Halogen displacement chemistry with silver and alkali metal salts: Preparation of SF5-esters, alcohols, aliphatic olefins, acids and an iodide

It has been found that treatment of SF5-alkyl halides, especially SF5(CH2)2Br, with silver salts such as CH3C(O)OAg, p-CH3C6H4SO3Ag, CF3SO3Ag and AgNO3 provides convenient pathways for preparing the following ester compounds: SF5CH2CH2R (R = CH3COO, TosO, CF3SO3, NO3), SF5(CH2)3OTos, and SF5(CF2)4(CH2)2OAc. Important derivatives prepared from these esters include SF5(CH2)2OH; SF5(CF2)4(CH2)2OH. Several alkenes SF5C(Br)CH2 and SF5CH2(COOCH3)CCHC(O)OCH3 are obtained using silver salts. The use of alkali metals salts with SF5(CH2)3Br is studied and yields SF5(CH2)3I; also, a pathway has been developed that extends for SF5(CH2)3− the chain by two-carbon atoms and also produces the first SF5-containing malonic acid.

For the first time it was found that silver oxy-salts can be used with SF5CH2CH2Br and other SF5-aliphatic and fluoroaliphatic systems resulting in new pathways and compounds for SF5-containing esters, alcohols and olefins. Also, a two-carbon chain extension is possible with the potassium salt of malonic ester; the first SF5-malonic acid is reported. The unique iodide, SF5(CH2)3I has been prepared.