Raymond E. Miller

A Convenient One-Step, High-Yield Preparation of Methylphosphonyl Dichloride from Dimethyl Methylphosphonate

Abstract Based on a 1H and 31P nmr study of the interactions of alkyl-phosphonyl dichlorides, RP(O)Cl2, with dialkyl alkylphosphonates, RP(O)(OR)2, a method was developed for the preparation of CH3P(O)Cl2 (R [dbnd] CH3) in 98% yield. This method consists of the slow addition of the phosphonate to an excess of refluxing SOCl2, thus suppressing irreversible side reactions. For R [dbnd] C2H5, a yield of 72% was achieved; for R [dbnd] C4H9 and ClCH2CH2 pure product could not be isolated.

Improved Syntheses and Characterization of the Isomers of 3-Methyl-1-Phenylphospholene 1-Oxide

Abstract Isomerically pure 3-methyl-1-phenyl-2-phospholene 1-oxide and 3-methyl-1-phenyl-3-phospholene 1-oxide were prepared and characterized by 1H (60 and 270 MHz), 31P and 13C nmr, IR, Laser Raman, and mass spectrometry. 1,4-Cycloaddition of isoprene and phenylphosphonous dichloride, after hydrolysis of the addition product, yielded a mixture of the above 2-isomer and small amounts of 3-isomer from which pure 2-isomer was separated by fractional crystallization. The analog reaction with phenylphosphonous dibromide gave isomerically pure 3-isomer. An improved and shortened work-up procedure for the phospholene oxides was used resulting in higher yields.

Studies Related to the Synthesis and Properties of 1-Phenylphospholene 1-Oxides

Abstract Isomerically pure 1-phenyl-2-phospholene 1-oxide and 1-phenyl-3-phospholene 1-oxide were prepared and characterized by 1H (60, 90 and 270 MHz), 31P and 13C nmr, IR, Laser Raman and mass spectrometry, and X-ray diffraction. Whereas the 1,4-cycloaddition of butadiene and phenylphosphonous dibromide, after hydrolysis of the addition product, yielded the above pure 3-isomer, the analog reaction with phenylphosphonous dichloride gave a mixture of the 2-isomer and small amounts of 3-isomer from which pure 2-isomer was separated by column chromatography.

THERMAL DECOMPOSITION OF PHOSPHINE COMPLEXES OF NICKEL (II) DIHALIDES

Abstract Thermogravimetric measurements show that complexes of nickel (II) dihalides with alkyl and aryl substituted phosphines in an oxygen containing atmosphere start to decompose near or above 200°C yielding solid phases based on nickel oxide and phosphorus pentoxide.

1-PHENOXYPHOSPHOLENE 1-OXIDES

Abstract Isomerically pure samples of the two isomers of 1-phenoxyphospholene 1-oxide were prepared and exhaustively characterized by 1H, 31P and 13C nmr, IR and mass spectrometry.

VICINAL DIBROMO-1-HYDROXYPHOSPHOLANE 1-OXIDES

Abstract 2,3-Dibromo-1-hydroxyphospholane 1-oxide and 3,4-dibromo-1-hydroxyphospholane 1-oxide were prepared in high yield by bromine addition to 1-hydroxyphosphol-2-ene 1-oxide or 1-hydroxyphosphol-3-ene 1-oxide, respectively. Both compounds were characterized by 1H, 31P and 13C nmr, IR, Laser Raman and mass spectrometry.