Download PDF
Synthesis 2001(9): 1327-1330
DOI: 10.1055/s-2001-15226
PAPER
© Georg Thieme Verlag Stuttgart · New York

Bis(1,3,4-Thiadiazolo)-1,3,5-Triazinium Halides 3; [1] Synthesis of Guanidyl- Functionalized 1,4,8,11-Tetraazacyclotetradecanes and Tris(2-amino-ethyl)amines: Application of a Novel Rearrangement

Martin Walthera, Kurt Wermanna, Helmar Görlsb, Ernst Anders*a
a Institut für Organische Chemie und Makromolekulare Chemie der Friedrich-Schiller-Universität, Humboldtstraße 10, Germany
b Institut für Anorganische und Analytische Chemie der Friedrich-Schiller-Universität, Lessingstraße 8, D-07743 Jena, Germany
Fax: +49(0)3641/948212; e-Mail: c5eran@rz.uni-jena.de;
Further Information

Publication History

Received 1 February 2001
Publication Date:
24 September 2004 (online)

    Permissions and Reprints All articles of this category

Abstract

The reaction of bis(1,3,4-thiadiazolo)-1,3,5-triazinium (or ”5/6/5î) halides 1 with 1,4,8,11-tetraazacyclotetradecane (2) and tris(2-aminoethyl)-amine (6) yields new N-functionalized cyclams (3a-d) as well as the complex tertiary amine 7. All of the NH or NH2 groups in 2 and 6 are transformed into (chiral) guanidyl moieties. The structure of a representative of 3 was confirmed by single crystal X-ray analysis.

Key words

nucleophilic additions - rearrangements - heterocycles - imines - chirality

    References and Notes

  • 1 Part 2, compare: Wermann K. Walther M. Günther W. Görls H. Anders E. J. Org. Chem.  2001,  66:  720 
    CrossrefSearch in Google Scholar
  • 2 Anders E. Wermann K. Wiedel B. Günther W. Görls H. Eur. J. Org. Chem.  1998,  2923 
    Crossref
  • 3 Anders E. Opitz A. Wermann K. Wiedel B. Walther M. Imhof W. Görls H. J. Org. Chem.  1999,  64:  3113 
    CrossrefSearch in Google Scholar
  • 4 Anders E. Vanden Eynde J.-J. Wermann K. In Advances in Heterocyclic Chemistry   Vol. 77:  Katritzky AR. Boulten A.-J. Academic Press; New York, San Francisco, London: 2000.  p.183 
    Search in Google Scholar
  • 5 Matti J. Ledoux C. Kesler E. Bull. Soc. Chim. Fr.  1959,  477 
  • Cyclams in coordination chemistry and catalysis:
  • 6a Kimura E. Tetrahedron  1992,  48:  6175 
    CrossrefSearch in Google Scholar
  • 6b König B. Pelka M. Möller O. Dix I. Jones PG. Chem. Ber./Recueil  1997,  130:  521 
    CrossrefSearch in Google Scholar
  • 6c Kimura E. J. Biol. Inorg. Chem.  1996,  431 
    Crossref
  • 6d Sakurai M. Furuki T. Inoue Y. J. Phys. Chem.  1995,  99:  17789 
    CrossrefSearch in Google Scholar
  • Examples for coordination properties of the trisamine-derivatives:
  • 7a Rai BL. Khodr H. Hider CR. Tetrahedron  1999,  55:  1129 
    Search in Google Scholar
  • 7b Chen D. Motekaitis RJ. Murase J. Martell AE. Tetrahedron  1995,  51:  77 
    Search in Google Scholar
  • 7d Walther D. Geßler S. Ritter U. Schmidt A. Hamza K. Imhof W. Görls H. Sieler J. Chem. Ber.  1995,  128:  281 
    Search in Google Scholar
  • 8 La Mattina JL. McCarthy PA. Reiter LA. Holt WF. Yeh Li.-An. J. Med. Chem.  1990,  33:  543 
    CrossrefSearch in Google Scholar
  • 9a Quintela MJ. Peinador C. Botana L. Estevez M. Riguera R. Bioorg. Med. Chem.  1997,  5:  1543 
    Search in Google Scholar
  • 9b Bogdanowicz-Szwed K. Krasodomska M. Monatsh. Chem.  1996,  12:  1273 
    Search in Google Scholar
  • 9c Otto-Jaworska T. Acta Pol. Pharm.  1992,  49:  77 
    Search in Google Scholar
  • 10 Turner S. Myers M. Gadie B. Hale SH. Horsley A. Nelson AJ. Pape R. Savillle JF. Doxey JC. Berridge TL. J. Med. Chem.  1988,  31:  906 
    CrossrefSearch in Google Scholar
  • 11 Review for cyclam and cyclen functionalization: Denant F. Brandès S. Guilard R. Synlett  2000,  561 
    Thieme Connect
  • 12 Nonius BV. COLLECT   Data Collection Software; Netherlands: 1998. 
  • 13 Otwinowski Z. Minor W. Processing of X-Ray Diffraction Data Collected in Oscillation Mode, In Methods in Enzymology. Macromolecular Crystallography, Part A   Vol. 276:  Carter CW. Sweet RM. Academic Press; New York: 1997.  p.307 
    Search in Google Scholar
  • 14 Sheldrick GM. Acta Crystallogr., Sect. A  1990,  46:  467 
    CrossrefSearch in Google Scholar
  • 15 Sheldrick GM. SHELXL-97   University of Göttingen; Germany: 1993. 
16

Further details of the crystal structure investigations of (3a) are available on request from the director of the Cambridge Crystallographic Data Center, 12 Union Road, GB-Cambridge CB2 1 EZ, on quoting the depository number 156254, the names of the authors, and the journal citation.

17

The 13C NMR spectra showed multiple signals in the expected area of chemical shifts because of the complicated diastereomeric mixtures.

18

Elemental analysis yields unsatisfactory values due to partial decomposition processes that take place during recrystallization after column chromatography. For this reason, fractional recrystallization was difficult to perform.