Vinyl Acetate → 4-Bromo-1-chloro-2-(4-(2-(vinyloxy)ethyl)benzyl)benzene

HRID 425085Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:18])=[C:6]([CH:17]=1)[CH2:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][OH:16])=[CH:10][CH:9]=1.C(=O)([O-])[O-].[Na+].[Na+].[C:25](OC=C)(=O)[CH3:26]>C1(C)C=CC=CC=1.C(OCC)(=O)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:18])=[C:6]([CH2:7][C:8]2[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][O:16][CH:25]=[CH2:26])=[CH:10][CH:9]=2)[CH:17]=1

Participants

Conditions

Temperature: 100 °C

Procedure

To a solution of 2-(4-(5-bromo-2-chlorobenzyl)phenyl)ethanol (intermediate BH) (500 mg, 1.46 mmol), [IrCl(cod)]2 (9.8 mg, 0.015 mmol) and sodium carbonate (93 mg, 0.87 mmol) in toluene (2 mL) was added vinyl acetate (0.27 mL, 2.91 mmol) under argon. The reaction mixture was heated to 100° C. and stirred for 2 h. The solution was allowed to cool to room temperature, and then diluted with 50 mL of ethyl acetate. The mixture was washed with water (20 mL) and then with brine (20 mL), and dried over sodium sulfate. The residue was concentrated and purified by column chromatography (eluent EA:PE:Et3N=1:20:0.01) to provide 445 mg of yellow solid. 1H-NMR (CDCl3, 400 MHz): δ 7.22˜7.14 (m, 3H), 7.10 (d, 2H), 7.04 (d, 2H), 6.40 (dd, J=14.4 and 6.8 Hz, 1H), 4.11 (dd, J=14.4 and 2.0 Hz, 1H), 3.96 (s, 2H), 3.93 (dd, J=6.8 and 2.0 Hz, 1H), 3.82 (t, J=7.2 Hz, 2H), 2.88 (t, J=7.2 Hz, 2H).

Workup

temperatureto cool to room temperature
washThe mixture was washed with water (20 mL)
dry with materialwith brine (20 mL), and dried over sodium sulfate
concentrationThe residue was concentrated
custompurified by column chromatography (eluent EA:PE:Et3N=1:20:0.01)

Sources & evidence

ORD record: ord-d5e12efae06c44f7bf8d5dfe1267e602
Source dataset: uspto-grants-2012_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08106021B2

Reaction notes

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