Benzylamine → HCID 21995436, compound

HRID 1977908Notes

Reaction equation

HRID 1977908 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[CH2:14][C:13](=O)O[C:10](=O)[CH2:9]2)=[CH:4][CH:3]=1.[CH2:16]([NH2:23])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>C1(C)C=CC=CC=1>[CH2:16]([N:23]1[CH2:13][CH2:14][CH:8]([C:5]2[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][CH:4]=2)[CH2:9][CH2:10]1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

4

Reactant 2

HCID 7504BenzylamineHCID 114927253-(4-bromophenyl)glutaric anhydride

Product 1

HCID 21995436HCID 21995436, compoundYield 50.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

To a 250 mL round-bottomed flask equipped with condenser and N2 inlet were added 4.77 g (17.72 mmol) 3-(4-bromophenyl)glutaric anhydride (prepared as described in J. Org. Chem., 21, 704 (1956)), 1.90 g (17.72 mmol) benzylamine, and 80 mL toluene. The reaction was refluxed 1.5 hours cooled, and concentrated. The residue was taken up in 80 mL acetic anhydride, and heated at 100° C. for 16 hours then cooled and evaporated several times with toluene to remove excess acetic anhydride. The residue was dissolved in 80 mL dry tetrahydrofuran and treated with 40 mL (80 mmol) of a 2 N solution of borane methyl sulfide in tetrahydrofuran. The reaction was refluxed 18 hours cooled, and evaporated, then dissolved in 80 mL ethanol and treated with 3.5 g sodium carbonate and 3.5 g cesium fluoride. The reaction was refluxed 16 hours cooled, and concentrated. The residue was taken up in water and ethyl acetate. The organic layer was separated, washed with brine, dried over sodium sulfate, and evaporated. The residue was chromatographed on silica gel using ethyl acetate/hexane as eluant to afford 2.94 g (50%) of an oil.

Workup

  1. customTo a 250 mL round-bottomed flask equipped with condenser and N2 inlet
  2. temperatureThe reaction was refluxed 1.5 hours
  3. temperaturecooled
  4. concentrationconcentrated
  5. temperaturethen cooled
  6. customevaporated several times with toluene
  7. customto remove excess acetic anhydride
  8. dissolutionThe residue was dissolved in 80 mL dry tetrahydrofuran
  9. additiontreated with 40 mL (80 mmol) of a 2 N solution of borane methyl sulfide in tetrahydrofuran
  10. temperatureThe reaction was refluxed 18 hours
  11. temperaturecooled
  12. customevaporated
  13. dissolutiondissolved in 80 mL ethanol
  14. additiontreated with 3.5 g sodium carbonate and 3.5 g cesium fluoride
  15. temperatureThe reaction was refluxed 16 hours
  16. temperaturecooled
  17. concentrationconcentrated
  18. customThe organic layer was separated
  19. washwashed with brine
  20. dry with materialdried over sodium sulfate
  21. customevaporated
  22. customThe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-e5870373ca7c4534962dbbc4c8b83e92
Source dataset
uspto-grants-2001_05
Patent number
US06235750B1

Reaction notes

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