4-Chloro-2-nitro-1-[[(tetrahydro-2H-pyran-2-yl)oxy]methyl]benzene → 5-Chloro-2-[[(tetrahydro-2H-pyran-2-yl)oxy]methyl]benzenamine

HRID 1063937Notes

Reaction equation

HRID 1063937 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][O:9][CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][O:11]2)=[C:4]([N+:16]([O-])=O)[CH:3]=1.[H][H]>[Ni].C(O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][O:9][CH:10]2[CH2:15][CH2:14][CH2:13][CH2:12][O:11]2)=[C:4]([NH2:16])[CH:3]=1

Participants

5

Reactant 2

HCID 222762154-Chloro-2-nitro-1-[[(tetrahydro-2H-pyran-2-yl)oxy]methyl]benzeneHCID 178418361HCID 178418361, compound2×

Product 1

HCID 222752965-Chloro-2-[[(tetrahydro-2H-pyran-2-yl)oxy]methyl]benzenamineYield 98.1%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

A Parr bottle containing 4-chloro-2-nitro-1-[[(tetrahydro-2H-pyran-2-yl)oxy]methyl]benzene (22.6 g, 82.8 mmol) and ethanol (150 mL) was treated with Raney nickel (50% slurry in water, 2.0 g), charged with hydrogen (60 psi) and rocked until hydrogen uptake ceased (3 h). The resultant suspension was filtered through celite, and the celite cake thoroughly washed with fresh ethanol (5×150 mL). The combined organic extracts were concentrated in vacuo to give an orange oil that crystallized on standing. Recrystallization (ethyl acetate/hexane) gave the title compound as a white solid (19.64 g, 98%). 1H NMR (CDCl3) δ7.00 (d, J=8 Hz, 1H), 6.65-6.60 (m, 2H), 4.72 (A of ABq, J=12 Hz, 1H), 4.79-4.77 (m, 1H), 4.45 (B of ABq, J=12 Hz, 1H), 4.27 (bs, 2H), 3.94-3.85 (m, 1H), 3.58-3.50 (m, I), 1.88-1.65 (m, 2H), 1.58-1.46 (m, 4H).

Workup

  1. custom(3 h)
  2. filtrationThe resultant suspension was filtered through celite
  3. washthe celite cake thoroughly washed with fresh ethanol (5×150 mL)
  4. concentrationThe combined organic extracts were concentrated in vacuo
  5. customto give an orange oil
  6. customthat crystallized
  7. customRecrystallization (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-0b057d96d1774ee7be2916b89c9e8d5c
Source dataset
uspto-grants-2005_11
Patent number
US06967196B1

Reaction notes

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