Water → methyl 2-bromo-4-(3,4-dichlorophenyl)-6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophene-5-carboxylate

HRID 1615553Notes

Reaction equation

[Br:1][C:2]1[S:6][C:5]([C:7](/[C:9](=[CH:14]/[C:15]2[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([Cl:22])[CH:16]=2)/[C:10]([O:12][CH3:13])=[O:11])=[O:8])=[CH:4][CH:3]=1.[Cl-].[Cl-].[Cl-].[Al+3].O>ClCCCl>[Br:1][C:2]1[S:6][C:5]2[C:7](=[O:8])[CH:9]([C:10]([O:12][CH3:13])=[O:11])[CH:14]([C:15]3[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([Cl:22])[CH:16]=3)[C:4]=2[CH:3]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of methyl (2Z)-2-[(5-bromo-2-thienyl)carbonyl]-3-(3,4-dichlorophenyl)acrylate (36.64 g, 87.22 mmol) and aluminum trichloride (14.0 g, 105 mmol) in 1,2-dichloroethane (687.2 mL) was heated at 80° C. under argon overnight. The mixture was then cooled to rt and water (20.4 mL) was added. The mixture was stirred for 30 min and then dryloaded on silica gel. Purified on two ISCO columns, 400 g, EtOAc in hex, 0-80% to afford the product as a yellow solid (31.6 g, 81.3%). LCMS: (AA) ES−: 417, 419. 1H NMR (400 MHz, CDCl3) δ 7.42 (d, J=8.3 Hz, 1H), 7.24 (d, J=2.1 Hz, 1H), 7.02-6.94 (m, 2H), 4.88 (d, J=3.5 Hz, 1H), 3.83 (s, 3H), 3.76 (d, J=3.5 Hz, 1H).

Workup

temperatureThe mixture was then cooled to rt
customPurified on two ISCO columns, 400 g, EtOAc in hex, 0-80%

Sources & evidence

ORD record: ord-baa727a34708404a8cb43f9bc440b9b7
Source dataset: uspto-grants-2014_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08765746B2

Reaction notes

Loading…