Alkoxy-substitutedN-acyliminium salts — synthesis, structure, reactivity

✍ Scribed by Funke, Wolfgang ;Hornig, Knut ;Würthwein, Ernst-Ulrich ;Möller, Manfred H.

• Book ID: 102789375
• Publisher: Wiley (John Wiley & Sons)
• Year: 1993
• Tongue: English
• Weight: 945 KB
• Volume: 126
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19931260917

✦ Synopsis

Alkylation of aliphatic imides 5 by use of oxonium salts takes place at one of the carbonyl oxygen atoms, leading to alkoxysubstituted N-acyliminium salts 1. These new reactive intermediates are fully characterized by IR, 'H-and 13C-NMR spectroscopy and X-ray analysis. The stereochemical and dynamical properties of the model compounds 6, 7 are investigated by ab initio model calculations (MP2/6-31G *//6-31G*). The barrier of rotation around the central C-N bond in 6 is cal-culated to 10.2 kcal/mol. The reaction with CH acids 8 yields new types of enamides (9); primary amines 10 are converted to N-acylamidines 11. Primary amidines 12 react with 1 to form new 1,3-diazabutadiene derivatives 13. The reaction with primary amides 14 gives N,N-bisacylamidines 15. With primary N-acylamidines 16 new doubly azavinylogous imides 17 (l-oxa-3,5-diazahexatriene derivatives) are formed.