Hydrazine → tert-Butyl (1S,9S)-9-amino-6,10-dioxooctahydro-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate

HRID 709370Notes

Reaction equation

HRID 709370 reaction equation
O=C1C2C(=CC=CC=2)C(=O)[N:3]1[C@@H:12]1[C:18](=[O:19])[N:17]2[C@H:20]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:21][CH2:22][CH2:23][N:16]2[C:15](=[O:31])[CH2:14][CH2:13]1.NN>C(O)C>[NH2:3][C@@H:12]1[C:18](=[O:19])[N:17]2[C@H:20]([C:24]([O:26][C:27]([CH3:29])([CH3:28])[CH3:30])=[O:25])[CH2:21][CH2:22][CH2:23][N:16]2[C:15](=[O:31])[CH2:14][CH2:13]1

Participants

4

Reactant 2

HCID 9321HydrazineHCID 13341490tert-butyl (4S,7S)-7-(1,3-dioxoisoindol-2-yl)-6,10-dioxo-2,3,4,7,8,9-hexahydro-1H-pyridazino[1,2-a]diazepine-4-carboxylate

Product 1

HCID 15434568tert-Butyl (1S,9S)-9-amino-6,10-dioxooctahydro-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylateYield 97.8%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

In a 200 mL round-bottomed flask, (1S,9S)-tert-butyl 9-(1,3-dioxoisoindolin-2-yl)-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate (5 g, 11.7 mmol) was combined with ethanol (50 ml) to give a colorless suspension. Hydrazine (825 mg, 808 μl, 25.7 mmol) was added and stirred at room temperature for 2 hr. The crude reaction mixture was concentrated in vacuo and evaporated with toluene. 2M aqueous acetic acid (50 ml) was added and stirred at room temperature overnight. The precipitate was filtered and the filtrate was basified with sodium carbonate solution. It was extracted with CH2Cl2 (2×150 ml). The combined organic layer was dried with MgSO4 and concentrated in vacuo to afford (1S,9S)-tert-butyl 9-amino-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate as a sticky white solid (3.4 g, 97.8%). ESI-LRMS m/e calcd for C14H23N3O4 [M+] 297. found 298 [M+H+].

Workup

  1. customto give a colorless suspension
  2. customThe crude reaction mixture
  3. concentrationwas concentrated in vacuo
  4. customevaporated with toluene
  5. addition2M aqueous acetic acid (50 ml) was added
  6. stirringstirred at room temperature overnight
  7. filtrationThe precipitate was filtered
  8. extractionIt was extracted with CH2Cl2 (2×150 ml)
  9. dry with materialThe combined organic layer was dried with MgSO4
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-bb0cd14b58754cc4ae162cdfad63fdb9
Source dataset
uspto-grants-2015_11
Patent number
US09180193B2

Reaction notes

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