Potassium Carbonate → 2-(5-Cyano-2-{[(2,4-dimethoxyphenyl)methyl]amino}anilino)-5-nitropyrimidin-4-yl thiocyanate

HRID 1363242Notes

Reaction equation

HRID 1363242 reaction equation
[CH3:1][O:2][C:3]1[CH:19]=[C:18]([O:20][CH3:21])[CH:17]=[CH:16][C:4]=1[CH2:5][NH:6][C:7]1[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][C:8]=1[NH2:15].C(=O)([O-])[O-].[K+].[K+].Cl[C:29]1[N:34]=[C:33]([S:35][C:36]#[N:37])[C:32]([N+:38]([O-:40])=[O:39])=[CH:31][N:30]=1>C(#N)C>[CH3:1][O:2][C:3]1[CH:19]=[C:18]([O:20][CH3:21])[CH:17]=[CH:16][C:4]=1[CH2:5][NH:6][C:7]1[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][C:8]=1[NH:15][C:29]1[N:34]=[C:33]([S:35][C:36]#[N:37])[C:32]([N+:38]([O-:40])=[O:39])=[CH:31][N:30]=1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 210775882-Chloro-5-nitropyrimidin-4-yl thiocyanateHCID 566052433-Amino-4-{[(2,4-dimethoxyphenyl)methyl]amino}benzonitrile

Product 1

HCID 566052112-(5-Cyano-2-{[(2,4-dimethoxyphenyl)methyl]amino}anilino)-5-nitropyrimidin-4-yl thiocyanateYield 6.5%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 4-(2,4-dimethoxybenzylamino)-3-aminobenzonitrile (3.9 g) in acetonitrile (100 mL) was cooled to 0° C. and treated with potassium carbonate (6.3 g) followed by a solution containing 3 g of 2-chloro-5-nitro-4-thiocyanatopyrimidine (WO 2003/032994) in acetonitrile (50 mL). The mixture was stirred for 30 minutes at 0° C. and 30 minutes at room temperature resulting in the formation of a precipitate. The mixture was quenched at 0° C. by the addition of 4% acetic acid (150 mL) and filtered. The precipitate was swirled in 100 mL acetonitrile and filtered again. The precipitate was washed with acetonitrile, which resulted in the slow dissolution of product into the filtrate. After air-drying, 1.5 g of the title compound remained as the precipitate cake. The filtrate was extracted with EtOAc, dried over Na2SO4, filtered, and concentrated in vacuo. Column chromatography (0→20% EtOAc/DCM) and recrystallization from acetonitrile provided 0.415 g of additional title compound.

Workup

  1. customresulting in the formation of a precipitate
  2. customThe mixture was quenched at 0° C. by the addition of 4% acetic acid (150 mL)
  3. filtrationfiltered
  4. filtrationfiltered again
  5. washThe precipitate was washed with acetonitrile, which
  6. customresulted in the slow dissolution of product into the filtrate
  7. customAfter air-drying
  8. extractionThe filtrate was extracted with EtOAc
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customColumn chromatography (0→20% EtOAc/DCM) and recrystallization from acetonitrile

Sources & evidence

ORD record
ord-c869e2adaff745a893465ba7ca8a81b5
Source dataset
uspto-grants-2011_02
Patent number
US07884109B2

Reaction notes

Loading…