N,N,N',N'-Tetramethylethylenediamine → 2-Bromo-3,4-bis(methyloxy)-1-{[(methyloxy)methyl]oxy}benzene
Reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([O:9][CH2:10][O:11][CH3:12])=[CH:5][C:4]=1[O:13][CH3:14].CN(CCN(C)C)C.C([Li])(C)(C)C.[Br:28]Br>C(OCC)C>[Br:28][C:5]1[C:4]([O:13][CH3:14])=[C:3]([O:2][CH3:1])[CH:8]=[CH:7][C:6]=1[O:9][CH2:10][O:11][CH3:12]Participants
6
Reactant 4
Product 1
Reagents, catalysts & solvents 1
Procedure
To a stirred solution of 1,2-bis(methyloxy)-4-{[(methyloxy)methyl]oxy}benzene (4.0 g) and TMEDA (3.93 ml) in dry diethyl ether (50 ml) was added tert-butyllithium (1.7M in pentane, 23.76 ml) at −70 C. The reaction was stirred at this temperature for 1 h before adding bromine (0.15 ml). This was allowed to stir at 0 C. for 3 h. The reaction was quenched by addition of 20% aqueous sodium dithionite and extracted with ethyl acetate. The organics were washed with dilute hydrochloric acid, aqueous sodium bicarbonate, brine and dried over sodium sulphate to yield a crude product. This was purified through silica, eluting with 0-10% ethyl acetate in hexane to give the title compound, 1.4 g
Workup
- stirringto stir at 0 C
- waitfor 3 h
- customThe reaction was quenched by addition of 20% aqueous sodium dithionite
- extractionextracted with ethyl acetate
- washThe organics were washed with dilute hydrochloric acid, aqueous sodium bicarbonate, brine
- dry with materialdried over sodium sulphate
- customto yield a crude product
- customThis was purified through silica
- washeluting with 0-10% ethyl acetate in hexane
Sources & evidence
- ORD record
- ord-7419c804e6f34923966e73fd441ad994
- Source dataset
- uspto-grants-2016_09
- Patent number
- US09447074B2
Reaction notes
Loading…