Acetic Acid → 2-Amino-3-(2,6-dichlorobenzyloxy)pyridine

HRID 425906Notes

Reaction equation

HRID 425906 reaction equation
CC(O)=O.[Cl:5][C:6]1[CH:22]=[CH:21][CH:20]=[C:19]([Cl:23])[C:7]=1[CH2:8][O:9][C:10]1[C:11]([N+:16]([O-])=O)=[N:12][CH:13]=[CH:14][CH:15]=1>[Fe].CCO>[Cl:5][C:6]1[CH:22]=[CH:21][CH:20]=[C:19]([Cl:23])[C:7]=1[CH2:8][O:9][C:10]1[C:11]([NH2:16])=[N:12][CH:13]=[CH:14][CH:15]=1

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 9010443-[(2,6-Dichlorobenzyl)oxy]-2-nitropyridine

Product 1

HCID 103783682-Amino-3-(2,6-dichlorobenzyloxy)pyridineYield 100%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 702EthanolSolvent

Procedure

To a stirred mixture of AcOH (650 mL) and EtOH (500 mL) was suspended 3-(2,6-dichloro-benzyloxy)-2-nitro-pyridine (37.4 g, 0.11 mol) and iron chips (69.4 g, 0.11 mol). The reaction was heated slowly to reflux and allowed to stir for 1 hr. The reaction was cooled to room temperature then filtered through a pad of celite. The resulting filtrate was neutralized with conc. NH4OH (600 mL) and then extracted with EtOAc (3×500 mL). The combined organic extracts were washed with saturated NaHCO3 (2×100 mL), H2O (2×100 mL) and brine (1×100 mL) then dried (Na2SO4), filtered and concentrated to dryness under vacuum to yield 3-(2,6-dichloro-benzyloxy)-pyridin-2-ylamine (32.4 g, 0.11 mol, 99%) as a light yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 7.56 (m, 3H), 7.46 (dd, 2H), 7.36 (d, 1H), 6.62 (dd, 1H), 6.18 (br s, 2H, NH2), 5.24 (s, 2H); MS m/z 270 [M+1].

Workup

  1. temperatureThe reaction was heated slowly
  2. temperatureto reflux
  3. filtrationthen filtered through a pad of celite
  4. extractionextracted with EtOAc (3×500 mL)
  5. washThe combined organic extracts were washed with saturated NaHCO3 (2×100 mL), H2O (2×100 mL) and brine (1×100 mL)
  6. dry with materialthen dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated to dryness under vacuum

Sources & evidence

ORD record
ord-9cbf3314cef84739be586ae5088ccd49
Source dataset
uspto-grants-2012_01
Patent number
US08106197B2

Reaction notes

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