Potassium Phosphate, Tribasic → N-(4-Methoxybenzyl)-6-(benzyloxy)naphthalen-2-amine

HRID 1511449Notes

Reaction equation

HRID 1511449 reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6]([CH2:7][NH2:8])=[CH:5][CH:4]=1.[CH2:11]([O:18][C:19]1[CH:28]=[CH:27][C:26]2[C:21](=[CH:22][CH:23]=[C:24](Br)[CH:25]=2)[CH:20]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].N1CCC[C@H]1C(O)=O>CS(C)=O>[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6]([CH2:7][NH:8][C:24]2[CH:23]=[CH:22][C:21]3[C:26](=[CH:27][CH:28]=[C:19]([O:18][CH2:11][C:12]4[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=4)[CH:20]=3)[CH:25]=2)=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 754524-MethoxybenzylamineHCID 145742L-ProlineHCID 6405952-(Benzyloxy)-6-bromonaphthalene

Product 1

HCID 25139545N-(4-Methoxybenzyl)-6-(benzyloxy)naphthalen-2-amineYield 27%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
80 °C

Procedure

4-Methoxy-benzylamine (3.40 mL, 3.59 g, 26.20 mmol) and anhydrous DMSO (5.20 mL) were added to a high-pressure flask charged with 36 (3.00 g, 9.58 mmol), K3PO4 (4.19 g, 19.73 mmol), CuII (290 mg, 1.52 mmol), and L-(−)-proline (255 mg, 2.21 mmol); the sealed flask was heated to 80° C. for 44 hours. After cooling to room temperature, reaction contents were partitioned between water (100 mL) and EtOAc (200 mL), then were extracted with EtOAc (2×200 mL). The combined organic layers were washed with saturated aqueous NaCl solution (500 mL), dried (Na2SO4), filtered, and concentrated. The residue was purified via column chromatography (SiO2, 7:1:1 Hexanes:CH2Cl2:EtOAc) to give 37 as a light orange amorphous solid (952 mg, 27%): 1H NMR (CDCl3, 500 MHz) δ 7.55 (d, J=8.7 Hz, 2H), 7.49 (m, 2H), 7.41 (m, 2H), 7.37-7.32 (m, 3H), 7.15 (dd, J=8.8, 2.6 Hz, 1H), 7.13 (m, 1H), 6.92 (dd, J=8.8, 2.3 Hz, 1H), 6.90 (d, J=8.7 Hz, 2H), 6.87 (m, 1H), 5.14 (s, 2H), 4.35 (s, 2H), 3.82 (s, 3H); 13C NMR (CDCl3, 125 MHz) δ 159.1, 154.6, 137.4, 130.7, 129.3 (2C), 128.8 (2C), 128.1, 128.0, 127.8 (2C), 119.4 (2C), 118.6, 114.3 (2C), 107.9, 70.3, 55.5; IR (film) νmax 3734, 1558, 1456, 1259, 1167, 847, 746, 702, 660 cm−1; HRMS (ESI+) m/z: [M+H]+ calcd for C25H23NO2, 370.1807; found, 370.1786.

Workup

  1. temperatureAfter cooling to room temperature
  2. customreaction contents
  3. customwere partitioned between water (100 mL) and EtOAc (200 mL)
  4. extractionwere extracted with EtOAc (2×200 mL)
  5. washThe combined organic layers were washed with saturated aqueous NaCl solution (500 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified via column chromatography (SiO2, 7:1:1 Hexanes:CH2Cl2:EtOAc)

Sources & evidence

ORD record
ord-b95199de15d2458eb9eb8ab61c57b0ca
Source dataset
uspto-grants-2012_07
Patent number
US08212012B2

Reaction notes

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