Ethyl 2-methylacetoacetate → Diethyl 2-acetyl-2-methyloctanedioate

HRID 2218530Notes

Reaction equation

CC(C)([O-])C.[K+].CC(C)([O-])C.[CH3:12][CH:13]([C:19]([CH3:21])=[O:20])[C:14]([O:16][CH2:17][CH3:18])=[O:15].[CH2:22]([O:24][C:25](=[O:32])[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30]Br)[CH3:23]>C(O)(C)(C)C>[C:25]([CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][C:13]([CH3:12])([C:19]([CH3:21])=[O:20])[C:14]([O:16][CH2:17][CH3:18])=[O:15])([O:24][CH2:22][CH3:23])=[O:32]

Participants

Conditions

Temperature: 50 °C

Procedure

A mixture of 1.34 g (12 mmol) potassium t-butoxide and 10 g t-butanol was stirred and heated until the t-butoxide had been dissolved. The solution was cooled to about 50° C. and 1.7 g (1 1.8 mmol) of ethyl 2-methylacetoacetate (I) was added dropwise. Ethyl-6-bromohexanoate (3 g, 13.5 mmol) was then added dropwise and the reaction mixture was stirred and refluxed for 5 hours. The mixture was filtered and the solvent was removed under reduced pressure. The residue was partitioned between 1 M HCl and chloroform. The organic layer Was dried over magnesium sulfate and purified on silica gel using 1:10 ethyl acetate/hexane as the eluent to yield 2.5 g (75%) of ethyl 2-(5-carboethoxypentyl)-2-methylacetoacetate (IIa) as yellow liquid.

Workup

dissolutionhad been dissolved
stirringthe reaction mixture was stirred
temperaturerefluxed for 5 hours
filtrationThe mixture was filtered
customthe solvent was removed under reduced pressure
customThe residue was partitioned between 1 M HCl and chloroform
dry with materialThe organic layer Was dried over magnesium sulfate
custompurified on silica gel using 1:10 ethyl acetate/hexane as the eluent

Sources & evidence

ORD record: ord-efee5df8318b40258542653521bd6cf2
Source dataset: uspto-grants-2008_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07411068B2

Reaction notes

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