Ammonium Chloride → HCID 57678400, compound

HRID 491497Notes

Reaction equation

HRID 491497 reaction equation
I[C:2]1[CH:16]=[C:15]([O:17][CH3:18])[C:14]([I:19])=[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-]>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.C1COCC1>[I:19][C:14]1[C:15]([O:17][CH3:18])=[CH:16][C:2]([C:25]#[C:24][Si:21]([CH3:23])([CH3:22])[CH3:20])=[C:3]([CH:13]=1)[O:4][C:5]1[C:6]([NH2:12])=[N:7][C:8]([NH2:11])=[N:9][CH:10]=1

Participants

8

Reactant 4

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

Product 1

HCID 57678400HCID 57678400, 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

5-(2,5-Diiodo-4-methoxy-phenoxy)-pyrimidine-2,4-diamine (1.2 g, 2.5 mmol), bis(triphenylphosphine)palladium dichloride (175 mg, 2.5 mmol), and CuI (25 mg, 0.125 mmol) were added to 7 mL dry THF. Trimethylsilylacetylene ((0.48 mL, 3.3 mmol), and diisopropylethylamine (3.5 mL) were added, and the reaction mixture was heated to 50° C. under nitrogen for 27 hours. The reaction mixture was cooled, poured into 15% aqueous NH4Cl and extracted into EtOAc. The combined organic layers were washed with brine, dried over MgSO4, filtered and concentrated under reduced pressure to give crude 5-(4-Methoxy-2,5-bis-trimethylsilanylethynyl-phenoxy)-pyrimidine -2,4-diamine together with monoacetylenes 5-(2-iodo-4-methoxy-5-trimethylsilanylethynyl-phenoxy)-pyrimidine-2,4-diamine and 5-(5-iodo-4-methoxy-2-trimethylsilanylethynyl-phenoxy)-pyrimidine-2,4-diamine. This residue was chromatographed on 125 g of flash silica (6:1:1 CH2Cl2:MeOH:NH4OH) to give 450 mg of 5-(4-Methoxy-2,5-bis-trimethylsilanylethynyl-phenoxy)-pyrimidine-2,4-diamine, MS (M+H)=425.

Workup

  1. temperatureThe reaction mixture was cooled
  2. extractionextracted into EtOAc
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-8a52e746ed94424ea108d613d7bcc4d5
Source dataset
uspto-grants-2009_05
Patent number
US07531547B2

Reaction notes

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