Cyclopropanecarboxaldehyde → 4-(6-Bromo-2-cyclopropyl-1,3-benzodiazol-1-yl)-1,3,5-triazin-2-amine

HRID 1398695Notes

Reaction equation

HRID 1398695 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][C:3]=1[NH:9][C:10]1[N:15]=[C:14]([NH2:16])[N:13]=[CH:12][N:11]=1.[CH:17]1([CH:20]=O)[CH2:19][CH2:18]1.OOS([O-])=O.[K+].C(=O)(O)[O-].[Na+]>CN(C=O)C>[Br:8][C:5]1[CH:6]=[CH:7][C:2]2[N:1]=[C:20]([CH:17]3[CH2:19][CH2:18]3)[N:9]([C:10]3[N:11]=[CH:12][N:13]=[C:14]([NH2:16])[N:15]=3)[C:3]=2[CH:4]=1

Participants

6

Reactant 4

HCID 123114CyclopropanecarboxaldehydeHCID 516892Sodium BicarbonateHCID 23707502Potassium hydroxy sulfiteHCID 681816982-N-(2-amino-5-bromophenyl)-1,3,5-triazine-2,4-diamine

Product 1

HCID 681815764-(6-Bromo-2-cyclopropyl-1,3-benzodiazol-1-yl)-1,3,5-triazin-2-amine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 2-N-(2-amino-5-bromophenyl)-1,3,5-triazine-2,4-diamine (6 g, 21.34 mmol) in DMF (60 mL) was added cyclopropanecarbaldehyde (2.07 ml, 27.75 mmol) followed by oxone (7.83 g, 12.81 mmol). The reaction mixture was stirred at RT for 24 hr. The reaction mixture was then cooled to 0° C. and saturated aqueous sodium bicarbonate introduced. A brown precipitate was removed by vacuum filtration. The solid was washed with DCM (100 ml). The organic phase of the filtrate was separated and the aqueous phase extracted with DCM (2×100 mL extractions). The combined organics were washed with brine and then dried (Na2SO4), filtered and concentrated in vacuo to furnish the crude title compound as a brown solid: 1H NMR (500 MHz, DMSO) delta 1.32-1.02 (4H, m), 7.41 (1H, dd, J=8.5, 1.9 Hz), 7.50 (1H, d, J=8.5), 8.05 (1H, s), 8.11 (1H, s), 8.49 (1H, d, J=1.8 Hz), 8.66 (1H, s); LC-MS: m/z=+330.90 (M+H)+. This compound of 85% purity LC-MS (UV) was used without further purification.

Workup

  1. temperatureThe reaction mixture was then cooled to 0° C.
  2. customA brown precipitate was removed by vacuum filtration
  3. washThe solid was washed with DCM (100 ml)
  4. customThe organic phase of the filtrate was separated
  5. extractionthe aqueous phase extracted with DCM (2×100 mL extractions)
  6. washThe combined organics were washed with brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9db5c66a416a4550971e802a835b2e69
Source dataset
uspto-grants-2014_12
Patent number
US08901313B2

Reaction notes

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