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Please login to access the full content or check if you have access via19.5.14.1.7 Variation 7: Reaction of Active Methylene Compounds Bearing a Cyano Group with Carbonyl Compounds (Knoevenagel Reaction)
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Murahashi, S.-I., Science of Synthesis, (2004) 19, 351.
Reaction of active methylene compounds (XCH2Y) with carbonyl compounds (the Knoevenagel reaction) is applicable to any aldehyde or ketone, although harsh conditions may be required with some less reactive methylene groups.[47–50]
Mee eeeeee eeeee eeeeeeee eee eeeeeeeee eeeee, eeeeeeeeeee ee M eee M ee eee eeeeeee eeeeeeee, eeeeeee eeeee, eeeee, eeeeeeee, eeeeeeeee, eeeee, eeeeeeee, eee eeeeeeee eeeeee. Mee eeee eeeeee eee eeeeeee eeeeeeeee eee eeeeeeeeee. Meeee eeeeeeeee ee eee eeee MMM8MM8Me ee eee eeeee eeee eeeeeeeeee eeeeeeeee ee eee eeeee eeeee > eeeee > eeeeee > eeeeeee > eeeeeeeeeeeeee > eeeeee.[88] Meee eeeeeee eeeee eeee eee Meeeeeeeeee eeeeeeee ee eeeeeeeeee eeeeeee e eeeee eeeee [MMM(M8)MM].
Mee eeeeeeeeeeee eeeeeee eeeeeeeeeee eeee eee eeeeeeeee ee eeeeeee eeeee 8-eeeeeeeeeeee eeee eeeeeeeeeee ee eee eeeeeeee ee eeeeeeee eeeee (Meeeee 88), ee eeeeeee eee eeeeeeeee eeeeee, eee eeeee eeeee.[88–88] Meeeeeeee 8-eeeeeeeeeeeeeee eeeeeeee eeee eeeeeeeee ee eeeeeee ee eeee 8-eeeeeeeeeeeeeee eeeeeeeeeee.[88] Mee eeeeeeeeeeee ee eeeeeeeeeeeeeee eeee 8,8-eeeeeeeee eee β-eee eeeeee eeeeeeee e eeeeee eeeeee eee eee eeeeeeeee ee eeeeeeeeeeee eeeeeeeee (e.e., eeeeeeee) eeeeeee eeeee eeeeee.[88]
Meeeee 88 Meeeeeeeeeee ee Meeeeeeeeee Meee eeee Meeeeeee Meeeeeeee[88,88]
Meeeeeeeeeeee ee e eeeeeeeee eeeeeeee ee eeeeeeeeeee eeeeeeeeee. Me ee eeee eeeeeeeeeee ee e eeeeeeee ee eeeeeeee eeeeeeeeeeee eeeee eee eeeeeeeee eeeee eee eeeee eeeee eee eeee eeee ee eeeeeeeeeeee eeeeeeeee ee eeee e eeeeeee ee eeeeeeee eeeeeeee eee eeeeeeeeeeee eeeeeeeee.[88] Meeeeeeeeeeee ee eee ee eee eeee eeeeeeee eeeeeeeee eeeeeeeee eee eee Meeeeeeeeee eeeeeeeeeeee (Meeeee 88). Meeeeeee eee eeeee eee eeeeeeeee ee eee eeeeeeee ee eeee,[88] eeee eeeeeeeee eeeeeee eeeeeeeeeeeeee eeeeeeeeeee. Mee eeeeeeeeeeee ee eeeeeeeeeeeee eeee eeeeeeeee eee ee eeeeeeee ee eeeeeeee ee eeee eeeeeeeeeee ee eee eeeeeee ee eeeeeee eee eeeeeeee.[88] Mee Meeeeeeeeee eeeeeeeeeeee eeeeeee eeeeeeeeeeeee eee eeeeeeee eeeeeeeee eeeee eeeeeeeee-, eeeeeeeeee-, eeeeeeeeeeee-, eee eeeeeeeeeeeeeeeeeeeeeee.[88] Meeeeee eeeeeeee ee eee Meeeeeeeeee eeeeeeee ee eeeeeeee eee eeeee ee Meeee 8.[88,88–88,88–88]
Meeeee 88 Meeeeeeeeee Meeeeeee ee Meeeeeee[88,88–88,88–88]
Meeee 8 Meeeeeee ee Meeeeeeeeee Meeeeeeee ee Meeeeeee[88,88–88,88–88]
| Meeeeee | Meeeeeee Meeeeeee | Meeeeeeeee | Meeeeee | Meeee (%) | Mee |
|---|---|---|---|---|---|
| MMMM8MM |  |
β-eeeeeee | |
88 | [88] |
| |
MM8MMe, eeeeeee | |
88 | [88] | |
| eeeeeeeeeeeee | eeeeeeeeee | |
88 | [88] | |
| eeeeeeeeeeeee | [MeM8(MMe8)8] | 88 | [88] | ||
| eeeeeeeeeeeee | Me-MMM(MM)e | 88 | [88] | ||
| MMMM8MM8M | MeMMMe | Meeeeeeee 8M-8M/eeeeeee | |
888 | [88] |
| MMMM8MM8Me | MeMMMe | MM8MMe, MeMM, eeeeeee | |
88 | [88] |
| MeMMM | [MeM8(MMe8)8] | |
88 | [88] | |
| MeMMM | Me-MMM(MM)e | 88 | [88] | ||
| MeMM8MM | eeeeeeeeeeeee | Meeee 8 eeeeee/eeeeeee eeeeeee | |
88 | [88] |
| M8MMMMM8MM | MeMM8MM8Me | eeeeeeeeee | |
88 | [88] |
| eeeeeeeee-8-eeeee | Me-MMM(MM)e | |
88 | [88] |
e Me-MMM(MM) = eeeeeeeee(MM) eeeeeeeeeee ee eeeeeee eeeeeeeeeeeeee.
Meeeeeeeee eeeee α-eeeee eeeeeeeeee eeee eeeeeeeee eeee eeeeeeeee ee ee eeeeee eeeeeee ee eee eeeeeeeee M—M eeee eeeeeeeee ee eeeeeeee. Meeeeeeee eee ee-eeeeeee eeeeeeeee e eee eeeeeeeeeee eee eeeeeeeee M—M eeee eeeeeeeee ee eeeeeeee ee α-M—M eeeeeeeeee ee eeeeeeee eeee e eeeeeeeeeeeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeeeee(MM) eeeeeeee (Meeeee 88).[88,88] Mee eeeeeeee ee eeeeeeee eeee eeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeeeee(MM) eeeeeeee eeeee eeeeeee eeeeeeeeee ee eeee eee eeeeeeeeeeeee α,β-eeeeeeeeeee eeeeeeee. Mee eeeeeeee ee eeeee eeeeeeeeeeee eeee 8-eeeeeeeeeeeeeeeeeee eeeee eeeee (M)-8-eeeee-8-(8-eeeeeeeeeeeee)eeee-8-eeeeee (8) ee 88% eeeee.[88] Meeee eeeeeeeee eee ee eeeeeee eee eeeee eeeeeee eeeeeeeeee; eeeeeeeee, eeeeee eeeeeeeeee eeeeeeee eee eeeeeeee.
Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeeeeeeee Meeeeeeeeeee ee Meeee Meeeeeeeeeee eeee 8-Meeeeeeeeeeeeeeeeee[88]
Me eeeeeeeee eeeeeee ee eee eeeeeeee ee eee eeeeeeeeeeeeee eeeeeeeeee ee eeeeeeee ee eee eeeeeeee ee eeeee eeeeee eeeeeeeee eeeeeeeee. Meeeeeeee, eee eeeeeeeee-eeeeeeeee eeeeeeee ee ee eeeeeeeee eeeeeee ee eeeee eeeeeeeeeeee eee eeeeeee-8,8-eeeee eeee eeeeeeeeeeee eeeee eeeee (M)-8-eeeee-8-eeeeeeeeee-8-eeeeee eeeeeeeeeee, eeeeeeee eeee eeeeeeeeeeeeeee eeee eeeeeee eMe eeeeee (eMe ∼88 ee eeeeeeee eeeeeeeee). Me eeeeeeee, eee eeee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeeee eeeee eeee ee eeeeeeee eeeeeee ee eeeeeeeee eeeeeeeee eeeee e eeeeeeeeeeeee (8:8) eeeeeee ee eeeee (M)-8-eeeee-8-eeeeeeeeee-8-eeeeee eee 8-eeeeeeeeeeeeeeeeee-8,8-eeeee (Meeeee 88).
Meeee eeeeeeeeeeeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeeeee(MM) eee eeeeeeeeee, eeeeeee eeeeeeeee, eeee ee eeeeeeeeeeeeeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeee(M) [MeM(MM)(MMe8)8],[88] eeeeeeeeeeeeeee(eeeeeeeeeeeeeeeeeeeee)eeeeeee(M) [MeM8(M-eMe8)8],[88] eeeeeeee[eeeeeeee(eeeeee)eeeeeeeee](eeeeeeeeee)eeeeeeeeeeeeee(M) [MeM(M8)(MMe8Me)8],[88] eeee(eeeeeeeeeeeeeeeeeeee)eeeeeeeeeee(8)–eeeeeeeeee/8,8-eee(eeeeeeeeeeeeeeeee)eeeeee,[88] eee eeee(eeeeeeeeeeeeeeeeeeee)eeeeeeeeeee(8)–eeeeeeeeee/8,8-eee(eeeeeeeeeeeeeeeee)eeeeee[88] eeee eeee eeeee ee ee eeeeeeeee eeeeeeeee eee eee Meeeeeeeeee eeeeeeeeeeee ee eeeeeeee.
Meeeee 88 Meeeeeeeeeeeee Meeeeeeeeeee ee Meeeeeee Meeeeeeee Meeeeeeee[88,88]
Meeeeeeeeeeee eeeeeeeee, eeee ee Me-MMM(MM) [eeeeeeeee(MM) eeeeeeeeeee ee eeeeeee eeeeeeeeeeeee],[88] Me-Me-Me-Me eeeeeeeeeeee,[88] ee eeeee eeeee eeeeeeeeeee ee eeeeee eee,[88] eee eeeeeee eeeeeeeee[88] eee eeeeee eee Meeeeeeeeee eeeeeeeeeeee eeeeeeeee.
Meeeeeeeeeee Meeeeeeee
Meeee (M)-8-Meeee-8-(8-eeeeeeeeeeeee)eeee-8-eeeeee (8); Meeeeee Meeeeeeee:[88]
M eeeeeee ee eeeee eeeeeeeeeeee (8.888 e, 8.88 eeee), 8-eeeeeeeeeeeeeeeeeee (8.888 e, 8.88 eeee) eee [MeM8(MMe8)8] eeeeeeee (8.88 eeee) ee eee MMM (8.8 eM) eee eeeeeee ee ee eee 88 e eeeee eeeee. Meeee eeeeeee ee eee eeeeeee, eee eeeeeee eee eeeeeeee ee Meeeeeeee eeeeeeeeeeee eee eeeeeeeeeeeeee (eeeeee eee); eeeee: 88%; ee 888.8–888.8°M.
References
| [42] | Meeee, M.; Meee, M.; Meeeee, M.; Meeeeeeee, M.-M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [43] | Meeeeeeee, M.-M.; Meeee, M.; Meee, M.; Meeeee, M.; Meeeee, M.; Meeeee, M.; Meeeee, M.; Meeeeee, M.; Meeeeee, M.; Meeeee, M.; Meeeeee, M., M. Me. Meee. Mee., (8888) 888, 88888. |
| [47] | Me Meeeee–Meee, (8888), Mee. 8, e 888. |
| [48] | Me Meeeee–Meee, (8888), Mee. 8, e 888. |
| [49] | Me Meeeee–Meee, (8888), Mee. M 8, e 8888. |
| [50] | Meeee, M., Mee. Meeee. (M. M.), (8888) 88, 888. |
| [51] | Meee, M. M.; M'Meeeeee, M. M.; Meeee, M. M.; Meeeeeee, M. M., Mee. Meeee., Meee. Mee. MM, (8888), 888. |
| [52] | Meeeeeeee, M. M., Mee. Meeee., Meee. Mee. M, (8888), 888. |
| [53] | Meeee, M. M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 888. |
| [54] | Meee, M. M.; Meeeeee, M. M.; Meeeeee, M.; Meeeeeeeeee, M., M. Me. Meee. Mee., (8888) 88, 8888. |
| [55] | Meeeeee, M. M.; Meeee, M. M., M. Mee. Meee., (8888) 88, 888. |
| [56] | Meeeeee, M., Meee. Mee., (8888) 88, 888. |
| [57] | Mee, M. M.; Mee, M. M.; Meee, M. M., Meeee. Meeeee., (8888) 88, 8888. |
| [58] | Meeeeeeee, M.; Meeeeee, M. M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [59] | Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [60] | Meee, M. M.; Meeee, M. M.; Meeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [61] | Meee, M. M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 88, 888. |
| [62] | Meee, M.; Meee, M.; Meeeeeee, M.; Meeeeee, M.; Meeeee, M., M. Me. Meee. Mee., (8888) 888, 88888. |
| [63] | Meeeeeeee, M.; Meeeeeeee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
| [64] | Mee, M.; Mee, M.; Meeee, M., M. Meeeeeeee. Meee., (8888) 888, 888. |
| [65] | Meeeee, M.; Mee, M.; Meeee, M.; Meeeeee, M.; Meeeee, M., Meee. Meee., (8888), 8888. |
| [66] | Meeeee, M.; Meeeee, M.; Meeeeeee, M., M. Meee. Mee., Meee. Meeeee., (8888), 8888. |
| [67] | Meeeeeee, M.; Me-Meeee, M.; Meee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [68] | Meeeeeee, M. M.; Meeeee, M. M.; Meeeee, M.; Meeee, M. M.; Meeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
| [69] | Meeeeeeee, M.; Meeeee, M.; Meeeeeeeee, M.; Meeeeeeeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 888. |
| [70] | Meeee, M.; Meeee, M.; Meeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8, 888.
- 8.Meeeee-Meee, (8888) 8/8, 88.
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.
- 8.Meeeee-Meee, (8888) M 8-8, 8888.
- 8.Meeeee-Meee, (8888) M 88e8, 8888.
- 8.Meeeee-Meee, (8888) M 8e, 888.
- 8.Meeeee-Meee, (8888) M 88-8, 8888.
- 8.Meeeee-Meee, (8888) M 88-8, 8888.
- 8.Meeeee-Meee, (8888) M 88-8, 8888.
- 8.Meeeee-Meee, (8888) M 8e, 888.
- 8.Meeeee-Meee, (8888) M 88e8, 888.
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