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

HRID 1645418Notes

Reaction equation

HRID 1645418 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-40549f25fa0e42a09b9e4cf6aba0c2f4
Source dataset
uspto-grants-2012_02
Patent number
US08124768B2

Reaction notes

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