Download PDF
Synthesis 2007(17): 2627-2630  
DOI: 10.1055/s-2007-983838
PAPER
© Georg Thieme Verlag Stuttgart · New York

α-Iminotrifluoroethylphosphonates: The First Representatives of N-H Imidoyl Phosphonates

Yuliya V. Rassukana, Mykola V. Kolotylo, Oleksii A. Sinitsa, Volodymir V. Pirozhenko, Petro P. Onys’ko*
Institute of Organic Chemistry, National Academy of Sciences, 5 Murmanskya St, 02094 Kiev, Ukraine
Fax: +38(44)5732643; e-Mail: onysko@rambler.ru;
Further Information

Publication History

Received 21 March 2007
Publication Date:
08 August 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

A convenient synthetic approach to previously unknown N-H imidoyl phosphonates, based on addition of dialkyl phosphites to trifluoroacetonitrile, has been developed. The synthetic potential of such imines, which exist as equilibrium mixtures of E/Z-isomers, was demonstrated by their easy reduction and functionalization with O- and P-centered nucleophiles, to afford derivatives of α-aminophosphonic acids containing a trifluoromethyl group. Furthermore, interaction with mercaptoacetic acid proceeds with intramolecular cyclization of the intermediate adduct to produce a novel 2-phosphorylated N-H thiazolidone. Interaction between the N-H imines and trichloroacetylisocyanate leads to novel, reactive, phosphorylated N-acylated imines.

Key words

imidoyl phosphonates - N-H imines - trifluoromethyl - aminophosphonates - E/Z-isomerism

    References

  • 1a Rassukana YuV. Onys’ko PP. Davydova KO. Sinitsa AD. Eur. J. Org. Chem.  2004,  3643 
    Google Scholar
  • 1b Rassukana YuV. Sinitsa AA. Onys’ko PP. Russ. Chem. Bull.  2005,  54:  2652 
    Google Scholar
  • 1c Kolotilo NV. Sinitsa AA. Rassukana YuV. Onys’ko PP. Zh. Obshch. Khim.  2006,  76:  1260 ; Chem. Abstr. 2006, 146, 316980
    Google Scholar
  • 2a Pudovik AN. Zimin MG. Konovalova IV. Pozhidaev VM. Vinogradov LI. Zh. Obshch. Khim.  1975,  45:  30 ; Chem. Abstr. 1975, 82, 140262c
    Google Scholar
  • 2b Zimin MG. Dvoinishnikova TA. Konovalova IV. Pudovik AN. Izv. Akad. Nauk SSSR, Ser. Khim.  1977,  499 ; Chem. Abstr. 1977, 88, 190978n
    Google Scholar
  • 3a Gosselin Fr. O’Shea P. Roy S. Reamer R. Chen Ch. Volante R. Org. Lett.  2005,  7:  355 
    CrossrefGoogle Scholar
  • 3b Chen G.-M. Brown HC. J. Am. Chem. Soc.  2000,  122:  4217 ; and references therein
    CrossrefGoogle Scholar
  • 4 Onys’ko PP. Kim TV. Kiseleva EI. Pustovit YuM. Sinitsa AD. Zh. Obshch. Khim.  2005,  75:  1263 ; Chem. Abstr. 2005, 145, 43868
    Google Scholar
  • 5a In Aminophosphonic and Aminophosphinic Acids. Chemistry and Biological Activity   Kukhar VP. Hudson HR. Chichester, Wiley & Sons; N.Y.: 2000. 
    Google Scholar
  • 5b Cherkasov RA. Galkin VI. Usp. Khim.  1998,  67:  940 
    Google Scholar
  • 6a Onys’ko PP. Kim TV. Kiseleva EI. Sinitsa AD. Zh. Obshch. Khim.  2004,  74:  1981 ; Chem. Abstr. 2004, 143, 267027
    Article in Thieme ConnectGoogle Scholar
  • 6b Flynn GA. Beight DW. Boehme EHW. Tetrahedron Lett.  1985,  26:  285 
    Article in Thieme ConnectGoogle Scholar
  • 6c Titanyuk ID. Vorob’eva DV. Osipov SN. Beletskaya IP. Synlett  2006,  1355 
    Article in Thieme ConnectGoogle Scholar
  • 7a Russel G. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  144:  793 
    CrossrefGoogle Scholar
  • 7b Ebetino FH. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  144:  9 
    CrossrefGoogle Scholar
  • 7c Widler L. Jaeggi KA. Green JR. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  144:  5 
    CrossrefGoogle Scholar
  • 7d Mönkkönen J. Makkonen N. Rogers MJ. Frith JC. Auriola S. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  144:  321 
    CrossrefGoogle Scholar
  • 8 Onys’ko PP. Rassukana YuV. Sinitsa AD. Zh. Obshch. Khim.  2002,  72:  1802 ; Chem. Abstr. 2002, 139, 101198
    Google Scholar
  • 9a Sinitsa OA. Kolotilo NV. Onys’ko PP. Ukr. Chem. J.  1998,  64:  5 ; Chem. Abstr. 1998, 131, 228737
    CrossrefGoogle Scholar
  • 9b Onys’ko PP. Zh. Obshch. Khim.  1999,  69:  158 ; Chem. Abstr. 1999, 131, 257626
    CrossrefGoogle Scholar
  • 9c Kolotilo NV. Sinitsa AA. Onys’ko PP. Russ. Chem. Bull.  1998,  47:  2044 
    CrossrefGoogle Scholar
  • 10 Onys’ko PP. Kim TV. Kiseleva EI. Pirozhenko VV. Sinitsa AD. Ukr. Khim. Zh.  2002,  68:  68 ; Chem. Abstr. 2002, 139, 53080
    Google Scholar