تفاعل #64745

معادلة التفاعل

hydride

cyclododecanol

benzyl chloride

→

Phenylmethoxycyclododecane

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المعالجة

1. 1
   أخرىreached between 60° and 70° C
2. 2
   أخرىwas observed at about 100° C.
3. 3
   أخرىresulted in a marked viscosity decrease
4. 4
   أخرىIf an efficient reflux condenser is not used
5. 5
   درجة الحرارةsome external cooling may
6. 6
   درجة الحرارةThe internal flask temperature increased to about 120° C. over ten minutes
7. 7
   درجة الحرارةThe reaction flask was heated at 120° to 125° C. for an additional hour
8. 8
   درجة الحرارةit was cooled to 25° C
9. 9
   أخرىThe 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
    استخلاصextracted with three 400 mL portions of hexane
12. 12
    أخرىThe organic layer was collected
13. 13
    غسيلwashed with two 100 mL portions of water and two 100 mL portions of aqueous sodium chloride solution
14. 14
    تجفيفThe product mixture was dried over magnesium sulfate
15. 15
    ترشيحfiltered
16. 16
    تركيزconcentrated at 50° C.
17. 17
    workup.DISTILLATIONThe product was distilled at 144°-146° C./0.2 mm
18. 18
    أخرىto give (180.7 g) 93.0% of the theoretical yield

الإجراء التجريبي

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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