Microwave-assisted studies on the reactions of the 4-Benzoyl-5-phenyl- 2,3-dihydro-2,3-furandione and derivatives

Article abstract of DOI:10.2174/157017810790796381

Varieties of heterocyclic compounds were prepared in good yield from 4-benzoyl-5-phenyl-2,3-dihydro-2,3- furandione under microwave irradiation conditions. The reaction revealed much shorter reaction times with comparable yields comparison to the corresponding thermal conditions.

Full text of DOI:10.2174/157017810790796381

Letters in Organic Chemistry, 2010, 7, 103-105
103
Microwave-Assisted Studies on the Reactions of the 4-Benzoyl-5-Phenyl-
2,3-Dihydro-2,3-Furandione and Derivatives
Esvet Akbas* and Ahmet Sener
Department of Chemistry, Faculty of Sciences, University of Yuzuncu Yil, 65080, Van, Turkey
Received November 05, 2009: Revised December 24, 2009: Accepted December 29, 2009
Abstract: Varieties of heterocyclic compounds were prepared in good yield from 4-benzoyl-5-phenyl-2,3-dihydro-2,3-
furandione under microwave irradiation conditions. The reaction revealed much shorter reaction times with comparable
yields comparison to the corresponding thermal conditions.
Keywords: Microwave-assisted, 2,3-furandione, synthesis, cyclic oxalyl compounds.
The interest in substituted 2,3-dihydro-2,3-furandiones is
caused by their high reactivity and the possibility of using
them as starting compounds for preparing various carbonyl
compounds of acyclic and heterocyclic series [1-4].
dione (1), but no literature precedent exists on the
microwave-promoted of this compound.
We now report that the synthesis of pyrazole-3-carbony-
lurea, aminobenzoates, pyrimidines [8], pyrazole carboxylic
acids [13,14], pyridazines [13,14] and pyrazolopyridazine
[20] derived from compound 1 were equally effective in
solvent both under thermal as well as under microwave-
induced conditions Scheme 1.
The reactions of substituted 2,3-dihydro-2,3-furandiones
have been studied with several semi/thiosemicarbazones,
ureas, thioureas, oximes, various hydrazines, some
acetanilides and amides under different conditions [5-13].
Most of these obtained compounds in general are well
known for their potential biological activities [14].
A variety of substrates were successfully reacted under
microwave condition; results are summarized in Table 1.
In the last few years there has been an increased interest
in the use of microwave heating in organic synthesis and it
forms now the basis of a number of commercial systems.
Some interesting features of this method are the rapid
reaction rates, simplicity, solvent-free conditions, and the
case of work-up after the reaction, and better selectivity.
Also, microwave irradiation generates rapid intense heating
of polar substances, which result in the reduction of reaction
time compared to conventional heating [15-18].
The time of 45-360 min was chosen for thermal heating
whereas microwave-induced reactions were performed at 50
W for 5–10 min with internal reaction temperatures. Under
both sets of conditions, the desired compounds were
obtained in good yield and in excellent purity by a simple
crystallization.
We selected the synthesis of these compounds as a model
reaction to study the effects of irradiation power and time on
the yields. The best yields obtained are 56% (5a) after 5 min
of irradiation using benzene as solvent.
Another improvement that can be made in the cyclic
oxalyl compound derivatives synthesis is the diminution of
the reaction time by using microwave technology. Indeed,
most published conventional synthetic procedures required
long reaction times that vary between 1-24 hours or more
time. Microwave heating is an area of increasing interest in
both industrial and academic studies because it can increase
the rate of reaction and in many cases improve product
yields [19].
In summary, the synthesis of cyclic oxalyl compound
derivatives has been accomplished followed by the
nucleophilic addition of urea, amines, and hidrazines under
microwave irradiation. The main advantages of this method
are short reaction times.
DATA FOR THE SELECTED COMPOUNDS
Compound 2
The purpose of the present work is to extend the 2,3-
dihydro-2,3-furandione reactions in order to synthesize some
heterocyclic derivatives. The reported method is suggested a
fast and efficient route for the preparation of cyclic oxalyl
compound derivatives.
IR(KBr): 3324 and 3060(2NH), 1704, 1686, 1658(C=O);
1H-NMR (CDCl3): 10.13 (1H, bs, NH, NHꢀOH), 8.13-8.10
(1H, t, -NH), 7.77-7.15 (15H, m, ArH), 5.84-5.77 (1H, m,
=CH), 5.08-5.01 (2H, t, CH2), 3.77-3.75 (2H, t, =CH2 ); 13C-
NMR (CDCl3): 190.93, 162.04 and 152.75 (C=O), 144.38,
144.21, 139.08, 138.00, 135.71, 134.21, 130.38, 130.12.
129.79, 129.78, 129.55, 129.29, 129.17, 128.21, 126.37,
122.73, 115.89, 42.07 (CH2). Microanalyses: C, 72.01; H,
4.90; N, 12.49%.
A survey of the literature reveals several reports on
reactions of the 4-benzoyl-5-phenyl-2,3-dihydro-2,3-furan-
*Address correspondence to this author at the Department of Chemistry,
Faculty of Sciences, University of Yuzuncu Yil, 65080, Van, Turkey; Tel:
+90 0505 562 60 70; Fax: +90 0432 225 10 88;
E-mail: esvakbas@hotmail.com
1570-1786/10 $55.00+.00
© 2010 Bentham Science Publishers Ltd.

104 Letters in Organic Chemistry, 2010, Vol. 7, No. 2
Akbas and Sener
H
O
O
N
O
NHCH2CH=CH2
Ph
N
Ph
N
Ph
O
O
N
O
O
N
O
NHCH2CH=CH2
Ph
Cl
NH2CONHCH2CH=CH2
Ph
N
Ph
O
O
O
+
H
Ph
O
H
N
Ph
N
O
N
Ph
Ph
Ph
OX
SOCl2
2
[Ref. 20]
3 a,b
O
N
O
O
OH
Ph
O
OH
Ph
+
XO
N
Ph
]
Ph
N
Ph
N
3
X=Et (a)
Me (b)
1
O
NH2
f.
2
Ph
4a
e
4b
R
.
+
t
Ph
a
HNH
Ph
O
e
O
N
H
h
P
N
N
O
Ph
Ph
N
O
Me
nv.
Ph
N
o
Ph
O
NH2CONHN=CPhMe
[C
PhNHNH2
O
Ph
N
O
[Conv. Heat. Ref. 8]
[Conv. Heat. Ref. 20]
N
Ph
8
N
14]
1
f.
2
e
H
Ph
R
.
t
a
6
NHN
O
3
O
O
OH
He
CH
nv.
Ph
O
o
OH
Ph
[C
+
N
N
Ph
Ph
N
CH3
N
O
CH3
5b
Ph
NH
5a
Ph
N
O
7
Scheme 1.
Table 1. Comparative Study of the Synthesis of 2-8
aYield (%)
bReaction time/min
Compound
2
Substrate
Solvents used
MW
CONV.
MW
CONV.
360
NH2CONHCH2CH=CH2
38%
29%
20%
xylene
5
NH2
O
3a
23%
benzene
10
180
OEt
NH2
O
3b
4a
28%
33%
22%
49%
p- xylene
10
5
180
60
OMe
PhNHNH2
benzene

Microwave-Assisted Studies on the Reactions
Letters in Organic Chemistry, 2010, Vol. 7, No. 2
105
(Table 1). Contd…..
aYield (%)
CONV.
bReaction time/min
Solvents used
Compound
Substrate
MW
MW
CONV.
4b
5a
5b
6
PhNHNH2
CH3NHNH2
11%
56%
36%
49%
23%
34%
10%
45%
40%
70%
36%
38%
benzene
benzene
benzene
xylene
5
5
60
60
CH3NHNH2
5
60
PhNHNH2
10
10
5
180
210
45
7
NH2CONH2
benzene
benzene
8
NH2CONHN=CPhMe
aIsolated yield.
bReaction times not optimized.
von 4-benzoyl-2,3-dioxo-5-phenyl-2,3-dihydrofuran mit o-
phenylendiamin. Synthesis, 1976, 477.
Compound 3a
IR(KBr): 3213 (NH), 1730, 1702, 1697, 1664, 1583
(C=O); H-NMR (CDCl3): 8.90 (1H, s, NH), 8.85 (1H, s, -
[7]
[8]
Akçamur, Y.; Altural, B.; Sarıpınar, E.; Kollenz, G.; Kappe, C.O.;
Peters, E.M.; von Schnering, H.G. A convenient snthesis of
functionalized 1H-pyrimidine-2-thiones[1]. J. Heterocycl. Chem.,
1988, 25, 1419.
Altural, B.; Akçamur, Y.; Sarıpınar, E.; Yıldırım, ꢂ.; Kollenz, G.
Reactions of cyclic oxalyl compounds, part 29: A simple synthesis
of functionalized 1H-pyrimidines. Monatsh. Chem., 1989, 120,
1015.
1
CH), 8.15-7.15 (14H, m, ArH), 4.53-4.42 (2H, q, -OCH2),
1.48-1.40 (3H, t, CH3); 13C-NMR (CDCl3): 201.05, 189.54,
181.85 and 169.42 (C=O), 148.02, 141.59, 138.01, 137.08,
136.40, 133.12, 125.85, 122.47, 121.65, 118.87, 63.74(-
OCH2), 16.25 (CH3). Microanalyses: C, 70.44; H, 4.68; N,
3.18%.
[9]
Ilhan, I.O.; Sarıpınar, E.; Akçamur, Y. Synthesis of some pyrazole-
3-carboxylic acid-hydrazide and pyrazolopyridazine compounds. J.
Heterocycl. Chem., 2005, 42(1), 117.
[10]
[11]
Yıldırım, ꢂ.; and Koca, I. 4-(4-Methylbenzoyl)-5-(4-methylphenyl)
furan-2,3-dione: Synthesis, thermolysis and reactions with aromatic
amines and diamines. Asian J. Chem., 2004, 16(2), 899.
Yıldırım, ꢂ.; and Ilhan, I.O. Experimental and theoretical
investigations of functionalization and cyclization reactions of 4-
benzoyl-5-phenyl-2,3-furandione with some acetanilides. Indian J.
Chem., Sect. B Org. Med. Chem., 1997, 36(12), 1138.
Compound 3b
IR(KBr): 1732, 1707, 1673, 1668, 1591 (C=O); 1H-NMR
(CDCl3): 8.71 (1H, s, NH), 8.67 (1H, s, -CH), 8.55-7.13
(14H, m, ArH), 3.02 (3H, s, CH3). Microanalyses: C, 69.90;
H, 4.41; N, 3.28%.
[12]
[13]
Sarıpınar, E.; Ilhan, I.O.; and Akçamur, Y.; Reactions of -oxo
ketenes with amides: EXPERIMENTAL data and semiempirical
AM1 molecular orbital calculations. Heterocycles, 2002, 57, 1445.
Akçamur, Y.; Penn, G.; Ziegler, E.; Sterk, H.; Kollenz, G.; Peters,
K.; Peters E.M.; von Schnering, H.G. Reaktionen mit cyclischen
ACKNOWLEDGEMENTS
The authors thank the research fund of Yuzuncu Yıl
University for financial support.
oxalylverbindungen, XXIV1
. Zur reaktion von 4-benzoyl-5-
phenyl-furan-2,3-dion mit phenylhydrazonen bzw. Phenylhydrazin.
Monatsh. Chem., 1986, 117, 231.
[14]
[15]
Akbaꢁ, E.; Berber, ꢂ.; ꢀener, A.; Hasanov, B. Synthesis and
antibacterial activity of 4-benzoyl-1-methyl-5-phenyl-1H-pyrazole-
3-carboxylic acid and derivatives. II. Farmaco, 2005, 60, 23.
Dandia, A.; Arya, K.; and Sati, M. Microwave assisted synthesis of
fluorinated hexahydro 1,3,5-triazine derivatives in aqueous medium
and one pot synthesis of 1,2,4-triazolo(4,3-a)1,3,5-triazines. Synth.
Commun., 2004, 34(6), 1141.
Stadler, A.; Kappe, C. O. Microwave-mediated Biginelli reactions
revisited. On the nature of rate and yield enhancements. J. Chem.
Soc., Perkin Trans, 2000, 2, 1363.
Mobinikhaledi, A.; Forughifar, N. Microwave-assisted synthesis of
some pyrimidine derivatives. Phosphorus Sulfur Silicon, 2006,
181(11), 2653.
Akbas, E.; Aslanoglu, F. Studies on reactions of pyrimidine
compounds. 21: microwave-assisted synthesis of 1,2,3,4-tetrahydro-
2-thioxopyrimidine derivatives. Phosphorus Sulfur Silicon, 2008,
183, 82.
REFERENCES
[1]
[2]
[3]
[4]
[5]
ꢀener, A.; Akbaꢁ, E.; ꢀener, M.K. Synthesis and some reactions of
4-benzoyl-5-phenyl-1-pyridin-2yl-1H-pyrazole-3-carboxylic acid.
Turkish J. Chem., 2004, 28, 271.
Akbas, E.; Sonmez, M.; Celebi, M.; Aslanoglu, F. Synthesis of
some transition metal complexes of ligands derived from 5-phenyl-
2,3-dihydro-2,3-furandione, J. Chem. Res., 2008, 256.
Akbaꢁ, E.; Aslanoglu, F. Syntheses of some new 1H-pyrazole,
pyridazin-3(2H)-one, and oxazin-4-one derivatives. Heteroatom
Chem., 2006, 17(1), 8.
[16]
[17]
[18]
Akbaꢁ, E.; Daskapan, T.; ꢀener, A. Reactions of substituted furan-
2,3-diones with C- and N- nucleophiles. Asian J. Chem., 2007,
19(3), 1913.
Nekrasov, D.D.; Kol'tsova1, S.V.; Radishevskaya, M.A. Interaction
of 5-aryl-2,3-dihydrofuran-2,3-diones with functionally substituted
hydrazides and diaminoglyoxal diphenylhydrazone. Chem.
Heterocycl. Comp., 2004, 40(3), 301.
[19]
[20]
Kappe, C.O. Controlled microwave heating in modern organic
synthesis. Angew. Chem. Int. Ed. Engl., 2004, 43, 6250.
Akçamur, Y.; ꢀener, A.; Ipekoglu, A.M. Functionalization and
cyclization reactions of 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-
carboxylic acid. J. Heterocycl. Chem., 1997, 34, 221.
[6]
Ott, W.; Ziegler, E.; Kollenz, G. Synthese von heterocyclen; 1921.
Reaktionen mit cyclischen oxalyl-verbindungen; 152. Umsetzung