Hydrazine → (3aS,4R,7aR)-2,2-dimethylhexahydro-1,3-benzodioxol-4-amine
Reaction equation
[CH3:1][C:2]1([CH3:22])[O:6][C@@H:5]2[CH2:7][CH2:8][CH2:9][C@@H:10]([N:11]3C(=O)C4C(=CC=CC=4)C3=O)[C@@H:4]2[O:3]1.NN>C(O)C>[CH3:1][C:2]1([CH3:22])[O:6][C@@H:5]2[CH2:7][CH2:8][CH2:9][C@@H:10]([NH2:11])[C@@H:4]2[O:3]1Participants
Conditions
- Temperature
- 0 °C
Procedure
The mixture of 2-[(3aS,4R,7aR)-2,2-dimethylhexahydro-1,3-benzodioxol-4-yl]-1H-isoindole-1,3(2H)-dione (20) (191.4 mmol, 50.00 g), hydrazine (308.4 mmol, 15.0 mL) in ethanol (500 mL) was refluxed for 4 h. The reaction was monitored by HPLC. HPLC analysis showed the reaction did not go to completion (86% conversion). Additional 3 mL of hydrazine was added to the reaction mixture and refluxed for 2 h. The reaction was cooled to 0° C. and filtered. The filter cake was washed with IPA and dried to afford the desired product 21 (9.52 g, 21% yield, purity in weight: 84% based on NMR). The filtrate was concentrated and the residue was taken up in IPA (about 200 mL). The by-product crystallized and was filtered out, and the filtrate was stripped of volatiles and dried to afford a second crop of the desired product 21(28.46 g, 64% yield). TLC (80% MeOH/EtOAc with 1 drop of acetic acid, stained by ninhydrin dip).
Workup
- temperaturewas refluxed for 4 h
- temperaturerefluxed for 2 h
- filtrationfiltered
- washThe filter cake was washed with IPA
- customdried
Sources & evidence
- ORD record
- ord-f753ed652409443abc2e07cb1c83f793
- Source dataset
- uspto-grants-2014_11
- Patent number
- US08889719B2
Reaction notes
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