Dimethylformamide → HCID 86653777, compound

HRID 1021204Notes

Reaction equation

HRID 1021204 reaction equation
Br[C:2]1[C:7]([CH3:8])=[C:6]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[C:5]([CH3:17])=[C:4]([CH3:18])[C:3]=1[O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[Li]CCCC.CN([CH:35]=[O:36])C.[NH4+].[Cl-]>C1(C)C=CC=CC=1.CCOCC.CCOC(C)=O.O>[CH2:20]([O:19][C:3]1[C:4]([CH3:18])=[C:5]([CH3:17])[C:6]([O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[C:7]([CH3:8])[C:2]=1[CH:35]=[O:36])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 86653776HCID 86653776, compoundHCID 178418339Butyllithium

Product 1

HCID 86653777HCID 86653777, compoundYield 89%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-bromo-1,4-bis(benzyloxy)-3,5,6-trimethylbenzene (5.002 g, 12.16 mmol) in 25 mL toluene and 25 mL Et2O cooled to 0° C., was added 8.2 mL n-BuLi (1.6 M in hexanes, 12.76 mmol) over ten minutes to give a clear yellow solution. After 20 min at 0° C. the solution was becoming cloudy. To this slightly cloudy solution was added DMF (3 mL, 40 mmol, 2.8 g) which clarified the solution instantly upon addition. After overnight stirring, 50 mL 20% aqueous NH4Cl was added followed by 100 mL H2O and 100 mL EtOAc. The layers were separated and the aqueous phase extracted 3×100 mL EtOAc and the combined organics washed 2×50 mL saturated aqueous NaCl, dried over Na2SO4 and concentrated to yield 3.90 g of 2,5-bis(benzyloxy)-3,4,6-trimethylbenzaldehyde as a yellow oil which solidified to a pale brown crystalline solid (3.90 g). MS M++H 361 m/z; 1H NMR (400 MHz, CDCl3) δ=10.51 (s, 1H), 7.51-7.37 (m, 10 H), 4.87 (s, 2 H), 4.74 (s, 2 H), 2.55 (s, 3 H), 2.30 (s, 3 H), 2.25 (s, 3 H) ppm plus DMF at 8.01, 2.96, 2.88 and CH2Cl2 at 5.30.

Workup

  1. customto give a clear yellow solution
  2. additioninstantly upon addition
  3. customThe layers were separated
  4. extractionthe aqueous phase extracted 3×100 mL EtOAc
  5. washthe combined organics washed 2×50 mL saturated aqueous NaCl
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-3b5ddc4b8b134156af4e3598dadaf9c5
Source dataset
uspto-grants-2014_05
Patent number
US08716527B2

Reaction notes

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