Chloromethylation Chloromethyl phosphonic dichloride

A similar condensation of 177b with chloromethyl phosphonic dichloride gave 2-chloromethyl-l,3,2-oxazaphospholidine-2-oxide 182 which was converted into the cyano derivative 183 by reaction with potassium cyanide in anhydrous dimethyl-sulfoxide (Scheme 51) [82],... 

The primary formaldehyde adduct, (chloromethyl)phosphonic dichloride, can be isolated by a suitable technique including exclusion of moisture ... 

The classical reaction between a (haloalkyl)phosphonic diester and NaN3, best carried out in a polar solvent, e.g dmf has been developed into an asymmetric synthesis. The reaction between (chloromethyl)phosphonic dichloride and the chiral auxiliary (5)-(phenylaminomethyl)pyrrolidine (314) is followed by separation of the product 1,3,2-diazaphosph(V)olidines 315 (R = H X = Cl) and 316 (R = H X = Cl), obtained in yields of 36 and 45%. Alkylation (BuLi, RX) of the cyclic diamides and reaction between the products and NaN3, to give 315 and 316 (R = alkyl X = N3), is then followed by acidoly-... 

Phosphonic and Phosphinic Adds and their Derivatives.—Oxidative chlorophos-phonylation of allyl chloride gives 60% bis(chloromethyl)methylphosphonic dichloride, which may readily be monodehydrochlorinated by triethylamine. Phosphonic bromofluorides and dibromides are both obtained, together with other products, when terminal alkenes react with phosphorus trichloride or tribromide in the presence of FCIO. ... 

---