Benzaldehyde → 2-Hydroxy 4-methoxy-5-(1,1-dimethylethyl)benzaldehyde

HRID 1165445Notes

Reaction equation

HRID 1165445 reaction equation
[CH:1](=[O:8])C1C=CC=CC=1.[CH3:9][O:10][C:11]1[CH:12]=[C:13]([OH:21])[CH:14]=[CH:15][C:16]=1[C:17]([CH3:20])([CH3:19])[CH3:18].COC(Cl)Cl.Cl>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[OH:21][C:13]1[CH:12]=[C:11]([O:10][CH3:9])[C:16]([C:17]([CH3:18])([CH3:20])[CH3:19])=[CH:15][C:14]=1[CH:1]=[O:8]

Participants

7

Reactant 4

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 21004Methane, dichloromethoxy-HCID 122529764-Tert-butyl-3-methoxyphenol

Product 1

HCID 198618272-Hydroxy 4-methoxy-5-(1,1-dimethylethyl)benzaldehydeYield 87%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

The benzaldehyde used in Example 6 was prepared as follows: (1) To a stirred solution of 2.91 g (16.14 mmol) of 3-methoxy-4-(1,1-dimethylethyl)phenol (see C. J. R. Adderley and F. R. Hewgill, J. Chem. Soc., (C), 1438, (1968) as an example of how to obtain this material) in 65 ml of methylene chloride and cooled in an ice-water bath was added 6.12 g (3.54 ml, 32.30 mmol) of titanium (IV) chloride followed by 3.06 g (2.41 ml, 26.64 mmol) of 1,1-dichlorodimethyl ether. The reaction mixture was stirred for 10 minutes and then poured into 16 ml of lN hydrochloric acid. The organic phase was separated, dried and evaporated. The residue was chromatographed on silica gel (146 g) using 1.5:98.5 (v/v) ether,hexane as eluent. There was obtained 2.92 g (14.01 mmol, 87%) of 2-hydroxy-4-methoxy-5-(1,1-dimethylethyl)benzaldehyde as a white solid after crystallization from pentane; mp 75°-78° C.

Workup

  1. customwas prepared
  2. temperaturecooled in an ice-water bath
  3. customThe organic phase was separated
  4. customdried
  5. customevaporated
  6. customThe residue was chromatographed on silica gel (146 g)

Sources & evidence

ORD record
ord-8fd7d4478c3e4267980fcf98f96b7636
Source dataset
uspto-grants-1990_03
Patent number
US04910202

Reaction notes

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