Water → 2-Allyloxy-5-methoxybenzylamine

HRID 501730Notes

Reaction equation

HRID 501730 reaction equation
[CH2:1]([O:4][C:5]1[CH:14]=[CH:13][C:12]([O:15][CH3:16])=[CH:11][C:6]=1[CH2:7][N:8]=[N+]=[N-])[CH:2]=[CH2:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O>C1COCC1>[CH2:1]([O:4][C:5]1[CH:14]=[CH:13][C:12]([O:15][CH3:16])=[CH:11][C:6]=1[CH2:7][NH2:8])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 962WaterHCID 11776TriphenylphosphineHCID 866223532-Allyloxy-5-methoxybenzyl azide

Product 1

HCID 608800312-Allyloxy-5-methoxybenzylamineYield 55%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Step AS (4). To a solution of 2-allyloxy-5-methoxybenzyl azide (4.5 g, 21 mmol) in 150 mL of anhydrous THF was added triphenylphosphine (10.8 g, 41 mmol) and 0.5 mL of water. The mixture was stirred at rt for 7 h. The reaction was concentrated under vacuum and the residue was partitioned between Et2O and 2 N HCl. The aqueous layer was basified with 2 N NaOH to pH 10 and extracted with EtOAc (3×40 mL). The organic layers were combined and washed with brine then dried over magnesium sulfate. After concentration, the residue was purified by silica gel chromatography, eluting with a mixture of 30% 2N ammonia in methanol and 70% EtOAc to yield 2-allyloxy-5-methoxybenzylamine as colorless oil (2.2 g, 55%). LC-MS (M+H)+=194; 1H NMR (400 MHz, CD3OD) δ ppm 3.75 (s, 3H) 4.08 (s, 2H) 4.60 (d, J=5.29 Hz, 2H) 5.22-5.30 (m, J=10.58 Hz, 1H) 5.35-5.44 (m, J=17.37 Hz, 1H) 6.01-6.15 (m, 1H) 6.89-6.96 (m, 2H) 6.96-7.02 (m, 1H).

Workup

  1. concentrationThe reaction was concentrated under vacuum
  2. customthe residue was partitioned between Et2O and 2 N HCl
  3. extractionextracted with EtOAc (3×40 mL)
  4. washwashed with brine
  5. dry with materialthen dried over magnesium sulfate
  6. concentrationAfter concentration
  7. customthe residue was purified by silica gel chromatography
  8. washeluting with a mixture of 30% 2N ammonia in methanol and 70% EtOAc

Sources & evidence

ORD record
ord-898e8d903d7e480fb1c174e29e8e65c7
Source dataset
uspto-grants-2010_08
Patent number
US07772221B2

Reaction notes

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