Diisopropylethylamine → HCID 59377753, compound

HRID 1691828Notes

Reaction equation

HRID 1691828 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5](I)=[CH:4][C:3]=1[NH2:10].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CCN(C(C)C)C(C)C.[CH3:62][S-:63].[Na+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Br:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([S:63][CH3:62])=[CH:4][C:3]=1[NH2:10]

Participants

7

Reactant 4

HCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 4378561Sodium methanethiolateHCID 59377877HCID 59377877, compound

Product 1

HCID 59377753HCID 59377753, compoundYield 50.6%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 2-bromo-4-chloro-5-iodo-phenylamine (0.573 g, 1.72 mmol) in dioxane (10 ml) was added Pd2(dba)3 (0.197 g, 0.2155 mmol), Xantphos (0.249 g, 0.431 mmol), Hunig base (0.60 ml, 3.448 mmol) and sodium thiomethoxide (0.133 g, 1.72 mmol). The mixture was heated at 80° C. for 6 hours. The mixture was cooled to room temperature and pH2 buffer was added. The mixture was extracted with EtOAc, and the combined organic layers were washed with water and brine, dried over MgSO4, filtered and concentrated to dryness under reduced pressure. Purification of the residue by flash chromatography (hex:EtOAc/7:3) gave 2-bromo-4-chloro-5-methylsulfanyl-phenylamine (0.22 g, 50%) as an oil.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. additionpH2 buffer was added
  3. extractionThe mixture was extracted with EtOAc
  4. washthe combined organic layers were washed with water and brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure
  8. customPurification of the residue by flash chromatography (hex:EtOAc/7:3)

Sources & evidence

ORD record
ord-6267fd04ff6c4a37977543cc0a625b61
Source dataset
uspto-grants-2012_04
Patent number
US08153809B2

Reaction notes

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