A highly active FeNi3-SiO2 magnetic nanoparticles catalyst for the preparation of 4H-benzo[b]pyrans and Spirooxindoles under mild conditions

Article abstract of DOI:10.1007/s13738-013-0243-3

A green and efficient method for the synthesis of various 4H-benzo[b]pyrans and Spirooxindoles in the presence of FeNi₃-SiO₂ as the nanocatalyst at room temperature is reported. High catalytic activity and ease of recovery from the r

Full text of DOI:10.1007/s13738-013-0243-3

J IRAN CHEM SOC
DOI 10.1007/s13738-013-0243-3
ORIGINAL PAPER
A highly active FeNi –SiO magnetic nanoparticles catalyst
3
2
for the preparation of 4H-benzo[b]pyrans and Spirooxindoles
under mild conditions
Mohammad Ali Nasseri Seyed Mohsen Sadeghzadeh
•
Received: 2 October 2012 / Accepted: 7 March 2013
Ó Iranian Chemical Society 2013
Abstract A green and efficient method for the synthesis
of various 4H-benzo[b]pyrans and Spirooxindoles in the
presence of FeNi –SiO as the nanocatalyst at room tem-
ionic liquid [13] were found to catalyze these reactions, and
catalysis including ammonium chloride [14], ethylenedia-
mine diacetate [15], surfactant metal carboxylates [16], L-
proline [17], triethylbenzyl ammonium (TEBA) salt [18],
and b-cyclodextrin [19] can also catalyze the synthesis of
various Spirooxindoles. However, some of the reported
methods have the following drawbacks: for example, use of
expensive reagents, long reaction times, low yields of
products, and use of an additional microwave oven.
3
2
perature is reported. High catalytic activity and ease of
recovery from the reaction mixture using an external
magnet, and several reuse times without significant losses
in performance are additional eco-friendly attributes of this
catalytic system.
Keywords FeNi –SiO ꢀ 4H-benzo[b]pyrans ꢀ
Many solid catalysts have been traditionally synthesized
in nano size per se or as nano materials inside a porous
matrix. Silica has been employed as both supports and
catalysts [20–26]. Among these, silica has resurfaced to the
fore as a solid acid catalyst due to its important charac-
teristics such as, particle size, surface chemistry, particle
shape, surface area, and other properties that are over-
whelmingly used as nanocatalyst or support for dispersing
active centers and reagents [27–31]. Nanocatalysts have
also been widely used for the organic synthesis in both
homogeneous and heterogeneous conditions [32–35].
The superparamagnetic nanoparticles, whose flocculation
and dispersion can be reversibly controlled by applying a
magnetic field, were recently employed in the catalytic
applications and received the immense attractions as a new
type of the recyclable support matrix. In the absence of the
external magnetic field, superparamagnetic nanoparticles
can be well dispersed in a reaction solution, providing large
surface area, which can be readily accessed by substrate
molecules [36]. Most importantly, the MNP-supported cat-
alyst could be recollected by using an external magnet con-
veniently without filtration or centrifugation. We have used
these newly synthesized FeNi –SiO as a magnetically
3
2
Spirooxindoles ꢀ Magnetic nanoparticles (MNPs) ꢀ
Green chemistry ꢀ One-pot synthesis
Introduction
4
H-Benzo[b]pyrans and Spirooxindoles are an important
class of compounds which have received considerable
attention in recent years due to their wide range of biolog-
ical activities. Compounds with these ring systems have
diverse pharmacological activities [1–5]. Consequently,
numerous methods have been reported from the synthesis of
4
H-Benzo[b]pyrans. A variety of reagents such as, HMTAB
[
6], TEBA [7], RE(PFO)3 [8], NaBr [9], (S)-proline [10],
the use of microwave irradiation [11], KF-basic alumina
under ultrasound irradiation [12], and amino-functionalized
3
2
M. A. Nasseri (&) ꢀ S. M. Sadeghzadeh
recyclable nanocatalyst for the efficient one-pot synthesis of
H-Benzo[b]pyrans and Spirooxindoles at room temperature
with good to excellent yield (Schemes 1, 5).
Department of Chemistry, College of Sciences,
Birjand University, P.O. Box 97175-615, Birjand, Iran
e-mail: mohammadali.nasseri@yahoo.com
4
123

J IRAN CHEM SOC
Scheme 1 Synthesis of 4H-
benzo[b]pyrans from 1,3-
Diketones, aldehydes, and
malononitrile in the presence
R
O
O
O
of FeNi
3
–SiO
2
O
CN
FeNi -SiO
CN
3
2
+
H
+
Water, r.t.
CN
3
R
O
4
NH2
1
2
Experimental
28 wt % concentrated ammonia aqueous solution
(
NH ꢀH O), followed by the addition of 0.20 g of tetraethyl
3
2
Materials and methods
orthosilicate (TEOS). After vigorous stirring for 24 h, the
final suspension was repeatedly washed, filtered for several
times, and dried at 60 °C in the air (Fig. 1) [37].
Chemical materials were purchased from Fluka and Merck in
high purity. Melting points were determined in open capil-
laries using an Electrothermal 9100 apparatus and are
uncorrected. FTIR spectra were recorded on a VERTEX 70
spectrometer (Bruker) in the transmission mode, in spectro-
scopic grade KBr pellets for all the powders. The particle size
and structure of FeNi –SiO MNPs were observed by using a
Characterization of catalyst
TEM images of FeNi and FeNi –SiO MNPs are shown in
2
3
3
Fig. 2. The average size of FeNi MNPs is about 25 nm
3
(Fig. 2a). After being coated with a silica layer, the typical
core–shell structure of the FeNi –SiO MNPs can be
3
2
Philips CM10 transmission electron microscope operating at
00 kV. Powder X-ray diffraction data were obtained using
3
2
1
observed. The dispersity of FeNi –SiO MNPs is also
3 2
Bruker D8 Advance model with Cu ka radiation. NMR
spectra were recorded in DMSO on a Bruker Advance DRX-
improved, and the average size increases to about 50 nm
(Fig. 2b). Figure 3 shows the XRD pattern of FeNi –SiO
3
2
4
00 MHz instrument spectrometer using TMS as internal
nanoparticle particles synthesized with [N H ꢀH O]/
2
4
2
standard. The purity determination of the products and
reaction monitoring were accomplished by TLC on silica gel
polygram SILG/UV 254 plates. Mass spectra were recorded
on Shimadzu GCMS-QP5050 mass spectrometer.
[FeNi ] molar ratio of 24:1. It can be seen that three
3
characteristic peaks for (FCC)-FeNi3 (2h = 44.3, 51.5,
75.9) from (111) (200) and (220) planes, are obtained. No
XRD peaks for a-Fe (i.e., at 2h of 65.2) and (FCC)-Ni (i.e.,
at 2h of 44.5, 51.8, and 76.4) can be observed. Besides the
peak of FeNi , the XRD pattern of FeNi –SiO core–shell
General procedure for the preparation of FeNi3
nanoparticles
3
3
2
nanoparticles presented a broad featureless XRD peak at
low diffraction angle, which corresponded to the amor-
The synthesis procedure is illustrated as follows: (1)
phous state SiO shells (JCPDS card No. 29-0085).
2
0
.01 mol FeCl ꢀ4H O and 0.03 mol NiCl ꢀ6H O were
2
2
2
2
dissolved into 200-mL distilled water, followed by the
addition of PEG (1.0 g, MW 6000). (2) Sodium hydroxide
General procedure for the synthesis
of 4H-benzo[b]pyrans
(
NaOH) was added to the solution and the pH value was
controlled in the range 12 B pH B 13. (3) Different
amount of hydrazine hydrate (N H ꢀH O, 80 % concen-
A mixture of 1,3-Diketone (1 mmol), aldehyde (1 mmol),
malononitrile (1 mmol), and FeNi –SiO MNPs (0.0007 g)
2
4
2
3
2
tration) was added to the above suspension. The reaction
was continued for about 24 h at room temperature. During
this period, the pH value was adjusted by NaOH and kept
in water (5 mL) was stirred at room temperature for
10–20 min (the progress of the reaction was monitored by
TLC). After completion, the reaction mixture was filtered
in the range 12 B pH B 13. The black FeNi MNPs were
3
then rinsed several times with ionized water [37].
General procedure for the preparation of FeNi –SiO
3
2
nanoparticles
0
.02 mol of FeNi MNPs were dispersed in a mixture of
3
Fig. 1 Schematic illustration of the synthesis for FeNi –SiO2
3
nanoparticles
8
0 mL of ethanol, 20 mL of deioned water, and 2.0 mL of
1
23

J IRAN CHEM SOC
3 3 2 3 2
Fig. 2 TEM images of a FeNi , b FeNi -SiO before use (b) and after reuse ten times. High agglomeration of FeNi –SiO can not be seen (c)
of product was observed. On the contrary, moderate yields
could be achieved when other organic solvents were
applied as the solvent (Table 1, entries 2–10). More strik-
ingly, we found that the reaction proceeded smoothly in
water and gave the desired product of 97 % yield (Table 1,
entry 1).
At this stage, the amount of catalyst necessary to pro-
mote the reaction efficiently was examined (Fig. 4). It was
observed that the variation for FeNi –SiO MNP had an
3
2
effective influence. The best amount of FeNi –SiO MNP
2
3
is 0.0007 g which afforded the desired product in 97 %
yields (Fig. 4).
It is important to note that the magnetic property of
FeNi –SiO facilitates its efficient recovery from the reac-
Fig. 3 XRD pattern of FeNi
[
3 2
–SiO MNPs synthesized with
3
2
N
2
H
4
ꢀH O]/[FeNi ] ratio of 24:1
2
3
tion mixture during work-up procedure (Fig. 5). The activity
of the recycled catalyst was also examined under the opti-
mized conditions. After the completion of reaction, the
catalyst was separated by an external magnet, washed with
methanol, and dried at the pump. The recovered catalyst was
reused for ten consecutive cycles without any significant
loss in catalytic activity (Fig. 6). The FeNi –SiO before use
and the precipitate washed with H O (5 mL) and EtOH
2
(
5 mL) to afford pure 4H-benzo[b]pyrans.
General procedure for the synthesis of Spirooxindoles
3
2
A mixture of 1,3-Diketone (1 mmol), isatin (1 mmol),
malononitrile (1 mmol), and FeNi –SiO MNPs (0.0007 g)
does not result in the change of the morphology and size of
the obtained FeNi –SiO after reuse (Fig. 2c).
3
2
3
2
in water (5 mL) was stirred at room temperature for
0–15 min. The precipitated solid was filtered, washed
To show the unique catalytic behavior of FeNi –SiO
3 2
1
MNPs in these reactions, we have performed one-pot
reaction of benzaldehyde (compound 2a), 5,5-dimethyl-
cyclohexane-1,3-dione (compound 1a), and malononitrile
(compound 3) in the presence of Na SeO , Tetra-methyl
with water followed by washing with a mixture of ethyl-
acetate/hexane (20:80), and then dried under vacuum. The
product obtained was further purified by recrystallization
from hot ethanol.
2
4
ammonium hydroxide, Nanosized Ce Mg Zr
x
O ,
2
1
1 - x
NaBr, and MgO (Table 2). As it is evident from Table 2,
FeNi –SiO is the most effective catalyst for this purpose,
3
2
Results and discussion
leading to the formation of 4H-benzo[b]pyran (compound
a) in a lesser time with better yield and reduces the
4
The effect of solvent on this reaction was examined and the
obtained results are summarized in Table 1. In n-Hexane,
amount of catalyst. The increased catalytic activity of
FeNi –SiO over the another catalysts may be attributed to
3
2
CHCl , and Dioxane (Table 1, entries 12–14), only a trace
3
the higher surface area of SiO2.
123

J IRAN CHEM SOC
Table 1 Solvent screening for the reaction between 5,5-dimethyl-
cyclohexane-1,3-dione, benzaldehydes, and malononitrile
100
9
8
a
Entry
Solvent
Yield (%)
9
6
1
2
3
4
5
6
7
8
9
H
2
O
97
9
4
EtOH
CH CN
THF
CH Cl
78
9
2
3
60
9
0
40
40
88
2
2
Toluene
EtOAC
MeOH
20
1
2
75
3
4
85
5
6
DMF
64
Reuse
7
8
9
1
1
1
1
1
0
1
2
3
4
DMSO
70
1
0
Solvent free
n-Hexane
76
Trace
Trace
Trace
Fig. 6 Reuses performance of the catalysts
CHCl
3
Dioxane
The catalytic activity of the Nano–FeNi –SiO particles
3
2
Reaction conditions: 5,5-dimethyl-cyclohexane-1,3-dione (1 mmol),
malononitrile (1 mmol), benzaldehyde (1 mmol), solvent (10 mL),
FeNi –SiO (0.001 g) at room temperature for 40 min
was compared with that of the Bulk–FeNi –SiO . For this
3
2
purpose, the reactions were carried out separately at room
temperature in water with both the catalysts for the
appropriate time (Table 3). The aliquots of the reaction
mixture were collected periodically at an interval of 5 min.
Table 3 shows the variation of the percentage preparation
of 4H-benzo[b]pyran with time, when Nano–FeNi –SiO
3
2
a
Isolated yields
3
2
and Bulk–FeNi –SiO were employed as catalysts. It is
3
2
evident that, the catalytic activity of the Nano–FeNi –SiO
3
2
is much greater than that of the Bulk–FeNi –SiO . After
3
2
1
4
5 min, Nano–FeNi –SiO showed 97 % preparation of
3 2
H-benzo[b]pyran as compared to 36 % with Bulk–FeNi3–
SiO . The increased catalytic activity of Nano–FeNi –SiO
2
2
3
over the Bulk–FeNi –SiO may be attributed to the higher
3
2
surface area of SiO2.
The catalytic activity of the FeNi –SiO nanoparticles
3
2
was compared with that of the Nano–SiO and Nano–
2
FeNi . For this purpose, the preparation of 4H-benzo[b]-
3
3 2
Fig. 4 Effect of increasing amount of FeNi –SiO on the preparation
pyran was carried out separately at room temperature in
of 4H-benzo[b]pyran (reaction of 5,5-dimethyl-cyclohexane-1,3-
dione, benzaldehyde and malononitrile in the presence of FeNi
SiO at room temperature in water)
water with three nanoparticles. After 15 min, FeNi –SiO
2
3
–
3
2
nanoparticles and Nano–SiO showed 97 % preparation of
2
Fig. 5 a Reaction mixture.
b Separation of FeNi –SiO
3
2
from the reaction mixture by an
external magnetic field
1
23

J IRAN CHEM SOC
Table 2 Effect of various
catalysts and solvent conditions
on the synthesis of 4H-
benzo[b]pyran
a
Entry Catalyst
Amount of catalyst Solvent
mol %)
Temp (°C)
Time
(min)
Yield
(%)
(
1
2
3
Na SeO
2
4
0.53
10
Water/EtOH Refluxed
(
60
97 [38]
1:1)
Tetra-methyl
ammonium hydroxide
H
2
O
Room
temperature
30–120 81 [39]
Nanosized Ce
1
Mg
x
Zr1- 34.8
EtOH
Reflux
35
91 [40]
x 2
O
4
5
NaBr
MgO
0.4
0.5
Neat
Neat
(MW)
Room
10
10
95 [41]
75 [42]
temperature
Room
temperature
6
FeNi –SiO
3
2
0.3
H
2
O
15
97
a
Isolated yields
Table 3 Comparison of the catalytic activity of Nano–FeNi
with Bulk–FeNi –SiO
3
–SiO
2
spectroscopic data of the products confirmed that these struc-
tures belong to octahydroxanthene (compound 5) (Scheme 3).
A mechanism for the reaction is outlined in Scheme 4.
The reaction occurs via initial formation of the cyano olefin
3
2
a
Entry Reaction time (min) Yield (%)
Nano–FeNi
SiO
3
–
3
Bulk–FeNi –
[A] from the condensation of aldehyde (1) and malono-
2
SiO
2
nitrile (2), which reacts with 1,3-Diketone (3) to give the
intermediate [B] which subsequently cyclises to afford the
desired compound (4). The nano silica in the first step plays
a key role in the cyclization process.
1
2
3
4
5
a
5
10
15
20
25
76
85
97
97
97
23
28
36
41
41
To further explore the potential of this protocol for
heterocyclic synthesis, we investigated one-pot reactions
involving 1,3-Diketone (compound 1), isatin (compound
Isolated yields
7), malononitrile (compound 3), and obtained Spirooxin-
doles (compound 6) in excellent yields (Scheme 5,
Table 5). A variety of isatin, both electron-donating and
electron-withdrawing groups on the aromatic ring, were
reacted with malononitrile and substituted 1,3-Diketones to
generate Spirooxindoles (compound 6). As can be seen
from Table 5, electronic effects and the nature of substit-
uents on the aromatic ring did not show strong obvious
effects in terms of yields under the reaction conditions. The
three-component cyclocondensation reaction proceeded
smoothly in water and was completed in 10–15 min; isatins
containing electron-withdrawing groups or electron-
donating were employed and reacted well to give the
desired products in excellent yields with high purity.
To further expand the scope of this approach, we
examined one-pot reactions involving acenaphthoquinone
(compound 8), instead of isatin (compound 7). Under these
conditions, a variety of desired spirochromenes (compound
9) was also produced in excellent yields (Scheme 6).
On the other hand, when ammonium acetate (compound
10) was treated as a substitute for malononitrile (compound
3) in this reaction and under similar conditions, not only a
highly prolonged time was required but also the products
were different. The spectroscopic data of the products
confirmed that these structures belong to spiroacridine
derivatives (compound 11a and b) (Scheme 7).
4
H-benzo[b]pyran as compared to 31 % with Nano–FeNi3.
The increased catalytic activity of FeNi –SiO nanoparti-
2
3
cles and Nano–SiO over the Nano–FeNi attributed to the
2
3
higher surface area of SiO and it is not arising from the
2
leached [Fe] species into the solution.
As can be seen from Table 4, the reaction of aromatic
aldehydes (compound 2) with malononitrile (compound 3)
and 1,3-diketones (compound 1) at room temperature in
water provided the corresponding 4H-benzo[b]pyran
derivatives (compound 4) in good yields. The results are
presented in Table 4 and indicate that aldehydes bearing
electron-withdrawing groups react more quickly than their
electron-donating aldehyde counterparts. For example,
aromatic aldehydes such as 4-chloro, 4-nitro, and 4-bromo
benzaldehydes react quickly with high-product yields in
comparison to 4-hydroxy, 4-methyl, and 4-methoxy benz-
aldehyde derivatives. The yield of 4H-benzo[b]pyrans
bearing group at ortho position on the aromatic ring is
lower than that of the 4H-benzo[b]pyrans bearing group at
para position on the aromatic ring (Scheme 2, Table 4).
0
On the other hand, when benzyl cyanide (compound 3 ) was
treated as a substitute for malononitrile in this reaction and
under similar conditions, not only a highly prolonged time was
required, but also the products were different. The
123

J IRAN CHEM SOC
3 2
Table 4 Synthesis of 4H-benzo[b]pyran derivatives catalyzed by FeNi –SiO
a,b
Entry
R
C
1,3-Diketone
Product
Time (min)
Yield (%)
mp (°C)
1
2
3
4
5
6
7
8
9
6
H
5
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1b
1b
1b
1b
1b
1b
1b
1c
1c
1c
1c
1c
4a
4b
4c
4d
4e
4f
15
10
15
20
10
10
10
15
20
20
10
20
15
10
10
20
10
10
20
20
10
20
15
10
20
20
10
97
98
96
92
97
95
95
93
91
92
97
91
96
97
96
92
96
94
92
92
96
93
96
97
92
91
98
228–230 [43]
207–209 [43]
135–137 [43]
223–225 [43]
179–180 [43]
222–223 [44]
200–202 [44]
152–154 [44]
201–202 [43]
205–206 [43]
192–194 [45]
199–201 [43]
239–241 [46]
226–229 [46]
213–215 [46]
214–216 [46]
235–236 [46]
196–198 [46]
193–195 [46]
234–236 [46]
213–215 [46]
168–170 [46]
193–195 [45]
173–175 [45]
180–182 [45]
140–142 [45]
183–185 [45]
4-ClC
2-Cl C
4-MeC
6 4
H
6 4
H
6
H
4
4-NO
2-NO
2
C
C
6
H
4
2
6
H
4
4-BrC
6
H
4
4
4g
4h
4i
2-BrC
6
H
4-MeOC
4-HOC
4-FC
4-Me
6 4
H
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
a
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
6
H
4
4j
6
H
4
4k
4l
2 6 4
NC H
C
6
H
5
4m
4n
4o
4p
4q
4r
4-ClC
2-ClC
6
H
4
4
6
H
6 4
4-MeC H
4-NO
2-NO
2
C
C
6
H
4
4
2
6
H
4-MeOC
4-HOC
4-FC
4-Me
6
H
4
4s
4t
6 4
H
6
H
4
4u
4v
4w
4x
4y
4z
2
NC
6
H
4
6 5
C H
4-ClC
4-MeC
4-MeOC
4-NO
H
6 4
6
H
4
6 4
H
0
2
C
6
H
4
4a
Reaction condition: benzaldehyde derivatives (1 mmol), 1,3-Diketones (1 mmol), malononitrile (1 mmol), FeNi
3
–SiO
2
(0.0007 g) at room
temperature in water
b
Yield refers to isolated product
Scheme 2 Synthesis of
derivatives 4 in the presence of
R
3 2
FeNi –SiO
O
O
O
O
CN
FeNi -SiO
CN
3
2
+
H
+
Water, r.t.
CN
3
R
O
4
NH2
1
2
O
O
O
O
O
O
O
1
a
1b
1c
1
23

J IRAN CHEM SOC
Scheme 3 Synthesis of
octahydroxanthene
O
O
O
5
O
O
CN
H
+
+
+
O
Ph
3/
1
2
O
Ph
O
4
NH2
Scheme 4 Suggested
mechanism for the preparation
of 4H-benzo[b]pyrans
SiO -FeNi3
2
O
O
FeNi -SiO2
3
CN
CN
+
H C
[2]
2
Ar
H
Ar
H
[
1]
FeNi -SiO2
3
Ar
O
O
O
Ar
CN
N
CN
R
R
R
C
O
R
OH
O
R
R
NH
[
3]
[A]
SiO -FeNi3
2
[B]
Ar
O
Ar
O
CN
CN
R
R
C
O
NH2
O
R
R
H HN
[4]
SiO -FeNi3
2
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J IRAN CHEM SOC
Scheme 5 Synthesis of
Spirooxindoles derivatives 6 in
the presence of Nano–SiO
2
O
O
O
O
O
R
NH2
NC
NC
FeNi3-SiO2
O +
+
Water, r.t
CN
N
O
H
N
H
1
a-d
7a-f
O
3
6a-l
O
O
O
O
O
O
O
O
1
a
1b
1c
1d
OH
OH
OH
N
H
O
N
O
O
O
Me
1
e
1f
1g
Table 5 Synthesis of Spirooxindoles from malononitrile, 1,3-dicarbonyl compounds, and isatins
a,b
Entry
R
1,3-Diketone
Product
Time (min)
Yield (%)
mp (°C)
1
2
3
4
5
6
7
8
9
H
1a
1b
1d
1c
1e
1f
6a
6b
6c
6d
6e
6f
15
15
15
15
15
15
15
10
10
15
10
15
96
97
93
95
94
95
93
92
94
95
95
92
[300 [47]
H
278–280 [48]
[300 [49]
H
H
271–273 [50]
[300 [51]
H
H
[300 [51]
H
1g
1a
1d
1d
1d
1d
6g
6h
6i
[300 [51]
CH
Br
Cl
3
275–278 [51]
260–263 [51]
256–259 [51]
270–272 [51]
217–219 [51]
1
1
1
a
0
1
2
6j
NO
2
6k
6l
OCH
3
Conditions: isatin (1 mmol), 1,3-diketone (1 mmol), malononitrile (1 mmol), and water (5 mL)
Isolated yields
b
Conclusions
temperature in water with high-product yields. This nano-
particle-based catalyst provides a new way for continuous
processes, because of its simple recyclability. From a sci-
entific point, our results expand the application of nano-
particles. This catalyst should be helpful to the development
of new catalytic systems.
In conclusion, the obtained results describe a novel, new,
and simple method for the synthesis of 4H-benzo[b]pyrans
and Spirooxindoles via one-pot, three-component reaction
using FeNi –SiO2 nanoparticles as catalyst at room
3
1
23

J IRAN CHEM SOC
Scheme 6 Synthesis of
spirochromenes using
acenaphthoquinone
H2N
O
O
O
NC
9
a
91%
O
O
O
O
1
a
NC
NC
+
+
or
H2N
O
O
O
NC
8
3
9
b
92%
O
O
1
b
O
Scheme 7 Synthesis of
spiroacridine
H
N
H
N
7
a
O
O
N
H
O
O
O
O
O
O
NH4OAC
or
or
+
+
O
O
NH
10
O
8
1
11a
5%
11b
8
82%
1
7. L. Yuling, C. Hui, S. Chunling, S. Daqing, J. Shunjun, J. Comb.
Chem. 12, 231 (2010)
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