Alkylation by Unsaturated Compounds

The preparation of substituted diphosphabicyclo-octatrienes or diphosphabarre-lenes (lO) was achieved by Krespan, McKusick and Cairns by direct reaction of red phosphorus with fluorinated acetylenes in the presence of a catalytic amount of iodine at 200 for 8 h under pressure. The reaction might possibly go through a diphosphorin intermediate (9), since phosphorin readily 

Similarly, reaction of red phosphorus with tetrafluoroethylene in the presence of iodine at 220 °C produced octafluoro-l-iodo-phospholane (77, 4%) and octafluoro-l,4-diiodo-l,4-diphosphorinane (72, 27 Free radicals have been suggested as intermediates in these reactions 

Under severe conditions (300 °C, 1000 atm.) white phosphorus is said to react with an olefin and hydrogen to give small yields of tertiary phosphines ) The yields are substantially improved by the presence of alkyl iodides. Thus, the yields obtained with ethylene are indicated in the equation below  

A patent claims that red phosphorus reacts with 1-pentene in the presence of AICI3 at 35 °C during 2 h to give a phosphorus containing olefin polymer suitable for use as a lubricating oil 

When phosphorus vapor with argon and ethylene, propylene, butene-1, propane, methane, ammonia or hydrazine was swept through a discharge tube, phosphine, PH3, was produced as the major gaseous constituent in aU cases  

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