6-Chloro-5-nitropyrimidine-2,4-diamine → 6-(5-Methyl-2-Furyl)-5-Nitropyrimidine-2,4-Diamine

HRID 732976Notes

Reaction equation

HRID 732976 reaction equation
Cl[C:2]1[N:7]=[C:6]([NH2:8])[N:5]=[C:4]([NH2:9])[C:3]=1[N+:10]([O-:12])=[O:11].C([O-])(O)=O.[Na+].[CH3:18][C:19]1[O:23][C:22](B(O)O)=[CH:21][CH:20]=1>C1COCC1.CCOC(C)=O.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:18][C:19]1[O:23][C:22]([C:2]2[N:7]=[C:6]([NH2:8])[N:5]=[C:4]([NH2:9])[C:3]=2[N+:10]([O-:12])=[O:11])=[CH:21][CH:20]=1

Participants

8

Reactant 3

HCID 2504496-Chloro-5-nitropyrimidine-2,4-diamineHCID 516892Sodium BicarbonateHCID 27343725-Methyl-2-furanboronic Acid

Product 1

HCID 218745306-(5-Methyl-2-Furyl)-5-Nitropyrimidine-2,4-DiamineYield 79.7%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 6-chloro-5-nitropyrimidine-2,4-diamine (10 g, 60% pure, 32 mmol) in THF (300 mL) was treated with saturated aq NaHCO3 (75 mL), 5-methylfuran-2-boronic acid (7.33 g, 0.058 mol) and Pd(PPh3)4 (1 g, 0.865 mmol) and refluxed with vigorous stirring under argon overnight. The mixture was cooled to room temperature, diluted with EtOAc (400 mL) and water (300 mL), filtered to remove insoluble material and the filtrate was extracted with EtOAc (2×100 mL). The combined organic phase was dried (MgSO4), concentrated in vacuo and the resulting solid triturated with dichloromethane and filtered to give the title compound (6 g, 72%) as a yellow solid; mp 196.3-196.9° C.; IR νmax (Nujol)/cm−1 3442, 3169, 2930, 1629, 1463, 1377, 1027, and 790; NMR δH (400 MHz, DMSO) 7.40 (2H, br s), 7.09 (2H, br s), 6.87 (1H, dd, J 0.5, 3.2 Hz), 6.26 (2H, dd, J 1.0, 3.3 Hz) and 2.28 (3H, s).

Workup

  1. temperaturerefluxed
  2. filtrationfiltered
  3. customto remove insoluble material
  4. extractionthe filtrate was extracted with EtOAc (2×100 mL)
  5. dry with materialThe combined organic phase was dried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customthe resulting solid triturated with dichloromethane
  8. filtrationfiltered

Sources & evidence

ORD record
ord-89fc5ca246f24e80ba43d89c41bfc5ce
Source dataset
uspto-grants-2009_09
Patent number
US07589097B2

Reaction notes

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