Benzenamine, 4-chloro-2-methoxy- → HCID 71062387, compound

HRID 1479129Notes

Reaction equation

HRID 1479129 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl:47][C:48]1[CH:54]=[CH:53][C:51]([NH2:52])=[C:50]([O:55][CH3:56])[CH:49]=1.I[C:58]1[CH:63]=[CH:62][C:61]([Cl:64])=[CH:60][CH:59]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:47][C:48]1[CH:54]=[CH:53][C:51]([NH:52][C:58]2[CH:63]=[CH:62][C:61]([Cl:64])=[CH:60][CH:59]=2)=[C:50]([O:55][CH3:56])[CH:49]=1

Participants

7

Reactant 4

HCID 7143Benzenamine, 4-chloro-2-methoxy-HCID 125101-Chloro-4-iodobenzeneHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxide

Product 1

HCID 71062387HCID 71062387, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

A solution of palladium (II) acetate (949 mg, Precious Metals Online) and (+/−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (2.63 g, Alfa-Aesar) in toluene (1000 mL) was heated to 50° C. under argon then cooled to room temperature. 4-Chloro-2-methoxyaniline (66.6 g), 4-iodochlorobenzene (105.81 g, Apollo Scientific) and sodium tert-butoxide (44.68 g, Alfa-Aesar) were added and the mixture was heated to reflux for 90 minutes. The mixture was cooled to room temperature, quenched with water (500 mL) then the organics were separated, dried (MgSO4) and concentrated. The residue was absorbed onto silica and columned eluting ethyl acetate/heptane mixtures to give the product as a dark orange oil that solidified on standing. Yield: 97.86 g. 1H NMR (400 MHz, CDCl3): δ 7.18-7.23 (2H, m, ArH), 7.12 (1H, d, ArH), 7.00-7.05 (2H, m, ArH), 6.82-6.85 (2H, m, ArH), 6.00 (1H, br s, NH), 3.87 (3H, s, OMe).

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 90 minutes
  3. temperatureThe mixture was cooled to room temperature
  4. customquenched with water (500 mL)
  5. customthe organics were separated
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customThe residue was absorbed onto silica
  9. washcolumned eluting ethyl acetate/heptane

Sources & evidence

ORD record
ord-b18740f833e64830a66363c8044b7e5f
Source dataset
uspto-grants-2016_08
Patent number
US09406886B2

Reaction notes

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