Studies on derivatives of 2,3-dihydro-4H-1,3,2-benzoxazaphosphorine. Synthesis and structure analysis of 2,3-disubstituted-2,3-dihydro-4H-1,3,2-benzoxazaphosphorin-4-one -(thio ne)-2-sulfide(oxide).

Abstract

A series of novel organocyclophosphorus compounds including twenty-three 2,3-disubstituted-2,3-dihydro-4H-1,3,2-benzoxazaphosphorin-4-one-2 -sulfide (compounds I) and three 2,3-disubstituted-2,3-dihydro-4H-1,3,2-benzoxazaphosphorin-4-th ion e-2-oxide (compounds II) have been synthesized. Their structures were determined by IR, UV, 1HNMR, X-ray diffraction and elemental analysis. Each of compounds I showed a strong absorption between 1290-1319 cm-1 in the IR spectrum. Comprehensive studies of the spectral data and experimental results indicated that this strong characteristic absorption is different from that of the P = O linkage and thus could be considered as a result of the stretching vibration of (unsaturated C)-N single bond. In the course of synthesis of the compounds, an abnormal product (Formula: see text) is frequently formed as an isomer of the expected product I (Formula: see text). However, by suitable choice of condensation conditions, either of the isomers could be made predominantly in yield and be readily isolated from the other by recrystallizing for several times from appropriate solvent. Data for the melting point, IR, UV and 1HNMR spectra of three pairs of the isomers are given, and primary analyses of the spectra are made as well.