Halogen displacement chemistry with silver and alkali metal salts: Preparation of SF 5-esters, alcohols, aliphatic olefins, acids and an iodide

• Published in: Journal of fluorine chemistry Vol. 127; no. 9; pp. 1188 - 1194
• Main Authors: Winter, R.W., Gard, G.L.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 2006
• Subjects: Pentafluorothio (SF 5); SF 5-alcohols; SF 5-esters; Silver and nucleophilic substituents; Sulfur hexafluoride derivatives; Sulfur hexafluoride derivatives; Silver and nucleophilic substituents; Pentafluorothio (SF 5); SF 5-esters; SF 5-alcohols
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2006.06.010

For the first time it was found that silver oxy-salts can be used with SF 5CH 2CH 2Br and other SF 5-aliphatic and fluoroaliphatic systems resulting in new pathways and compounds for SF 5-containing esters, alcohols and olefins. Also, a two-carbon chain extension is possible with the potassium salt of malonic ester; the first SF 5-malonic acid is reported. The unique iodide, SF 5(CH 2) 3I has been prepared. It has been found that treatment of SF 5-alkyl halides, especially SF 5(CH 2) 2Br, with silver salts such as CH 3C(O)OAg, p-CH 3C 6H 4SO 3Ag, CF 3SO 3Ag and AgNO 3 provides convenient pathways for preparing the following ester compounds: SF 5CH 2CH 2R (R = CH 3COO, TosO, CF 3SO 3, NO 3), SF 5(CH 2) 3OTos, and SF 5(CF 2) 4(CH 2) 2OAc. Important derivatives prepared from these esters include SF 5(CH 2) 2OH; SF 5(CF 2) 4(CH 2) 2OH. Several alkenes SF 5C(Br) CH 2 and SF 5CH 2(COOCH 3)C CHC(O)OCH 3 are obtained using silver salts. The use of alkali metals salts with SF 5(CH 2) 3Br is studied and yields SF 5(CH 2) 3I; also, a pathway has been developed that extends for SF 5(CH 2) 3− the chain by two-carbon atoms and also produces the first SF 5-containing malonic acid.