O-Phenylenediamine → HCID 66835989, compound

HRID 2404486Notes

Reaction equation

HRID 2404486 reaction equation
[C:1]1([NH2:8])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[NH2:7].C[Al](C)C.CO[C:15](=O)[CH:16]([C:25]1[CH:30]=[CH:29][CH:28]=[C:27]([Br:31])[CH:26]=1)[S:17][C:18]1[CH2:19][CH2:20][N:21]([CH3:24])[CH2:22][CH:23]=1.[OH-].[Na+]>C1(C)C=CC=CC=1.O>[Br:31][C:27]1[CH:26]=[C:25]([CH:16]([S:17][C:18]2[CH2:23][CH2:22][N:21]([CH3:24])[CH2:20][CH:19]=2)[C:15]2[NH:8][C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=3[N:7]=2)[CH:30]=[CH:29][CH:28]=1

Participants

7

Reactant 4

HCID 7243O-PhenylenediamineHCID 14798Sodium HydroxideHCID 16682925TrimethylaluminumHCID 66835810HCID 66835810, compound

Product 1

HCID 66835989HCID 66835989, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent3×

Conditions

Temperature
75 °C

Procedure

To a solution of 1,2-phenylenediamine (213 mg) in toluene (2 mL) is added dropwise a solution of 2M trimethylaluminium in toluene (1 ml). The reaction mixture is heated at 75° C. for 2 hours then a solution of (3-bromophenyl)(1-methyl-1,2,3,6-tetrahydropyridin-4-ylsulfanyl)acetic acid methyl ester (example 530B, 358 mg) in toluene (2 mL) is added, and the heating is continued at 75° C. for 3 hours. Water is added and the reaction mixture is made alkaline by adding 1N sodium hydroxide. The aqueous phase is extracted by ethyl acetate. The organic phase is washed by water, brine, then dried over magnesium sulfate and concentrated. The residue is the dissolved in acetic acid (5 mL) and the reaction mixture is refluxed for 3 hours. The solvent is removed under reduced pressure. Water is added and the reaction mixture is made alkaline by adding 2N sodium hydroxide. The aqueous phase is extracted by ethyl acetate. The organic phase is washed by water, brine, then dried over magnesium sulfate and concentrated. The residual solid is triturated with acetonitrile, filtered and the solid is washed with diethyl ether to give 2-[(3-bromophenyl)(1-methyl-1,2,3,6-tetrahydropyridin-4-ylsulfanyl)methyl]-1H-benzimidazole melting at 189° C.

Workup

  1. extractionThe aqueous phase is extracted by ethyl acetate
  2. washThe organic phase is washed by water, brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated
  5. dissolutiondissolved in acetic acid (5 mL)
  6. temperaturethe reaction mixture is refluxed for 3 hours
  7. customThe solvent is removed under reduced pressure
  8. additionWater is added
  9. additionby adding 2N sodium hydroxide
  10. extractionThe aqueous phase is extracted by ethyl acetate
  11. washThe organic phase is washed by water, brine
  12. dry with materialdried over magnesium sulfate
  13. concentrationconcentrated
  14. customThe residual solid is triturated with acetonitrile
  15. filtrationfiltered
  16. washthe solid is washed with diethyl ether

Sources & evidence

ORD record
ord-20ab1e84cc4649568dd73b3a26336ada
Source dataset
uspto-grants-2014_08
Patent number
US08802664B2

Reaction notes

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