Zeolite-induced heterocyclization: A superior method of synthesis of imidazolidinones

Article abstract of DOI:10.1039/a901435g

A superior method for synthesis of imidazolidinones by catalytic action of H-Y zeolite from the reaction of α-aminocarboxamides with carbonyl compounds is described.

Full text of DOI:10.1039/a901435g

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498 J. CHEM. RESEARCH (S), 1999
J. Chem. Research (S),
1999, 498^499y
Zeolite-induced Heterocyclization: a Superior
Method of Synthesis of Imidazolidinonesy
Massoud A. Nooshabadi, Kioumars Aghapoor, Mohammad
Bolourtchian and Majid M. Heravi*
Chemistry & Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran, Iran
A superior method for synthesis of imidazolidinones by catalytic action of H-Y zeolite from the reaction of
a-aminocarboxamides with carbonyl compounds is described.
Structure^activity relationships of antiepileptic agents
show that synthesis of imidazolidinones could be of interest
from the biological and synthetic points of view.1
Imidazolidinones can be prepared by the interaction of
b-aminonitriles with aldehydes and ketones in the presence
of sodium alkoxide,2 or by the reaction of o-carbo-
benzoxyamino acid amides with carbonyl compounds in
the presence of a catalytic amount of a sulfonic acid,
followed by removal of the carbobenzoxy group by catalytic
hydrogenation.3 Recently the preparation of these
heterocyclic systems by the reaction of a-aminocarbox-
amides with carbonyl compounds using p-toluenesulfonic
acid as catalyst has been reported.1
imidazolidinones 3a were obtained. Most probably the
reactants pass through the pore openings where the reaction
takes place. To establish the generality of the method, 1a
and a-amino-a-ethylacetamide 1b11 were treated with vari-
ous carbonyl compounds 2a^f in the presence of H-Y zeolite
in re£uxing MeOH, giving good to high yields of the cor-
responding imidazolidinones 3a^f and 4a^f (Scheme 1,
Table 1). The use of HZSM-5 zeolite and montmorillonite
K-10 gave products with lower yields, showing that the
acidity of catalyst is likely to play an important role in
the activation of 2.
It is also noteworthy that in these reactions, which could
give two diastereomeric products, both diastereomers were
obtained.
The preparation of ¢ne chemicals following environ-
mentally benign strategies represents a great challenge in
In summary, in comparison with other methods which
have drawbacks from the standpoint of yield, price of cata-
lyst (sodium methoxide) or corrosiveness, the advantages
of the present method are apparent from the availability
of inexpensive H-Y zeolite, heterogeneous conditions and
easy work-up. The simplicity of method make it a con-
venient route to imidazolidinones.
6
organic synthesis today.4
The use of environmentally
friendly solid acid catalysts is now the best way for the syn-
thesis of speci¢c target compounds with minimum pro-
duction of pollutants as well as reduction of the cost.7
Zeolites and other solid acids as catalysts for various
organic reactions received considerable attention in the last
decade, not only in terms of yield and selectivity, but also
concerning the work-up and e¥uent pollution.8 In spite
of this, however, their application in heterocyclization
reactions has not fully been explored.
In continuation of our studies to develop selective and
preparatively useful methodology, based on the use of solid
acids as promoters for the synthesis of ¢ne chemicals,9
we report a ``one pot'' synthesis of imidazolidinones by
the catalytic action of H-Y zeolite on the reaction of
carboxamides with carbonyl compounds.
Experimental
The melting points are uncorrected and were obtained by a Ko£er
Richart type 7841 melting point apparatus. The IR spectra were
recorded on a Perkin^Elmer 781 spectrometer, 1H NMR spectra
on a Brucker Ac 80 spectrometer and the Mass spectra on a Fisson
800 Trio instrument at 70 eV.
General Procedure for the Preparation of Imidazolidinones 3a^f,
4a^f.öA solution of an appropriate a-aminocarboxamide (1a or
1b) (0.67 mmol), carbonyl compound (0.67 mmol and H-Y zeolite
(0.2 g) in MeOH (10 ml) was re£uxed for the indicated time. The
reaction was monitored by TLC. The catalyst was ¢ltered o¡ and
the solvent evaporated to dryness under reduced pressure. The crude
product was crystallized from EtOH to a¡ord the corresponding
imidazolidinones (Table 1).
Ph
O
O
H
C
HN
NH
Compound 3a: 1H NMR (CDCl3) d 1.45 (s, 6 H, 2CH3), 2.1 (s, br,
1 H, NH), 4.6 (s, 1 H, CH), 7.3 (s, 5 H, Ph) and 7.6 (s, br, 1 H, NH);
IR, (KBr disc) j 3170, 3078, 2977, 1714, 1442 and 751 cm 1; MS
O
NH2
NH2
R1 R2
3a–f
R1
R2
1a
‡
H–Y Zeolite, MeOH
O
m/z (relative intensity), 190 (71, M ) 175 (9), 148 (11), 147 (100),
C2H5
O
H
C
C2H5
146 (42), 100 (69), 104 (20), 91 (21), 79 (22), 77 (25) and 58 (23).
NH2
NH2
HN
NH
R1 R2
4a–f
Table 1
1b
Carbonyl compound
Yield
Scheme 1
Substrate
R1
R2
t/h
Product
(%)
1a
2a
2b
2c
2d
2e
2f
2a
2b
2c
2d
2e
2f
CH3
CH3
12
6
4
15
5
48
4
4
5
6
4
3a
3b
3c
3d
3e
3f
4a
4b
4c
4d
4e
4f
63
75
65
70
55
None
80
85
79
91
83
20
Attempts involving the reaction of a-amino-a-phenyl-
acetamide10 1a with acetone 2a in re£uxing MeOH in
the absence of catalyst failed. When the same reaction
was carried out in re£uxing MeOH and a catalytic amount
of H-Y zeolite (acid type zeolite, average pore size 20 Ð,
surface area 200 Æ m2 g 1) high yields of the corresponding
‰CH2Š
4
‰CH2Š
5
CH3
Ph
C2H5
H
CH3
Ph
1b
* To receive any correspondence.
y This is a Short Paper as de¢ned in the Instructions for Authors,
Section 5.0 [see J. Chem. Research (S), 1999, Issue 1]; there is
therefore no corresponding material in J. Chem. Research (M).
48

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J. CHEM. RESEARCH (S), 1999 499
Compound 3b: 1H NMR (CDCl3) d 1.8 (s, 8 H), 2.4 (s, br, 1 H, NH),
4.5 (s, 1 H, CH), 7.3 (s, 5 H, Ph) and 8.1 (s, br, 1 H, NH); IR, (KBr
disc) n 3153, 1704, 1449 and 669 cm 1; MS m/z (relative intensity),
Received, 22nd February 1999; Accepted, 12th May 1999
Paper E/9/01435G
‡
216 (31, M ), 187 (85), 173 (31), 172 (62), 106 (100), 104 (38), 79
(8) and 77 (11).
Compound 3c: 1H NMR (CDCl3) d 1.6 (s, 10 H), 2.15 (s, br, 1 H,
NH), 4.6 (s, 1 H, CH), 7.5 (m, 5 H, Ph) and 8.2 (s, br, 1 H, NH);
‡
IR, (KBr disc) n MS m/z (relative intensity), 230 (25, M ), 188 (12),
References
187 (100), 106 (88), 704 (19), 79 (38), 79 (29), 77 (25) and 54 (22).
Compound 4a: 1H NMR (CDCl3) d 1.1 (t, 3 H, CH3), 1.45 (s, 6 H,
1
A. Khalaj, R. D. Bazaz and M. Shekarchi, Monatsh. Chem.,
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2CH3), 1.75 (q, 2 H, CH2), 2.15 (br, 1 H, NH), 3.5 (m, 1 H, CH)
1
and 8.1 (s, br, 1 H, NH); IR, (KBr disc) n 3100, 1700 and 1420 cm
;
2
3
4
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‡
MS m/z (relative intensity), 142 (2, M ), 99 (52), 85 (48), 84 (100),
82 (8) and 69 (69).
Compound 4b: 1H NMR (CDCl3) d 0.99 (t, 3 H, CH3), 1.7 (q, 3 H,
CH3), 1.8 (s, 8 H, 4CH2), 1.95 (s, br, 1 H, NH), 3.4 (m, 1 H, CH)
and 8.1 (s, br, 1 H, NH); IR, (KBr disc) n 3150, 2900, 1700 and 1410
5
cm 1; MS m/z (relative intensity), 168 (24, M ), 140 (28), 139 (100),
6
7
W. F, Halderich and E. Heitmann, Catal. Today, 1997, 353.
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53, 7999.
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‡
111 (71) and 58 (78).
Compound 4c: 1H NMR (CDCl3) d 0.98 (t, 3 H, CH3), 1.4 (m, 10,
4CH2), 1.7 (q, 2 H, CH2), 1.8 (br, 1 H, NH), 3.4 (m, 1 H, CH)
and 6.9 (s, br, 1 H, NH); IR, (KBr disc) n 3150, 2920, 1690 and 1425;
8
‡
MS m/z (relative intensity), 184 (5, M ), 183 (11), 182 (30), 153 (15),
139 (100), 120 (28), 111 (18) and 97 (20).
Compound 4f: 1H NMR (CDCl3) d 0.99 (t, 3 H, CH3), 1.5 (s, 3 H,
CH3), 1.7 (q, 2 H, CH2), 2.0 (s, br, 1 H, NH), 3.5 (m, 1 H, CH),
7.4 (m, 5 H, Ph) and 8.1 (s, br, 1 H, NH); IR, (KBr disc) n 3200, 2805,
9
1690 and 1450 cm 1; MS m/z (relative intensity), 190 (11, M ), 189
‡
(99), 161 (51), 160 (72), 78 (25) and 77 (65).
We thank Dr A. R. Garakani, Research Institute of
petroleum Industry of Iran, for the supply of HY Zeolite.
Research supported by the National Research Council of
Iran (NRCI) as a National Research Project under grant
number 3708.
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