Hydrochloric Acid → 4-Propynoyl-2,6-di-tert-butylphenol

Beteiligte Stoffe

Reaktionsschritte

A solution of 3.40 g (20.0 mmol) of bis(trimethylsilyl)acetylene and 4.03 g (15.0 mmol) of 3,5-di-t-butyl-4-hydroxybenzoyl chloride [which is prepared from 3,5-di-t-butyl-4-hydroxybenzoic acid by treatment with oxalyl chloride (benzene, 60°, 2h)] in 80 mL of methylene chloride is treated at -78° with 1.78 mL (16.5 mmol) of titanium tetrachloride. The resulting dark mixture is stirred at -78° for 30 minutes and then is allowed to warm to 0° and stirred for an additional 30 minutes. The reaction solution is poured into 3N HCl and the layers are separated. The aqueous portion is extracted with pentane and the combined organic phase is washed with sat. NaCl and dried (MgSO4). The crude silylacetylene intermediate is concentrated, dissolved in 100 mL of methanol and then is treated at room temperature with 20 mL of 0.01M borax. After stirring the mixture at 25° overnight, it is poured into 3N HCl and the aqueous layer is extracted with pentane. The combined organic phase is washed with sat. NaCl and dried (MgSO4). Recyrstallization from hexane affords 2.40 g (62%) of the title compound: mp 100°-101°; IR (CCl4) 3620(s), 3300(m), 2950(s), 2090(m), 1640(s), 1580(s), 1290(s), 1215(vs) cm-1 ; 1H-NMR (CDCl3)δ(ppm) 1.45(s, 18H), 3.30(s, 1H), 5.80(s, 1H), 8.00(s, 2H); 13C-NMR (CDCl3)δ30.09, 34.41, 79.84, 80.80, 127.76, 128.51, 136.34, 160.02, 176.67 ppm.

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