Cesium carbonate → HCID 68351647, compound

HRID 2401157Notes

Reaction equation

HRID 2401157 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:12]=[CH:11][NH:10][N:9]=2)=[CH:4][CH:3]=1.[CH:13]1(B(O)O)[CH2:15][CH2:14]1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C)C1C=CN=CC=1.C([O-])(=O)C.[Cu+2].C([O-])(=O)C.O1CCOCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:12]=[CH:11][N:10]([CH:13]3[CH2:15][CH2:14]3)[N:9]=2)=[CH:6][CH:7]=1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 2760897Cyclopropylboronic acidHCID 178419346HCID 178419346, compound

Product 1

HCID 68351647HCID 68351647, compound

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 142844-(Dimethylamino)pyridineCatalystHCID 312751,4-DioxaneSolvent

Procedure

A solution of 3-(4-bromophenyl)-1H-pyrazole (302 g, 1.35 mol), cyclopropylboronic acid (233 g, 2.71 mol), copper(II) acetate (246 g, 1.35 mol), 4-(dimethylamino)pyridine (662 g, 5.42 mol), cesium carbonate (1103 g, 3.39 mol), and 1,4-dioxane (8 L) was stirred at 90° C. for 36 h. The reaction mixture was cooled to room temperature before being filtered through Celite™, which was washed with EtOAc (4 L). The filtrate was acidified to pH 5 with 2 N HCl. The aqueous layer was extracted with EtOAc (12 L). The organic layers were combined, washed with brine, dried over MgSO4, filtered, and evaporated under reduced pressure. The resulting residue was purified on an ISCO 1500 g column eluting with a 0-20% EtOAc/Heptane gradient to afford the title compound. LC-MS: calculated for C12H11BrN2 262.01, 264.01, observed m/e: 263.04, 265.06 (M+H)+ (Rt 1.19/2 min).

Workup

  1. filtrationbefore being filtered through Celite™, which
  2. washwas washed with EtOAc (4 L)
  3. extractionThe aqueous layer was extracted with EtOAc (12 L)
  4. washwashed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated under reduced pressure
  8. customThe resulting residue was purified on an ISCO 1500 g column
  9. washeluting with a 0-20% EtOAc/Heptane gradient

Sources & evidence

ORD record
ord-6bfab3135e1d4a3496f25d6698db8a1a
Source dataset
uspto-grants-2014_08
Patent number
US08796258B2

Reaction notes

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