Benzyl Bromide → benzyl(1R,cis,Z)2,2-dimethyl-3-[3-oxo-3-tert.-butoxy-1-propenyl]-cyclopropane-carboxylate

HRID 569543Notes

Reaction equation

[CH3:1][C:2]1([CH3:17])[C@@H:4](/[CH:5]=[CH:6]\[C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10])[C@H:3]1[C:14]([OH:16])=[O:15].[H-].[Na+].[CH2:20](Br)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.P(O)(O)([O-])=O.[Na+]>O1CCCC1>[CH3:1][C:2]1([CH3:17])[C@@H:4](/[CH:5]=[CH:6]\[C:7](=[O:13])[O:8][C:9]([CH3:10])([CH3:11])[CH3:12])[C@H:3]1[C:14]([O:16][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:15]

Participants

Conditions

Temperature: 15 °C

Procedure

A solution of 25 g of (1R,cis,Z)2,2-dimethyl-3-[3-oxo-3-tert.-butoxy-1-propenyl]-cyclopropane-carboxylic acid in 250 ml of tetrahydrofuran were added at 10° C. to a mixture of 2.6 g of sodium hydride in 100 ml of tetrahydrofuran and the mixture was stirred at 15° C. for 30 minutes. A solution of 35 ml of benzyl bromide in 100 ml of tetrahydrofuran was added to the mixture which was heated at 50° C. for 48 hours and then was cooled and poured into aqueous monosodium phosphate solution. The mixture was extracted with isopropyl ether and the organic phase was washed with water, dried and evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and was eluted with a 9-1 hexane-isopropyl ether mixture to obtain 30 g of benzyl(1R,cis,Z)2,2-dimethyl-3-[3-oxo-3-tert.-butoxy-1-propenyl]-cyclopropane-carboxylate.

Workup

temperaturewas heated at 50° C. for 48 hours
temperaturewas cooled
extractionThe mixture was extracted with isopropyl ether
washthe organic phase was washed with water
customdried
customevaporated to dryness under reduced pressure
customThe residue was chromatographed over silica gel
washwas eluted with a 9-1 hexane-isopropyl ether mixture

Sources & evidence

ORD record: ord-606a3f91ab6c4b618cb46260210e047e
Source dataset: uspto-grants-1988_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04732903

Reaction notes

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