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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;
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Publication History

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

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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

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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.