反应 #64745

反应方程式

hydride

cyclododecanol

benzyl chloride

→

Phenylmethoxycyclododecane

反应条件

后处理

1. 1
   其他reached between 60° and 70° C
2. 2
   其他was observed at about 100° C.
3. 3
   其他resulted in a marked viscosity decrease
4. 4
   其他If an efficient reflux condenser is not used
5. 5
   温度some external cooling may
6. 6
   温度The internal flask temperature increased to about 120° C. over ten minutes
7. 7
   温度The reaction flask was heated at 120° to 125° C. for an additional hour
8. 8
   温度it was cooled to 25° C
9. 9
   其他The excess hydride was carefully destroyed by the addition of 100 mL of 95% ethanol under an argon atmosphere
10. 10
    workup.ADDITIONThe mixture was treated with 500 mL of aqueous saturated sodium chloride solution
11. 11
    萃取extracted with three 400 mL portions of hexane
12. 12
    其他The organic layer was collected
13. 13
    洗涤washed with two 100 mL portions of water and two 100 mL portions of aqueous sodium chloride solution
14. 14
    干燥The product mixture was dried over magnesium sulfate
15. 15
    过滤filtered
16. 16
    浓缩concentrated at 50° C.
17. 17
    workup.DISTILLATIONThe product was distilled at 144°-146° C./0.2 mm
18. 18
    其他to give (180.7 g) 93.0% of the theoretical yield

实验过程

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.

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