Methyl iodide → 3,4-Diaminopyridine

HRID 967979Notes

Reaction equation

HRID 967979 reaction equation
[CH2:1]([CH:3]([NH:6][C:7]1[CH:12]=[C:11]([CH3:13])[N:10]=[C:9]([O:14][C:15]2[C:20]([CH3:21])=[CH:19][C:18]([CH3:22])=[CH:17][C:16]=2[CH3:23])[C:8]=1[NH2:24])[CH2:4][CH3:5])[CH3:2].[Li]N([Si](C)(C)C)[Si](C)(C)[CH3:28].CI>C1COCC1>[N:10]1[CH:11]=[CH:12][C:7]([NH2:6])=[C:8]([NH2:24])[CH:9]=1.[CH2:1]([CH:3]([NH:6][C:7]1[CH:12]=[C:11]([CH3:13])[N:10]=[C:9]([O:14][C:15]2[C:20]([CH3:21])=[CH:19][C:18]([CH3:22])=[CH:17][C:16]=2[CH3:23])[C:8]=1[NH:24][CH3:28])[CH2:4][CH3:5])[CH3:2]

Participants

6

Reactant 3

HCID 6328Methyl iodideHCID 219121512-(2,4,6-trimethylphenoxy)-N4-(1-ethylpropyl)-6-methyl-pyridine-3,4-diamineHCID 178418261HCID 178418261, compound

Product 2

HCID 59183,4-DiaminopyridineHCID 21912312N4-(1-ethyl-propyl)-6,N3-dimethyl-2-(2,4,6-trimethyl-phenoxy)-pyridine-3,4-diamine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of N4-(1-ethyl-propyl)-6-methyl-2-(2,4,6-trimethyl-phenoxy)-pyridine-3,4-diamine (0.250 g, 0.763 mmol) in dry THF (6 ml) was treated with 1M LiN(SiMe3)2 in THF (1.0 ml, 1.0 mmol) at −78° C. and stirred for 10 min. an excess of methyl iodide was added and the resulting mixture was stirred at room temperature overnight. The mixture was quenched with water and extracted with ethyl acetate. The organic layer was dried and concentrated to give a crude material. The crude material was purified through silica gel column chromatography using 5% ethyl acetate in hexane as eluent to give N4-(1-ethyl-propyl)-6,N3,N3-trimethyl-2,4,6-trimethyl-phenoxy)-pyridine-3,4-diamine and N4-(1-ethyl-propyl)-6,N3-dimethyl-2-(2,4,6-trimethyl-phenoxy)-pyridine-3,4-diamine.

Workup

  1. additionwas added
  2. customThe mixture was quenched with water
  3. extractionextracted with ethyl acetate
  4. customThe organic layer was dried
  5. concentrationconcentrated
  6. customto give a crude material
  7. customThe crude material was purified through silica gel column chromatography

Sources & evidence

ORD record
ord-b9fcad36dba14aeeb4a5b96506198056
Source dataset
uspto-grants-2005_10
Patent number
US06956047B1

Reaction notes

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