Diisopropylethylamine → HCID 86701005, compound

HRID 515612Notes

Reaction equation

HRID 515612 reaction equation
CCN(C(C)C)C(C)C.[N:10]1([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:15][CH2:14][NH:13][CH2:12][CH2:11]1.[Cl:23][C:24]([Cl:34])([O:26][C:27](=O)[O:28]C(Cl)(Cl)Cl)[Cl:25]>C(Cl)Cl>[N:10]1([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:15][CH2:14][N:13]([C:27]([O:26][C:24]([Cl:34])([Cl:25])[Cl:23])=[O:28])[CH2:12][CH2:11]1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 94429TriphosgeneHCID 143452tert-Butyl piperazine-1-carboxylate

Product 1

HCID 86701005HCID 86701005, compoundYield 107.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

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. filtrationfiltered
  2. concentrationconcentrated

Sources & evidence

ORD record
ord-6356fd003a2a4dc2a9e322ae7f5372e1
Source dataset
uspto-grants-2015_08
Patent number
US09108966B2

Reaction notes

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