4-Iodoaniline → 2',4'-Dichloro-[1,1'-biphenyl]-4-amine

HRID 405188Notes

Reaction equation

HRID 405188 reaction equation
I[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[Cl:9][C:10]1[CH:15]=[C:14]([Cl:16])[CH:13]=[CH:12][C:11]=1B(O)O.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.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]>[Cl:9][C:10]1[CH:15]=[C:14]([Cl:16])[CH:13]=[CH:12][C:11]=1[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 108934-IodoanilineHCID 11430Potassium CarbonateHCID 2734659(2,4-Dichlorophenyl)boronic acid

Product 1

HCID 99647252',4'-Dichloro-[1,1'-biphenyl]-4-amine

Reagents, catalysts & solvents 2

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

Conditions

Temperature
70 °C

Procedure

4-Iodoaniline (6.9 g, 31.7 mmol), (2,4-dichlorophenyl)boronic acid (7.3 g, 38.0 mmol), Pd(dppf)Cl2 (1.3 g, 1.6 mmol), and 2M aqueous K2CO3 (31.7, 63.4 mmol) were dissolved in 1,4-dioxane (127 mL) and the resulting mixture was heated to 70° C. After 2.5 d the resulting mixture was cooled to room temperature, concentrated, diluted with EtOAc and 4M aqueous NaCl, and the layers were separated. The aqueous layer was extracted with EtOAc and the combined organics were dried (Na2SO4), concentrated, and purified via column chromatography to yield the title compound.

Workup

  1. temperatureAfter 2.5 d the resulting mixture was cooled to room temperature
  2. concentrationconcentrated
  3. additiondiluted with EtOAc and 4M aqueous NaCl
  4. customthe layers were separated
  5. extractionThe aqueous layer was extracted with EtOAc
  6. dry with materialthe combined organics were dried (Na2SO4)
  7. concentrationconcentrated
  8. custompurified via column chromatography

Sources & evidence

ORD record
ord-70f8c933c2d54f4198c7ae1695175cad
Source dataset
uspto-grants-2014_06
Patent number
US08748624B2

Reaction notes

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