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

HRID 1280455Notes

Reaction equation

HRID 1280455 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, 10 mmol) and diethoxymethylenemalonate (2.16 g, 10 mmol) 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 data 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-ce3f2991dff14eb59e8c8ae7f68f8be7
Source dataset
uspto-grants-2002_09
Patent number
US06451811B2

Reaction notes

Loading…