Conversion of 2(3H)-furanones bearing indole nuclei into novel amide, pyrrolone, and imidazole derivatives

Article abstract of DOI:10.1002/hc.10175

The article discussed about the conversion of 2(3H)-Furanones bearing indole nuclei into novel amide, pyrrolone, and imidazole derivatives. All purposed structures were confirmed by NMR, mass spectra and chemical evidence. The treatment of N-Acetylisatin derivatives with anthranilic acid under different conditions was also discussed.

Full text of DOI:10.1002/hc.10175

Heteroatom Chemistry
Volume 14, Number 5, 2003
Conversion of 2(3H )-Furanones Bearing
Indole Nuclei Into Novel Amide, Pyrrolone,
and Imidazole Derivatives
Abdel-Sattar S. Hamad Elgazwy,1 H. T. Zaky,2 M. I. Mohamed,2
H. M. Ahmed,2 and N. G. Kandile2
1Department of Chemistry, Faculty of Science, University of Ain Shams, Abbassia 11566,
Cairo, Egypt
2Department of Chemistry, Faculty of Girls, University of Ain Shams, Heliopolis 11757,
Cairo, Egypt
Received 3 March 2003; revised 16 March 2003
[6] and a precursor for the synthesis of other het-
ABSTRACT: 2(3H)-Furanones 1a–d having exo-
erocycles [5,7–9]. Substituted isatins are found in
cyclic double bond and N-acetylisatin nucleus were
plants, melosatin alkaloids can be obtained from
converted into the corresponding novel amides,
the caribbean tumorigenic plant Melochia tomen-
pyrrolones, and imidazoles via nitrogen nucle-
tosa [10–12], as well as in fungi, 6-(3ꢁ-methylbuten-
ophiles. All purposed structures were confirmed by
2ꢁ-yl)isatin was isolated from Streptomyces albus [13]
NMR, mass spectra GC/MS, and chemical evi-
and 5-(3ꢁ-methylbuten-2ꢁ-yl)isatin from Chaetomium
ꢀ
C
dence. 2003 Wiley Periodicals, Inc. Heteroatom Chem
globosum [14]. The interest in isatin derivatives
stems from their pharmacological [15–16] and in-
dustrial application [17,18].
14:434–442, 2003; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.10175
INTRODUCTION
RESULTS AND DISCUSSION
Nitrogen heterocycles constitute an important class
of natural and nonnatural products many of which
exhibit useful biological activity [1–4]. Isatin, and
a number of its derivatives, posses a reactive keto-
carbonyl group that readily undergoes condensation
reactions under mild conditions [5]. It was there-
fore speculated that isatin would be a suitable elec-
trophilic component for the Baylis–Hillman reaction
The preparation of (3E)-1-acetyl-3(5-aryl-2-oxofur-
an-3(2H)-ylidene)-1,3-dihydro-2H-indol-2-ones 1a–
d has already been described [19] as part of our
previous investigation on 2-(3H)-furanones [20–24].
These form only as E-isomers. This is consistent
with the result described by Long et al. who stud-
ied monosubstituted 3-methyleneoxindoles and de-
tected for most of them only the E-isomer [25].
In this paper we examine the reactivity of 1a–d
toward some nitrogen nucleophiles. N-Acetylisatin
derivatives 1a–d were treated with anthranilic acid
and o-phenylenediamine under different conditions
(Scheme 1). With anthranilic acid in refluxing acetic
acid, ring opening occurs with the formation of the
E-isomers of amides 2a–d in 59–78% yield (i). This
Correspondence to: Abdel-Sattar S. Hamad Elgazwy, Group de
Quimica Organometalica, Departamento de Quimica Inorgan-
ica, Facultad de Quimica, Universidad de Murcia, Aptdo. 4021,
E-30071 Murcia, Spain; e-mail: abhamad@um.es.
Contract grant sponsor: Ain Shams University, Egypt.
Contract grant number: EG-SHAMS-2, 2003.
2003 Wiley Periodicals, Inc.
c
ꢀ
434

Conversion of 2(3H )-Furanones Bearing Indole Nuclei Into Novel Amide, Pyrrolone, and Imidazole Derivatives 435
acid in the presence of a catalytic amount of sodium
acetate (3 mol%) over 3 h to afford benzoimida-
zoles 4a–d in 49–82% yield (v). These were found
by direct comparison to be identical with the prod-
ucts that formed from the treatment of 2e–h with
CH3CO2H/CH3CO2Na (3 mol%) at refluxing temper-
ature (vii). These reactions revealed acid catalysis to
be essential for the ring closure of 2e–h. This reaction
condition was consistent with that described by Ni-
ume et al. for the formation of spiro-benzimidazoles
from the reaction of isatin with o-phenylenediamine
in polar aprotic solvent [26].
In addition, we have examined the reactions of
1a–d with N-aminophthalimide 5 with or without
solvent (Scheme 2). When the reaction took place in
refluxing ethanol, ring opening occurs to give amides
6a–d in 40–67% yield. But the reaction is carried out
with pure form with heating above melting point
over 2–3 h afforded N-aminopyrrolones 7a in 46%
yield.
Amide 6b was treated with equimolar amount
of benzylamine in ethanol to give hydrazide 8b in
62% yield and not N,Nꢁ-dibenzylphthalimide as we
expected [27]. Hydrazide 8b remains under our in-
vestigations and for the coversion of this type of com-
pounds into other heterocyclic compounds with an-
ticipated biological activity.
EXPERIMENTAL
Melting points were determined on a Boetius hot-
stage apparatus and are uncorrected. Chromato-
graphic separations were performed using silica gel
(Merck, 70–230 mesh). Thin-layer chromatography
was carried out on Macherey-Nagel precoated sil-
ica plate (0.25 mm layer thickness). 1H and 13C
NMR spectra were recorded with a Gemini 200 spec-
trometer in CDCl3 solution unless otherwise spec-
ified (internal standard TMS). Mass spectra were
SCHEME 1
reaction was repeated in the presence of a catalytic
amount of sodium acetate (3 mol%) with ring open-
ing and closure to give imides 3a–d in 61–80% yield
(iii). These compounds when heated neat in the pres-
ence of a catalytic amount of fused sodium acetate
(3 mol%) were found (by direct comparison of ana-
lytical data) to yield products identical to those ob-
tained by ring closure of amides 2a–d (vi).
The interaction of 1a–d with o-phenylenedi-
amine was examined with or without solvent. When
the reaction took place in refluxing ethanol over
3–5 h, ring opening occurred with the formation
of 2e–h in 75–85% yield (ii). But when the reac-
tion took place by heating of pure form to above
melting point in the presence of a catalytic amount
of sodium acetate (3 mol%), the imides 3e–h were
formed in 56–63% yield (iv). These were found by
direct comparison to be identical with the products
formed from the ring closure of 2e–h during heating
of pure form with fused sodium acetate (3 mol%)
(vi). This reaction was repeated with refluxing acetic
SCHEME 2

436 Hamad et al.
TABLE 1 13C Chemical Shifts δ C[H3]CDCl3 for 1b
(3E)-1-Acetyl-3-[(5-(4-methylphenyl)-2-oxofuran-
3(2H)-ylidene]-1,3-dihydro-2H-indol-2-one (1b).
Reddish-brown crystals 2.83 g, 82% yield, 224–226◦C
(lit. [19,27] 225–227◦C); IR (KBr pellet): 3431–3158,
(br) for (NH), 1826 (C O), 1614–1645 (C O), 1595
(C N), 1538 (C C) cm−1; LRMS (EI): m/z 345 (M+,
25), 303 (50), 119 (100), 85 (50); GC: tR = 2.81 min;
column: DB-5 6 m × 0.01 mm + 1 m guard column:
1
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/5 min; H
NMR (CDCl3, 200 MHz): δ 8.97 [d, 2H, J = 7.78 Hz,
CH3 C6H4-(2)], 8.23 [d, 2H, J = 8.06 Hz,CH3 C6H4-
(3)], 7.93 (s, 1H, CH ), 7.71 [d, 2H, J = 8.14 Hz,
Isatin-H (7)], 7.40 [t, 1H, J = 6.66 Hz, Isatin-H(6)],
7.33 [t, 1H, J = 6.28 Hz, Isatin-H(5)], 7.21 [d, 1H,
J = 7.8 Hz, Isatin-H(4)], 2.72 (s, 3H, COCH3) 2.39
(s, 3H, CH3); Calcd. for C21H15NO4 (345.04): C,
73.03; H, 4.37; N, 4.05. Found: C, 73.10; H, 4.30; N,
4.00.
C-2
C-3
C-3a
C-4
C-5
C-6
C-7
C-7a
C-8
C-9
163.2
134.7
133.1
127.3
124.1
129.5
118.1
142.8
170.3
47.8
C-10
C-11
C-12
C-13
C-14
C-15
C-16
C-17
C-18
134.1
106.0
162.1
168.8
131.1
129.2
128.4
105.9
28.8
(3E)-1-Acetyl-3[5-(4-methoxyphenyl)-2-oxofuran-
3(2H)-ylidene]-1,3-dihydro-2H-indol-2-one
(1c).
Reddish-brown crystals 2.71 g, 75% yield, mp 228–
230◦C; IR (KBr pellet): 3735–3433 for (NH), 1782 (s),
for (C O), 1609–1745 (m), for (C O), 11595–633
(s), for (C N), 1536 (C C) cm−1; LRMS (EI): m/z
361 (M+, 10), 310 (33.5), 263 (0.73), 262 (1.32), 246
(1.5), 203 (2.01), 202 (1.1), 135 (100), 101 (2), 92
(10); 77 (21), 63 (3.7), 61 (4.5); GC: tR = 6.919 min;
column: DB-5 6 m × 0.01 mm + 1 m guard column:
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/10 min;
1H NMR (CDCl3, 200 MHz): δ 9.07 [d, 2H,
J = 7.8 Hz, CH3O C6H4-(2)], 8.34 [d, 2H, J = 7.8
taken on a VG Trio-2 and GC/MS-QPL000EX (EI,
70 eV) apparatus. IR spectra were recorded with a
Perkin-Elmer 1430 instrument in KBr disks. Elemen-
tal analyses were performed by M-H-W Laboratories
(Phoenix, AZ) at Microanalytical Center of Cairo and
Ain Shams Universities.
General Procedure for 1a–d
2-(3H)-Furanones 1a–d were prepared following the
literature method [19,27], via condensation reac-
tions of isatin (0.01 mol) with 3-aroylpropionic acid
(0.01 mol) in (10 ml) acetic anhydride and fused
sodium acetate (0.03 mol) under Perkin conditions,
which yielded the corresponding E-isomers as the
only product, with no detectable amount of the
Z-isomers being identified by TLC and 1H NMR.
The reddish-green precipitate was collected by fil-
teration and recrystallized from acetic acid to give
1a–d.
Hz,CH3O C6H4-(3)], 8.00 (s, 1H,
CH ), 7.83
[d, 2H, J = 9.02 Hz, Isatin-H (7)], 7.44 [t, 1H,
J = 8.2 Hz, Isatin-H(6)], 7.27 [t, 1H, J = 5.8 Hz,
Isatin-H(5)], 7.03 [d, 1H, J = 9.06 Hz, Isatin-H(4)],
3.89 (s, 3H, OCH3) 2.76 (s, 3H, COCH3). Calcd.
for C21H15NO5 (361.35); C, 69.80; H, 4.18; N, 3.87.
Found: C, 69.90.; H, 4.30; N, 3.80.
(3E)-1-Acetyl-3[5-(4-chlorophenyl)-2-oxofuran-
3(2H)-ylidene]-1,3-dihydro-2H-indol-2-one (1d).
Reddish-brown crystals 3.11 g, 85% yield, mp 216–
217◦C; IR (KBr pellet): 3431–3145 (br), for ( NH);
1771 (s), for (C O), 1610–1653 (m), (C O), 1596
(m), (C N) 1538 (C C) cm−1; LRMS (EI): m/z 365
(M+, 25), 366 (8.5), 320 (5), 325 (22), 323 (11.5), 322
(82.22), 256 (7.20), 240 (3.34), 184 (20.03), 140 (19.5),
141 (34.45), 140 (10.93), 139.95 (100), 133 (10.17),
120 (17.3), 113 (25), 112 (12.11), 111 (52.5), 100
(10.17), 60 (57), 57 (70), 56 (34); GC: tR = 1.89 min;
column: DB-5 6 m × 0.01 mm + 1 m guard column:
(3E)-1-Acetyl-3(2-oxo-5-phenylfuran-3(2H)-ylide-
ne)-1,3-dihydro-2H-indol-2-one(1a). Reddish-green
crystals 2.65 g, 80% yield, mp 210–211◦C (lit. [19,27]
209–211◦C); IR, 3445–3155 (bv) for (NH), 1790
(C O), 1715–1730 (C O), 1550 (C N), 1500 (C C)
cm−1; 1H NMR (CDCl3, 200 MHz): δ 8.89–8.34
[m, 5H, Ph-H), 8.22 (s, 1H, CH ), 7.83 [d, 2H,
J = 9.0 Hz, Isatin-H (7)], 7.44 [t, 1H, J = 9.0 Hz,
Isatin-H(6)], 7.27 [t, 1H, J = 9.0 Hz, Isatin-H(5)],
7.03 [d, 1H, J = 9.0 Hz, Isatin-H(4)], 2.75 (s, 3H,
COCH3). Calcd. for C20H13NO4 (331.3): C, 72.50; H,
3.95; N, 4.22. Found: C, 72.40; H, 4.20; N, 4.20.
1
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/5 min; H
NMR (CDCl3, 200 MHz): δ 9.05 [d, 2H, J = 8.06 Hz,
Cl C6H4-(2)], 8.30 [d, 2H, J = 7.8 Hz, Cl C6H4-(3)],

Conversion of 2(3H )-Furanones Bearing Indole Nuclei Into Novel Amide, Pyrrolone, and Imidazole Derivatives 437
50◦C/2 min/20◦C/1 min/250◦C/10 min; 1H NMR
(CDCl3, 200 MHz): δ 13.62 (bs, 1H, CO2H), 8.89
(bs, 1H, CONH), 7.98 (s, 1H, Ar-H), 7.86 [d, 2H,
J = 9.06 Hz, CH3 C6H4-(2)], 7.68–7.09 [m, 7H,
Ar-H), 7.02 [d, 2H, J = 9.06 Hz, CH3 C6H4-(3)],
6.85 [d, 1H, J = 6.00 Hz, Isatin-H(4)], 6.82 (s, 2H,
CH2), 3.89 (s, 3H, OCH3), 2.77 (s, 3H, COCH3).
Calcd. for C28H22N2O7 (498.49); C, 67.46; H, 4.44; N,
5.61; Found: C, 67.90; H, 4.50; N, 6.00.
8.05 (s, 1H, CH ), 7.82 [d, 2H, J = 6.8 Hz, Isatin-H
(7)], 7.60 [t, 1H, J = 7 Hz, Isatin-H(6)], 7.50 [t, 1H,
J = 7 Hz, Isatin-H(4)], 7.23 [t, 1H, J = 6.8 Hz,
Isatin-H(5)], 2.75 (s, 3H, COCH3). Calcd. for
C20H12ClNO4 (365.77): C, 65.67; H, 3.30; N, 3.82; Cl,
9.69; Found: C, 65.60; H, 3.40; N, 3.90; Cl, 9.50.
General Procedure for 2a–d
To a suspension of 1a–d (0.01 mol) in (25 ml) acetic
acid, anthranilic acid (0.01 mol) was added and the
reaction mixture was refluxed for 2 days, then cooled.
The reddish soild precipitate was collected by filter-
ation and recrystallized from acetic acid to give 2a–d.
2-{[(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-4(4-chlorophenyl)-4-oxobutanoyl]amino}-
benzoic Acid (2d). Brown crystals 3.65 g, 72%
yield, mp 245–247◦C; IR (KBr pellet): 3419–3064
(broad band) for (OH and NH), 1705.4 (m) for
(C O), 1599.5 (m) for (C O), 1545.6 (s), and 1486
(m) for (C N) cm−1; LRMS (EI): m/z 505 (M+,
8), 442 (8.7), 384 (8.72), 383 (10.87), 296 (12),
256 (511.4), 234 (10), 210 (9), 191 (10), 190 (10),
156 (10), 148 (20.8), 140.95 (39.8), 139 (100), 134
(9.8), 132 (14), 129 (19.46), 128 (20), 111 (93.2),
75 (77.10); 1H NMR (CDCl3, 200 MHz): δ 13.66
(bs, 1H, CO2H), 8.88 (bs, 1H, CONH), 7.98 (s,
1H, Ar-H), 7.87 [d, 2H, J = 9.06 Hz, Cl C6H4-(2)],
7.68–7.09 [m, 6H, Ar-H), 7.02 [d, 2H, J = 9.06 Hz,
Cl C6H4-(3)], 6.85 [d, 1H, J = 6.00 Hz, Isatin-H(4)],
6.82 (s, 2H, CH2), 3.89 (s, 3H, OCH3), 2.11 (s,
3H, COCH3); GC: tR = 8.017 min; column: DB-5
6 m × 0.01 mm + 1 m guard column: temp. prog:
50◦C/2 min/20◦C/1 min/250◦C/10 min. Calcd. for
C27H19ClN2O6 (502.9); C, 64.48; H, 3.80; N, 5.57; Cl,
7.04; Found: C, 64.50; H, 3.70; N, 5.32; Cl, 7.70.
2-{[(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-4-oxo-4-phenylbutanoyl]amino} benzoic
Acid (2a). Brown crystals 3.05 g, 65% yield, mp
125–127◦C; IR (KBr pellet): 3423 (broad band) for
(NH), 1686 (m) for (C O), 1602 (v) for (C O), 1550
1
(s), 1517 (s) for (C N) cm−1; H NMR (CDCl3, 200
MHz): δ 13.59 (bs, 1H, CO2H), 8.88 (bs, 1H, CONH),
7.98–6.85 (m, 13H, Ar-H), 6.82 (s, 2H, CH2), 2.78
(s, 3H, COCH3). Calcd. for C27H20N2O6 (468.46); C,
69.22; H, 4.30; N, 5.97; Found: C, 69.50; H, 4.50; N,
6.00.
2-{[(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-4(4-methylphenyl)-4-oxobutanoyl]amino}-
benzoic Acid (2b). Brown crystals 3.77 g, 78% yield,
mp 175–177◦C; IR (KBr pellet): 3250–3425 (broad
band) for (OH and NH), 1770.3 (s) for (C O), 1702
(m) for (C O), 1611.5 (v) for (C O), 1542.1 (s),
and 1503 (s) for (C N). cm−1; 1H NMR (CDCl3,
200 MHz): δ 13.63 (bs, 1H, CO2H), 8.9 (bs, 1H,
CONH) , 7.86 [d, 2H, J = 9.06 Hz, CH3 C6H4-(2)],
7.75–7.11 [m, 8H, Ar-H), 7.02 [d, 2H, J = 9.06 Hz,
CH3 C6H4-(3)], 6.84 (s, 2H, CH2), 2.75 (s, 3H,
COCH3), 2.32 (s, 3H, CH3). Calcd. for C28H22N2O6
(482.49); C, 69.70; H, 4.59; N, 5.80; Found: C, 69.80;
H, 4.50; N, 6.10.
General Procedure for 2e–h
To a suspension of 1a–d (0.01 mol) in (25 ml) ethanol,
o-phenylenediamine (0.01 mol) was added with re-
fluxing for 3 h and then cooled. The brown precip-
itate was collected by filteration and recrystallized
from ethanol to give 2e–h.
2-{[(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-4(4-methoxyphenyl)-4-oxobutanoyl]-ami-
no}benzoic Acid (2c). Brown crystals 2.95 g, 59%
yield, mp 270–272◦C, IR (KBr pellet): 3018.4–3173.5
(bv) for (OH and NH), 1768.8 (v) for (C O),
1694.1 (v) for (C O), 1613.6 (v) for (C O), 1544.6
(v), and 1502.9 (v) for (C N) cm−1; LRMS (EI):
m/z 440 (M+ − 58), 1.3), 391 (2), 320 (19.4), 319
(80.81), 291 (7), 283 (5.45), 248 (7.50), 220 (5.89),
155 (25.7), 135 (100), 120 (20), 107 (12.7), 101
(20.77), 92 (35.73), 77 (20.44), 76 (10), 75 (12.94),
64 (12.2); GC: tR = 7.134 min; column: DB-5 6
m × 0.01 mm + 1 m guard column: temp. prog:
(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-
ylidene)-N-(2-aminophenyl)-4-oxo-4-phenylbutanam-
ide (2e). Brown crystals 3.61 g, 82% yield, mp
263–264◦C; IR (KBr pellet): 3452–3153, 3059.2
(broad band) for ( NH, NH2), 1745.6 (s), 1684.7
(v), for (C O), 1606.1 (v) for (C O), 1544.5 (s),
1
and 1457.9 (s) for (C N) cm−1; H NMR (CDCl3,
200 MHz): δ 8.77 (bs, 2H, NH2), 8.55 (bs, 1H, CONH),
8.30–6.96 (m, 13H, Ar-H), 6.94 (s, 2H, CH2), 2.69
(s, 3H, COCH3). Calcd. for C26H21N3O4 (439.47); C,
71.05; H, 4.81; N, 9.56; Found: C, 71.20; H, 4.60; N,
9.90.

438 Hamad et al.
(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-
N, 8.86; Cl, 7.48; Found: C, 65.50; H, 4.10; N, 8.50;
Cl, 7.80.
ylidene)-N-(2-aminophenyl)-4(4-methylphenyl)-4-ox-
obutanamide (2f). Brown crystals 3.85 g, 85%
yield, mp 244–245◦C; IR (KBr pellet): 3447.6,
3145.7, 3045, 3005.7 (broad band) for ( NH, NH2),
1745.6 (s), 1679.8 (v), for (C O), 1608.7 (v) for
(C O), 1550.7 (s) for (C N) cm−1; 1H NMR (CDCl3,
200 MHz): δ 8.75 (bs, 2H, NH), 8.71 (bs, 1H, CONH),
8.45 (d, 2H, J = 7.8 Hz,CH3 C6H4-(3) ), 8.12 (d, 2H,
J = 7.8 Hz, CH3 C6H4-(2), 7.18-6.96 (m, 8H, Ar-H),
5.94 (s, 2H, CH2), 2.51 (s, 3H, COCH3), 1.65 (s,
3H, CH3). Calcd. for C27H23N3O4 (453.50); C, 71.51;
H, 5.11; N, 9.26; Found: C, 71.20; H, 5.10; N, 9.70.
General Procedure for 3a–d
A mixture of 1a,b,d (0.01 mol) and sodium acetate
(0.03 mol) was fused for 3 h, above melting point,
then cooled. The reddish-brown solid was collected
and recrystallized from ethanol to give 3a,b,d. Com-
pounds 3a–d were obtained by mixing 2a–d with
freshly prepared sodium acetate (0.03 mol) at melt-
ing point for 2–5 h, and were found by direct com-
parison of analytical data to be identical.
(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-
ylidene)-N-(2-aminophenyl)-4(4-methoyphenyl)-4-ox-
obutanamide (2g). Brown crystals 3.52 g, 75%
yield, mp 232–234◦C; IR (KBr pellet): 3449.3,
3165.5, 3091.2 (broad band) for ( NH, NH2),
1688.2 (v), for (C O), 1608.0 (v) for (C O), 1540.2
(s) for (C N) cm−1; LRMS (EI): m/z 469 (M+, 25.5),
468 (M+ − 1) 27.66), 400 (21.2), 399 (21), 371 (21),
360 (21), 349 (23), 348 (27), 307 (21), 305 (21), 301
(27), 291 (30), 283 (25), 283 (23), 275 (23), 251.7
(40), 251 (100), 230 (23), 222 (31), 216 (25), 206
(27), 174 (21), 171 (21), 170 (23), 185 (27), 180 (21),
159 (23), 151 (21), 149 (23), 129 (25), 100 (25), 90
(23), 72 (23), 59 (21); GC: tR = 7.955 min; column:
DB-5 6 m × 0.01 mm + 1 m guard column: temp.
prog: 50◦C/2 min/20◦C/1 min/250◦C/10 min; 1H NMR
(CDCl3, 200 MHz): δ 8.77 (bs, 2H, NH), 8.72 (s,
1H, CONH), 8.38 (d, 2H, J = 7.8 Hz, CH3O C6H4-
(3)), 8.17 (d, 2H, J = 7.8 Hz, CH3O C6H4-(2)),
8.18–6.65 (m, 8H, Ar-H), 5.98 (s, 2H, CH2), 3.89
(s, 3H, OCH3), 1.61 (s, 3H, COCH3). Calcd. for
C27H23N3O5 (469.50); C, 69.07; H, 4.93; N, 8.94;
Found: C, 68.80; H, 4.70; N, 9.10.
2-[(3E)-3-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-5-phenyl-2-oxo-2,3-dihydro-1H-pyrrol-1-
yl]benzoic Acid (3a). Reddish-brown crystals 3.13
g, 69% yield, mp >300◦C; IR (KBr pellet): 3629.9–
3407.1, 3059.0 (broad band) for ( OH), 1704.4 (s)
1
for (C O), 1660.6 (m), 1601.4 for (C O) cm−1; H
NMR (CDCl3, 200 MHz): δ 13.59 (bs, 1H, CO2H),
8.20–6.85 (m, 13H, Ar-H), 6.82 (s, 1H, CH C), 2.78
(s, 3H, COCH3). Calcd. for C27H18N2O5 (450.45); C,
71.99; H, 4.02; N, 6.21; Found: C, 72.30; H, 4.20; N,
6.00.
2-[(3E)-3-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-5-(4-methylphenyl)-2-oxo-2,3-dihydro-1H-
pyrrol-1-yl]benzoic Acid (3b). Reddish-brown crys-
tals 3.75 g, 80% yield, mp >300◦C; IR (KBr pellet):
3425.8 (broad band) for ( OH), 1688.3 (s) for
(C O), 1593.8 (v) for (C O) cm−1; 1H NMR (CDCl3,
200 MHz): δ 13.55 (bs, 1H, CO2H), 7.88 [d, 2H,
J = 9.06 Hz, CH3 C6H4-(2) ], 7.75–7.09 [m, 8H,
Ar-H), 7.02 [d, 2H, J = 9.06 Hz, CH3 C6H4-(3)], 6.84
(s, 1H, CH C), 2.75 (s, 3H, COCH3), 2.32 (s, 3H,
CH3). Calcd. for C28H20N2O5 (464.48); C, 72.40; H,
4.34; N, 6.03; Found: C, 72.30; H, 4.20; N, 6.20.
(2E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-
ylidene)-N-(2-aminophenyl)-4(4-chlorophenyl)-4-ox-
obutanamide (2h). Brown crystals 3.8 g, 80% yield,
mp 260–262◦C; IR (KBr pellet): 3447.8, 3157.3,
3051.8 (broad band) for ( NH, NH2), 1679.6.2 (v),
for (C O), 1602.2 (v) for (C O), 1582.2 (s), 1527.6
(s) for (C N) cm−1; LRMS (EI): m/z 476 (M+ − 2.5),
14), 445 (M+ − 28.5), 18), 443 (13), 398 (>5), 348
(>5), 299 (30), 298 (100), 270 (47), 255 (>5), 159
(47), 139 (72), 115 (44), 77 (42); GC: tR = 9.438 min;
column: DB-5 6 m × 0.01 mm + 1 m guard column:
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/10 min; 1H
NMR (CDCl3, 200 MHz): δ 8.96 (bs, 2H, NH), 8.88 (s,
1H, CONH), 8.42 (d, 2H, J = 8.8 Hz,Cl C6H4-(3)),
8.15 (d, 2H, J = 8.8 Hz, Cl C6H4-(2)), 8.12–6.77 (m,
8H, Ar-H), 6.34 (s, 2H, CH2), 1.77 (s, 3H, COCH3).
Calcd. for C26H20ClN3O4 (473.91); C, 65.89; H, 4.25;
2-[(3E)-3-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-5-(4-methoxyphenyl)-2-oxo-2,3-dihydro-
1H-pyrrol-1-yl]benzoic Acid (3c). To a suspension
of 1d (0.01 mol) in (25 ml) acetic acid, anthranilic
acid (0.01 mol) was added with refluxing for 40 h,
then cooled to solidify the product. The reddish-
brown precipitate was collected by filteration and
recrystallized from acetic acid to give a brown
crystals 2.94 g, 61% yield, mp 263–265◦C; IR (KBr
pellet): 3230.3, 3118.8 (broad band) for ( OH),
1715 (s) for (C O), 1685.3 (m), 1587.9 (s) for (C O)
cm−1; LRMS (EI): m/z 450 (M+ − 30), >5), 319 (20),
200 (8), 235 (100), 170 (40), 137 (30); GC: tR = 6.139
min; column: DB-5 6 m × 0.01 mm + 1 m guard col-
umn: temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/10
1
min; H NMR (CDCl3, 200 MHz): δ 13.62 (bs, 1H,

Conversion of 2(3H )-Furanones Bearing Indole Nuclei Into Novel Amide, Pyrrolone, and Imidazole Derivatives 439
CO2H), 7.98 (s, 1H, Ar-H), 7.86 [d, 2H, J = 9.06 Hz,
63% yield, mp 279–281◦C; IR (KBr pellet): 3431.6
(broad band) for (NH2), 1687.9 (s) for (C O),
1639.6 (s), 1561.6 (v) for (C O) cm−1; 1H NMR
(CDCl3, 200 MHz): δ 8.75 (bs, 2H, NH), 8.55 (d, 2H,
J = 7.8 Hz, CH3 C6H4-(3)), 8.12 (d, 2H, J = 7.8
Hz, CH3 C6H4-(2), 7.18–6.96 (m, 8H, Ar-H), 7.94 (s,
1H, CH C ), 2.76 (s, 3H, COCH3), 1.65 (s, 3H,
CH3). Calcd. for C27H21N3O3 (435.48); C, 74.46; H,
4.86; N, 9.64; Found: C, 74.50; H, 4.50; N, 9.50.
CH3 C6H4-(2)], 7.82–7.12 [m, 8H, Ar-H), 7.10 [d, 2H,
J = 9.06 Hz, CH3 C6H4-(3)], 6.82 (s, 2H, CH C ),
3.89 (s, 3H, OCH3), 2.77 (s, 3H, COCH3). Calcd.
for C28H20N2O6 (480.48); C, 69.99; H, 4.19; N, 5.83;
Found: C, 69.90; H, 4.20; N, 6.10.
2-[(3E)-3-(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-5-(4-chlorophenyl)-2-oxo-2,3-dihydro-
1H-pyrrol-1-yl]benzoic Acid (3d). Reddish-brown
crystals 3.40 g, 70% yield, mp >300◦C; IR (KBr
pellet): 3063.6–3402.6 (broad band) for ( OH),
1671.8.3 (s) for (C O), 1597.1 (m) for (C O) cm−1;
LRMS (EI): m/z 455 (M+ − 29.5), 66.5), 398 (85),
348 (>5), 397 (30), 396 (100), 395 (50), 331 (29),
251 (20), 205 (15), 146 (33.47); GC: tR = 9.028 min;
column: DB-5 6 m × 0.01 mm + 1 m guard column:
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/10 min;
1H NMR (CDCl3, 200 MHz): δ 13.69 (bs, 1H, CO2H),
7.87 [d, 2H, J = 9.06 Hz, Cl C6H4-(2)], 7.98–7.09
[m, 7H, Ar-H), 7.02 [d, 2H, J = 9.06 Hz, Cl C6H4-
(3)], 6.85 [d, 1H, J = 6.00 Hz, Isatin-H(4)], 6.84
(s, 2H, CH C ), 3.89 (s, 3H, OCH3), 2.11 (s,
3H, COCH3). Calcd. for C27H17ClN2O5 (484.89); C,
66.88; H, 3.53; N, 5.77; Cl, 7.31; Found: C, 66.90; H,
3.70; N, 5.96; Cl, 6.90.
(3E)-1-Acetyl-3-[1-(2-aminophenyl)-5-(4-methox-
yphenyl)-2-oxo-1,2-dihyro-3H-pyrrol-3-ylidene]-1,3-
dihydro-2H-indol-2-one (3g). Reddish-brown crys-
tals 2.53 g, 56% yield, mp >300◦C; IR (KBr pel-
let): 3283.4, 3177.2, 3431.6 (broad band) for (NH2),
1680.1 (s) for (C O), 1601.6 (s), 1559.6 (v) for (C O)
cm−1; LRMS (EI): m/z 330 (M+ − 121), >5), 298 (2.7),
295 (17.53), 291 (100), 277 (2.3), 255 (28), 251 (20),
250 (5.5), 223 (18), 187 (15), 186 (55.45), 160 (3.27),
159 (20), 131 (50), 76 (40); GC: tR = 7.260 min;
column: DB-5 6 m × 0.01 mm + 1 m guard column:
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/10 min;
1H NMR (CDCl3, 200 MHz): δ 8.77 (bs, 2H, NH), 8.38
(d, 2H, J = 7.8 Hz, CH3O C6H4-(3)), 8.17 (d, 2H,
J = 7.8 Hz, CH3O C6H4-(2)), 8.18–6.65 (m, 8H, Ar-
H), 6.98 (s, 2H, CH C), 3.89 (s, 3H, OCH3), 2.61
(s, 3H, COCH3). Calcd. for C27H21N3O4 (451.48); C,
71.82; H, 4.68; N, 9.30; Found: C, 71.70; H, 4.70; N,
9.50.
General Procedure for 3e–h
A mixture of 2(3H)furanones 1a–d (0.01 mol), o-
phenylenediamine (0.01 mol), and freshly prepared
sodium acetate (0.03 mol) was fused at melting point
for 2–3 h, then cooled. The soild product was col-
lected and recrystallized from ethanol to give 3e–h,
which was formed from the reaction of 2e–h with
freshly prepared sodium acetate (0.03 mol) at melt-
ing point for 2–5 h. Compounds 3e–h were found by
direct comparison (mp and mixed mp) and GC/MS
spectral data to be identical in all aspects with the
authentic products.
(3E)-1-Acetyl-3-[1-(2-aminophenyl)-5-(4-chloro-
phenyl)-2-oxo-1,2-dihyro-3H-pyrrol-3-ylidene]-1,3-
dihydro-2H-indol-2-one (3h). Yellow crystals 2.65
g, 58% yield, mp 269–270◦C; IR (KBr pellet): 3429.4,
3284.5, 3179.6 (broad band) for (NH2), 1678.6 (s)
for (C O), 1601.8 (s), 1560.4 (v) for (C O) cm−1;
LRMS (EI): m/z 463 (M+ − 7.5), 2.5), 301 (1.9), 348
(>5), 298 (10), 297 (3), 271 (8.33), 159 (11.75), 139
(40), 131 (40), 114 (10.5), 113 (35.39), 112 (10),
111 (100), 105 (11), 104 (20), 80 (20.7), 77 (30),
75 (80), 52 (23); GC: tR = 6.476 min; column: DB-5
6 m × 0.01 mm + 1 m guard column: temp. prog:
50◦C/2 min/20◦C/1 min/250◦C/10 min; 1H NMR
(CDCl3, 200 MHz): δ 8.98 (bs, 2H, NH), 8.72 (d, 2H,
J = 8.8 Hz, Cl C6H4-(3)), 8.15 (d, 2H, J = 8.8 Hz,
Cl C6H4-(2)), 8.71–6.77 (m, 8H, Ar-H), 7.84 (s,
1H, CH C ), 2.77 (s, 3H, COCH3). Calcd. for
C26H18ClN3O3 (455.90); C, 68.49; H, 3.97; N, 9.21; Cl,
7.77; Found: C, 68.60; H, 4.10; N, 9.50; Cl, 8.00.
(3E)-1-Acetyl-3-[1-(2-aminophenyl)-5-phenyl-2-
oxo-1,2-dihyro-3H-pyrrol-3-ylidene]-1,3-dihydro-2H-
indol-2-one (3e). Brown crystals 2.55 g, 60% yield,
mp 235–237◦C; IR (KBr pellet): 3429.4 (broad band)
for (NH2), 1678.6 (s) for (C O), 1600.9 (s), 1562.2
1
(v) for (C O) cm−1; H NMR (CDCl3, 200 MHz): δ
8.89 (bs, 2H, NH2), 8.55–6.96 (m, 13H, Ar-H), 7.65
(s, 1H, CH C), 2.70 (s, 3H, COCH3). Calcd. for
C26H19N3O3 (421.45).; C, 74.09; H, 4.54; N, 9.97;
Found: C, 74.50; H, 4.70; N, 10.00.
General Procedure for 4a–d
To a suspension of 1a–d (0.01 mol) in (25 ml) acetic
acid, o-phenylenediamine (0.01 mol) was added in
the presence of freshly prepared fused sodium ac-
etate (0.03 mol). The reaction mixture was refluxed
(3E)-1-Acetyl-3-[1-(2-aminophenyl)-5-(4-methyl-
phenyl)-2-oxo-1,2-dihyro-3H-pyrrol-3-ylidene]-1,3-
dihydro-2H-indol-2-one (3f). Brown crystals 2.75 g,

440 Hamad et al.
for 5 h and then cooled. The yellowish precipitate
was collected by filteration, washed with water, and
recrystallized from acetic acid to give 4a–d, which
was formed from the reaction of 2e–h with acetic
acid/sodium acetate (0.03 mol) for 5 h at refluxing
temperature. Compounds 4a–d were found by direct
comparison (mp and mixed mp) and GC/MS spectral
data to be identical with the authentic products.
(3E)-1-Acetyl-3-[1-(1H-benzimidazol-2-yl)-3-(chl-
orophenyl)-3-oxopropylidene]-1,3-dihydro-2H-indol-
2-one (4d). Brown crystals 3.6 g, 79% yield, mp
271–273◦C; IR (KBr pellet): 3164.9–3089.3 (bm),
1689.2 (v), 1608.0 (v), for (C O), 1538.5 (s) for
(C N) cm−1; LRMS (EI): m/z 455 (M+), >5), 301
(10), 300 (10), 299 (14), 298 (83), 295 (11), 269 (40),
107 (27), 159 (42), 140 (32), 139 (100), 134 (10),
131 (33), 117 (27), 112 (23), 110 (75), 103 (20), 90
(23), 77 (30), 76 (24), 74 (40), 73 (15), 64 (13), 63
(15), 62 (25), 53 (11), 51 (27); GC: tR = 7.215 min;
column; DB-5 6 m × 0.01 mm + 1 m guard column:
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/5 min;
1H NMR (CDCl3, 200 MHz): δ 9.96 (bs, 2H, NH),
8.53 (d, 2H, J = 8.8 Hz, Cl C6H4-(3)), 8.15 (d, 2H,
J = 8.8 Hz, Cl C6H4-(2)), 8.50–6.77 (m, 8H, Ar-H),
6.94 (s, 2H, CH2), 2.77 (s, 3H, COCH3). Calcd. for
C26H18ClN3O3 (455.90); C, 68.49; H, 3.97; N, 9.21; Cl,
7.77; Found: C, 68.50; H, 4.00; N, 9.10; Cl, 7.80.
(3E)-1-Acetyl-3-[1-(1H-benzimidazol-2-yl)-3-phe-
nyl-3-oxopropylidene]-1,3-dihydro-2H-indol-2-
one (4a). Yellow crystals 2.07 g, 49% yield, mp
258–259◦C; IR (KBr pellet): 3452.5–3142.1, 3052.2
(bm), 1686 (m), 1612.4 (v), for (C O), 1554.4 (s),
1
and 1507.3 (s) for (C N) cm−1; H NMR (CDCl3,
200 MHz): δ 9.78 (bs, 1H, NH), 8.70–6.96 (m, 13H,
Ar-H), 6.94 (s, 2H, CH2), 2.69 (s, 3H, COCH3).
Calcd. for C26H19N3O3 (421.45); C, 74.09; H, 4.54; N,
9.97; Found: C, 74.30; H, 4.20; N, 9.60.
(3E)-1-Acetyl-3-[1-(1H-benzimidazol-2-yl)-3-(me-
thylphenyl)-3-oxopropylidene]-1,3-dihydro-2H-indol-
2-one (4b). Yellow crystals 3.57 g, 82% yield, mp
241–242◦C; IR (KBr pellet): 3446.1–3183.9, 3149.1
(bm), 1679.4 (m), 1608.5 (v), for (C O), 1551.8
(s) for (C N) cm−1; 1H NMR (CDCl3, 200 MHz):
δ 9.75 (bs, 1H, NH), 8.45 (d, 2H, J = 7.8 Hz,
CH3 C6H4-(3)), 8.22 (d, 2H, J = 7.8 Hz, CH3 C6H4-
(2), 7.98–6.96 (m, 8H, Ar-H), 5.94 (s, 2H, CH2),
2.51 (s, 3H, COCH3), 1.69 (s, 3H, CH3). Calcd.
for C27H21N3O3 (435.48); C, 74.46; H, 4.86; N, 9.64;
Found: C, 74.00; H, 5.00; N, 9.00.
General Procedure for 6a–d
To a suspension of 1a–d (0.01 mol) in (25 ml) ethanol,
N-aminophthalimide (0.01 mol) was added with re-
fluxing for 3 h, then cooled. The reddish-brown pre-
cipitate was collected by filteration and recrystallized
from ethanol to give 6a–d.
(2E)-2(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-yli-
dene)-N-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)-4-
phenyl-4-oxobutanamide (6a). Brown crystals 2.5
g, 50% yield, mp 158–160◦C; IR (KBr pellet): 3340.7
(m), 3266.2 (m), 1783.6 (s), 1722.1 (v) for (C O)
and 1607.5 (s), 1543.4 (s) for (C N) cm−1; LRMS
(EI): m/z 493 (M+), >5), 475 (M+ − 18), >5), 488
(>5), 381 (15), 288 (30), 261 (7), 216 (5), 106 (7),
105 (100), 76 (50); GC: tR = 6.719 min; column:
DB-5 6 m × 0.01 mm + 1 m guard column: temp.
prog: 50◦C/2 min/20◦C/1 min/250◦C/10 min; 1H NMR
(CDCl3, 200 MHz): δ 10.11 (s, 1H, NH), 8.34–7.25
[m, 13H, Ar-H), 4.20 (s, 2H, CH2), 2.77 (s, 3H,
COCH3). Calcd. for C28H19N3O6 (493.47); C, 68.15;
H, 3.88; N, 8.51; Found: C, 68.10; H, 3.90; N, 8.90.
(3E)-1-Acetyl-3-[1-(1H-benzimidazol-2-yl)-3-(me-
thoxyphenyl ) - 3 -oxopropylidene]-1, 3-dihydro- 2H -
indol-2-one (4c). Brown crystals 3.39 g, 75% yield,
mp 238–240◦C; IR (KBr pellet): 3038.7–2860.3
(bm), 1682.3 (v), 1597.7 (v), for (C O), 1541.7 (s)
for (C N) cm−1; LRMS (EI): m/z 453 (M+ + 2),
8), 340 (7.5), 321 (8.9), 311 (7), 295 (8), 294 (35),
265 (34), 235 (27), 224 (26), 221 (17), 193 (13),
187 (15), 185 (15), 158 (21), 152 (15), 151 (19),
135 (100), 130 (29.5), 121 (17), 115 (39), 114 (39),
107 (42), 105 (38), 102 (17), 92 (30), 90 (52), 97
(38), 85 (20), 76 (24), 71 (24), 85 (28), 83 (40), 82
(45), 54 (33), 51 (30); GC: tR = 6.973 min; column:
DB-5 6 m × 0.01 mm + 1 m guard column: temp.
prog: 50◦C/2 min/20◦C/1 min/250◦C/5 min.; 1H NMR
(CDCl3, 200 MHz): δ 9.03 (bs, 2H, NH), 8.38 (d,
2H, J = 8.9 Hz, CH3O C6H4-(2)), 8.17 [(d, 2H,
J = 8.9 Hz, CH3O C6H4-(3)], 8.18–6.65 (m, 8H,
Ar-H), 6.97 (s, 2H, CH2), 3.89 (s, 3H, OCH3), 2.61
(s, 3H, COCH3) ppm; Anal. Calcd. for C27H21N3O4
(451.48); C, 71.82; H, 4.68; N, 9.30; Found: C, 71.50;
H, 4.50; N, 9.40.
(2E)-2(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-
ylidene)-N-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)-
4-(4-methylphenyl)-4-oxobutanamide (6b). Reddish-
brown crystals 3.4 g, 67% yield, mp 120–122◦C;
IR (KBr pellet): 3427.5 (bv), 1722.2 (v), 1663.7
(s), for (C O), 1615.1 (s) for (C O) cm−1; LRMS
(EI): m/z 506 (M+ − 1), (>5), 399 (>5), 391 (>5),
337 (>5), 229 (>5), 173 (>5), 119 (100), 104
(10), 79 (10); GC: tR = 6.950 min; column: DB-5
6 m × 0.01 mm + 1 m guard column: temp. prog:
50◦C/2 min/20◦C/1 min/250◦C/5 min; 1H NMR

Conversion of 2(3H )-Furanones Bearing Indole Nuclei Into Novel Amide, Pyrrolone, and Imidazole Derivatives 441
(CDCl3, 200 MHz): δ 10.52 (s, 1H, NH), 8.75 (d, 2H,
(KBr pellet): 3427.8–3207.9 (broad band) for (OH),
1746.0 (bv) for (C O), 1605.2.5 (s) for (C O) cm−1;
1H NMR (CDCl3, 200 MHz): δ 8.85–6.96 (m, 13H,
Ar-H), 7.94 (s, 2H, CH C), 2.69 (s, 3H, COCH3).
Calcd. for C28H17N3O5 (475.46); C, 70.73; H, 3.60; N,
8.83; Found: C, 70.50; H, 3.30; N, 8.50.
J = 7.8 Hz, CH3 C6H4-(2)), 8.12 (d, 2H, J = 7.8 Hz,
CH3 C6H4-(3), 7.18–6.96 (m, 8H, Ar-H), 5.94 (s, 2H,
CH2), 2.51 (s, 3H, COCH3), 1.65 (s, 3H, CH3).
Calcd. for C29H21N3O6 (507.50); C, 68.63; H, 4.17; N,
8.27; Found: C, 69.00; H, 4.30; N, 8.70.
(2E)-2(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-
ylidene)-N-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)-
4-(4-methoxyphenyl)-4-oxobutanamide (6c). Brown
crystals 2.1 g, 40% yield, mp 279–281◦C; IR (KBr
pellet): 3425.8 (bm), 3166.9 (bs), 3018.8 (bm), 2901.9
(bv), 1722.5 (s), 1661.6 (v) for (C O), 1601.7(s),
1560.4 (s), 1494.6 (v) for (C O) cm−1; LRMS (EI):
m/z 554 (M+ + 1), >5), 371 (>5), 319 (>5), 248
(2), 220 (1), 162 (30.23), 161 (2), 135 (6), 132 (6),
118 (2), 106 (2.9), 105 (25), 104 (35), 102 (2), 101
(3), 92 (7), 91 (6), 77(89), 76 (84), 75 (53), 74
(88), 73 (22), 63 (19), 62 (19), 61 (20), 53 (40), 52
(23), 51 (100); GC: tR = 7.159 min; column: DB-5
6 m × 0.01 mm + 1 m guard column: temp. prog:
50◦C/2 min/20◦C/1 min/250◦C/10 min; 1H NMR
(CDCl3, 200 MHz): δ 10.72 (s, 1H, NH), 8.68 (d, 2H,
J = 7.8 Hz, CH3O C6H4-(2)), 8.47 (d, 2H, J = 7.8
Hz, CH3O C6H4-(3)), 8.68–6.65 (m, 8H, Ar-H), 5.98
(s, 2H, CH2), 3.89 (s, 3H, OCH3), 1.61 (s, 3H,
COCH3). Calcd. for C29H21N3O7 (523.50); C, 66.53;
H, 4.04; N, 8.02; Found: C, 66.80; H, 4.10; N, 8.40.
2-({2-[(3E)-2-(1-Acetyl-2-oxo-1,2-dihydro-3H-
indol-3-ylidene)-4-(4-methylphenyl)-4-oxobutanoyl]-
hydrzino}-carbonyl-N-benzyl-benzamide (8b). To
a
suspension of 6b (0.01 mol) in (10 ml) ethanol,
benzylamine (0.01 mol) was added with stirring
at room temperature for 24 h. The yellowish solid
precipitate was collected by filteration and recrys-
tallized from ethanol to give yellow crystal 3.81 g,
62% yield, mp >300◦C; IR (KBr pellet): 3420.6
(br.), (NH), 3173.7, 3103.9 ( NH NH ), 1718.7
(v) for (C O), 1668.5 (v) for (C O) cm−1; LRMS
(EI): m/z 304 [(M+ − 310), 8.8], 303 (35.23), 275
(21.31), 247 (5.9), 232 (9.11), 323 (11.5), 156 (15),
127 (10), 110 (24), 101 (26.2), 92 (10), 91 (100),
90 (24), 89 (37), 65 (35.94); GC: tR = 8.006 min;
column: DB-5 6 m × 0.01 mm + 1 m guard column:
temp. prog: 50◦C/2 min/20◦C/1 min/250◦C/10 min):
1H NMR (CDCl3, 200 MHz): δ 11.77–11.73 (bs,
2H, NHNH ), 9.55 (s, 1H, CONH), 8.80–6.96 (m,
13H, Ar-H), 8.75 (d, 2H, J = 7.8 Hz, CH3 C6H4-(2)),
8.53 (d, 2H, J = 7.8 Hz, CH3 C6H4-(3), 5.94 (s, 2H,
CH2), 4.21 (s, 2H, CH2), 2.51 (s, 3H, COCH3),
1.65 (s, 3H, CH3). Calcd. for C36H30N4O6 (614.66):
C, 70.34; H, 4.91; N, 9.11; Found: C, 69.90; H, 4.60;
N, 9.00.
(2E)-2(1-Acetyl-2-oxo-1,2-dihydro-3H-indol-3-
ylidene)-N-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)-
4-(4-chlorophenyl)-4-oxobutanamide (6d). Reddish-
brown crystals 3.2 g, 60% yield, mp 117–119◦C;
IR (KBr pellet): 3482.6 (bs), 3340.5 (m), 3265.9
(s), 1783.5 (s), 1721.8 (v) for (C O), 1607.1 (s)
for (C O) cm−1; LRMS (EI): m/z 526 (M+ − 1.5),
2.43), 514 (3), 503 (10), 502 (100), 55 (2.2), 125
(5), 96 (47), 95 (100), 79 (10), 78 (9), 65(23), 61
(47), 58 (27.77); GC: tR = 3.736 min; column: DB-5
6 m × 0.01 mm + 1 m guard column: temp. prog:
50◦C/2 min/20◦C/1 min/250◦C/5 min; 1H NMR
(CDCl3, 200 MHz): δ 12.76 (s, 1H, NH), 7.88–7.42
[m, 12H, Ar-H), 4.21 (s, 2H, CH2), 2.76 (s, 3H,
COCH3). Calcd. for C28H18ClN3O6 (527.92); C,
63.70; H, 3.43; N, 7.95; Cl, 6.71; Found: C, 64.10; H,
3.50; N, 8.00; Cl, 6.90.
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