Sodium Carbonate → 3-Chloro-4-(2-methyl-5-nitrophenyl)pyridine

HRID 1915674Notes

Reaction equation

HRID 1915674 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH3:11].O.[Cl:13][C:14]1[CH:15]=[N:16][CH:17]=[CH:18][C:19]=1B(O)O.C(=O)([O-])[O-].[Na+].[Na+]>C(COC)OC.O.[Pd](Cl)Cl.C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[Cl:13][C:14]1[CH:15]=[N:16][CH:17]=[CH:18][C:19]=1[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH3:11]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 821892-Bromo-4-nitrotolueneHCID 179987563-Chloro-4-pyridineboronic acid hydrate

Product 1

HCID 220408203-Chloro-4-(2-methyl-5-nitrophenyl)pyridine

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

Nitrogen was bubbled through a solution of 2-bromo-1-methyl-4-nitrobenzene (1 eq) in dimethoxyethane and water (3:1) for 0.5 h. Bis(diphenylphosphino)ferrocene Palladium(II)chloride (0.05 eq) followed by 3-chloro-4-pyridine boronic acid hydrate (1 eq) and sodium carbonate (3 eq) was added and the mixture was heated to 90° C. for 16 h under nitrogen. The reaction mixture was concentrated and partitioned between ethyl acetate and water. The organic layer was washed with brine and dried with sodium sulfate and concentrated. Purification on silica gel gave 3-chloro-4-(2-methyl-5-nitrophenyl)pyridine. MS: MH+=248.

Workup

  1. additionwas added
  2. concentrationThe reaction mixture was concentrated
  3. custompartitioned between ethyl acetate and water
  4. washThe organic layer was washed with brine
  5. dry with materialdried with sodium sulfate
  6. concentrationconcentrated
  7. customPurification on silica gel

Sources & evidence

ORD record
ord-8e7f28b176f24cb0bd585a2cda6eb9d2
Source dataset
uspto-grants-2013_12
Patent number
US08614330B2

Reaction notes

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