Реакция #64745

Уравнение реакции

hydride

cyclododecanol

benzyl chloride

→

Phenylmethoxycyclododecane

Условия реакции

Обработка

1. 1
   Другоеreached between 60° and 70° C
2. 2
   Другоеwas observed at about 100° C.
3. 3
   Другоеresulted in a marked viscosity decrease
4. 4
   ДругоеIf an efficient reflux condenser is not used
5. 5
   Температураsome external cooling may
6. 6
   ТемператураThe internal flask temperature increased to about 120° C. over ten minutes
7. 7
   ТемператураThe reaction flask was heated at 120° to 125° C. for an additional hour
8. 8
   Температураit was cooled to 25° C
9. 9
   ДругоеThe 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
    Экстракцияextracted with three 400 mL portions of hexane
12. 12
    ДругоеThe organic layer was collected
13. 13
    Промывкаwashed with two 100 mL portions of water and two 100 mL portions of aqueous sodium chloride solution
14. 14
    СушкаThe product mixture was dried over magnesium sulfate
15. 15
    Фильтрацияfiltered
16. 16
    Концентрированиеconcentrated at 50° C.
17. 17
    workup.DISTILLATIONThe product was distilled at 144°-146° C./0.2 mm
18. 18
    Другоеto give (180.7 g) 93.0% of the theoretical yield

Методика

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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