174966-22-4Relevant academic research and scientific papers
Synthesis and Properties of N-Phosphorylated Aminomethylene-Dimethylphosphine Oxides and -Sulfides
Kaukorat, Thomas,Neda, Ion,Schmutzler, Reinhard
, p. 1818 - 1832 (2007/10/03)
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)Cl 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 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 tetrafluorophosphorane 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)(1+) (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. - Keywords: N-Methylaminomethyl Grouping; Diphosphorus Compounds; Oxidation; NMR Spectra; Unusual Reaction Behaviour
