Tetrahydrofuran → 2-(3-Hydroxy-1,1-dimethyl-3-trifluoromethylhex-5-ynyl)benzoic acid

HRID 2387311Notes

Reaction equation

HRID 2387311 reaction equation
[CH3:1][C:2]1([CH3:21])[CH2:8][C:7]([CH2:13][C:14]#[CH:15])([C:9]([F:12])([F:11])[F:10])[O:6][CH:5]([OH:16])[C:4]2[CH:17]=[CH:18][CH:19]=[CH:20][C:3]1=2.CC(=CC)C.C1C[O:30]CC1.Cl([O-])=O.[Na+].P([O-])([O-])(O)=O.[Na+].[Na+]>C(O)(C)(C)C.O>[OH:6][C:7]([C:9]([F:12])([F:11])[F:10])([CH2:13][C:14]#[CH:15])[CH2:8][C:2]([C:3]1[CH:20]=[CH:19][CH:18]=[CH:17][C:4]=1[C:5]([OH:30])=[O:16])([CH3:21])[CH3:1]

Participants

8

Reactant 5

HCID 8028TetrahydrofuranHCID 105532-Methyl-2-buteneHCID 24203Sodium Phosphate, DibasicHCID 23668197Sodium ChloriteHCID 580261785,5-Dimethyl-3-prop-2-ynyl-3-trifluoromethyl-1,3,4,5-tetrahydrobenzo[c]oxepin-1-ol

Product 1

HCID 580261462-(3-Hydroxy-1,1-dimethyl-3-trifluoromethylhex-5-ynyl)benzoic acidYield 87.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6386tert-ButanolSolvent

Procedure

To a solution of 5,5-dimethyl-3-prop-2-ynyl-3-trifluoromethyl-1,3,4,5-tetrahydrobenzo[c]oxepin-1-ol (2.50 g, 8.38 mmol) in tert-BuOH (75 mL) was added a 2.0 M solution of 2-methyl-2-butene in THF (58 mL, 117 mmol). To this solution was added a solution of sodium chlorite (4.74 g, 42.0 mmol) and sodium hydrogen phosphate (11.57 g, 84.0 mmol) in water (37.5 mL). The reaction mixture was stirred for 6 hours then the volatiles were removed in vacuo. The aqueous mixture was then acidified to pH=1 with aqueous 1M HCl, extracted with 300 mL of ethyl acetate, dried with magnesium sulfate, filtered, and concentrated in vacuo. The crude was purified by flash chromatography (120 g SiO2, hexanes to 1:1 hexanes:EtOAc) to give 2-(3-hydroxy-1,1-dimethyl-3-trifluoromethylhex-5-ynyl)benzoic acid (2.30 g, 87%). MS (ES+) m/z 315 [M+H]+.

Workup

  1. customthe volatiles were removed in vacuo
  2. extractionextracted with 300 mL of ethyl acetate
  3. dry with materialdried with magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude was purified by flash chromatography (120 g SiO2, hexanes to 1:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-4876a167f73f41e884f69c96e799ef9f
Source dataset
uspto-grants-2012_09
Patent number
US08268859B2

Reaction notes

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