p-Toluenesulfonic acid → 2H-Pyran, tetrahydro-2-[(2-methyl-3-nitrophenyl)methoxy]-

HRID 2295862Notes

Reaction equation

HRID 2295862 reaction equation
[CH3:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][C:3]=1[CH2:11][OH:12].[O:13]1[CH:18]=[CH:17][CH2:16][CH2:15][CH2:14]1.CC1C=CC(S(O)(=O)=O)=CC=1>C(Cl)Cl.C1(C)C=CC=CC=1.[Ni]>[O:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH:14]1[O:12][CH2:11][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([N+:8]([O-:10])=[O:9])[C:2]=1[CH3:1]

Participants

7

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 80803,4-dihydro-2H-pyranHCID 902892-Methyl-3-nitrobenzyl alcohol

Product 1

HCID 111185162H-Pyran, tetrahydro-2-[(2-methyl-3-nitrophenyl)methoxy]-Yield 98.4%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 100 g (0.598 mol) of 2-methyl-3-nitrophenylmethanol, 75.5 g (0.897 mol) of dihydropyran, and 15.0 g (0.06 mol) of the pyridinium salt of 4-methylbenzenesulfonic acid in 1 L of methylene chloride was stirred at ambient temperature for 24 hours. The reaction mixture was washed with two portions of 200 mL each of a saturated aqueous solution of sodium chloride, dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to give a residual oil. The oil was subjected to column chromatography on silica gel, eluting with methylene chloride. The appropriate fractions were combined and concentrated under reduced pressure to give a residual oil. The oil was dissolved in 1 L of toluene, and was stirred in a Morton flask for 19 hours in the presence of 5 g of powdered Raney nickel. The mixture was filtered, and the filtrate concentrated under reduced pressure to give 147.8 g of 3-nitro-2-methylbenzenemethanol tetrahydropyranyl ether.

Workup

  1. washThe reaction mixture was washed with two portions of 200 mL each of a saturated aqueous solution of sodium chloride
  2. dry with materialdried with magnesium sulfate
  3. filtrationfiltered
  4. concentrationthe filtrate concentrated under reduced pressure
  5. customto give a residual oil
  6. washeluting with methylene chloride
  7. concentrationconcentrated under reduced pressure
  8. customto give a residual oil
  9. filtrationThe mixture was filtered
  10. concentrationthe filtrate concentrated under reduced pressure

Sources & evidence

ORD record
ord-3d5dfacd866e47d0b4f52a4d63b486f9
Source dataset
uspto-grants-1984_01
Patent number
US04426524

Reaction notes

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