89609-47-2Relevant articles and documents
Aminoethynyl Metallations, 13. - Synthesis and Reactions of 3-Aminopropiolamidines
Himbert, Gerhard,Schwickerath, Willi
, p. 85 - 97 (2007/10/02)
The lithium aminoacetylides 1 react with the carbodiimides 2 to give the lithium propiolamidinates 3, which are hydrolyzed to yield the 3-aminopropiolamidines 4. 3 can directly be converted into the persubstituted ynamine carboxamidines 5 by adding methyl iodide.The amidines 4 with less activated C/C-triple bonds (NR1R2 = N(Me)Ph or NPh2) react with thioformaldehyde dioxide or with diphenyl ketene exclusively at the NH group with formation of the sulfonamides 6 or of an carboxamide 7.The more reactive (diethylaminoacetylene)carboxamidine 4h adds a second molecule of ketene to furnish the cyclobutenone derivative 8.The propiolamidine 4b with a diphenylamino group at the triple bond reacts with concentrated hydrochloric acid under formation of the amidinium salt 9 and partly by addition of a second molecule of hydrochloride to the triple bond to give 10.Adding tosyl azide to 4 we obtained via the triazole 11 by two successive 1,5-cyclizations the amidino-1,2,3-triazoles 12.The 3-aminopropiolamidines 4 bearing at least one aryl group in the amidine moiety cyclize to give the 2,4-diaminoquinolines 17 if they are chromatographed on silica gel.The same or analogously substituted quinolines 17 are obtained by the reaction of the simple ynamines 15 (H, Me, or Ph in the β-position) with the corresponding carbodiimides 2. 2-Anilino-4-diethylamino-3-methylquinoline (17e) is hydrolyzed in acidic solution to give the 4-quinolone derivative 19.
