Triaziridine. 6. Mitteilung. Substituententransformationen an Triaziridinen

✍ Scribed by Hans Hilpert; Lienhard Hoesch; André S. Dreiding

• Book ID: 102859235
• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: German
• Weight: 732 KB
• Volume: 69
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19860690833

✦ Synopsis

Substituent Transformations on Triaziridines

Several novel triaziridines were prepared by substituent transformations starting from the known dialkyl-triaziridine-carboxylates l a x , with the aim to study the influence of the substitution pattern on the properties of the triaziridine ring. The dialkyl-triaziridines 2a+ were obtained by (t-BuO-)-mediated demethylation and decarboxylation and the dialkyl-triaziridine-rnethanols 4a-c by LiAIH, reduction. Further reduction of the tosylates of 4a, b with LiAIH, gave the methyl-dialkyl-triaziridines 3a, b. The dialkyl-triaziridines Za, c could not be N-methylated directly with CH,I, but the anions 10a, c, obtained from 2a, c with CH3Li, yielded 3a, c. N-Methylation of 2a with (CH&OBF, did not afford 3a but rather the methyl-triaziridinium salt 11. The dialkyl-triaziridine 2c has pK:, > 14, its protonated species < 2. A concept that the electron pairs on the triaziridine N-atoms are more strongly localized than on amine N-atoms explains a) that the dialkyl-triaziridine 2c is hardly basic, b ) that the LiAlH, reductions of the esters 1 stop at the stage of the methanols 4, and c) that the methanols 4a, b do not cleave like aminomethanols.