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The new functionalized aminomethylenediphosphonates with moieties of various amino acids are synthesized via unique reaction of tris(trimethylsilyl) phosphite and N-formyl amino acids at the presence of effective catalyst – trimethylsilyl triflate under m

The use of simple and inexpensive NiCl2?6 H2O as a catalyst precursor for C?P bond formation in the presence of commercially available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu, SiMe3) along with several alkynes is presented. Control experiments showed the in situ formation of (RO)2P(O)H as the species that undergo the addition into the C≡C bond at the alkynes to yield the product of P?H addition. The hydrophosphonylation of diphenylacetylene with P(OEt)3, P(OiPr)3, and P(OSiMe3)3 proceeds in high yields (>92 %) without the need of a specific solvent or ligand. This method is useful for the preparation of organophosphonates for both phenylacetylene as a terminal alkyne model and internal alkynes in yields that range from good to modest.

A synthetic method of di(trimethylsilyl)phosphite belongs to the technical field of compound synthesis. Trimethylchlorosilane and orthophosphorous acid which are adopted as raw materials undergo a reaction to obtain the di(trimethylsilyl)phosphite. The method comprises the following steps: placing orthophosphorous acid in methanamide, introducing nitrogen, stirring the orthophosphorous acid in methanamide for 15-20 min, adding the trimethylchlorosilane, simultaneously adding benzyltriethylammonium chloride and/or tetrabutylammonium hydrogen sulfate, continuously introducing nitrogen, controlling the reaction temperature to be less than 40 DEG C, and carrying out a one-step reaction to obtain the di(trimethylsilyl)phosphite. The synthetic method has the advantages of simplicity, easiness in operation, mild and stable reaction process, and high yield and high purity of the obtained di(trimethylsilyl)phosphite.

The tris(trimethylsilyl) phosphite (TMSPi) is considered as an ideal electrolyte additive for lithium ion batteries. In this work, its positive effect as well as its failure mechanism in a LiPF6 containing electrolyte was studied by means of selected electrochemical, structural and analytical techniques. The LiNi0.5Co0.2Mn0.3O2/graphite cells with TMSPi as electrolyte additive were cycled between 2.8 and 4.6 V. Thanks to the compact cathode electrolyte interphase formed by the oxidative decomposition of TMSPi in a freshly prepared TMSPi containing electrolyte, both the discharge capacity and the cycling stability of cells were enhanced. However, our results also show that TMSPi actually reacts with LiPF6 at room temperature. TMSPi is consumed by this spontaneous reaction after aging for certain time. In addition, a part of the fluorophosphates, generated from the hydrolysis of LiPF6, is bonded to one or two TMS groups, causing a decrease in the fluorophosphate content in the CEI film. Consequently, the cycling stability of the lithium ion cells with aged TMSPi containing electrolyte deteriorates. The obtained results offer important insights into the practical application of TMSPi, which means that TMSPi can only be used as an effective additive in a freshly prepared LiPF6 containing electrolyte.

Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate and trimethylsilyl [3-(trimethylsilyl)propyl]-phosphinate are obtained by the reaction of bis(trimethylsiloxy)phosphine with trimethylallylsilane and converted into [3-(trimethylsilyl)propyl]phosphinic and [3-(trimethylsilyl) propyl]phosphonic acid, respectively, by the reaction with methanol.

The synthesis and anti-HIV activity of selected (acyloxy)-alkyl esters of trisodium phosphonoformate (foscarnet sodium) are described. The conversion of bis(trimethylsilyl) (alkoxycarbonyl)phosphonates 11a-d to the corresponding disilver salts 12a-d and their subsequent reaction with iodoalkyl acrylates 4a-c gave the desired bis(acyloxyalkyl) phosphonates 6- 9(a-c). Of the analogs tested, only the dichlorophenyl analog 9a showed a dose-dependent inhibition of HIV activity in H9 cells. Using 31P-NMR, bioreversibility has been investigated in an attempt to rationalize these results.

The reaction of tris(trimethylsilyl) phosphite with halohydrins does not lead to an Arbuzov product but to bis(trimethylsilyl) esters of 3-halo-2-trimethylsiloxypropylphosphonic acids.Methanolysis and neutralization affords the 3-halo-2-hydroxypropylphosphonic acids and their salts.Key words: Tris(trimethylsilyl) phosphite; epichlorohydrin; epibromohydrin; 3-halo-2-hydroxypropylphosphonic acids.

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The reactions of silyl phosphites, i.e., tris(trimethylsilyl)phosphite (1), diethyl trimethylsilyl phosphite (11), and bis(trimethylsilyl) ethyl phosphite (12), with a variety of α-halo carbonyl compounds gave the 1:1 carbonyl addition products (6, 13, and 14), enol phosphates (5 and 26), and/or 2-oxophosphonates (4 and 25).Substituents on the phosphites and the α-halo carbonyl compounds have influenced the product ratios.The results of these reactions strongly suggest that the Perkow reaction proceeds via an initial attack of phosphite on the carbonyl carbon of the α-halo carbonyl compound.Treatment of bis(trimethylsilyl) 1--2-halo phosphonates (6) with sodium methoxide in methanol followed by retrimethylsilylation gave bis(trimethylsilyl) 1,2-epoxy phosphonates (17), bis(trimethylsilyl) 2-oxo phosphonates (4), and bis(trimethylsilyl) methyl phosphate (21).On the other hand, diethyl 1-hydroxy-2-halo phosphonates (22) were converted by treatment with different bases to 1,2-epoxy phosphonates (23) predominantly in good yields.When some of tri-n-butyltin alkoxides were used as bases, enol phosphates (26) were obtained selectively.Several bis(trimethylsilyl) esters obtained in the above reactions were successfully converted to the corresponding monoanilinium salts in high yields by treatment with aniline-containing alcohols.