反应详情

温度

125 °C

The hydride was mixed, under an argon atmosphere and by mechanical stirring, with cyclododecanol (130.0 g. 0.71 mol) and benzyl chloride (650.0 g, 5.14 mol). The reaction mixture was heated to 125° C. The mixture became very viscous when the temperature reached between 60° and 70° C. A mild exotherm was observed at about 100° C. which resulted in a marked viscosity decrease. If an efficient reflux condenser is not used, some external cooling may be necessary during the mild exotherm. The internal flask temperature increased to about 120° C. over ten minutes. The reaction flask was heated at 120° to 125° C. for an additional hour and then it was cooled to 25° C. The excess hydride was carefully destroyed by the addition of 100 mL of 95% ethanol under an argon atmosphere. The mixture was treated with 500 mL of aqueous saturated sodium chloride solution and extracted with three 400 mL portions of hexane. The organic layer was collected, washed with two 100 mL portions of water and two 100 mL portions of aqueous sodium chloride solution. The product mixture was dried over magnesium sulfate, filtered, and concentrated at 50° C. and 15 mm. The product was distilled at 144°-146° C./0.2 mm to give (180.7 g) 93.0% of the theoretical yield. Gas chromatography ("GC") showed that the product was 99% of a single component, IR (neat, cm-1) 2930, 2865, 1475, 1455, 1095 (C-O-C), 1070, 740; 13C NMR (ppm CDC13) 139.31, 128.17, 127.54, 127.21, 76.26 (α-ring carbon), 70.22 (α-chain carbon), 28.91, 24.75, 24.31, 23.30, 23.19, 20.81; MS, m/z (relative intensity) 274 (M+, 1.5), 245(0.1), 230(0.4), 183(8.2), 174(0.9),160(1.0), 145(0.8), 133(2.3), 118(2.7), 104(10.4), 91(100), 81(3.2), 65(12.7), 56(2.1). Anal calcd for C19H30O:C,83.15;H,11.02. Found: C,83.33;H,11.18.

1. customreached between 60° and 70° C
2. customwas observed at about 100° C.
3. customresulted in a marked viscosity decrease
4. customIf an efficient reflux condenser is not used
5. temperaturesome external cooling may
6. temperatureThe internal flask temperature increased to about 120° C. over ten minutes
7. temperatureThe reaction flask was heated at 120° to 125° C. for an additional hour
8. temperatureit was cooled to 25° C
9. customThe excess hydride was carefully destroyed by the addition of 100 mL of 95% ethanol under an argon atmosphere
10. additionThe mixture was treated with 500 mL of aqueous saturated sodium chloride solution
11. extractionextracted with three 400 mL portions of hexane
12. customThe organic layer was collected
13. washwashed with two 100 mL portions of water and two 100 mL portions of aqueous sodium chloride solution
14. dry with materialThe product mixture was dried over magnesium sulfate
15. filtrationfiltered
16. concentrationconcentrated at 50° C.
17. distillationThe product was distilled at 144°-146° C./0.2 mm
18. customto give (180.7 g) 93.0% of the theoretical yield