Synthesis and Reactions of some new spiro {INDENO[1,2-b] PYRAN-4,3'-INDOLINES}

Article abstract of DOI:10.3987/COM-07-11277

Indan-1,3-dione (1) reacted with 3-dicyanomethylidene-2-oxoindolines (2a-c) in refluxed ethanol to afford 2-amino-3-cyanospiro {5H-indeno[1,2-b] pyrane-4,3'-(1'-substitutedindoline)}-2',5-diones (3a-c) which underwent different reactions to afford new spi

Full text of DOI:10.3987/COM-07-11277

HETEROCYCLES, Vol. 75, No. 4, 2008
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HETEROCYCLES, Vol. 75, No. 4, 2008, pp. 955 - 963. © The Japan Institute of Heterocyclic Chemistry
Received, 25th November, 2007, Accepted, 8th January, 2008, Published online, 11th January, 2008. COM-07-11277
SYNTHESIS AND REACTIONS OF SOME NEW SPIRO {INDENO[1,2-b]
PYRAN-4,3'-INDOLINES}
Maher F. El-Zohry,* Yasser A. Elossaily, Thanaa A. Mohamed, and Essam
M. Hussein
Department of Chemistry, Faculty of Science, Assiut University, Assiut 71516,
Egypt
*Corresponding author: e-mail: mfzohry@yahoo.com
Abstract- Indan-1,3-dione (1) reacted with 3-dicyanomethylidene-2-oxoindolines
(2a-c) in refluxed ethanol to afford 2-amino-3-cyanospiro{5H-indeno[1,2-b]
pyrane-4,3'-(1’-substitutedindoline)}-2’,5-diones (3a-c) which underwent
different reactions to afford new spiro{indeno[2',1':5,6] pyrano[2,3-d]pyrimidine-
5,3'-(1’-substitutedindoline)} (4a,b)-(12a,b) which are analogues of some
reported biologically active spiropolycyclic compounds.
Several authors1-11 reported the synthesis and application of spiroheterocyclic derivatives. From this point
of view and in continuation to our previous work12-20 we report herein the synthesis of some new
spiroheterocycles of pyrans and pyranopyrimidines containing indoline moiety. Our syntheses started
with the reaction of indan-2,3-dione (1) with 3-dicyanomethylidene-2-oxoindolines (2a-c) in absolute
ethanol and catalytic amount of triethyl amine to give 2-amino-3-cyanospiro{5H-indeno [1,2-b]pyran-
4,3'-indoline} derivatives (3a-c) via a type of Michael addition shown in (Scheme 1).
The structures of the prepared compounds (3a-c) were established from their elemental analyses and
spectral data. The IR spectrum of compound (3a) showed characteristic absorption bands at ύ 3350-3300
for NH2, 3200 for NH, 2200, for CN, 1725, and 1700 cm-1 corresponding to C=O in indene and indoline
1
rings respectively. The H-NMR spectrum of (3b) showed multiplet signal at δ 7.81-6.38 for aromatic
protons and singlet signals at 4.80, 3.20, for NH2, and methyl protons, respectively.
Compounds (3a,b) were subject to further reactions to give fused spiroheterocyclic systems incorporate
pyrimidine nucleus in addition to indeno[1,2-b]pyran and indoline moieties. Thus the reaction of (3a,b)
with formic acid gave spiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline} derivatives
(4a,b). Reaction of (3b) with acetic anhydride/pyridine mixture (2/1, v/v) afforded 1',2-dimethylspiro-

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HETEROCYCLES, Vol. 75, No. 4, 2008
{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2',4,6(3H)-trione (5). Compounds (4a,b)
and 5 were formed via Dimroth rearrangement illustrated in (Scheme 2).
R
O
N
H
O
H
O
H
O
B
+
O
C
CN
N
2a-c
1
BH 1,4-addition
R
R
N
N
O
O
H
O
O
CN
CN
O
O
C
C
H
R
HN
HN
R
N
N
O
O
O
O
CN
CN
1,3-proton shift
NH2
O
O
H
NH
3a-c
a, R= H; b, R=Me; c, R= Et
Scheme 1
The IR spectrum of compounds (4a), (4b), and (5) revealed absorption bands at ύ 3300, 3350, 3400
respectively, are corresponding to NH group with disappearance of the absorption bands corresponding to
NH group with disappearance of the absorption bands corresponding to the cyano and amino groups. The
1H-NMR spectrum of compounds (4a) and (4b) revealed a singlet signal for one proton at δ 11.64, 11.12
respectively, are exchanged with D2O indicated to NH proton with absence of the signal corresponding to
1
NH2 protons. However, the H-NMR spectrum of compound (5) revealed a singlet signal at δ 11.60
exchanged with D2O for NH proton, and two singlet signals at 3.46 and 2.50 for two methyl protons.
Interaction of (3a,b) with formamide afforded 4-aminospiro{6H-indeno[2',1':5,6]pyrano[2,3-d]
pyrimidine-5,3'-indoline} derivatives (6a,b). Reaction of (3a,b) with malononitrile in pyridine or dry
dioxane/Et3N afforded the condensation product 2-amino-3-cyano-5-dicyanomethylidenespiro{5H-indeno

HETEROCYCLES, Vol. 75, No. 4, 2008
957
[1,2-b]pyran-4,3'-indoline} derivatives (7a,b) rather than spiro{indeno[2',1':5,6]pyrano[2,3-b] pyridine-
5,3'-indoline} derivatives (8a,b) or spiro{indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}
derivatives (9a,b). Reaction of (3a,b) with phenyl isocyanate in refluxed pyridine afforded 4-iminospiro
{1,2,3,4-tetrahydro-6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline} derivatives (10a,b). The
reaction of (3a,b) with triethyl orthoformate in the presence of a few drops of glacial acetic acid gave
ethoxymethyleniminospiro{5H-indeno[1,2-b]pyran-4,3'-indoline} derivatives (11a,b). Finally, com-
pounds (11a,b) reacted with hydrazine hydrate in benzene to afford 6-hydrazono-4-iminospiro{3,4-di-
hydro-6H-indeno-[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline} derivatives (12a,b) (Scheme 3).
R
R
N
N
O
O
N
O
O
NH
N
O
NH
Dimroth
O
rearrangment
O
O
4a,b
HCO2H
reflux
H3C
R
N
N
O
O
N
O
O
O
NH
CN
Ac2O/pyridine
Dimroth rearrangment
Me
O
NH2
O
5
3a,b
Scheme 2
The chemical structures of all compounds (6a,b)-(12a,b) were established based on their elemental and
spectral analyses. The IR spectrum of compounds (6a) and (6b) revealed absorption band at ύ 3390-3300
corresponding to NH2 group with disappearance of the absorption band corresponding to the cyano group.
The structures of 2-amino-3-cyano-5-dicyanomethylidenespiro{5H-indeno[1,2-b]pyrane-4,3'-indoline}
1
derivatives (7a,b) were tentatively preferred for these products based on its H-NMR spectrum of
compound (7a) for example, shown the following signals: two singlet signals at δ 10.76, and 4.71
exchanged with D2O for NH, and NH2 protons respectively and the absence of any protons attached to sp3
carbons. The IR spectrum of compounds (10a,b) shown the absorption bands at ύ 3320, and 3290 for two
NH groups with absence of the absorption band corresponding to cyano group. The IR spectrum of
1
compounds (11a,b) shown the disappearance of the band for NH2 group, and the H-NMR spectrum of

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HETEROCYCLES, Vol. 75, No. 4, 2008
compound (11b) shown the following signals: multiplet signals at δ 7.69-6.81 for aromatic protons,
singlet signal at 5.16 for the methine proton, quartet and triplet signals at 4.05 and 1.12 respectively for
ethyl protons, and singlet signal at 3.21 for the methyl protons. The IR spectrum of compounds (12b)
revealed the absorption bands ύ 3360-3210 for NH2, 3150 for NH group with absence of the band for
cyano group and its 1H-NMR spectrum shown the absence of signals corresponding to ethyl protons.
The previously discussed reactions described a simple synthetic procedure to prepare new spirohetero-
cyclic derivatives of indenopyrans and indenopyranopyrimidines which might have important biological
applications.
R
R
N
N
O
NH2
NH2
O
O
CN
O
N
NH2
O
N
O
N
8a,b
R
9a,b
CN
N
CN
O
R
NC
N
CN
O
NH2
O
CH2(CN)2
N
NH2
O
7a,b
R
O
N
N
6a,b
O
O
CN
R
N
NH2
O
O
NH
O
3a,b
N
O
O
N
CH(OEt)3
AcOH
H
10a,b
R
R
N
N
H2N
N
NH
O
O
O
NH2
N
CN
NH2-NH2.H2O
O
N
N=CH-O-Et
O
12a,b
11a,b
Scheme 3

HETEROCYCLES, Vol. 75, No. 4, 2008
959
EXPERIMENTAL
The time required for completion of each reaction was monitored by TLC. Melting points are uncorrected
and were measured on a Gallen Kamp apparatus. The IR spectra were recorded on a Shimadz 470 IR
1
spectrometer (KBr) ύ cm-1. The H-NMR spectra were measured on Varian EM-200 MHz spectrometer
with TMS as internal standard. Mass spectra were determined on a Jeol-600 spectrometer. Elemental
analyses were performed on an elemental analyses system GmbH varioel V2.3.
Synthesis of 2-amino-3-cyanospiro{5H-indeno[1,2-b]pyran-4,3'-indoline}-2’,5-dione and its 1’-alkyl
derivatives (3a-c):
General procedure19: A mixture of indan-1,3-dione (1) (1.46 g, 0.01 mol) and 3-dicyanomethylidine-2-
oxoindolines (2a-c) (0.01 mol) in absolute EtOH (20 mL) in the presence of Et3N (1 mL) was stirred at rt
for 3 h, and/or refluxed for 2 h. Then the product was precipitated, collected by filtration, dried, and
recrystallized from AcOH.
2-Amino-3-cyanospiro{5H-indeno[1,2-b]pyran-4,3'-indoline}-2’,5-dione (3a)
Brown crystals; yield (81%); mp 171-174°C; IR: ύ cm-1 3350, 3300 (NH2), 3200 (NH), 2200 (CN), 1725
1
(C=O), 1700 (C=O); H-NMR (DMSO-d6): δ 9.45 (s, 1H, NH), 7.75-6.56 (m, 8H, Ar-H), 4.75 (s, 2H,
NH2); Anal. Calcd for C20H11N3O3 (341.17): C, 70.38; H, 3.25; N, 12.31. Found: C, 70.35; H, 3.30; N,
12.24.
2-Amino-3-cyano-1’-methylspiro{5H-indeno[1,2-b]pyran-4,3'-indoline}-2’,5-dione (3b)
Bright brown crystals; yield (60%); mp 230-233°C; IR: ύ cm-1 3310-3200 (NH2), 2200 (CN), 1718
1
(C=O), 1705 (C=O); H-NMR (DMSO-d6): δ 7.81-6.38 (m, 8H, Ar-H), 4.81 (s, 2H, NH2), 3.20 (s, 3H,
CH3); Anal. Calcd for C21H13N3O3 (355.18): C, 70.98; H, 3.69; N, 11.83. Found: C, 70.92; H, 3.64; N,
11.78.
2-Amino-3-cyano-1’-ethylspiro{5H-indeno[1,2-b]pyran-4,3'-indoline}-2’,5-dione (3c)
Bright orange crystals; yield (45%); mp 208-210°C; IR: ύ cm-1 3300-3200 (NH2), 2200 (CN), 1710
1
(C=O); H-NMR (DMSO-d6): δ 7.51-6.60 (m, 8H, Ar-H), 3.50 (s, 2H, NH2), 2.75 (q, 2H, CH2), 0.95
(s,3H, CH3); Anal. Calcd for C22H15N3O3 (369.19): C, 71.54; H, 4.09; N, 11.38. Found: C, 71.48; H, 4.05;
N, 11.35.
Synthesis of spiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2’,4,6(3H)-trione and
its 1’-methyl derivative (4a,b):
General procedure: A mixture of 3a or 3b (0.01 mol) and formic acid (5 mL, 85%) was heated under
reflux for 5 h. After cooling the reaction mixture was poured into an ice/water mixture and the formed
solid product thus formed was filtered off, dried and recrystallized from AcOH.
Spiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2’,4,6(3H)-trione (4a)
Scarlet red crystals; yield (50%); mp 161-165°C; IR: ύ cm-1 3300 (NH), 1710 (C=O), 1700 (C=O), 1620

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HETEROCYCLES, Vol. 75, No. 4, 2008
(C=N); 1H-NMR (DMSO-d6): δ 11.64 (s, 1H, NH indoline), 10.59 (s, 1H, NH pyrimidine), 7.90-6.91 (m,
9H, Ar-H and CH pyrimidine); Anal. Calcd for C21H11N3O4 (369.17): C, 68.29; H, 3.00; N, 11.38. Found:
C, 68.25; H, 2.89; N, 11.16.
1’-Methylspiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2’,4,6(3H)-trione (4b)
Brown crystals; yield (50%); mp 155-157°C; IR: ύ cm-1 3350 (NH), 1710 (C=O), 1700 (C=O), 1620
1
(C=N); H-NMR (DMSO-d6): δ 11.21 (s, 1H, NH pyrimidine), 7.90-6.94 (m, 9H, Ar-H and CH
pyrimidine), 3.50 (s, 3H, CH3); Anal. Calcd for C22H13N3O4 (383.18): C, 68.93; H, 3.42; N, 10.96. Found:
C, 68.80; H, 3.31; N, 10.76.
Synthesis of 1',2-dimethylspiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2',4,6-
(3H)-trione (5):
A solution of 3b (3.55 g, 0.01 mol) in Ac2O/pyridine mixture (15 mL, 2/1 v/v) was heated in water bath
for 5h. Then cooled to rt, poured into an ice/water mixture, the formed solid product was collected by
filtration, washed several times with cold water, dried and recrystallized from EtOH/AcOH (3/1) to give
brown crystals; yield (66%); mp 241-245°C; IR: ύ cm-1 3400 (NH), 1715 (C=O), 1700 (C=O), 1650
1
(C=N); H-NMR (DMSO-d6): δ 11.61 (s, 1H, NH), 7.95-6.90 (m, 8H, Ar-H), 3.46 (s, 3H, CH3), 2.50 (s,
3H, CH3); Anal. Calcd for C23H15N3O4 (397.19): C, 69.52; H, 3.80; N, 10.57. Found: C, 69.42; H, 3.58;
N, 10.56.
Synthesis of 4-aminospiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2’,6-dione
and its 1’-methyl derivative (6a,b):
General procedure: A mixture of 3a or 3b (0.05 mol), formamide (10 mL), and DMF (1 mL) was heated
under reflux for 4 h. The reaction mixture was cooled, then poured into an ice/water mixture and the
formed product was filtered off, washed several times by cold water, dried and recrystallized from EtOH.
4-Aminospiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2’,6-dione (6a)
Green crystals; yield (40%); mp 220-224°C; IR: ύ cm-1 3390-3300 (NH2), 3290 (NH), 1700 (C=O), 1690
(C=O); 1H-NMR (DMSO-d6): δ 10.65 (s, 1H, NH), 7.90-6.94 (m, 9H, Ar-H and CH pyrimidine), 5.61 (s,
2H, NH2); Anal. Calcd for C21H12N4O3 (368.18): C, 68.48; H, 3.28; N, 15.210. Found: C, 68.38; H, 3.11;
N, 15.21.
4-Amino-1’-methylspiro{6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-indoline}-2’,6-dione (6b)
Green crystals; yield (46%); mp 240-243°C; IR: ύ cm-1 3340-3200 (NH2), 1710 (C=O), 1690 (C=O), 1625
(C=N); 1H-NMR (DMSO-d6): δ 7.91-6.95 (m, 9H, Ar-H and CH pyrimidine), 5.52 (s, 2H, NH2), 3.46 (s,
3H, CH3); Anal. Calcd for C22H14N4O3 (382.19): C, 69.10; H, 3.69; N, 14.65. Found: C, 68.02; H, 3.59;
N, 14.21.
Synthesis of 2-amino-3-cyano-5-dicyanomethylidenespiro{5H-indeno[1,2-b]pyran-4,3'-indolin}-2’-
one and its 1’-methyl derivative (7a,b):

HETEROCYCLES, Vol. 75, No. 4, 2008
961
General procedure A: A mixture of 3a or 3b (0.05 mol) and malononitrile (0.33 g, 0.05 mol) in pyridine
(10 mL) was heated under reflux for 3 h. The reaction mixture was cooled to rt, then poured into an
ice/water mixture containing a few drops of AcOH. The formed solid product was filtered off, washed by
cold water, dried and recrystallized from dioxane.
General procedure B: A mixture of 3a or 3b (0.05 mol) and malononitrile (0.33 g, 0.05 mol) in dry
dioxane (10 mL) in the presence of catalytic amount of Et3N was stirred at rt for 2 h. The formed solid
product was collected by filtration, dried and recrystallized from dioxane.
2-Amino-3-cyano-5-dicyanomethylidenespiro{5H-indeno[1,2-b]pyran-4,3’-indolin}-2’-one (7a)
Violet crystals; yield (68%); mp 178-180°C; IR: ύ cm-1 3320, 3210 (NH2), 3190 (NH), 2200 (CN), 2190
1
(CN), 1700 (C=O); H-NMR (DMSO-d6): δ 10.76 (s, 1H, NH), 8.00-6.50 (m, 8H, Ar-H), 4.71 (s, 2H,
NH2); Anal. Calcd for C23H11N5O2 (389.21): C, 70.95; H, 2.85; N, 17.99. Found: C, 70.81; H, 2.73; N,
17.89.
2-Amino-3-cyano-5-dicyanomethylidene-1’-methylspiro{5H-indeno[1,2-b]pyran-4,3’-indolin}-2’-
one (7b)
Violet crystals; yield (70%); mp 190-193°C; IR: ύ cm-1 3300-3200 (NH2), 2200 (CN), 2190 (CN), 1705
1
(C=O); H-NMR (DMSO-d6): δ 8.05-6.60 (m, 8H, Ar-H), 4.70 (s, 2H, NH2), 3.60 (s, 3H, CH3); Anal.
Calcd for C24H13N5O2 (403.22): C, 71.46; H, 3.25; N, 17.36. Found: C, 71.39; H, 3.06; N, 17.35.
Synthesis
of
4-imino-2,2’,6-trioxospiro{1,2,3,4-tetrahydro-6H-indeno[2',1':5,6]pyrano[2,3-d]
pyrimidine-5,3'-indoline} and its 1’-methyl derivative (10a,b):
General procedure: A solution of 3a or 3b (0.01 mol) in pyridine (15 mL) and phenylisocyanate (0.01
mol) was heated under reflux for 5 h. The reaction mixture was cooled to rt, and then poured into an
ice/water mixture; the formed product was collected by filtration, washed several times by cold water,
dried and recrystallized from EtOH.
4-Imino-2,2’,6-trioxospiro{1,2,3,4-tetrahydro-6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimidine-5,3'-
indoline} (10a)
Green crystals; yield (40%); mp 182-185°C; IR: ύ cm-1 3320 (NH), 3290 (NH), 3190 (NH), 1710 (C=O),
1
1700 (C=O), 1645 (C=N); H-NMR (DMSO-d6): δ 10.45 (s, 1H, NH), 8.60 (s, 1H, NH), 7.81 (s, 1H,
NH), 7.65-6.60 (m, 13H, Ar-H); Anal. Calcd for C27H16N4O4 (460.23): C, 70.43; H, 3.50; N, 12.17.
Found: C, 70.40; H, 3.32; N, 12.10.
4-Imino-1’-methyl-2,2’,6-trioxospiro{1,2,3,4-tetrahydro-6H-indeno[2',1':5,6]pyrano[2,3-d]pyrimi-
dine-5,3'-indoline} (10b)
Brown crystals; yield (45%); mp 190-192°C; IR: ύ cm-1 3320 (NH), 3290 (NH), 3190 (NH), 1710 (C=O),
1
1700 (C=O), 1640 (C=N); H-NMR (DMSO-d6): δ 8.80 (s, 1H, NH), 7.85 (s, 1H, NH), 7.60-6.80 (m,
13H, Ar-H), 3.42 (s, 3H, CH3); Anal. Calcd for C28H18N4O4 (474.24): C, 70.88; H, 3.82; N, 11.81. Found:

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HETEROCYCLES, Vol. 75, No. 4, 2008
C, 70.78; H, 3.78; N, 11.75.
Synthesis of 3-cyano-2-ethoxymethyleniminospiro{5H-indeno[1,2-b]pyrane-4,3'-indoline}-2’,5-dione
and its 1’-methyl derivative (11a,b):
General procedure: A mixture of 3a or 3b (0.01 mol) and triethyl orthoformate (0.5 mol)/glacial AcOH (1
mL) was heated under reflux for 5 h. The reaction mixture was cooled then the solvent was removed
under vacuum, the formed product was collected by filtration, washed several times by cold water, dried
and recrystallized from EtOH.
3-Cyano-2-ethoxymethyleniminospiro{5H-indeno[1,2-b]pyran-4,3'-indoline}-2’,5-dione (11a)
Brown crystals; yield (65%); mp 150-154°C; IR: ύ cm-1 3250 (NH), 2210 (CN), 1715 (C=O), 1705
1
(C=O), 1665 (C=N); H-NMR (DMSO-d6): δ 10.40 (s, 1H, NH), 7.67-6.80 (m, 8H, Ar-H), 5.05 (s, 1H,
CH), 4.10 (q, 2H, CH2), 1.35 (t, 3H, CH3); Anal. Calcd for C23H15N3O4 (397.19): C, 69.52; H, 3.80; N,
10.57. Found: C, 69.46; H, 3.70; N, 10.49.
3-Cyano-2-ethoxymethylenimino-1’-methylospiro{5H-indeno[1,2-b]pyran-4,3'-indoline}-2’,5-dione
(11b)
Brown crystals; yield (67%); mp 165-167°C; IR: ύ cm-1 2200 (CN), 1715 (C=O), 1705 (C=O), 1660
1
(C=N); H-NMR (DMSO-d6): δ 7.69-6.81 (m, 8H, Ar-H), 5.16 (s, 1H, CH), 4.05 (q, 2H, CH2), 3.21 (s,
3H, CH3), 1.12 (t, 3H, CH3); Anal. Calcd for C24H17N3O4 (411.20): C, 70.07; H, 4.16; N, 10.21. Found:
C, 69.91; H, 4.10; N, 10.09.
Synthesis
of
3-amino-6-hydrazono-4-iminospiro{3,4-dihydro-6H-indeno[2',1':5,6]pyran[2,3-d]
pyrimidine-5,3'-indolin}-2’-one and its 1’-methyl derivative (12a,b):
General procedure: A mixture of 11a or 11b (0.01 mol) and hydrazine hydrate (80%) (0.015 mol) in
benzene (15 mL) was stirred at rt for 1 h. The formed product was collected by filtration, dried and
recrystallized from benzene.
3-Amino-6-hydrazono-4-iminospiro{3,4-dihydro-6H-indeno[2',1':5,6]pyran[2,3-d]pyrimidine-5,3'-
indolin}-2’-one (12a)
Scarlet red crystals; yield (65%); mp 200-204°C; IR: ύ cm-1 3370, 3210 (NH2), 3160 (NH), 1700 (C=O),
1
1680 (C=N); H-NMR (DMSO-d6): δ 10.54 (s, 1H, NH), 10.47 (s, 1H, NH), 9.56 (s, 2H, NH2), 9.49 (s,
2H, NH2), 8.74-6.49 (m, 9H, Ar-H); Anal. Calcd for C21H15N7O2 (397.19): C, 63.47; H, 3.80; N, 24.67.
Found: C, 63.39; H, 3.68; N, 24.57.
3-amino-6-hydrazono-4-imino-1’-methylspiro{3,4-dihydro-6H-indeno[2',1':5,6]pyran[2,3-d]pyrim-
idine-5,3'-indolin}-2’-one (12b)
Red crystals; yield (60%); mp 185-188°C; IR: ύ cm-1 3360, 3210 (NH2), 3150 (NH), 1705 (C=O), 1680
1
(C=N); H-NMR (DMSO-d6): δ 10.54 (s, 1H, NH), 9.61 (s, 2H, NH2), 9.45 (s, 2H, NH2), 8.33-6.50 (m,
9H, Ar-H), 3.11 (s, 3H, CH3); Anal. Calcd for C22H17N7O2 (411.20): C, 64.23; H, 4.16; N, 23.83. Found:

HETEROCYCLES, Vol. 75, No. 4, 2008
963
C, 64.10; H, 4.00; N, 23.75.
REFERENCES
1. S. Hirotani and E. Kaji, Tetrahedron, 1999, 55, 4255.
2. D. B. Reddy, S. A Reddy, and A. Padmaja, Heteroatom Chem., 1999, 10, 313.
3. G. S. Singh, T. Singh, and R. Lakhan, Indian J. Chem. Sect. B: Org. Chem. Incl. Med. Chem., 1997,
36B, 951.
4. L. A. Paquette, T. B. Lowinger, D. G. Bolin, and B. M. Branan, J. Org. Chem., 1996, 61, 7489.
5. A. Miyashita and J. Hama, Jpn. Kokai Tokkyo Koho Jp 08, 245, 627 [96, 245, 62] (Cl.
CO7D491/107), 24 Sep. 1996, Appl.95/51, 082, 10 Mar. 1995; 7 PP. (Chem. Abstr., 1997, Vol. 126,
18798w).
6. A. Trani, C. Dallanoce, G. Panzone, F. Ripamonti, B. P. Goldstein, and R. Ciabatti, J. Med. Chem.,
1997, 40, 967.
7. T. C. McMorris, Y. Hu, and M. J. Kelner, Chem. Commun., 1997, 315.
8. F. R. Kinder, R. Wang, W. E. Bauta, and K. W. Bair, Synth. Commun., 1997, 27, 521.
9. K. H. Chikhalia and K. R. Desia, J. Inst. Chem. (India), 1998, 70, 121.
10. P. Hamley, T. McInally, and A. Tinker, PCT Int. Appl. WO 98 46, 611, (Cl. CO7D491 10), 22 Oct.
1998, SE Appl. 97/1, 396, 15 Apr. 1997; 32 PP. (Chem. Abstr., 1998, Vol. 129, 316237f).
11. T. R. Kelly, Q. Li, and V. B. Lohray, U.S. US 5, 166, 208 (Cl. 514-278; CO7D 22/20), 24 Nov.
1992, Appl. 774, 780, 09 Oct. 1991; 22 PP. (Chem. Abstr., 1993, Vol. 118, 191434g).
12. M. S. Al-Thebeiti and M. F. El-Zohry, Phosphorus, Sulfur, and Silicon, 1994, 88, 251.
13. M. S. Al-Thebeiti and M. F. El-Zohry, Heterocycles, 1995, 41, 2475.
14. M. F. El-Zohry, I. M. A. Awad, Z. A. Hozien, and A. A. Abdel-Hafez, Indian J. Chem., 1993, 32B,
1109.
15. A. A. Al-Ahmadi and M. F. El-Zohry, Phosphorus, Sulfur, and Silicon, 1994, 97, 35.
16. M. S. Al-Thebeiti and M. F. El-Zohry, Indian J. Chem., 1998, 37B, 804.
17. A. A. Abdel-Hafez and M. F. El-Zohry, Heterocycl. Commun., 2001, 7, 583.
18. M. F. El-Zohry, A. A. Al-Ahmadi, and F. A. Aquily, Heterocycl. Commun., 2002, 8, 187.
19. M. F. El-Zohry, Y. A. Elossaily, Th. A. Mohamed, and E. M. Hussein, Heterocycl. Commun., 2007
in press.
20. M. F. El-Zohry, Y. A. Elossaily, Th. A. Mohamed, and E. M. Hussein, Phosphorus, Sulfur, and
Silicon, 2007, in press.