Ammonium Hydroxide → (3,5-Dimethylpyridin-2-yl)methanamine

HRID 1592448Notes

Reaction equation

HRID 1592448 reaction equation
[CH3:1][C:2]1[C:3]([CH:9]=[N:10]O)=[N:4][CH:5]=[C:6]([CH3:8])[CH:7]=1.[NH4+].[OH-].C([O-])(=O)C.[NH4+]>[Zn].CCO>[CH3:1][C:2]1[C:3]([CH2:9][NH2:10])=[N:4][CH:5]=[C:6]([CH3:8])[CH:7]=1

Participants

6

Reactant 3

HCID 14923Ammonium HydroxideHCID 517165Ammonium AcetateHCID 1363418953,5-Dimethyl-pyridine-2-carbaldehyde oxime

Product 1

HCID 18507412(3,5-Dimethylpyridin-2-yl)methanamine

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 702EthanolSolvent

Conditions

Temperature
55 °C

Procedure

3,5-Dimethyl-pyridine-2-carbaldehyde oxime (3.15 g, 21.0 mmol), NH4OH (105 mL), ammonium acetate (3.24 g, 42.0 mmol), zinc dust (8.24 g, 126 mol) and EtOH (35 mL) were combined and warmed to 55° C. The mixture was stirred for 20 h, then cooled to ambient temperature and filtered through a celite pad to remove the zinc. The celite pad was thoroughly washed with methanol. The filtrate was concentrated in vacuo and the resulting aqueous mixture was extracted with CH2Cl2 (8×250 mL). The aqueous layer was basified to pH 14 with 10 N NaOH and extracted further with CH2Cl2/i-PrOH, 95:5 (5×250 mL). The combined organic layers were dried over Na2SO4 and concentrate in vacuo. Purification by flash chromatography on silica gel (CH2Cl2/MeOH/NH4OH, 95:4:1) afforded C-(3,5-dimethyl-pyridin-2-yl)-methylamine as an orange oil. 1H NMR (CDCl3) δ 2.26 (s, 3H), 2.28 (s, 3H), 3.91 (s, 2H), 7.24 (s, 1H), 8.23 (s, 1H).

Workup

  1. temperaturecooled to ambient temperature
  2. filtrationfiltered through a celite pad
  3. customto remove the zinc
  4. washThe celite pad was thoroughly washed with methanol
  5. concentrationThe filtrate was concentrated in vacuo
  6. extractionthe resulting aqueous mixture was extracted with CH2Cl2 (8×250 mL)
  7. extractionextracted further with CH2Cl2/i-PrOH, 95:5 (5×250 mL)
  8. dry with materialThe combined organic layers were dried over Na2SO4
  9. concentrationconcentrate in vacuo
  10. customPurification by flash chromatography on silica gel (CH2Cl2/MeOH/NH4OH, 95:4:1)

Sources & evidence

ORD record
ord-0d7c87d6726248c5952fac12929410fb
Source dataset
uspto-grants-2007_11
Patent number
US07291631B2

Reaction notes

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