反应详情

温度

0 °C

To an oven-dried 25 mL round bottom flask equipped with a Teflon-coated magnetic stir bar and rubber septum was added dicyclohexyl-(2′,4′,6′-triisopropyl-biphenyl-2-yl)-phosphane (476 mg, 1.00 mmol) and CH2Cl2 (1.0 mL). The solution was cooled to 0° C. using an ice/water bath and then concentrated H2SO4 (1.00 mL) and fuming sulfuric acid (3.0 mL, 20% SO3) were added dropwise. The solution was allowed to warm to room temperature and stir for 24 h. At this time it was cooled to 0° C. using an ice/water bath and crushed ice (˜10 g) was added. The solution turned cloudy and white in color. An aqueous solution of NaOH (6.0 M, ˜20.0 mL) was then added dropwise to the cooled solution until it became neutral (pH ˜7.0 as judged by pH paper). The aqueous solution was extracted with CH2Cl2 (3×50 mL) and concentrated under reduced pressure to give a beige solid. The crude material was then dissolved in a minimum amount of cold methanol (˜20 mL), filtered and concentrated (this cycle was repeated) to give sodium 2′-(dicyclohexyl-phosphanyl)-2,6-diisopropyl-biphenyl-4-sulfonate (4) as a beige solid (503 mg, 94%). Mp=>250° C. 1H NMR (400 MHz, CD3OD) δ: 7.52 (s, 2H), 7.46 (m, 1H), 7.22 (m, 2H), 6.90 (m, 1H), 2.24 (m, 1H), 0.71-1.83 (34H). 13C NMR (125 MHz, CD3OD) δ: 148.4, 147.9, 147.8, 147.5, 145.6, 142.8, 137.4, 137.2, 133.92, 133.91, 132.43, 132.42, 129.3, 128.1, 121.3, 121.0, 40.1, 39.9, 39.7, 39.5, 39.3, 38.8, 35.8, 35.7, 32.5, 32.3, 31.9, 30.8, 30.6, 28.7, 28.6, 28.4, 28.3, 27.7, 26.0, 25.9, 23.3, 23.1. 31P NMR (162 MHz, CD3OD) δ: −10.7. IR (neat, cm−1): 3459, 2927, 2851, 1634, 1463, 1447, 1184, 1078, 1040. Anal. Calcd for C30H42NaO3PS: C, 67.14; H, 7.89. Found: C, 66.93; H, 7.77.

1. customTo an oven-dried 25 mL round bottom flask equipped with a Teflon-coated magnetic stir bar
2. temperatureto warm to room temperature
3. temperatureAt this time it was cooled to 0° C.
4. additionwas added
5. extractionThe aqueous solution was extracted with CH2Cl2 (3×50 mL)
6. concentrationconcentrated under reduced pressure
7. customto give a beige solid
8. filtrationfiltered
9. concentrationconcentrated (this cycle