Cesium carbonate → HCID 10171371, compound

HRID 2099498Notes

Reaction equation

HRID 2099498 reaction equation
[NH:1]1[CH:5]=[C:4]([C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][N:7]=2)[CH:3]=[N:2]1.Br[C:13]1[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].[NH4+].[Cl-]>CC1C=CC=CC=1C.C(S([O-])(=O)=O)(F)(F)F.C(S([O-])(=O)=O)(F)(F)F.[Cu+2].ClCCl>[N:15]1[CH:16]=[CH:17][CH:18]=[C:13]([N:1]2[CH:5]=[C:4]([C:6]3[CH:11]=[CH:10][CH:9]=[CH:8][N:7]=3)[CH:3]=[N:2]2)[CH:14]=1

Participants

9

Reactant 5

HCID 10796Cesium carbonateHCID 122863-BromopyridineHCID 25517Ammonium ChlorideHCID 95417Dibenzylidene acetoneHCID 35789812-(1H-pyrazol-4-yl)pyridine

Product 1

HCID 10171371HCID 10171371, compound

Reagents, catalysts & solvents 3

HCID 2734996copper(II) trifluoromethanesulfonateCatalystHCID 6344DichloromethaneSolventHCID 7237O-XyleneSolvent

Procedure

2-(1H-Pyrazol-4-yl)pyridine (292 mg, 2 mmol), 3-bromopyridine (0.23 mL, 2.4 mmol), Cu(OTf)2 (50 mg, 0.1 mmol), dibenzylideneacetone (24 mg, 0.1 mmol), Cs2CO3 (780 mg, 2.4 mmol) and 1,10-phenanthracene (360 mg, 2.4 mmol) in dry o-xylene (1.5 mL) under Ar (g) were heated at 115° C. for 18 h. After cooling to ambient temperature, NH4Cl (20 mL) and dichloromethane (20 mL) were added and the reaction mixture shaken, the dichloromethane layer was separated and the aqueous layer shaken with dichloromethane (2×20 mL). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to a brown oil. This was purified by liquid chromatography on silica gel eluting with EtOAc to give a solid that was further purified by HPLC to afford 2-(1-pyridin-3-yl-1H-pyrazol-4-yl)pyridine. 1H NMR (CD3Cl, 300 MHz) δ 9.08 (1H, d), 8.58-8.64 (2H, m), 8.56 (1H, s), 8.24 (1H, s), 8.12 (1H, ddd), 7.73 (1H, ddd), 7.56-7.59 (1H, m), 7.45 (1H, dd), 7.19 (1H, ddd). MS (ESI) 223 (M+H)+

Workup

  1. customthe dichloromethane layer was separated
  2. stirringthe aqueous layer shaken with dichloromethane (2×20 mL)
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. concentrationconcentrated in vacuo to a brown oil
  5. customThis was purified by liquid chromatography on silica gel eluting with EtOAc
  6. customto give a solid
  7. customthat was further purified by HPLC

Sources & evidence

ORD record
ord-2eddc24c364b4326af59546f1700e594
Source dataset
uspto-grants-2009_08
Patent number
US07569592B2

Reaction notes

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