Ammonium Chloride → 5-{2-Iodo-5-[(trimethylsilyl)ethynyl]phenoxy}pyrimidine-2,4-diamine

HRID 491500Notes

Reaction equation

HRID 491500 reaction equation
[I:1][C:2]1[CH:16]=[C:15](OC)[C:14](I)=[CH:13][C:3]=1[O:4][C:5]1[C:6]([NH2:12])=[N:7][C:8]([NH2:11])=[N:9][CH:10]=1.[CH3:20][Si:21]([C:24]#[CH:25])([CH3:23])[CH3:22].C(N(C(C)C)CC)(C)C.[NH4+].[Cl-]>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:20][Si:21]([CH3:23])([CH3:22])[C:24]#[C:25][C:2]1[CH:16]=[CH:15][C:14]([Si:21]([CH3:23])([CH3:22])[CH3:20])=[CH:13][C:3]=1[O:4][C:5]1[C:6]([NH2:12])=[N:7][C:8]([NH2:11])=[N:9][CH:10]=1.[I:1][C:2]1[CH:16]=[CH:15][C:14]([C:25]#[C:24][Si:21]([CH3:23])([CH3:22])[CH3:20])=[CH:13][C:3]=1[O:4][C:5]1[C:6]([NH2:12])=[N:7][C:8]([NH2:11])=[N:9][CH:10]=1

Participants

9

Reactant 4

HCID 25517Ammonium ChlorideHCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 57678441HCID 57678441, compound

Product 2

HCID 688390485-{2-Iodo-5-[(trimethylsilyl)ethynyl]phenoxy}pyrimidine-2,4-diamineHCID 86611075HCID 86611075, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

To a mixture of 5-(2,5-diiodo-4-methoxy-phenoxy)-pyrimidine-2,4-diamine (2.043 g, 4.5 mmol), bis(triphenylphosphine)palladium dichloride (0.316 g, 0.45 mmol) and CuI (43 mg, 0.225 mmol) in 14 mL dry THF was added trimethylsilylacetylene (0.441 g, 4.5 mmol), followed by diisopropylethylamine (7 mL). The reaction mixture was heated at 50° C. under nitrogen atmosphere for 20 hours. The reaction mixture was cooled, poured into saturated aqueous NH4Cl and extracted with dichloromethane. The combined organic layers were washed with water and brine, dried over MgSO4, filtered and concentrated under reduced pressure. The residue was chromatographed on silica (4% MeOH in CH2Cl2 with 0.1% NH4OH) to give 0.350 g of 5-(2,5-Bis-trimethylsilanylethynyl-phenoxy)-pyrimidine-2,4-diamine as a first fraction, and 0.41 g of 5-(2-Iodo-5-trimethylsilanylethynyl-phenoxy)-pyrimidine-2,4-diamine as a second fraction.

Workup

  1. temperatureThe reaction mixture was cooled
  2. extractionextracted with dichloromethane
  3. washThe combined organic layers were washed with water and brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was chromatographed on silica (4% MeOH in CH2Cl2 with 0.1% NH4OH)

Sources & evidence

ORD record
ord-693ad4e86d6a42158314cef0eb688d83
Source dataset
uspto-grants-2009_05
Patent number
US07531547B2

Reaction notes

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