65868-58-8Relevant academic research and scientific papers
Silyl Phosphites. 15. Reactions of Silyl Phosphites with α-Halo Carbonyl Compounds. Elucidation of the Mechanism of the Perkow Reaction and Related Reactions with Confirmed Experiments
Sekine, Mitsuo,Okimoto, Kiyomi,Yamada, Khoji,Hata, Tsujiaki
, p. 2097 - 2107 (2007/10/02)
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.
Dealkylation Reaction of Acetals, Phosphonate, and Phosphate Esters with Chlorotrimethylsilane/Metal Halide Reagent in Acetonitrile, and Its Application to the Synthesis of Phosphonic Acids and Vinyl Phosphates
Morita, Tsuyoshi,Okamoto, Yoshiki,Sakurai, Hiroshi
, p. 267 - 273 (2007/10/02)
A mild and efficient method has been developed for carbon-oxygen bond cleavage using chlorotrimethylsilane/sodium iodide in acetonitrile.It was applied to synthetic transformation under nonaqueous and neutral conditions, such as acetal deprotection and the synthesis of phosphonic acids from the corresponding dialkyl phosphonates via methanolysis of their silyl esters.Effectiveness of various kinds of metal or ammonium iodides for this type of dealkylation was examined in the acetonitrile solution by 1H NMR.Satisfactory results were also obtained with lithium or potassium iodide in place of sodium iodide.However, copper(I) or quarternary ammonium iodide was ineffective.Chlorotrimethylsilane/lithium bromide in acetonitrile is effective for selective dealkylation of multifunctional phosphonic esters or dialkyl vinyl phosphates.
