Cesium carbonate → HCID 69071885, compound

HRID 1822371Notes

Reaction equation

HRID 1822371 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([OH:26])[CH:5]=[C:6]([O:8][C:9]2[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][C:10]=2[O:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:7]=1.[CH2:27]([O:29][C:30](=[O:41])[CH2:31][O:32][C:33]1[CH:38]=[CH:37][C:36](Br)=[CH:35][C:34]=1[CH3:40])[CH3:28].C(=O)([O-])[O-].[Cs+].[Cs+].CC(C)(C(=O)CC(=O)C(C)(C)C)C>CN1CCCC1=O.O.[Cu]Cl>[CH2:27]([O:29][C:30](=[O:41])[CH2:31][O:32][C:33]1[CH:38]=[CH:37][C:36]([O:26][C:4]2[CH:5]=[C:6]([O:8][C:9]3[CH:14]=[CH:13][C:12]([C:15]([F:17])([F:18])[F:16])=[CH:11][C:10]=3[O:19][C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=3)[CH:7]=[C:2]([CH3:1])[CH:3]=2)=[CH:35][C:34]=1[CH3:40])[CH3:28]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 707002,2,6,6-Tetramethyl-3,5-heptanedioneHCID 57894166HCID 57894166, compoundHCID 57894204HCID 57894204, compound

Product 1

HCID 69071885HCID 69071885, compoundYield 13%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
120 °C

Procedure

Intermediates 3-methyl-5-(2-phenoxy-4-trifluoromethyl-phenoxy)-phenol (0.49 g, 1.36 mmol) and (4-bromo-2-methyl-phenoxy)-acetic acid ethyl ester (0.37 g, 1.36 mol) were combined with cesium carbonate (0.53 g, 1.63 mol), and 2,2,6,6-tetramethyl-3,5-heptanedione (0.063 g, 0.342 mmol) in 1-methyl-2-pyrrolidinone (10 mL) is purged with N2, and then copper (I) chloride (0.067 g, 0.677 mmol) is added. The reaction mixture is heated to 120° C. for 20 hours under N2. The mixture is diluted with water and extracted with Et2O. The organic layer is dried (Na2SO4), and the solvent is removed in vacuo to afford crude product that is absorbed on silica gel and purified by flash chromatography using 9/1 hexanes/ethyl acetate to afford 0.094 g (13%) {2-methyl-4-[3-methyl-5-(2-phenoxy-4-trifluoromethyl-phenoxy)-phenoxy]-phenoxy}-acetic acid ethyl ester that was saponified with ethanol and 5 N NaOH to afford 0.072 g (81%) 1H NMR (400 MHz, CDCl3); MS (ES+) m/z mass calcd for C29H23O6F3 524, found 525 (M+1, 100%).

Workup

  1. customis purged with N2
  2. extractionextracted with Et2O
  3. dry with materialThe organic layer is dried (Na2SO4)
  4. customthe solvent is removed in vacuo
  5. customto afford crude product that
  6. customis absorbed on silica gel
  7. custompurified by flash chromatography

Sources & evidence

ORD record
ord-def5d493e5454e18871f080871679854
Source dataset
uspto-grants-2009_10
Patent number
US07608639B2

Reaction notes

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