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

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

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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.