N,N,N',N'-Tetramethylethylenediamine → 2-Bromo-3,4-bis(methyloxy)-1-{[(methyloxy)methyl]oxy}benzene

HRID 879990Notes

Reaction equation

HRID 879990 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

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 24408BromineHCID 149105661,2-Dimethoxy-4-(methoxymethoxy)benzeneHCID 178418306HCID 178418306, compound

Product 1

HCID 117374882-Bromo-3,4-bis(methyloxy)-1-{[(methyloxy)methyl]oxy}benzene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

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

  1. stirringto stir at 0 C for 3 h
  2. customThe reaction was quenched by addition of 20% aqueous sodium dithionite
  3. extractionextracted with ethyl acetate
  4. washThe organics were washed with dilute hydrochloric acid, aqueous sodium bicarbonate, brine
  5. dry with materialdried over sodium sulphate
  6. customto yield a crude product
  7. customThis was purified through silica
  8. washeluting with 0-10% ethyl acetate in hexane

Sources & evidence

ORD record
ord-d78fdde0049b4daa852955a7066ef81b
Source dataset
uspto-grants-2015_03
Patent number
US08993560B2

Reaction notes

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