o-Hydroxylaminobenzaldehydes and the N-Acylated Derivatives Thereof
DOI:
https://doi.org/10.29356/jmcs.v49i1.1317Keywords:
O-hydroxyaminobenzaldehydes, reduction, anthranil, N-acyl, benzoxozinonesAbstract
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 dimethoxybenzaldeyhde (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-hydroxylaminobenzaldehydes 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., 6b→12b→13b) to a greater or lesser extent under the reaction conditions.
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-hidroxil- aminobenzaldehídos sufren una nueva
reacción oxidoreductiva interna bajo termólisis generando ácidos oacilaminobenzóicos los cuales son convertidos en 2-substituidos-4H-
3,1-benzoxazin-4-onas (e.g., 6b→12b→13b) en mayor o menor
grado, bajo las condiciones de reacción.
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