Phenol, 3-(1,1-dimethylethyl)- → 4-tert-Butyl-2-hydroxybenzaldehyde

HRID 1869947Notes

Reaction equation

HRID 1869947 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([OH:11])[CH:8]=[CH:9][CH:10]=1)([CH3:4])([CH3:3])[CH3:2].Cl[CH:13]([O:15]C(Cl)Cl)Cl>ClCCl.[Ti](Cl)(Cl)(Cl)Cl>[C:1]([C:5]1[CH:10]=[CH:9][C:8]([CH:13]=[O:15])=[C:7]([OH:11])[CH:6]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 2

HCID 11450Phenol, 3-(1,1-dimethylethyl)-HCID 558102Bis(dichloromethyl) ether

Product 1

HCID 137652724-tert-Butyl-2-hydroxybenzaldehydeYield 77%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

A stirred, cooled (ice bath) solution of 3-tert-butyl phenol (1.5 g, 10 mmol) in anhydrous dichloromethane was treated with titanium tetrachloride (1.86 mL, 17 mmol) followed by ∀,∀-dichloromethyl ether (0.9 mL, 20 mmol). The reaction was allowed to warm to ambient temperature over 1 h, quenched cautiously with ice and water and extracted with dichloromethane. The organic extract was washed with water and brine, dried over sodium sulfate, filtered and evaporated in vacuo to a residue that was subjected to flash column chromatography using 2-2.5% ethyl acetate in hexane as the eluent to afford the title compound (1.37 g, 77%). 1H NMR (300 MHz, CDCl3): δ 11.02 (s, 1H), 9.81 (s, 1H), 7.45 (d, J=8.2 Hz, 1H), 7.03 (dd, J=8.2, 1.7 Hz, 1H), 6.99 (d, J=1.7 Hz, 1H), 1.31 (s, 9H).

Workup

  1. customquenched cautiously with ice and water
  2. extractionextracted with dichloromethane
  3. extractionThe organic extract
  4. washwas washed with water and brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. customevaporated in vacuo to a residue that

Sources & evidence

ORD record
ord-752e2f03011143cc9b01f25124c050c9
Source dataset
uspto-grants-2009_12
Patent number
US07638648B2

Reaction notes

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