反応 #2460289

反応方程式

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

methyl 2-bromobenzoate

→

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

溶媒

pyridine

pyridine

diethyl ether

反応条件

後処理

1. 1
   洗浄To a stirred suspension under argon of sodium hydride (60% dispersion in mineral oil, 1.1 g, 46.5 mmol, washed with ligroin
2. 2
   その他to remove the oil) in pyridine (60 mL)
3. 3
   温度the mixture was heated
4. 4
   温度at reflux 16 h
5. 5
   温度cooled
6. 6
   洗浄washed successively with 10% aqueous HCl, water, and brine
7. 7
   乾燥dried over Na2SO4
8. 8
   その他The solvent was removed at reduced pressure
9. 9
   その他This crude product was purified by column chromatography
10. 10
    その他to give 25.5 g, 78% of theory) of a light brown oil

実験手順

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).

出典