Cl
3-Cl
3-NO2
3,4-Cl2
H
3
4
4
5
6
7g
7h
7i
7
8
4-CH3
4-CH3O
4-Cl
H
9
7j
10
11
12
13
7k
8a
8a
8a
208–209 [16]
H
4-Cl
–
–
H
4-NO2
–
a
All the reaction were carried out with 1.5 mol% of 6b in water.
b
Isolated yields.
structure, rather than remaining simply mixtures of added strong
acid with dissolved zwitterions, in which case some retention of
premixing characteristics.
2.2. Synthesis of 1,8-dioxo-decahydroacridine derivatives
In a typical general experimental procedure, a solution of an
aromatic aldehyde, 5,5-di- methyl-1,3-cyclohexanedione and
p-toluidine in water was heated under refluxing water in the
presence of various Brønsted acid for a certain period of time
required to complete the reaction. The results were summarized in
Table 1.
It was found that with only 1 mol% of 6a, the reaction finished
within 4 h and afforded modest yield which was even higher than
that of p-dodecylbenzenesulfonic acid (DBSA), a Brønsted acid–
surfactant combined catalyst. Owned two sulfonic acid groups,
The Brønsted acidic imidazolium salts containing perfluor-
oalkyl tails 6a and 6b are stable in atmosphere with weak
absorption of moisture. Both of them show good solubility in
water. As a matter of fact, fluorous compounds 6a and 6b have
potential use as surfactant, antimicrobial or Brønsted acidic
catalyst which must be much more superior than their hydroalk-
yled counterparts. Here we first investigated their catalytic
activities for three-component synthesis of 1,8-dioxo-decahy-
droacridine derivatives in water.
Scheme 4.

W. Shen et al. / Journal of Fluorine Chemistry 130 (2009) 522–527
525
compound 6b was two more times effective than 6a. With only
1.5 mol% amounts, 6b provided as high as 86% yield. Further study
showed that use of just 1.5 mol% of 6b was sufficient to provided
satisfied yield in 4 h. An increase in the amount of catalyst did not
improve the result to any great extent. After the reaction was
completed, the product would congregate to form a hard lump.
Then, the separation of the product could simply be carried out by
decanting the supernatant liquid which could be recycled. Thus,
the catalyst could be reused for several times for the synthesis of 7a
without significant loss of activity.
After optimizing the reaction conditions, the catalytic system
was applied to synthesize structurally diverse 1,8-dioxo-9,10-
diaryl-decahydroacridine derivatives. The results were summarized
in Table 2 which showed that aromatic amines substituted with
electron-donating group gave expected molecules 7, while the ones
substituted with electron-withdrawing group or none gave
compound 8. The reason may be that aromatic amines substituted
with electron-withdrawing group or none did not have enough
nucleophilicity so the reaction stopped at Michael adduct stage and
the adducts are quite readily cyclized to afford octahydroxanthones
8a (Scheme 4). The effect of electron and the nature of substituents
on the ring of aromatic aldehydes did not show expected strong
effects in terms of yields under these reaction conditions.
Benzaldehyde and other aromatic aldehydes were employed and
they were found to react well to give the corresponding 1,8-dioxo-
9,10-diaryl-decahydroacridine in good yields.
White solid; Mp: 48–50 8C; 1H NMR (400 MHz, CDCl3):
= 2.04–2.14 (m, 4H), 4.06 (t, J = 6.6 Hz, 2H), 6.92 (s, 1H), 7.10
d
(s, 1H), 7.48 (s, 1H); MS (EI) m/z 528 (M+). Anal. Calcd for
C
14H9F17N2: C, 31.83; H, 1.72; N, 5.30. Found: C, 31.78; H, 1.78; N,
5.24.
4.2.2. Single fluorotailed zwitterionic compound (5a)
Compound 4 (1.12 g, 2.1 mmol) was dissolved in acetone (4 ml),
and then 1,3-propane sultone (0.26 g, 2.1 mmol) was added to the
solution. The solution was stirred under dry nitrogen at room
temperature for 72 h. The insoluble zwitterion was separated by
filtration. It was further recrystallized from ethanol to give the pure
product (0.71 g, 51%).
White solid; Mp 240–241 8C; 1H NMR (400 MHz, CD3OD):
= 2.12–2.21 (m, 2H), 2.24–2.43 (m, 4H), 2.84 (t, J = 7.0 Hz, 2H),
3.47 (t, J = 7.8 Hz, 2H), 4.36 (t, J = 7.2 Hz, 2H), 7.72 (d, J = 2.0 Hz, 1H),
7.74 (d, J = 1.6 Hz, 1H), 9.07 (s, 1H). MS (FAB) m/z: 651 [M+H]. Anal.
Calcd for C17H15F17N2O3S: C, 31.40; H, 2.32; N, 4.31. Found: C,
31.49; H, 2.38; N, 4.40.
d
4.2.3. Single fluorotailed Brønsted acidic imidazolium salts (6a)
In a 25 ml flask equimolar quantities of PTSA hydrate and the
zwitterion 5 was dissolved in 10 ml ethanol, the mixture was
heated to reflux for 2 h and then cooled to room temperature. The
solvent was removed in reduced pressure, and the residue was
washed repeatedly with toluene and ether to remove nonionic
residues, and dried in vacuum. The product was formed
quantitatively with high purity.
3. Conclusions
White solid; Mp: 127–129 8C; 1H NMR (400 MHz, CD3OD):
In summary, a novel type of Brønsted acidic imidazolium salts
containing perfluoroalkyl tails was prepared. With little loading,
the acidic imidazolium salts served as a highly effective catalyst for
three-component one-pot synthesis of 1,8-dioxo-9,10-diaryl-
decahydroacridines in water in good to excellent yields. The
mother liquid containing catalyst could be easily recycled and
reused without obvious loss of activities. Further studies of other
use for compound 6a and 6b are in progress.
d = 2.08 (m, 4H), 2.14 (m, 2H), 2.32 (s, 3H), 2.50 (t, J = 7.0 Hz, 2H),
2.71 (t, J = 7.8 Hz, 2H), 4.12 (t, J = 7.2 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H),
7.36 (s, 1H), 7.56 (s, 1H), 7.65 (d, J = 8.8 Hz, 2H), 8.92 (s, 1H); 19F
NMR (376 MHz, CD3OD):
d
= ꢁ80.74 (t, J = 7.5 Hz, 3F), ꢁ114.22 (t,
J = 15.0 Hz, 2F), ꢁ121.89 (m, 6F), ꢁ122.70 (s, 2F), ꢁ123.41 (s, 2F),
ꢁ126.08 (s, 2F); ESI-MS: 651.06 [cation]+. Anal. Calcd for
C24H23F17N2O6S2: C, 35.04; H, 2.82; N, 3.41. Found: C, 35.11; H,
2.76; N, 3.48.
4. Experimental
4.2.4. 1,10-di(1H,1H,2H,2H,3H,3H-perfluoroundecyl)-2,20-
biimidazole (4b)
4.1. Methods and apparatus
Following the general procedure for N-alkylation described for
compound 4a, two equivalents of 3 was used, and the crude
product was purified by chromatography (CH2Cl2/CH3OH, 20:1) to
afford 4b (56%).
Melting points were determined on a Kofler hot plate. 1H NMR
spectra were recorded on a BRUKER AM 400 (400 MHz) using TMS
as internal standard. 19F NMR spectra were recorded on a BRUKER
WP-500SY (376 MHz) spectrometer and were taken with CFCl3 as
internal standard. Coupling constants (J) are given in Hz. Elemental
analysis was carried out by using a Perkin-Elmer 2400 CHNS
analyzer. All solvents were distilled and dried according to the
standard procedures. All the chemicals were of reagent grade and
were used without further purification.
White solid; Mp: 105–107 8C; 1H NMR (400 MHz, CDCl3):
d
= 2.06–2.14 (m, 8H), 4.65 (t, J = 6.4 Hz, 4H), 6.99 (s, 2H), 7.12 (s,
2H); MS (FAB) m/z: 1055 [M+H]+. Anal. Calcd for C28H16F34N4: C,
31.89; H, 1.53; N, 5.31. Found: C, 31.81; H, 1.62; N, 5.27.
4.2.5. Double fluorotailed zwitterionic compound (5b)
Following the general procedure described for compound 5a,
three equivalents of 1,3-propanesultone were used to give 5b as a
white solid (53%).
4.2. Synthesis of the Brønsted acidic IL 6
White solid; Mp: 281–283 8C; 1H NMR (400 MHz, CD3OD):
4.2.1. 1-(1H,1H,2H,2H,3H,3H-perfluoroundecyl)-1H-imidazole (4a)
d = 2.12–2.21 (m, 4H), 2.24–2.43 (m, 8H), 2.84 (t, J = 7.0 Hz, 4H),
3.47 (t, J = 7.8 Hz, 4H), 4.36 (t, J = 7.2 Hz, 4H), 7.47 (d, J = 2.0 Hz, 2H),
7.58 (d, J = 1.6 Hz, 2H); MS (FAB) m/z: 1299 [M+H]. Anal. Calcd for
In a 25 ml flask imidazole (3.4 mmol, 0.23 g), 6 ml DMF and 0.5 ml
of 40% aqueous NaOH were stirred for 1 h. The mixture turned
brown after which 3-perfluorooctyl-1-iodopropane 3 (3.7 mmol,
2.20 g) dissolved in DMF (3 ml) was added slowly. The mixture
was stirred overnight at room temperature. The reaction crude
was poured into H2O (30 ml), extracted with chloroform
(3 ꢀ 20 ml). The combined organic layer was washed with H2O
(3 ꢀ 20 ml), dried by Na2SO4. After evaporating the solvent, the
residue was chromatographed on silica gel. Elution with CH2Cl2/
CH3OH (25:1) afforded the pure product (1.31 g, 73%).
C34H28F34N4O6S2: C, 31.44; H, 2.17; N, 4.31. Found: C, 31.51; H,
2.09; N, 4.36.
4.2.6. Double fluorotailed Brønsted acidic imidazolium salts (6b)
Following the general procedure described for compound 6a,
two equivalents of PTSA were used to give 6b in quantitative yield.
White solid; Mp: 157–159 8C; 1H NMR (400 MHz, CD3OD):
d
= 2.11–2.23 (m, 4H), 2.26–2.43 (m, 8H), 2.35 (s, 6H), 2.84 (t,
J = 7.0 Hz, 4H), 3.47 (t, J = 7.8 Hz, 4H), 4.36 (t, J = 7.2 Hz, 4H), 7.32 (s,

526
W. Shen et al. / Journal of Fluorine Chemistry 130 (2009) 522–527
4H), 7.57 (d, J = 2.0 Hz, 2H), 7.66 (s, 4H), 7.74 (d, J = 1.6 Hz, 2H); 19
NMR (376 MHz, CD3OD):
J = 15.0 Hz, 4F), ꢁ122.30 (m, 4F), ꢁ122.41 (m, 8F), ꢁ123.25 (s, 4F),
ꢁ123.96 (s, 4F), ꢁ126.64 (s, 4F); ESI-MS: 650.43 [cation]2+. Anal.
Calcd for C48H44F34N4O12S4: C, 35.09; H, 2.70; N, 3.41. Found: C,
35.13; H, 2.76; N, 3.38.
F
(400 MHz, CDCl3): d = 0.82 (s, 6H), 0.95 (s, 6H), 1.83 (d,
d
= ꢁ81.46 (t, J = 7.5 Hz, 6F), ꢁ113.52 (t,
J = 18.0 Hz, 2H), 2.04–2.21 (m, 6H), 2.43 (s, 3H), 3.92 (s, 3H),
5.21 (s, 1H), 6.79 (d, J = 8.4 Hz, 2H), 7.09 (d, J = 7.2 Hz, 2H), 7.33 (t,
J = 4.8 Hz, 4H); MS (EI) m/z 469 (M+). Anal. Calcd for C31H35NO3: C,
79.28; H, 7.51; N, 2.98. Found: C, 79.33; H, 7.47; N, 2.87.
3,3,6,6-Tetramethyl-1,8-dioxo-9-(4-methoxyphenyl)-10-(4-meth-
oxyphenyl)-decahydroacridine (7j). IR (KBr): 3077, 2980, 2926,
2865, 1645, 1582, 1474, 1387, 1152, 1135 cmꢁ1 1H NMR
;
4.3. General procedure for the preparation of 7
(400 MHz, CDCl3):
d = 0.81 (s, 6H), 0.96 (s, 6H), 1.86 (d,
A mixture of an aromatic aldehyde (1.0 mmol), 5,5-dimethyl-
1,3-cyclohexanedione (2.0 mmol), an aromatic amine (1.0 mmol)
and compound 6b (1.5 mol%) in water (8 ml) was stirred at reflux
for 4 h. After completion of the reactions, the mixture was cooled to
r.t. and solid was filtered off and washed with H2O (40 ml) and the
crude products were obtained. The crude products were purified
by recrystallization from EtOH. The mother solution containing of
the catalyst could be reused again.
J = 18.0 Hz, 2H), 2.04–2.22 (m, 6H), 3.75 (s, 3H), 3.92 (s, 3H),
5.21 (s, 1H), 6.78 (d, J = 7.8 Hz, 2H), 7.03 (d, J = 6.8 Hz, 2H), 7.13 (d,
J = 8.4 Hz, 2H), 7.34 (t, J = 7.2 Hz, 2H); MS (EI) m/z 485 (M+). Anal.
Calcd for C30H32ClNO2: C, 76.67; H, 7.26; N, 2.88. Found: C, 76.74;
H, 7.37; N, 2.79.
3,3,6,6-Tetramethyl-1,8-dioxo-9-(4-chlorophenyl)-10-(4-methox-
yphenyl)-decahydroacridine (7k). IR (KBr): 3024, 2973, 2925, 2885,
1640, 1578, 1535, 1460, 1305, 1150 cmꢁ1 1H NMR (400 MHz,
;
The spectral (1H NMR and MS) and analytical data of all the
compounds are given below. Among which 7h–k were unknown
compounds.
3,3,6,6-Tetramethyl-1,8-dioxo-9-benzene-10-(4-methylphenyl)-
decahydroacridine (7a). 1H NMR (400 MHz, CDCl3):
d = 0.82 (s, 6H),
CDCl3): d = 0.82 (s, 6H), 0.97 (s, 6H), 1.86 (d, J = 17.4 Hz, 2H), 2.06–
2.23 (m, 6H), 3.93 (s, 3H), 5.25 (s, 1H), 7.05 (d, J = 7.8 Hz, 2H), 7.20
(t, J = 7.6 Hz, 2H), 7.25 (m, 2H), 7.42 (d, J = 7.2 Hz, 2H); MS (EI) m/z
489 (M+). Anal. Calcd for C30H32ClNO3: C, 73.53; H, 6.58; N, 2.86.
Found: C, 73.46; H, 6.71; N, 2.88.
0.95 (s, 6H), 1.89 (d, J = 16.0 Hz, 2H), 2.05–2.21 (m, 6H), 2.50 (s, 3H),
5.34 (s, 1H), 7.11 (d, J = 6.4 Hz, 2H), 7.18–7.26 (m, 5H), 7.36 (d,
J = 6.4 Hz, 2H); MS (EI) m/z 439 (M+).
3,3,6,6-Tetramethyl-1,8-dioxo-9-(4-methylphenyl)-10-(4-
methylphenyl)-decahydroacridine (7b). 1H NMR (400 MHz, CDCl3):
3,3,6,6-Tetramethyl-1,8-dioxo-9-benzene-octahydroxanthene
(8a). 1H NMR (400 MHz, CDCl3):
d = 1.10 (s, 6H), 1.23 (s, 6H), 2.30–
2.48 (m, 8H), 5.54 (s, 1H), 7.10 (d, J = 8.4 Hz, 2H), 7.17 (t, J = 7.2 Hz,
1H), 7.25–7.28 (m, 2H); MS (EI) m/z 350 (M+). Anal. Calcd for
23H26O3: C, 78.83; H, 7.48. Found: C, 78.74; H, 7.59.
C
d
= 0.83 (s, 6H), 0.95 (s, 6H), 1.83 (d, J = 17.4 Hz, 2H), 2.05–2.21 (m,
6H), 2.49 (s, 3H), 2.61 (s, 3H), 5.23 (s, 1H), 6.82 (d, J = 8.4 Hz, 2H),
7.11 (d, J = 7.6 Hz, 2H), 7.32 (t, J = 8.4 Hz, 4H); MS (EI) m/z 453 (M+).
3,3,6,6-Tetramethyl-1,8-dioxo-9-(4-methoxyphenyl)-10-(4-
Acknowledgements
This project was financially supported by the National Nature
Science Foundation of China (20672035) and Key Laboratory of
Organofluorine Chemistry, Shanghai Institute of Organic Chem-
istry, Chinese Academy of Sciences.
methylphenyl)-decahydroacridine (7c). 1H NMR (400 MHz, CDCl3):
d
= 0.81 (s, 6 H), 0.94 (s, 6H), 1.83 (d, J = 18.0 Hz, 2H), 2.04–2.21 (m,
6H), 2.48 (s, 3H), 3.75 (s, 3H), 5.21 (s, 1H), 6.79 (d, J = 8.4 Hz, 2H),
7.09 (d, J = 7.2 Hz, 2H), 7.33 (t, J = 4.8 Hz, 4H); MS (EI) m/z 469 (M+).
3,3,6,6-Tetramethyl-1,8-dioxo-9-(4-chlorophenyl)-10-(4-methyl-
phenyl)-decahydroacridine (7d). 1H NMR (400 MHz, CDCl3):
d = 0.80
References
[1] (a) P. Wasserscheid, W. Keim, Angew. Chem., Int. Ed. 39 (2000) 3773–3789;
(b) T. Welton, Chem. Rev. 99 (1999) 2071–2083;
(s, 6H), 0.94 (s, 6H), 1.83 (d, J = 17.4 Hz, 2H), 2.05–2.21 (m, 6H), 2.49
(s, 3H), 5.23 (s, 1H), 7.08 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 7.6 Hz, 2H),
7.36 (t, J = 8.4 Hz, 4H); MS (EI) m/z 473 (M+).
3,3,6,6-Tetramethyl-1,8-dioxo-9-(3-chlorophenyl)-10-(4-methyl-
phenyl)-decahydroacridine (7e). 1H NMR (400 MHz, CDCl3):
d = 0.84
(s, 6H), 0.92 (s, 6H), 1.84 (d, J = 16.8 Hz, 2H), 2.08–2.24 (m, 6H), 2.48
(s, 3H), 5.36 (s, 1H), 7.12 (s, 1H), 7.18 (d, J = 7.6 Hz, 2H), 7.22–7.30
(m, 3H), 7.36 (d, J = 6.4 Hz, 2H); MS (EI) m/z 473 (M+).
3,3,6,6-Tetramethyl-1,8-dioxo-9-(3-nitrophenyl)-10-(4-methyl-
phenyl)-decahydroacridine (7f). 1H NMR (400 MHz, CDCl3):
d = 0.80
(s, 6H), 0.95 (s, 6H), 1.89 (d, J = 16.2 Hz, 2H), 2.04–2.21 (m, 6H), 2.53
(s, 3H), 5.40 (s, 1H), 7.12 (d, J = 6.4 Hz, 2H), 7.23–7.32 (m, 4H), 7.34
(d, J = 6.4 Hz, 2H); MS (EI) m/z 484 (M+).
3,3,6,6-Tetramethyl-1,8-dioxo-9-(3,4-dichlorophenyl)-10-(4-
methylphenyl)-decahydroacridine (7g). 1H NMR (400 MHz, CDCl3):
(c) R. Sheldon, Chem. Commun. (2001) 2399–2407;
(d) J. Dupont, R.F. de Souza, P.A.Z. Suarez, Chem. Rev. 102 (2002) 36670–43691.
[2] (a) V.I. Parvulescu, C. Hardacre, Chem. Rev. 107 (2007) 2615–2665;
(b) M. Haumann, A. Riisager, Chem. Rev. 108 (2008) 1474–1497;
(c) R. Sebesta, I. Kmentova, S. Toma, Green Chem. 10 (2008) 484–496.
[3] (a) W.S. Miao, T.H. Chan, Acc. Chem. Res. 39 (2006) 897–908;
(b) W.S. Miao, T.H. Chan, Adv. Synth. Catal. 348 (2006) 1711–1718;
(c) J.Y. Huang, M. Lei, Y.G. Wang, Tetrahedron Lett. 47 (2006) 3047–3050;
(d) S.D. Yang, L.Y. Wu, Z.Y. Yan, Z.L. Pan, Y.M. Liang, J. Mol. Catal. A: Chem. 268
(2007) 107–111;
(e) L.Y. Wu, Z.Y. Yan, Y.X. Xie, Y.N. Liu, Y.M. Liang, Tetrahedron: Asmmetry 18
(2007) 2086–2090;
(f) S. Doherty, P. Goodrich, C. Hardcare, J.G. Knight, M.T. Nguyen, C. Paun, Adv.
Synth. Catal. 349 (2007) 951–963;
(g) J. Vitz, D.H. Mac, S. Legoupy, Green Chem. 9 (2007) 431–433;
(h) A.K. Pathak, C.K. Yerneni, Z. Young, V. Pathak, Org. Lett. 10 (2008) 145–148;
(i) S. Doherty, P. Goodrich, C. Hardcare, C. Paun, Adv. Synth. Catal. 350 (2008)
295–302.
d
= 0.81 (s, 6H), 0.92 (s, 6H), 1.89 (d, J = 16.0 Hz, 2H), 2.06–2.24 (m,
[4] (a) J.H. Davis, Chem. Lett. 33 (2004) 1072–1077;
(b) S. Lee, Chem. Commun. (2006) 1049–1063;
6H), 2.54 (s, 3H), 5.38 (s, 1H), 6.89–6.93 (m, 2H), 7.18 (d, J = 7.6 Hz,
2H), 7.24 (s, 1H), 7.39 (d, J = 8.4 Hz, 2H); MS (EI) m/z 507 (M+).
3,3,6,6-Tetramethyl-1,8-dioxo-9-benzene-10-(4-methoxyphe-
nyl)-decahydroacridine (7h). IR (KBr): 3062, 2960, 2875, 1665,
(c) A. Winkel, P. Reddy, R. Wilhelm, Synthesis (2008) 999–1016.
[5] (a) D. Fang, J. Luo, X. Zhou, Z. Ye, Z. Liu, J. Mol. Catal. A: Chem. 274 (2007) 208–
211;
(b) M. Lombardo, F. Pasi, C. Trombini, Green Chem. 9 (2007) 321–322;
(c) P.S. Kulkarni, L.C. Branco, J.G. Crespo, Chem. Eur. J. 13 (2007) 8470–8477;
(d) A. Ouadi, O. Klimchuk, C. Gaillard, Green Chem. 9 (2007) 1160–1162;
(e) W. Chen, Y.Y. Zhang, L.B. Zhu, J. Am. Chem. Soc. 129 (2007) 13879–13886;
(f) L. Yadav, R. Patel, V.P. Srivastava, Synlett (2008) 583–585;
(g) S. Hanelt, J. Liebscher. Synlett (2008) 1058–1060.
1588, 1490, 1395, 1126 cmꢁ1; 1H NMR (400 MHz, CDCl3):
d = 0.80
(s, 6H), 0.95 (s, 6H), 1.85 (d, J = 18.4 Hz, 2H), 2.05–2.21 (m, 6H), 3.92
(s, 3H), 5.27 (s, 1H), 7.04 (d, J = 7.8 Hz, 2H), 7.11 (t, J = 7.6 Hz, 3H),
7.25 (m, 2H), 7.42 (d, J = 7.2 Hz, 2H); MS (EI) m/z 455 (M+). Anal.
Calcd for C30H33NO3: C, 79.09; H, 7.30; N, 3.07. Found: C, 79.15; H,
7.28; N, 2.91.
3,3,6,6-Tetramethyl-1,8-dioxo-9-(4-methylphenyl)-10-(4-meth-
oxyphenyl)-decahydroacridine (7i). IR (KBr): 3058, 2983, 2930,
2895, 1653, 1582, 1485, 1378, 1170, 1145 cmꢁ1
[6] (a) R.J. Chorvat, K.J. Rorig, J. Org. Chem. 53 (1988) 5779–5781;
(b) N. Martin, M. Quinteiro, C. Seoane, L. Soto, A. Mora, M. Suarez, E. Ockoa, A.
Morals, J. Heterocyl. Chem. 32 (1995) 235–238;
(c) M. Suarez, A. Loupy, E. Salfran, L. Moran, E. Rolando, Heterocycles 51 (1999)
21–27.
[7] B. Das, P. Thirupathi, I. Mahender, V.S. Reddy, Y.K. Rao, J. Mol. Catal. A: Chem. 247
(2006) 233–239.
;
1H NMR

W. Shen et al. / Journal of Fluorine Chemistry 130 (2009) 522–527
527
[8] V.A. Chebanov, V.E. Saraev, K.M. Kobzar, S.M. Desenko, V.D. Orlov, E.A. Gura, Chem.
Heterocycl. Comp. 40 (2004) 475–479.
[13] J.M. Vincent, A. Rabion, V.K. Yachandra, R.H. Fish, Angew. Chem., Int. Ed. Engl. 36
(1997) 2346–2349.
[9] T.S. Jin, J.S. Zhang, T.T. Guo, A.Q. Wang, T.S. Li, Synthesis (2004) 2001–2005.
[10] W. Shen, L.M. Wang, H. Tian, J. Fluorine Chem. 129 (2008) 267–273.
[11] W. Shen, L.M. Wang, J.J. Feng, H. Tian, Tetrahedron Lett. 49 (2008) 4047–4049.
[12] H. Shao, W.D. Meng, F.L. Qing, J. Fluorine Chem. 125 (2004) 721–724.
[14] J.C. Xiao, B. Twamley, J.M. Shreeve, Org. Lett. 6 (2004) 3845–3847.
[15] X.S. Wang, M.M. Zhang, H. Jiang, D.Q. Shi, S.J. Tu, X.Y. Wei, Z.M. Zong, Synthesis
(2006) 4187–4199.
[16] A.N. Pyrko, Chem. Heterocycl. Comp. 32 (1996) 742–753.