SciELO - Scientific Electronic Library Online

 
vol.49 issue1Highly Efficient Inversion of the C-3 Configuration in 1,2-0-Isopropylidenefuranose Derivatives by an Adapted Swern Oxidation/Sodium Borohydride Reduction Protocol in One PotOn-line Solid-Phase Extraction-Liquid Chromatographic Method for the Determination of Carbofuran and 7-Phenolcarbofuran in Cervical-Uterine Epithelial Tissue author indexsubject indexsearch form
Home Pagealphabetic serial listing  

Services on Demand

Journal

Article

Indicators

Related links

  • Have no similar articlesSimilars in SciELO

Share


Journal of the Mexican Chemical Society

Print version ISSN 1870-249X

J. Mex. Chem. Soc vol.49 n.1 México  2005

 

Article

 

0-Hydroxylaminobenzaldehydes and the N-Acylated Derivatives Thereof

 

Joseph M. Muchowski* and Michael L. Maddox

 

Chemistry, Roche Palo Alto, 3431 Hillview Avenue, Palo Alto, CA 94304, U.S.A.

 

Received March 9, 2005
Accepted March 29, 2005

 

Abstract

Ethyl acetate solutions of o-hydroxylaminobenzaldehydes (1a, 8c, 8d) can be generated by reduction of the corresponding nitro compounds with zinc and ammonium chloride in a two phase ethyl acetate-water system at room temperature, but 2-nitro-3,6-dimethoxy-benzaldeyhde (4b) is converted into the anthranil 11 under these conditions. The N-acylated compounds derived from 1a and 8c exist exclusively as the cyclic tautomers (6a-c and 9a) in solution and in the solid state, whereas the N-acetyl compound 9b is in equilibrium with the open chain form 10 in solution, but only the cyclic form is present in the solid state. The N-acylated-o-hydroxylaminobenzalde-hydes undergo a novel internal redox reaction on thermolysis generating o-acylaminobenzoic acids which are converted into 2-substituted-4H-3,1-benzoxazin-4-ones (e.g., 6b12b13b) to a greater or lesser extent under the reaction conditions.

Keywords: O-hydroxyaminobenzaldehydes, reduction, anthranil, N-acyl, benzoxozinones.

 

Resumen

Soluciones de o-hidroxilaminobenzaldehídos (1a, 8c, 8d) en acetato de etilo se pueden generar por medio de la reducción del correspondiente compuesto nitro con zinc y cloruro de amonio en un sistema bifásico de acetato de etilo-agua a temperatura ambiente, sin embargo, el 2-nitro-3,6-dimetoxibenz-aldehido (4b) se convierte en el antralino 11 bajo estas condiciones. Los compuestos N-acilados derivados de 1a y 8c existen exclusivamente como los tautómeros cíclicos (6a-c y 9a) en solución y en el estado sólido, mientras que el compuesto N-acetilo 9b esta en equilibrio con la forma abierta 10 en solución, pero solo la forma cíclica está presente en el estado sólido. Los N-acilados o-hidroxilaminobenzaldehídos sufren una nueva reacción oxidoreductiva interna bajo termólisis generando ácidos o-acilaminobenzóicos los cuales son convertidos en 2-substituidos-4H-3,1-benzoxazin-4-onas (e.g., 6b12b13b) en mayor o menor grado, bajo las condiciones de reacción.

Palabras clave: O-hidroxiaminobenzaldehídos, reducción, antranilo, N-acilo, benzoxazinones.

 

DESCARGAR ARTÍCULO EN FORMATO PDF

 

References and Notes

1. Bamberger, E.; Elger, F. Ber. 1903, 36, 3645.         [ Links ]

2. Bamberger, E. Ber. 1918, 51, 613.         [ Links ]

3. Bakke, J.M.; Engan, H-J. Acta Chem. Scand. B 1978, 32, 230.         [ Links ]

4. Fijalek, Z.; Zuman,T. Electroanalysis 1993, 5, 53.         [ Links ]

5. Blanco, M.; Avendaño, C.; Cabezas, N.; Menéndez, J.C. Heterocycles 1993, 36, 1387.         [ Links ]

6. Kamm, O. Org. Syn. Coll. Vol. 1, 1932, 445.         [ Links ]

7. Gupta, V.K.; Tandon, S.G. J. Ind. Chem. Soc. 1969, 46, 831.         [ Links ]

8. Kim, B.Y.; Jun, Y.M.; Choi, Y.R.; Lee, D.B.; Baik, W. Heterocycles 1998, 48, 749.         [ Links ]

9. Fernández, M.; López, F.; Tapia, R.; Valderrama, J.A. Synth. Commun. 1989, 19, 3087.         [ Links ]

10. Richman, R.J.; Hassner, A. J. Org. Chem. 1968, 33, 2548.         [ Links ]

11. Steiger, R.E. J. Org. Chem. 1944, 9, 396.         [ Links ]

12. Rubenstein, L. J. Chem. Soc. 1925, 127, 1998.         [ Links ]

13. Blanco, M.; Avendaño, C.; Cabezas, N.; Menédez, J.C. Synth. Commun. 1993, 23, 1351.         [ Links ]

14. Compound 4b can also be named 6-nitro-2,5-dimethoxybenzalde-hyde [12]. This seems to have led to some confusion in the literature as indicated by the title of the article by Blanco, et. al. [13], viz, "Re-examination of the synthesis of 3,5-dimethoxy-2-nitrobenzaldehyde".

15. Thummel, R.P.; Chirayil, S.; Hery, C.; Lim, J-L.; Wang, T-L. J.Org. Chem. 1993, 58, 1666.         [ Links ]

16. Muchowski, J.M.; Maddox, M.L. Can. J. Chem. 2004, 82, 461.         [ Links ]

17. Bamberger, E. Ber. 1894, 27, 1348, 1548.         [ Links ]

18. Bamberger, E. Ber. 1902, 35, 732.         [ Links ]

19. Schneller, S.W.; Ibay, A.C.; Christ, W.J.; Bruns, R.F. J. Med. Chem. 1989, 32, 2247.         [ Links ]

20. Walker, G.N. J. Amer. Chem. Soc. 1955, 77, 6698.         [ Links ]

Creative Commons License All the contents of this journal, except where otherwise noted, is licensed under a Creative Commons Attribution License