A facile synthesis of imidazolidine-2,4,5-trione

Article abstract of DOI:10.3184/174751914X14116560440865

When glycoluril was oxidised with potassium persulfate, the main product was imidazolidine-2,4,5-trione. The structure of product was confirmed by IR, ESI, 1H NMR and X.ray crystal structure determination.

Full text of DOI:10.3184/174751914X14116560440865

JOURNAL OF CHEMICAL RESEARCH 2014
VOL. 38 OCTOBER, 625–626
RESEARCH PAPER 625
A facile synthesis of imidazolidine-2,4,5-trione
De-Li Yang, Jia-Rong Li, Hong-Yan Lu, Pan Zhang and Da-Xin Shi*
School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081, P.R. China
When glycoluril was oxidised with potassium persulfate, the main product was imidazolidine-2,4,5-trione. The structure of
product was confirmed by IR, ESI, 1H NMR and X-ray crystal structure determination.
Keywords: glycoluril, oxidation, imidazolidine-2,4,5-trione, potassium persulfate
Imidazolidine-2,4,5-trione is a useful intermediate which can
be used to synthesise imidazo[1,2-a]pyridines, -pyrazines,
-pyrimidines, and some other nitrogen-bridgehead fused
heterocycles.1 This compound was first prepared by
Heinrich and Ernst in 1913 by the condensation of urea and
oxalyl dichloride.2 Several methods3–5 have been developed
subsequently for the preparation of imidazolidine-2,4,5-trione,
but many of these require a toxic solvent, an expensive catalyst
or a long reaction time.
Glycoluril is a rigid bicyclic molecule which is used as
a bleaching activator in industry,6,7 structural units for
cucurbituril8,9 and as raw material for explosives.10 Recently,
many methods for the construction of glycoluril have been
reported,11–16 but its oxidation has never been described.
When we studied the oxidation of glycoluril, imidazolidine-
2,4,5-trione instead of the expected dihydroxy glycoluril was
obtained. We now report these results.
was important, and 75 °C was the best choice. The reaction
could not be completed at low temperatures, and the refluxing
temperature did not enhance the yield of product because of
the decomposition of the raw material. The amount of oxidant
was optimal at 1 equiv. and the reaction time was optimal at 2 h
longer times did not improve the yield.
As shown in Figs 1 and 2, the structure of imidazole skeleton
in imidazolidine-2,4,5-trione is not an envelope structure, all
the atoms are in one plane. In the molecule, all C and N atoms
are of sp3 hybridisation, and the structure of molecule is not
a standard pentagon. In the crystal lattice, every molecule
is linked to other four molecules by four adjacent O•••H–N
hydrogen bonds, named quadruple hydrogen bonding. There
are two hydrogen bonding donors and two hydrogen bonding
acceptor in one molecule, the generality of multimers is in the
DAAD sequence.20
Results and discussion
Potassium persulfate (K2S2O8) is a mild oxidant that has been
widely used in organic chemistry17 because of its safety and
high efficiency. Kim et al.18 have accomplished that the direct
perhydroxylation of cucurbituril (CB[n]) using K2S2O8 as an
oxidant to yield (HO)2nCB[n]. Consequently, we thought that
the glycoluril may be oxidised by this reagent (Scheme 1).
Glycoluril was obtained by the condensation of urea and
glyoxal according to the literature method19 A solution of
glycoluril and K2S2O8 in water was stirred for 2 hours at 75 °C.
A white solid, which is soluble in water and ethyl acetate, was
1
obtained. Based on the characterisation of H NMR, IR, and
MS spectroscopy, its structure was imidazolidine-2,4,5-trione
and was confirmed by X-ray diffraction (Fig. 1).
The optimal reaction conditions were identified (Table 1).
The results showed that the effect of reaction temperature
Fig. 1 Molecular structure of imidazolidine-2,4,5-trione at 30%probability
thermal ellipsoids.
O
NH
O
HN
O
O
O
HN
HN
NH
NH
O
H
O
H
K2S2O8
O
H3BO3
O
O
H2N
NH2
H
2O
NH
HN
O
HN
H
O
NH
H
Scheme 1 Synthesis of imidazolidine-2,4,5-trione.
* Correspondent. E-mail: jrli@bit.edu.cn

626 JOURNAL OF CHEMICAL RESEARCH 2014
O
O
O
O
O
O
HN
NH
HN
NH
O
H2N
NH2
HN
HN
NH
NH
K2S2O8
HN
O
NH
O
H
O
HN
H
O
NH
H
O
HN
NH2
O
O
Scheme 2 Possible mechanism for the reaction.
Table 1 Optimal conditions for the synthesis of imidazolidine-2,4,5-
trionea
Entry
Temp/°C. K2S2O8/mmol
Time/h
Yield/%
1
2
3
4
5
6
RT
20
40
75
75
Reflux
1
1
1
1
2
2
4
4
4
2
4
2
0
15
38
95
93
80
aConditions: Glycoluril (1 mmol, 1.42 g), distilled water (5 mL).
This work was financially supported by the Foundation of
Beijing Key Laboratory for Chemical Power Source and
Catalysis, No. 2014CX02026.
Fig. 2 The interactions between molecules.
Received 1 September 2014; accepted 15 September 2014
Paper 1402860 doi: 10.3184/174751914X14116560440865
Published online: 17 October 2014
The possible mechanism for the reaction is shown in
Scheme 2. The protons of the glycoluril were firstly oxidised
to hydroxy, then dihydroxy glycoluril was not stable and
transformed to imidazolidine-2,4,5-trione.
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operational simplicity and mild conditions. The structure of
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General procedure
Glycoluril (1 mmol) was added in 5 mL of distilled water. Then K2S2O8
(1 mmol) was added to the solution and the system were stirred for
2 hours at 75 °C. The reaction mixture was extracted by ethyl acetate
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recrystallised from petroleum/ethyl acetate to give a colourless single
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Imidazolidine-2,4,5-trione: White solid; yield 95%; m.p. 238–240°C
(1it.22 236–240 °C); IR (KBr, cm–1): 3052, 2708, 2488, 1745, 1377,
1341, 1230, 993; 1H NMR: (400 MHz, DMSO-d6) δH 11.75 (2H, br); ESI
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