p-Toluenesulfonic acid → HCID 86658141, compound

HRID 408810Notes

Reaction equation

HRID 408810 reaction equation
[NH2:1][C:2]1[C:3]([NH:10][CH2:11][C:12]([CH3:15])([OH:14])[CH3:13])=[N:4][C:5]([CH3:9])=[N:6][C:7]=1[Cl:8].[Cl:16][C:17]1[CH:24]=[CH:23][CH:22]=[CH:21][C:18]=1[CH:19]=O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>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:19]([C:18]1[CH:21]=[CH:22][CH:23]=[CH:24][C:17]=1[Cl:16])[N:10]2[CH2:11][C:12]([CH3:15])([OH:14])[CH3:13]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 69962-ChlorobenzaldehydeHCID 58459084HCID 58459084, compound

Product 1

HCID 86658141HCID 86658141, compoundYield 56.9%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent2×

Procedure

Heat a mixture of 1-(5-amino-6-chloro-2-methylpyrimidin-4-ylamino)-2-methylpropan-2-ol (0.5 g, 0.002 mol), 2-chlorobenzaldehyde (0.6 g, 0.004 mol), p-toluene sulfonic acid (0.1 g) and molecular sieves (1.0 g) in toluene (25 mL) to 130° C. for 16 h. Remove the molecular sieves by filtration through diatomaceous earth, and concentrate the filtrate under reduced pressure to give a residue. Dissolve the residue in dry dichloromethane (5 mL) and add DDQ (0.47 g, 0.002 mol) at 0° C. Stir the reaction mixture at room temperature for 2 h. Dilute the reaction mixture with dichloromethane, wash with 1 N 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 methanol:dichloromethane (2:98) to give the title compound (0.4 g). ES/MS m/z 351 (M+1).

Workup

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

Sources & evidence

ORD record
ord-9db7123d29214c188d98c4a335cb6236
Source dataset
uspto-grants-2014_06
Patent number
US08759360B2

Reaction notes

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