Reactions of some pyrrole-2,3-diones with hydrazine hydrate and o-phenylenediamine

Article abstract of DOI:10.1002/jhet.5570440514

(Chemical Equation Presented) 2,3-Dihydro-1H-pyrrole-2,3-diones 1a-d react with hydrazine hydrate 2 and o-phenylenediamine 4 under different conditions to yield the pyrazole-3-carboxamide derivatives 3a-d, the pyrrol-2-ones 5a-d and the quinoxaline-2-one

Full text of DOI:10.1002/jhet.5570440514

Sep-Oct 2007
1065
Reactions of Some Pyrrole-2,3-diones with Hydrazine Hydrate and
o-Phenylenediamine*
Emin Sarıpınar**, Süleyman Karataꢀ and ꢁlhan Özer ꢁlhan
Department of Chemistry, Arts and Sciences Faculty, Erciyes University, 38039 Kayseri-Turkey, e-mail:
emin@erciyes.edu.tr, fax: 00 90 352 4378802
*Dedicated to the memory of Prof. Dr. Yunus Akçamur
Received October 19, 2006
Ar
O
1
O
H2N-NH2
-H2O
NH-Ar2
N
Ar
N
H
1
Ar
1
O
O
Ar
O
1
OH
O
O
H2N
O
Ar
H2N
H2N
N
N
1
N
Ar1
Ar1
+
N
Ar2
H
Ar
1
Ar
O
N
H
2
N
Ar2
H
2,3-Dihydro-1H-pyrrole-2,3-diones 1a-d react with hydrazine hydrate 2 and o-phenylenediamine 4
under different conditions to yield the pyrazole-3-carboxamide derivatives 3a-d, the pyrrol-2-ones 5a-d
and the quinoxaline-2-one derivatives 6a-d, respectively. Hydrolysis of the quinoxaline-2-one derivatives
6a-d gave a substituted furo[2,3-b]quinoxaline 7. The structures of the synthesized compounds were
assigned on the basis of analytical results as well as spectroscopic data.
J. Heterocyclic Chem., 44, 1065 (2007).
INTRODUCTION
insecticidal) [14]. Oxidation of both nitrogens of the
quinoxaline ring dramatically increased the diversity of
certain biological properties, such as antibacterial
activity [15] and hypoxia-selective anticancer activity
[16]. Recently, reactions of cyclic oxalyl compounds
have been reported to give corresponding heterocyclic
compounds [17].
4-Acyl substituted heterocyclic 2,3-diones, e.g. 2,3-
dihydro-1H-furan-2,3-diones or 2,3-dihydro-1H-pyrrole-
2,3-diones adds various isocyanides [1], isocyanates
[2], carbodiimides [3], ketenimines [4], diphenylketene
[5], imines [6], and alkenes [7], via [2+2], [4+1], or
[4+2] cycloaddition processes affording novel mono-
and bicyclic systems. N-Phenylimino-2,3-dihydro-1H-
furan-2,3-diones, obtainable e.g. by the reactions of 4-
acyl-2,3-dihydro-1H-furan-2,3-diones with tosyl-
sulfinylamines or arylalkylcarbo-diimides or -imines,
thermally rearrange to 4-acyl-2,3-dihydro-1H-pyrole-
2,3-diones [3a,6b]. The thermal decarbonylation of 4-
acyl-2,3-dihydro-1H-pyrrole-2,3-diones leads to the
formation of highly reactive acyl(N-arylimidoyl)-
ketenes [8]. In general, the pyrazole nucleus and its
chemistry [9] have found considerable attention during
the decades due to outstanding biological activities
such as antipyretic, analgetic, anti-fungal and anti-
inflammatory activities [10], as well as to interesting
properties in commercially important dyestuffs [11].
Quinoxaline derivatives are an important class of
nitrogen-containing heterocycles and they constitute
useful intermediates in organic synthesis. Some of
them are applied for dyes [12] and for building blocks
in the synthesis of organic semiconductors [13] and
show interesting biological properties (antibacterial,
antiviral, anticancer, antifungal, antihelmintic,
RESULTS AND DISCUSSION
In the present study, we carried out the reaction of the
2,3-dihydro-1H-pyrrol-2,3-diones 1a-d, easily made from
2,3-dihydro-1H-furan-2,3-dione with Schiff bases at 60-
70 °C furnish [18], with hydrazine hydrate (2) and o-
phenylenediamine (4) yielding pyrazole-3-carboxamide
derivatives 3a-d, the pyrrol-2-ones 5a-d and the
quinoxaline-2-one
derivatives
6a-d,
respectively.
Hydrolysis of the quinoxaline-2-ones derivatives 6a-d
gave corrresponding furo[2,3-b]quinoxaline 7. The
reaction equations are shown in schemes. The structures
of synthesized compounds were assigned on the basis of
analytical results as well as spectroscopic data.
The reaction of the 2,3-dihydro-1H-pyrrol-2,3-diones
1a-d with hydrazine hydrate 2 (Scheme I) yields pyrazole-
3-carboxamide derivatives 3a-d. Product 3a obtained in
45% yield by treating 1a with hydrazine hydrate 2 and
refluxing in benzene for 1 h. The moderate yield of the
reaction can be explained by the chemical behaviour of
pyrrolediones 1a-d towards H-active nucleophiles. In
compounds 1a-d carbon atoms C-2, C-3 and C-5

1066
E. Sarıpınar, S. Karataꢀ and ꢁ. Ö. ꢁlhan
Vol 44
represent electrophilic sites of different reactivity and
could be used for the construction of new heterocyclic
systems upon reaction with nucleophiles, as furandiones
[19]. It should start with a nucleophilic attack of the lone
pair electrons of nitrogen atom of 2 at the antibonding
orbital of ꢀ* of C5 position of the pyrrolediones ring
similar to a Michael-type addition. In the ir spectrum of
compound 3a the -NH absorption band was found to be at
ca. 3450-3250 cm-1. The C=O absorption was at 1700
cm-1. The 1H nmr signals were at ꢁ 12.81 and 10.50 (-NH)
and 7.75-6.66 ppm (m, ArH) and the 13C nmr signals were
found to be at ꢁ 194.99 (PhCO), 165.88 (N-C=O), 159.67
(C-3), 161.96 ppm (C-5) and elemental analysis data
confirm the structure of 3a.
seen at 1719 and 1675 cm-1, respectively. The 1H
nmr signals were found to be at ꢁ 12.58 and 9.78 (s,
2H, -NH), 9.39 (s, enol-OH), 8.12-6.74 (m, ArH),
6.24 (s, keto-CH), 3.86 and 3.76 ppm (q, 6H, -
OCH3). The 13C nmr signals were at ꢁ 191.24 (Ar-
C=O), 181.01 (C-3), 164.46 (C-2), 149.32-121.92
(aromatic C), 116.15 (C-4), 99.53 (C-5) and 57.35
ppm (2CH3O).
The nucleophilic addition of o-phenylenediamine 4 to
pyrrol-2,3-diones 1a-d provided quinoxaline-2-ones 6a-
d in 65-73% yields. All reactions were carried out at
room temperature in inert solvent [20]. These products
arise from the sequential attacks of the aromatic
diamine to the C-3 and C-2 atoms of the pyrrole-2,3-
diones 1a-d respectively, followed by elimination of
water and ring opening of the pyrrole-2,3-dione.
Therefore, the presence of tautomeric forms of 6a-d, as
well as the stability of the compounds of 6a-d were also
confirmed by these reactions, outlined briefly in
Scheme II. The 13C nmr spectrum of 6a exhibits
significant line broadenings for the aryl carbonyl
(195.98 ppm), lactam C (158.01 ppm), C-3 (155.51
ppm), respectively. In the ir spectrum of 6a,
characteristic absorption bands at about 3400-3250 cm-1
NH, 1670 and 1610 cm-1 (C=O) were observed, as well
Scheme I
Ar
O
Ar1
1
O
O
-H2O
O
NH-Ar2
O
+
H2N-NH2
N
Ar1
N
H
3
Ar1
2
N
Ar2
1
1, 3
a
b
c
d
Ar1 : p-CH3OC6H4-
1
Ar2
CH3
as, the H nmr spectrum of 6a shows that (NH) protons
appear at 12.40 and 11.9 ppm, respectively. Other
spectral and analytical data of 6a-d are in full
agreement with their proposed structures as well.
CH3
Also the hydrolysis of 6a-d in n-butyl alcohol leads
to corresponding furo[2,3-b]quinoxaline 7, the C=O
absorption band were found to be at about 1650 cm-1.
The reaction of 1a-d with 4 are depending on the
reaction temperatures, 5a-d are obtained from
refluxed solution, 6a-d are obtained at room
Scheme II
Ar
1
OH
O
H2N
O
D
N
Tautomers
Tautomers
N
H
Ar
1
Ar
2
Ar
1
5
O
O
H2N
H2N
O
+
O
N
Ar
N
Ar
1
1
-H2O
Ar
Ar
2
1
4
O
N
N
H
6
1
H
Ar2
Ar1 : p-CH3OC6H4-
1,5,6
a
b
c
d
Ar2
CH3
CH3
1
temperature. In the ir spectrum of compound 5a, -
OH and -NH absorption bands were found to be at
3610-3380 cm-1, the C=O absorption bands were
The H nmr signals were found to be at ꢁ 8.16-6.90
(m, 12H, ArH), 3.87 and 3.65 ppm (s, 6H, 2CH3O)
(Scheme III).

Sep-Oct 2007
Reactions of Some Pyrrole-2,3-diones with Hydrazine Hydrate and o-Phenylenediamine
1067
Scheme III
Ar1
benzene at room temperature for 24 h. The solvent was
evaporated and the remaining oily residue was treated with dry
diethyl ether and stirred for 24 h. to give the white crude product
which was recrystallized from n-butyl alcohol and allowed to
dry on P2O5; resulting in yield 55% (0.57 g ); mp 230-231°C; ir:
3450-3250 (b, N-H), 1710 cm-1(C=O); 1H nmr (CDCl3): ꢀ 12.35
and 10.47 (2H, -NH), 7.72-6.68 (m, 12H, ArH), 3.76 (s, 3H,
CH3), 3.69 (s, 3H, CH3) and 2.31 ppm (s, CH3); 13C nmr
(CDCl3): ꢀ 194.96 (ArCO), 165.81 (N-C=O), 161.90 (C-5),
159.06 (C-3), 137.44-114.89 (aromatic C), 57.39 (2CH3), 22.88
ppm (CH3). Anal. Calcd. for C26H23N3O4; C, 70.73; H, 5.25; N,
9.52. Found; C, 70.99; H, 5.45; N, 9.75.
N
O
ꢀ
ROH, H2O,
6a-d
-NHAr2
-H2O
Ar1
O
N
7
Ar1 : p-CH3OC6H4-
EXPERIMENTAL
Solvents were dried by refluxing over the appropriate drying
agent and distilled before use. Melting points were determined
on an Electrothermal 9200 apparatus and are uncorrected.
Microanalyses were performed on a Carlo Erba elemental
analyser, model 1108. The ir spectra were recorded on a
Shimadzu Model 435 V-04 spectrophotometer, using potassium
4-(4-Methoxylbenzoyl)-5-(4-methoxylphenyl)-1H-pyrazole-3-
carboxylic 1-naphthylamide (3d). 4-(4-Methoxybenzoyl)-5-(4-
methoxyphenyl)-1-(1-naphtyl)-2,3-1H-pyrrole-2,3-dione 1d (1.0
g, 2.16 mmol) and hydrazine hydrate 2 (0.11 g, 2.16 mmol) were
refluxed in benzene (50 mL) for 1 h. or stirred in benzene at
room temperature for 24 h. The solvent was evaporated and the
remaining oily residue was treated with dry diethyl ether and
stirred for 24 h. to give the white crude product which was
recrystallized from n-butyl alcohol and allowed to dry on P2O5;
resulting in yield 45% (0.46 g ); mp 136.5-138°C; ir: 3500-3250
(b, N-H), 1725 cm-1(C=O); 1H nmr (CDCl3): ꢀ 12.38 and 10.73
(2H, -NH), 8.29-6.65 (m, 15H, ArH), 3.75 (s, 3H, CH3), and
3.68 ppm (s, 3H, CH3); 13C nmr (CDCl3): ꢀ 194.85 (ArCO),
165.89 (N-C=O), 161.89 (C-5), 160.12 (C-3), 136.11-114.72
(aromatic C), and 57.19 ppm (2CH3). Anal. Calcd. for
C29H23N3O4; C, 72.94; H, 4.85; N, 8.80. Found; C, 72.97; H,
4.89; N, 8.58.
1
bromide pellets. The H and 13C nmr spectra were recorded on
Varian Gemini 200 istrument. The chemical shifts are reported
in ppm from tetramethylsilane as an internal standard and are
given in ꢀ (ppm). All experiments were followed by TLC using
DC Alufolien Kieselgel 60 F254 Merck and Camag TLC lamp
(254/366 nm).
4-(4-Methoxylbenzoyl)-5-(4-methoxyphenyl)-1H-pyrazole-
3-carboxylic phenylamide (3a). 4-(4-Methoxybenzoyl)-5-(4-
methoxyphenyl)-1-phenyl-2,3-1H-pyrrole-2,3-dione 1a (1.0 g,
2.42 mmol) and hydrazine hydrate 2 (0.12 g, 2.42 mmol) were
refluxed in benzene (50 mL) for 1 h. or stirred in benzene at
room temperature for 24 h. The solvent was evaporated and the
remaining oily residue was treated with dry diethyl ether and
stirred for 24 h. to give the white crude product which was
recrystallized from n-butyl alcohol and allowed to dry on P2O5;
resulting in yield 45% (0.46 g ); mp 224-225°C; ir: 3450-3250
(b, N-H), 1700 cm-1 (C=O); 1H nmr (CDCl3): ꢀ 12.81 and 10.50
(2H, -NH), 7.75-6.66 (m, 13H, ArH), 3.76 (s, 3H, CH3) and 3.66
ppm (s, 3H, CH3); 13C nmr (CDCl3): ꢀ 194.99 (ArCO), 165.88
(N-C=O), 161.96 (C-5), 159.67 (C-3), 139.73-115.01 (aromatic
C), 57.39 ppm (2CH3). Anal. Calcd. for C25H21N3O4; C, 70.25;
H, 4.95; N, 9.83. Found; C, 70.10; H, 5.05; N, 9.82.
5-(2-Aminophenyl)amino-3-hydroxy-4-(4-methoxylben-
zoyl)-5-(4-methoxylphenyl)-1-phenyl-2,5-dihydro-2H-pyrrol-
2-one (5a). 4-(4-Methoxybenzoyl)-5-(4-methoxyphenyl)-1-
phenyl-2,3-1H-pyrrole-2,3-dione 1a (1.0 g, 2.42 mmol) and o-
phenylenediamine 4 (0.26 g, 2.42 mmol) were refluxed in
benzene (50 mL) for 1 h. The solvent was evaporated and the
remaining oily residue was treated with dry diethyl ether and
stirred for 24 h. to give the yellow crude product which was
recrystallized from n-butyl alcohol and allowed to dry on P2O5;
resulting in yield 55% (0.69 g ); mp 184°C; ir: 3610-3380 (br,
1
NH and OH), 3360 (NH2), 1719, 1675 (C=O); H nmr (DMSO-
4-(4-Methoxylbenzoyl)-5-(4-methoxylphenyl)-1H-pyrazole-
3-carboxylic 2-methylphenylamide (3b). 4-(4-Methoxyben-
zoyl)-5-(4-methoxyphenyl)-1-(2-methylphenyl)-1H-pyrrole-2,3-
dione 1b (1.0 g, 2.34 mmol) and hydrazine hydrate 2 (0.12 g,
2.34 mmol) were refluxed in benzene (50 mL) for 1 h. or stirred
in benzene at room temperature for 24 h. The solvent was
evaporated and the remaining oily residue was treated with dry
diethyl ether and stirred for 24 h. to give the white crude product
which was recrystallized from n-butyl alcohol and allowed to
d6): ꢀ 12.58 (br, -NH) , 9.78 (s, -NHO), 9.39 (s, enol-OH), 8.12-
6.74 (m, 17H, Ar-H), 6.24 (s, keto-CH), 3.86 (s, 3H, CH3), and
3.76 ppm (s, 3H, CH3O); 13C nmr (DMSO-d6): ꢀ 191.24
(ArCO), 181.01 (C-3), 164.46 (C-2), 149.32-121.92 (aromatic
C), 116.15 (C-4), 99.53 (C-5), and 57.35 ppm (2CH3O). Anal.
Calcd. for C31H27N3O5; C, 71.39; H, 5.22; N, 8.06. Found; C,
71.45; H, 5.48; N, 7.85.
5-(2-Aminophenyl)amino-3-hydroxy-4-(4-methoxylbenzoyl)-
1-(2-methylphenyl)-5-(4-methoxyphenyl)-2,5-dihydro-2H-
pyrrol-2-one (5b). 4-(4-Methoxybenzoyl)-5-(4-methoxyphenyl)-1-
(2-methylphenyl)-1H-pyrrole-2,3-dione 1b (1.0 g, 2.34 mmol)
and o-phenylenediamine 4 (0.25 g, 2.34 mmol) were refluxed in
benzene (50 mL) for 1 h. The solvent was evaporated and the
remaining oily residue was treated with dry diethyl ether and
stirred for 24 h. to give the yellow crude product which was
recrystallized from n-butyl alcohol and allowed to dry on P2O5;
resulting in yield 55% (0.69 g ); mp 204°C; ir: 3620-3380 (br,
dry on P2O5; resulting in yield 50% (0.52 g); mp 215-216°C; ir:
1
3500-3150 (b, N-H), 1720 cm-1 (C=O); H nmr (CDCl3):
ꢀ
12.40 and 10.11 (2H, -NH), 8.06-6.69 (m, 12H, ArH), 3.77 (s,
3H, CH3), 3.72 (s, 3H, CH3) and 2.45 ppm (s, CH3); 13C nmr
(CDCl3): ꢀ 194.58 (ArCO), 165.86 (N-C=O), 161.89 (C-5),
159.34 (C-3), 134.56-114.89 (aromatic C), 57.40 (2CH3), 20.13
ppm (CH3). Anal. Calcd. for C26H23N3O4; C, 70.73; H, 5.25; N,
9.52. Found; C, 70.68; H, 5.37; N, 9.43.
1
NH and OH), 3370 (NH2), 1711, 1680 (C=O); H nmr (DMSO-
4-(4-Methoxylbenzoyl)-5-(4-methoxylphenyl)-1H-pyrazole-3-
carboxylic 4-methylphenylamide (3c). 4-(4-Methoxybenzoyl)-
5-(4-methoxyphenyl)-1-(4-methylphenyl)-1H-pyrrole-2,3-dione
1c (1.0 g, 2.34 mmol) and hydrazine hydrate (2) (0.12 g, 2.34
mmol) were refluxed in benzene (50 mL) for 1 h. or stirred in
d6): ꢀ 12.61 (br, -NH) , 9.77 (s, -NHO), 9.32 (s, enol-OH), 8.10-
6.75 (m, 16H, Ar-H), 6.23 (s, keto-CH), 3.85 (s, 3H, CH3), 3.76
(s, 3H, CH3O), and 2.36 ppm (s, CH3); 13C nmr (DMSO-d6): ꢀ
191.21 (ArCO), 181.90 (C-3), 163.90 (C-2), 149.29-123.54

1068
E. Sarıpınar, S. Karataꢀ and ꢁ. Ö. ꢁlhan
Vol 44
(aromatic C), 116.35 (C-4), 99.44 (C-5), 57.37 (2CH3O), and
22.89 ppm (CH3). Anal. Calcd. for C32H29N3O5; C, 71.76; H,
5.46; N, 7.85. Found; C, 72.01; H, 5.77; N, 7.67.
3.53 (s, 3H, CH3O), and 2.52 ppm (s, CH3); 13C nmr (DMSO-
d6): ꢀ196.52 (ArCO), 158.55 (lactam C), 156.72 (C-3), 134.05-
114.88 (aromatic C), 57.23 and 56.99 (2CH3O) and 20.67 ppm
(CH3). Anal. Calcd. for C32H27N3O4; C, 74.26; H, 5.26; N, 8.12.
Found; C, 74.54; H, 5.50; N, 7.82.
5-(2-Aminophenyl)amino-3-hydroxy-4-(4-methoxylben-
zoyl)-1-(4-methylphenyl)-5-(4-methoxyphenyl)-2,5-dihydro-
2H-pyrrol-2-one (5c). 4-(4-Methoxybenzoyl)-5-(4-methoxy-
phenyl)-1-(4-methylphenyl)-1H-pyrrole-2,3-dione 1c (1.0 g,
2.34 mmol) and o-phenylenediamine 4 (0.25 g, 2.34 mmol) were
refluxed in benzene (50 mL) for 1 h. The solvent was evaporated
and the remaining oily residue was treated with dry diethyl ether
and stirred for 24 h. to give the yellow crude product which was
recrystallized from n-butyl alcohol and allowed to dry on P2O5;
resulting in yield 58% (0.73 g ); mp 220-221°C; ir: 3615-3380
(br, NH and OH), 3360 (NH2), 1716, 1680 (C=O); 1H nmr
(DMSO-d6): ꢀ 12.52 (br, -NH) , 9.79 (s, -NHO), 9.34 (s, enol-
OH), 8.07-6.74 (m, 16H, Ar-H), 6.24 (s, keto-CH), 3.85 (s, 3H,
CH3), 3.74 (s, 3H, CH3O), and 2.30 ppm (s, CH3); 13C nmr
(DMSO-d6): ꢀ191.22 (ArCO), 181.75 (C-3), 163.91 (C-2),
149.16-121.95 (aromatic C), 115.77 (C-4), 99.53 (C-5), 57.35
(2CH3O), and 22.90 ppm (CH3). Anal. Calcd. for C32H29N3O5;
C, 71.76; H, 5.46; N, 7.85. Found; C, 71.99; H, 5.57; N, 7.82.
5-(2-Aminophenyl)amino-3-hydroxy-4-(4-methoxylbenzoyl)-
5-(4-methoxyphenyl)-1-(1-naphthyl)-2,5-dihydro-2H-pyrrol-2-
one (5d). 4-(4-Methoxybenzoyl)-5-(4-methoxyphenyl)-1-(1-
naphtyl)-2,3-1H-pyrrole-2,3-dione 1d (1.0 g, 2.16 mmol) and o-
phenylenediamine 4 (0.23 g, 2.16 mmol) were refluxed in
benzene (50 mL) for 1 h. The solvent was evaporated and the
remaining oily residue was treated with dry diethyl ether and
stirred for 24 h. to give the yellow crude product which was
recrystallized from n-butyl alcohol and allowed to dry on P2O5;
resulting in yield 55% (0,68 g ); mp 193°C; ir: 3610-3400 (br, NH
3-[1-(4-Methoxylbenzoyl)-2-(4-methoxylphenyl)-2-p-tolyl-
aminovinyl]-1H-quinoxalin-2-one (6c). 4-(4-Methoxybenzoyl)-
5-(4-methoxyphenyl)-1-(4-methylphenyl)-1H-pyrrole-2,3-dione
1c (1.0 g, 2.34 mmol) and o-phenylenediamine 4 (0.25 g, 2.34
mmol) were stirred in benzene (50 mL) at 25°C for 24 h. The
orange crystaline product was filtered and recrystallized from
benzene and allowed to dry on P2O5; resulting in yield 70%
(0.85 g); mp 152-153°C; ir: 3450-3208 (NH), 1685, (C=O),
1
1648 (C=O); H nmr (DMSO-d6): ꢀ 12.44 and 12.01 (-NH),
7.88-7.11 (m, 16H, Ar-H), 6.32 (s, C-H), 3.78 (s, 3H, CH3O),
3.69 (s, 3H, CH3O), and 2.23 ppm (s, CH3); 13C nmr (DMSO-
d6): ꢀ 196.53 (ArCO), 158.51 (lactam C), 156.42 (C-3), 134.11-
114.89 (aromatic C), 57.22 and 57.02 (2CH3O) and 20.55 ppm
(CH3). Anal. Calcd. for C32H27N3O4; C, 74.26; H, 5.26; N, 8.12.
Found; C, 74.61; H, 5.41; N, 7.87.
3-[1-(4-Methoxylbenzoyl)-2-(4-methoxylphenyl)-2-naphthyl-
aminovinyl]-1H-quinoxalin-2-one (6d). 4-(4-Methoxybenzoyl)-
5-(4-methoxyphenyl)-1-(1-naphtyl)-2,3-1H-pyrrole-2,3-dione 1d
(1.0 g, 2.16 mmol) and o-phenylenediamine 4 (0.25 g, 2.34
mmol) were stirred in benzene (50 mL) at 25°C for 24 h. The
orange crystaline product was filtered and recrystallized from
benzene and allowed to dry on P2O5; resulting in yield 65%
(0.77 g); mp 209°C; ir: 3500-3250 (NH), 1680, (C=O), 1625
(C=O); 1H nmr (DMSO-d6): ꢀ 12.07 (-NH), 8.41-6.91 (m, 19H,
Ar-H), 6.74 (s, C-H) and 3.83 (s, 3H, CH3O), and 3.59 ppm (s,
3H, CH3O); 13C nmr (DMSO-d6): ꢀ 194.73 (ArCO), 158.97
(lactam C), 155.98 (C-3), 133.01-115.07 (aromatic C), and 56.99
and 54.65 ppm (2CH3O). Anal. Calcd. for C35H27N3O4; C,
75.93; H, 4.92; N, 7.59. Found; C, 75.93; H, 4.75; N, 7.56.
4-(4-Methoxylphenyl)[2-(4-methoxylphenyl)furo[2,3-b]-
quinoxalin-3-yl]methanone (7). Compounds of 6a-d (1 g, 2.34
mmol) were heated until they were dissolved in n-butyl alcohol
and kept at 25 °C for 24 h. The yellow product was filtered and
allowed to dry on P2O5; resulting in yield 47% (0.45 g); mp 235-
1
and OH), 3260 (NH2), 1715, 1675 (C=O); H nmr (DMSO-d6):
ꢀ12.66 (br, -NH) , 9.96 (s, -NHO), 9.82 (s, enol-OH), 8.19-6.75
(m, 19H, Ar-H), 6.29 (s, keto-CH), and 3.85 (s, 3H, CH3), and
3.76 (s, 3H, CH3O); 13C nmr (DMSO-d6): ꢀ 191.28 (ArCO),
179.81 (C-3), 163.87 (C-2), 147.22-121.55 (aromatic C), 115.34
(C-4), 99.52 (C-5), 57.35 (2CH3O). Anal. Calcd. for C35H29N3O5;
C, 73.54; H, 5.11; N, 7.35. Found; C, 73.25; H, 5.11; N, 7.17.
3-[1-(4-Methoxylbenzoyl)-2-(4-methoxylphenyl)-2-phenyl-
aminovinyl]-1H-quinoxalin-2-one (6a). 4-(4-Methoxybenzoyl)-5-
(4-methoxyphenyl)-1-phenyl-2,3-1H-pyrrole-2,3-dione 1a (1.0
g, 2.42 mmol) and o-phenylenediamine 4 (0.26 g, 2.42 mmol)
were stirred in benzene (50 mL) at 25°C for 24 h. The orange
crystaline product was filtered and recrystallized from benzene
and allowed to dry on P2O5; resulting in yield 69% (0,84 g); mp
1
236°C; ir: 1650 (C=O); H nmr (DMSO-d6): ꢀ 8.16-6.90 (m,
12H, Ar-H), 3.87 (s, 3H, CH3O), and 3.65 ppm (s, 3H, CH3O);
13C nmr (DMSO-d6): ꢀ 189.80 (ArCO), 172.68 (N-C=O),
167.81 (C1=O), 137.54 (Ar-C3-OH, in enol form) 134.15-
114.98 (aromatic C), and 56.24 ppm (2CH3O). Anal. Calcd. for
C25H18N2O4; C, 73.17; H, 4.39; N, 6.83. Found; C, 73.31; H,
4.67; N, 6.99.
1
159-160°C; ir: 3400-3250 (NH), 1670, (C=O), 1610 (C=O); H
nmr (DMSO-d6): ꢀ 12.40 and 11.90 (-NH), 8.21-7.19 (m, 17H,
Ar-H), 6.25 (s, C-H), and 3.84 (s, 3H, CH3O), and 3.67 ppm (s,
3H, CH3O); 13C nmr (DMSO-d6): ꢀ195.98 (ArCO), 158.01
(lactam C), 155.51 (C-3), 134.01-115.02 (aromatic C), and 57.01
and 56.24 ppm (2CH3O). Anal. Calcd. for C31H25N3O4; C,
73.94; H, 5.00; N, 8.34. Found; C, 73.57; H, 4.73; N, 8.07.
3-[1-(4-Methoxylbenzoyl)-2-(4-methoxylphenyl)-2-o-tolyl-
aminovinyl]-1H-quinoxalin-2-one (6b). 4-(4-Methoxyben-
zoyl)-5-(4-methoxyphenyl)-1-(2-methylphenyl)-1H-pyrrole-2,3-
dione 1b (1.0 g, 2.34 mmol) and o-phenylenediamine 4 (0.26 g,
2.34 mmol) were stirred in benzene (50 mL) at 25°C for 24 h.
The orange crystaline product was filtered and recrystallized
from benzene and allowed to dry on P2O5; resulting in yield 73%
(0.88 g); mp 165-166°C; ir: 3300-3230 (NH), 1690, (C=O),
Acknowledgement. This project was financially supported by
the Science and Technical Research Council of Turkey
(TÜBꢁTAK, project no:TBAG-AY/118), Resarch Center of
Erciyes University. Authors want to express their gratitude to D.
Unal and Dr. S. Patat.
REFERENCES
** To whom correspondence should be addressed.
[1a] Kollenz, G.; Ott, W.; Ziegler, E.; Peters, K.; von Schnering,
H.G.; Quast, H. Liebigs Ann. Chem., 1980 1801; [b] Kollenz, G.; Ott,
W.; Ziegler, E.; Peters, K.; von Schnering, H.G.; Formacek, V.; Quast,
H. Liebigs Ann. Chem., 1984 1137.
1
1630 (C=O); H nmr (DMSO-d6): ꢀ 12.51 and 12.10 (-NH),
7.89-7.05 (m, 16H, Ar-H), 6.84 (s, C-H), 3.78 (s, 3H, CH3O),
[2a] Peters, K.; Kollenz, G. Chem., Ber., 1981, 114, 1206; [b]
Kollenz, G.; Penn, G.; Dolenz, G.; Akçamur, Y.; Peters, K.; Peters, E.-

Sep-Oct 2007
Reactions of Some Pyrrole-2,3-diones with Hydrazine Hydrate and o-Phenylenediamine
1069
M.; von Schnering, H. G. Chem. Ber., 1984, 117, 1299; [c] El-Nabi, H.
A.; Kollenz, G. Monatsh. Chem., 1997, 128, 381.
[3a] Kollenz, G.; Penn, G.; Ott, W.; Peters, K.; Peters, E.-M.; von
Schnering, H. G. Chem.Ber., 1984, 117, 1310; [b] Heilmayer, W.;
Kappe, C. O.; Sterk, H.; Kollenz, G.; Peters, K.; Peters, E.-M.; von
Schnering H. G.; Walz, L. Chem.Ber., 1993, 126, 2061.
[4] Kollenz, G.; Penn, G.; Ott, W.; Peters, K.; Peters, E.-M.; von
Schnering, H. G. Heterocycles, 1987, 26, 625.
[5] Terpetschnig, E.; Penn, G.; Kollenz, G.; Peters, K.; Peters,
E.-M.; von Schnering, H. G. Tetrahedron, 1991, 47, 3045.
[6a] Ott, W. Synthesis, 1976 478; [b] Ott, W.; Terpetschnig, E.;
Sterk, H.; Kollenz, G. Synthesis, 1987 176.
[7] Kollenz, G.; Terpetschnig, E.; Sterk, H.; Peters, K.; Peters,
E.-M. Tetrahedron, 1999, 55, 2973.
[8a] Cappe, C. O.; Kollenz, G.; Wentrup, C. J. Chem. Commun.,
1992 485; [b] Cappe, C. O.; Kollenz, G.; Leung-Toung, R.; Wentrup, C.
J. Chem. Commun., 1992, 488.
[9a] Kost, A. N.; Grandberg, I. I. Adv. Heterocyclic Chem., 1966,
6, 347; [b] Sammes, M. P.; Katritzky, A. R. Adv. Heterocyclic Chem.,
1983, 34, 1; [c] Elguero, J. in Comprehensive Heterocyclic Chem., Vol
4, Katritzky, A. R.; Rees, C. W. Eds, Pergamon Press, Oxford, 1984,
Chapter 4,4; [d] Theobald, R. S. in: Coffey S.; Ansell, M. F. (Eds.),
Rodd’s Chemistry of Carbon Compounds, 2nd Edn., Vol IVc, Elsevier
Science Publishers, Amsterdam, p 1 (1986). [e] Elnagdi, M. H.;
Elgemeie, G. E. H.; Abd-Elmaksoud, F. A. E. Heterocycles, 1985, 23,
3121; [f] Mullins, S. T. in: Coffey S.; Ansell, M. F. (Eds.), Rodd’s
Chemistry of Carbon Compounds, Suppl. of Vol IVc/d , Elsevier Science
Publishers, Amsterdam, p 1 (1994).
[13a] O'Brien, D.; Weaver, M. S.; Lidzey, D. G.; Bradley, D. D. C.
Appl. Phys. Lett., 1996, 69, 881; [b] Dailey, S.; Feast, W. J.; Peace, R. J.;
Sage, I. C.; Till, S.; Wood, E. L. J. Mater. Chem., 2001, 11, 2238.
[14a] Cheeseman G. W. H.; Cookson, R. F. ed. by Weissberger,
A.; Taylor, E. C. The Chemistry of Heterocyclic Compounds, Vol. 35,
Wiley, J.; Sons, New York, 1979, pp. 1–27, 35-38; [b] Porter, A. E. A.
Comprehensive Heterocyclic Chemistry, 1984, Vol. 3, ed. by Katrizky
A. R.; Rees, C. W. Pergamon, New York, pp.157–197; [c] Gazit, A.;
App, H.; McMahon, G.; Chen, J.; Levitzki, A.; Bohmer, F. D. J. Med.
Chem., 1996, 39, 2170; [d] Sehlstedt, U.; Aich, P.; Bergman, J.;
Vallberg, H.; Norden, B.; Graslund, A. J. Mol. Biol., 1998, 278, 31.
[15a] Musatova, I. S.; Elina, A. S.; Padeiskaya, E. N.; Shipilova, L.
D.; Yakobson, G. G.; Furin, G. G. Khim. Farm. Zh., 1982, 16, 934; [b]
Musatova, I. S.; Elina, A. S.; Padeiskaya, E. N. Khim. Farm. Zh., 1982,
16, 1063; [c] Monge, A.; Gil, M. J.; Pascual M. A.; Gastelurrutia, M. A.
An. R. Acad. Farm., 1983, 49, 37 ; Chem. Abstr., 1983, 99, 194924s,;
[d] Monge, A.; Gil, M. J.; Pascual, M. A. An. R. Acad. Farm., 1983, 49,
199.
[16] Ganley, B.; Chowdhury, G.; Bhansali, J.; Daniels, J. S.; Gates
K. S. Bioorg. Med. Chem., 2001, 9, 2395.
[17a] Ziegler, E.; Eder, M.; Belegratis, K.; Prewedourakis, E.
Monatsh. Chem., 1967, 98, 2249; [b] Kollenz, G.; Kappe, C. O.; El
Nabey, H. A. Heterocycles, 1991, 32, 669; [c] Saalfrank, R. W.; Lutz,
T.; Hörner, B.; Gündel, J.; Peters, K.; von Schnering, H. G. Chem. Ber.,
1991, 124, 2289; [d] Sarıpınar, E.; Güzel, Y.; Önal, Z.; ꢀlhan, ꢀ. Ö.
Akçamur, Y. J. Chem., Soc., Pak., 2000, 22, 308.
[18] Sarıpınar, E.; Karataꢁ, S. J. Heterocyclic Chem., 2005, 42,
787.
[10a] Knorr, L. Ber., 1884, 17, 549; [b] Heming, A. E.; Kuzell, W.
C. Antibiot. Chemother., 1953, 3, 634; [c] Hermann, E.; Gabliks, J.
Cancer Chemother. Rept., 1961, 14, 85; [d] Ha, H. J.; Oh, S. J.; Lee, S.
K.; Song, C. E. Korean J. Med. Chem., 1996, 6; [e] Maggio, B.;
Daidone, G.; Rafa, D.;Plescia, S.; Mantione, L.; Cutuli, V. M. C.;
Mangano, N. G.; Eur Caruso, A. J. Med. Chem., 2001, 36, 737.
[11a] Hanson, G. A. Bull. Soc. Chim. Belg., 1958, 67, 707; [b]
Neunhoeffer, O.; Alsdorf, G.; Ulrich, H. Chem. Ber., 1959, 92, 252; [c]
Baroni, E. E.; Kovyrzina, K. A. Zh. Obshch. Khim., 1961, 31, 1641.
[12] Brock, E. D.; Lewis, D. M.; Yousaf, T. I.; Harper, H. H.
PCT Int. Appl. 1999 pp. 44.
[19a] Yıldırım, ꢀ.; Sarıpınar, E.; Güzel, Y.; Patat, ꢂ.; Akçamur, Y.
J. Mol. Struct., (Theochem), 1995, 334, 165; [b] ꢂener, A.;
Kasımoꢃulları, R.; ꢂener, M. K.; Bıldırıcı, ꢀ.; Akçamur, Y. J.
Heterocyclic Chem., 2002, 39, 869; [c] Kappe, C. O.; Terpetschnig, E.;
Penn, G.; Kollenz, G.; Peters, K.; Peters, E. M.; von Schnering, H. G.
Liebigs Ann., 1995, 537; [d] ꢀlhan, ꢀ. Ö.; Sarıpınar, E.; Akçamur, Y. J.
Heterocyclic Chem., 2005, 42, 117.
[20a] Ott, W.; Ziegler, E.; Kollenz, G. Synthesis, 1976, 7, 477; [b]
Kollenz, G.; Kriwetz, G.; Ott, W.; Ziegler, E. Liebigs Ann. Chem., 1977
1964; [c] Sarıpınar, E.; Saglam, E. G.; Oncel, ꢀ.; ꢀlhan, ꢀ. Ö.; Goktaꢁ, L.;
Kok, T. R.; Akcamur, Y. Heterocycles, 2005, 65, 2161.