p-Toluenesulfonic acid → 2-(2-fluoro-4-nitrobenzyloxy)-tetrahydro-2H-pyran

HRID 64337Notes

Reaction equation

HRID 64337 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH2:11][OH:12].CC1C=CC(S(O)(=O)=O)=CC=1.[CH2:24]1[CH2:29][O:28][CH:27]=[CH:26][CH2:25]1>C(Cl)Cl>[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH2:11][O:12][CH:27]1[CH2:26][CH2:25][CH2:24][CH2:29][O:28]1

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 80803,4-dihydro-2H-pyranHCID 17981733(2-Fluoro-4-nitrophenyl)methanol

Product 1

HCID 1176682542-(2-fluoro-4-nitrobenzyloxy)-tetrahydro-2H-pyranYield 80%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (2-fluoro-4-nitrophenyl)methanol (755 mg, 4.42 mmol) in 10 mL of DCM was added TsOH (100 mg, 0.13 mmol) and DHP (408 mg, 4.86 mmol). After stirring at RT for 16 hr, the mixture was concentrated. The residue was partitioned between 100 mL of EA and 100 mL of brine. The combined organic layers were washed with brine (100 mL×2), dried over Na2SO4, concentrated and purified by chromatography column on silica gel (elution with PE/EA) to afford 900 mg (80%) of 2-(2-fluoro-4-nitrobenzyloxy)-tetrahydro-2H-pyran as a colorless oil. 1H NMR (400 MHz, DMSO-d6) δ 8.34 (dd, J=3.0, 6.2 Hz, 1H), 8.26-8.30 (m, 1H), 7.53 (t, J=9.2 Hz, 1H), 4.82-4.76 (m, 2H), 4.62 (d, J=12.0 Hz, 1H), 3.80-3.74 (m, 1H), 3.52-3.47 (m, 1H), 1.76-1.64 (m, 2H) and 1.58-1.45 (m, 4H).

Workup

  1. concentrationthe mixture was concentrated
  2. customThe residue was partitioned between 100 mL of EA and 100 mL of brine
  3. washThe combined organic layers were washed with brine (100 mL×2)
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated
  6. custompurified by chromatography column on silica gel (elution with PE/EA)

Sources & evidence

ORD record
ord-04971a0ba2924bd1822021d7353d6e74
Source dataset
uspto-grants-2016_09
Patent number
US09447106B2

Reaction notes

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