4-Bromoanisole → HCID 69507613, compound

HRID 1270023Notes

Reaction equation

[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([O:9][CH3:10])=[CH:5][CH:4]=1.[P:11](Cl)(Cl)(Cl)=[O:12].[C:16]([Mg]Cl)([CH3:19])([CH3:18])[CH3:17].[CH3:22][O:23][C:24]1[CH:29]=[CH:28][C:27]([Mg]Br)=[CH:26][CH:25]=1>BrCCBr.O1CCCC1>[CH3:10][O:9][C:6]1[CH:7]=[CH:8][C:3]([P:11](=[O:12])([C:27]2[CH:28]=[CH:29][C:24]([O:23][CH3:22])=[CH:25][CH:26]=2)[C:16]([CH3:19])([CH3:18])[CH3:17])=[CH:4][CH:5]=1

Participants

Conditions

Temperature: 67 °C

Procedure

Magnesium (30.1 g, 1.24 mol), tetrahydrofuran (400 mL), and 1,2-dibromoethane (1 drop) were stirred under nitrogen for 1 h. The mixture was then heated to reflux and the heating stopped. 4-Bromoanisole (224.4 g, 1.20 mol) was added as a mixture at a rate to maintain a slow reflux (67° C.) over a period of 4 h. The reaction mixture was then held for a further 3 h at 70° C. To a tetrahydrofuran (500 mL) solution of phosphorus oxychloride (92.0 g, 0.60 mol) was added by drop tert-butylmagnesium chloride (300 mL, 2.0 M, 0.60 mole) over 5.5 h and held at 40° C. for 1 h. Then the 4-methoxy-phenylmagnesium bromide solution prepared above was added by drop over 2 h at a rate to maintain 40° C. The mixture was allowed to stir for 2 days at rt. The reaction mixture was worked up to yield a pale-yellow sticky solid (135.6 g, 71%). 31P NMR (d6-DMSO): δ 44.7 (s, 43.0%), 37.8 (s, 7.0%), 26.5 (s, 7.6%), 25.4 (s, 36.4%), 14.9 (s, 6.0%).

Workup

temperatureThe mixture was then heated
temperatureto reflux
temperatureto maintain
waitheld at 40° C. for 1 h
additionabove was added by drop over 2 h at a rate
temperatureto maintain 40° C

Sources & evidence

ORD record: ord-9950310197c6461396b43580068c4ad6
Source dataset: uspto-grants-2007_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07201957B2

Reaction notes

Loading…