Sodium Iodide → 4-N-(2-amino-5-iodophenyl)pyrimidine-2,4-diamine

HRID 1398643Notes

Reaction equation

HRID 1398643 reaction equation
[I-:1].[Na+].[NH2:3][C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][C:5]=1[NH:11][C:12]1[CH:17]=[CH:16][N:15]=[C:14]([NH2:18])[N:13]=1.O1CCOCC1.CNCCNC>[Cu]I.CN(C=O)C>[NH2:3][C:4]1[CH:9]=[CH:8][C:7]([I:1])=[CH:6][C:5]=1[NH:11][C:12]1[CH:17]=[CH:16][N:15]=[C:14]([NH2:18])[N:13]=1

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 8070N,N'-DimethylethylenediamineHCID 312751,4-DioxaneHCID 681818104-N-(2-amino-5-bromophenyl)pyrimidine-2,4-diamine

Product 1

HCID 681818414-N-(2-amino-5-iodophenyl)pyrimidine-2,4-diamineYield 57.1%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
115 °C

Procedure

A pressure tube containing copper(I) iodide (61.2 mg, 0.32 mmol), sodium iodide (963.18 mg, 6.43 mmol) and 4-N-(2-amino-5-bromophenyl)pyrimidine-2,4-diamine (900 mg, 3.21 mmol) was flushed with nitrogen before the addition of 1,4-dioxane (4.0 mL), DMF (4.0 ml) and N,N′-dimethylethane-1,2-diamine (0.035 ml, 0.32 mmol). The vessel was sealed and stirred at 115° C. overnight. After cooling to RT, the reaction mixture was poured into ice water (7 ml) and the resulting solution extracted with DCM (2×100 mL). The combined organics were dried (Na2SO4), filtered and concentrated in vacuo. Purification by column chromatography (Biotage, 3-14% methanol gradient in DCM) furnished the title compound (600 mg, 57% yield); 1H NMR (500 MHz, DMSO) delta 5.04 (2H, d, J=11.6 Hz), 5.78-5.73 (1H, m), 6.11-6.02 (2H, m), 6.57 (1H, d, J=8.4 Hz), 7.18 (1H, dd, J=8.4, 2.0 Hz), 7.47-7.38 (1H, m), 7.75 (1H, d, J=5.3 Hz), 8.20-8.12 (1H, m); LC-MS: m/z=+327.8 (M+H)+.

Workup

  1. customThe vessel was sealed
  2. temperatureAfter cooling to RT
  3. extractionthe resulting solution extracted with DCM (2×100 mL)
  4. dry with materialThe combined organics were dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by column chromatography (Biotage, 3-14% methanol gradient in DCM)

Sources & evidence

ORD record
ord-2836947017cd4d64adc90ed819d61bcd
Source dataset
uspto-grants-2014_12
Patent number
US08901313B2

Reaction notes

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