Phosphorus dichlorofluoride

As a matter of interest, we obtained a compound, diethyl phosphorofluoridite (IX), of a lower state of oxidation than the corresponding phosphorofluoridate by the action of phosphorus dichlorofluoride on ethyl alcohol. The new compound, unlike the phosphorofluoridate, was readily hydrolysed by water, was relatively non-toxic and did not produce myosis.1... 

The myotic, toxic and other physiological properties of the dialkyl phosphorofluoridates, POF(O.R)2, have been fully described on pp. 42, 68 et seq. In 19444 we described an analogous compound of the phosphorofluoridite series, namely, diethyl phosphorofluoridite, PF(OEt)2. This could not be prepared by the action of sodium fluoride on the corresponding diethyl phosphorochloridite (the preparation of which is considered below). We obtained it, however, by the action of ethyl alcohol on phosphorus dichlorofluoride,... 

The phosphorus dichlorofluoride required for the above condensation was prepared by the fluorination of phosphorus trichloride by a modification of the method of Booth and Bozarth.1... 

Among many esters, di w propyl and diisopropyl phosphoro-fluoridate were prepared by the action of phosphorus oxy-dichlorofluoride on ra-propyl and isopropyl alcohol respectively. The n-ester was less toxic and possessed only feeble myotic... 

In view of the rapid toxic action and myotic effect of the dialkyl phosphorofluoridates and of the high toxicity of some of the phosphorodiamidic fluorides, we prepared2 and examined a hybrid molecule containing the essential features of each type of compound. The first to be examined was ethyl phenyl-phosphoramidofluoridate (VII). One mol. of phosphorus oxy-dichlorofluoride was added to 1 mol. of ethyl alcohol, and the resulting ethyl phosphorofluoridochloridate (which it was not necessary to isolate) was treated with aniline. 

As we have seen (pp. 50 et seq.) the reaction between phosphorus o dichlorofluoride and alcohols, phenols and thiols, affords dialkyl, dicycloalkyl, diaryl phosphorofluoridates and dialkyl phosphorodithiolates. In a Report to the Ministry of Supply on fluorophosphonates a description was given of a new type of nitrogen fluorophosphonate formed by the action of 4 mol. of aniline on 1 mol. of phosphorus oxydichlorofluoride, the fluorine atom being unaffected ... 

Later, American workers described the preparation of this type of compound by a method which necessitated the loss of two thirds of the fluorine concerned in the reaction. They pre-pared tetramethylphosphorodiamidic fluoride (bisdimethyl aminofluorophosphine oxide) (II) by the action of phosphorus oxyfluoride on the calculated quantity of dimethylamine. In addition, it should be emphasized that phosphorus oxyfluoride is a gas and is more difficult than the hquid phosphorus oxy-dichlorofluoride to manipulate. In Report no. 14 on fluoro-phosphonates to the Ministry of Supply it was shown that our reaction could also be apphed to the preparation of tetramethyl-... 

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See also in sourсe #XX -- [ ]

See also in sourсe #XX -- [ ]

See also in sourсe #XX -- [ ]

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