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Li, W-R., Science of Synthesis, (2005) 21, 209.
Primary amines and short-chain carboxamides (e.g., dimethylformamide) undergo direct transamidation, but the reaction times are long. However, aluminum trichloride activates N-unsubstituted (e.g., 128, R2 = R3 = H), N-substituted (e.g., 128, R2 = H; R3 ≠ H), and N,N-disubstituted amides (e.g., 128, R2 ≠ H; R3 ≠ H) toward transamidation (Scheme 29).[139] Primary amines (e.g., 129, R4 = H) give higher yields of the product (e.g., 130) than secondary (e.g., 128, R4 ≠ H) amines, whereas N-substituted amides give better yields than N-unsubstituted amides. The reactions of unactivated N,N-disubstituted amides (e.g., Scheme 29) with benzylamine give low yields, and the benzoyl group is less readily transferred than the acetyl group. Reaction does not occur in the case of aromatic or sterically hindered amines or of amides bearing bulky substituents.
Meeeee 88 Meeeeeeeeeeeee ee Meeeeeeeeee Meeeee[888]
M8 | M8 | M8 | M8 | MeMe8 (eee eeeee) | Meee (e) ee 88°M | Meeeee (%) | Mee |
---|---|---|---|---|---|---|---|
Me | M | M | M | 8.8 | 88 | 88 | [888] |
Me | M | M | Me | 8.8 | 88.8 | 88 | [888] |
Me | M | Me | Me | 8.8 | 8.8 | 88 | [888] |
Me | M | Me | M | 8.8 | 8.8 | 88 | [888] |
Me | M | Me | Me | 8.8 | 88.8 | 88 | [888] |
Me | M | Me | M | 8.8 | 88 | 88 | [888] |
Me | M | Me | Me | 8.8 | 88.8 | 8 | [888] |
Me | M | e-Me | M | 8.8 | 88.8 | 8 | [888] |
e-Me | M | Me | M | 8.8 | 88 | 8 | [888] |
Me | Me | Me | M | 8.8 | 88 | 88 | [888] |
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Meeeee 88 Meeeeeeeeeeee ee M-Meeeeeeeeeeeeeeee eeee Meeeeee Meeee Meeeee[888]
M8 | Meeeeeee | Meeeee (%) | Mee |
---|---|---|---|
Me | Me(MMe)8 | 88 | [888] |
Me | Me(MMe8)8 | 88 | [888] |
(MM8)8MMe8 | Me(MMe)8 | 88 | [888] |
(MM8)8MMe8 | Me(MMe8)8 | 88 | [888] |
(MM8)8MMe | Me(MMe)8 | 88 | [888] |
(MM8)8MMe | Me(MMe8)8 | 8 | [888] |
e Me MM.
Meeeeeeeeeee Meeeeeeee
Meeeee 888; Meeeeee Meeeeeeee:[888]
MMMMMMM: Meeeeeee eeeeeeeeeee eeee ee e eeeeee eeeeeeee ee eee eeeeeee eee eeeeee eeeeeeeee eeee eeeee.
Me eeeee 888 (8 eeeee, 88 eeee) eee ee eeeee 888 [8.8 ee 8.8 eeeee] eeee eeeee ee e eeeeeeeeee ee MeMe8 [8.8 eeeee ee 8.8 eeeee] ee 8,8-eeeeeeeeeeeeee (88 eM) ee 8 ºM. Mee eeeeeee eee eeeeeee ee 88 ºM, eee eee eeeeeeee eee eeeeeeeee ee MM eeeeeeeeeeee ee MMM. M eeeeeee ee eee eee M8M eee eeeee eee eee eeeeeee eeeee eee eeeeee eeeee eeee eeeee eeee eeeee (MeMM8). Mee eeeeeeee 888 eeee eeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MMMe8/MeMM).
References
[139] | Mee, M.; Meee, M. M. M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[140] | Meeeee, M. M.; Meeee, M. M.; Meeeeee, M. M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 8-8, 888.