With Aldehydes, Ketones, and Carbonic Acids

The addition of PH3 to ketones or carbonic acid esters containing carbon-carbon double bonds is described in Table 18 on pp. 272/3. 

The addition reaction of PH3 to carbonyl compounds has been described in detail in various reviews during the last three decades [7, 8] and to some extent in [13 to 15, 17]. 

In the absence of acids, PH3 reacts with anhydrous paraformaldehyde (mole ratio 1 3) at 100 C and 35 to 40 atm to give tris(hydroxymethyl)phosphane, (HOCH2)3P [108,109]. For the reaction of paraformaldehyde pellets with gaseous PH3 an activation energy of 9.7 kcal/mol between 90 and 110°C was found [110]. Reaction of paraformaldehyde with PH3 in an aqueous medium in the presence of platinum salts (e.g., PtCl2, PtCU, K2PtCl4) yields the same product. The reaction also proceeds in an acetonitrile suspension. The reaction (PH3 CH20=1 4) in an 

Formaldehyde in concentrated aqueous hydrochloric acid solution reacts with PH3 at 25 C [123, 124] or 80°C [125] to form (HOCH2)4PCl. This reaction explains the absorption in aqueous dioxane solution which is first-order with respect to PH3, CH2O, and HCl. The reaction rate is independent of the HCl concentration above 0.1 mol/L. The initial rates of reaction were determined at 25 C [126]  

PH3 reacts with a mixture of aqueous formaldehyde and diethylamine at ambient temperature to give tris(diethylaminomethyl)phosphane [130]. Reactions of PH3 and CH2O with urea in hydrochloric acid, with guanidinium sulfate or dicyandiamide, and with tri-n-butylamine yield viscous syrups with a phosphorus content of 4.6, 5.65, and 2.63%, respectively [131]. 

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