Ethyl Acetate → HCID 26596852, compound

HRID 515613Notes

Reaction equation

HRID 515613 reaction equation
[N:1]1([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:6][CH2:5][N:4]([C:7](OC(Cl)(Cl)Cl)=[O:8])[CH2:3][CH2:2]1.O.[NH2:22][NH2:23].CCOC(C)=O>C1COCC1.[Cl-].[Na+]>[NH:22]([C:7]([N:4]1[CH2:5][CH2:6][N:1]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:2][CH2:3]1)=[O:8])[NH2:23]

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 24654Hydrazine hydrate (1:1)HCID 86701005HCID 86701005, compound

Product 1

HCID 26596852HCID 26596852, compound

Reagents, catalysts & solvents 2

HCID 5234Sodium ChlorideSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

DIPEA (105 g, 0.81 mol) was added to a solution of tert-butyl piperazine-1-carboxylate (25.0 g, 0.134 mol) in DCM (250 mL) at 0° C., followed by the addition of triphosgene (92 g, 0.27 mol) in portions over a 40 min time period. The reaction mixture was stirred for at rt for 3 hrs, filtered and concentrated to afford 1-tert-butyl 4-trichloromethyl piperazine-1,4-dicarboxylate (50 g) as an oil. A solution of 1-tert-butyl 4-trichloromethyl piperazine-1,4-dicarboxylate (50 g, 0.145 mol) in THF (50 mL) was added dropwise over a 30 minute period to a solution of hydrazine hydrate (18 mL, 0.434 mol) in THF (150 mL). The reaction mixture was stirred at rt for 2 hrs, diluted with saturated sodium chloride (50 mL) and exacted with EtOAc (3×). The combined organic layer was washed with saturated sodium chloride (2×), dried with Na2SO4, and concentrated. The residue was purified by crystallization (3:1 petroleum ether/EtOAc) to obtain of tert-butyl 4-(hydrazinecarbonyl)piperazine-1-carboxylate, (13 g, 40% for two steps). ESI-MS (EI+, m/z): 245 [M+H]+. 1H-NMR (500 MHz, CDCl3): δ5.92 (s, 1H), 3.45-3.35 (m, 8H), 1.41 (s, 9H).

Workup

  1. washThe combined organic layer was washed with saturated sodium chloride (2×)
  2. dry with materialdried with Na2SO4
  3. concentrationconcentrated
  4. customThe residue was purified by crystallization (3:1 petroleum ether/EtOAc)

Sources & evidence

ORD record
ord-2bbf4cacbe6a40e68299933442cc9e0a
Source dataset
uspto-grants-2015_08
Patent number
US09108966B2

Reaction notes

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