The reactivity of organophosphorus compounds. Part XXX. Iminophospholes and a new synthesis of benzofurazans via intramolecular rearrangement of 1-o-nitroarylimino-1,2,5-triphenylphospholes
作者:J. I. G. Cadogan、Robert J. Scott、Robert D. Gee、Ian Gosney
DOI:10.1039/p19740001694
日期:——
1-aroylimino-1,2,5-triphenylphospholes (2; X = PhCO and p-NO2·C6H4CO), but these decomposed at this temperature to give the corresponding aryl cyanides and the phosphole oxide. The use of copper-bronze reduced the decomposition point of the dioxazolidin-2-ones sufficiently for the iminophospholes to be isolated. Base catalysed decomposition of ethyl N-(p-nitrophenylsulphonyloxy)carbamate (4) in the presence of
已经合成了一系列的N-取代的1-亚氨基-1,2,5-三苯基磷(2)。芳基,甲磺酰基,芳基磺酰基,乙氧基羰基,苯氧基羰基和二苯基次膦酰基叠氮化物与1,2,5-三苯基膦的反应得到相应的N-取代的1-亚氨基膦[2; X = Ar,MeSO 2,ArSO 2,EtO 2 C,PhO 2 C和Ph 2 P(O)],通过非亚硝基苯路线的收率很高。甲苯磺酰磷(2; X =甲苯磺酰基)也是通过无水氯胺-T反应制得的。与磷脂。苯甲酰叠氮化物通过分解反应,然后进行库尔修斯重排反应,而不是与相对较弱的亲核性1,2,5-三苯基磷脂反应(参见Ph 3 P)。缺电子的4-硝基苯甲酰基和2,4-二硝基苯甲酰基叠氮化物给出相应的1-芳基氨基-1,2,5-三苯基磷[2; X = C 6 H ^ 4 NO 2 - p和2,4-(NO 2)2 C ^ 6 ħ 3在6和55%的产率分别]。在铜存在下的5,7-二甲基四唑并[1,5-