You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via45.10.8.1.1.1 Variation 1: Condensation Reactions with Active Methylene Compounds Initiated by Acetic Anhydride
Please login to access the full content or check if you have access via
Ito, S.; Morita, N., Science of Synthesis, (2010) 45, 463.
8,8-Dicyanoheptafulvenes 133, including 2,6-disubstituted derivatives, are prepared by reactions of the corresponding tropones 132 with malononitrile in refluxing acetic anhydride (Scheme 40).[164] Related to this method are the reactions of methyl cyanoacetate with substituted and annulated tropone derivatives.[165–168] Steric hindrance in 2-substituted tropones 134 is thought to be the cause for nucleophilic attack further away from the substituent. Therefore, condensation of 2-substituted tropones 134 with active methylene compounds such as methyl cyanoacetate gives isomeric mixtures of 1-, 2-, and 3-substituted heptafulvenes 135, 136, and 137 (Scheme 40).[165]
Meeeee 88 Meeeeeeeeee ee Meeeeeeeeeeee ee Meeeeeeeeeee Meeeeeeee ee Meeeeeee eeee Meeeee Meeeeeeee Meeeeeeee Meeeeeeee ee Meee Meeeeeeee[888,888]
M8 | M8 | Meeee (%) | Mee | 888 | 888 | 888 |
---|---|---|---|---|---|
Me | MM8Me | 88 | 8 | 8 | [888] |
Me | MM8Me | – | 88 | 8 | [888] |
Me | 8-M8MM8M8 | – | 8 | 8 | [888] |
eMe | MM8Me | – | 88 | 8 | [888] |
eMe | 8-M8MM8M8 | 8 | 88 | 8 | [888] |
Meeeeeeeeeee Meeeeeeee
Meeeeeeeee-8,8,8-eeeeeeeeeeeeeeeeeeeeeeeee (888, M8 = M); Meeeeee Meeeeeeee:[888]
M eeee ee eeeeeee (888, M8 = M; 8.888 e, 88.8 eeee) eee eeeeeeeeeeeee (8.88 e, 88.8 eeee) ee Me8M (88 eM) eee eeeeeeee eee 8.8 e. Mee eeeeeeee eeeeeeeeee eeee eeee eeeeeee eeeee eeeeeee eeeeeeee, eeeeeee eeeeeee eeeeeeee. Mee eeeeeeee eeee eeeeeeeee ee eeeeeeeeee eee eeeeee eeee MeMM, eeeeee eee eeeeeee ee eeeeee eeeeeee (8.888 e). Mee eeeeeeee eee eeeeeeeeeeee eee eeeeeeeeeeeeeee [eeeeee eee, eeeeeee (MMMMMMM: eeeeeeeeee)]; eeee eeeeeeee eeee eeeeeee (8.888 e); eeeee: 8.888 e (88%); ee 888–888°M.
References
[164] | Mee, M.; Meeeeeee, M.; Meeeeeee, M., Meee. Meee. Mee. Mee., (8888) 88, 8888. |
[165] | Meee, M.; Mee, M. M.; Meee, M.; Meeeeeeee, M., Meee. Meee., (8888), 888. |
[166] | Meeee, M.; Mee, M. M.; Meee, M.; Meee, M.; Meeeeeeee, M., Meeeeeeeeeee, (8888) 88, 8888. |
[167] | Meeee, M.; Mee, M. M.; Meee, M.; Meeeeeeee, M., Meee Meeeeeee Meeeeeee Meeeee (Meeeee Meeeeee Meeeeeeee), (8888) 88, 888; Meee. Meeee., (8888) 888, 888888. |
[168] | Meeee, M.; Mee, M. M.; Meee, M.; Meee, M.; Meeeeeeee, M., Meee. Meee. Mee. Mee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8e, 888.