反应详情

温度

94 °C

A one liter capacity four neck flask was charged with 4.26 g (0.177 mol) of magnesium, the atmosphere in the flask was replaced with nitrogen gas and then a small amount of iodine was added thereto. To this were added 20 ml of dry tetrahydrofuran and, using an injector, 0.6 ml of 1,2-dibromoethane in that order. Through a dropping funnel and spending 7 hours, to this was added dropwise a mixture solution of 330 ml toluene and 90 ml tetrahydrofuran containing 32.5 g (0.0774 mol) of 2,2'-dibromo-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene synthesized in (1). During this step, temperature of the reaction solution was kept at 80° to 90° C. After completion of the dropwise addition, the reaction mixture was stirred at 94° C. for 19 hours. After cooling to 5° C., to the reaction mixture was added dropwise 34.27 g (0.148 mol) of diphenylphosphinic acid chloride spending 30 minutes. Next, the reaction mixture was stirred at 72° C. for 3.5 hours. The resulting reaction mixture was cooled to room temperature and mixed with 100 ml of water, heated to 80° C. and stirred for 20 minutes, and then cooled again to room temperature and allowed to stand overnight. The thus precipitated white solid was collected by filtration, washed twice with 100 ml of water, washed again with 100 ml of hexane-toluene (9:1) mixture solution and then dried at 70° C. for 7 hours under a reduced pressure (0.1 mmHg) to obtain 32.8 g of the title compound with a yield of 64.1%.

1. customwas kept at 80° to 90° C
2. additionAfter completion of the dropwise addition
3. temperatureAfter cooling to 5° C., to the reaction mixture
4. stirringNext, the reaction mixture was stirred at 72° C. for 3.5 hours
5. customThe resulting reaction mixture
6. temperaturewas cooled to room temperature
7. temperatureheated to 80° C.
8. stirringstirred for 20 minutes
9. temperaturecooled again to room temperature
10. waitto stand overnight
11. filtrationThe thus precipitated white solid was collected by filtration
12. washwashed twice with 100 ml of water
13. washwashed again with 100 ml of hexane-toluene (9:1) mixture solution
14. customdried at 70° C. for 7 hours under a reduced pressure (0.1 mmHg)