Allyl bromide → Cyclopropanecarboxylic acid, 1-(2-propenyl)-, 1,1-dimethylethyl ester

HRID 2111758Notes

Reaction equation

C([N-][CH:5]([CH3:7])[CH3:6])(C)C.[Li+].C(NC(C)C)(C)C.C([Li])CCC.[C:21]([O:25][C:26]([CH:28]1[CH2:30][CH2:29]1)=[O:27])([CH3:24])([CH3:23])[CH3:22].C(Br)C=C.[Cl-].[NH4+]>C1COCC1>[C:21]([O:25][C:26]([C:28]1([CH2:7][CH:5]=[CH2:6])[CH2:30][CH2:29]1)=[O:27])([CH3:24])([CH3:23])[CH3:22]

Participants

Conditions

Temperature: 0 °C

Procedure

Lithium diisopropyl amide was generated from 7.5 g (58.1 mmol) diisopropyl amine and 23.2 mL of 2.5 M n-butyl lithium in 200 mL THF at 0° C. under nitrogen. After stirring for 30 minutes at 0° C. the solution was taken to −78° C. where 7.5 g (52.8 mmol) of cyclopropanecarboxylic acid tert-butyl ester in 30 mL of THF was added dropwise over 5 min. After 4 h 12.8 g (106 mmol) of allyl bromide in 30 mL THF was added drop-wise over 10 min. to the clear golden solution. The reaction was allowed to slowly warm to room temperature. After 19 hours the reaction was poured into aqueous saturated ammonium chloride solution, extracted with ether, dried and concentrated to deliver an oil which was purified via Kugelrohr distillation (approx. 20 mm Hg; 60-75° C. oven) to deliver 5.4 g (56%) of the desired product as a clear colorless oil.

Workup

customwas taken to −78° C.
additionwas added dropwise over 5 min
temperatureto slowly warm to room temperature
extractionextracted with ether
customdried
concentrationconcentrated
distillationwas purified via Kugelrohr distillation (approx. 20 mm Hg; 60-75° C. oven)

Sources & evidence

ORD record: ord-5a94c7c8c175445e97d86ad83bfdeb15
Source dataset: uspto-grants-2009_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07521445B2

Reaction notes

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