p-Toluenesulfonic acid → HCID 86675238, compound

HRID 2370062Notes

Reaction equation

HRID 2370062 reaction equation
[NH2:1][C:2]1[C:3]([NH:10][CH2:11][C:12]([NH2:14])=[O:13])=[N:4][C:5]([CH3:9])=[N:6][C:7]=1[Cl:8].[Cl:15][C:16]1[CH:23]=[CH:22][CH:21]=[CH:20][C:17]=1[CH:18]=O.C1(C)C=CC(S(O)(=O)=O)=CC=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1.ClCCl>[Cl:8][C:7]1[N:6]=[C:5]([CH3:9])[N:4]=[C:3]2[C:2]=1[N:1]=[C:18]([C:17]1[CH:20]=[CH:21][CH:22]=[CH:23][C:16]=1[Cl:15])[N:10]2[CH2:11][C:12]([NH2:14])=[O:13]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 69962-ChlorobenzaldehydeHCID 86675239HCID 86675239, compound

Product 1

HCID 86675238HCID 86675238, compoundYield 8.9%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent2×

Procedure

Heat a mixture of 2-[(5-amino-6-chloro-2-methyl-pyrimidin-4-yl)amino]acetamide (2.2 g, 0.01 mol), 2-chlorobenzaldehyde (2.86 g, 0.02 mol), p-toluene sulfonic acid (0.2 g) and molecular sieves (1.0 g) in toluene (50 mL) to reflux for 16 h. Cool and remove the sieves by filtration through diatomaceous earth. Concentrate the filtrate under reduced pressure to afford a residue. Dissolve the residue in dry dichloromethane (50 mL) and add 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.3 g, 0.01 mol) at 0° C. Allow to warm to room temperature and stir for 2 h. Dilute the reaction mixture with dichloromethane, wash with 1 N aqueous sodium hydroxide solution, water, and brine. Dry the organic layer over anhydrous sodium sulfate, filter, and concentrate to give a residue. Purify the residue on a silica gel column eluting with dichloromethane:methanol (98:2) to provide the title compound (0.3 g). ES/MS m/z 336 (M+1).

Workup

  1. temperatureHeat
  2. temperatureto reflux for 16 h
  3. temperatureCool
  4. customremove the sieves
  5. filtrationby filtration through diatomaceous earth
  6. concentrationConcentrate the filtrate under reduced pressure
  7. customto afford a residue
  8. washwash with 1 N aqueous sodium hydroxide solution, water, and brine
  9. dry with materialDry the organic layer over anhydrous sodium sulfate
  10. filtrationfilter
  11. concentrationconcentrate
  12. customto give a residue
  13. customPurify the residue on a silica gel column
  14. washeluting with dichloromethane:methanol (98:2)

Sources & evidence

ORD record
ord-f7ea7c312cd44f1f909ae4f60bd6380f
Source dataset
uspto-grants-2014_04
Patent number
US08710063B2

Reaction notes

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