Synthese und Eigenschaften von N-phosphorylierten Aminomethylen-dimethylphosphinoxiden und -sulfiden / Synthesis and Properties of N-Phosphorylated Aminomethylene-Dimethylphosphine Oxides and -Sulfides
Zeitschrift für Naturforschung. B, A journal of chemical sciences
In the reaction of N-methylaminomethylene-dimethylphosphine oxide and sulfide with diethylaminotrimethylsilane, N-methyl-N-trimethylsilyl-aminomethylene-dimethylphosphine oxide (1) and sulfide (2) were formed. These compounds were allowed to react with a series of P(III)C1 compounds to give the corresponding methylaminomethylene-bridged diphosphorus compounds (3 - 10) with phosphorus in the combination λ4P(V)/λ3P(III). In the oxidation of some of these compounds by the hydrogen peroxide-urea
... en peroxide-urea 1:1-adduct (NH2)2CO ·H2O2 or sulfur, the corresponding λ4P-CH2-N(Me)-λ4P-derivatives (11 - 16) were formed. Different reaction behaviour was observed depending on the substituent at λ4P or on the oxidizing agent. Reaction of 1 with trimethylsilylmethyl tetrafiuorophosphorane and with bromotriphenylphosphonium bromide furnished, besides trimethylhalosilane, the corresponding diphosphorus compounds (17 ) and (18) with phosphorus in the combination λ4P(V)/λ5P(V) (17) and λ4P(V)/λ4P(V)+ (18). Oxidation of N-diphenylphosphino-N-methyl-aminomethylene-dimethylphosphine oxide (3) by tetrachloro-o-benzoquinone led to the corresponding addition product in impure form. Reaction of 3 with hexafluoroacetone (HFA) yielded a mixture of two products which could not be separated. Both oxidation (>N-PPh2 → >N-P(:O)Ph2) and insertion of HFA into the P-N-bond (>N-PPh2 → >NC(CF3)2-O-PPh2) occurred. In the reaction of 1 with methyldichlorophosphine, both the mono- and disubstituted products, 22 and 23, were formed, independently of the reaction conditions and molar ratio of the starting compounds. The reaction of 1 with bis(diethylamino)chlorophosphine was unusual. Upon separation of both trimethylchlorosilane and dimethylaminotrimethylsilane, compounds 24 - 26 were formed, with the central phosphorus atom bearing one, two or three methylaminomethylene-dimethylphosphine oxide groups, respectively. Simultaneously, tris(diethylamino)phosphine was formed.