Cesium carbonate → 5-(2,5-Dimethyl-4-nitrophenoxy)pyrimidine

HRID 2361248Notes

Reaction equation

HRID 2361248 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[CH3:12].[N:13]1[CH:18]=[C:17]([OH:19])[CH:16]=[N:15][CH:14]=1.CC(C)(C(=O)CC(=O)C(C)(C)C)C.C(=O)([O-])[O-].[Cs+].[Cs+]>CN1CCCC1=O.CCOC(C)=O.[Cu]Cl>[CH3:12][C:3]1[CH:4]=[C:5]([N+:9]([O-:11])=[O:10])[C:6]([CH3:8])=[CH:7][C:2]=1[O:19][C:17]1[CH:18]=[N:13][CH:14]=[N:15][CH:16]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 707002,2,6,6-Tetramethyl-3,5-heptanedioneHCID 565855Pyrimidin-5-olHCID 8258081-Bromo-2,5-dimethyl-4-nitrobenzene

Product 1

HCID 679951355-(2,5-Dimethyl-4-nitrophenoxy)pyrimidineYield 44.7%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

A solution of 1-bromo-2,5-dimethyl-4-nitrobenzene (3.53 g, 15.34 mmol), pyrimidin-5-ol (1.474 g, 15.34 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (0.141 g, 0.767 mmol), cesium carbonate (5.15 g, 15.80 mmol) and copper(I) chloride (0.410 g, 4.14 mmol) in N-methyl-2-pyrrolidinone (15.34 mL) was heated in a sealed pressure tube at 130° C. and stirred overnight. The reaction was cooled to room temperature, diluted with EtOAc and washed with water (2×) and brine, successively, dried over Na2SO4, filtered and concentrated in vacuo. This was triturated with diethyl ether to give the first crop of the desired product (1.682 g) as a light tan solid. The filtrate was concentrated in vacuo, and the residue was purified by flash chromatography using an ISCO 80 g column eluting with 0-50% EtOAc/hexanes. Appropriate fractions were collected and concentrated in vacuo to give the second crop of the desired product (0.3973 g) as an off-white solid.

Workup

  1. washwashed with water (2×) and brine
  2. dry with materialsuccessively, dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThis was triturated with diethyl ether

Sources & evidence

ORD record
ord-f5e0a32df1674ca49b43717bb053863c
Source dataset
uspto-grants-2014_04
Patent number
US08685969B2

Reaction notes

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