ChemInform Abstract: Synthesis and Properties of N-Phosphorylated Aminomethylene- Dimethylphosphine Oxides and -Sulfides (original) (raw)

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 A4P(V)/A3P(III). In the oxidation of some of these compounds by the hydrogen peroxide-urea l:l-adduct (NH2)2C0 H20 2 or sulfur, the corresponding A4P-CH2-N(Me)-A4P-derivatives (11-16) were formed. Different reaction behaviour was observed depending on the substituent at A4P or on the oxidizing agent. Reaction of 1 with trimethylsilylmethyl tetrafiuorophosphorane and with bromotriphenylphosphonium bromide furnished, besides trimethylhalosilane, the corresponding diphos phorus compounds (17) and (18) with phosphorus in the combination A4P(V)/A5P(V) (17) and A4P(V)/A4P(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. Re action of 3 with hexafluoroacetone (HFA) yielded a mixture of two products which could not be separated. Both oxidation (>N-PPh2-* >N-P(:0)Ph2) and insertion of HFA into the P-N-bond (>N-PPh2-► >NC(CF3)2-0-P P h 2) 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 phospho rus atom bearing one, two or three methylaminomethylene-dimethylphosphine oxide groups, respectively. Simultaneously, tris(diethylamino)phosphine was formed.