Open Journal of Synthesis Theory and Applications, 2012, 1, 44-57
http://dx.doi.org/10.4236/ojsta.2012.13008 Published Online October 2012 (http://www.SciRP.org/journal/ojsta)
A Simple and Convenient Synthesis of Isolated-Fused
Heterocycles Based on:
2-Imino-N-phenyl-2H-chromene-3-carboxamide
Islam H. El Azab*, Fawi M. Abd El Latif
Chemistry Department, Faculty of Science, Aswan University, Aswan, Egypt
Received June 23, 2012; revised July 26, 2012; accepted August 29, 2012
ABSTRACT
Starting from 2-imino-N-phenyl-2H-chromene-3-carbox-amide, (1) a series of functionalized chromenes were achieved;
such as, 2-ethoxy-2,3-dihydro-3-phenylchromeno[2,3-d]pyrimidin-4-one (2), and 2-hydrazinyl-2,3-dihydro-3-phenyl-
chromeno-[2,3-d]pyrimidin-4-one (3). Furthermore, reactions of (3) with some of laboratory available compounds gave
pyrazoles (4 - 9, 12, 13a, 13b), tetrazoles (11), 2-(2-benzylidenehydrazinyl)-3-phenyl-3H-chromeno[2,3-d]pyrimidin-
4(10H)-oneisoxazoles (14), 5-chloro-1-(4-oxo-3-phenyl-4,10-dihydro-3H-chromeno[2,3-d]pyrimidin-2-yl)-3-phenyl-2,
3-dihydro-1H-pyrazole-4-carbonitrile (17), pyrimidines (28a, b), pyridines (29a - 29e, 30, 33a, 33b), benzo[b][1,
4]oxazepin-2- amines (32a, b), 3-chloro-4-(2-imino-2H-chromen-3-yl)-1-phenyl-4-(phenylamino) azetidin-2-one (34a-
34e) and 2-(2- imino-2H-chromen-3-yl)-3-phenyl-2-(phenyl amino)thiazolidin-4-onee (35a -35e). The structures of these
compounds were established by elemental analysis, IR, MS and NMR spectral analysis.
Keywords: 2-Imino-2H-chromen-3-ylChromeno[2,3-d]pyrimidin-4-one;
 -Lactam; Thiazolidin-4-ones
1. Introduction
Natural and synthetic coumarin derivatives represent, now-
adays, an important group of organic compounds that are
used as antibiotics [1,2] fungicides [3] anti-inflammatory
[4], anticoagulant [5] and antitumor agents [6,7]. Regard-
ing their high fluorescence ability, they are widely used as
optical whitening agents, brighteners, laser dyes and also
as fluorescent probes [8] in biology and medicine [9].
Also, The 4 H-chromene derivatives ethyl 4-((ethoxy-
carbonyl) (cyano) methyl)-2-amino-6-bromo-4H-chromene-
3-carboxylate (HA 14-1) has demonstrated promising an-
tifungal activities [10], antiviral agent [11], antiprolifera-
tion agent [12]. Due to the unique biological and pharma-
cological activity, chromene derivatives have attracted
considerable attention thus; different processes for the
synthesis of chromenes have been reported during the past
few years. The importance of the chromone nucleus is evi-
denced by the continued appearance of new and improved
methods for their synthesis, despite the several existing
methods for the synthesis of chromene derivatives [13-20],
there still is demand for general synthetic strategies which
can efficiently provide variously substituted chromene
systems.
2. Experimental
2.1. Instruments
All melting points are measured using Galenkanp melting
point apparatus and are uncorrected. Elemental analyses
were carried out at the Microanalytical Center of Cairo
University. IR (KBr pellets υ = cm–1) spectra were de-
termined in 1650 FT-IR instrument (Cairo University),
1H-NMR spectra (δ = ppm) were accomplished using 300
MHz NMR Spectrometer and mass spectroscopy were re-
corded on GCMS-QP-1000 EX spectrometer (Cairo Uni-
versity).
2.2. Material and Reagents
Hydrazine hydrate, phenyhydrazine, benzaldehyde and its
substituted derivatives, aniline and its substituted de-
rivatives, thioglycolic acid, acetylacetone, phosoryl chlo-
ride, ethyl acetoacetate and chloroacetyl chloride were
purchased from Alderich Chemical Co.
Triethylamine, thiourea, urea, o-phenylenediamine, o-
aminothiophenol and 2-cyanomethy benzimidazole were
purchased from British Drug Houses (BDH).
Acetophenone, malononitrile, 2-chloro acetamide, pip-
eridine, ethoxymethylene-malononitrile, sodium azide and
*Corresponding author.

I. H. EL AZAB, F. M. ABD EL LATIF 45
5-amino-(1H)-1,2,4-triazole were purchased from Merck
Co., Germany.
2.3. Solvents
Dimethyformamide, benzene, pyridine, ethanol and ace-
tone were purchased from El-Nasr Pharmaceutical and
Chemical Co. (ADWIC), Egypt.
2.4. Organic Preparations
Preparation of 2-ethoxy-2, 3-dihydro-3-phenylchro-
meno[2,3-d]pyrimidin -4 -o ne ( 2) . A mixture of 1 (2.64 g,
0.01 mol) and triethoxymethane (1.48 mL, 0.05 mol) in 20
mL of dimethylformamide was refluxed 8 h. Then the
reaction mixture was poured into 150 mL of crushed ice
then the resultant solid was collected by filtration to pro-
vide 2 (1.5 g, 60%) as a pale yellow solid; m.p. 285˚C -
287˚C. 1HNMR (CDCl3): δ 1.2 (t, 3H, CH3), 3.9 (q, 2H,
CH2) and 6.7 - 7.9 (m, 11H, Ar-H). MS: m/z 320 ([M]+,
65%). Calcd for C19H16N2O3 (320.34). Calcd: C 71.24, H
5.03, N 8.74 %. Found: C 70.14, H 5.01, N 7.88%.
Preparation of 2-hydrazinyl-2, 3-dihydro-3-phenyl
chromeno[2,3-d]pyrim-idin-4-one (3). A mixture of 2
(3.20 g, 0.01 mol) and hydrazine hydrate (0.5 mL, 0.01
mol) in 30 mL ethanol containing 0.1 mL piperidine was
refluxed for 8 hr. The reaction mixture was concentrated
under reduced pressure and the residue washed with aci-
dified cold water and then triturated with methanol. The
formed pale yellow product was filtered, washed well with
methanol. Yield 66%, m.p. 250˚C - 252˚C. IR: 1670 (C =O),
3282 (NH) and 3432 (NH2). 1H NMR (DMSO): 4.82 (s, br,
2H, NH2, D2O, exchangeable), 5.1 (s, 1H, CH- methine),
6.7 - 7.9 (m, 11H, Ar-H) and 8.85 (s, br, 1H, NH, D2O,
exchangeable). MS: m/z 309([M+3] +
, 45%). Calcd for
C17H14N4O2 (306.32): C 66.66, H 4.61, N 18.29%. Found:
C 66.01, H 3.20, N 17.66 %.
Preparation of 3-amino-3-(3-amino-5-oxo-1-(4-oxo-
3-phenyl-3,4-dihydro-2H-chromeno[2,3-d]pyrimidin-2-
yl)-1H-pyrazol-4(5H)-ylidene)propanenitrile (5), and
its derivatives, (7 - 10, 12, 13a, b).
General procedu re: To a solution of hydrazide 3 (3.06
g, 0.01 mol) and ethyl 3-amino-2,4-dicyanobut-2-enoate
(1.79 mL, 0.01 mol) in 30 mL ethanol containing 0.1 mL
piperidine was refluxed for 6 h. then allowed to cool. The
formed solid was filtered off, washed with methanol to af-
ford the pyrazoile derivative 5. Analogously, diethyl malo-
nate (1.60 mL, 0.01mol), ethyl 2-cyanoacetate (1.13 mL),
ethyl 3-oxobutanoate (1.30 mL), pentane-2,4-dione (1.00
mL), 2-(ethoxymethylene) malononitrile (1.22 gm) and
2-cyano-N-phenylacetamide (1.60 gm) were reacted with
compound 3 to yield (7 - 10, 12, 13a, b), respectively.
3-A m i n o - 3-( 3- amin o-5 - oxo- 1-( 4-oxo-3-pheny l- 3 ,4 -
dihdro-2H-chromeno-[2,3-d]pyrimidin-2-yl)-1H-pyra-
zol-4(5H)-ylidene)propanenitrile (5). Yellow crystals
(MeOH), yield 70%, m.p. 250˚C - 252˚C. IR: 1699 (CO),
2219 (CN), 3422 (NH2). 1H NMR (DMSO): 2.9 (s, 2H,
CH2), 3.5 (s, 2H, NH2), 3.7 (s, 2H, NH2), 6.7 - 7.9 (m, 10H,
Ar-H). MS: m/z 439 ([M+], 60%). Calcd for C23H17N7O3
(439.43). C 62.87, H 3.90, N 22.31%. Found: C 61.01, H
3.20, N 21.89%.
1-(3,4-dihydro-4-oxo-3-phenyl-2H-chromeno[2,3-d]-
pyrimidin-2-yl)pyrazo-lidine-3,5-dione, (7). Pale yel-
low crystals (MeOH), yield 66%. m.p. 280˚C -282˚C. IR:
υ (cm–1) 1685 - 1705 (C=O), 3212 (NH), 1HNMR (CDCl3):
δ 3.2 (s, 2H, CH2), 5.8 (s, 1H, CH-methine ), 8.1 (s, 1H,
NH of pyrazole ring) and 6.1 - 7.8 (m, 10H, Ar-H). MS:
m/z 374 ([M]+, 55%). Calcd for C20H14N4O4 (374.35).
Calcd: C 64.17, H 3.77, N 14.97%. Found: C 63.33, H
2.91, N 14.15%.
Compound 5. Yield 70%, m.p. 257˚C - 259˚C. IR:
1699 (CO), 2219 (CN), 3422 (NH2). 1H NMR (DMSO):
2.9 (s, 2H, CH2), 3.5 (s, 2H, NH2), 3.7 (s, 2H, NH2), 6.7 -
7.9 (m, 10H, Ar-H). MS: m/z 439 ([M+], 60%). Calcd for
C23H17N7O3 (439.43). C 62.87, H 3.90, N 22.31 %. Found:
C 61.01, H 3.20, N 21.89%.
Compound 8. Pale green crystals (Ethanol), yield 50%,
m.p. 250˚C - 252˚C, IR: υ (cm–1) 1685-1705(C=O), 3432
(NH2), MS: m/z 373 ([M]+,65%). Calcd for C20H15N5O3
(373.36). Calcd: C 64.34, H 4.05, N 18.76%. Found: C
63.33, H 3.91, N 17.15%.
Compound 9. Brown crystals (Ethanol), yield 55%,
m.p. 190˚C - 192˚C. IR: υ (cm–1) 1685-1705 (C=O),
1HNMR (CDCl3): δ 1.1 (s, 3H, CH3), 2.5 (s, 2H, CH2), 5.8
(s, 1H, CH-methine), 6.7 - 7.9 (m, 10H, Ar-H). MS: m/z
370 ([M-2]+, 60%). Calcd for C23H16N4O3 (372.38). Calcd:
C 67.73, H 4.33, N 15.05%. Found: C 67.17, H 3.31, N
14.15%.
Compound 10. Pale green crystals (Ethanol), yield 59
%, m.p. 270˚C-2˚C. IR: υ (cm–1) 1685 - 1705(C=O), MS:
m/z 369 ([M-1]+, 66%). Calcd for C22H18N4O2 (370.4).
Calcd: C 71.34, H 4.90, N 15.13%. Found: C 70.17, H
3.31, N 14.15%.
Preparation of 1-phenyl-tetrazolo[4’,5’:2,3] pyimi-
do[4,5-b]chromen-12-one, (11).
To a stirred cold solution of 3 (0.306 g, 0.001 mol) in 30
mL of glacial acetic acid, a cold solution of sodium nitrite
(0.7 g, 0.01 mol) in 10 mL of H2O was added drop wise
stirring at 5˚C. The mixture was stirred for further four
hours at room temperature. The solid that precipitated was
collected by filtration, washed with water and air dried to
afford 55% yield of the tetrazolo derivative 11. Yield 55%,
m.p. 250˚C - 252˚C. IR: 1699 (CO). MS: m/z 317 ([M+],
60%). Ca lcd for C17H11N5O2 (317.3). C 64.35, H 3.49, N
22.07%. Found: C 63.01, H 2.20, N 21.89%.
Compound 12. Yellow crystals (Ethanol), yield 55%,
m.p. 259˚C - 261˚C. IR: υ (cm–1) 1685 - 1705(C=O), 2219
(CN), 3212 - 3423 (NH2), MS: m/z 382 ([M + 1]+, 50%).
Calcd for C21H14N6O2 (382.37). Calcd: C 65.96, H 3.69, N

I. H. EL AZAB, F. M. ABD EL LATIF 46
21.98%. Found: C 64.17, H 2.31, N 20.15%.
Compound 13a. Yellow crystals (Ethanol), yield 62%,
m.p. 150˚C - 152˚C. IR: υ (cm–1) 1685 - 1705(C=O), 3212 -
3432 (NH2), 1HNMR (CDCl3): δ 4.1 (s, 2H, NH2), 4.3 (s,
1H, NHPh), 6.2 (s, 1H, = CH-), 6.7 - 7.9 (m, 10H, Ar-H).
MS: m/z 448([M]+,40%). Calcd for C26H20N6O2 (448.48).
Calcd: C 69.63, H 4.49, N 18.74%. Found: C 68.17, H
3.31, N 17.15%.
Compound 13b. Pale yellow crystals (MeOH), yield
50%, m.p. 180˚C - 182˚C. IR: υ (cm–1) 1685 - 1705(C=O),
3212 - 3432 (NH2), MS: m/z 456 ([M + 1]+, 35%). Calcd
for C23H17N7O2S (455.49). Calcd: C 60.65, H 3.76, N
71.53, S 7.04%. Found: C 59.17, H 2.66, N 70.26, S 6.54%.
Preparation of 2-(2-benzylidenehydrazinyl)-3-phenyl-
3H-chromeno[2,3-d]pyri-midin-4(10H)-one, (14). A mix-
ture of the 2-hydrazinyl-3-phenyl-2H-chromeno [2,3-d]pyri-
midin-4(3H)-one 3 (3.06 g, 0.01 mol) and benzaldehyde
(1.06, 0.01 mol) in 20 mL ethanol containing 0.1 mL of
piperidine was refluxed for 8 hr. The reaction mixture was
concentrated, cooled then poured into ice/H2O mixture the
solid product thus so formed was filtered, washed for
several times with water to afford 14 (1.66 g, 61% ) as a
brown solid; m.p. 225˚C - 227˚C. IR: υ (cm-1) 1705 (C=O),
3322 (NH). 1HNMR (CDCl3): δ 6.7 - 7.9 (m, 14H, Ar-H),
8.11 (s, 1H, CH=) and 10.11 (s, 1H, NH). MS: m/z 397
([M]+, 65%). Calcd for C24H18N4O2 (394.43). Calcd: C
73.08, H 4.60, N 14.20 %. Found: C 72.14, H 4.01, N
13.88%.
Preparation of 5-oxo-1-(4-oxo-3-phenyl-4, 10-dihy-
dro-3H-chromeno[2,3-d]pyrimidin-2-yl)-3-phenylpyra
zolidine-4-carbonitrile, (16). A solution of benzylidene-
hydrazinyl 14 (3.94 g, 0.01 mol) and ethyl 2-cyanoacetate
(1.13 mL) in 30 mL ethanol containing 0.1 mL piperidine
was refluxed for 6 h. then allowed to cool. The formed
solid was filtered off, washed with methanol to afford the
pyrazole derivative 16 (2.45 g, 61%) as a brown solid; m.p.
295˚C - 297˚C. IR: υ (cm–1) 1670 (C=O), 2217 (CN), 3432
(NH). 1HNMR (CDCl3): δ 3.98 (s, 1H, NH), 4.12 (s, 1H,
C-3 pyrazole), 4.21 (s, 1H, C-4 pyrazole) and 6.7 - 7.9 (m,
14H, Ar-H). MS: m/z 462 ([M + 1]+, 55%). Calcd for
C27H19N5O3 (461.47). Calcd: C 70.27, H 4.15, N 15.18 %.
Found: C 69.12, H 4.01, N 14.11%.
Preparation of 5-chloro-1-(4-oxo-3-phenyl-4,10-dihy-
dro-3H-chromeno[2,3-d]pyrimidin-2-yl)-3-phenyl-2, 3-
dihydro-1H-pyrazole-4-carbonitrile, (17). A suspen-
sion of 1.0 g of 16 in 10 ml of phosphoryl chloride was
heated at 90˚C for 5 hr and, after cooling, crushed ice was
added. The solution was then made basic with concen-
trated ammonium hydroxide (pH = 8) and the solid that
precipitated was collected by filtration, washed with water
and purified by crystallization to give 17 as a Yellow solid;
m.p. 189˚C - 191˚C. IR: υ (cm–1) 1700 (C=O), 2217 (CN),
3425 (NH). 1HNMR (CDCl3): δ 3.98 (s, 1H, NH), 4.61 (s,
1H, C-3 pyrazole) and 6.7 - 7.9 (m, 14H, Ar-H). MS: m/z
478 ([M-1]+, 16%). Calcd for C27H18N5O2Cl (479.92).
Calcd: C 67.57, H 3.78, N 14.59%. Found: C 66.12, H
3.21, N 14.51%.
Preparation of 2-(4-amino-3-phenyl-2, 3-dihydro-
1H-pyrazolo[4,3-e][1, 2, 4]-triazolo[1,5-a] pyrimidin-
1-yl)-3-phenyl-3H-chromeno[2,3-d]pyrimidin-4(10H)-
one, (18). Amixtuer of 17 (4.79 g, 0.01 mol) and 5-
amino-1,2,4-1H-triazole (0.84 g) in 30 mL ethanol con-
taining 0.1 mL piperidine was refluxed for 3 hr. then
allowed to cool. The formed brownish solid was filtered
off, washed with methanol to afford the pyrazoile deriva-
tive 18 (2.4 g, 50%) as a brownish solid; m.p. 156˚C -
158˚C. IR: υ (cm–1) 1670 (C=O), 3432 (NH). 1HNMR
(DMSO): δ 3.98 (s, br, 1H, NH), 5.21 (s, 1H, C-3 pyra-
zole), 6.13 (s, br, 2H, NH2) and 6.7 - 7.9 (m, 14H, Ar-H)
and 8.71 (s, 1H, methine proton of triazole ring). MS: m/z
527 ([M]+, 25%). Calcd for C29H21N9O2 (527.54). Calcd:
C 66.03, H 4.01, N 23.90 %. Found: C 65.31, H 3.22, N
22.84%.
Preparation of 4-amino-7-(methylthio)-1-(4-oxo-3-
phenyl-4,10-dihy dr o- 3H-chromeno[2,3-d]py r imidin-2-
yl)-3-phenyl-2,3-dihydro-1H-dipyrazolo [1,5-a:4’,3’-e]
pyrimidine-6-carbonitrile, (19). Amixtuer of 17 (4.79 g,
0.01 mol) and 5-amino-3-(methylthio)-1H-pyrazole-4- car-
bonitrile (1.54 g, 0.01 mol ) in 30 mL ethanol containing
0.1 mL piperidine was refluxed for 5 h. then allowed to
cool. The formed pale yellow solid was filtered off,
washed with methanol to afford the pyrazoile derivative
19 (2.4 g, 50%) as a pale yellow solid (MeOH); m.p. 240˚C -
242˚C. IR: υ (cm–1) 1670 (C=O), 2221 (CN), 3432 (NH).
1HNMR (DMSO): δ 3.54 (s, 3H, SCH3), 3.98 (s, br, 1H,
NH), 5.21 (s, 1H, C-3 pyrazole), 6.13 (s, br, 2H, NH2) and
6.7 - 7.9 (m, 14H, Ar-H) and 8.71 (s, 1H, methine proton
of triazole ring). MS: m/z 597 ([M]+, 35 %). Calcd for
C32H23N9O2S (597.65). Calcd: C 64.31, H 3.88, N 21.09
%. Found: C 63.56, H 2.52, N 20.78%.
Preparation 5-methoxy-1-(4-oxo-3-phenyl-4, 10-di-
hydro-3H-chromeno[2,3-d]py-rimidin-2-yl)-3-phenyl-
2,3-dihydro-1H-pyrazole-4-carbonitrile, (20). A solu-
tion of 10 mmol of freshly prepared sodium methoxide
and 1.0 mmol of the chloro derivatives 17 in 10 ml of
anhydrous methanol was refluxed for 4 hr then the reac-
tion mixture was evaporated to dryness in vacuo. The crude
residue was treated with water and neutralized with 10%
hydrochloric acid, and the solid precipitate, collected by
filtration, was purified by crystallization to obtain 20 as
yellow crystals (DMSO-HCl); yield 30%. m.p. 288˚C -
290˚C. IR: υ (cm–1) 1699 (C=O), 2219 (CN), 3422 (NH).
1HNMR (DMSO): δ 3.82 (s, 3H, OCH3), 3.98 (s, br, 1H,
NH), 4.61 (s, 1H, C-3 pyrazole) and 6.7 - 7.9 (m, 14H,
Ar-H). MS: m/z 475 ([M]+, 62%). Calcd for C28H23N9O2S
(597.65). Calcd: C 64.31, H 3.88, N 21.09 %. Found: C
63.56, H 2.52, N 20.78%.
Prepar atio n 5-azido-1-(4-oxo-3-phenyl-4, 10-dihy-

I. H. EL AZAB, F. M. ABD EL LATIF 47
dro-3H-chromeno[2,3-d]pyri-midin-2-yl)-3-phenyl-2,3
-dihydro-1H-pyrazole-4-carbonitrile, (21). A solution
of the chloro compound 17 (1.437 g, 3 mmol) in acetone
(5 mL) was stirred and ice-cooled. The solution of NaN3
(0.13 g, 2 mmol) in water (1 mL) was added drop wise in
the solution and this mixture was stirred for 1 hr at room
temperature. After evaporation of acetone, the crude
product was separated by filtration and recrystallized from
dichlormethane. We have obtained (0.9 g, 62%) of 21 as
Yellow solid with mp 150˚C - 152˚C [21, 22]. IR: υ (cm–1)
1699 (C=O), 2217 (CN), 3422 (NH). 1HNMR (DMSO): δ
3.98 (s, br, 1H, NH), 4.61 (s, 1H, C-3 pyrazole) and 6.7 -
7.9 (m, 14H, Ar-H). MS: m/z 486 ([M]+, 32%). Calcd for
C27H18N8O2 (486.48). Calcd: C 66.66, H 3.73, N 23.03%.
Found: C 65.76, H 2.56, N 22.73%.
Preparation of 2-(4-amino- 3-phenyl-2,3-dihydro-
pyrazolo [3 ,4 -c]pyrazol-1(6H)-yl)-3-phenyl-3H-chro-
meno[2,3-d]pyrimidin-4(10H)-one, (23). A mixture of
17 (3.20 g, 0.01 mol) and hydrazine hydrate (0.5 mL, 0.01
mol) in 20 mL DMF containing 0.1 mL piperidine was
refluxed for 8 hr. The reaction mixture was concentrated
under reduced pressure and the residue washed with aci-
dified cold water and then triturated with methanol. The
formed yellow product was filtered, washed well with
methanol. Yield 58%, m.p. 150˚C - 152˚C. IR: 1670
(C=O), 3432 (NH) and 3455 (NH2). 1H NMR (DMSO):
3.98 (s, br, 1H, NH), 5.21 (s, 1H, CH- methine), 6.7 - 7.9
(m, 11H, Ar-H) and 9.21 (s, 1H, NH). MS: m/z 475([M] +,
64%). Calcd for C27H21N7O2 (475.50): C 68.20, H 4.45, N
20.62%. Found: C 67.03, H 3.32, N 19.23%.
Preparation of 3-(2-imino-2H- chromen-3-yl)-1-phe-
nyl-3-(phenylamino) prop-2-en-1-one, (24a) and its
derivatives (24b-e).
General procedure: A mixture of the 2-imino-N-
phenyl-2H-chromene-3-carboxamide 1 (2.64 g, 0.01 mol)
and acetophenone (1.2 ml, 0.01 mol), p-hydroxyacetophe-
none (1.36 g, 0.01 mol), p-nitroacetophenone (1.65 g, 0.01
mol), o-nitroacetophenone (1.65 g, 0.01 mol) and p-chloro-
acetophenone (1.54 g, 0.01 mol) respectively, in 20 mL
DMF containing 0.1ml of piperidine was refluxed for 8 hr.
The reaction mixture was concentrated, cooled then poured
into ice/H2O mixture the solid product thus so formed was
filtered, washed for several times with water to afford 24a -
24e derivatives.
Compound 24a. Yellow crystals (MeOH), yield 60%.
m.p. 182˚C - 184˚C. IR: υ (cm–1) 1665 - 1705 (C=O), 3322
(NH), 1HNMR (DMSO): δ 4.1 (s, 1H, NH-amine), 6.5 (s,
1H, CH-ethylene), 7.1-7.6 (m, 15H, Ar-H), 11.5 (s, 1H,
=NH). MS: m/z 366 ([M]+,40%). Calcd for C24H18N2O2
(366.41). Calcd: C 78.67, H 4.95, N 7.65%. Found: C
77.17, H 4.01, N 8.15%.
Compound 24b. Pale green crystals (MeOH), yield
55%, m.p. 220˚C - 222˚C. IR: υ (cm–1) 1665 - 1705(C=O),
3445 (OH), 1HNMR (CDCl3): δ 4.1 (s, 1H, NH-amine),
6.5 (s, 1H, CH-ethylene), 7.1 - 7.6 (m, 14H, Ar-H), 11.5 (s,
1H, =NH) and 9.9 (s, 1H, phenolic OH). MS: m/z 383 ([M +
1]+, 60%). Calcd for C24H18N2O3 (382.41). Calcd: C 75.38,
H 4.74, N 7.33%. Found: C 74.17, H 3.91, N 6.15%.
Compound 24c. Brown crystals (Ethanol), yield 65%,
m.p. 190˚C - 192˚C. IR: υ (cm–1) 1665 - 1705(C=O),
1HNMR (DMSO): δ 4.1(s, 1H, NH-amine), 6.5(s, 1H,
CH-ethylene), 7.1 - 7.6 (m, 14H, Ar-H), 11.5 (s, 1H, =NH).
MS: m/z 411([M]+, 62%). Calcd for C24H17N3O4 (411.41).
Calcd: C 70.07, H 4.16, N 10.21%. Found: C 69.17, H
3.31, N 9.15%.
Compound 2 4d. Brown crystals (Ethanol), yield 59 %,
m.p. 170˚C -172˚C. IR: υ (cm–1) 1665 - 1705(C=O). MS:
m/z 410 ([M-1]+, 52%). Calcd for C24H17N3O4 (411.41).
Calcd: C70.07, H 4.16, N 10.21%. Found: C 69.17, H
3.31, N 9.15%.
Compound 24e. Yellow crystals (Ethanol), yield 55%,
m.p. 255˚C - 257˚C. IR: υ (cm–1) 1665 - 1705(C=O),
1HNMR (DMSO): δ 4.1 (s, 1H, NH-amine), 6.5 (s, 1H,
CH-ethylene), 7.1 - 7.6 (m, 14H, Ar-H), 11.5 (s, 1H, =NH).
MS: m/z 400 ([M]+,60%). Calcd for C24H17N2O2Cl (400.86).
Calcd: C 71.91, H 4.27, N 6.99, Cl8.84%. Found : C 70.17,
H 3.31, N 5.15, Cl7.18%.
Preparation of 2-imino-N,N'-diphenyl-2H-chrom-
ene-3-carboxamidines, (25a) and its derivatives (25b-
25e).
General procedure: A mixture of equimolar amount of
compound 1 (2.64 g, 0.01 mol) and aniline (0.93 ml, 0.01
mol), p-hydroxyaniline (1.09 g, 0.01 mol), p-nitroaniline
(1.38 g, 0.01 mol), o-nitroaniline ( 1.38 g, 0.01 mol and
p-chloroaniline (1.27 g, 0.01 mol), respectively in 30 mL
ethanol containing 0.1 mL of piperidine was refluxed for 5
hr. The reaction mixture was concentrated, poured into
ice/H2O mixture, and the solid product thus formed, fil-
tered, washed for several times with water and crystallized
from methanol.
Compound 25a. Pale brown crystals (Methanol), yield
58%, m.p. 205˚C - 207˚C. IR: υ (cm–1) 3380(NH), 1HNMR
(CDCl3): δ 4.1 (s, 1H, NH-amine), 7.1 - 7.6(m, 15H, Ar-
H), 11.5(s, 1H, =NH). MS: m/z 339 ([M]+, 65%). Calcd
for C22H17N3O(339.39). C 77.86, H 5.05, N 12.38%.
Found: C 76.66, H 4.52, N 11.12%.
Compound 25b. Yellow crystals (Methanol), yield 60%,
m.p. 210˚C - 212˚C. IR: υ (cm–1) 3380(NH), 3445 (OH),
1HNMR (DMSO): δ 4.1(s, 1H, NH-amine), 7.1- 7.6(m,
14H, Ar-H), 11.5 (s, 1H, = NH) and 9.9 (s, 1H, phenolic
OH). MS: m/z 357 ([M+2]+, 50%). Calc d for C22H17N3O2
(355.39). C 74.35, H 4.82, N 11.82%. Found : C 73.45, H
3.52, N 10.12%.
Compound 25c. Pale yellow crystals (Methanol), yield
64%, m.p. 285˚C - 287˚C. 1HNMR (DMSO): δ 4.1 (s, 1H,
NH-amine), 7.1 - 7.6 (m, 14H, Ar-H), 11.5 (s, 1H, = NH),
MS: m/z 385 ([M + 1]+, 55%). Calcd for C22H16N4O3Cl
(384.39). C 68.74, H 4.20, N 14.58%. Found: C 67.72, H

I. H. EL AZAB, F. M. ABD EL LATIF 48
3.52, N 13.12%.
Compound 25d. Yellow crystals (Methanol), yield 60%,
m.p. 215˚C - 117˚C. MS: m/z 384([M]+, 55%). Calcd for
C22H16N4O3Cl (384.39). C 68.74, H 4.20, N 14.58%.
Found: C 67.72, H 3.52, N 13.12%.
Compound 25e. Pale brown crystals (methanol), yield
55%, m.p. 230˚C - 232˚C. 1HNMR (DMSO): δ 4.1 (s, 1H,
NH-amine), 7.1 - 7.6 (m, 14H, Ar-H), 11.5 (s, 1H, =NH),
MS: m/z 372([M − 1]+, 70%). Cal cd for C22H16N3OCl
(373.83). C 70.68, H 4.31, N 11.24, Cl 9.48%. Found : C
69.45, H 3.52, N 11.12, Cl 8.48%.
Preparation of 4,5-dihydro-5-(2-imino-2H-chromen-
3-yl)-N,3-diphenyl-1H-pyrazol-5 -a mine, (26a) a- nd it s
derivatives (26b an d 27).
General procedure: A mixture of 24a (3.66 g, 0.01
mol) and hydrazine hydrate (0.05 ml, 0.01 mol), phenyl
hydrazine (1.08 ml, 0.01 mol) and hydroxylamine hy-
drochloride (0.69 gm, 0.01 mol) containing 0.1 ml pipe-
ridine was refluxed for 8 hr. The reaction mixture was
concentrated under reduced pressure and the residue
washed with acidified cold water and then triturated with
methanol, and the solid product thus formed, filtered,
washed for several times with water and crystallized from
methanol.
Compound 26a. Pale brown crystals (methanol), yield
66%, m.p. 155˚C - 157˚C. IR: 3117 - 3293 (NH). 1H
NMR (DMSO): 2.9 (s, 2H, CH2), 4.1 (s, 1H, NH-amine),
7.1 (s, H, NH hydrazide), 7.2 - 7.8 (m, 15H, Ar-H), 11.5 (s,
1H, =NH). MS: m/z 383([M+3]+, 55%). Calcd for
C24H20N4O (380.44): C 75.77, H 5.30, N 14.73%. Found: C
74.01, H 4.20, N 13.66%.
Compound 26b. Brown crystals (Methanol), yield 50%,
m.p. 295˚C - 297˚C. IR: 3117 - 3293 (NH). 1H NMR
(DMSO): 1.9 (s, 2H, CH2), 4.1 (s, 1H, NH-amine), 7.1 (s,
H, NH hydrazide), 7.2 - 7.8 (m, 20H, Ar-H) and 11.5 (s,
1H, =NH). MS: m/z 456 ([M+], 75%). Calcd for C30H24N4O
(456.54): C 78.92, H 5.30, N 12.27%. Found: C 77.01, H
4.20, N 11.66%.
Compound 27. Pale brown crystals (Methanol), yield
55%, m.p. 230˚C - 232˚C. IR: 3117 - 3293 (NH). 1H NMR
(DMSO): 1.9 (s, 2H, CH2), 4.1(s, 1H, NH-amine), 7.2 -
7.8 (m, 15H, Ar-H) and 11.5 (s, 1H, = NH). MS: m/z 383
([M+2] +, 30%). Calcd for C24H19N3O2 (381.43): C 75.57,
H 5.02, N 11.02%. Found: C 74.01, H 4.20, N 10.66%.
Preparation of 4,5-dihydro-4-(2-imino- 2H-chromen-
3-yl)-6-phenyl-4-(phenyl-amino) pyrimi-din-2(1-H)-one,
(28a), and its derivative (28b).
General procedure: A mixture of equimolar amounts
of 24a (3.66 g, 0.01 mol) and urea (0.60 g, 0.01 mol) or
thiourea (0.76 g, 0.01 mol) and 0.1 mL piperidine was
refluxed for 8 h. in 30 mL of ethanol. The solvent was
evaporated under vacuum, and the residue was poured to
30 ml acidified cold water and then triturated with metha-
nol. The product were filtered and crystallized from etha-
nol.
Compound 28a. Brown crystals (Ethanol); yield 67%,
m.p. 196˚C - 198˚C. IR: 1685 - 1705 (C=O), 3063 - 3288
(NH). 1H NMR (DMSO): 2.9 (s, 2H, CH2), 4.1 (s, 1H,
NH-amine), 7.2 - 7.8 (m, 15H, Ar-H), 8.1 (s, H, NH-amide)
and 11.5 (s, 1H, = NH), MS: m/z 408 ([M]+, 45%). Calcd
for C25H20N4O2 (408.45): C 73.51, H 4.94, N 13.72%.
Found: C 72.01, H 3.20, N 12.66%.
Compound 28b. Brown crystals (Methanol), yield
59%, m.p. 210˚C - 112˚C. IR: 1230 (C=S), 3063 - 3288
(NH), MS: m/z 422 ([M-2]+, 35%). Calcd for C25H20N4OS
(424.52): C 70.73, H 4.75, N 13.20%. Found: C 69.01, H
3.20, N 12.66%.
Preparation of 1, 2, 5, 6-tetrahydro-6-(2-imino-2H-
chromen-3-yl)-2-oxo-4-phenyl-6-(phenylamino) pyrine-
carbonitrile, (29a) and its derivatives (29b - 29e) and
(30).
General procedure: A mixture of 24a (3.66 g, 0.01
mol) and cyanoacetamide (0.84 g, 0.01 mol) in 30 ml of
ethanol in the presence of 0.1 ml of piperidine was re-
fluxed for 8 h. The reaction mixture was concentrated
under vacuum and the residue washed with acidified cold
water and then triturated with methanol. The solid product
formed was filtered and crystallized from ethanol to afford
29a in 65% yield. In analogously, the Chalcone 24a was
reacted with cyanothioacetamide (1.0 g, 0.01 mol), 2-
cyano-N-p-tolylacetamide (1.74 g, 0.01 mol), 2-cyanoace-
tohydrazide (0.99 g, 0.01 mol), 2-cyano-N-phenylace-
tamide (1.6 g, 0.01 mol) and 2-chloroacetamide (0.93 g,
0.01 mol) to yield the pyridine derivatives 29b -29e and
30 respectively.
Compound 29a. Yellow crystals (Methanol), yield 56%,
m.p. 184˚C - 186˚C. IR: 1689 - 1705 (C=O), 2220 (CN),
3188 - 3244(NH). 1H NMR (DMSO): 2.9 (s, 2H, CH2),
4.1 (s, 1H, NH-amine), 7.2 - 7.8 (m, 15H, Ar-H), 8.1 (s, H,
NH-amide) and 11.5 (s, 1H, =NH), MS: m/z 432 ([M]+,
65%). Calcd for C27H20N4O2 (432.47). C 74.98, H 4.66, N
12.95%. Found: C 73.01, H 3.20, N 11.66%.
Compound 29b. Pale yellow crystals (Methanol), yield
50%, m.p. 240˚C - 242˚C. IR: 1251 (C=S), 2218 (CN),
3188 - 3244 (NH). MS: m/z 448 ([M]+, 45%). Calcd for
C27H20N4OS (448.54). C 72.30, H 4.49, N 12.49, S 7.15%.
Found: C 71.11, H 3.21, N 11.12, S 6.55%.
Compound 29c. Pale red crystals (Methanol), yield 60%,
m.p. 235˚C - 238˚C, IR: 1689 – 1705 (C=O), 2210 (CN),
3188 - 3244 (NH), MS: m/z 522 ([M] +, 40%). Calcd for
C34H26N4O2 (522.6): C 78.14, H 5.01, N 10.72%. Found:
C 77.01, H 4.20, N 9.66%.
Compound 29d. Pale red crystals (Methanol), yield 75%,
m.p. 217˚C - 219˚C. IR: 1689 – 1705 (C=O), 2210 (CN),
3188 - 3344 (NH and NH2). MS: m/z 447 ([M] +, 35%).
Calcd for C27H21N5O2 (447.49): C 71.47, H 4.73, N
15.65%. Found: C 70.01, H 3.20, N 14.66%.
Compound 29e. Yellow crystals (Methanol), yield 35%,

I. H. EL AZAB, F. M. ABD EL LATIF 49
m.p. 280˚C - 282˚C. IR: 1689 - 1705 (C=O), 2210 (CN),
3188 - 3344 (NH and NH2). 1H NMR (DMSO): 1.9 (s, 2H,
CH2), 2.1 (s, 2H, NH2), 4.1 (s, 1H, -NHPh), 7.2 - 7.8 (m,
20H, Ar-H) and 11.5 (s, 1H, =NH), MS: m/z 510 [M + 2]+,
50 %). Calcd for C33H24N4O2 (508.57). C 77.93, H 4.76, N
11.02%. Found: C 76.41, H 3.10, N 10.06%.
Compound 30. Brown crystals (Methanol), yield 50%,
m.p. 220˚C - 222˚C. IR: 1699 - 1705 (C=O), 3188 - 3244
(NH). 1H NMR (DMSO): 1.9 (s, 2H, CH2), 4.1 (s, 1H, NH-
amine), 7.2 - 7.8 (m, 15H, Ar-H), 8.1 (s, H, NH) and 11.5 (s,
1H, =NH), MS: m/z 441 ([M]+, 55%). Calcd for
C26H20N3O2Cl (441.91). C 70.67, H 4.56, N 9.51, Cl 8.02%.
Found: C 69.11, H 3.20, N 8.26, Cl 7.61%.
Preparation of 2-(2-imino-2H-chromen-3-yl)-4-phe-
nyl-2-(phenylamino)pyrido-[1,2-a]benzim-idazo-lo-5-
carbonitriles, (31). A mixture of 24a (3.66 g, 0.01 mol),
2-cyanomethylbenzimidazole (1.57 g, 0.01 mol) and 0.1
mL of piperidine in 30 mL of ethanol was refluxed for 8 h.
The solvent was evaporated under vacuum and the residue
was washed by acidified cold water and then triturated
with methanol. The solid product was filtered and crys-
tallized from ethanol, as brown crystals, yield 65%, m.p.
278˚C - 280˚C. IR: 2220 (CN), 3188 - 3244 (NH). 1H
NMR (CDCl3): 2.9 (s, 2H, CH2), 4.1 (s, 1H, NH-amine),
6.9 - 7.6 (m, 19H, Ar-H) and 11.5 (s, 1H, =NH), MS: m/z
505 ([M] +, 35%). Ca lcd for C33H23N5O (505.57): C 78.40,
H 4.59, N 13.85%. Found: C 77.01, H 3.20, N 12.66%.
Preparation of 2,3-dihydro-2-(2-imino-2H-chrom-e-
n-3-yl)-N,4-diphenyl-benzo[b][1,4]oxazepin-2-amine,
(32a) and its derivatives, (32b).
Genera l procedure : A mixture of an equimolar amounts
of 24a (3.66 g, 0.01 mol) and (1.09 g, 0.01 mol) o-
aminophenol and (1.25 g, 0.01 mol) o-aminothiophenol
respectively, in 30 mL ethanol containing 0.1 mL of piperi-
dine was refluxed for 8 hr. The reaction mixture was con-
centrated, cooled then poured into ice/H2O mixture. The
solid product thus so formed was filtered, washed for sev-
eral times with water and crystallized from ethanol.
Compound 32a. Brown crystals (Ethanol), yield 60%,
m.p. 282˚C - 284˚C, IR: 3289(NH), 1H NMR (DMSO):
2.9(s, 2H, CH2), 4.1(s, 1H, NH-amine), 6.7 - 7.3 (m, 19H,
Ar-H) and 11.5(s, 1H, = NH), MS: m/z 457 ([M] +, 55%).
Calcd for C30H23N3O2 (457.52): C 78.75, H 5.07, N 9.18%.
Found: C 77.01, H 4.20, N 8.66%.
Compound 32b. Yellow crystals (Ethanol), yield 45 %,
m.p. 270˚C-272˚C. IR: 3188-3244(NH), 1H NMR (CDCl3):
1.9 (s, 2H, CH2), 4.1 (s, 1H, NH-amine), 6.9 - 7.6 (m, 19H,
Ar-H) and 11.5 (s, 1H, =NH), MS: m/z 476 ([M+3]+, 45%).
Calcd for C30H23N3OS (473.59). C 76.08, H 4.90, N 8.87,
S 6.77%. Found: C 77.01, H 3.20, N 12.66, S 5.12%.
Preparation of 2-(dicyanomethylene)-1,2,5,6-tetra-
hydro-6-(2-imino-2H-chromen-3-yl)-4-phenyl-6-(phe-
nylamino)pyridine-3-carbonitrile, (33a) and its de-
rivatives (33b).
General procedure: A mixture of 24a (0.366 g, 0.001
mol) and 2-aminoprop-1-ene-1,1,3-tricarbonitrile (0.132
g, 0.001 mol) in 30 mL of ethanol in the presence of 0.1
mL of piperidine was refluxed for 8 h. The reaction mix-
ture was concentrated under vacuum and the residue
washed with acidified cold water and then triturated with
methanol. The solid product formed was filtered and
crystallized from methanol to afford 33a in 60% yield. In
analogously, the Chalcone 34a was reacted with ethyl
3-amino-2, 4-dicyanobut-2-enoate (1.79 g, 0.01 mol) to
yield the pyridine derivative 33b.
Compound 33a. Yellow crystals (Methanol), yield 60%,
m.p. 184˚C - 186˚C. IR: 2219 (CN), 3289 (NH). 1H NMR
(DMSO): 2.9 (s, 2H, CH2), 4.1 (s, 1H, NH-amine), 6.7 -
7.3 (m, 15H, Ar-H), 8.1 (s, H, NH) and 11.5 (s, 1H, =NH),
MS: m/z 482 ([M+2]+, 35%). Calcd for C30H20N6O
(480.52). C 74.99, H 4.20, N 17.49%. Found: C 73.01, H
3.20, N 16.66%.
Compound 33b. Pale yellow crystals (Methanol), yield
45%, m.p. 240˚C - 242˚C. IR: 2219 (CN), 3289 (NH). 1H
NMR (DMSO): δ 1.2 (t, 3H, CH3), 2.2 (s, 2H, CH2), 3.7 (q,
2H, CH2), 4.1 (s, 1H, NH-amine), 6.7 - 7.9 (m, 15H, Ar-H)
and 11.5 (s, 1H, =NH), MS: m/z 527 ([M]+, 35%). Calcd
for C32H25N5O3 (527.57). Calcd: C 72.85, H 4.78, N 13.27%.
Found: C 71.14, H 3.01, N 12.88%.
Preparation of 3-chloro-4- (2-imino-2H-chromen-3-
yl)-1-phenyl-4-(phenyl-amino) azetidin-2-one, (34a) and
its derivatives, (34b - 34e).
Compound 34a. Brown crystals (Methanol) yield 60%,
m.p. 280˚C - 282˚C. IR: 1705 (C=O), 3289 (NH). 1H
NMR (DMSO): 4.1 (s, 1H, NH-amine), 5.2 (s, 1H, CH,
C-3 of β-lactam ring), 7.1 - 7.6 (m, 15H, Ar-H) and 11.5 (s,
1H, =NH), MS: m/z 415 ([M]+, 40%), Calc d for
C24H18N3O2Cl (415.87): C 69.31, H 4.36, N 10.10, Cl
8.5279%. Found: C 68.19, H 3.21, N 9.18, Cl 7.12%.
Compound 34b. Pale yellow crystals (Methanol), yield
63%, m.p. 275˚C - 277˚C. IR: 1705(C=O), 3289 (NH),
3388(OH). 1H NMR (DMSO): 4.1 (s, 1H, NH-amine), 5.2
(s, 1H, CH, C-3 of β-lactam ring), 7.1 - 7.6 (m, 14H, Ar-H),
11.5 (s, 1H, =NH) and 10.1 (s, 1H, phenolic OH). MS: m/z
431([M]+, 55%), Calcd for C24H18N3O3Cl (431.87): C
66.75, H 4.20, N 9.73, Cl 8.21%. Found: C 65.09, H 3.52,
N 9.08, Cl 7.12%.
Compound 34c. Pale brown crystals (Methanol), yield
70%, m.p. 210˚C - 212˚C. IR: 1705 (C=O), 3289 (NH). 1H
NMR (CDCl3): 4.1 (s, 1H, NH-amine), 5.2 (s, 1H, CH,
C-3 of β-lactam ring), 7.1 - 7.6 (m, 14H, Ar-H) and 11.5 (s,
1H, =NH). MS: m/z 460([M]+, 40%), Calcd for C24H17N4O4Cl
(460.87): C 62.55, H 3.72, N 12.16, Cl 7.69%. Found: C
61.07, H 2.22, N 11.18, Cl 6.11%.
Compound 34d. Brown crystals (Ethanol), yield 62%,
m.p. 175˚C - 177˚C. IR: 1705 (C=O), 3289 (NH). MS: m/z
461 ([M + 1]+, 55%), Calcd for C24H17N4O4Cl (460.87): C
62.55, H 3.72, N 12.16, Cl 7.69%. Found: C 61.17, H 2.25,

I. H. EL AZAB, F. M. ABD EL LATIF 50
N 11.48, Cl 6.21%.
Compound 34e. Yellow crystals (Ethanol), yield 55%,
m.p. 250˚C - 252˚C. IR: 1705 (C=O), 3289 (NH). 1H
NMR (CDCl3): 4.1 (s, 1H, NH-amine), 5.2 (s, 1H, CH, C-3
of β-lactam ring), 7.1 - 7.6(m, 14H, Ar-H) and 11.5 (s, 1H,
=NH). MS: m/z 450([M]+, 65%), Calcd for C24H17N3O2Cl2
(450.32): C 64.01, H 3.81, N 9.33, Cl 7.11%. Found: C
63.07, H 2.82, N 8.18, Cl 6.41%.
Preparation of 2-(2-imino-2H- chromen-3-yl)-3-phe-
nyl-2-(phenylamino) thiazolidin-4-one, (35a) and its
derivatives (35b - 35 e ).
General procedure: An equimolar mixture of 25a (0.99
g, 0.003 mol) and thioglycolic acid (0.276 mL, 0.003 mol)
in dry benzene (20 mL) was refluxed for 10 h. The reac-
tion mixture was evaporated to dryness under reduced
pressure. The thiazolidinone was separated off, washed
with ether and crystallized from ethanol. Analogously,
25b - 25e reacted with thioglycolic acid to yield 35b - 35e.
Compound 35a. Yellow crystals (ethanol), yield 60%,
m.p. 185˚C - 187˚C. IR: 1230 (CS), 1695 (C=O), 3289
(NH). 1H NMR (DMSO): 3.8 (s, 2H, CH2), 4.1(s, 1H, NH-
amine), 6.8 - 7.8 (m, 15H, Ar-H) and 11.5 (s, 1H, =NH).
MS: m/z 411 ([M − 2]+, 35%). Calcd for C24H19N3O2S
(413.49): C 69.71, H 4.63, N 10.16, S 7.91%. Found: C
68.46, H 3.17, N 9.46, S 6.55%.
Compound 35b. Yellow crystals (Methanol), yield 70%,
m.p. 215˚C - 117˚C. IR: 1230 (CS), 1695 (C=O), 3289
(NH). 1H NMR (DMSO): 3.8 (s, 2H, CH2), 4.1 (s, 1H, NH-
amine), 6.8 - 7.8 (m, 15H, Ar-H), 11.5 (s, 1H, =NH) and
10.1 (s, 1H, phenolic OH). MS: m/z 429([M]+, 44%). Calcd
for C24H19N3O3S (429.49): C 67.12, H 4.46, N 9.78, S
7.47%. Found: C 66.46, H 3.17, N 8.46, S 6.25%.
Compound 35c. Pale brown crystals (Ethanol), yield
76%, m.p. 198˚C - 200˚C. IR: 1230 (CS), 1695 (C=O),
3289 (NH). 1H NMR (DMSO): 3.8 (s, 2H, CH2), 4.1 (s,
1H, NH-amine), 6.8 - 7.8 (m, 14H, Ar-H) and 11.5 (s, 1H,
=NH). MS: m/z 457 ([M-1]+, 55%). Calcd for C24H18N4O4S
(458.49): C 62.87, H 3.96, N 12.22, S 6.99%. Found: C
61.66, H 3.17, N 11.16, S 5.55%.
Compound 35d. Yellow crystals (Ethanol), yield 65%,
m.p. 290˚C - 292˚C. IR: 1230 (CS), 1695 (C=O), 3289
(NH). MS: m/z 458 ([M]+, 55%). Calcd for C24H18N4O4S
(458.49): C 62.87, H 3.96, N 12.22, S 6.99%. Found: C
61.12, H 3.74, N 11.18, S 6.25%.
Compound 35e. Brown crystals (Methanol), yield 62%,
m.p. 235˚C - 237˚C. IR: 1230 (CS), 1695 (C=O), 3289
(NH). 1H NMR (DMSO): 3.8 (s, 2H, CH2), 4.1 (s, 1H,
NH-amine), 6.8 - 7.8 (m, 14H, Ar-H) and 11.5 (s, 1H, =NH).
MS: m/z 447 ([M]+, 65%). Calcd for C24H18N3O2SCl
(447.94): C 64.35, H 4.05, N 9.38, S 7.91%. Fo und: C
63.63, H 3.57, N 9.16, S 6.55%.
3. Results and Discussion
The synthetic procedures adopted to obtain the target
compounds are depicted in Schemes 1 - 10. The starting
compound, 2-imino-N-phenyl-2H-chromene-3-carboxami-
de 1, was prepared according to the previously reported
procedure [18]. Thus, refluxing of compound 1 with triethyl
orthoformate in dimethylformamide affording 2-ethoxy-2,3-
dihydro-3-phenylchromeno[2,3-d]pyrimidin-4-one 2, (Sche-
me 1). The structure of the later product was based on IR,
1H NMR, and mass spectra. The IR spectrum of 2 showed
the lack of any absorption of the NH functions, and the 1H
NMR spectrum (CDCl3) displayed a triplet at δ 1.2 and a
quartet at 3.9 ppm due to the ethoxy protons and a multi-
plet at 6.7 - 7.9 ppm due to aromatic protons, respectively.
The MS of 2 showed the [M]+ ion at m/z 320 (65%). Fur-
thermore, compound 2 was allowed to react with hydrazine
hydrate in ethanolic solution using piperidine as a catalyst
yielding 2-hydrazinyl-2, 3-dihydro-3-phenyl-chromeno[2,3-
d] pyrimidin-4-one, 3. The structure of 3 was confirmed
based on elemental and spectroscopic analysis. The IR
spectrum of 3 showed the presence of absorption bands at
υ 1670, 3282 and 3432 cm–1 due to CO, NH and NH2
groups, respectively. The 1H NMR spectrum (DMSO)
displayed three signals at δ 4.82, 5.1 and 8.85 due to NH2,
pyrimidine proton and NH respectively, and a multiplet at
6.7 - 7.9 ppm, for aromatic protons. While, the MS of 3
showed m/z at 309 ([M + 3]+, 45%).
Compound 3 was utilized as a key intermediate for the
synthesis of some new pyrazole derivatives based on mild
and efficient reaction of compound 3 with some of labo-
ratory available compounds. Thus, Compound 3 reacted
with ethyl 3-amino-2,4-dicyanobut-2-enoate in boiling
DMF containing a catalytic amount of piperidine. Two
isomeric products seemed possible for this reaction 5 or 6,
(Scheme 2). Structure 6 ruled out based on analytical and
spectroscopic data (IR, 1H NMR and MS). Thus, the IR
spectra of the product 5 showed the presence of absorption
bands at υ 1699, 2219 and 3422 cm–1 due to C=O, CN and
NH2 groups, respectively. Accordingly, the 1H NMR
spectrum (DMSO) of the product 5 showed three singlet
signals at δ 2.9, 3.5 and 3.7 due to the methylene and two
NH2 groups respectively, and a multiplet at 6.7 - 7.9 ppm,
due to aromatic protons. The MS of 5 displayed [M]+ at
m/z 439 (60%). It is note worth that, trial to cyclise 5 in
boiling pyridine was unsuccessful, (Scheme 2).
Also, compound 3 reacted with diethyl malonate in boil-
ing DMF containing a catalytic amount of piperidine af-
forded 1-(3,4-dihydro-4-oxo-3-phenyl-2H-chromeno[2,
3-d]pyrimidin-2-yl)pyrazolidine-3,5-dione 7, (Scheme 3).
The structure of 7 was confirmed based on elemental and
O
NHPh
NH
O
1
CH(OC2H5)3
O N
N
OPh
OEt
2
H2NNH2.H2O
Ethanol/Pip. O N
N
OPh
NHNH2
3
DMF,Piperidine
Schemes 1. Synthetic route to variously substituted 2, 3-
dihydro-3 -phe ny lchrome no[2,3 - d] pyrimidin-4-one.

I. H. EL AZAB, F. M. ABD EL LATIF 51
spectroscopic analysis. The IR spectra 7 showed the pres-
ence of absorption band centered between υ 1685 - 1705,
3212 cm-1 due to CO and NH functions respectively.
Accordingly, the 1H NMR spectrum (CDCl3) of 7 showed
three singlet signals at δ 3.2, 5.8 and 8.1 ppm due to the
methylene, methine and NH pyrazole ring protons re-
spectively, and a multiplet at δ 6.1 - 7.8 for aromatic pro-
tons. The MS of 7 displayed m/z at 374 ([M]+, 55%).
Similarly, compound 3 was allowed to react with ethyl
2-cyanoacetate, ethyl 3-oxobutanoate and pentane-2,4-dione
to afford the corresponding pyrazole derivatives 8 - 10
respectively, (Schemes 3).
Likewise, compound 3 was reacted with 2-(ethoxyme-
thylene) malononitrile and 2-cyano-N-phenylacetamide
gave the corresponding pyrazole derivatives 12, 13a, b
respectively, (Scheme 4). While the reaction of com-
pound 3 with nitrous acid afforded the tetrazolo[1,5-
a]pyrimidine derivatives 11, (Scheme 4). The structure of
these compounds was in agreement with analytical and
spectroscopic data. The IR spectrum of 11 showed the
presence of absorption bands at υ 1699 cm–1 due to CO
group. While, the MS of compound 11 showed m/z at
317([M]+, 60%), ( Scheme 4).
On the other hand, the hydrazine 3 reacted with aro-
matic aldehydes afforded 2-(2-benzylidenehydrazinyl)-3-
phenyl-3H-chromeno[2,3-d]pyrimidin-4-one 14, which
was cyclized to 5-oxo-1-(4-oxo-3-phenyl-4,10-dihydro-
3H-chromeno[2,3-d]pyrimi-din-2-yl)-3-phenylpyrazolid-
ine-4-carbonitrile 16 by treatment with ethyl cyanoace-
tate. It seemed that the addition of active methylene hy-
drogen of ethyl cyanoacetate to the imino carbon of 14
gave the intermediate 15, which subsequently cyclized
via elimination of ethanol molecule yielding 16. The MS
of 16 showed m/z at 462 (M + 1)+, 55%. Its IR spectrum
revealed absorption bands at υ 3432 cm-1 (NH), 2217cm-1
(CN) and 1670 cm-1 (CO). The 1H NMR spectrum showed
a multiplet signals at δ 6.71 - 7.92 for aromatic protons
and three singlet signals at δ 3.98, 4.12 and 4.21 due to -NH,
the two methine protons of pyrazole ring, respectively,
(Scheme 5). The compound 16 was transformed in to the
chloro derivatives 17, by treatment with phosphoryl chlo-
ride (Scheme 5). The MS of 17 showed at m/z at 478 ([M
− 1]+, 16%). The IR spectrum of 17 showed the presence
of absorption band at ν 1700 cm-1 due to C=O, 2217 cm-1
due to CN and 3425 cm-1 due to NH function. The
1HNMR of compound 17 showed singlet signals at δ ppm
3.98 and 4.61 due to NH and methane proton of pyrazole
ring.
Compound 17 was utilized as a useful starting material
for the synthesis of a variety heterocycle-isolated coumarin
derivatives based on mild and efficient reaction of com-
pound 17 with some of laboratory available compounds.
Thus, compound 17 reacted with 5-amine-1H-1,2,4-tri-
azole in boiling DMF containing a catalytic amount of
piperidine afforded 2-(4-amino-3-phenyl-2,3-dihydro-1H-
pyrazolo[4,3- e][1 ,2,4 ] tr iazolo[1,5-a]pyrimidin-1-yl)-3-phe-
nyl-3H-chromeno[2,3-d]pyrimidin-4(10H)-one 18, (Sche-
me 6). Similarly, compound 17 reacted with 5-amino-3-
(methylthio)-1H-pyrazole-4-carbonitrile yielded 4-amino-
7-( meth yl th io )-1-(4-oxo-3-p hen yl -4 ,10-dihydro-3H-chro-
meno[2,3-d]pyrimidin-2-yl)-3-phenyl-2, 3-dihydro-1H-di-
pyrazolo[1,5-a:4’,3’-e]pyrimidine-6-carbonitrile 19. The
O N
N
OPh
6
NNH2
O
H2NCN
DMF, Piperidine
Reflux
CN
CO2C2H5
H2N
NC
O N
N
N
Ph
O
N
N
NH2
H2N
O
3
O N
N
OPh
NN
O
H2N
CN
NH2
5
CN
Pyridene/Reflux
-EtOH
4
Scheme 2. Synthetic rpute to prepare isolated pyrazole derivatives and reaction conditions.
Y- CH2CO2Et
O N
N
OPh
N
Y
NH 2
O
ON
N
O
Ph
7;X =O, Z = NH
8;X=NH
2,Z=N
9;X=CH
3,Z=N
NZ
O
X
DMF, Piperidine
Reflux
O N
N
OPh
NNCH3
H3C
MeMe
OO
10
DMF, Piperidine
Reflu x
3
Y=-CO
2Et, CN, -COCH3,
Scheme 3. Synthetic rpute to isolated oxazole 7 and pyrazole derivatives 8 - 10, and reaction conditions.

I. H. EL AZAB, F. M. ABD EL LATIF 52
3
HN O2
O
N
OPh
NN
N
N
EtO
CN
CN
O N
N
O
Ph
NN
NH2
CN
11
12
NHCOCH2CN
O N
N
O
Ph
NN
NH2 ArH2N
Ar
DMF, Piperidine
DMF, Piperidine
Reflux
Refl ux
13a,Ar= phenyl
b, Ar = thiazole
O N
N
O
Ph
N
CN
NH2
ArH2N
O N
N
OPh
N
CN
NH 2
CN
Scheme 4. Synthetic rpute to isolated pyrazole derivatives and r e ac tion conditions.
3O
N
OPh
NN
H
NO
N
OPh
NN
H
H
N
O
N
OPh
NNNH
O
CN
PhCHO
DMF, Piperidine
Ref lux
CNCH2CO2C2H5
DMF, Piperidine
Ref lux
POCl 3
O
N
OPh
NNNH
Cl CN
14
15
16
17
CN
EtO
O
-EtOH
Scheme 5. Synthetic rpute to isolated pyrazole derivatives and r e ac tion conditions.
17
CH3ONa
DMF, Piperidine
Reflux
O
N
OPh
NNNH
H3CO CN
20
O
N
OPh
NNNH
N3CN
21
NaN3NNH
NH2
NC
H3CS O
N
OPh
NNNH
19
N
N
N
NH 2
NC
H3CS
O
N
OPh
NNNH
18
N
N
N
NNH 2
N
NNH
NH 2
DMF,PiperidineDMF,Piperidine
DMF,Piperidine
Reflux
HN2NH2
Reflux Reflux
Reflux
DMF, Piperidine
O
N
OPh
NNNH
HN
CN
22
NH2
O
N
OPh
NNNH
23
HN
NNH 2
Scheme 6. Synthetic rpute to isolated and/or fused pyrazole derivatives 18 - 23, and reaction conditions.

I. H. EL AZAB, F. M. ABD EL LATIF 53
structure of these compounds was confirmed based on
elemental and spectroscopic analysis. (See experimental
section). Also, the chloro derivative 17 was converted to
the 5-methoxy-1-(4-oxo-3-phenyl-4,10-dihydro-3H-chro-
meno[2,3-d]pyrimidin-2-yl)-3-phenyl-2,3-dihy-dro-1H-
pyrazole-4-carbonitrile 20 by refluxing with MeONa,
(Scheme 6). Structure 20 confirmed based on analytical
and spectroscopic data (IR, 1H NMR and MS). Thus, the
IR spectra of the product 20 showed the presence of ab-
sorption bands at υ 1699, 2219 and 3422 cm–1 due to C=O,
CN and NH groups, respectively. Accordingly, the 1H
NMR spectrum (DMSO) of the product 20 showed three
singlet signals at δ 3.82, 3.98 and 4.61 due to the -OCH3,
-NH, and methine protons respectively, and a multiplet at
6.7 - 7.9 ppm, due to aromatic protons. The MS of 20
displayed [M]+ at m/z 475 (62%). We prepared 5-azido-1-
(4-oxo-3-phenyl-4,10-dihydro -3H-c hromeno[2,3-d]pyrimi-
din-2-yl)-3-phenyl-2, 3-dihydro-1H-pyrazole-4-carboni-
trile 21 from the chloro compound 17 by reaction with
NaN3 in acetone [21, 22] .The structure of 21 was in agree-
ment with analytical and spectroscopic data. The IR
spectrum of 21 showed the presence of absorption bands
at υ 1699 cm–1 due to CO, 2217 cm–1 due to CN and 3422
cm–1 due to NH groups. While, the MS of compound 21
showed m/z at 486([M]+, 32%). In further reactions,
chloro compound 17 on treatment with hydrazine hydrate
in DMF containing a catalytic amount of piperidine at
reflux temperature afforded 2-(4-amino-3-phenyl-2,3-di-
hydro-pyrazolo[3,4 -c]pyrazol-1(6H)-yl)-3-phenyl-3H-chro-
meno[2,3-d] pyrimidin-4(10H)-one 23, The formation of
23 may be proceeded via an initial elimination of HCl
molecule to give the intermediate 22, which cyclized by
nucleophilic addition of the amino function into the cyano
group yielded 23, (Scheme 6). The IR spectrum of 23
showed the presence of absorption bands at υ 1670 cm–1
due to (CO) and 3432 - 3455 cm–1 due to (NH, NH2) with
the absence of any characteristic absorption of (CN) group.
The 1H NMR spectrum of 23 showed four singlet at δ 3.98,
5.21, 6.53 and 9.21 ppm due to the -NH amine, methine of
pyrazole ring, amino and imino group respectively, and a
multiplet at δ 6.97 - 7.81 for aromatic protons. The MS of
23 displayed m/z at 475 (M+, 15%).
On the other hand, the carboxamide 1 easily condensed
with acetophenone derivatives in DMF containing a cata-
lytic amount of piperidine at reflux temperature to afford
chromenochalcones 24a - 24e via elimination of water
(Scheme 7). The IR spectrum of 24a showed absorption
bands at υ 1665 - 1705 and 3322 due to CO and NH groups
respectively, the Ms of 24a showed m/z at 366 ([M]+,
40%). While, the 1HNMR spectrum of 24a (DMSO)
showed three singlet signals at δ 4.1, 6.5 and 11.5 ppm due
to the NH- amine, methylene and NH-imino groups re-
spectively, and a multiplet at δ 7.1 - 7.6 for aromatic pro-
tons.
Likewise, compound 1 reacts with some aromatic amines
to afford the corresponding Schiff's base 25a - 25e, (Sche-
me 7). The IR spectrum of 25a showed the presence of
absorption bands at υ 3380, due to NH function, with the
absence of any characteristic absorption of a C=O group.
The 1H NMR spectrum (CDCl3) displayed two signals at δ
4.1, 3.7 and 11.5 due to NH-amine, and NH-imino groups
respectively, and a multiplet at 7.1 - 7.6 ppm, for aromatic
protons. While, the MS of 25a showed m/z at 339([M]+,
65%).
The reactivity of exocyclic C = C conjugated with the
carbonyl group in 24a - 24e was investigated by reaction
with hydrazines, hydroxylamine, urea, thiourea and some
laboratory available active methylene compounds. The
nature of the products obtained characterized by elemental
and spectroscopic data, indicates that the reaction pro-
ceeded via condensation followed by a nucleophilic attack
through α, β-unsaturated ketonic group. Pyrazoles/isoxazole
derivatives 26a - 26b and 27 were synthesized by treating
24a with equimolar ratios of hydrazine hydrate (or phenyl-
hydrzine or hydroxylamine respectively) in ethanol con-
taining a catalytic amount of piperidine, (Scheme 8). The
structure of these compounds was established based on
analytical and spectroscopic data. The IR spectra 26a
showed the presence of absorption band centered between
υ 3117 - 3293 cm–1 due to NH function, with the absence
of any characteristic absorption of a C=O group. Accord-
ingly, the 1H NMR spectrum (DMSO) of 26a showed four
singlet signals at δ 2.9, 4.1, 7.1 and 11.5 ppm due to the
proton at C-4 of pyrazole, NH- amine, NH- hydrazide and
=NH imino respectively, and a multiplet at δ 7.2 - 7.8 for
aromatic protons. The MS of 26a displayed m/z at 383
([M+3]+, 55%). The activation exerted by the carbonyl
group on the exocyclic double bond in 24a renders them
available for the cyclocondensation addition of various
amino compounds such as urea and thiourea. Thus, when
the chalcone 24a was reacted with an equimolar quantity
of urea or thiourea respectively, (Scheme 7) an initial
condensation of one amino group with the carbonyl func-
tion occurred releasing water, followed by a nucleophilic
addition of the second amino group to the double bond
forming 4,5-dihydro-4-(2-imino-2H-chromen-3-yl)-6-phe-
nyl-4-(phenylamino)pyrimidin-2(1H)-ones, 28a and/or
thione 28b. The structures of the synthesized compounds
were confirmed by analytical and spectroscopic data (IR,
1H NMR and MS). The IR spectra 28a showed the pres-
ence of absorption bands centered between υ 1685 - 1705,
3063 - 3288 cm–1 due to C=O and NH functions, respec-
tively. The 1H NMR spectrum (DMSO) of 28a showed
four singlet signals at δ 2.9, 4.1, 8.1 and 11.5 ppm due to
the proton at C-4 of pyrimidine, NH-amine, NH-amide
and NH-imino protons , respectively and a multiplet at δ
7.2 - 7.8 for aromatic protons. The MS of 28a showed a
peak at m/z 408 ([M]+, 45%). New pyridine derivatives

I. H. EL AZAB, F. M. ABD EL LATIF 54
have been prepared via condensation of 24a with the
active methylene groups of cyanoacetamide, cyanothioace-
tamide, 2-cyano-N-p-tolylacetamide, 2-cyanoacetohy-dra-
zide and 2-cyano-N-phenylacetamide respectively, followed
by a nucleophilic addition of the amino/imino group to the
double bond, afforded 1,2,5,6-tetrahydro-6-(2-imino-2H-
chromen-3-yl)-2-oxo(thioxo)-4-phenyl-6-(phenylamino)
pyridine-3-carbonitriles 29a - 29e , respectively (Scheme
8). The IR spectrum of 29a showed the presence of ab-
sorption bands at υ 1689 - 1705, 2220 and 3188 - 3244
cm–1 due to C=O, CN, and NH functions, respectively, and
the 1H NMR spectrum (DMSO) displayed three singlet
signals at δ 2.9, 4.1 and 8.1 due to the proton at C-5 of
pyridine, NH-amine and NH amide, respectively, and a
multiplet at 7.2 - 7.6 ppm, respectively. The MS of 29a
showed a peak at m/z 432 ([M]+, 65%).
Similarly, compound 24a reacted with 2-chloroaceta-
mide to afford 3-chloro-5, 6-dihydro-6-(2-imino-2H-chro-
men-3-yl)-4-phenyl-6-(phenylamino)pyridin-2(1H)-one
30, (Scheme 9). Also, 2-(cyanomethyl) benzimidazole,
reacted with the chalcone 24a, in ethanol using piperidine
as a catalyst gave the 2-(2-imino- 2H-chromen-3-yl)-4-
phenyl-2-(phenylamino) pyrido[1,2-a]ben-zimidazolo-5-
carbonitriles, derivative probably via initial condensation
of the activated methylene group with the carbonyl func-
tion releasing water, followed by a nucleophilic addition
of the NH group at the double bond of compound 24a to
afford 31, (Scheme 9). The structure of 31 was assigned
based on IR, 1H NMR, and mass spectra. The IR spectrum
showed the presence of absorption bands at υ 2220 cm–1
and 3188 - 3244 cm–1 due to CN and NH functions re-
spectively, while that due to C=O was completely disap-
peared, and the 1H NMR spectrum (CDCl3) displayed
three singlet at δ 2.9, 4.1 and 11.5 due to the C-3 proton,
NH-amine and NH-imino protons respectively, and a
multiplet at δ 6.9 - 7.6 ppm, for aromatic protons. The MS
showed the [M]+ ion at m/z 505 (35%). Similarly, the
chalcone 24a was reacted with amino phenols in ethanolic
solution containing a catalytic amount of piperidine to
give 2,3-dihydro-2-(2-imino-2H-chromen-3-yl)-N,4-diphe-
nyl-benzo[b][1,4]azepine derivatives , 32a, b (Scheme 9).
The IR spectrum of 32a showed the presence of absorp-
tion bands at υ 3289 cm–1 due to NH function, the 1H
NMR spectrum (DMSO) of 32a displayed three singlet
signals at δ 2.9, 4.1 and 11.5 due to the C-3 protons, NH-
amine and NH-imino protons respectively, and a multiplet
at 6.7 - 7.3 ppm for aromatic protons. While, the MS of
32a showed a peak at m/z 457 ([M]+, 55%). Also, com-
und 24a was reacted with 2-aminoprop-1-ene-1, 1,3-tri-
carbonitrile and/or ethyl 3-amino-2,4-dicyanobut-2-enoate
to afford 2-(dicyano- methylene)-1,2,5,6-tetrahydro-6-(2-
imino-2H-chromen-3-yl)-4-phenyl-6-(phenylamino)pyri-
dine-3-carbonitrile, 33a and 2-(1-cyano-2-oxobutylidene)-
1,2,5,6-tetrahydro-6-(2-imino-2H-chromen-3-yl)-4-phenyl-
6-(phenylamino) pyridine-3-carbonitrile 33b, respectively.
The structure of these products was established based on
the IR spectrum of 33a which showed the presence of ab-
sorption bands at υ 2219 and 3289 cm–1 due to C=O and
NH functions, respectively. The 1H NMR spectrum (DMSO)
of 33a displayed two singlet signals at δ 2.9 and 4.1 due to
the C-3 protons and NH-amine and a multiplet at 6.7 - 7.3
ppm for aromatic protons. While, the MS of 33a showed a
peak at m/z 482 ([M + 2]+, 35%).
On the other hand, the new synthesized Schiff’s bases
2-imino-N, N’-diphenyl-2H-chromene-3-carboxamidines,
25a - 25e, were used to prepare new compounds. Thus, cy-
cloaddition of chloroacetyl chloride to 25a - 25e pro-
ceeded smoothly in ethanolic solution containing triethy-
lamine as a catalyst to give the β-lactam, derivatives 34a -
34e, (Sc heme 10 ). The IR spectra of 34a - 34e showed the
24a -e
a,Ar= Ph
b,Ar=p-(OH)C6H4
c,Ar=p-(NO2)C6H4
d,Ar=o-(NO
2)C 6H4
e, Ar=p-(Cl)C6H4
ONH
1
ArNH2ONH
NHPh
NAr
25a-e
DMF/Reflex
DM F/Ref lex
Scheme 7
O
NHPh
Ar
Ar COCH3
Scheme 7. Synthetic rpute to chalcones 24a - e and Schiff’s bases 25a - e.

I. H. EL AZAB, F. M. ABD EL LATIF 55
24a
H2NNHX
X= H,Ph
NN
NHPh
Ph
NO
NH Ph
Ph
H2NOH
HN N
NHPh
Ph
O
28a,X=O
b,X=S
ONH
ONH
ONH 26a ,b
a, x = H
b, x = Ph
27
N
NHPh
Ph
X
ONH
CN
29a,X=O,Y=H
b,X=S,Y=H
c,X=O,Y=p-( CH 3)C6H4
d, X =O,Y =NH
2
e,X=O,Y=Ph
Ehanol/Reflex
X
CNCH2CNHY
Y
Ehanol/Ref lex
Ehanol/Reflex
Ehanol/ Reflex
Scheme 8
H2NCNH2
XX
Scheme 8. Synthetic rpute to isolated pyrazole, isoxazole, pyrimidine and pyridine derivatives 26ab, 27, 28a,b and 29a - e.
CN
X
H2N
Y
33a, Y= X=CN
b, Y=CN,X=CO
2C2H5
Ehanol/Ref lex
HN
NHPh
Ph
ONH
Y
X NC
ClCH2CONH2
Ehanol/Ref lex
30
HN
NHPh
Ph
O
ONH
Cl
N
H
NCN
Ehanol/Reflex
N
N
CN
Ph
NHPh
ONH
NH 2XH
N
X
Ph
NHPh
ONH
32a,X=O
b,X=S
Ehanol/ Reflex
31
24a
Scheme 9. Synthetic rpute for the pr e par ation of compounds 30 - 33a,b.
34a-e
ONH
25a-e
ONH
35a-e
ClCH2COCl
HSCH2COOH
benzene
TEA
NAr
Cl
NHPh
O
N
S
Ar
NHPh
O
Scheme 10a,Ar= Ph
b,Ar=p-(OH)C6H4
c,Ar=p-(NO2)C6H4
d,Ar=o-(NO
2)C6H4
e, Ar = p-(Cl)C6H4
Scheme 10. Synthetic rpute for the preparation of β-latame 34a,b. and thiazolodinone derivatives 35a - e.

I. H. EL AZAB, F. M. ABD EL LATIF 56
presence of absorption bands due to C=O and NH func-
tions respectively. The 1H NMR spectrum (DMSO) of 34c
showed three singlet signals at δ 4.1, 5.2 and 11.5 ppm for
NH-amine, the proton at C3 of the β-lactam unit and
NH-imino protons respectively and a multiplet at δ 7.1 -
7.6 for aromatic protons. The MS of 34c showed the [M]+
ion at m/z 460 (40%). Also, the Schiff’s bases 25a - 25e
were reacted with equimolar ratio of thioglycolic acid in
boiling benzene using water separator system, the thiol
group of thioglycolic acid could be added to the imino
carbon atoms of Schiff’s bases 25a - 25e followed by
smooth cyclization to afford 2-(2-imino-2H-chromen-3-
yl)-3-phenyl-2-(phenylamino) thiazolidin-4-ones, 35a -
35e (Scheme 10). The IR spectra of 35 showed bands due
to CS, CO and NH groups, respectively. While, the 1HNMR
spectrum of 35a (DMSO) showed three singlet signals at δ
3.8, 4.1 and 5.8 for the methylene of thiazolidinone, NH-
amine and NH-imino protons respectively and a multiplet
at δ 6.8 - 7.8 for aromatic protons. In the MS of 35a showed
m/z at 411 ([M-2]+, 35%).
4. Conclusion
Despite the several existing methods for the synthesis of
chromene derivatives, there still is demand for general
strategies, which can efficiently provide variously sub-
stituted chromene systems. Thus, this work opened a new
avenue for the synthesis of a variety of 2-imino-N-ph-
enyl-2H-chromene-3-carboxamide, derivatives.
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