2-Pyridinamine, 5-bromo-6-methyl- → HCID 178469685, compound

HRID 2227161Notes

Reaction equation

HRID 2227161 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([CH3:8])[C:5]([Br:9])=[CH:4][CH:3]=1.[CH2:10]([O:12][C:13](=[C:17]([C:21]([O-])=O)[C:18]([O-])=[O:19])[O:14]CC)[CH3:11]>>[Br:9][C:5]1[CH:4]=[C:3]2[C:2](=[N:7][C:6]=1[CH3:8])[N:1]=[CH:21][C:17]([C:13]([O:12][CH2:10][CH3:11])=[O:14])=[C:18]2[OH:19]

Participants

3

Reactant 2

HCID 1706782-Pyridinamine, 5-bromo-6-methyl-HCID 23435867Diethoxymethylenemalonate

Product 1

HCID 178469685HCID 178469685, compoundYield 35%

Conditions

Temperature
250 °C

Procedure

A solution of 6-amino-3-bromo-2-methylpyridine (1.89 g) and diethoxymethylenemalonate (2.16 g) is heated at 110° C. for 30 min. The reaction is cooled and the residue is recrystallized from EtOH. To the resulting solid is dissolved in 45 mL of Ph2O. The mixture is heated to 250° C. for 3 h. The solution is then cooled to room temperature and the resulting precipitate is collected and dried. The crude product is chromatographed on silica (Biotage flash 40M, 2% MeOH/CH2Cl2 eluent). Fractions homogeneous by TLC are collected and concentrated to yield 1.075 g (35%) of the desired product as a yellow solid. Physical characteristics are as follows: m.p. 270° C. (dec.); 1H NMR (DMSO-d6) δ 12.73, 8.49, 8.47, 4.21, 2.67, 1.27.

Workup

  1. temperatureThe reaction is cooled
  2. customthe residue is recrystallized from EtOH
  3. dissolutionTo the resulting solid is dissolved in 45 mL of Ph2O
  4. temperatureThe solution is then cooled to room temperature
  5. customthe resulting precipitate is collected
  6. customdried
  7. customThe crude product is chromatographed on silica (Biotage flash 40M, 2% MeOH/CH2Cl2 eluent)
  8. customFractions homogeneous by TLC are collected
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-e33cb9c712d5481092fd79be09c4c56e
Source dataset
uspto-grants-2002_07
Patent number
US06413958B2

Reaction notes

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