Dimethylformamide → HCID 86653777, compound

HRID 1519112Notes

Reaction equation

HRID 1519112 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-]>CCOC(C)=O.O.CCOCC.C1(C)C=CC=CC=1>[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

Conditions

Temperature
0 °C

Procedure

2-Bromo-1,4-bis(benzyloxy)-3,5,6-trimethylbenzene (5.002 g, 12.16 mmol) was dissolved into 25 mL toluene and 25 mL Et2O and cooled to 0° C. To this stirred yellow solution was added 8.2 mL n-BuLi (1.6 M in hexanes, 12.76 mmol, 1.05 equiv.) over ten minutes to give a clear yellow solution. After 20 min at 0° C. the solution became 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 a yellow oil which solidified to give 2,5-bis(benzyloxy)-3,4,6-trimethylbenzaldehyde as a pale brown solid (3.90 g). MS M++H=361 m/z; 1H NMR (400 MHz, CDCl3) d=10.51 (s, 1H), 7.51-7.37 (m, 10H), 4.87 (s, 2H), 4.74 (s, 2H), 2.55 (s, 3H), 2.30 (s, 3H), 2.25 (s, 3H) ppm.

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 to a yellow oil which

Sources & evidence

ORD record
ord-2a90949d1f7c4820873294e74f0a9737
Source dataset
uspto-grants-2015_07
Patent number
US09073873B2

Reaction notes

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