tert-Butyl carbazate → N'-(oxan-4-yl)(tert-butoxy)carbohydrazide

HRID 476031

Reaction equation

HRID 476031 reaction equation
[O:1]1[CH2:6][CH2:5][C:4](=O)[CH2:3][CH2:2]1.[NH:8]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[NH2:9].C([BH3-])#N.[Na+]>CO>[O:1]1[CH2:6][CH2:5][CH:4]([NH:9][NH:8][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:3][CH2:2]1

Participants

5

Reactant 3

HCID 70091tert-Butyl carbazateHCID 121599Tetrahydro-4H-pyran-4-oneHCID 5003444Sodium cyanoborohydride

Product 1

HCID 45092245N'-(oxan-4-yl)(tert-butoxy)carbohydrazide

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Tetrahydro-4H-pyran-4-one (9.69 g, 97 mmol) was added to a solution of 1,1-dimethylethyl hydrazinecarboxylate (14.07 g, 106 mmol) in methanol (100 mL) and stirred at room temperature for 3 h. The solvent was removed in vacuo, and the crude residue was suspended in acetic acid (140 mL). Next added sodium cyanoborohydride (6.69 g, 106 mmol) in portions over 3 minutes. The contents were stirred at room temperature for 60 h. The solvent was removed in vacuo, and the crude residue was suspended in DCM (100 mL). The reaction mixture was adjusted to pH 7 with 6N NaOH. The layers were separated, and the aq. layer extracted with DCM. The combined organic layers were washed with saturated NaHCO3, and brine. The organic layer was dried over MgSO4, filtered, and concentrated in vacuo to afford the product as a solid, 18.4 g (88%). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.22 (m, 2H), 1.39 (s, 9H), 1.43-1.48 (m, 1H), 1.59-1.69 (m, 2H), 2.82-2.98 (m, 1H), 3.20-3.32 (m, 2H), 3.80 (d, J=11.62 Hz, 2H), 4.36 (br. s., 1H), 8.07-8.34 (m, 1H).

Workup

  1. customThe solvent was removed in vacuo
  2. stirringThe contents were stirred at room temperature for 60 h
  3. customThe solvent was removed in vacuo
  4. customThe layers were separated
  5. extractionthe aq. layer extracted with DCM
  6. washThe combined organic layers were washed with saturated NaHCO3, and brine
  7. dry with materialThe organic layer was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d414010c5d534e81a6d04d754262102c
Source dataset
uspto-grants-2014_01
Patent number
US08637509B2

Linked notes

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