Water → HCID 67027125, compound

HRID 1908844Notes

Reaction equation

HRID 1908844 reaction equation
[CH2:1]([N:3]([CH2:13][CH3:14])[C:4]1[CH:9]=[C:8]([CH3:10])[CH:7]=[C:6]([CH:11]=[CH2:12])[N:5]=1)[CH3:2].C[N+]1([O-])CC[O:19]CC1.[OH2:23]>C(O)(C)(C)C.CC(C)=O.CC(=O)OCC.O=[Os](=O)(=O)=O>[CH2:13]([N:3]([CH2:1][CH3:2])[C:4]1[N:5]=[C:6]([CH:11]([OH:19])[CH2:12][OH:23])[CH:7]=[C:8]([CH3:10])[CH:9]=1)[CH3:14]

Participants

8

Reactant 3

HCID 962WaterHCID 82029Methyl morpholine oxideHCID 67026903HCID 67026903, compound

Product 1

HCID 67027125HCID 67027125, compound

Reagents, catalysts & solvents 4

HCID 30318Osmium TetroxideCatalystHCID 180AcetoneSolventHCID 6386tert-ButanolSolventHCID 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. washwashed with water (50 mL)
  2. extractionextract
  3. dry with materialis dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-f8ac70d3333648798108ad919361b44c
Source dataset
uspto-grants-2013_12
Patent number
US08598208B2

Reaction notes

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