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

HRID 1854644Notes

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 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 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 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-f8e9b014a2ff41bd99c5dae9fa6f27a1
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08962797B2

Reaction notes

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