Dimethylformamide → (1S,9S)-tert-butyl 9-(benzyloxycarbonylamino)-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate

HRID 709371Notes

Reaction equation

HRID 709371 reaction equation
[NH2:1][C@@H:2]1[C:8](=[O:9])[N:7]2[C@H:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:11][CH2:12][CH2:13][N:6]2[C:5](=[O:21])[CH2:4][CH2:3]1.CN(C=O)C.C(=O)([O-])[O-].[Na+].[Na+].[C:33](Cl)(=[O:42])[O:34][CH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1>[Cl-].[Na+].O.O>[C:17]([O:16][C:14]([C@H:10]1[N:7]2[C:8](=[O:9])[C@@H:2]([NH:1][C:33]([O:34][CH2:35][C:36]3[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=3)=[O:42])[CH2:3][CH2:4][C:5](=[O:21])[N:6]2[CH2:13][CH2:12][CH2:11]1)=[O:15])([CH3:18])([CH3:20])[CH3:19]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 10387Benzyl chloroformateHCID 15434568tert-Butyl (1S,9S)-9-amino-6,10-dioxooctahydro-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate

Product 1

HCID 67022104(1S,9S)-tert-butyl 9-(benzyloxycarbonylamino)-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylateYield 99.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
0 °C

Procedure

In a 20 mL pear-shaped flask, (1S,9S)-tert-butyl 9-amino-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate (0.9 g, 3.03 mmol) was combined with DMF (8 ml) to give a colorless solution and cooled to 0° C. Sodium carbonate (385 mg, 3.63 mmol) and benzyl carbonochloridate (516 mg, 432 μl, 3.03 mmol) were added and stirred at room temperature for 6 hr. It was diluted with brine and H2O, extracted with EtOAc (2×60 ml). The combined organic layer was washed with brine and H2O, dried with MgSO4, filtered and concentrated in vacuo to afford (1S,9S)-tert-butyl-9-(benzyloxycarbonylamino)-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate as an oil (1.3 g, 99.5%). ESI-LRMS m/e calcd for C18H21N3O6 [M+] 431. found 432 [M+H+]. The crude was used without further purification.

Workup

  1. customto give a colorless solution
  2. extractionextracted with EtOAc (2×60 ml)
  3. washThe combined organic layer was washed with brine and H2O
  4. dry with materialdried with MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a8c4065d93c047e98afca90d11f21b7e
Source dataset
uspto-grants-2015_11
Patent number
US09180193B2

Reaction notes

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