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

HRID 403609Notes

Reaction equation

[CH3:1]C(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]CBr)[CH3:23]>C(O)(C)(C)C>[C:19]([C:13]([CH3:1])([CH2:12][CH2:29][CH2:28][CH2:27][CH2:26][C:25]([O:24][CH2:22][CH3:23])=[O:32])[C:14]([O:16][CH2:17][CH3:18])=[O:15])(=[O:20])[CH3:21]

Participants

Conditions

Temperature: 50 °C

Procedure

A mixture of 13.4 g (0.12 mol) of potassium tert-butoxide and 100 g of tert-butanol was stirred and heated until the tert-butoxide totally dissolved. The solution was cooled to about 50° C. and 17 g (0.12 mmol) of ethyl 2-methylacetoacetate was added dropwise. Ethyl-6-bromohexanoate (30 g, 0.13 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 1M 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 25 g (75%) of diethyl 2-acetyl-2-methyloctanedioate (3) as yellow liquid.

Workup

dissolutiontotally 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 1M 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-96fae9994a7949ca97cedca55f9d43e6
Source dataset: uspto-grants-2014_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08748446B2

Reaction notes

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