RSS-Feed abonnieren
DOI: 10.1055/s-0029-1216812
Synthesis of Perfluoroalkylthio-Substituted Ferrocenes
Publikationsverlauf
Publikationsdatum:
27. Mai 2009 (online)

Abstract
Mono- and bis(trifluoromethylthio)-substituted and perfluorooctanesulfonylferrocene derivatives were prepared by nucleophilic substitution reactions on the ferrocene core. Thus, Hg(SCF3)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 CF3SSCF3 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 SCF3 group appears to be almost as electron-withdrawing as a trifluoromethyl group on the ferrocene core.
Key words
electrochemistry - ferrocene - fluoro compounds - trifluoromethyl
- 1
Purser S.Moore PR.Swallow S.Gouverneur V. Chem. Soc. Rev. 2008, 37: 320 -
2a
Ainsworth SJ. Chem. Eng. News 2007, 85 (37): 13 -
2b
Thayer AM. Chem. Eng. News 2006, 84 (23): 15 -
3a
Popov VI.Lieb M.Haas A. Ukr. Khim. Zh. (Russ. Ed.) 1990, 56: 1115 ; Chem. Abstr. 1990, 114, 57248 -
3b
Hedberg FL.Rosenberg H. J. Organomet. Chem. 1971, 28: C14 -
3c
Rosenberg H. inventors; US Patent 3432533. ; Chem. Abstr. 1969, 71, 3486 -
4a
Akiyama T.Kato K.Kajitani M.Sakaguchi Y.Nakamura J.Hayashi H.Sugimori A. Bull. Chem. Soc. Jpn. 1988, 61: 3531 -
4b
Sugimori A,Kato K, andAkiyama T. inventors; Japanese Patent JP 61027927. ; Chem. Abstr. 1986, 105, 208591 -
5a
Ferrocenes: Homogeneous Catalysis, Organic
Synthesis, Material Science
Togni A.Hayashi T. VCH; Weinheim: 1995. -
5b
Ferrocenes
Stepnicka P. Wiley; Chichester: 2008. -
6a
Metzler-Nolte N. Spec. Chem. Mag. 2002, 34 -
6b
van Staveren DR.Metzler-Nolte N. Chem. Rev. 2004, 104: 5931 -
6c
Kirin SI.Kraatz H.-B.Metzler-Nolte N. Chem. Soc. Rev. 2006, 35: 348 -
6d
Metzler-Nolte N. In Bioorganometallics Jaouen G., Wiley-VCH; Weinheim: 2006. p.125-179 -
6e
Metzler-Nolte N. In Comprehensive Organometallic Chemistry IIICrabtree R.Mingos DMP. Elsevier; Amsterdam: 2006. p.883-920 -
6f
Salmain M.Metzler-Nolte N. In FerrocenesStepnicka P. Wiley; Chichester: 2008. p.499-639 -
7a
van Staveren DR.Weyhermüller T.Metzler-Nolte N. Dalton Trans. 2003, 210 -
7b
Barisic L.Dropucic M.Rapic V.Pritzkow H.Kirin SI.Metzler-Nolte N. Chem. Commun. 2004, 2004 -
7c
Kirin SI.Wissenbach D.Metzler-Nolte N. New J. Chem. 2005, 1168 -
7d
Noor F.Wüstholz A.Kinscherf R.Metzler-Nolte N. Angew. Chem. Int. Ed. 2005, 44: 2429 -
7e
Barisic L.Rapic V.Metzler-Nolte N. Eur. J. Inorg. Chem. 2006, 4019 -
7f
Chantson J.Varga Falzacappa MV.Crovella S.Metzler-Nolte N. ChemMedChem 2006, 1: 1268 -
7g
Hoffmanns U.Metzler-Nolte N. Bioconjugate Chem. 2006, 17: 204 -
7h
Kirin SI.Schatzschneider U.de Hatten X.Weyhermüller T.Metzler-Nolte N. J. Organomet. Chem. 2006, 691: 3451 -
7i
Jios JL.Kirin SI.Buceta NN.Weyhermüller T.Védova COD.Metzler-Nolte N. J. Organomet. Chem. 2007, 692: 4209 -
7j
de Hatten X.Bothe E.Merz K.Huc I.
Metzler-Nolte -
7k
Köster SD.Dittrich J.Gasser G.Hüsken N.Castañeda ICH.Jios JL.Védova COD.
Metzler-Nolte -
7l
Noor F.Kinscherf R.Bonaterra G. A.Metzler-Nolte N. ChemBioChem 2009, 10: 493 -
8a
Hess A.Metzler-Nolte N. Chem. Commun. 1999, 885 -
8b
Verheijen JC.van der Marel GA.van Boom JH.Metzler-Nolte N. Bioconjugate Chem. 2000, 11: 741 -
8c
Maurer A.Kraatz H.-B.Metzler-Nolte N. Eur. J. Inorg. Chem. 2005, 3207 -
8d
Gasser G.Hüsken N.Köster SD.Metzler-Nolte N. Chem. Commun. 2008, 3675 -
9a
Müller-Westhoff UT.Yang Z.Ingram G. J. Organomet. Chem. 1993, 463: 163 -
9b
Sanders R.Müller-Westhoff UT. J. Organomet. Chem. 1996, 512: 219 - 10
Dong T.-Y.Lai L.-L. J. Organomet. Chem. 1996, 509: 131 - 11
Slocum DW.Koonvitsky BW.Ernst CR. J. Organomet. Chem. 1972, 38: 125 - 12
Cech D.Wohlpfeil R.Etzold G. Nucl. Acids Res. 1975, 11: 2183 - 13
Haas A.Lieb M. J. Heterocycl. Chem. 1986, 23: 1079 - 15
Fish RW.Rosenblum M. J. Org. Chem. 1965, 30: 1253 - 16
Deck PA.Jackson WF.Fronczek FR. Organometallics 1996, 15: 5287
References
Lieb, M.; Metzler-Nolte, N. unpublished results.