Alkylations by Unsaturated Compounds

Reaction of red phosphorus with hexafluoro-2-butyne in the presence of a catalytic amount of iodine at 200° for 8 hr. results in the direct formation of 2,3,o,6,7,8-hexakis-(trifluoromcthy))-l, 4-dipho.sphabicyclo-[2.2.2. jocta-2,5,7-triene in 43% yield (21). The same product was 

White phosphorus is reported to react with an olefin and hydrogen at 300° and 1000 atm. to give small yields of tertiary phosphines (22). The reaction is substantially improved by the presence of an alkyl iodide. Thus, 0.33 mole of phosphorus, 1.04 moles of ethylene,- 0.05 mole of methyl iodide, and 800-980 atm. of hydrogen heated at 250° for 15 hr. is reported to give triethylphosphine in 4% yield based on phosphorus and tetraethylphosphonium iodide in 17% 3deld based on phosphorus or 100% yield based on methyl iodide. 

Red phosphorus is reported to react with 1-pentene in the presence of aluminum chloride at 35° during 2 hr. to give a phosphorus-containing olefin polymer suitable for use as a lubricating oil (23). 

Reaction of a lubricating oil (a complex mixture of aromatic molecules having aliphatic side chains) w ith white phosphorus at 150-300° followed by oxidation with air at 90-120° gives a solution of oil-soluble phosphorus compounds believed to contain phosphonic acid groups (24). 

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