HCID 67027125, compound → HCID 86657317, compound

HRID 1908845Notes

Reaction equation

HRID 1908845 reaction equation
[CH2:1]([N:3]([CH2:15][CH3:16])[C:4]1[N:9]=[C:8]([CH:10]([OH:13])CO)[CH:7]=[C:6]([CH3:14])[CH:5]=1)[CH3:2]>C1COCC1.O.CC(=O)OCC>[CH2:15]([N:3]([CH2:1][CH3:2])[C:4]1[N:9]=[C:8]([CH:10]=[O:13])[CH:7]=[C:6]([CH3:14])[CH:5]=1)[CH3:16]

Participants

5

Reactant 1

HCID 67027125HCID 67027125, compound

Product 1

HCID 86657317HCID 86657317, compoundYield 90.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of diethyl-(4-methyl-6-vinyl-pyridin-2-yl)-amine (457 mg, 2.40 mmol), N-methyl-morpholine-N-oxide (885 mg), and OsO4 (5 mg, 20 μmol, 200 μL of a 2.5% solution in tert.-butanol) in acetone (16 mL) and water (2 mL) is stirred at rt for 18 h. The mixture is diluted with EA (200 mL) and washed with water (50 mL). The org. extract is dried over MgSO4, filtered and concentrated to give crude 1-(6-diethylamino-4-methyl-pyridin-2-yl)ethane-1,2-diol (550 mg) as a brown oil; LC-MS: tR=0.55 min, [M+1]+=225.03. 1H NMR (CDCl3): δ 1.20 (t, J=7.0 Hz, 6H), 2.27 (s, 3H), 3.51 (q, J=7.0 Hz, 4H), 3.71 (dd, J=11.3, 5.8 Hz, 1H), 3.75 (s br, 1H), 3.88 (dd, J=11.0, 3.8 Hz, 1H), 4.62 (t, J=4.8 Hz, 1H), 6.22 (s, 1H), 6.33 (s, 1H). A solution of the above crude 1-(6-diethylamino-4-methyl-pyridin-2-yl)-ethane-1,2-diol (550 mg, 2.45 mmol) and NaIO4 (857 mg, 4.01 mmol) in THF (18 mL) and water (3 mL) is stirred at rt for 7 h before another portion of NaIO4 (524 mg, 2.45 mmol) is added. Stirring is continued for 16 h. The mixture is diluted with EA, washed with water, dried over MgSO4, filtered and concentrated to give crude 6-diethylamino-4-methyl-pyridine-2-carbaldehyde (427 mg) as a green oil; LC-MS: tR=0.55 min, [M+1]+=193.01; 1H NMR (CDCl3): δ 1.22 (t, J=7.0 Hz, 6H), 2.34 (s, 3H), 3.60 (q, J=7.0 Hz, 4H), 6.49 (s, 1H), 7.04 (s, 1H), 9.89 (s, 1H).

Workup

  1. additionis added
  2. washwashed with water
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-b6c3829ca95446f5aa60459350545b83
Source dataset
uspto-grants-2013_12
Patent number
US08598208B2

Reaction notes

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