4-Bromopyridinium chloride → 1245915-23-4

HRID 1890252Notes

Reaction equation

HRID 1890252 reaction equation
Cl.Br[C:3]1[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=1.[C:9]([C:11]1[CH:16]=[CH:15][C:14]([C:17]([F:20])([F:19])[F:18])=[CH:13][CH:12]=1)#[CH:10]>C(N(CC)CC)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[F:18][C:17]([F:19])([F:20])[C:14]1[CH:13]=[CH:12][C:11]([C:9]#[C:10][C:3]2[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=2)=[CH:16][CH:15]=1

Participants

6

Reactant 2

HCID 881004-Bromopyridinium chlorideHCID 43482951-Ethynyl-4-(trifluoromethyl)benzene

Product 1

HCID 674415791245915-23-4

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
90 °C

Procedure

Under argon, a mixture of 1.20 g (6.17 mmol) of 4-bromopyridine hydrochloride, 1.57 g (9.26 mmol) of 1-ethynyl-4-(trifluoromethyl)benzene, 88 mg (0.46 mmol) of copper(I) iodide and 251 mg (0.31 mmol) of Pd(dppf)Cl2 in 10 ml of triethylamine is heated at 90° C. for 3 h. After concentration, the reaction mixture is taken up in 100 ml of ethyl acetate and washed with 2×100 ml of 1M HCl. The aqueous phase is adjusted to pH 10 using aqueous sodium hydroxide solution and extracted with 3×100 ml of chloroform. The combined organic phases are washed with saturated aqueous NaCl solution, dried over Na2SO4 and freed from the solvent under reduced pressure. This gives 380 mg (24%) of the desired product; log P(HCOOH): 2.86; 1H-NMR (DMSO-d6) δ: 8.66 (d, 2H), 7.84 (s, 4H), 7.58 (d, 2H)

Workup

  1. concentrationAfter concentration
  2. washwashed with 2×100 ml of 1M HCl
  3. extractionextracted with 3×100 ml of chloroform
  4. washThe combined organic phases are washed with saturated aqueous NaCl solution
  5. dry with materialdried over Na2SO4

Sources & evidence

ORD record
ord-3445dc44c8de449eb51c7b31522d5736
Source dataset
uspto-grants-2013_08
Patent number
US08507472B2

Reaction notes

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