Hydrochloric Acid → 4-(Trimethylsilyl)but-3-yn-2-ol
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Cl[CH2:2][C:3]([O-:5])=O.[CH2:6]([Mg]Br)[CH3:7].[CH3:10][Si:11](Cl)([CH3:13])[CH3:12].Cl>CCOCC>[CH3:10][Si:11]([CH3:13])([CH3:12])[C:6]#[C:7][CH:3]([OH:5])[CH3:2]Cl[CH2:2][C:3]([O-:5])=O.[CH2:6]([Mg]Br)[CH3:7].[CH3:10][Si:11](Cl)([CH3:13])[CH3:12].Cl>CCOCC>[CH3:10][Si:11]([CH3:13])([CH3:12])[C:6]#[C:7][CH:3]([OH:5])[CH3:2]To a solution of ii (10.0 g, 0.14 mol) in ether (200 mL) was added ethylmagnesium bromide (105 mL, 3M in THF, 0.32 mol) dropwise at 0° C. The resulting solution was refluxed for 1.5 h. After the reaction solution was cooled to 0° C., trimethylsilyl chloride (40 mL, 0.32 mol) was added. The solution was warmed to room temperature and stirred overnight. Hydrochloric acid (100 mL, 10%) was added at 0° C. After 20 min, the two layers were separated. The aqueous layer was extracted with ether (2×50 mL). The combined organic solutions were dried over anhydrous magnesium sulfate, filtered and concentrated. Distillation of the residue gave 19.9 g (98%) ii-a as a colorless liquid: bp 80.5°-83.5° C./17.5 mm Hg; IR (neat) 3337, 2175, 1452, 1251, 1119, 1048, and 946 cm-1 ; 1H NMR (CDCl3, 300 MHz) δ 4.42 (q, J=6.6 Hz, 1 H, CHOH), 3.12 (br S, 1 H, OH), 1,16 (d, J=6.6 Hz, 3 H, CHCH3), and 0.08 (s, 9 H, SiCH3); 13C NMR (CDCl3, 75.5 MHz) δ 108.12, 88.19, 58.61, 24. 05, and 0.01.
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