1-Iodo-4-nitrobenzene → 5-methyl-N-(4-nitrophenyl)-7-phenylimidazo[5,1-f][1,2,4]triazin-2-amine

HRID 2374896Notes

Reaction equation

HRID 2374896 reaction equation
Cl.[CH3:2][C:3]1[N:4]=[C:5]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[N:6]2[C:11]=1[CH:10]=[N:9][C:8]([NH2:12])=[N:7]2.I[C:20]1[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][CH:21]=1.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(C)([O-])C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[CH3:2][C:3]1[N:4]=[C:5]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[N:6]2[C:11]=1[CH:10]=[N:9][C:8]([NH:12][C:20]1[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][CH:21]=1)=[N:7]2

Participants

7

Reactant 4

HCID 124951-Iodo-4-nitrobenzeneHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 688705435-Methyl-7-phenylimidazo[5,1-f][1,2,4]triazin-2-amine hydrochloride

Product 1

HCID 112449025-methyl-N-(4-nitrophenyl)-7-phenylimidazo[5,1-f][1,2,4]triazin-2-amineYield 23.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 5-methyl-7-phenylimidazo[5,1-f][1,2,4]triazin-2-amine hydrochloride (0.026 g, 0.10 mmol), 1-iodo-4-nitrobenzene (0.027 g, 0.11 mmol), tris(dibenzylideneacetone)dipalladium (2.7 mg, 0.0030 mmol), (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (5.6 mg, 0.0090 mmol) and sodium t-butoxide (0.025 g, 0.23 mmol) was added toluene (1 mL). The solution was heated to 80° C. for two hours. After cooling to room temperature, the solution was filtered, and silica gel (1 g) was added, followed by evaporation of the volatiles under reduced pressure. The pre-adsorbed solids were loaded into a solid loading cartridge and subjected to a gradient elution using ethyl acetate:hexanes (50:50) to ethyl acetate:hexanes (100:0) using a RediSep silica gel cartridge (4 g; ISCO). The appropriate fractions were combined and concentrated under reduced pressure to give 5-methyl-N-(4-nitrophenyl)-7-phenylimidazo[5,1-f][1,2,4]triazin-2-amine (0.0080 g) as a yellow solid. 1H NMR (CDCl3): δ8.86 (s, 1H), 8.78 (s, 1H), 8.48-8.40 (m, 2H), 8.26 (d, J=9.4 Hz, 2H), 7.81 (d, J=9.3 Hz, 2H), 7.61-7.36 (m, 3H), 2.65 (s, 3H). MS m/z 347 (M+1).

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationthe solution was filtered
  3. additionsilica gel (1 g) was added
  4. customfollowed by evaporation of the volatiles under reduced pressure
  5. washsubjected to a gradient elution
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-418c4940c7644eeebded05f8951738c9
Source dataset
uspto-grants-2008_12
Patent number
US07462614B2

Reaction notes

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