One-pot three-component synthesis of the spiroacenaphthylene derivatives

Article abstract of DOI:10.1016/j.tet.2010.05.067

A facile and efficient one-pot three-component synthesis of the spiroacenaphthylene derivatives was achieved, via the reaction of acenaphthequinone, malononitrile/ethylcyanoacetate and various reagents including a-methylencarbonyl compounds/enols.

Full text of DOI:10.1016/j.tet.2010.05.067

Tetrahedron 66 (2010) 5345e5348
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One-pot three-component synthesis of the spiroacenaphthylene derivatives
*
Mina Saeedi, Majid M. Heravi , Yahya S. Beheshtiha, Hossein A. Oskooie
Department of Chemistry, School of Sciences, Alzahra University, PO Box 1993891176, Vanak, Tehran, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
A facile and efficient one-pot three-component synthesis of the spiroacenaphthylene derivatives was
Received 2 March 2010
Received in revised form 28 April 2010
Accepted 17 May 2010
achieved, via the reaction of acenaphthequinone, malononitrile/ethylcyanoacetate and various reagents
including a-methylencarbonyl compounds/enols.
Ó 2010 Elsevier Ltd. All rights reserved.
Available online 9 June 2010
Keywords:
Spiroacenaphthylene derivatives
Multicomponent reaction
Acenaphthenequinone
1. Introduction
a long time to be present in phytochemicals either in alkaloids,
lactones or terpenoids.7 Biological activities of spiro compounds
containing pyrans have also been proved. They also show good
activity as hypertensive agents.8 They have been the subject of
great interest as potential novel analgesic agents.9
The synthesis of heterocycles by multicomponent reactions of-
ten involves classic carbonyl condensation chemistry10,11 and basic
catalysts play important role in MCRs. Triethylamine is an efficient
and inexpensive base and its efficiency as a basic catalyst has been
explored frequently.12,13 The broad spectrum of applications of
acenaphthenequinone 1 and its derivatives as biologically active
compounds, dyes, etc.14 has prompted us to explore its reaction
In multicomponent reactions (MCRs), three or more reactants
come together in a single reaction vessel to form new products that
contain structural units of all the components. This type of reaction
becomes increasingly important in organic and medicinal chem-
istry because it allows to obtain highly sophisticated polyfunctional
molecules through simple one-pot procedures. Multicomponent
reactions have been successfully employed to generate highly di-
verse combinatorial libraries for high-throughput screening of bi-
ological and pharmacological activities. The use of three or more
building blocks in a one-pot, high-yield multicomponent reaction
leads to a wide structural and functional diversity combined with
excellent combinatorial efficiency. Over the past decade, industrial
and academic research has made powerful MCR strategies into one
of the most efficient and cost-effective tools for combinatorial
synthesis.1e3 The development of novel MCRs is an intellectually
challenging task since one has to consider not only the reactivity
match of the starting materials but also the reactivity of the in-
termediate molecules generated in situ, their compatibility and
their compartmentalization.4
with malononitrile/ethylcyanoacetate 2 and
compounds/enols 3 in MCR (Scheme 1).
a-methylencarbonyl
2. Results and discussion
In continuation of our investigations of the synthesis of novel
heterocyclic compounds and designing novel procedures in multi-
component reactions,15e18 we have developed an efficient protocol
for the solution phase synthesis of new spiroacenaphthylene de-
rivatives, through the three-component condensation of acenaph-
thequinone, malononitrile/ethylcyanoacetate and various reagents
Heterocycles containing the pyran ring are important targets in
synthetic and medicinal chemistry because this fragment is a key
moiety in numerous biologically active compounds and natural
products.5,6 Spiro compounds represent an important class of
naturally occurring substances characterized by highly pronounced
biological properties. The spiro functionality has been known for
including a-methylencarbonyl compounds/enols (Scheme 1).
During our work we found out that, Dabiri et al.19 reported the
synthesis of 4e and 4f through the three-component condensation
of acenaphthequinone, malononitrile/ethylcyanoacetate and
dimedon in the presence of ammonium salt. Herein, we wish to
reveal our results, using a wide variety of compounds 3 and
a straightforward procedure in the absence of complex and
expensive catalyst.
* Corresponding author. Tel.: þ98 21 88044051; fax: þ98 21 88041344; e-mail
address: mmh1331@yahoo.com (M.M. Heravi).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.05.067

5346
M. Saeedi et al. / Tetrahedron 66 (2010) 5345e5348
H2N
Table 1
O
Z
O
O
Synthesis of spiroacenaphthylene derivatives 4
O
CN
Z
Et3N
EtOH
Entry
Z
Reactant 3
Product
Time (h) Yielda (%)
O
1
CN
4
85
3
2
4
1
Z= CN, COOEt
O
O
O
O
2
3
COOEt
4.5
80
75
HN
NH
O
=
O
O
O
OH
CN
6
O
O
N
O
O
N
H
OH
4
5
6
7
CN
6
65
80
80
60
O
N
N
O
O
N
N
NO2
O
O
CN
4
O
Cl
NO2
Scheme 1. Three-component synthesis of spiroacenaphthylene derivatives.
COOEt
CN
4.5
8
The synthesis of 4 includes a two-step reaction: Knoevenagel
condensation to obtain unsaturated nitriles 5 from acenaph-
thenequinone 1 and malononitrile/ethylcyanoacetate 2 and in-
teraction of 5 with the active
a-methylencarbonyl compounds/
enols 3 catalyzed by triethylamine (Et3N).
A plausible mechanism for the reaction is shown in Scheme 2.
Compound 1 undergoes Knoevenagel condensation with malono-
nitrile/ethylcyanoacetate. Unsaturated nitriles 5 are formed very
easily in ethanol even in the absence of Et3N. Reactant 3 undergoes
Michael addition to reagent 5, followed by cycloaddition onto the
nitrile. Eventually, after tautomeric proton shift compound 4 is
formed.
8
9
CN
CN
4
4
65
65
Z
O
O
O
CN
O
Knoevenagel
condensation
+ Et3N
- Et3NH+
3
ZCH2CN
1
2
5
10
11
12
CN
5
5
7
4
70
65
40
60
H2N
N
HN
O
O
O
Z
Z
Z
O
O
O
tautomeric
shift
CN
4
Scheme 2. Plausible mechanism for the formation of 4.
COOEt
CN
As shown in Table 1, to establish the generality of the method,
a wide variety of suitable substrates were employed. Various re-
actants 3 including 1,3-diketones, pyrazolones and enoles were
used and the reactions afforded the corresponding products. In
addition, the reaction with ethylcyanoacetate or malononitrile also
proceeded smoothly; however, the reaction times needed, when
ethylcyanoacetate employed as one of the substrates, were longer
13
a
Isolated yield.

M. Saeedi et al. / Tetrahedron 66 (2010) 5345e5348
5347
than those of malononitrile, which is probably due to the lower
reactivity of cyanoacetates (Table 1).
124.7, 124.2, 124.0, 120.7, 116.4, 105.3, 56.0, 52.0, 11.0; MS, m/z (%):
438 (Mþ, 15), 402 (30), 326 (100), 69 (35).
4.2.4. 30-Amino-50-(2,4-dinitrophenyl)-70-methyl-2-oxo-2H,5H0-
spiro[acenaphthylene-1,10-pyrano[2,3-c]pyrazole]-20-carbonite. Light
yellow powder (0.32 g, 65%). Mp >300 ꢀCz. Found: C, 60.37; H,
2.81; N, 17.11. C25H14N6O6 requires C, 60.73; H, 2.85; N, 17.00%; nmax
(KBr) 3440, 3315, 2222, 1726, 1662, 1616, 1593, 1497, 1423,
3. Conclusion
In summary, we have developed a new facile protocol for the
synthesis of new spiroacenaphthylene derivatives from the re-
action of acenaphthenequinone, malononitrile/ethylcyanoacetate
1339 cmꢁ1
; dH (500 MHz, DMSO-d6) 8.64e7.68 (10H, m, ArH), 7.26
and a-methylencarbonyl compounds/enols.
(2H, s, NH2), 1.21 (3H, s, Me); dC (125 MHz, DMSO-d6) 204.7, 164.0,
157.0, 151.7, 150.8, 150.4, 146.9, 146.7, 144.9, 143.8, 141.9, 141.8, 132.5,
129.4, 129.0, 125.0, 124.3, 124.2, 124.1, 120.5, 116.7, 105.9, 56.7, 52.2,
9.7; MS, m/z (%): 494 (Mþ, 10), 327 (100), 258 (30), 69 (35).
4. Experimental section
4.1. General
4.2.5. 20-Amino-70,70-dimethyl-2,50-dioxo-50,60,70,80-tetrahydro-2H-
spiro[acenaphthylene-1,40-chromene]-30-carbonitrile (4e). Light yel-
low powder (0.30 g, 80%). Mp 268e270 ꢀC; [Found: C, 74. 63; H,
4.79; N, 7.47. C23H18N2O3 requires C, 74.58; H, 4.90; N, 7.56%; nmax
Melting points were measured, using a capillary tube method
with a Bamstead Electrothermal 9200 apparatus. 1H and 13C NMR
spectra were recorded on a Bruker AQS-AVANCE spectrometer at
500 and 125 MHz, using TMS as an internal standard (CDCl3 solu-
tion). FTIR spectra were recorded using, KBr disks on FT-IR Bruker
Tensor 27 instrument. Mass spectra were documented on an Agi-
lent Technology (HP) mass spectrometer operating at an ionization
potential of 70 eV. The elemental analysis was performed with an
Elemetar Analysensystem GmbH VarioEL CHNS mode.
(KBr) 3368, 3296, 2957, 2193, 1718, 1664, 1600 cmꢁ1
; dH (500 MHz,
DMSO-d6) 8.35e7.46 (6H, m, ArH), 7.39 (2H, s, NH2), 2.71 (2H, s,
CH2), 2.17 (1H, d, J 16.1 Hz, CHaHb), 2.12 (1H, d, J 16.0 Hz, CHaHb), 1.12
(3H, s, Me), 1.10 (3H, s, Me); dC (125 MHz, DMSO-d6) 204.4, 196.2,
165.4,159.7,144.1,141.4,133.1,132.3,130.7,129.8,129.3,125.4,122.3,
120.7, 118.4, 112.9, 64.4, 58.9, 51.9, 50.6, 32.9, 28.3, 28.1; MS, m/z (%):
370 (Mþ, 75), 286 (100), 259 (44), 83 (25).
4.2. General procedure for the synthesis of compounds 4
4.2.6. Ethyl-20-amino-70,70-dimethyl-2,50-dioxo-50,60,70,80-tetrahydro-
2H-spiro[acenaphthylene-1,40-chromene]-30-carboxylate (4f). White
powder (0.33 g, 80%). Mp 259e262 ꢀC. Found: C, 71.63; H, 5.80; N,
3.40. C25H23NO5 requires C, 71.93; H, 5.55; N, 3.36%; nmax (KBr)
Acenaphthenequinone 1 (0.182 g, 1 mmol), malononitrile/eth-
ylcyanoacetate 2 (1 mmol), compound 3 (1 mmol) were dissolved
under heating in ethanol (5 mL) and Et3N (0.3 mL) was then added.
The reaction mixture was then heated at reflux for the indicated
time (Table 1) and cooled to 4 ꢀC overnight. The solid, which sep-
arated was filtered off, washed three times with ethanol and dried
at 60e70 ꢀC. Spiroacenaphthylene derivatives were analytically
pure without recrystallization.
3379, 3269, 2958, 1719, 1688, 1520 cmꢁ1
; dH (500 MHz, DMSO-d6)
8.18e7.31 (6H, m, ArH), 8.01 (2H, s, NH2), 3.36 (2H, q, J 3.3, 7.3 Hz,
eCH2Me), 2.71 (1H, d, J 17.6, CHaHb), 2.61 (1H, d, J 17.6 Hz, CHaHb),
0
0
0
0
2.14 (1H, d, J 16.0 Hz, CHa Hb ), 1.99 (1H, d, J 16.0 Hz, CHa Hb ), 1.09
(3H, s, Me), 1.02 (3H, s, Me), 0.04 (3H, t, J 7.1 Hz, eCH2Me); dC
(125 MHz, DMSO-d6) 206.0, 196.1, 168.3, 163.6, 160.3, 146.2, 141.5,
136.9, 130.3, 130.1, 129.1, 128.6, 124.6, 120.0, 119.8, 115.7, 78.1, 68.5,
59.3, 51.6, 50.9, 32.5, 28.6, 27.6, 13.1; MS, m/z (%): 417 (Mþ, 20), 344
(100), 271 (28), 83 (25).
4.2.1. 30-Amino-70-methyl-2-oxo-2H,5H0-spiro[acenaphthylene-1,10-
pyrano[2,3-c]pyrazolo-20-carbonitrile (4a). Pale yellow powder
(0.28 g, 85%). Mp 298e299 ꢀC. Found: C, 69.90; H, 3.36; N, 17.32.
C19H12N4O2 requires C, 69.51; H, 3.68; N, 17.06%; nmax (KBr) 3422,
3321, 3146, 2187, 1710, 1640, 1580, 1517 cmꢁ1
;
dH (500 MHz, DMSO-
4.2.7. 30-Amino-2,60,80-trioxo-50,60,70,80-tetrahydro-2H-spiro[ace-
naphthylene-1,10-pyrano[2,3-d]pyrimidine]-2-carbonitrile (4g). Light
yellow powder (0.21 g, 60%). Mp >300 ꢀC. Found: C, 63.31; H, 2.89;
N,15.56. C19H10N4O4 requires C, 63.69; H, 2.81; N,15.64%; nmax (KBr)
d6) 8.48e7.54 (6H, m, ArH), 7.38 (2H, s, NH2), 4.43 (1H, s, NH), 1.15
(3H, s, Me); dC (125 MHz, DMSO-d6) 204.7, 163.4, 156.1, 141.9, 141.8,
135.6, 133.4, 131.4, 130.8, 130.3, 129.8, 125.8, 123.4, 122.1, 119.7, 97.2,
56.8, 52.5, 9.9; MS, m/z (%): 328 (Mþ, 5), 299 (25), 230 (30), 43 (65).
3407, 3134, 2983, 2682, 2195,1687,1579 cmꢁ1
; dH (500 MHz, DMSO-
d6) 9.63 (1H, s, NH), 8.39e7.33 (6H, m, ArH), 8.18 (2H, s, NH2), 4.71
(1H, s, NH); dC (125 MHz, DMSO-d6) 203.6, 167.9, 166.9, 165.4, 159.7,
145.0,141.9,133.9,132.9,130.9,129.9,129.8,125.8,122.8,118.7,112.3,
79.0, 67.9, 58.4; MS, m/z (%): 358 (Mþ, 10), 272 (100), 57 (35).
4.2.2. Ethyl-30-amino-70-methyl-2-oxo-2H,50H-spiro[acenaph-
thylene-1,10-pyrano[2,3-c]pyrazole]-20-carboxylate (4b). Light yel-
low powder (0.30 g, 80%). Mp 247e248 ꢀC. Found: C, 67.57; H, 4.44;
N, 11.37. C21H17N3O4 reqires C, 67.19; H, 4.56; N, 11.19%; nmax (KBr)
3387, 3264, 3057, 2978, 2920, 1714, 1688, 1599, 1549 cmꢁ1
;
dH
4.2.8. 50-Acetyl-20-amino-60-methyl-2-oxo-2H-spiro[acenaph-
thylene-1,40-pyran]-30-carbonitrile (4h). Light yellow powder
(0.21 g, 65%). Mp >300 ꢀC. Found: C, 72.32; H, 4.31; N, 8.51.
C20H14N2O3 requires C, 72.72; H, 4.27; N, 8.48%; nmax (KBr) 3425,
(500 MHz, DMSO-d6) 12.19 (1H, s, NH), 8.37e7.31 (6H, m, ArH), 8.35
(2H, s, NH2), 3.38 (2H, q, J 7.0 Hz, eOCH2Me), 1.02 (3H, s, Me), 0.04
(3H, t, J 7.0 Hz, eOCH2Me); dC (125 MHz, DMSO-d6) 205.7, 168.9,
163.9, 155.1, 146.3, 141.2, 135.5, 133.5, 132.3, 130.4, 129.9, 129.2,
124.3, 121.9, 120.0, 99.2, 75.8, 59.1, 52.5, 12.9, 10.2; MS, m/z (%): 375
(Mþ, 5), 336 (100), 305 (30), 83 (25).
2983, 2200, 1712, 1566 cmꢁ1
; dH (500 MHz, DMSO-d6) 8.48e7.54
(6H, m, ArH), 7.38 (2H, s, NH2), 2.09 (3H, s, Me), 1.61 (3H, s, -COMe);
dC (125 MHz, DMSO-d6) 204.4, 199.5, 163.2, 156.1, 141.4, 135.4, 133.6,
131.6, 130.1, 130.0, 129.0, 126.0, 124.0, 123.0, 119.9, 99.3, 60.8, 56.9,
29.8, 19.9; MS, m/z (%): 330 (Mþ, 5), 287 (100), 271 (10), 43 (30).
4.2.3. 30-Amino-50-(4-chlorophenyl)-70-methyl-2-oxo-2H,5H0-spiro
[acenaphthylene-1,10-pyrano[2,3-c]pyrazole]-20-carbonite (4c). Light
yellow powder (0.33 g, 75%). Mp >300 ꢀC. Found: C, 68.02; H, 3.29;
N, 12.81. C25H15N4O2Cl reqires C, 68.42; H, 3.45; N, 12.77%; nmax
4.2.9. Ethyl-20-amino-30-cyano-60-methyl-2-oxo-2H-spiro[acenaph-
thylene-1,40-pyran]-50-carboxylate (4i). Light yellow powder
(0.23 g, 65%). Mp >300 ꢀC. Found: C, 70.01; H, 4.51; N, 7.81.
C21H16N2O4 requires C, 69.99; H, 4.48; N, 7.77%; nmax (KBr) 3440,
(KBr) 3423, 3206, 2216, 1720, 1621, 1576 cmꢁ1
; dH (500 MHz,
DMSO-d6) 8.52e7.54 (10H, m, ArH), 7.38 (2H, s, NH2), 1.15 (3H, s,
Me); dC (125 MHz, DMSO-d6) 203.4, 163.5, 156.5, 151.4, 150.8, 150.6,
146.8, 146.2, 144.7, 143.6, 141.4, 141.3, 132.8, 129.7, 129.3, 124.8,
2983, 2223, 1719, 1623, 1573 cmꢁ1
;
dH (500 MHz, DMSO-d6)
8.07e7.20 (6H, m, ArH), 8.04 (2H, s, NH2), 3.38 (2H, q, J 7.0 Hz,

5348
M. Saeedi et al. / Tetrahedron 66 (2010) 5345e5348
eCH2Me), 2.38 (3H, s, Me), 1.17 (3H, t, J 7.0 Hz, eCH2Me); dC
(125 MHz, DMSO-d6) 203.9, 168.2, 165.9, 156.0, 141.5, 135.5, 133.2,
132.4, 130.3, 130.1, 129.4, 129.3, 124.1, 121.7, 120.3, 99.9, 75.5, 59.9,
52.5, 19.0, 10.2; MS, m/z (%): 360 (Mþ, 5), 287 (100), 272 (35), 83
(30).
2978, 2987, 2199, 1723, 1607, 1577 cmꢁ1
; dH (500 MHz, DMSO-d6)
8.33e7.60 (10H, m, ArH), 7.33 (2H, s, NH2); dC (125 MHz, DMSO-d6)
203.6, 167.91, 166.9, 165.4, 159.7, 145.0, 141.9, 136.5, 133.9, 132.9,
130.9, 130.0, 129.9, 125.8, 122.8, 120.8, 119.2, 118.7, 115.6, 112.3, 98.0,
79.0, 67.9, 58.4; MS, m/z (%): 392 (Mþ, 5), 340 (5), 151 (25).
4.2.10. 20-Amino-2-oxo-2H-spiro[acenaphthylene-1,40-benzo[h]chro-
mene]-30-carbonitrile (4j). Light yellow powder (0.26 g, 70%). Mp
>300 ꢀC. Found: C, 80.31; H, 3.58; N, 7.32. C25H14N2O2 requires C,
80.20; H, 3.77; N, 7.48%; nmax (KBr) 3426, 3062, 2200, 1714, 1622,
Acknowledgements
M.M.H. is grateful for the partial financial support from Alzahra
University.
1576 cmꢁ1
; dH (500 MHz, DMSO-d6) 8.18e7.25 (12H, m, ArH), 8.03
(2H, s, NH2); dC (125 MHz, DMSO-d6) 203.8, 163.5, 156.1, 142.9,
142.0, 141.8, 139.9, 138.6, 135.6, 133.5, 132.7, 131.5, 130.8, 130.3,
129.9, 127.8, 126.8, 125.8, 123.7, 123.4, 122.2, 119.7, 98.2, 56.8, 52.6;
MS, m/z (%): 374 (Mþ, 5), 353 (10), 236 (15), 144 (20), 86 (100).
Supplementary data
Supplementary data associated with this article can be found in
online version at doi:10.1016/j.tet.2010.05.067.
4.2.11. 30-Amino-2,90-dioxo-2H,90H-spiro[acenaphthylene-1,10-in-
deno[1,2-b]pyran]-20-carbonitrile (4k). Light yellow powder (0.24 g,
65%). Mp >300 ꢀC. Found: C, 76.28; H, 3.13; N, 7.43. C24H12N2O3
requires C, 76.59; H, 3.21; N, 7.44%; nmax (KBr) 3419, 2980, 2204,
References and notes
1. Zhu, J.; Bienaymé, H. In Multicomponent Reactions; Wiley-VCH: Weinheim,
2005.
1706, 1568 cmꢁ1
; dH (500 MHz, DMSO-d6) 8.23e7.35 (10H, m, ArH),
2. Domling, A. Comb. Chem. High Throughput Screen. 1998, 1, 1.
3. Bienayme, H.; Hulme, C.; Oddon, G.; Schmitt, P. Chem.dEur. J. 2000, 6, 3321.
4. Ramon, D. J.; Yus, M. Angew. Chem., Int. Ed. 2005, 44, 1602.
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6. Latif, Z.; Hartley, T. G.; Rice, M. J.; Waigh, R. D.; Waterman, P. G. J. Nat. Prod. 1998,
61, 614.
8.21 (2H, s, NH2); dC (125 MHz, DMSO-d6) 202.9, 188.8, 168.4, 163.4,
146.2, 145.6, 144.4, 141.4, 141.3, 138.3, 135.5, 133.7, 132.7, 132.6,
132.0, 131.1, 130.6, 130.1, 129.4, 125.4, 123.6, 122.6, 66.5, 65.1; MS,
m/z (%): 376 (Mþ, 5), 324 (30), 176 (40), 57 (80).
7. Pradhan, R.; Patra, M.; Behera, A. K.; Mishra, B. K.; Behera, R. K. Tetrahedron
2006, 62, 779.
4.2.12. Ethyl-30-amino-2,90-dioxo-2H,90H-spiro[acenaphthylene-1,10-
indeno[1,2-b]pyran]-20-carboxylate (4l). Light yellow powder
(0.17 g, 40%). Mp >300 ꢀC. Found: C, 73.08; H, 4.13; N, 3.33.
C26H17NO5 requires C, 73.75; H, 4.05; N, 3.31%; nmax (KBr) 3423,
8. Gadwood, R. C.; Kamdar, B. V.; Dubray, L. A. C.; Wolfe, M. L.; Smith, M. P.; Watt,
W.; Mizsak, S. A.; Groppit, V. E. J. Med. Chem. 1993, 36, 1480.
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3053, 2979, 2187, 1709, 1672 cmꢁ1
; dH (500 MHz, DMSO-d6)
8.27e7.20 (10H, m, ArH), 8.19 (2H, s, NH2), 3.36 (2H, q, J 7.1 Hz,
eOCH2Me), 1.04 (3H, t, J 7.1 Hz, eOCH2Me); dC (125 MHz, DMSO-d6)
202.6, 188.6, 170.4, 168.4, 163.4, 144.2, 144.1, 142.0, 141.4, 138.4,
135.4, 133.0, 132.6, 132.3, 131.3, 131.2, 130.1, 130.0, 129.0, 125.0,
123.9, 122.9, 95.4, 70.1, 66.5, 14.0; MS, m/z (%): 423 (Mþ, 10), 350
(15), 298 (10), 97 (40).
14. Ashry, E. S. H. E.; Hamid, H. A.; Kassem, A. A.; Shoukry, M. Molecules 2002, 7,
155.
15. Heravi, M. M.; Baghernejad, B.; Oskooie, H. A. Mol. Divers. 2009, 13, 395.
16. Heravi, M. M.; Baghernejad, B.; Oskooie, H. A. Tetrahedron Lett. 2009, 50, 767.
17. Heravi, M. M.; Baghernejad, B.; Oskooie, H. A.; Hekmatshoar, R. Tetrahedron Lett.
2008, 49, 6101.
18. Heravi, M. M.; Sadjadi, S.; Haj, N. M.; Oskooie, H. A.; Hekmatshoar, R.; Bamo-
harram, F. F. Tetrahedron Lett. 2009, 50, 943.
4.2.13. 20-Amino-2,50-dioxo-2H,50H-spiro[acenaphthylene-1,40-pyr-
ano[3,2-c]chromene]-30-carbonitrile (4m). Light yellow powder
(0.23 g, 60%). Mp >300 ꢀC. Found: C, 73.10; H, 3.21; N, 7.11.
C24H12N2O4 requires C, 73.47; H, 3.08; N, 7.14%; nmax (KBr) 3424,
19. Dabiri, M.; Bahramnejad, M.; Baghbanzadeh, M. Tetrahedron 2009, 65, 9443.