Hydrazine hydrate (1:1) → tert-Butyl 4-(hydrazinecarbonyl)piperidine-1-carboxylate

HRID 713469Notes

Reaction equation

HRID 713469 reaction equation
C([C:3]1([C:16]([O-:18])=O)[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1)C.O.[NH2:20][NH2:21]>CCO.C(Cl)Cl.C(#N)C>[NH:20]([C:16]([CH:3]1[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1)=[O:18])[NH2:21]

Participants

6

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 263398931-tert-Butyl 4-ethylpiperidine-1,4-dicarboxylate

Product 1

HCID 22713165tert-Butyl 4-(hydrazinecarbonyl)piperidine-1-carboxylateYield 90.7%

Reagents, catalysts & solvents 3

HCID 6342AcetonitrileCatalystHCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 1-tert-butyl 4-ethylpiperidine-1,4-dicarboxylate (10 g, 38.9 mmol, 1.0 eq) in EtOH (100 mL) was added hydrazine hydrate (18.67 g, 389 mmol, 10 eq.) and the mixture was refluxed for 8 h. The reaction was cooled to room temperature and upon evaporation of the solvent gave a viscous liquid which was redissolved in CH2Cl2, washed with water (3×50 mL), then brine (50 mL). The organic layers were combined, dried over Na2SO4 and the solvent evaporated, leaving an yellowish oil, which upon addition of a few drops of ACN and re-evaporated yielded the title compound (8.6 g, 35.3 mmol). 1H NMR (400 MHz, MeOD) δ ppm 4.09 (d, J=13.14 Hz, 2H) 2.70-2.85 (br. s., 2H) 2.23-2.43 (m, 1H) 1.66-1.77 (m, 2H) 1.49-1.66 (m, 2H) 1.40-1.49 (m, 9H). MS (m/z, MH−): 242.2

Workup

  1. temperaturethe mixture was refluxed for 8 h
  2. customgave a viscous liquid which
  3. washwashed with water (3×50 mL)
  4. dry with materialdried over Na2SO4
  5. customthe solvent evaporated
  6. customleaving an yellowish oil, which
  7. customre-evaporated

Sources & evidence

ORD record
ord-751fff96dd694258a9d713525c4fd246
Source dataset
uspto-grants-2015_11
Patent number
US09181266B2

Reaction notes

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