반응 #41167

반응 방정식

HCl

methanol

N′-[4-(tert-Butyl-dimethyl-silanyloxy)-cyclohexylidene]-hydrazinecarboxylic acid tert-butyl ester

Sodium cyanoborohydride

→

4-hydrazino-cyclohexanol hydrochloride

수율 96.0%

용매

tetrahydrofuran

반응 조건

후처리

1. 1
   온도was refluxed for 1.5 hours
2. 2
   온도refluxing
3. 3
   기타reaction
4. 4
   기타resulting in precipitation of a white solid
5. 5
   온도The mixture was heated at 70° C. for 6 hours
6. 6
   온도cooled to room temperature
7. 7
   농축The reaction mixture was concentrated
8. 8
   기타azeotroped with toluene
9. 9
   기타to remove nearly all of the water
10. 10
    workup.DISSOLUTIONThe residue was then dissolved in hot isopropanol
11. 11
    온도cooled back down to room temperature
12. 12
    기타Any insoluble material was removed by filtration
13. 13
    workup.ADDITIONThe filtrate was diluted with ether
14. 14
    온도chilled
15. 15
    workup.ADDITIONThe material dropped out of solution as an oil/gum
16. 16
    기타The mother liquor was removed by decantation
17. 17
    세척The oil/gum was then washed with ether
18. 18
    기타dried in vacuo

실험 절차

N′-[4-(tert-Butyl-dimethyl-silanyloxy)-cyclohexylidene]-hydrazinecarboxylic acid tert-butyl ester (4.103 g, 11.98 mmol) was dissolved in dry tetrahydrofuran (11.5 mL) and dry methanol (15.0 mL). Sodium cyanoborohydride (0.945 g, 14.29 mmol) was added portionwise. When the effervescence subsided the mixture was refluxed for 1.5 hours. At this time a small additional amount of sodium cyanoborohydride (0.047 g, 0.75 mmol) was added and refluxing was continued for another 30 minutes to insure complete reaction. After cooling to room temperature, 6N HCl (10 mL) was added, resulting in precipitation of a white solid. The mixture was heated at 70° C. for 6 hours and then cooled to room temperature and stirred for 12 hours. The reaction mixture was concentrated and azeotroped with toluene to remove nearly all of the water. The residue was then dissolved in hot isopropanol and cooled back down to room temperature. Any insoluble material was removed by filtration. The filtrate was diluted with ether and chilled. The material dropped out of solution as an oil/gum. The mother liquor was removed by decantation. The oil/gum was then washed with ether and dried in vacuo to give 4-hydrazino-cyclohexanol hydrochloride (1.920 g, 96%). A second crop (0.261 g, 13%) was collected from the mother liquor. The yield was greater than theoretical due to the presence of trapped solvent and small impurities. The material was used without any further purification.

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