2-Iodotoluene → 246853-44-1

HRID 928885Notes

Reaction equation

HRID 928885 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1I.[C:9]1([CH3:17])[C:10]([C:15]#[N:16])=[CH:11][CH:12]=[CH:13][CH:14]=1.[H-].[H-].[H-].[H-].[Li+].[Al+3].[OH-].[Na+]>C1COCC1.O>[C:9]1([CH3:17])[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[CH:15]([C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[CH3:1])[NH2:16]

Participants

7

Reactant 4

HCID 51282-IodotolueneHCID 107212-MethylbenzonitrileHCID 14798Sodium HydroxideHCID 21226445Aluminium lithium hydride

Product 1

HCID 10560454246853-44-1Yield 96%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
23 °C

Procedure

The following procedure was adapted from Zhang et al. (Org. Lett. 2008, 10, 5429-5432). To Mg turnings (1.53 g, 63.0 mmol, 1.50 equiv) in THF (50 mL) in an oven-dried round-bottom flask fitted with a reflux condenser was added 2-methyliodobenzene (11.0 g, 6.40 mL, 1.20 equiv) dropwise. The reaction mixture was heated to reflux for 1 h. To the reaction mixture was added o-tolunitrile (4.94 g, 5.00 mL, 42.2 mmol, 1.00 equiv) and the reaction mixture was heated to reflux for 22 h. The reaction mixture was cooled to 23° C. and a suspension of LiAlH4 (1.97 g, 51.9 mmol, 1.23 equiv) in THF (50 mL) was added and the reaction mixture was heated to reflux for 25 h. The reaction mixture was cooled to 23° C. and H2O (2 mL) was added dropwise. A solution of NaOH (2 mL, 1 M in H2O) was added slowly and 8 mL H2O was added. The reaction mixture was filtered through a celite pad, eluting with EtOAc, and concentrated. The residue was purified by Kugelrohr distillation (240 mTorr, 200° C.) to give di-o-tolylmethanamine as a yellow oil (8.52 g, 96% yield).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 1 h
  3. temperaturethe reaction mixture was heated
  4. temperatureto reflux for 22 h
  5. additionwas added
  6. temperaturethe reaction mixture was heated
  7. temperatureto reflux for 25 h
  8. temperatureThe reaction mixture was cooled to 23° C.
  9. filtrationThe reaction mixture was filtered through a celite pad
  10. washeluting with EtOAc
  11. concentrationconcentrated
  12. distillationThe residue was purified by Kugelrohr distillation (240 mTorr, 200° C.)

Sources & evidence

ORD record
ord-bb44d9ce65f146c49afd5872616a207f
Source dataset
uspto-grants-2016_03
Patent number
US09290591B2

Reaction notes

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