Phosgene → HCID 69131963, compound

HRID 750754Notes

Reaction equation

HRID 750754 reaction equation
[C:1](Cl)(Cl)=[O:2].[CH2:5]([O:12][C:13]([N:15]1[CH2:20][CH2:19][NH:18][CH2:17][CH2:16]1)=[O:14])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C(N(C(C)C)CC)(C)C.[C:30]([O:34][C:35]([NH:37][NH2:38])=[O:36])([CH3:33])([CH3:32])[CH3:31]>C(Cl)Cl>[CH2:5]([O:12][C:13]([N:15]1[CH2:20][CH2:19][N:18]([C:1]([N:37]([C:35]([O:34][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:36])[NH2:38])=[O:2])[CH2:17][CH2:16]1)=[O:14])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

6

Reactant 4

HCID 6371PhosgeneHCID 70091tert-Butyl carbazateHCID 81531Diisopropylethylamine2×HCID 643495Benzyl piperazine-1-carboxylate

Product 1

HCID 69131963HCID 69131963, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a phosgene solution (20% solution in toluene) at 0° C. was added piperazine-1-carboxylic acid benzyl ester (0.385 mL, 1.996 mmol) and diisopropylethyl amine (0.383 mL, 4.397 mmol) in 5 mL of CH2Cl2 dropwise. The resulting pale yellow mixture was stirred 2 h warming to room temperature under Ar. The phosgene solution was removed by vacuum distillation. 20 mL of anhydrous CH2Cl2 was added. The reaction vessel was cooled to 0° C. and hydrazinecarboxylic acid tert-butyl ester and diisopropylethyl amine (0.383 mL, 4.397 mmol) was added in one portion. The reaction was warmed to room temperature and stirred for 1 h. The reaction was quenched with 10 mL of saturated NaHCO3, diluted with 30 mL of EtOAc, then washed with 2×30 mL of saturated NH4Cl solution and 30 mL of brine. The organic phase was dried over MgSO4, filtered and concentrated to provide 720 mg of 4-(N-tert-butoxycarbonyl-hydrazinocarbonyl)-piperazine-1-carboxylic acid benzyl ester as a white solid.

Workup

  1. customThe phosgene solution was removed by vacuum distillation
  2. addition20 mL of anhydrous CH2Cl2 was added
  3. temperatureThe reaction vessel was cooled to 0° C.
  4. temperatureThe reaction was warmed to room temperature
  5. stirringstirred for 1 h
  6. customThe reaction was quenched with 10 mL of saturated NaHCO3
  7. additiondiluted with 30 mL of EtOAc
  8. washwashed with 2×30 mL of saturated NH4Cl solution and 30 mL of brine
  9. dry with materialThe organic phase was dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-bb5fa7fa08c746c4aae4b2efa8a41dc4
Source dataset
uspto-grants-2008_07
Patent number
US07405225B2

Reaction notes

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