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

HRID 408042Notes

Reaction equation

HRID 408042 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 Chem-Glass 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 ⅓volume and used without further purification. 1H NMR (CDCl3) δ 6.79 (dd, 1 H, J=4.6, 7.6 Hz), 7.19-7.60 (m, 9 H), 7.79-7.95 (m, 2 H), 8.16 (dd, 1 H, 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-c876a0606aa94da2bd5ae0922ee5380a
Source dataset
uspto-grants-2014_06
Patent number
US08754230B2

Reaction notes

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