2-PHOSPHAINDOLIZINES

被引：75

作者：

BANSAL, RK ^{[1
]}

KARAGHIOSOFF, K ^{[1
]}

GUPTA, N ^{[1
]}

SCHMIDPETER, A ^{[1
]}

SPINDLER, C ^{[1
]}

机构：

[1] UNIV MUNICH,INST ANORGAN CHEM,W-8000 MUNICH 2,GERMANY

来源：

CHEMISCHE BERICHTE | 1991年 / 124卷 / 03期

关键词：

1,3-AZAPHOSPHOLE, ANNULATION TO PYRIDINE; 2-PHOSPHAINDOLIZINES; PYRIDINIUM BROMIDES, 1,2-DIALKYL; PHOSPHORUS(III); CHLORIDE; CONDENSATION WITH CH2 GROUPS; CALCULATIONS; MNDO;

D O I：

10.1002/cber.19911240309

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Pyridinium bromides 3 prepared by alkylation of 2-methyl-, 2-ethyl-, and 2-benzylpyridines 1 with methyl bromides 2 bearing an electron-withdrawing group (COPh, CN, CO2Et, C6H4NO2) are condensed with PCl3 in the presence of Et3N to give 2-phosphaindolizines 4. The 1-unsubstituted representatives 9 (prepared from 8) may undergo a substitution reaction at this position with an excess of PCl3. 1- and 2-phosphaindolizines are 1,3-azaphospholes with a pyridine ring a-annulated to the 1,2 and 1,5 bond, respectively. The different types of annulation result in characteristic differences in charge distribution, P-31-NMR shift, and chemical behavior. 2-Phosphaindolizines 4 and 9 are stable in dry air and do not undergo alkylation. Compounds 9 hydrolyze to give zwitterionic (1-alkyl-2-pyridino)methylphosphinates 13. The phosphorus atom of a 2-phosphaindolizine can act as a ligand atom as shown by the example of a Cr(CO)5 complex.

引用

页码：475 / 480

页数：6

共 34 条

[1] 2-METHYLPYRIDINIUM SALTS AS 1,4-DINUCLEOPHILES - QUINOLIZINIUM SALTS FROM THE WESTPHAL CONDENSATION [J].