Cesium carbonate → (S)-tert-butyl 2-((4-nitro-1H-pyrazol-1-yl)methyl)morpholine-4-carboxylate

HRID 522629

Reaction equation

CS(O[CH2:6][C@H:7]1[O:12][CH2:11][CH2:10][N:9]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:8]1)(=O)=O.[N+:20]([C:23]1[CH:24]=[N:25][NH:26][CH:27]=1)([O-:22])=[O:21].C(=O)([O-])[O-].[Cs+].[Cs+]>C(#N)C>[N+:20]([C:23]1[CH:24]=[N:25][N:26]([CH2:6][C@H:7]2[O:12][CH2:11][CH2:10][N:9]([C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[CH2:8]2)[CH:27]=1)([O-:22])=[O:21]

Participants

Conditions

Temperature: 55 °C

Procedure

To a solution of (S)-tert-butyl 2-((methylsulfonyloxy)methyl)morpholine-4-carboxylate (2.8 g, 9.5 mmol) and 4-nitro-1H-pyrazole (715 mg, 6.3 mmol) in acetonitrile (100 mL) was added cesium carbonate (6.2 g, 19.0 mmol). The reaction mixture was stirred at 55° C. overnight and then concentrated. The residue was dissolved in ethyl acetate (100 mL), washed with water (50 mL), dried over sodium sulfate, filtered and concentrated. The crude sample was purified by silica gel chromatography, eluting with petroleum ether:ethyl acetate=8:1, to afford (S)-tert-butyl 2-((4-nitro-1H-pyrazol-1-yl)methyl)morpholine-4-carboxylate as a yellow oil (2.12 g, 71%). MS (ES+) C13H20N4O5 requires: 312, found: 257 [M+H-56]+.

Workup

concentrationconcentrated
dissolutionThe residue was dissolved in ethyl acetate (100 mL)
washwashed with water (50 mL)
dry with materialdried over sodium sulfate
filtrationfiltered
concentrationconcentrated
customThe crude sample was purified by silica gel chromatography
washeluting with petroleum ether

Sources & evidence

ORD record: ord-569ae0dfd35e4a7a8fd5e1dd96f9ab2f
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09334263B2

Linked notes

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