Methyl 5-methyl-3-oxohexanoate → Methyl 5-methyl-2-nitro-3-oxohexanoate

HRID 1427363Notes

Reaction equation

HRID 1427363 reaction equation
[N:1]([O-:3])=[O:2].[Na+].[CH3:5][CH:6]([CH3:15])[CH2:7][C:8](=[O:14])[CH2:9][C:10]([O:12][CH3:13])=[O:11]>O.C(O)(=O)C>[CH3:5][CH:6]([CH3:15])[CH2:7][C:8](=[O:14])[CH:9]([N+:1]([O-:3])=[O:2])[C:10]([O:12][CH3:13])=[O:11]

Participants

5

Reactant 2

HCID 121701Methyl 5-methyl-3-oxohexanoateHCID 23668193Sodium Nitrite

Product 1

HCID 42609287Methyl 5-methyl-2-nitro-3-oxohexanoate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

A solution of sodium nitrite (232 g, 3.36 mol) in water (560 mL) was added drop-wise over 1.5 hours to a solution of methyl 5-methyl-3-oxohexanoate (400 g, 2.53 mol) in glacial acetic acid (510 mL) at 20 to 25° C. Stirring was continued at room temperature for 2 hours. Water (1.3 L) was added, and the reaction mixture was stirred for an additional 18 hours. The mixture was then extracted with ethyl acetate (3×2.5 L), and the combined organic layers were washed sequentially with water (2.5 L), with aqueous sodium bicarbonate solution (2.5 L), and with saturated aqueous sodium chloride solution (1.0 L). After drying over sodium sulfate, the organic extracts were concentrated in vacuo to afford the product as a yellow liquid, which was used directly in the next step. Yield: 456 g, 2.24 mol, 89%.

Workup

  1. stirringthe reaction mixture was stirred for an additional 18 hours
  2. extractionThe mixture was then extracted with ethyl acetate (3×2.5 L)
  3. washthe combined organic layers were washed sequentially with water (2.5 L), with aqueous sodium bicarbonate solution (2.5 L)
  4. dry with materialAfter drying over sodium sulfate
  5. concentrationthe organic extracts were concentrated in vacuo

Sources & evidence

ORD record
ord-f1f5ce66f8fc41eda4ac5ac72eb074c5
Source dataset
uspto-grants-2015_01
Patent number
US08933224B2

Reaction notes

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