Reaction #2460289

Reaction equation

2,4-di-(tert-amyl)phenol

methyl 2-bromobenzoate

→

methyl 2,4-di-(tert-amyl)phenoxybenzoate

Solvents

pyridine

pyridine

diethyl ether

Conditions

Workup

1. 1
   WashTo a stirred suspension under argon of sodium hydride (60% dispersion in mineral oil, 1.1 g, 46.5 mmol, washed with ligroin
2. 2
   Otherto remove the oil) in pyridine (60 mL)
3. 3
   Temperaturethe mixture was heated
4. 4
   Temperatureat reflux 16 h
5. 5
   Temperaturecooled
6. 6
   Washwashed successively with 10% aqueous HCl, water, and brine
7. 7
   Dryingdried over Na2SO4
8. 8
   OtherThe solvent was removed at reduced pressure
9. 9
   OtherThis crude product was purified by column chromatography
10. 10
    Otherto give 25.5 g, 78% of theory) of a light brown oil

Procedure

First, methyl 2,4-di-(tert-amyl)phenoxybenzoate was prepared. To a stirred suspension under argon of sodium hydride (60% dispersion in mineral oil, 1.1 g, 46.5 mmol, washed with ligroin to remove the oil) in pyridine (60 mL) was added dropwise a solution of 2,4-di-(tert-amyl)phenol (12.0 g, 51.2 mmol) in 20 mL of pyridine. The mixture was stirred for 2 h at room temperature and then treated dropwise with a solution of methyl 2-bromobenzoate (10 g, 46.5 mmol) in 10 mL of pyridine. Copper (I) chloride (1.15 g, 11.6 mmol) was added, and the mixture was heated at reflux 16 h and then cooled to ambient. The mixture was diluted with diethyl ether, washed successively with 10% aqueous HCl, water, and brine, and then dried over Na2SO4. The solvent was removed at reduced pressure to deposit dark brown oil. This crude product was purified by column chromatography to give 25.5 g, 78% of theory) of a light brown oil. 1H NMR (CDCl3): δ 0.70 (t, 6H), 1.3 (s, 6H), 1.4 (s, 6H), 1.63 (q, 2H), 1.85 (q, 2H), 3.85 (s, 3H), 6.68 (d, 1H), 6.82 (d, 1H), 7.05 (m, 2H), 7.3 (br s, 1H), 7.35 (t, 1H), 7.9 (dd, 1H).

Source