Ethanol → HCID 19362825, compound

HRID 850290Notes

Reaction equation

HRID 850290 reaction equation
[C:1]1([CH:7]([NH2:15])[CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[CH2:17][C:18]#[CH:19].[C:20](=O)([O-])[O-].[K+].[K+].[CH3:26][CH2:27]O>[OH-].[Na+]>[CH2:17]([N:15]([CH:7]([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH2:8][C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)[CH2:20][C:27]#[CH:26])[C:18]#[CH:19]

Participants

6

Reactant 4

HCID 702EthanolHCID 7842Propargyl bromide2×HCID 11430Potassium CarbonateHCID 264821,2-Diphenylethylamine

Product 1

HCID 19362825HCID 19362825, compoundYield 19%

Reagents, catalysts & solvents 1

HCID 14798Sodium HydroxideSolvent

Procedure

To a stirred solution of 1,2diphenylethylamine (930 mg, 4.20 mmol) in EtOH (30 ml) were added 3-bromo-1-propyne (700 mg, 5.30 mmol) and potassium carbonate (1.38 g, 10.0 mmol). The mixture was refluxed for 16 h and then more 3-bromo-1-propyne (100 mg) was added. The mixture was refluxed another 6 h and then it was cooled, diluted with 1 N NaOH (200 ml) and extracted with CH2Cl2. The extract was dried (MgSO4) and concentrated. The residue was purified by flash chromatography. Elution with 1:1 hexanes-CH2Cl2 gave first N,N-di-propargyl-1,2-diphenylethylamine (218 mg, 19%) [1H NMR (CDCl3) δ2.34 (t, 2), 2.83 (dd, 1), 3.53 (dd, 1), 3.63 (dd, 2), 3.71 (dd, 2), 3.85 (dd, 1), 6.89-692 (m, 2), 7.14-7.26 (m, 8); 13C NMR (CDCl3) δ40.5 (t), 40.9 (t), 68.2 (d), 73.4 (d), 79.4 (d), 126.1, 127.6, 128.1, 128.3, 128.8, 129.7, 129.8 (all d), 138.8, 140.8 (all s)] followed by N-propargyl-1,2-diphenylethylamine. Distillation at 180° C./0.5 mm gave the pure compound (583 mg, 59%) as a colorless oil: 1H NMR (CDCl3) δ1.69 (bs, 1), 2.20 (t, 1), 2.95 (dd, 1), 3.06 (dd, 1), 3.24 (dd, 1), 3.36 (dd, 1), 4.21 (dd, 1), 7.25-7.50 (m, 10); 13C NMR (CDCl3) δ36.0 (t), 45.1 (t), 62.6 (d), 71.6 (d), 82.2 (s), 126.7, 127.6, 127.8, 128.7, 129.5 (all d), 138.6, 142.7 (all s).

Workup

  1. temperatureThe mixture was refluxed for 16 h
  2. temperatureThe mixture was refluxed another 6 h
  3. temperatureit was cooled
  4. extractionextracted with CH2Cl2
  5. dry with materialThe extract was dried (MgSO4)
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography
  8. washElution with 1:1 hexanes-CH2Cl2

Sources & evidence

ORD record
ord-96e8d869885b471487adc9efc63fca6e
Source dataset
uspto-grants-2000_01
Patent number
US06017910

Reaction notes

Loading…