溴取代叔羟基.pdf

Organic Syntheses, Coll. Vol. 10, p.88 (2004); Vol. 78, p.142 (2002). BICYCLOPROPYLIDENE [ Cyclopropane, cyclopropylidene ] Submitted by Armin de Meijere, Sergei I. Kozhushkov, and Thomas Späth1 . Checked by Florence Geneste and Andrew B. Holmes. 1. Procedure A. 1-Cyclopropylcyclopropanol. A 4-L, four-necked, round-bottomed flask equipped with a mechanical stirrer, thermometer and reflux condenser is charged under nitrogen with 120.2 g (122 mL, 1.2 mol) of methyl cyclopropanecarboxylate (Note 1), 85.3 g (89.3 mL; 0.30 mol) of titanium tetraisopropoxide , and 1.45 L of anhydrous ether (Note 2). To the well-stirred solution, 840 mL (2.52 mol) of ethylmagnesium bromide as a 3 M solution in ether is added over a period of 4 hr (Notes 3, 4). The temperature is maintained between 20°C and 25°C with a water bath. After the addition is complete the black or dark-brown mixture is stirred for an additional 0.5 hr at the same temperature, then cooled to −5°C, and the reaction is quenched by careful addition of 1.56 L of ice-cold aqueous 10% sulfuric acid while the temperature is maintained between −5°C and 0°C with an acetone-dry ice bath. The mixture is stirred at 0°C for an additional 1 hr, in which time the precipitate should have completely dissolved (Note 5), and then is transferred to a 4-L separatory funnel. The inorganic phase is extracted with 360 mL of ether (Note 6). The combined ethereal phases are washed with two 600-mL portions of saturated sodium hydrogen carbonate solution, 600 mL of saturated brine, dried over anhydrous magnesium sulfate , and filtered. The solvent is removed from the filtrate under water-aspirator vacuum at 20°C (Note 7)to give 116 g (99%) of 1