3-Hydroxybenzaldehyde → 3-Tert-butoxybenzaldehyde

HRID 990443Notes

Reaction equation

HRID 990443 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6].[C:10](OC(=N)C(Cl)(Cl)Cl)([CH3:13])([CH3:12])[CH3:11].B(F)(F)F.CCOCC.C(=O)(O)[O-].[Na+]>C(Cl)Cl.C1CCCCC1.CCCCCC.C(OCC)(=O)C>[C:10]([O:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[O:6])([CH3:13])([CH3:12])[CH3:11]

Participants

9

Reactant 4

HCID 1013-HydroxybenzaldehydeHCID 8000Boron trifluoride etherateHCID 516892Sodium BicarbonateHCID 2734700Tert-butyl 2,2,2-trichloroethanimidate

Product 1

HCID 157122243-Tert-butoxybenzaldehydeYield 32%

Reagents, catalysts & solvents 4

HCID 6344DichloromethaneSolvent2×HCID 8058HexaneSolventHCID 8078CyclohexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

EX-654A) 3-Hydroxybenzaldehyde (4.08 g, 33.4 mmol) was slurried in 50 mL of anhydrous CH2Cl2 and added to t-butyl-2,2,2-trichloroacetimidate (25.0 g, 114 mmol) in 200 mL of anhydrous cyclohexane with an additional 50 mL of CH2Cl2 used in transfer. The mixture was stirred under nitrogen until uniform, then boron trifluoride diethyl etherate (0.50 mL, 4 mmol) was added via syringe and stirring was continued for 1 h. Powdered sodium bicarbonate (50 g, 0.6 mmol) was added, and the solution was filtered through a silica gel plug, washing the plug with hexane. The solvent was evaporated to give crude product 3.54 g (59%) as an amber oil (85% pure by GC analysis). Chromatography on silica gel eluting with 0-10% ethyl acetate in hexane gave 1.88 g (32%) of pure 3-t-butoxybenzaldehyde product as a colorless oil. 1H NMR (C6D6) δ9.59 (s, 1H), 7.44 (br s, 1H), 7.20 (d t, 1H), 6.92 (m, 2H), 1.07 (s, 9H).

Workup

  1. stirringstirring
  2. filtrationthe solution was filtered through a silica gel plug
  3. washwashing the plug with hexane
  4. customThe solvent was evaporated
  5. customto give crude product 3.54 g (59%) as an amber oil (85% pure by GC analysis)

Sources & evidence

ORD record
ord-44f52485bf874692b811ec8717f154ad
Source dataset
uspto-grants-2002_10
Patent number
US06458803B1

Reaction notes

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