Trimethyl orthoformate → 1-Bromomethyl-3-dimethoxymethyl-5-methyl-benzene

HRID 426173Notes

Reaction equation

HRID 426173 reaction equation
[Br:1][CH2:2][C:3]1[CH:4]=[C:5]([CH:8]=[C:9]([CH3:11])[CH:10]=1)C=O.[CH:12](OC)([O:15][CH3:16])[O:13][CH3:14].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>CO>[Br:1][CH2:2][C:3]1[CH:10]=[C:9]([CH3:11])[CH:8]=[C:5]([CH:12]([O:15][CH3:16])[O:13][CH3:14])[CH:4]=1

Participants

5

Reactant 3

HCID 9005Trimethyl orthoformateHCID 521998p-Toluenesulfonic acid monohydrateHCID 591847343-Bromomethyl-5-methyl-benzaldehyde

Product 1

HCID 591848751-Bromomethyl-3-dimethoxymethyl-5-methyl-benzene

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of crude 3-bromomethyl-5-methyl-benzaldehyde (21 g, 98.51 mmol), trimethyl orthoformate (21.88 ml), and p-toluenesulfonic acid monohydrate (1.9 g) in anhydrous methanol (100 ml) was refluxed for 2 hr. After cooling to room temperature, the mixture was evaporated in vacuo. The residue was dissolved in ether, washed with aqueous sodium bicarbonate solution, dried with anhydrous magnesium sulfate, filtered, and evaporated in vacuo to give a crude product as a pale brown oil. The crude product was purified by silica gel column chromatography (eluent, ether:hexanes (1:9)) to afford 7.6 g (29% for 2 steps) of a colorless oil. 1H NMR (300 MHz, CDCl3) δ 2.35 (3H, s), 3.33 (6H, s), 4.47 (2H, s), 5.32 (1H, s), 7.17 (1H, s), 7.19 (1H, s), 7.27 (1H, s).

Workup

  1. temperaturewas refluxed for 2 hr
  2. customthe mixture was evaporated in vacuo
  3. dissolutionThe residue was dissolved in ether
  4. washwashed with aqueous sodium bicarbonate solution
  5. dry with materialdried with anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customevaporated in vacuo

Sources & evidence

ORD record
ord-42e93b9f3caa4f4596dbfc57b74446be
Source dataset
uspto-grants-2012_01
Patent number
US08106064B2

Reaction notes

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