Ethanol → N-(5-cyclopropyl-1H-pyrazol-3-yl)-2-phenyl-pyrimidine-4,5-diamine

HRID 1484845Notes

Reaction equation

HRID 1484845 reaction equation
[CH:1]1([C:4]2[NH:8][N:7]=[C:6]([NH:9][C:10]3[C:15]([N+:16]([O-])=O)=[CH:14][N:13]=[C:12]([C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=4)[N:11]=3)[CH:5]=2)[CH2:3][CH2:2]1.[NH4+].[Cl-].CCO.C1COCC1>C(Cl)Cl.[Fe].O>[CH:1]1([C:4]2[NH:8][N:7]=[C:6]([NH:9][C:10]3[C:15]([NH2:16])=[CH:14][N:13]=[C:12]([C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=4)[N:11]=3)[CH:5]=2)[CH2:3][CH2:2]1

Participants

8

Reactant 4

HCID 702EthanolHCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 50943074N-(5-cyclopropyl-1H-pyrazol-3-yl)-5-nitro-2-phenyl-pyrimidin-4-amine

Product 1

HCID 50943070N-(5-cyclopropyl-1H-pyrazol-3-yl)-2-phenyl-pyrimidine-4,5-diamineYield 77.2%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
23 °C

Procedure

A mixture of N-(5-cyclopropyl-1H-pyrazol-3-yl)-5-nitro-2-phenylpyrimidin-4-amine (500 mg, 1.55 mmol, 1.0 eq), NH4Cl (1.0 g, 19.39 mmol, 12.5 eq), EtOH (12 mL), THF (12 mL) and H2O (5 mL) was heated to reflux. Iron powder (0.59 g, 10.54 mmol, 6.8 eq) was added in three portions over 15 minutes under N2 atmosphere. The resulting mixture was continued to reflux for 1 hour, cooled down to 23° C., diluted with CH2Cl2 and filtered through celite. The organic phase was washed (brine), dried (Na2SO4), filtered and concentrated to give target product N-(5-cyclopropyl-1H-pyrazol-3-yl)-2-phenylpyrimidine-4,5-diamine (Compound 5) (350 mg, 38.6%). LC-MS (m/z)=293.1 [M+H]+. 1H-NMR (300 MHz, DMSO-d6): δ 0.71-0.72 (m, 2H), 0.95-1.00 (m, 2H), 1.92-1.95 (m, 1H), 5.29 (s, 2H), 6.59 (s, 1H), 7.31-7.43 (m, 3H), 7.81 (s, 1H), 8.18 (d, J=6.9 Hz, 2H), 8.81 (s, 1H), 12.02 (s, 1H).

Workup

  1. temperaturewas heated to reflux
  2. temperatureto reflux for 1 hour
  3. filtrationfiltered through celite
  4. washThe organic phase was washed (brine)
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-461cd5aa24de47e0839d2e5c3cad2286
Source dataset
uspto-grants-2016_08
Patent number
US09422271B2

Reaction notes

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