Abstract
An ideal reaction system, which is aimed at sustainable chemistry, was developed. Under solvent-free conditions, quinazoline-2,4(1H ,3H )-diones were obtained in good to excellent yields from 2-aminobenzonitriles with only carbon dioxide (1 bar) and a catalytic amount of base (DBU or DBN). For example, 6,7-dimethoxyquinazoline-2,4(1H ,3H )-dione, which is a key intermediate of several drugs (Prazosin, Bunazosin, and Doxazosin) was synthesized successfully in 97% yield [DBU (0.2 equiv), CO2 (1 bar), 120 °C].
Key words
carbon dioxide - carbonylation - cyclization - catalytic - quinazoline - quinazolidinone
References
1 Goto S.
Tsuboi H.
Kagara K.
Chem. Express
1993,
8:
761
2 Kagara K, Goto S, and Tsuboi H. inventors; JP 1,025,767.
; Chem. Abstr . 1989 , 111 , 97274
3 Mohri S.
J. Synth. Org. Chem., Jpn.
2001,
59:
514
4 5 6 7 Pastor G.
Blanchard C.
Montginoul C.
Torreilles E.
Giral L.
Texier A.
Bull. Soc. Chim. Fr.
1975,
1331
8 Khalifa M.
Osman AN.
Ibrahim MG.
Ossman ARE.
Ismail MA.
Pharmazie
1982,
37:
115
9 Michman M.
Patai S.
Wiesel Y.
Org. Prep. Proced. Int.
1978,
10:
13
10 Lange NA.
Sheibley FE.
Org. Synth. Coll. Vol. II
John Wiley & Sons;
London:
1943.
p.79
11 Vorbrüeggen H.
Krolikiewicz K.
Tetrahedron
1994,
50:
6549
12 The use of the chemical fixation of carbon dioxide in fine chemicals production is of importance both in terms of the environmental problems of global warming and the effective utilization of chemical resources. Carbon dioxide is an attractive C1 building block in organic synthesis as it is highly abundant, inexpensive, nontoxic, and nonflammable. However, due to the inert nature of carbon dioxide, efficient processes for chemical fixation remain significant synthetic challenges.
13 Mizuno T.
Okamoto N.
Ito T.
Miyata T.
Tetrahedron Lett.
2000,
41:
1051
14 Mizuno T.
Okamoto N.
Ito T.
Miyata T.
Heteroat. Chem.
2000,
11:
428
15 Mizuno T.
Ishino Y.
Tetrahedron
2002,
58:
3155
16 Mizuno T.
Iwai T.
Ishino Y.
Tetrahedron Lett.
2004,
45:
7073
17 Haruki E. In
Organic and Bio-organic Chemistry of Carbon Dioxide
Inoue S.
Yamazaki N.
Kodansha Ltd.;
Tokyo:
1981.
p.5
18 Haruki E.
Arakawa M.
Matsumura N.
Otsuji Y.
Imoto E.
Chem. Lett.
1974,
427
19 Hori Y.
Nagano Y.
Fukuhara T.
Teramoto S.
Taniguchi H.
Nippon Kagaku Kaishi
1987,
1408
20 Pérez ER.
Silva MO.
Costa VC.
Rodrigues-Filho UP.
Franco DW.
Tetrahedron Lett.
2002,
43:
4091
21 Mavrovic I. In
Kirk-Othmer Encyclopedia of Chemical Technology
2nd ed., Vol. 21:
Mark HF.
Interscience Publishers;
New York:
1970.
p.37
