Dichloromethane → 4-[6-(trifluoromethyl)pyridin-3-yl]-9H-carbazole

HRID 1877480Notes

Reaction equation

HRID 1877480 reaction equation
[F:1][C:2]([F:13])([F:12])[C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][N:4]=1.C(=O)([O-])[O-].[Cs+].[Cs+].ClCCl.FC(F)(F)S(O[C:29]1[C:41]2[C:40]3[C:35](=[CH:36][CH:37]=[CH:38][CH:39]=3)[NH:34][C:33]=2[CH:32]=[CH:31][CH:30]=1)(=O)=O>O1CCOCC1.O.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:1][C:2]([F:13])([F:12])[C:3]1[N:4]=[CH:5][C:6]([C:29]2[C:41]3[C:40]4[C:35](=[CH:36][CH:37]=[CH:38][CH:39]=4)[NH:34][C:33]=3[CH:32]=[CH:31][CH:30]=2)=[CH:7][CH:8]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 10796Cesium carbonateHCID 251342782-(Trifluoromethyl)pyridine-5-boronic AcidHCID 583383234-Trifluoromethanesulphonyloxycarbazole

Product 1

HCID 673081124-[6-(trifluoromethyl)pyridin-3-yl]-9H-carbazoleYield 49.6%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

0.96 g of [2-trifluoromethylpyridin-5-yl]boronic acid, 4.55 g of caesium carbonate and 0.13 g of 1,1′-bis(diphenylphosphino)ferrocenepalladium(II) dichloride as a complex with dichloromethane (1/1) [PdCl2(dppf).CH2Cl2] are successively added, under argon, to a solution of 1.1 g of 4-trifluoromethanesulphonyloxycarbazole, obtained in stage 1 of Example 1, in a mixture of 50 ml of dioxane and 17 ml of water. The reaction mixture is refluxed for 5 hours, filtered through celite and concentrated under reduced pressure. The residue is subsequently purified by silica gel chromatography, elution being carried out with a mixture of cyclohexane and ethyl acetate (85/15 by volume) so as to give 0.54 g of 4-[6-(trifluoromethyl)pyridin-3-yl]-9H-carbazole in the form of a pale yellow oil, the characteristics of which are the following:

Workup

  1. temperatureThe reaction mixture is refluxed for 5 hours
  2. filtrationfiltered through celite and
  3. concentrationconcentrated under reduced pressure
  4. customThe residue is subsequently purified by silica gel chromatography, elution
  5. additionbeing carried out with a mixture of cyclohexane and ethyl acetate (85/15 by volume) so as

Sources & evidence

ORD record
ord-908408c3dd9f4875a5d115f68391208e
Source dataset
uspto-grants-2012_11
Patent number
US08309721B2

Reaction notes

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