Réaction #2460289

Équation de réaction

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

methyl 2-bromobenzoate

→

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

Solvants

pyridine

pyridine

diethyl ether

Conditions de réaction

Traitement

1. 1
   LavageTo a stirred suspension under argon of sodium hydride (60% dispersion in mineral oil, 1.1 g, 46.5 mmol, washed with ligroin
2. 2
   Autreto remove the oil) in pyridine (60 mL)
3. 3
   Températurethe mixture was heated
4. 4
   Températureat reflux 16 h
5. 5
   Températurecooled
6. 6
   Lavagewashed successively with 10% aqueous HCl, water, and brine
7. 7
   Séchagedried over Na2SO4
8. 8
   AutreThe solvent was removed at reduced pressure
9. 9
   AutreThis crude product was purified by column chromatography
10. 10
    Autreto give 25.5 g, 78% of theory) of a light brown oil

Mode opératoire

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