SUBJECTS charcoal 272 chloride

Various 2-oxo compounds have been subjected to a variety of reactions. Alkylation and acylation result in the formation of 1,3-disubstituted products.Similarly the Mannich reaction with morpholine gives products such as the bis compound 107. Halogenation of the 0x0 compound 108 with bromine in acetic acid," or chlorine in acetic acid, ° or with sulfuryl chloride results in formation of the monohalo derivatives 109. The chlorine atom in 109 (R = Cl) can be removed by hydrogenation over palladium on charcoal. Nitration of the chloro compound 110 with a mixture of nitric and sulfuric acids provides the nitro derivative 111, which may be catalytically reduced to the amino compound 112. If the reduction is carried out in the presence of an aldehyde, the product is a substituted amino derivative (113). Alternatively the amine 112 can be condensed with an aldehyde and the resultant Schiff base reduced to give the product 113. 

Ethyldiphenylphosphine oxide 397 Diphenylphosphinic acid (0.22 g) is converted into the acid chloride by 1-2 hours boiling under reflux with thionyl chloride (0.5 ml) in toluene. About half the solvent is then distilled off and the residual solution is diluted with benzene and dropped at room temperature into a Grignard solution prepared from magnesium (0.25 g) and ethyl bromide (2.5 ml). The reaction is complete after half an hour s boiling under reflux. The product is hydrolysed by ice and hydrochloric acid, the aqueous layer is washed with ether, and ether phases are united, dried, and evaporated. The residue is subjected to steam-distillation and then extracted several times with ether. The residue left on evaporation of these extracts crystallizes at once or on short storage and is decolorized in acetone by charcoal. Recrystallization from ether-light petroleum or aqueous acetone affords the oxide, m.p. 123-124° (67%). 

---