Potassium Phosphate, Tribasic → HCID 58934571, compound

HRID 855154Notes

Reaction equation

HRID 855154 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1OS(C(F)(F)F)(=O)=O)[O:8][CH:7]([C:20]([F:23])([F:22])[F:21])[C:6]([C:24]([O:26]CC)=[O:25])=[CH:5]2.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[CH3:37][C:38]1[C:43]([CH3:44])=[CH:42][CH:41]=[CH:40][C:39]=1B(O)O.O.[OH-].[Li+]>O.C(OCC)(=O)C>[CH3:37][C:38]1[C:43]([CH3:44])=[CH:42][CH:41]=[CH:40][C:39]=1[C:11]1[CH:10]=[C:9]2[C:4]([CH:5]=[C:6]([C:24]([OH:26])=[O:25])[CH:7]([C:20]([F:23])([F:22])[F:21])[O:8]2)=[CH:3][C:2]=1[CH3:1]

Participants

7

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 168937Lithium hydroxide, monohydrateHCID 27733952,3-Dimethylphenylboronic acidHCID 58934716HCID 58934716, compound

Product 1

HCID 58934571HCID 58934571, compoundYield 15.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

To the mixture of ethyl 6-methyl-2-(trifluoromethyl)-7-{[(trifluoromethyl) sulfonyl]-oxy}-2H-chromene-3-carboxylate (0.3 g, 0.7 mmol), tetrakistriphenylpalladium (0)(4.5 mg, 0.035 mmol), powdered potassium phosphate (222 mg, 1.05 mmol) and 2,3-dimethylphenylboronic acid (106 mg, 0.84 mmol) was added 5 mL of anhydrous dixoane. The resulting mixiture was heated to 85° C. and stirred for 6 hrs. After cooling to room temperature, to the reaction was added 100 mL of ethyl acetate. The organic phases were washed with brine, and dried over anhydrous magnesium sulfate. After removing the solvents, the residue was purified on silica gel column with 1:9 EtOAc/hexane. The collected fraction was evaporated to dryness, the residue was dissolved in 6 mL of 1:1 THF/ethanol, to the resulting solution was added lithium hydroxide hydrate (117 mg, 2.8 mmol), followed by addition of 3 mL of water. The resulting mixture was heated to 80° C. and stirred for 1.5 hr. After removing the volatiles, the residue was acidified at 0° C. with ice-cold dilute HCl. The product was then extracted with EtOAc. After removing the volatiles, the residue was purified on reverse phase HPLC. It gave 39 mg of a light yellow solid product. 1H NMR (CDCl3/CD3OD/300 MHz) 7.85(s, 1H), 7.21-7.14(m, 3H), 6.96(dd, J=6.9 Hz, 15.6 Hz, 1H), 6.79(s, 1H), 5.71(q, J=7.2 Hz, 1H), 2.35(s, 3H), 2.00(s, 6H). 19F NMR(CDCl3/300 MHz) −78.81. 13C NMR (CDCl3/CD3OD/300 MHz) 167.3, 151.5, 148.1, 140.6(d, J=4.8 Hz), 138.5, 137.3, 134.1(d, J=13.7 Hz), 130.7, 129.4, 126.8, 126.6, 125.6, 123.9(q, J=287.9 Hz), 118.0, 117.2, 115.9, 70.8(q, J=32.9 Hz), 20.7, 19.1, 16.6. LC-MS(ES+): 363.2(M+1, 100). High resolution MS(ES−): m/z calc. For C20H]6F3O3: 361.1052(M−H), found: 361.1036.

Workup

  1. additionwas added 5 mL of anhydrous dixoane
  2. temperatureAfter cooling to room temperature, to the reaction
  3. washThe organic phases were washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customAfter removing the solvents
  6. customthe residue was purified on silica gel column with 1:9 EtOAc/hexane
  7. customThe collected fraction was evaporated to dryness
  8. dissolutionthe residue was dissolved in 6 mL of 1:1 THF/ethanol, to the resulting solution
  9. temperatureThe resulting mixture was heated to 80° C.
  10. stirringstirred for 1.5 hr
  11. customAfter removing the volatiles
  12. customwas acidified at 0° C. with ice-cold dilute HCl
  13. extractionThe product was then extracted with EtOAc
  14. customAfter removing the volatiles
  15. customthe residue was purified on reverse phase HPLC

Sources & evidence

ORD record
ord-d6c88d39fecd404eb4cfd281cc86dd40
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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