Cesium carbonate → 3-Chloro-N-(diphenylmethylene)pyridin-2-amine

HRID 2380944Notes

Reaction equation

HRID 2380944 reaction equation
Cl[C:2]1[C:7]([Cl:8])=[CH:6][CH:5]=[CH:4][N:3]=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].[C:61](=[NH:74])([C:68]1[CH:73]=[CH:72][CH:71]=[CH:70][CH:69]=1)[C:62]1[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=1>CC([O-])=O.CC([O-])=O.[Pd+2].C1COCC1>[Cl:8][C:7]1[C:2]([N:74]=[C:61]([C:62]2[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=2)[C:68]2[CH:73]=[CH:72][CH:71]=[CH:70][CH:69]=2)=[N:3][CH:4]=[CH:5][CH:6]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 169882,3-DichloropyridineHCID 136809Benzophenone imineHCID 634876Binap, (A+-)-

Product 1

HCID 581335953-Chloro-N-(diphenylmethylene)pyridin-2-amine

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

2,3-Dichloropyridine (105.00 g, 710 mmol), Pd(OAc)2 (3.98 g, 17.74 mmol), rac-BINAP (16.57 g, 26.61 mmol), cesium carbonate (346.76 g, 1065 mmol), THF (1.05 L), and benzophenone imine (124.67 mL, 745 mmol) were added to a 2 L CHEMGLASS® Reactor fitted with a mechanical stirrer and reflux condenser. The mixture was heated to reflux with stirring for 18 h. The material was filtered, washed with THF (100 mL). The resulting filtrate was concentrated in vacuo to ⅓ volume and used without further purification. 1H NMR (CDCl3) δ 6.79 (dd, 1H, J=4.6, 7.6 Hz), 7.19-7.60 (m, 9H), 7.79-7.95 (m, 2H), 8.16 (dd, 1H, J=1.5, 5.1 Hz); MS (ESI+) m/z 293.1 (M+H)+.

Workup

  1. customfitted with a mechanical stirrer
  2. temperaturereflux condenser
  3. temperatureThe mixture was heated
  4. temperatureto reflux
  5. filtrationThe material was filtered
  6. washwashed with THF (100 mL)
  7. concentrationThe resulting filtrate was concentrated in vacuo
  8. customused without further purification

Sources & evidence

ORD record
ord-ea38783b2f224ab18cd9b317b52fbd39
Source dataset
uspto-grants-2012_09
Patent number
US08258118B2

Reaction notes

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