Methyl acetoacetate → Ammonia

HRID 247369Notes

Reaction equation

HRID 247369 reaction equation
[N:1]1ON=C2C(C=O)=CC=CC=12.[CH3:12][O:13][C:14](=[O:19])[CH2:15][C:16]([CH3:18])=[O:17].N1CCCCC1.COC(=O)C(C(=O)C)=CC1C2C(=NON=2)C=CC=1.[CH3:44][N:45]([CH3:55])[CH2:46]COC(=O)/C=C(\N)/C>C1C=CC=CC=1.O1CCOCC1.C(O)(=O)C>[CH3:44][N:45]([CH3:55])[CH2:46][CH2:12][O:13][C:14](=[O:19])[CH2:15][C:16]([CH3:18])=[O:17].[NH3:1]

Participants

10

Reactant 5

HCID 7757Methyl acetoacetateHCID 8082PiperidineHCID 102908732,1,3-Benzoxadiazole-4-carbaldehydeHCID 125291873-Aminocrotonic acid-(2-dimethylaminoethyl)esterHCID 534332132-Acetyl-3-benzofurazan-4-yl-acrylic acid methyl ester

Product 2

HCID 222AmmoniaHCID 125291702-(Dimethylamino)ethyl 3-oxobutanoate

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 241BenzeneSolventHCID 312751,4-DioxaneSolvent

Procedure

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°).

Sources & evidence

ORD record
ord-f29eca7ed8a44004bccdb125e00b9758
Source dataset
uspto-grants-1987_11
Patent number
US04707482

Reaction notes

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