Radical Anion Arylation Diethyl Phenylphosphonate

Submitted by Joseph F. Bunnett and Robert H. Weiss1 Checked by S. C. Busman and O L Chapman 

After irradiation, the flask is removed from the reactor, and about 50 g. (0.62 mole) of solid ammonium nitrate is added with 

An ammonia condenser is an enlarged cold finger design. The interior of the finger is a reservoir for dry ice and 2-propanol. 

When ammonia distilled from sodium metal is used, the yield is 3-5% greater, but use of ammonia straight from the tank is recommended because of the greater convenience. 

Commercial diethyl phosphonate, (C2H50)2P(0)H, formerly known as diethyl phosphite, from Aldrich Chemical Co., Inc., was used without further purification. 

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Nitrogen heterocycles continue to be valuable reagents and provide new synthetic approaches such as NITRONES FOR INTRAMOLECULAR -1,3 - DIPOLAR CYCLOADDITIONS HEXAHYDRO-1,3,3,6-TETRAMETHYL-2,l-BENZISOX AZOLINE. Substituting on a pyrrolidine can be accomplished by using NUCLEOPHILIC a - sec - AM IN O ALKYL ATION 2-(DI-PHENYLHYDROXYMETHYL)PYRROLIDINE. Arene oxides have considerable importance for cancer studies, and the example ARENE OXIDE SYNTHESIS PHENANTHRENE 9,10-OXIDE has been included. An aromatic reaction illustrates RADICAL ANION ARYLATION DIETHYL PHENYLPHOSPHONATE. 

Bunnett, J.F., and Weiss, R.H., Radical anion arylation. Diethyl phenylphosphonate (phosphonic acid, phenyl-diethyl ester), Org. Synth., 58, 134, 1978 Org. Synth. Coll. Vol. VI, 451, 1988. 

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