Journal of Fluonne Chemistry, 48 (1990) 407-420 407 Q Y THE I EMINAL PENTAFLUOROSULFANYL. SF+ GROUPS JON B. NIELSEN+ and JOSEPH S. THRASHER* Department of Chemistry, The University of Alabama, Tuscaloosa, AL 35487-0336 (U.S.A.) SUMMARY The pet-fluorinated tertiary amines (SF5)2NCF3 [l], (SF5)2NC2F5, and (SF5)2NC3F7 have been prepared by the following scheme. Their overall yields were found to decrease markedly with respect to increases in the length of the perfluoro- 15OOC SF5N=C(CI)Rf + l/2 HgF2 - SF5N =C(F)Rf + l/2 HgC12 -196 to -78’C SF5N=C(F)Rf + CIF - SF5N(CI)CF2Rf hv 2 SF5N(CI)CF2Rf - (SF5)2NCF2Rf + Cl2 + l/2 RfCF2N =NCF2Rf alkyl chain. In fact, attempts to prepare (SF5)2NC4Fg have been unsuccessful thus far. The N-chloroamines were also reacted with simple olefins to give a variety of addition products such as SF5N(CF3)CH2CH2CI, SF5N(CF3)CF2CF2CI, SF5N(C2F5)CH2CH2CI, and SF5N(C4Fg)CH2CH2CI. ‘Present Address: Los Alamos National Laboratory, INC-4, MS-C345 Los Alamos, NM 87545 (U.S.A.) 0022-l 139/90/$3.50 0 Elsewer Sequola/Prmted in The Netherlands