INTERACTION OF LABILE N-ALKOXY-N-CHLORO-N’-ARYLUREAS AND N-ACETOXY-N-ALKOXYUREAS WITH TRIMETHYL PHOSPHITE
DOI:
https://doi.org/10.15421/jchemtech.v33i3.332948Keywords:
N-alkoxy-N-chloro-N’-arylureas; trimethyl phosphite; dimethyl N-alkoxy-N-(N’-arylcarbamoyl)phosphoroamidates; synthesis.Abstract
The freshly synthesized N-alkoxy-N-chloro-N’-4-bromophenylureas undergo reaction with trimethyl phosphite in diethyl ether at room temperature yielding respectively dimethyl N-alkoxy-N-(N’-4-bromophenylcarbamoyl)phosphoroamidates with high yields. The unstable N-alkoxy-N-chloro-N’-phenylureas, freshly synthesized at -30°C, interact with trimethyl phosphite in diethyl ether at this low temperature to produce previously unknown dimethyl N-alkoxy-N-(N’-phenylcarbamoyl)phosphoroamidates. This reaction is the first example of the nucleofilic substitution at the nitrogen atom for unstable N-alkoxy-N-chloro-N’-phenylureas. Careful conditions selection and precise control made it possible to pevent premature destruction of the starting N-alkoxy-N-chloro-N’-4-bromophenylureas and N-alkoxy-N-chloro-N’-phenylureas. In contrast, N-acetoxy-N-alkoxyureas do not react with trimethyl phosphite under the same conditions. The structures of the resulting dimethyl N-alkoxy-N-(N’-4-bromophenylcarbamoyl)phosphoroamidates and dimethyl N-alkoxy-N-(N’-phenylcarbamoyl)phosphoroamidates were confirmed by ¹H, ³¹P, and ¹³C NMR spectroscopy, as well as mass spectrometry. A comparative analysis of ¹H, ³¹P and ¹³C NMR spectra of these dimethyl N-alkoxy-N-(N’-arylcarbamoyl)phosphoroamidates with those of dialkyl N-alkoxy-N-(N’-4-nitrophenylcarbamoyl)phosphoroamidates revealed numerous shared features and general structural characteristics of N-alkoxy-N-(N’-arylcarbamoyl)phosphoroamidates.
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