Methyl morpholine oxide → Methyl 5-nitro-2-(2-oxoethyl)benzoate

HRID 1465770Notes

Reaction equation

HRID 1465770 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:14][CH:15]=C)=[C:8]([CH:13]=1)[C:9]([O:11][CH3:12])=[O:10])([O-:3])=[O:2].C[N+]1([O-])CC[O:21]CC1.I([O-])(=O)(=O)=O.[Na+]>O.C1COCC1.CCOC(C)=O.[Os](=O)(=O)(=O)=O>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:14][CH:15]=[O:21])=[C:8]([CH:13]=1)[C:9]([O:11][CH3:12])=[O:10])([O-:3])=[O:2]

Participants

8

Reactant 3

HCID 82029Methyl morpholine oxideHCID 23667635Sodium periodateHCID 89524965Methyl 5-nitro-2-(prop-2-en-1-yl)benzoate

Product 1

HCID 89525047Methyl 5-nitro-2-(2-oxoethyl)benzoate

Reagents, catalysts & solvents 4

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of Methyl 5-nitro-2-(prop-2-en-1-yl)benzoate (0.20 g, 0.90 mmol) in water (2 mL) and THF (5 mL) was added osmium tetroxide (0.57 mL 2.5% solution, 0.045 mmol) and NMO (0.16 g, 1.4 mmol). The mixture was allowed to stir at RT for 16 hours and monitored by TLC. The reaction was diluted with EtOAc, washed with NH4Cl and brine, and concentrated. The residue was redissolved in MeOH and water. After cooling the solution to 0° C., an aqueous solution of sodium periodate (0.39 g, 1.8 mmol) was dropped into the reaction and allowed to stir for 2 hours. The reaction was diluted with water, extracted with EtOAc, dried over sodium sulfate, and concentrated. The crude residue was purified by silica gel chromatography to provide Methyl 5-nitro-2-(2-oxoethyl)benzoate. 1H-NMR (400 MHz, CDCl3) δ ppm 9.48 (S, 1H), 8.97 (s, 1H), 8.39 (d, J=8.0 Hz, 1H), 7.46 (d, J=8.0 Hz, 1H), 4.31 (s, 2H), 3.98 (s, 3H).

Workup

  1. washwashed with NH4Cl and brine
  2. concentrationconcentrated
  3. dissolutionThe residue was redissolved in MeOH
  4. temperatureAfter cooling the solution to 0° C.
  5. stirringto stir for 2 hours
  6. extractionextracted with EtOAc
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated
  9. customThe crude residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-004eaad52ab046a38e26ef8814120824
Source dataset
uspto-grants-2015_04
Patent number
US08999991B2

Reaction notes

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