New method for the synthesis of phosphonic and phosphinic esters and their thio analogs Communication 15. Addition of phenyl-and alkyl-phosphonous esters to methacrylic and acrylic esters

The Phosphonous Acids and Their Derivatives.

“…The products are described in table 16. Partial esters of phosphonous acids are formed when a phosphonous dichloride is added to an alcohol at ice-cold temperatures (20,174,275,281). In the absence of a tertiary amine, the phosphonous diester initially formed is attacked by the hydrogen chloride, generating the monoester and liberating alkyl chloride: R'PCl, + 2ROH -R'P(OR), + 2HCI R'P(OR), + HC1 -R'PH(0)0R + RC1…”

“…A better technique for preparing monoesters is to add the alcohol in a slow stream under the surface of the phosphonous dichloride while keeping the system under slightly reduced pressure to draw off the hydrogen chloride as it is formed (20,281). Acid-sensitive monoesters may be prepared by the reaction of phosphonous dichlorides with alcohols in the presence of one equivalent of a tertiary amine such as pyridine (107, 269).…”

“…With esters of aliphatic phosphonous acids it is necessary to use the same alkyl radical in the alkoxide as in the ester (281). This is not the case with esters of aromatic phosphonous acids (281). Phosphonous acid esters also react with ,ß-unsaturated ketones (280), ,/5-unsaturated nitriles (38, 279), ,/3-unsaturated phosphonic esters (279, 283), When diethylcarbamoyl chloride is used in this reaction, the product is an ester of diethylamidoformylphosphonic acid (23).…”

“…Condensation reactions Condensation reactions of phosphonous monoesters have been studied rather extensively in recent years, since reliable methods for their synthesis have been developed.Phosphonous monoesters undergo base-catalyzed condensation reactions with a wide variety of ,/3-unsaturated compounds. As an example may be given the reaction with a,¡8-unsaturated esters(38,275,281, «PH(0)0R + CH,=CHCOOCH, -> CJLP(0)(0R)CH,CH,C00CH,…”