Citric Acid → HCID 68006026, compound

HRID 1026531Notes

Reaction equation

HRID 1026531 reaction equation
[H-].[Na+].[OH:3][C:4]1([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:6][CH2:5]1.Cl[C:15]1[C:20]([N+:21]([O-:23])=[O:22])=[CH:19][C:18]([Cl:24])=[CH:17][N:16]=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1(C)C=CC=CC=1>[Cl:24][C:18]1[CH:19]=[C:20]([N+:21]([O-:23])=[O:22])[C:15]([O:3][C:4]2([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:6][CH2:5]2)=[N:16][CH:17]=1

Participants

6

Reactant 4

HCID 311Citric AcidHCID 24758Sodium hydrideHCID 80633312,5-Dichloro-3-nitropyridineHCID 68006372HCID 68006372, compound

Product 1

HCID 68006026HCID 68006026, compoundYield 82.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent3×

Procedure

Under ice cooling, to a toluene suspension (60 ml) of 63% sodium hydride (2.81 g) was added dropwise a toluene solution (30 ml) of tert-butyl 1-hydroxycyclopropanecarboxylate (11.65 g) over 15 minutes, followed by stirring as it stood for 30 minutes, and further at room temperature for 2 hours. After cooling again using an ice bath, a toluene solution (30 ml) of 2,5-dichloro-3-nitropyridine (7.13 g) was added, and the temperature was brought back to room temperature, followed by stirring for 3 hours. After a 10% aqueous citric acid solution was added, the separated organic layer was washed with saturated sodium chloride solution, and the aqueous layer was extracted with ethyl acetate. The collected organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to afford tert-butyl 1-[(5-chloro-3-nitropyridin-2-yl)oxy]cyclopropanecarboxylate (9.61 g).

Workup

  1. waitfurther at room temperature for 2 hours
  2. temperatureAfter cooling again
  3. customwas brought back to room temperature
  4. stirringby stirring for 3 hours
  5. washthe separated organic layer was washed with saturated sodium chloride solution
  6. extractionthe aqueous layer was extracted with ethyl acetate
  7. dry with materialThe collected organic layer was dried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-d47ca927243f4dffb76bfa780fac819f
Source dataset
uspto-grants-2014_05
Patent number
US08729095B2

Reaction notes

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