Acetic Acid → HCID 86696075, compound

HRID 718505Notes

Reaction equation

HRID 718505 reaction equation
C([Li])CCC.[CH2:6]([O:8][C:9]1[CH:22]=[CH:21][C:20]2[C:19]3[C:14](=[C:15]([F:23])[CH:16]=[CH:17][CH:18]=3)[C:13]([F:25])([F:24])[C:12]([F:27])([F:26])[C:11]=2[C:10]=1[F:28])[CH3:7].B(OC)(OC)[O:30]C.C(O)(=O)C.O.OO>C1COCC1>[CH2:6]([O:8][C:9]1[C:10]([F:28])=[C:11]2[C:20]([C:19]3[CH:18]=[CH:17][C:16]([OH:30])=[C:15]([F:23])[C:14]=3[C:13]([F:24])([F:25])[C:12]2([F:27])[F:26])=[CH:21][CH:22]=1)[CH3:7]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 8470Trimethyl borateHCID 449047Hydrogen peroxide waterHCID 86696076HCID 86696076, compoundHCID 178418339Butyllithium

Product 1

HCID 86696075HCID 86696075, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-60 °C

Procedure

Under a nitrogen atmosphere, n-butyllithium (1.63 M, 8.71 mL, 14.20 mmol) was slowly added dropwise, at −60° C. or lower, to a THF (40 mL) solution of compound (87) (4.29 g, 12.91 mmol) prepared in Example 11. The reaction mixture was agitated at −60° C. or lower for 1 hour, and then trimethyl borate (1.61 g, 15.49 mmol) was slowly added dropwise thereto. The reaction mixture was returned to room temperature, and then acetic acid (1.16 g, 19.37 mmol) and hydrogen peroxide water (2.93 g, 25.80 mmol) were added thereto, and the resultant mixture was agitated for 3 hours. The reaction mixture was quenched with a saturated aqueous solution of ammonium chloride, and extracted with 50 mL of toluene three times. Combined organic layers were washed with a sodium thiosulfate aqueous solution, a saturated aqueous solution of sodium hydrogencarbonate, water and saturated brine, and then dried over magnesium sulfate, and a solvent was distilled off by an evaporator. The residue was purified by silica gel column chromatography, and thus 7-ethoxy-1,8,9,9,10,10-hexafluoro-9,10-dihydrophenanthrene-2-ol (91) (3.76 g, yield 84.0%) was obtained.

Workup

  1. customwas returned to room temperature
  2. customThe reaction mixture was quenched with a saturated aqueous solution of ammonium chloride
  3. extractionextracted with 50 mL of toluene three times
  4. washCombined organic layers were washed with a sodium thiosulfate aqueous solution
  5. dry with materiala saturated aqueous solution of sodium hydrogencarbonate, water and saturated brine, and then dried over magnesium sulfate
  6. distillationa solvent was distilled off by an evaporator
  7. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-d2b951937d2c48c586cf673fbdcfa6df
Source dataset
uspto-grants-2015_11
Patent number
US09193908B2

Reaction notes

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