Ph 2NH and PCl 3 interacted at a molar ratio of 1∶1 05 and slow elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H 2O to produce a very hard brown solid believed to be...Ph 2NH and PCl 3 interacted at a molar ratio of 1∶1 05 and slow elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H 2O to produce a very hard brown solid believed to be a mixture of 5,10 dihydrophenophosphazine 10 oxide(1a) and 10,10(5H,5H) spirobipenophosphazinium chloride(1b). This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10 hydroxy 5,10 dihydropheno phosphazine 10 oxide(2) with a higher yield(45%) than that of the literature(27%). When treated with excess SOCl 2, compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in 70% as treated with NaOMe in methanol. Compound 2 could also be converted to a bisanion when treated with NaH in DMF. The resulted bisanion reacted with MeI to give 5 methyl 10 hydroxy 5,10 dihydrophenophosphazine 10 oxide in a 73% yield which would be converted to 5 methyl 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in a 56% yield by the same way of synthesizing 10 methoxy 5,10 dihydrophenophosphazine 10 oxide. All these compounds obtained were identified by surveying their melting points, and spectra and elemental analysis.展开更多
基金Supported by National Natural Science Foundation of China(No.2 9972 0 0 6 ) .
文摘Ph 2NH and PCl 3 interacted at a molar ratio of 1∶1 05 and slow elevated temperature and then at 210-220 ℃ for 6 h. The brown solution obtained was treated with H 2O to produce a very hard brown solid believed to be a mixture of 5,10 dihydrophenophosphazine 10 oxide(1a) and 10,10(5H,5H) spirobipenophosphazinium chloride(1b). This brown solid was directly oxidized with peracetic acid in HOAc prior to the separation of them to give compound 10 hydroxy 5,10 dihydropheno phosphazine 10 oxide(2) with a higher yield(45%) than that of the literature(27%). When treated with excess SOCl 2, compound 2 could quantitatively be converted to the corresponding phosphinyl chloride and the latter could further be transformed into 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in 70% as treated with NaOMe in methanol. Compound 2 could also be converted to a bisanion when treated with NaH in DMF. The resulted bisanion reacted with MeI to give 5 methyl 10 hydroxy 5,10 dihydrophenophosphazine 10 oxide in a 73% yield which would be converted to 5 methyl 10 methoxy 5,10 dihydrophenophosphazine 10 oxide in a 56% yield by the same way of synthesizing 10 methoxy 5,10 dihydrophenophosphazine 10 oxide. All these compounds obtained were identified by surveying their melting points, and spectra and elemental analysis.
