Synthesis of Perfluoroalkylthio-Substituted Ferrocenes

Abstract

Mono-and bis(trifluoromethylthio)-substituted and perfluorooctanesulfonylferrocene derivatives were prepared by nucleophilic substitution reactions on the ferrocene core. Thus, Hg(SCF 3 ) 2 was activated in situ by Cu and used for nucleophilic displacement reactions of bromide. Trifluoromethylsulfonylferrocene was not accessible by this method. The reaction of lithioferrocene with trifluoromethylsulfonyl chloride gave chloroferrocene in small yield, presumably due to the high lattice energy of solid LiF. On the other hand, the known trifluoromethylferrocene was obtained as the only isolable compound from the photochemical reaction of CF 3 SSCF 3 with ferrocene. The same product was detected in small amounts in the reaction of chloromercuryferrocene with trifluoromethylsulfonyl chloride. It thus appears that most established methods for trifluoromethylation of purely organic compounds fail for ferrocene due to concurring redox reactions. The new compounds have been comprehensively characterized by elemental analyses, NMR and IR spectroscopy, mass spectrometry, and electrochemistry. The SCF 3 group appears to be almost as electronwithdrawing as a trifluoromethyl group on the ferrocene core.

Synthesis of long straight‐chain alkane substituted ferrocene with ultra‐robust oil solubility as multifunctional organometallic additive

“…Moreover, the characteristic peaks at 2.71, 1.72, 1.28, and 0.91 ppm belonged to ‐CH 2 ‐ and ‐CH 3 groups in the alkyl side chain of TFc, respectively 40 . Additionally, the signals at 4.10~4.27 ppm belonged to ‐CH‐ groups of cyclopentadienyl rings in MFc 40,41 . The feature peaks of ‐CH 2 ‐ and ‐CH 3 groups in MFc were observed at 2.26, 1.57, 1.28, and 0.9 ppm, respectively 42,43 .…”