2-[[3-[Hydroxymethyl]-7-oxabicyclo[2.2.1]hept-2-yl]methyl]-4-fluoro-1-phenylmethoxy-benzene → 2-[[3-Carboxy-7-oxabicyclo[2.2.1]hept-2-yl]methyl]-4-fluoro-1-phenylmethoxybenzene

HRID 252232Notes

Reaction equation

HRID 252232 reaction equation
[OH:1][CH2:2][CH:3]1[CH:8]2[O:9][CH:5]([CH2:6][CH2:7]2)[CH:4]1[CH2:10][C:11]1[CH:16]=[C:15]([F:17])[CH:14]=[CH:13][C:12]=1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.CC(C)=[O:28].OS(O)(=O)=O.O=[Cr](=O)=O>CC(C)=O.[O-2].[Cr+3].[O-2].[O-2].[Cr+3]>[C:2]([CH:3]1[CH:8]2[O:9][CH:5]([CH2:6][CH2:7]2)[CH:4]1[CH2:10][C:11]1[CH:16]=[C:15]([F:17])[CH:14]=[CH:13][C:12]=1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)([OH:28])=[O:1]

Participants

5

Reactant 2

HCID 597080332-[[3-[Hydroxymethyl]-7-oxabicyclo[2.2.1]hept-2-yl]methyl]-4-fluoro-1-phenylmethoxy-benzeneHCID 131709961Jones' reagent2×

Product 1

HCID 597080212-[[3-Carboxy-7-oxabicyclo[2.2.1]hept-2-yl]methyl]-4-fluoro-1-phenylmethoxybenzene

Reagents, catalysts & solvents 2

HCID 165971Chromium oxideCatalystHCID 180AcetoneSolvent

Procedure

To a solution of [1S-(1α, 2α, 3α, 4α)]-2-[[3-[hydroxymethyl]-7-oxabicyclo[2.2.1]hept-2-yl]methyl]-4-fluoro-1-phenylmethoxy-benzene (0.812 g, 2.37 mmol) in acetone (20 mL) was added Jones reagent (1 mL) (The Jones reagent was prepared by dissolving 534 mg of Chromium oxide in 0.46 mL of acid sulphuric concentrated and 1.54 mL of water) and the resulting mixture was stirred for 10 min. Then, more Jones reagent (1 mL) was added and the mixture was stirred for 1 h. After, 2-propanol (0.6 mL) was added and the reaction was stirred for 5 min. Then the reaction was stopped, the chromium salts were filtered and the solvent was evaporated under vacuum. The crude product was partitioned between chloroform (30 mL) and 2 M HCl (15 mL). The organic phase was separated; it was washed with brine (15 mL), dried (Na2SO4), filtered and the solvent was evaporated “under vacuum” to give the titled compound as a dark solid which was used in the next step without any additional purification. 1H-NMR (CDCl3, 300 MHz) δ 7.35 (m, 5H, ArH), 6.86 (m, 3H, ArH), 5.05 (s, 2H, —OCH2Ph), 4.84 (bs, 1H, —CH—O—), 4.33 (bs, 1H, —CH—O—), 2.87 (m, 2H, —CH—), 2.57 (m, 2H, —CH2—), 1.72 (m, 2H, —CH2—CH2—), 1.34 (m, 2H, —CH2—CH2—).

Workup

  1. customwas prepared
  2. concentrationsulphuric concentrated
  3. additionThen, more Jones reagent (1 mL) was added
  4. stirringthe mixture was stirred for 1 h
  5. additionAfter, 2-propanol (0.6 mL) was added
  6. stirringthe reaction was stirred for 5 min
  7. filtrationthe chromium salts were filtered
  8. customthe solvent was evaporated under vacuum
  9. customThe crude product was partitioned between chloroform (30 mL) and 2 M HCl (15 mL)
  10. customThe organic phase was separated
  11. washit was washed with brine (15 mL)
  12. dry with materialdried (Na2SO4)
  13. filtrationfiltered
  14. customthe solvent was evaporated “under vacuum”

Sources & evidence

ORD record
ord-8ea70e873b2f4f68b5537b3979e91f23
Source dataset
uspto-grants-2011_01
Patent number
US07868032B2

Reaction notes

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