- DOI:
http://dx.doi.org/10.1002/chem.201502286
procedure:
To a solution of diethyl oxalate (1.46 g, 10 mmol) in THF (40 mL) at -40 oC, cyclohexyl
magnesium bromide (1.0 M in THF, 10 mL) was added dropwise for 10 min. The reaction
mixture was warmed to 0 °C for 5 min, and quenched with 10% (v/v) HCl (4.0 mL), water
S5
(20 mL) was then added. The mixture was extracted with ethyl acetate (2 x 40 mL). The
combined organic phase was washed with water (20 mL), brine (20 mL), dried with
sodium sulfate, and then filtered. The filtrated solution was concentrated to give the crude
product, ethyl 2-cyclohexyl-2-oxoacetate, which was used directly without purification
in the next step.
To a solution of ethyl 2-cyclohexyl-2-oxoacetate in MeOH (25 mL) was added water
(60 mL) and NaOH (50 wt %, 20 mL) at room temperature. The reaction mixture was
stirred at 60 °C for 1.5 h. The reaction mixture was cooled with ice/water bath, and
acidified with 15 % (v/v) HCl (pH=1.0). The mixture was extracted with ethyl acetate (2
x 100 mL). The extracts were washed with brine, and dried with sodium sulfate. After
filtration, the solvent was removed to give a white solid S14 (1.40 g, 90 %).[/cut]
Поделитесь пожалуйста Вашим мнением по пунктам.
1. стоит ли доверять этой методе?
2. почему кетогруппа продукта не реагирует с Гриньяром?
3. насколько эта реакция может быть перенесена на другие Гриньяры (например адамант-1-илмагнийбромид)?
Благодарю за отклики.
