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Z. Naturforsch. 2014,
69b, 332 – 350
doi:10.5560/ZNB.2014-3269
Orthoamides and Iminium Salts LXXXIII [1]. The Synthesis of Strong Formylating Reagents on Large Preparative Scale: Triformamide (Triformylamine)
Orthoamide und Iminiumsalze, LXXXIII [1]. Die Synthese von starken Formylierungsmitteln im präparativen Großmaßstab: Triformamid (Triformylamin)
1 Fakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstr. 1, D-73430 Aalen, Germany
2 Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
Reprint requests to Prof. Dr. Willi Kantlehner. Fax: +49(7361)5762250. E-mail:
willi.kantlehner@htw-aalen.de
Received October 3, 2013 / published online March 17, 2014
Frau Professor Sabine Laschat zum Geburtstag gewidmet
The preparation of sodium diformamide (7) from formamide and sodium methanolate under azeotropic removal of methanol with cyclohexane, or from formamide and sodium ethanolate in ethanol, is described. Diformamide (8) can be prepared by treatment of sodium diformamide (7) with formic acid. Triformamide (triformylamine) (1) is formed in the reaction of sodium diformamide with inorganic acid halides such as SOCl2, SO2Cl2 or PCl3 in acetonitrile at low temperatures. Triformamide (1) can be prepared on a large scale by the action of methanesulfonyl chloride on finely powdered sodium diformamide (7) in acetonitrile. Tris(diformylamino)methane (4) can be formed as a side product.
A procedure was developed for the large-scale preparation of N, N-diformylacetamide (6) from sodium diformamide and acetyl chloride. Triformamide (1) can be prepared from N, N-diformylacetamide (6) and diformamide with good yields.
Key words: Large-scale Preparation, Formylating Reagents, Sodium Diformamide, Diformamide, Triformamide, N, N-Diformylacetamide, Tris(diformylamino)methane