113502-18-4Relevant academic research and scientific papers
P-chiral phosphinoselenoic chlorides and phosphinochalcogenoselenoic acid esters: Synthesis, characterisation, and conformational studies
Kimura, Tsutomu,Murai, Toshiaki
, p. 952 - 959 (2007/10/03)
(Chemical Equation Presented) P-Chiral alkyl or aryl phenylphosphinoselenoic chlorides were obtained by reacting PhPCl2 with Grignard reagents and elemental selenium. P-Chiral dialkyl chlorides were also obtained by treating PCl3 with two different Grignard reagents and elemental selenium. The structure of the chloride was determined by X-ray molecular structure analysis. P-Chiral phosphinochalcogenoselenoic acid esters bearing a P=Se double bond were synthesized by treating the chlorides with alkali metal alkoxide and chalcogenolates, whereas those bearing a P-Se single bond were obtained by sequential treatment of the chlorides with sodium hydroxide, sulfide or selenide, and alkyl iodides. X-ray molecular structure analyses of esters showed that they adopted gauche conformations. The computational results supported the observed conformational preference. Natural bond orbital analyses of the model compounds showed that two types of nonbonding orbital interactions, nE′ → σ*P=E and nE → σ*P-E′, are important in these compounds. Linear correlations were observed between the experimental 77Se NMR chemical shifts or the coupling constants of P-Se bonds in the esters and the calculated P-Se bond lengths of the model compounds.
Phosphoric-Carboxylic Anhydrides. New Synthetic Procedures and Reactions with Nucleophiles. Reexamination of the Reaction of Se-alkyl-phosphoroselenoates with Alcohols and Mercuric Trifluoroacetate
Wasiak, J.,Helinski, J.,Dabkowski, W.,Skrzypczynski, Z.,Michalski, J.
, p. 1027 - 1032 (2007/10/02)
Phosphorus trimethylsilyl esters RR'P(O)OSiMe3 react smoothly with carboxylic anhydrides to give phosphoric-carboxylic anhydrides RR'P(O)-O-COR" in excellent yield.A similar reaction proceeds between stannyl esters RR'P(O)OSnMe3 and carboxylic anhydrides.We also have found that the anhydrides RR'P(O)-O-COCF3 are formed in almost quantitative yield when the phosphorus acid halides RR'P(O)X (X=Cl,Br,I) are allowed to react with trifluoroacetic anhydride in the presence of N-methylimidazole. We were able to confirm again that acyclic phosphoric-carboxylic anhydrides exhibit acetylating properties towards amines and alcohols.Our findings contradict with those of Wozniak, Krzyzanowska and Stec relating to the reaction of Se-alkylphosphoroselenoates RR'P(O)SeR" with mercuric trifluoroacetate Hg(OCOCF3)2.Our interpretation of this reaction differs entirely from those presented by the above mentioned authors. Key words: phosphorus-carboxylic anhydrides, Se-alkyl-phosphoroselenoates
