Science of Synthesis

Judd, W. R.; Katz, C. E.; Aubé, J., Science of Synthesis, (2005) 21, 162.

The thermal conversion of N,N-diaryl imidates into N,N-diaryl amides is known as the Chapman rearrangement (‌Scheme 38‌).[‌89‌] Although the reaction was discovered by Mumm, Hesse, and Volquartz in 1915, its name is derived from the chemist who studied the mechanism and first applied the rearrangement to a general synthesis of diphenyl­amines.[‌90‌] Mono-, di-, and trialkyl-substituted imidates can also undergo the rearrangement; however, reaction with these substrates requires catalysis by sulfuric acid, iodo­methane, or methyl sulfate, and occurs by a distinctly different mechanism to that of the classical Chapman rearrangement of aryl imidates. In many cases, the rearrangement requires heating of the aryl imidate to a high temperature (280–300°C), either neat or in the presence of solvent. Refluxing in tetraethylene glycol dimethyl ether (tetraglyme; bp 276°C) is optimal for many rearrangements.[‌91‌]

‌Meeeee 88‌ Mee Meeeeee Meeeeeeeeeeee[‌88‌]

M,M-Meeeee eeeeeeee (eeee eeeeee eeeee eeeeee ee eeeee eeeeee), eeeee eee eeee ee eeeeeeee eeeeeeeee ee eee Meeeeee eeeeeeeeeeeee, eee ee eeeeeeee ee eeeeeeee M-eeee eeeeee eeee eeeeeeeeee eeeeeeeeeeeee ee eeeeeeee eee eeeeeeeeeeeee eeeee eeeeeeee, eeeeeeee ee eeeeeeee eeee ee eeee eeeee eee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeee Meeeeeeeeee ee M,M-Meeeee Meeeeeee[‌88‌]

Mee Meeeeee eeeeeeeeeeeee eeeeee eeeeeee ee eeeeeeeeeeeeee[‌88‌] eeeeeeeeeeee eeeeeeee eeeeeeeeeeee eeee eeeeeeee eee eeeeee ee eeeeeeee ee eee eeeeeeeee eeee eeeee, eeeeeeeee ee e 8,8-eeeee ee eee eeee eeeee eeee eeeeee ee eeeeeeee (‌Meeeee 88‌).[‌88‌] Meeeeeee-eeeeeeeeeee eeeeeeeeeeee ee eee eeeeeee eeee eeee ee e eeeeeee eeeeeeee ee eeeeeeeeeee eee eeeeeee ee eeeeeeee eeeeee eeeeeee ee eeeeeeee eeeeee.[‌88‌] Me eeeee ee eeeeeeee, eee eeeeee ee eeeeeeee eee eeeee- eee, ee e eeeeee eeeeee, eeee-eeeeeeeeeee eeeee.[‌88‌] Meeeeeee-eeeeeeeeeee eeeeeeeeeeee ee eee M-eeeeeeeee eeee eeeeeeee eee eeeeeeee eeee ee eeeeee eee eeeeeeee eeee eeeeeeeeeeee. Meee eeeee eeee eeeee eee eee eeeeee-eeeeee eeee eeeee, eeeeee eee eeeeee ee eeee eeeeeeeeee.[‌88‌] Meeee eeeeeeee ee eee eeeeeee eee Meeeeee eeeeeeeeeeeee eeeee eeeeeee eeeeeeeeee eeeee, eeeeeeeeee ee e eeeeee ee eee eeeeeeeee ee eee eeeee eeeee ee eeeeeeeeeee eee eeeeeeeeee eeeeeeee eeeeee.

‌Meeeee 88‌ Meeeeeeee ee eee Meeeeee Meeeeeeeeeeee[‌88‌]

M eeeeee ee eeeee- eee eeeeeee-eeeeeeeeeee eeeeeeee (e.e., ‌88‌ ee eee eeeeeeee ee eeee M,M-eeeeee eeeee ‌88‌) eee ee eeeeeeeeeeee eeee ee eee Meeeeee eeeeeeeeeeeee. Meeeeeee eeeeeee eeeeeee eeee eeeeeeeeeeee, eeeeeeeee eeeeee, eeeee, eeeeee, eeeeeee, eee eeeee eeeeee, eeee eeee eeeeeeeeee eeeeeeee.[‌88‌] Meee eeeeeeeeeeeeee eeeeeeee eee eeeee ee ‌Meeeee 88‌.[‌88‌,‌88‌–‌88‌]

‌Meeeee 88‌ Meeeeeee ee eee Meeeeee Meeeeeeeeeeee[‌88‌,‌88‌–‌88‌]

Meeeeeeeeeee Meeeeeeee

M-(8-Meeeeeeeeeee)-M-eeeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

8-Meeeeeeeeeee (8.88 e, 88 eeee) eee eeeee ee eeeee MeMM (88 eM) eeeeeeeeee Me (8.88 e, 88 eeee). M eeee ee M-eeeeeeeeeeeeeeeeeeeeeeeeee eeeeeeee (8.88 e, 88 eeee) ee Me8M (88 eM) eee eeee eeeee ee eee eeeeeee eeeeeee ee ee. Mee eeeeeeeee eeee eee eeeeeee ee ee eeeeeeeee, eeeeeee eeee M8M, eee eeeeeeeee eeee Me8M. Mee eeeeeeee Me8M eeeeeeee eeee eeeeee eeee 88% ee MeMM eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeeeeeeee ee eee eeeeeeeee eeeeeee (MeMM) eeee eee eeeeeee ‌88‌; eeeee: 8.88 e (88%); ee 88–88°M.

Meeeeee ‌88‌ (8.8 e, 8.8 eeee) ee eeeeeeeeeeeee eeeeee eeeeeeee eeeee (88 eM) eee eeeeeeee eee 8 e. Mee eeeeee eeee eee eeee eeeeee eeee M8M eee eee eeeeeeeee eeeee eee eeeeeeeeeeeeee (MeMM) ee eeee eee eeeee eeeee ‌88‌; eeeee: 8.8 e (88%); ee 888°M.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8-8, 8888.
• 8.Meeeee-Meee, (8888) M 8-8, 888.
• 8.Meeeee-Meee, (8888) M 88e, 8888.
• 8.Meeeee-Meee, (8888) M 88e, 8888.