p-Chlorothiophenol → 2-[(4-Chloro-phenylsulfanyl)-(2,3,6-trifluoro-phenyl)-methyl]-malonic Acid Dimethyl Ester

HRID 564305Notes

Reaction equation

[CH3:1][O:2][C:3](=[O:19])[C:4](=[CH:9][C:10]1[C:15]([F:16])=[CH:14][CH:13]=[C:12]([F:17])[C:11]=1[F:18])[C:5]([O:7][CH3:8])=[O:6].[Cl:20][C:21]1[CH:26]=[CH:25][C:24]([SH:27])=[CH:23][CH:22]=1.C([O-])([O-])=O.[K+].[K+].C(OCC)(=O)C>C1COCC1.O>[CH3:1][O:2][C:3](=[O:19])[CH:4]([CH:9]([S:27][C:24]1[CH:25]=[CH:26][C:21]([Cl:20])=[CH:22][CH:23]=1)[C:10]1[C:15]([F:16])=[CH:14][CH:13]=[C:12]([F:17])[C:11]=1[F:18])[C:5]([O:7][CH3:8])=[O:6]

Participants

Conditions

Temperature: 60 °C

Procedure

2-(2,3,6-Trifluoro-benzylidene)-malonic acid dimethyl ester (6.5 g, 23.7 mmol) and 4-chlorothiophenol (5.1 g, 35.5 mmol) were dissolved in 100 mL THF. K2CO3 (5 g, excess) was added, the reaction mixture was stirred at 60° C. for three hours. 300 mL of EtOAc and 300 mL of water were added. The organic layer was separated, washed with water, dried over Na2SO4 and concentrated. The product was purified by column chromatography using EtOAc/hexane as the eluent. (Gradient from 0/100 to 25/75 in 45 min, 7.1 g, 72%). 1H NMR (CDCl3 400 MHz) δ 7.26 (m, 4H), 7.03 (m, 1H), 6.75 (m, 1H), 5.08 (d, J=11.7 Hz, 1H), 4.34 (d, J=12.4 Hz, 1H), 3.84 (s, 3H), 3.56 (s, 3H).

Workup

customThe organic layer was separated
washwashed with water
dry with materialdried over Na2SO4
concentrationconcentrated
customThe product was purified by column chromatography
custom(Gradient from 0/100 to 25/75 in 45 min, 7.1 g, 72%)

Sources & evidence

ORD record: ord-899813c9722f4af8b1209a3e8ecdd9e4
Source dataset: uspto-grants-2011_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08067621B2

Reaction notes

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