4-Aminobenzonitrile → HCID 505532, compound

HRID 1363896Notes

Reaction equation

HRID 1363896 reaction equation
Cl[C:2]1[N:7]=[C:6](Cl)[N:5]=[C:4]([NH:9][C:10]2[C:15]([Br:16])=[CH:14][C:13]([CH3:17])=[CH:12][C:11]=2[Br:18])[N:3]=1.[NH2:19][C:20]1[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[CH:22][CH:21]=1.C([N:31](CC)C(C)C)(C)C.[OH-].[Na+]>O1CCOCC1.C(OCC)(=O)C>[NH2:31][C:6]1[N:5]=[C:4]([NH:9][C:10]2[C:15]([Br:16])=[CH:14][C:13]([CH3:17])=[CH:12][C:11]=2[Br:18])[N:3]=[C:2]([NH:19][C:20]2[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[CH:22][CH:21]=2)[N:7]=1

Participants

7

Reactant 4

HCID 133964-AminobenzonitrileHCID 14798Sodium HydroxideHCID 81531DiisopropylethylamineHCID 23501194HCID 23501194, compound

Product 1

HCID 505532HCID 505532, compoundYield 9.7%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

4,6-dichloro-N-(2,6-dibromo-4-methylphenyl)-1,3,5-triazin-2-amine (0.00651 mol), was dissolved in 1,4-dioxane (30 ml). Sequentially, 4-aminobenzonitrile (0.0066 mol) and N,N-diisopropylethylamine (0.0066 mol) were added, and the clear solution was heated to reflux for 4 days. The reaction was allowed to cool to room temperature overnight, and the mixture was diluted with ethyl acetate and treated with cold 1 M NaOH. The layers were separated, and the organic phase was re-extracted with fresh 1 M NaOH. The combined aqueous phases were treated with solid NaOH to maintain pH>10 and backwashed with ethyl acetate (2×). The combined organic phases were dried, filtered and concentrated. The residue was separated and purified by flash column chromatography over silica gel (eluent: CH2Cl2). The desired fractions were combined, treated with CH3CN, triturated with CH3CN, filtered off and dried, yielding 0.30 g (8.0%) of 4-[[4-amino-[(2,6-dibromo-4-methylphenyl)amino]-1,3,5-triazin-2-yl]amino]benzonitrile.

Workup

  1. temperaturethe clear solution was heated
  2. temperatureto reflux for 4 days
  3. customThe layers were separated
  4. extractionthe organic phase was re-extracted with fresh 1 M NaOH
  5. additionThe combined aqueous phases were treated with solid NaOH
  6. temperatureto maintain pH>10
  7. customThe combined organic phases were dried
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was separated
  11. custompurified by flash column chromatography over silica gel (eluent: CH2Cl2)
  12. additiontreated with CH3CN
  13. customtriturated with CH3CN
  14. filtrationfiltered off
  15. customdried

Sources & evidence

ORD record
ord-98b57285a8b54bc4976ec2d0cbc92774
Source dataset
uspto-grants-2011_02
Patent number
US07887845B2

Reaction notes

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