Boron trifluoride etherate → 2,5-Dimethoxy-3,6-bis(methoxymethoxy)benzaldehyde

HRID 1588130Notes

Reaction equation

HRID 1588130 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([O:9][CH2:10][O:11][CH3:12])[C:6]([O:13][CH3:14])=[CH:5][C:4]=1[O:15][CH2:16][O:17][CH3:18].CN(C)CCN(C)C.C([Li])CCC.B(F)(F)F.C[CH2:37][O:38]CC>O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C.C(OCC)C.C1C=CC=CC=1.CN(C)C=O>[CH3:1][O:2][C:3]1[C:4]([O:15][CH2:16][O:17][CH3:18])=[CH:5][C:6]([O:13][CH3:14])=[C:7]([O:9][CH2:10][O:11][CH3:12])[C:8]=1[CH:37]=[O:38]

Participants

10

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 10061046HCID 10061046, compoundHCID 178418339Butyllithium

Product 1

HCID 136754192,5-Dimethoxy-3,6-bis(methoxymethoxy)benzaldehyde

Reagents, catalysts & solvents 5

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-78 °C

Procedure

10 Grams of 1,4-dimethoxy-2,5-bis(methoxymethoxy)benzene was dissolved in 500 ml of anhydrous tetrahydrofuran and 50 ml of hexamethylphosphoric triamide. Next 7 ml of N,N,N',N'-tetramethylethylenediamine (TMEDA) was added thereto, and under argon gas stream, the reaction mixture was cooled to -78° C. Then 30 ml of n-butyllithium (1.6M solution) was added dropwise to the reaction mixture and stirred for 30 minutes. Next, 10 ml of anhydrous N,N-dimethylformamide (DMF) was added, further 0.5 ml of boron trifluoride-diethyl ether (BF3 ·Et2O) (47% ether solution) was added as the reaction accelerator to the reaction mixture, and the mixture was stirred at -78° C. for 2 hours. The temperature of the reaction mixture was elevated to room temperature, then the solvent was removed by evaporation under reduced pressure, to the residue thus obtained was added 300 ml of benzene and 300 ml of diethyl ether, then the organic layer was washed 4 times with 200 ml of water, and further washed three times with 100 ml of a saturated sodium chloride aqueous solution. After concentrated the organic layer under reduced pressure, the resultant residue was treated on a silica gel column chromatography, and eluted with 20% ethyl acetate-n-hexane solution to yield 6 g of 2,5-dimethoxy-3,6-bis(methoxymethoxy)benzaldehyde. Light yellow powdery substance.

Workup

  1. stirringthe mixture was stirred at -78° C. for 2 hours
  2. customwas elevated to room temperature
  3. customthe solvent was removed by evaporation under reduced pressure, to the residue
  4. customthus obtained
  5. washthe organic layer was washed 4 times with 200 ml of water
  6. washfurther washed three times with 100 ml of a saturated sodium chloride aqueous solution
  7. concentrationAfter concentrated the organic layer under reduced pressure
  8. additionthe resultant residue was treated on a silica gel column chromatography
  9. washeluted with 20% ethyl acetate-n-hexane solution

Sources & evidence

ORD record
ord-7fe4471b1a2741c9ae5ca282cafccd76
Source dataset
uspto-grants-1993_06
Patent number
US05220042

Reaction notes

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