A New Synthetic Method of 1,4-Dihydro-2H-3,1-benzoxazin-2-ones: Selenium-Catalyzed Reductive Carbonylation of Aromatic Nitro Compounds with Carbon Monoxide

Abstract

It was confirmed that selenium catalyzed the reaction of 2-nitrobenzyl alcohols with carbon monoxide to afford 1,4-dihydro-2H-3,1-benzoxazin-2-ones in good yields. Similarly, seven-membered cyclic carbamate was prepared by the reaction of 2-(2-nitrophenyl)ethanol with carbon monoxide.

selenium - carbon monoxide - 1,4-dihydro-2H-3,1-benzoxazin-2-ones - carbonylation - carbamates

References

1a Consonni R. Croce PD. Ferraccioli R. La Rosa C. J. Chem. Soc., Perkin Trans. 1  1996,  1809 

1b Ohno M. Sato H. Eguchi S. Synlett  1999,  207 

2 Testa E. Fontanella L. Farmaco, Ed. Sci.  1966,  549 

3 Ohno M. Sato H. Eguchi S. Synlett  1999,  207 

4a Cenini S. Console S. Crotti C. Tollari S. J. Organomet. Chem.  1993,  451:  157 

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4c Braunstein P. Devenish R. Gallezot P. Heaton BT. Humphreys CJ. Kervennal J. Mulley S. Ries M. Angew. Chem., Int. Ed. Engl.  1988,  27:  927 

5 Nishiyama Y. Maema R. Ohno K. Hirose M. Sonoda N. Tetrahedron Lett.  1999,  40:  5717 

6 Nishiyama Y. Hirose M. Kitagaito W. Sonoda N. Tetrahedron Lett.  2002,  43:  1855 

7 Recently, Gang et al. reported the synthesis of benzoxazolinone by the selenium-catalyzed carbonylation of o-nitrophenol with carbon monoxide. See: Gang L. Junzhu C. Shiwei L. Cuihua Xueban  2003,  24:  5 

8 We also showed the selenium catalyzed the synthetic method of cyclic ureas, urethanes and quinazolinedione by the carbonylation of aromatic amines with carbon monoxide. See: Yoshida T. Kambe N. Murai S. Sonoda N. Bull. Chem. Soc. Jpn.  1987,  60:  1793 

9

When 1a was treated with carbon monoxide and water (5 equiv) in the presence of a catalytic amount of selenium at 150 °C for 5 h, 2a was not obtained and 2-aminobenzyl alcohol was formed in 87% yield.

10

A Typical Procedure is as follows: In a 50 mL stainless steel autoclave were placed o-nitrobenzyl alcohol (77 mg, 0.5 mmol), selenium (8 mg, 0.1 mmol), N-methylpyrrodine (425mg, 5 mmol), THF (5 mL) and a magnetic stirring bar. The mixture was stirred under pressurized carbon monoxide (30 atm) at 140 °C for 5 h. After the evacuation of the excess carbon monoxide at r.t., the deposited selenium was filtered off; the solution was then extracted with diisopropyl ether (30 mL × 3). The organic layer was dried over MgSO₄ and the solvent was evaporated in vacuo. The residual solid was recrystallized from CH₂Cl₂-C₆H₁₄ to give 1,4-dihydro-2H-1,3-benzoxazine-2-one in 85% yield.
Compound 2g: ¹H NMR (d ₆-DMSO): δ = 2.50 (s, 1 H), 3.34 (br s, 1 H), 5.17 (t, J = 5.2 Hz, 1 H), 5.35 (t, J = 4.0 Hz, 1 H), 6.83 (t, J = 8.0 Hz, 1 H), 6.98 (t, J = 8.0 Hz, 1 H), 7.21 (q, J = 8.0 Hz, 2 H), 10.41 (s, 1 H). ¹³C NMR: δ = 63.8, 79.5, 113.4, 118.6, 121.8, 124.9, 128.4, 136.0, 150.5. IR: 659.6, 753.5, 1058.8, 1087.6, 1263.6, 1291.8, 1413.6, 1692.5, 1686.7, 2947.0, 3090.8, 3154.1, 3235.4, 3333.2 cm^-1.
Compound 2h: ¹H NMR (d ₆-DMSO): δ = 3.21 (t, J = 4.8 Hz, 2 H), 4.52 (t, J = 4.8 Hz, 2 H), 6.97 (d, J = 7.6 Hz, 1 H), 7.00 (t, J = 7.6 Hz, 1 H), 7.09 (d, J = 7.6 Hz, 1 H), 7.17 (t, J = 7.6 Hz, 1 H), 8.83 (s, 1 H). ¹³C NMR: δ = 34.5, 68.1, 119.4, 123.1, 126.2, 127.7, 130.3, 136.0, 157.2. IR: 679.7, 741.9, 756.5, 1058.4, 1090.9, 1277.5, 1339.7, 1420.6, 1682.3, 3102.0, 3238.0 cm^-1.

11 Kondo K. Yokoyama S. Miyoshi N. Murai S. Sonoda N. Angew. Chem., Int. Ed. Engl.  1979,  18:  691