tert-Butyl acrylate → 4-((E)-2-tert-Butoxycarbonyl-vinyl)-3-methyl-benzoic Acid Methyl Ester

HRID 220820Notes

Reaction equation

Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12].[C:13]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])(=[O:16])[CH:14]=[CH2:15].C([O-])(=O)C.[Na+]>CC(N(C)C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:9][O:8][C:6](=[O:7])[C:5]1[CH:10]=[CH:11][C:2](/[CH:15]=[CH:14]/[C:13]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[C:3]([CH3:12])[CH:4]=1

Participants

Conditions

Temperature: 140 °C

Procedure

Tetrakis(triphenylphosphine)palladium (0) (5.0 g, 4.33 mmol) was added to a stirred solution of methyl 4-bromo-3-methylbenzoate (9.93 g, 43.3 mmol), tert-butyl acrylate (50 ml, 341.3 mmol) and sodium acetate (35.8 g, 436.4 mmol) in DMA (350 ml). The mixture was heated at 140° C. for 5 h, filtered through Celite® filter agent and the filtrate was concentrated in vacuo. The residue was redissolved in EtOAc, washed with 0.3M KHSO4 then brine, dried and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (eluant; 15% EtOAc:85% hexane to 20% EtOAc:80% hexane) to yield the title compound (4.81 g, 40%).

Workup

filtrationfiltered through Celite®
filtrationfilter agent
concentrationthe filtrate was concentrated in vacuo
dissolutionThe residue was redissolved in EtOAc
washwashed with 0.3M KHSO4
dry with materialbrine, dried
concentrationconcentrated in vacuo
customThe residue was purified by flash chromatography on silica gel (eluant; 15% EtOAc:85% hexane to 20% EtOAc:80% hexane)

Sources & evidence

ORD record: ord-1f0a08724f0c49a089dcf31bcc33b40b
Source dataset: uspto-grants-2012_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08202858B2

Reaction notes

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