SYNTHESIS N-ALKOXY-1-(DIMETHOXYPHOSPHORYLOXY)BENZIMIDATES FROM N-ALKOXY-N-CHLOROBENZAMIDES
DOI:
https://doi.org/10.15421/jchemtech.v32i3.298733Keywords:
N-alkoxy-N-chlorobenzamides, trimethyl phosphite, N-alkoxy-1-(dimethoxyphosphoryloxy)benzimidates, synthesis, structure, XRD study, N–O-migration of dimethoxyphosphoryl groupAbstract
Aim. To synthesize of N-alkoxy-1-(dimethoxyphosphoryloxy)benzimidates from the interaction of N-alkoxy-N-chlorobenzamides with trimethylphosphite. To investigate N-alkoxy-1-(dimethoxyphosphoryloxy)-benzimidates structure using the XRD study. Methods. Mass spectrometry, 1H, 31P and 13C NMR spectroscopy, XRD study. Results. This study explores the reaction of N-alkoxy-N-chlorobenzamides with trimethylphosphite in ether resulting in the formation N-alkoxy-1-(dimethoxyphosphoryloxy)benzimidates. The obtained benzimidates are identified as the products of the nucleophilic substitution at nitrogen followed by an unusual N–O-migration of dimethoxyphosphoryl group. This reaction presents an original synthetic pathway to the N-alkoxy-1-phosphoryloxy imidates. In this research the possibility of the N-alkoxy-N-chlorobenzamides interaction with P-nucleophiles has been proved. The structure of N-alkoxy-1-(dimethoxyphosphoryloxy)benzimidates has been confirmed by the 1H, 31P and 13C NMR spectra, mass spectra and XRD study. The XRD study of N-methoxy-1-(dimethoxyphosphoryloxy)-4-nitrobenzimidate has demonstrated that this compound is Z-isomer, and 4-nitrophenyl moiety and N-methoxy group are in a trans position towards to the C=N double bond. The coplanarity of the aromatic ring and the π-system of the C=N double bond is evident from the XRD data. Conclusions. As the result of our study the feasibility of N-alkoxy-1-(phosphoryloxy)benzimidates formation through the interaction of N-alkoxy-N-chlorobenzamides with trialkylphosphites has been elucidated. This outcome holds significant value for a better understanding of the synthetic importance of N-alkoxy-N-chlorobenzamides. The structural elucidation of Z-N-alkoxy-1-(dimethoxyphosphoryloxy)benzimidates has been done. A novel kind of the intramolecular N–O-migration of the phosphoryl group has established.
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