Cesium carbonate → HCID 69312058, compound

HRID 1609946Notes

Reaction equation

HRID 1609946 reaction equation
[CH2:1]([O:3][C:4](=[O:17])[C:5]([O:8][C:9]1[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][C:10]=1[CH3:16])([CH3:7])[CH3:6])[CH3:2].[CH3:18][C:19]1[O:23][C:22]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[N:21][C:20]=1[CH2:30][CH2:31]OS(C1C=CC(C)=CC=1)(=O)=O.C([O-])([O-])=O.[Cs+].[Cs+]>CN(C=O)C>[CH2:1]([O:3][C:4](=[O:17])[C:5]([CH3:6])([O:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][CH2:31][CH2:30][C:20]2[N:21]=[C:22]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[O:23][C:19]=2[CH3:18])=[CH:11][C:10]=1[CH3:16])[CH3:7])[CH3:2]

Participants

5

Reactant 3

HCID 10796Cesium carbonate2×HCID 120517392-(5-Methyl-2-phenyloxazol-4-yl)ethyl 4-methylbenzenesulfonate2×HCID 16756990Ethyl 2-(4-hydroxy-2-methylphenoxy)-2-methylpropanoate

Product 1

HCID 69312058HCID 69312058, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A mixture of 2-(4-hydroxy-2-methyl-phenoxy)-2-methyl-propionic acid ethyl ester (4.50 g, 18.9 mmol), toluene-4-sulfonic acid 2-(5-methyl-2-phenyl-oxazol-4-yl)ethyl ester (Japan Tobacco Inc WO 9518125) (8.43 g, 23.6 mmol), and Cs2CO3 (7.68 g, 23.6 mmol) was heated at 55° C. in DMF (45 mL) for 20 h. Additional toluene-4-sulfonic acid 2-(5-methyl-2-phenyl-oxazol-4-yl)ethyl ester (2.81 g, 7.86 mmol) and Cs2CO3 (2.56 g, 7.86 mmol) were added, and the mixture was heated at 55° C. in DMF (45 mL) for 6 h. The reaction mixture cooled and partitioned between EtOAc (200 mL) and H2O (100 mL). The organic layer was washed with brine (50 mL). The aqueous layers were extracted further with EtOAc (200 mL). The combined organic layers were dried (Na2SO4) and concentrated. The crude product was purified by flash chromatography using hexanes:ethyl acetate (6:1 to 4:1) to give an oil (5.81 g, 73%): 1H NMR (400 MHz, CDCl3) δ 1.27 (t, 3H, J=7.1 Hz), 1.51 (s, 6H), 2.18 (s, 3H), 2.36 (s, 3H), 2.95 (t, 2H, J=6.6 Hz), 4.17 (t, 2H, J=6.6 Hz), 4.24 (q, 2H, J=7.1 Hz), 6.57 (dd, 1H, J=2.9, 8.8 Hz), 6.65 (d, 1H, J=9.3 Hz), 6.69 (d, 1H, J=2.9 Hz), 7.38-7.45 (m, 3H), 7.98-8.00 (m, 2H); MS (ES) m/e 424.2 [M+1].

Workup

  1. temperatureThe reaction mixture cooled
  2. custompartitioned between EtOAc (200 mL) and H2O (100 mL)
  3. washThe organic layer was washed with brine (50 mL)
  4. extractionThe aqueous layers were extracted further with EtOAc (200 mL)
  5. dry with materialThe combined organic layers were dried (Na2SO4)
  6. concentrationconcentrated
  7. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-bafc96ea511947778aa9ea46ac1605c5
Source dataset
uspto-grants-2006_01
Patent number
US06982278B2

Reaction notes

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