Sodium Hydroxide → Benzyl 4-[2-(tert-butoxycarbonyl)hydrazinyl]piperidine-1-carboxylate

HRID 418258Notes

Reaction equation

HRID 418258 reaction equation
O=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[CH2:4][CH2:3]1.[C:18]([O:22][C:23](=[O:26])[NH:24][NH2:25])([CH3:21])([CH3:20])[CH3:19].C([BH3-])#N.[Na+].[OH-].[Na+]>CO.C(O)(=O)C>[C:18]([O:22][C:23]([NH:24][NH:25][CH:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[CH2:4][CH2:3]1)=[O:26])([CH3:21])([CH3:20])[CH3:19]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 70091tert-Butyl carbazateHCID 643496Benzyl 4-oxopiperidine-1-carboxylateHCID 5003444Sodium cyanoborohydride

Product 1

HCID 11573844Benzyl 4-[2-(tert-butoxycarbonyl)hydrazinyl]piperidine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 887MethanolSolvent

Procedure

To a solution of benzyl 4-oxopiperidine-1-carboxylate (4.08 g, 17.5 mmol) in 50 mL of methanol was added tert-butylcarbazate (2.31 g, 17.5 mmol). The mixture was stirred at room temperature for 3 h and then was concentrated in vacuo to afford a white foam. This residue was taken up in 50 mL of 50% glacial acetic acid. To the resulting suspension was added sodium cyanoborohydride (1.1 g, 17.5 mmol) portionwise with vigorous stirring at room temperature. After the addition was complete the mixture was stirred for 3 h at room temperature. The mixture was neutralized with 1N NaOH/solid NaOH and then extracted twice with methylene chloride. The combined organics were washed with sat'd aq sodium bicarbonate and brine, dried (Na2SO4), filtered through a pad of silica gel and concentrated in vacuo to afford Example 12A, benzyl 4-(2-(tert-butoxycarbonyl)hydrazinyl)piperidine-1-carboxylate, as a solid (6.0 g) which was pure enough to be used without purification. LRMS (ESI): 350.1 (M+H)+.

Workup

  1. concentrationwas concentrated in vacuo
  2. customto afford a white foam
  3. stirringwith vigorous stirring at room temperature
  4. additionAfter the addition
  5. stirringwas stirred for 3 h at room temperature
  6. extractionextracted twice with methylene chloride
  7. washThe combined organics were washed with sat'd aq sodium bicarbonate and brine
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered through a pad of silica gel
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6bc5c1ce60f644628d364f8342964ce2
Source dataset
uspto-grants-2012_01
Patent number
US08093257B2

Reaction notes

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