HuagongsheHuagongshe Chemistry Print Report · For research reference only
Methyl acetoacetate → Ammonia
Participants
| Role | Name | HCID | Charge |
|---|---|---|---|
| Reactant | Methyl acetoacetate | HCID 7757 | — |
| Reactant | Piperidine | HCID 8082 | — |
| Reactant | 2,1,3-Benzoxadiazole-4-carbaldehyde | HCID 10290873 | — |
| Reactant | 3-Aminocrotonic acid-(2-dimethylaminoethyl)ester | HCID 12529187 | — |
| Reactant | 2-Acetyl-3-benzofurazan-4-yl-acrylic acid methyl ester | HCID 53433213 | — |
| Solvent | Acetic Acid | HCID 176 | — |
| Solvent | Benzene | HCID 241 | — |
| Solvent | 1,4-Dioxane | HCID 31275 | — |
| Product | Ammonia | HCID 222 | — |
| Product | 2-(Dimethylamino)ethyl 3-oxobutanoate | HCID 12529170 | — |
Reaction Steps
2,1,3-Benzoxadiazol-4-carbaldehyde is reacted with aceto-acetic acid methyl ester in benzene in the presence of catalytic amounts of piperidine and acetic acid. The resultant 2-acetyl-3-(2,1,3-benzoxadiazol-4-yl)-2-propenoic acid methyl ester (crystalline, mixture of Z and E isomers) is cyclized in dioxane under refluxing with an equivalent amount of 3-aminocrotonic acid-(2-dimethylaminoethyl)ester {M.P. 56°; obtained by reaction of aceto-acetic acid-(2-dimethylaminoetyl)ester [B.P.0.01 mm 140°-150°, obtained by reaction of diketen with 2-dimethylaminoethanol at 70°], with ammonia gas at 60°}, to give 4-(2,1,3-benzoxadiazol-4-yl)-1,4-dihydro-5-methoxycarbonyl-2,6-dimethyl-3-pyridine carboxylic acid-(2-dimethylaminoethyl)ester (M.P. 161°).
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
|---|---|
| Patent number | US04707482 |
| Source dataset | uspto-grants-1987_11 |
| ORD ID | ord-f29eca7ed8a44004bccdb125e00b9758 |
| Source note | uspto-grants-1987_11 |