Hydrochloric Acid → 4-Hydrazinylcyclohexanol hydrochloride

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.

1. temperaturewas refluxed for 1.5 hours
2. temperaturerefluxing
3. customreaction
4. customresulting in precipitation of a white solid
5. temperatureThe mixture was heated at 70° C. for 6 hours
6. temperaturecooled to room temperature
7. concentrationThe reaction mixture was concentrated
8. customazeotroped with toluene
9. customto remove nearly all of the water
10. dissolutionThe residue was then dissolved in hot isopropanol
11. temperaturecooled back down to room temperature
12. customAny insoluble material was removed by filtration
13. additionThe filtrate was diluted with ether
14. temperaturechilled
15. additionThe material dropped out of solution as an oil/gum
16. customThe mother liquor was removed by decantation
17. washThe oil/gum was then washed with ether
18. customdried in vacuo

ORDレコード

ord-8b2fc696d54c44e1a08ac331fbbdcfe5

出典データセット

uspto-grants-2010_06

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07728029B2