Methane, dichloromethoxy- → 2,5-Dimethoxy-3,4,6-trimethylbenzaldehyde

HRID 1030602Notes

Reaction equation

HRID 1030602 reaction equation
C[O:2][C:3]1[CH:8]=[C:7]([CH3:9])[C:6]([O:10][CH3:11])=[C:5]([CH3:12])[C:4]=1[CH3:13].[CH3:14][O:15][CH:16](Cl)Cl>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[CH3:14][O:15][C:16]1[C:4]([CH3:13])=[C:5]([CH3:12])[C:6]([O:10][CH3:11])=[C:7]([CH3:9])[C:8]=1[CH:3]=[O:2]

Participants

5

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 109240691,4-Dimethoxy-2,3,5-trimethyl-benzene

Product 1

HCID 27526052,5-Dimethoxy-3,4,6-trimethylbenzaldehyde

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

1,4-Dimethoxy-2,3,5-trimethylbenzene, 9.00 g (50 mmole), was dissolved in CH2C12(60 ml) and stirred with ice-cooling. After addition of 14.4 g (50×2.5 mmole) of dichloromethyl methyl ether, 13.8 ml (50×2.5 mmole) of titanium tetrachloride dissolved in CH2Cl2 (30 ml) was added dropwise over 15 minutes. After stirring for further 15 minutes with ice-cooling, the ice bath was removed and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into crashed ice (about 200 g) and stirred vigorously for 30 minutes. The CH2Cl2 layer was washed with water (3 times), and dried (MgSO4), from which CH2Cl2 was evaporated off. The residue was recrystallized from isopropyl ether/hexane (1:1), to give 6.18 g of 2,5-dimethoxy-3,4,6-trimethylbenzaldehyde. The mother liquor was concentrated, and the residue was purified with silica gel (60 g) column chromatography (eluted with isopropyl ether), to give 3.70 g of 2,5-dimethoxy-3,4,6-trimethylbenzaldehyde.

Workup

  1. temperaturecooling
  2. additionwas added dropwise over 15 minutes
  3. stirringAfter stirring for further 15 minutes with ice-
  4. temperaturecooling
  5. customthe ice bath was removed
  6. stirringthe mixture was stirred at room temperature for 4 hours
  7. additionThe reaction mixture was poured
  8. stirringstirred vigorously for 30 minutes
  9. washThe CH2Cl2 layer was washed with water (3 times)
  10. dry with materialdried (MgSO4)
  11. customfrom which CH2Cl2 was evaporated off
  12. customThe residue was recrystallized from isopropyl ether/hexane (1:1)

Sources & evidence

ORD record
ord-296db0549eac49fa9b461ad8ce2a9ce6
Source dataset
uspto-grants-1992_04
Patent number
US05106858

Reaction notes

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