Benzylamine → N2,N4-Dibenzyl-3-nitro-6-trifluoromethyl-pyridine-2,4-diamine

HRID 639621Notes

Reaction equation

HRID 639621 reaction equation
[N+:1]([C:4]1[C:5](O)=[N:6][C:7]([C:11]([F:14])([F:13])[F:12])=[CH:8][C:9]=1O)([O-:3])=[O:2].CC[N:18]([CH2:21][CH3:22])CC.O(S(C(F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O.[CH2:38]([NH2:45])[C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1>C(Cl)Cl.CCOC(C)=O.CCCCC>[CH2:38]([NH:45][C:5]1[C:4]([N+:1]([O-:3])=[O:2])=[C:9]([NH:18][CH2:21][C:22]2[CH:4]=[CH:9][CH:8]=[CH:7][CH:11]=2)[CH:8]=[C:7]([C:11]([F:14])([F:13])[F:12])[N:6]=1)[C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1

Participants

8

Reactant 4

HCID 7504BenzylamineHCID 8471TriethylamineHCID 67749Trifluoromethanesulfonic anhydrideHCID 178526877HCID 178526877, compound

Product 1

HCID 67453795N2,N4-Dibenzyl-3-nitro-6-trifluoromethyl-pyridine-2,4-diamineYield 160.3%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8003PentaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A second batch of 3-Nitro-6-trifluoromethyl-pyridine-2,4-diol (11.06 g, 49.4 mmol) was dissolved in DCM (100 mL) and Et3N (13.8 ml, 98.7 mmol) was added. The mixture was cooled to 0° C. and Tf2O (16.2 ml, 98.7 mmol) was added dropwise. The mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was concentrated in vacuo and the residue was dissolved in THF (100 ml). BnNH2 (16.2 ml, 148 mmol) was added and the mixture was stirred at 50° C. for 24 h. The reaction mixture was cooled to room temperature and concentrated in vacuo. The residue was treated with water (100 ml) and extracted with EtOAc (200 ml). The extract was washed with brine (50 ml), dried over MgSO4 and concentrated in vacuo to give the crude (53 g). The two crudes were combined. Column chromatography through silica eluting with 95:5→90:10 Pentane:EtOAc gave the title compound (15.93 g) as a yellow solid.

Workup

  1. temperatureto warm to room temperature
  2. concentrationThe reaction mixture was concentrated in vacuo
  3. dissolutionthe residue was dissolved in THF (100 ml)
  4. stirringthe mixture was stirred at 50° C. for 24 h
  5. temperatureThe reaction mixture was cooled to room temperature
  6. concentrationconcentrated in vacuo
  7. additionThe residue was treated with water (100 ml)
  8. extractionextracted with EtOAc (200 ml)
  9. washThe extract was washed with brine (50 ml)
  10. dry with materialdried over MgSO4
  11. concentrationconcentrated in vacuo
  12. customto give the crude (53 g)

Sources & evidence

ORD record
ord-06b5712b7ffb473798c71c0e109f6be1
Source dataset
uspto-grants-2010_04
Patent number
US07691877B2

Reaction notes

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