Methyl dichlorophosphite

Almost diastereomerically pure (2i ,55)-l,3-diaza-2-methoxy-3-alkyl-2-phosphabicyclo[3.3.0]octanes (201a-d) were formed in the reaction of (S)-2-anilinomethyl)-pyrrolidines (197b-e) with methyl dichlorophosphite in the presence of NEt3 (Scheme 55) [86], With these ligands, high stereoselectivity (ee s up to 91%) was observed in the Pd catalyzed ally lie animation reaction [86],... 

Methyl chlorofluorophosphite, 4 141 analysis of, 4 143 Methyl dichlorophosphite, 4 63 Methyl difluorophosphite, 4 141 analysis of, 4 143 Methylgermanium oxide, 3 67 Methylgermanium sulfide, 3 67 Methylgermanium triiodide, 3 64 analysis of, 3 66... 

Ethyl dichlorophosphite and methyl dichlorophosphite have been prepared by the reaction of 1 mol of the appropriate alcohol with 1 mol of phosphorus(III) chloride.1 The ethyl compound has also been prepared from triethyl phosphite and phosphorus(III) chloride.2 The method outlined below is essentially the former however, several improvements have been incorporated. Among the difficulties encountered in the preparation of these compounds are the following Side reactions occur between the generated hydrogen chloride and the ester, giving an alkyl chloride and phosphorous acid disproportionation may occur in the case of the ethyl ester, the necessary vacuum distillation causes losses of the relatively low boiling product. 

University of New Mexico, Albuquerque, N.M. (These checkers worked with methyl dichlorophosphite.)... 

Methyl dichlorophosphite hydrolyzes readily and fumes in air. It reacts rapidly with aqueous sodium hydroxide. Mercury is attacked slowly by the compound, as is Lubri-seal stopcock grease. It reacts with sublimed antimony-... 

The mixture of reaction products is fractionally distilled in a modified Dufton column as described in synthesis 45. The yields based on methyl dichlorophosphite are chloro-fluorophosphite, about 8%, and difluorophosphite, about 40%. 

This procedure, although not widely used since it does indeed have some severe restrictions, has nevertheless proved useful in a few cases. The reaction involves bubbling oxygen or air through a mixture of the hydrocarbon and PCI3 and the results accord with equation 26. The case most widely reported and one which has always provided excellent results is that of cyclohexane " % and it has been claimed that a second dichlorophosphonylation step can occur Ethyl or methyl dichlorophosphites can be used to replace the PCl3. ... 

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