In the reactions of bis(trimethylsilyl)methylenechlorophosphine (7) and chloro(phenyltrimethylsilylmethylene)phosphine (16) with metalated diazomethane derivatives (N2=C(M)R), the primarily formed substituted phosphavinyldiazoalkanes[methylene(1-diazoalkyl)phosphines] (13a, b and 17) can only, if at all, be isolated and characterized spectroscopically at - 78°C. At the latest during thawing, they undergo [1,5] cyclization reactions to furnish the 1H-1, 2,4-diazaphospheles 15 or 18. The silyl groups bonded to the nitrogen atoms in the latter compounds can be readily cleaved hydrolytically to give the corresponding N-unsubstituted 1H-1,2,4-diazaphospholes 11 and 19. (Diazotrimethylsilylmethyl)phenyltrimethylsilylmethylene)phosphine (17) takes part in a 1,3-dipolar cycloaddition reaction with (2,2-dimethylpropylidyne) phosphine (20) to produce 3-tert-butyl-1-trimethylsilyl-5-(phenyltrimethylsilylmethylene) phosphino-1-H-1,2,4-diazaphosphole (23).
在双(三甲基
硅基)亚
甲基氯化膦(7)和
氯(苯基三甲基
硅基亚甲基)膦(16)与
金属化
重氮甲烷衍
生物(N2=C(M)R)的反应中,主要形成的取代
磷酰重氮
烷烃[亚甲基(1-重氮烷基)膦](13a、b 和 17)只能(如果有的话)在零下 78°C 分离出来,并通过光谱鉴定。最迟在解冻过程中,它们会发生[1,5]环化反应,生成 1H-1,2,4-二氮杂膦 15 或 18。后一种化合物中与氮原子结合的
硅基很容易被
水解,生成相应的 N-未取代的 1H-1,2,4-二氮
磷环 11 和 19。 (重氮三甲基
硅甲基)苯基三甲基
硅亚甲基)膦 (17) 与(2,2-二甲基
丙炔)膦 (20) 发生 1,3 双极环加成反应,生成 3-叔丁基-1-三甲基
硅基-5-(苯基三甲基
硅亚甲基)膦-1-H-1,2,4-二氮杂膦孔 (23)。