Synthesis and decomposition of parabanic acid derivatives

Article abstract of DOI:10.14233/ajchem.2013.13307a

As a part of a research program related to the synthesis of pharmacologically and agrochemically interesting parabanic acid derivatives, we synthesized imidazolidine-2,4,5-trionylimidazolidine (6), 2-thioxoimidazolidine- 1-ylimidazolidine (7), benzo[d]-isothiazol-2-yl imidazolidine-2,4,5-thriones (8a-c), 2-thioxobenzo[d]-isothiazol-2-yl imidazolidine-4,5-dione (9a-c) and 1-benzoimidazole-3- imidazolidine-2,4,5-triones (10a-c), 1-phenylurea (11), 1-ethyl-3-[(3-ethylthioureido)methyl]urea (12) and 1-ethyl-3-[(3- methylthioureido) methyl]urea (13) were obtained in basic solution through ultrasound.

Full text of DOI:10.14233/ajchem.2013.13307a

Asian Journal of Chemistry; Vol. 25, No. 1 (2013), 505-508
http://dx.doi.org/10.14233/ajchem.2013.13307A
Synthesis and Decomposition of Parabanic Acid Derivatives
1
1
2
S.K. CHOI , S.G. LEE , D.I. JUNG1,* and J.T. HAHN
1Department of Chemistry, Dong-A University, Busan 604714, South Korea
2Department of Beautycare, Youngdong University, Youngdong 370701, South Korea
*Corresponding author: Fax: +82 51 2007249; Tel: +82 51 2007249; E-mail: dijung@dau.ac.kr
(Received: 22 December 2011;
Accepted: 2 August 2012)
AJC-11911
As a part of a research program related to the synthesis of pharmacologically and agrochemically interesting parabanic acid derivatives,
we synthesized imidazolidine-2,4,5-trionylimidazolidine (6), 2-thioxoimidazolidine-1-ylimidazolidine (7), benzo[d]-isothiazol-2-yl
imidazolidine-2,4,5-thriones (8a-c), 2-thioxobenzo[d]-isothiazol-2-yl imidazolidine-4,5-dione (9a-c) and 1-benzoimidazole-3-
imidazolidine-2,4,5-triones (10a-c), 1-phenylurea (11), 1-ethyl-3-[(3-ethylthioureido)methyl]urea (12) and 1-ethyl-3-[(3-methyl-
thioureido)methyl]urea (13) were obtained in basic solution through ultrasound.
Key Words: Parabanic acid, Benzimidazole, 1,2-Benzisothiazol-3-one-1,1-dioxide, Agrochemical fungicide, Urea derivatives.
H2
C
(S)
O
O
O
(S)
O
O
H2
C
INTRODUCTION
N
H2
C
N
Ph
Me
R
R
N
O
N
O
N
O
N
N
O
N
O
N
O
N
Parabanic acid(imidazolidine-2,4,5-trione, oxalylurea)
resulting from the oxidation of biological fundamental comp-
ounds such as uric acid, guanine, uracil and alloxanic acid has
attracted the attention of agricultural and medicinal chemists
for many decades1,2. Parabanic acid derivatives are useful
phamaceuticals for the treatment of diabetic complications
such as diabetic neuropathy, diabetic cataracts and diabetic
dermotopathy3-6. Further, parabanic acid derivatives are known
for their herbicidal, plant growth regulating and fungicidal
properties7. Polymers containing imidazolidine-2,4,5-trione
(parabanic) rings are known as highly thermally stable polymers
S
O
O
O
O
3
2
1
EXPERIMENTAL
Melting points were determined on a Büchi 510 capillary
melting point apparatus and uncorrected. Infrared spectra were
recorded on a Perkin-Elmer 683 spectro-photometer. NMR
spectra were recorded on a Varian XL-300 or Brüker AC 200
FT-NMR spectrometer in CDCl3 containing Me4Si as an
internal reference. Mass spectra were obtained by using JEOL
JMS DX 303 or HP 5892 Mass Spectrometer.
with improved chemical resistance in organic solvents8-13
.
General procedure for the synthesis of 6,7: To a solution
of 1-chloromethyl-imidazolidine-2,4,5-triones (4) (or 1-chloro-
methyl-2-thioxo-imidazolidine-4,5-diones (5), 1.13 × 10-2 mol)
in dry THF (15 mL) under nitrogen at room temperature was
added solution of 2,4,5-imidazolidinetriones (or 2-thioxo-
imidazolidine-4,5-diones, 1.13 × 10-2 mol) and triethylamine
(0.4 mL) in dry THF (15 mL). The reaction mixture was stirred
at room temperature for 0.5 h.After 0.5 h, the reaction mixture
was refluxed at 60-65 ºC for 7 h. The reaction mixture was
cooled again to room temperature and THF (75 mL) was added.
The combined organic layers were dried over anhydrous
Na2SO4, filtered and concentrated in vacuo. The residue was
purified by flash column chromatography on silica gel eluted
with only CH2Cl2, to provide products 6,7.
Recently, many marine imidazol alkaloids have been isolated
from sponges and their antitumor and antibacterial activities
have also been identified 14,15. In our previous works to obtain
new agrochemicals, we reported the synthesis of new saccharin
derivatives containing the 2,4,5-imidazolidinetrione group16.
As a part of research program related to the synthetic study of
pharmacologically and agrochemically important imida-
zolidines16, we chose to identify imidazolidine-2,4,5-trione and
imidazolidine-2,4,5-trione,2-thioxo-imidazolidine-4,5-dione,
benzimidazole, orsaccharin rings as active components for the
desired property, the synthesis of (imidazolidine-2,4,5-trionyl)
imidazolidine-2,4,5-triones (1), 2,4,5-imidazolidinetrionyl-
1,2-benzisothiazol-3-one-1,1-di-oxide 2, 4,5-dioxo-2-thioxo-
imidazolidin-1-ylmethyl-imidazolidine-2,4,5-triones (2) and
1-benzoimidazole-1-yl-3-imidazolidine-2,4,5-trione (3) are
already reported.
1-[(3-Phenylimidazolidine-2,4,5-trionyl)methyl]-3-
methyl-imidazolidine-2,4,5-trione (6): m.p. 247-249 ºC;

506 Choi et al.
Asian J. Chem.
1H NMR (200 MHz, DMSO) 3.08 (s, 3H), 5.43 (s, 2H), 7.52
(m, 5H); 13C NMR (50 MHz, DMSO) 157.2, 156.1, 155.9,
155.7, 152.8, 151.7, 130.2, 129.3, 128.9, 126.5, 40.6, 24.5;
GC/MS m/z 330 ([M+]);Anal. calcd. for C14H10N4O6: C, 50.92;
H, 3.05; N, 16.96. Found : C, 50.95; H, 3.04; N, 16.94.
1-[(4,5-Dioxo-3-phenyl-2-thioxoimidazolidin-1-
yl)methyl]-3-ethyl-imidazolidine-2,4,5-trione (7): m.p. 217-
218 ºC; 1H NMR (200 MHz, DMSO) 1.11 (t, J = 7.1 Hz, 6H),
3.51 (d, J = 6.9 Hz, 2H), 5.53 (s, 2H), 3.80 (d, J = 7.0 Hz, 2H);
13C NMR (50 MHz, DMSO) 180.1, 156.7, 156.0, 154.9, 154.7,
152.4, 43.6, 36.6, 33.8, 12.9, 12.5; GC/MS m/z 360([M+]);
Anal. calcd. for C15H12N4O5S: C, 50.00; H, 3.36; N, 15.55.
Found : C, 50.03; H, 3.35; N, 15.59.
1-Chloromethyl-3-ethyl-imidazolidine-2,4,5-trione
(4b): Yield 64 %; m.p. 83-84 ºC; IR (KBr, νmax, cm-1) 2982,
2865, 1735, 1409, 1298, 1208, 1128; Mass m/z (rel. intensity,
%) 192 ([M+1]+, 5), 190 ([M-1]+, 10), 175 (2), 162 (1), 154
(30), 127 (15), 99 (10), 70 (45), 56 (100); 1H NMR (200 MHz,
CDCl3) 1.27-1.34 (t, 3H, CH3), 3.70-3.81 (q, 2H, CH2Cl), 5.39
(s, 2H, CH2Cl).
1-Chloromethyl-3-phenyl-imidazolidine-2,4,5-trione
(4c):Yield 70 %; m.p. 130-131 ºC; IR (KBr, νmax, cm-1) 1780,
1730, 1500, 1440, 1295, 1190; Mass m/z (rel. intensity, %)
238 ([M]+, 27), 119 (100), 91 (23); 1H NMR (200 MHz, CDCl3)
5.6 (s, 2H, CH2Cl), 7.4-7.5 (m, 5H, phenyl).
1-Methyl-3-(1,1,3-trioxo-1,3-dihydro-16-benzo[d]-
isothiazol-2-yl-methyl)-imidazolidine-2,4,5-trione (8a):Yield
40 %; m.p. 192-193 ºC; IR (KBr, νmax, cm-1): 1749, 1453, 1340,
1291, 1245, 1179; Mass m/z (rel. intensity, %) 323 ([M]+, 1),
259 (15), 223 (4), 196 (100), 174 (20), 169 (17), 132 (20), 121
(5), 104 (22), 76 (15), 70 (9); 1H NMR (200 MHz, Acetone-d6)
3.14 (s, 3H, CH3), 5.70 (s, 2H, CH2), 8.05-8.21 (m, 4H, phenyl).
1-Ethyl-3-(1,1,3-trioxo-1,3-dihydro-16-benzo-[d]
isothiazol-2-yl-methyl)-imidazolidine-2,4,5-trione (8b):
Yield 54 %; m.p. 182-183 ºC; IR (KBr, νmax, cm-1): 2981, 2885,
1746, 1425, 1340, 1293, 1251, 1180, 1115; Mass m/z (rel.
intensity, %) 337 ([M]+, 2), 273 (8), 223 (4), 196 (100), 174
The typical experimental procedure for 1-phenyl-3-(1,1,3-
trioxox-1,3-dihydro-16-benzo[d]isothiazol-2-ylmethyl)-
imidazolidine-2,4,5-trione (6) is as follows: To a solution of
1-chloromethyl-3-phenylimidazolidine-2,4,5-trione (4c) (2.38
g, 10 mmol) in dry THF (15 mL) under nitrogen at room tem-
perature was added solution of saccharin (2.01 g, 11 mmol)
and triethylamine (1.2 mL) in dry THF (15 mL). The reaction
mixture was stirred at room temperature for 0.5 h. After 0.5 h,
the reaction mixture was refluxed at 55-60 ºC for 5 h. The
reaction mixture was cooled again to room temperature and
THF (50 mL) was added. The combined organic layers were
dried over anhydrous Na2SO4, filtered and concentrated in
vacuo. The residue was purified by flash column chromato-
graphy on silica gel eluted with only CH2Cl2, to provide the
1-phenyl-3-(1,1,3-trioxo-1,3-dihydro-16-benzo[d]isothiazol-
2-yl-methyl)-imidazolidine-2,4,5-trione 6 as a white crystal-
1
(15), 169 (14), 132 (20); H NMR (200 MHz, Acetone-d6)
1.18-1.28 (t, 3H, CH3), 3.64-3.75 (q, 2H, CH2), 5.70 (s, 2H,
N-CH2-N), 8.02-8.22 (m, 4H, phenyl).
1-Phenyl-3-(1,1,3-trioxo-1,3-dihydro-16-benzo[d]-
isothiazol-2-yl-methyl)-imidazolidine-2,4,5-trione (8c):Yield
50 %; m.p. 191-192 ºC; IR (KBr, νmax, cm-1): 1785, 1750, 1410,
1330, 1290, 1250; Mass m/z (rel. intensity, %) 385 ([M]+, 40),
196 (100), 169 (20), 119 (80), 91 (45), 77 (33); 1H NMR (200
MHz, CDCl3) 5.84 (s, 2H, CH2), 7.4-8.1 (m, 9H, phenyl).
1-Chloromethyl-3-methyl-2-thioxo-imidazolidine-4,5-
dione (5a): Yield 45 %; m.p. 97-98 ºC; IR (KBr, νmax, cm-1):
1784, 1772, 1405, 1378, 1354; Mass m/z (rel. intensity, %)
192 ([M]+), 1; 1H NMR (200 MHz, Acetone-d6) 3.38 (s, 3H,
CH3), 5.76 (s, 2H, CH2).
1
line solid (1.93 g, 50 %). m.p. 191-192 ºC; H NMR (200
MHz, CDCl3) 5.84 (s, 2H, CH2), 7,4-8.1 (m, 9H, phenyl); Mass
m/z (rel. intensity, %) 385 ([M+], 40), 196 (100), 91, 77.
The typical experimental procedure for 1-ethyl-2-thioxo-
3-(1,1,3-tri-oxo-1,3-dihydro-16-benzo[d]isothiazol-2-
ylmethyl)-imidazolidine-4,5-dione (7) is as follows: To a
solution of 1-ethyl-2-thioxo-imidazolidine-4,5-dione (5b) (1 g,
4.8 mmol) in the dry THF (10 mL) under nitrogen at room
temperature was added solution of saccharin (1.5 g, 8.2 mmol)
and triethylamine (1.1 mL) in the dry THF (10 mL). The
reaction mixture was stirred at room temperature for 0.5 h.
After 0.5 h, the mixture was refluxed 55-60 ºC for 5 h. The
reaction mixture was cooled again to room temperature and
THF (50 mL) was added. The combined organic layers were
dried over anhydrous Na2SO4, filtered and concentrated in
vacuo. The residue was purified by flash column chromatog-
raphy on silica gel eluted with only CH2Cl2, to provide the 1-
ethyl-2-thioxo-3-(1,1,3-trioxo-1,3-dihydro-16-benzo[d]
isothiazol-2-ylmethyl)-imidazolidine-4,5-dione (7) as a yellow
1-Chloromethyl-3-ethyl-2-thioxo-imidazolidine-4,5-
dione (5b):Yield 45 %; m.p. 108-109 ºC; IR (KBr, νmax, cm-1):
1780, 1740, 1402, 1370, 1230, 1135; Mass m/z (rel. intensity,
%) 206 ([M]+); 1H NMR (200 MHz, Acetone-d6) 1.21-1.28 (t,
3H, CH3), 3.95-4.06 (q, 2H, CH2), 5.75 (s, 2H, CH2Cl).
1-Chloromethyl-3-phenyl-2-thioxo-imidazolidine-4,5-
dione (5c):Yield 40 %; m.p. 149-150 ºC; IR (KBr, νmax, cm-1):
1780, 1650, 1520, 1500, 1400, 1230; Mass m/z (rel. intensity,
%) 254 ([M]+); 1H NMR (200 MHz, Acetone-d6) 5.87 (s, 2H,
CH2Cl), 7.43-7.60 (m, 5H, phenyl).
1
crystalline solid (1.68 g, 49 %). m.p. 157-158 ºC; H NMR
1-Methyl-2-thioxo-3-(1,1,3-trioxo-1,3-dihydro-16-
benzo[d]isothiazol-2-ylmethyl)-imidazolidine-4,5-dione
(9a):Yield 40 %; m.p. 173-174 ºC; IR (KBr, νmax, cm-1): 1780,
1400, 1340, 1290, 1250, 1170, 1100; Mass m/z (rel. intensity,
%) 339 ([M]+); 1H NMR (200 MHz, Acetone-d6) 3.39 (s, 3H,
CH3), 6.04 (s, 2H, N-CH2-N), 8.10-8.17 (m, 4H, phenyl).
1-Ethyl-2-thioxo-3-(1,1,3-trioxo-1,3-dihydro-16-
benzo[d]isothiazol-2-yl-methyl)-imidazolidine-4,5-dione
(9b):Yield 49 %; m.p. 157-158 ºC; IR (KBr, νmax, cm-1): 1780,
1740, 1720, 1390, 1330, 1280, 1240, 1175; Mass m/z (rel.
(200 MHz, acetone-d6) 1.17 (t, 3H, -CH3), 3.99-4.06 (q, 2H,
-CH2), 6.04 (s, 2H, N-CH2-N), 8.05-8.20 (m, 4H, phenyl); IR
(KBr, νmax, cm-1): 1780, 1740, 1720, 1390, 1330, 1280, 1240,
1175; Mass m/z (rel. intensity, %) 352 ([M+]).
1-Chloromethyl-3-methyl-imidazolidine-2,4,5-trione
(4a):Yield 50 %; m.p. 149-150 ºC; IR (KBr, νmax, cm-1): 1731,
1459, 1407, 1306, 1129; Mass m/z (rel. intensity, %) 179
([M+2]+, 5), 176 ([M]+, 20), 141 (100), 113 (30), 94 (5), 70
(35), 56 (85); 1H NMR (200 MHz, CDCl3) 3.23 (s, 3H, CH3),
5.40 (s, 2H, CH2Cl).
1
intensity, %) 353 ([M]+); H NMR (200 MHz, Acetone-d6)

Vol. 25, No. 1 (2013)
Synthesis and Decomposition of Parabanic Acid Derivatives 507
1.17 (s, 3H, CH3), 3.99-4.06 (s, 2H, CH2), 6.04 (s, 2H, N-
CH2-N), 8.05-8.20 (m, 4H, phenyl).
yielded a mixture of the expected N-hydroxy methyl dericatives
and imidazolidine-2,4,5-triones. However, the instability of
N-hydroxy methyl derivatives made it isolation very difficult.
The use of column chromatography as a method of purification
was not successful, whatever the eluent or support(silica gel,
alumina) was used, because the Rf value was the same for the
two compounds. For this reaction, the next chloriration step,
using a large excess of thionyl chloride, was realized starting
directly from a mixture of N-hydroxy methyl derivatives and
imidazolidine-2,4,5-triones. The chlorinated precursors 4,5
were easily isolated by column chromatography and the
product had a much higher Rf value the starting material.
1-Phenyl-2-thioxo-3-(1,1,3-trioxo-1,3-dihydro-16-
benzo[d]isothiazol-2-ylmethyl)-imidazolidine-4,5-dione
(9c):Yield 30 %; m.p. 170-171 ºC; IR (KBr, νmax, cm-1): 1785,
1720, 1400, 1370, 1360, 1300, 1250, 1180; Mass m/z (rel.
intensity, %) 402 ([M]+); 1H NMR (200 MHz, acetone-d6) 6.58
(s, 2H, CH2), 7.84-8.63 (m, 9H, phenyl).
1-Benzoimidazole-1-yl-methyl-3-imidazolidine-2,4,5-
trione (10a): Rf 0.7 (TLC eluent; n-Hexane : EtOAc = 1 : 25,
v/v); yield 75 %; m.p. 188-189 ºC; IR (KBr, νmax, cm-1): 3846,
1778, 1452, 1344, 1244, 756; Mass m/z (rel. intensity, %) 258
(100), 173 (7), 145 (9), 131 (100), 118 (15), 104 (12), 90 (15),
77 (20), 56 (64), 51 (12); 1H NMR (200 MHz, CDCl3) 3.18 (s,
3H, CH3), 6.18 (s, 2H, N-CH2-N), 7.25-7.78 (m, 4H, phenyl),
8.2 (s, 1H, benzimidazole).
O
S
CH2Cl
CH2Cl
R
R
N
O
N
O
N
O
N
O
1-Benzoimidazole-1-yl-ethyl-3-imidazolidine-2,4,5-
trione (10b): Rf 0.7 (TLC eluent; n-Hexane: EtOAc = 1 : 25,
v/v); yield 50 %; m.p. 179-180 ºC; IR (KBr, νmax, cm-1): 3541,
2984, 1736, 1425, 1242, 796; Mass m/z (rel. intensity, %) 272
(93), 245 (2), 173 (5), 145 (7), 131 (100), 118 (11), 104 (8),
90 (10), 77 (14), 56 (57), 51 (8); 1H NMR (200 MHz, CDCl3)
1.25 (t, 3H, CH3), 3.65 (q, 2H, CH2), 5.97 (s, 2H, N-CH2-N),
7.25-7.82 (m, 4H, phenyl), 8.19 (s, 1H, benzimidazole).
1-Benzoimidazole-1-yl-phenyl-3-imidazolidine-2,4,5-
trione (10c): Rf 0.7 (TLC eluent; n-Hexane : EtOAc = 1 : 25,
v/v); yield 45 %; m.p. 187-188 ºC; IR (KBr, νmax, cm-1) 3884,
2924, 1767, 1741, 1242; Mass m/z (rel. intensity, %) 320 (61),
173 (5), 145 (4), 131 (100), 119 (7), 91 (8), 77 (12), 64 (6), 56
(26); 1H NMR (200 MHz, CDCl3) 6.15 (s, 2H, N-CH2-N), 7.15-
7.85 (m, 9H, phenyl), 8.25 (s, 1H, benzimidazole).
4
5
When the chlorinated products 4 and 5 were allowed to
react with N-methylimidazolidine-2,4,5-trione and N-phenyl-
imidazolidine-2,4,5-trione, respectively, 1-[(3-phenylimidaz-
olidine-2,4,5-trionyl)methyl]-3-methyl-imidazolidine-2,4,5-
trione 6 and 1-[(4,5-dioxo-3-phenyl-2-thioxoimidazolidin-1-
yl)methyl]-3-ethylimidazolidine-2,4,5-trione 7 were obtained
in good yields, as shown in Table-1. When chlorinated products
4 and 5 were allowed to react with 1,2-benzothiazole-3-one-
1,1-dioxide by same methods, saccharin derivatives 8,9 con-
taining imidazolidine-2,4,5-trionyl, 2-thioxo-imidaz-olidine-
4,5-dionyl groups were obtained in good yields as shown in
the Table-1. We also tried to obtain various parabanic acid
derivatives from the reactions of the chlorinated reactants 4,5
with benzimidazole. 1-Benzoimidazole-1-yl-methyl-3-
imidazolidine-2,4,5-trione 10a (yield, 75 %), 1-benzoimi-
1-Phenylurea (11): Isolated yield 41%; Rf 0.35 (TLC elu-
ent; EtOAc : n-Hexane = 1 : 5, v/v); Mass m/z (rel. intensity, %)
135; 1H NMR (200 MHz, CDCl3) 6.20 (s, 1H), 7.19 (m, 1H),
7.43 (m, 2H), 7.61 (dd, 2H), 8.9 (s, 1H); 13C NMR (50 MHz,
CDCl3) 121.6, 128.0, 128.9, 139.4; Anal. calcd. for C7H8N2O :
C, 61.75; H, 5.92; N, 3.47; Found : C, 61.73; H, 5.91; N, 3.44.
1-Ethyl-3-[(3-ethylthioureido)methyl]urea (12): Iso-
lated yield 26 %; Rf 0.35 (TLC eluent; EtOAc : n-Hexane = 1
: 8, v/v); Mass m/z (rel. intensity, %) 204 (29), 167 (29), 149
TABLE-1
YIELDS OF PRODUCTS 6~10
Yielda
(%)
m.p.
(ºC)
Entry
1
Product
O
O
H2
C
Ph
Me
N
N
O
N
O
N
O
76
69
247-249
217-218
O
O
1
(100), 104 (43), 76 (38), 70 (55), 55 (100); H NMR (200
6
S
MHz, CDCl3) 6.20 (s, 1H), 7.19 (m, 1H), 7.43 (m, 2H), 7.61
(dd, 2H), 8.9 (s, 1H); 13C NMR (50 MHz, CDCl3) 14.5, 15.3,
34.2, 40.2, 62.3, 157.9, 182.2; Anal. calcd. for C7H16N4O-S :
C, 41.15; H, 7.89; N, 27.40; O, 7.83; S, 15.7; Found: C, 41.13;
H, 7.88; N, 27.40; O, 7.79; S, 15.64.
H2
C
Ph
Et
N
N
N
N
2
3
4
O
O
O
O
7
O
O
R; a = Me
b = Et
52
54
192-193
182-183
H2
C
R
1-Ethyl-3-[(3-methylthioureido)methyl]urea (13): Isolated
yield 23 %; Rf 0.35 (TLC eluent; EtOAc: n-Hexane = 1 : 8, v/v);
Mass m/z (rel. intensity, %) 190 (5), 119 (100), 91 (95), 77 (5),
N
N
S
O
O
O
O
c = Ph
50
40
191-192
173-175
8a-c
1
O
S
R; a = Me
64 (81), 51 (31); H NMR (200 MHz, CDCl3) 6.20 (s, 1H),
H2
C
7.19 (m, 1H), 7.43 (m, 2H), 7.61 (dd, 2H), 8.9 (s, 1H); 13C NMR
(50 MHz, CDCl3) 14.5, 31.0, 34.3, 62.3, 157.7, 182.2; Anal.
calcd. for C6H14N4OS : C, 37.88; H, 7.42; N, 29.45; O, 8.41;
S, 16.85; Found: C, 37.84; H, 7.40; N, 29.41; O, 8.40; S, 16.82.
N
R
N
b = Et
49
157-159
S
O
O
O
O
c = Ph
R; a = Me
b = Et
30
75
191-192
188-189
9a-c
H2
C
O
N
N
R
N
O
N
50
45
179-180
187-188
5
RESULTS AND DISCUSSION
O
c = Ph
The basic catalyzed condeusation between imidazolidin-
2,4,5-triones and paraformaldehyde in aqueous solution
10a-c
aIsolated yields

508 Choi et al.
Asian J. Chem.
dazole-1-yl-ethyl-3-imidazolidine-2,4,5-trione (10b) (yield,
50 %) and 1-benzoimidazole-1-yl-phenyl-3-imidazolidine-
2,4,5-trione (10c) (yield, 45 %) were obtaines in good yields,
as shown in Table-1.
ACKNOWLEDGEMENTS
This work was supported by the grant from Dong-A
University (2012).
Biological tests for tesring the phytocidal, herbicidal and
insecticidal properties of the new synthesized compounds (6-
10) are currently in progress. As a part of a research program
related to the synthesis study of bioactive organo chemicals,
we also report the synthesis of Di-urea derivatives in the reaction
of 1-phenylimidazolidine-2,4,5-trione, 1-ethyl-3-[(3-ethyl-4,5-
dioxo-2-thioxoimidazolidin-1-yl)methyl]-imidazolidine-2,4,5-
trione and 1-ethyl-3-[(3-methyl-4,5-dioxo-2-thioxoimid-
azolidin-1-yl)methyl]-imidazolidine-2,4,5-trione with hydrolysis
in basic solution through ultrasound.
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O
S
S
O
O
C2H5
CH3
10. G. Caraculacu, C. Gaina, V. Gaina and A.A. Caraculacu, Eur. Polym. J.,
29, 1143 (1993).
C2H5
C2H5
C
N
H
N
H
N
H
N
H
N
H
N
H
N
H
N
H
N
H
NH2
11. G. Caraculacu, C. Gaina, A.A. Caraculacu and G. Stoica, Eur. Polym. J.,
31, 987 (1995).
11
12
13
12. E. Scortanu, I. Nicolaescu, G. Caraculacu, I. Diaconu andA.A. Caraculacu,
Eur. Polym. J., 34, 1265 (1998).
TABLE-2
YIELDS OF OBTAINED PRODUCTS 11,
12, 13 THROUGH ULTRASOUND
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875 (1998).
Reaction
Yield*
(ºC)
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Entry
1
Product
time (h)
O
C
N
H
NH2
20
41
26
11
S
O
C2H5
C2H5
N
H
N
H
N
H
N
H
2
3
8
8
12
S
O
C2H5
CH3
N
H
N
H
N
H
N
H
23
13
*Isolated yield