p-Toluenesulfonic acid → 2-Bromo-1-(diethoxymethyl)-4-fluorobenzene

HRID 428025Notes

Reaction equation

HRID 428025 reaction equation
[Br:1][C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1C=O.BrC1C=C(F)C=CC=1C.C(O[CH:23]([O:27][CH2:28][CH3:29])[O:24][CH2:25][CH3:26])C.C1(C)C=CC(S(O)(=O)=O)=CC=1>C(O)C.C(=O)([O-])[O-].[Na+].[Na+]>[CH2:28]([O:27][CH:23]([O:24][CH2:25][CH3:26])[C:3]1[CH:6]=[CH:7][C:8]([F:10])=[CH:9][C:2]=1[Br:1])[CH3:29]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 31214Ethyl orthoformateHCID 740162-Bromo-4-fluorotolueneHCID 27733192-Bromo-4-fluorobenzaldehyde

Product 1

HCID 183576052-Bromo-1-(diethoxymethyl)-4-fluorobenzene

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 10340Sodium CarbonateSolvent

Procedure

To a solution of 6.5 g of 2-bromo4-fluoro-benzaldehyde (prepared by the oxidation of 2-bromo-4-fluoro-toluene by the method reported by V. J. Bauer, B. J. Duffy, D. Hoffman, S. S. Klioze, R. W. Kosley, Jr., A. R. McFadden, L. L. Martin, H. H. Ong and H. M. Geyer III, J. Med. Chem., 1976, 19, 1315) in 25 ml of ethanol was added triethylorthoformate followed by 0.05 g of p-toluene sulfonic acid. The solution was stirred at room temperature for 2.25 h then diluted with 100 ml of a 5% sodium carbonate solution and extracted with two 100 ml portions of ether. The combined organic layers were washed with 50 ml of brine and dried over sodium sulfate. Evaporation of the solvent yielded 8.8 g of 2-bromo4-fluoro-benzaldehyde diethyl acetal as an oil, 1H NMR (200 MHz; CDCl3) δH 5.60 (CHO3).

Workup

  1. extractionextracted with two 100 ml portions of ether
  2. washThe combined organic layers were washed with 50 ml of brine
  3. dry with materialdried over sodium sulfate
  4. customEvaporation of the solvent

Sources & evidence

ORD record
ord-004b082d24bb459191da304bdf2ad281
Source dataset
uspto-grants-2001_11
Patent number
US06313139B1

Reaction notes

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