Phosphoric Acid → HCID 90022049, compound

HRID 1488154Notes

Reaction equation

HRID 1488154 reaction equation
CC1C=CC(S(O[CH2:12][C:13](F)([F:15])[F:14])(=O)=O)=CC=1.[Li]CCCC.C(B([CH2:27][CH3:28])CC)C.Cl[C:30]([C:32]1[C:33]([CH3:43])=[CH:34][C:35]([CH3:42])=[C:36]([CH:41]=1)[C:37]([O:39][CH3:40])=[O:38])=[O:31].OP(O)(O)=O>C1COCC1.[Cu]I.CN(C)P(N(C)C)(N(C)C)=O>[F:14][C:13]([F:15])=[C:12]([CH2:27][CH3:28])[C:30]([C:32]1[C:33]([CH3:43])=[CH:34][C:35]([CH3:42])=[C:36]([CH:41]=1)[C:37]([O:39][CH3:40])=[O:38])=[O:31]

Participants

9

Reactant 5

HCID 1004Phosphoric AcidHCID 7357TriethylboraneHCID 67942Ethanol, 2,2,2-trifluoro-, 1-(4-methylbenzenesulfonate)HCID 90021625HCID 90021625, compound2×HCID 178418339Butyllithium

Product 1

HCID 90022049HCID 90022049, compoundYield 38%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-78 °C

Procedure

Into a 100-mL three neck round-bottom flask, which was purged and maintained with an inert atmosphere of argon, was placed a solution of 2,2,2-trifluoroethyl 4-methylbenzenesulfonate (1.00 g, 3.93 mmol) in THF (30 mL). The solution was cooled to −78° C., then n-BuLi (5.0 mL, 1.6 M in hexane, 8.0 mmol) was added drop-wise and the mixture was stirred at −78° C. for 40 min Triethylborane (TEB) (5.0 mL, 1 M in THF, 5.0 mmol) was slowly added and the mixture was stirred at −78° C. for 1 h, then at room temperature for 3 h. The solution was cooled to 0° C., then hexamethylphosphoramide (HMPA) (6 mL) and CuI (1.5 g, 7.9 mmol) were added and the mixture was stirred at room temperature for 30 min. A solution of methyl 5-(chlorocarbonyl)-2,4-dimethylbenzoate (compound 255.2, 530 mg, 2.34 mmol) in THF (30 mL) was carefully added and stirred at room temperature for 30 min. The pH of the mixture was carefully adjusted to 7 with aqueous H3PO4 and the mixture was partitioned. The aqueous phase was extracted with ethyl acetate (3×20 mL) and the combined organic layers were concentrated under reduced pressure. The residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:40) as eluent to obtain the title compound as a yellow oil (250 mg, 38%).

Workup

  1. customInto a 100-mL three neck round-bottom flask, which was purged
  2. temperaturemaintained with an inert atmosphere of argon
  3. additionwas slowly added
  4. waitat room temperature for 3 h
  5. temperatureThe solution was cooled to 0° C.
  6. stirringthe mixture was stirred at room temperature for 30 min
  7. stirringstirred at room temperature for 30 min
  8. customthe mixture was partitioned
  9. extractionThe aqueous phase was extracted with ethyl acetate (3×20 mL)
  10. concentrationthe combined organic layers were concentrated under reduced pressure
  11. customThe residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:40) as eluent

Sources & evidence

ORD record
ord-2156aa5c089a4153bb6ac31985b95e2c
Source dataset
uspto-grants-2016_08
Patent number
US09428502B2

Reaction notes

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