Sodium Carbonate → HCID 66552352, compound

HRID 1615865Notes

Reaction equation

HRID 1615865 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.[CH2:11]([O:13][C:14]([C:16]1[CH:17]=[C:18](B(O)O)[CH:19]=[CH:20][CH:21]=1)=[O:15])[CH3:12].C([O-])([O-])=O.[Na+].[Na+].C(P(C(C)(C)C)C1C=CC=CC=1C1C(C(C)C)=CC(C(C)C)=CC=1C(C)C)(C)(C)C>O1CCOCC1.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([C:20]2[CH:21]=[C:16]([CH:17]=[CH:18][CH:19]=2)[C:14]([O:13][CH2:11][CH3:12])=[O:15])=[N:3][CH:4]=1)([O-:10])=[O:9]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 783082-Chloro-5-nitropyridineHCID 3249312(3-Ethoxycarbonylphenyl)boronic acidHCID 11618717Di-tert-butyl(2',4',6'-tris(propan-2-yl)-(1,1'-biphenyl)-2-yl)phosphane

Product 1

HCID 66552352HCID 66552352, compoundYield 89.1%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 2-chloro-5-nitropyridine (5.23 g, 32.99 mmol) in dioxane (170 mL) was added 3-(ethoxycarbonyl)phenylboronic acid (6.28 g, 32.99 mmol) and 1N Na2CO3 aqueous solution (82.5 mL, 82.5 mmol). The reaction mixture was degassed using Argon gas for 20 min followed by the addition of dichlorobis(triphenylphospine)palladium(II) (1.38 g, 1.99 mmol) and 2-di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl (1.26 g, 2.97 mmol). The reaction flask was put into the preheated oil-bath at 90° C. The reaction mixture was further stirred at 90° C. for a period of 10 h after which it was filtered and partitioned between ethyl acetate and water. The organic layer was separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified by flash column chromatography using a 95:5 v/v hexane:ethyl acetate as solvent to afford ethyl 3-(5-nitropyridin-2-yl)benzoate (8.0 g, 89% yield) as a bright yellow solid.

Workup

  1. customThe reaction mixture was degassed
  2. customfor 20 min
  3. customwas put into the preheated oil-bath at 90° C
  4. filtrationwas filtered
  5. custompartitioned between ethyl acetate and water
  6. customThe organic layer was separated
  7. extractionthe aqueous layer was extracted with ethyl acetate
  8. washThe combined organic extracts were washed with brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe crude product was purified by flash column chromatography

Sources & evidence

ORD record
ord-952093072c85457482faef3a26046497
Source dataset
uspto-grants-2014_07
Patent number
US08765747B2

Reaction notes

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