반응 #64745

반응 방정식

hydride

cyclododecanol

benzyl chloride

→

Phenylmethoxycyclododecane

반응 조건

후처리

1. 1
   기타reached between 60° and 70° C
2. 2
   기타was observed at about 100° C.
3. 3
   기타resulted in a marked viscosity decrease
4. 4
   기타If an efficient reflux condenser is not used
5. 5
   온도some external cooling may
6. 6
   온도The internal flask temperature increased to about 120° C. over ten minutes
7. 7
   온도The reaction flask was heated at 120° to 125° C. for an additional hour
8. 8
   온도it was cooled to 25° C
9. 9
   기타The 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
    추출extracted with three 400 mL portions of hexane
12. 12
    기타The organic layer was collected
13. 13
    세척washed with two 100 mL portions of water and two 100 mL portions of aqueous sodium chloride solution
14. 14
    건조The product mixture was dried over magnesium sulfate
15. 15
    여과filtered
16. 16
    농축concentrated at 50° C.
17. 17
    workup.DISTILLATIONThe product was distilled at 144°-146° C./0.2 mm
18. 18
    기타to give (180.7 g) 93.0% of the theoretical yield

실험 절차

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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