Nitromethane → HCID 57626337, compound

HRID 1891822Notes

Reaction equation

HRID 1891822 reaction equation
[O:1]([C:8]1[CH:9]=[CH:10][C:11]([CH:14]=O)=[N:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[O-].[Li+].[N+:19]([CH3:22])([O-:21])=[O:20].C(OC(=O)C)(=O)C.C(N(CC)CC)C.[BH4-].[Na+]>C(OCC)(=O)C.O.C(O)(=O)C.CS(C)=O.CO>[N+:19]([CH2:22][CH2:14][C:11]1[CH:10]=[CH:9][C:8]([O:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:13][N:12]=1)([O-:21])=[O:20]

Participants

12

Reactant 6

HCID 6375NitromethaneHCID 7918Acetic AnhydrideHCID 8471TriethylamineHCID 4177230Lithium methanolateHCID 4311764Sodium borohydrideHCID 544159545-Phenoxypicolinaldehyde

Product 1

HCID 57626337HCID 57626337, compoundYield 8.9%

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 679Dimethyl SulfoxideSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 5-phenoxy-pyridine-2-carbaldehyde (700 mg, 3.5 mmol) described in Manufacturing Example 121-1-3, lithium methoxide (170 mg, 4.6 mmol), nitromethane (280 mg, 4.6 mmol), and methanol (10 mL) was dissolved by irradiating ultrasonic wave for 2 minutes at room temperature, after which the reaction solution was concentrated under a reduced pressure. Acetic anhydride (30 mL) and triethylamine (1.1 g, 11 mmol) were added to the residue, which was stirred for 10 minutes at room temperature, after which the reaction solution was concentrated under a reduced pressure. Ethyl acetate was added to the residue, and the organic layer was separated and washed with saturated aqueous sodium chloride once and then dried over anhydrous magnesium sulfate. The solvent was evaporated under a reduced pressure, dimethyl sulfoxide (5.0 mL), acetic acid (0.50 mL), and sodium borohydride (270 mg, 7.0 mmol) were added to the residue, which was stirred for 5 minutes at room temperature. Water and ethyl acetate were added to the reaction solution, and then the ethyl acetate layer was separated and washed with aqueous sodium bicarbonate, water, and saturated aqueous sodium chloride. The solvent was evaporated under a reduced pressure, and the residue was purified first by silica gel column chromatography (heptane:ethyl acetate=2:1) and then NH silica gel column chromatography (heptane:ethyl acetate=4:1 then 2:1) to obtain the title compound (76 mg, 8.9%).

Workup

  1. dissolutionwas dissolved
  2. customby irradiating ultrasonic wave for 2 minutes at room temperature
  3. concentrationafter which the reaction solution was concentrated under a reduced pressure
  4. concentrationafter which the reaction solution was concentrated under a reduced pressure
  5. additionEthyl acetate was added to the residue
  6. customthe organic layer was separated
  7. washwashed with saturated aqueous sodium chloride once
  8. dry with materialdried over anhydrous magnesium sulfate
  9. additionwere added to the residue, which
  10. stirringwas stirred for 5 minutes at room temperature
  11. customthe ethyl acetate layer was separated
  12. washwashed with aqueous sodium bicarbonate, water, and saturated aqueous sodium chloride
  13. customThe solvent was evaporated under a reduced pressure
  14. customthe residue was purified first by silica gel column chromatography (heptane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-d92517a9585e4c9fa25984c7a158ec26
Source dataset
uspto-grants-2013_08
Patent number
US08507530B2

Reaction notes

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