Sulfuric Acid → 2-(1-Amino-2-methyl-1-oxopropan-2-yl)-4-tert-butyl-5-nitrophenyl methyl carbonate

HRID 1915104Notes

Reaction equation

[C:1](=[O:20])([O:18][CH3:19])[O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:5][C:4]=1[C:13]([C:16]#[N:17])([CH3:15])[CH3:14].[N+:21]([O-])([O-:23])=[O:22].[K+].[OH:26]S(O)(=O)=O>C(Cl)Cl>[C:1](=[O:20])([O:18][CH3:19])[O:2][C:3]1[CH:8]=[C:7]([N+:21]([O-:23])=[O:22])[C:6]([C:9]([CH3:11])([CH3:12])[CH3:10])=[CH:5][C:4]=1[C:13]([CH3:14])([CH3:15])[C:16]([NH2:17])=[O:26]

Participants

Conditions

Temperature: 30 °C

Procedure

To a stirred mixture of compound 16 (10.0 g, 36.3 mmol) and KNO3 (5.51 g, 54.5 mmol) in DCM (1000 mL) was added dropwise 98% H2SO4 (145.4 g, 1.45 mol) at 0° C. The mixture was stirred at 30° C. for 4 days. The H2SO4 layer was then separated and poured into ice-water (50 g) and then extracted with DCM (100 mL×3). The combined organic layers were washed with water, aqueous NaHCO3 solution and brine, then dried over MgSO4 and concentrated in vacuo. The residue was purified via column chromatography on silica gel (Petroleum ether/EtOAc 20:1→10:1→5:1→3:1) to give compound 17 as a yellow solid. 1H NMR (CDCl3; 400 MHz) δ 8.05 (s), δ 7.74 (s), δ 7.61 (s), δ 7.32 (s), δ 5.32 (s), δ 3.91 (s), δ 3.92 (s), δ 1.62 (s), δ 1.59 (s), δ 1.42 (s), δ 1.38 (s).

Workup

customThe H2SO4 layer was then separated
additionpoured into ice-water (50 g)
extractionextracted with DCM (100 mL×3)
washThe combined organic layers were washed with water, aqueous NaHCO3 solution and brine
dry with materialdried over MgSO4
concentrationconcentrated in vacuo
customThe residue was purified via column chromatography on silica gel (Petroleum ether/EtOAc 20:1→10:1→5:1→3:1)

Sources & evidence

ORD record: ord-33c5d71e248c4041871398dc799f9d90
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08614325B2

Reaction notes

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