Cesium carbonate → 3-Bromo-4-chloro-5-cyclopropylpyridine

HRID 1521565Notes

Reaction equation

HRID 1521565 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Br:9])[C:7]=1[Cl:8].[CH:10]1(B(O)O)[CH2:12][CH2:11]1.C(=O)([O-])[O-].[Cs+].[Cs+].O1CCOCC1>O>[Br:9][C:6]1[CH:5]=[N:4][CH:3]=[C:2]([CH:10]2[CH2:12][CH2:11]2)[C:7]=1[Cl:8]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 8170943,5-Dibromo-4-chloropyridineHCID 2760897Cyclopropylboronic acid

Product 1

HCID 709778753-Bromo-4-chloro-5-cyclopropylpyridine

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred solution of 3,5-dibromo-4-chloropyridine (X, 0.5 g, 1.84 mmol) and cyclopropylboronic acid (0.17 g, 2.02 mmol), cesium carbonate (1.19 g, 3.68 mmol) in the mixture of 1,4-dioxan (10 mL) and water (2 mL). The reaction mass was purged with nitrogen for 15 min. Then catalyst Pd (dppf)2Cl2 (0.075 g, 0.09 mmol) was added and allowed to stir at 100° C. for 4 h. The reaction mixture was filtered through Mite bed and filter bed was thoroughly washed with ethyl acetate. The collected organic parts were concentrated under vacuum to afford the crude compound, which was purified by column chromatography using 10-40% ethyl acetate/hexane as an eluent to obtain title compound. MS (M+1): 233.0.

Workup

  1. customThe reaction mass was purged with nitrogen for 15 min
  2. filtrationThe reaction mixture was filtered through Mite bed
  3. filtrationfilter bed
  4. washwas thoroughly washed with ethyl acetate
  5. concentrationThe collected organic parts were concentrated under vacuum
  6. customto afford the crude compound, which
  7. customwas purified by column chromatography

Sources & evidence

ORD record
ord-cab961102af34701863775feefb14831
Source dataset
uspto-grants-2015_07
Patent number
US09073929B2

Reaction notes

Loading…