Pyridine → HCID 67026915, compound

HRID 1908846Notes

Reaction equation

HRID 1908846 reaction equation
[CH2:1]([N:3]([CH2:13][CH3:14])[C:4]1[N:9]=[C:8]([CH:10]=O)[CH:7]=[C:6]([CH3:12])[CH:5]=1)[CH3:2].Cl.NO.[N:18]1C=CC=CC=1.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O>CN1C(=O)CCC1.C(Cl)Cl>[CH2:1]([N:3]([CH2:13][CH3:14])[C:4]1[N:9]=[C:8]([C:10]#[N:18])[CH:7]=[C:6]([CH3:12])[CH:5]=1)[CH3:2]

Participants

7

Reactant 4

HCID 1049PyridineHCID 67749Trifluoromethanesulfonic anhydrideHCID 443297Hydroxyamine hydrochlorideHCID 86657317HCID 86657317, compound

Product 1

HCID 67026915HCID 67026915, compoundYield 78.3%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

A solution of 6-diethylamino-4-methyl-pyridine-2-carbaldehyde (427 mg, 2.22 mmol) and hydroxylamine hydrochloride (232 mg, 3.33 mmol) in NMP (10 mL) is stirred at 80° C. for 3 h, then at 90° C. for 10 h under microwave irradiation. The solution is cooled to 0° C. before pyridine (1.10 g, 11.3 mmol) and trifluoromethane sulfonic anhydride (3.15 g, 11.2 mmol) is added. The mixture is warmed to rt and stirred for 18 h before it is diluted with DCM (100 mL) and washed with 10% aq. citric acid solution (50 mL) followed by sat. aq. Na2CO3 solution. The org. extract is dried over MgSO4, filtered and concentrated. The crude product is purified by CC on silica gel eluting with heptane:EA 7:3 to give 6-diethylamino-4-methyl-pyridine-2-carbonitrile (329 mg) as a pale yellow solid; LC-MS: tR=1.02 min, [M+1]+=190.02. 1H NMR (CDCl3): δ 1.19 (t, J=7.0 Hz, 6H), 2.28 (s, 3H), 3.52 (q, J=7.0 Hz, 4H), 6.44 (s, 1H), 6.74 (s, 1H).

Workup

  1. customat 90° C. for 10 h under microwave irradiation
  2. additionis added
  3. washwashed with 10% aq. citric acid solution (50 mL)
  4. extractionextract
  5. dry with materialis dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product is purified by CC on silica gel eluting with heptane:EA 7:3

Sources & evidence

ORD record
ord-bc2370d830cd4f018ca9a1cfebb7ddae
Source dataset
uspto-grants-2013_12
Patent number
US08598208B2

Reaction notes

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