Phosphoryl chlorides phosphorous acid ester

Nakagome and co-workers effected the successful cyclization of N-ethyl-N-arylaminomethylenemalonates (749) in poly phosphoric acid, prepared from orthophosphoric acid and phosphorus pentoxide in polyphosphate ester (PPE), prepared from phosphorus pentoxide and anhydrous diethyl ether in chloroform in phosphoryl chloride on the action of boron trifluoride etherate on the action of acetic anhydride and concentrated sulfuric acid or on the action of phosphorus pentoxide in benzene [71GEP2033971, 71JHC357 76JAP(K) 18440]. Depending on the work-up process, l-ethyl-4-oxoquinoline-3-carboxylates (750, R1 = Et), l-ethyl-4-oxoquinoline-3-carboxylic acids (750, R2 = H) and 3-ethoxycarbonyl-4-chloroquinolinium iodides (751) were obtained. Only the cyclization of... 

HETEROCYCLES Copper phcnylace-tylide. Dichlorobis(benzonitrile)palladium. N-Dichloromethylene-N,N-dimcthylammo-nium chloride. Diiminosuccinonitrile. Dimethyl acetylenedicarboxylate. Dipotassium cyanodithioimidocarbonate. Ethoxy-carbonyl isothiocyanate. Ethyldiisopropyl-amine. Ethylene oxide. Hydrogen fluoride. Isocyanomethane-phosphoric acid diethyl ester. Lead tetraacetate. Lithium aluminium hydride. Methylhydrazine. Phosphoryl chloride. Polyphosphate ester. Polyphosphoric acid. Potassium amide. Potassium hydroxide. Tolythiomethyl isocyanide. Tosylmethyl isocyanide, Trichlo-romethylisocyanide dichloride. Trimethyl-silyldiazomethane. 

Phosphorus trichloride is the starting material used most frequently for the preparation of the esters, amides and anhydrides of phosphoric and phos-phorothioic acids. It can be oxidised to phosphoryl chloride (4) and, heated with sulfur in the presence of a catalyst, to thiophosphoryl chloride (5) (Perot, 1962). 

The ester fluorides of phosphoric acid and phosphonic adds were the earliest known examples of biologically active phosphorus compounds. Sarin (2) and soman (3), previously mentioned, did not attain practical importance because of their high toxicity, but they were the starting point for the development of other derivatives more suitable for agricultural purposes. Within this framework Schrader developed N,N,N, N -tetramethyl phosphorodiamidofluoridate (14), which is used under the name dimefox. It is produced by the reaction of phosphoryl chloride with dimethylamine and the subsequent interaction of the phosphoro-chloridate formed with sodium fluoride (Schrader, 1947). 

In this procedure, a-glycerol phosphate is acylated directly using acyl anhydrides (Lapidot et aL, 1969). The acyl anhydrides are prepared with dicyclohexyl-carbodi-imide (Rosenthal, 1975). Optically active or racemic phosphatidic acids can be prepared and either saturated or unsaturated acyl residues added. The method depends on the ability of the fatty acid salt to suppress the formation of mixed phosphoric-carboxylic anhydrides with the consequent phosphorylation of adjacent hydroxy groups. The use of acyl anhydrides rather then acyl chlorides probably prevents the formation of glycerol chlorhydrin esters (Aneja and Chadha, 1971a). 

---