O-Phenylenediamine → Coumarin 7

HRID 1168657Notes

Reaction equation

HRID 1168657 reaction equation
[C:1]1([NH2:8])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[NH2:7].[CH2:9]1[CH2:29][N:28]2[C:12]3[C:13](C[CH2:26][CH2:27]2)=[C:14]2[O:21][C:19](=[O:20])[C:18]([C:22](O)=O)=[CH:17][C:15]2=[CH:16][C:11]=3C1.S(OS(C(F)(F)F)(=O)=O)(C(F)(F)F)(=O)=O.C1(P(=O)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[CH3:9][CH2:29][N:28]([C:12]1[CH:11]=[CH:16][C:15]2[CH:17]=[C:18]([C:22]3[NH:8][C:1]4[C:2](=[CH:3][CH:4]=[CH:5][CH:6]=4)[N:7]=3)[C:19]([O:21][C:14]=2[CH:13]=1)=[O:20])[CH2:27][CH3:26]

Participants

6

Reactant 4

HCID 7243O-Phenylenediamine2×HCID 13097Triphenylphosphine OxideHCID 67749Trifluoromethanesulfonic anhydrideHCID 108770Coumarin 3432×

Product 1

HCID 94381Coumarin 7

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

The diphenyl analog of coumarin 7 was prepared by the dehydration/condensation (J. B. Hendrickson, M. S. Hussoin, J. Org. Chem. 1987, 52, 4139-4140) of o-phenylenediamine with the diphenyl analog of coumarin 343. A solution of 7.9 ml of triflic anhydride in 150 ml methylene chloride was added to a solution of 26.16 g triphenylphosphine oxide in 150 ml methylene chloride at 0° C. under nitrogen atmosphere. The resulting mixture was allowed to come to room temperature and a solution of 2.54 g o-phenylenediamine and 7 g diphenyl analog of coumarin 343 prepared according to the method of Example 2 in 80 ml methylene chloride was added dropwise. The slurry was stirred overnight. The reaction mixture was washed with 5% sodium bicarbonate, water and brine, dried of magnesium sulfate, filtered, and rotary evaporated to remove the solvent. The product was isolated by flash column chromatography in methylene chloride.

Workup

  1. customto come to room temperature
  2. additionwas added dropwise
  3. washThe reaction mixture was washed with 5% sodium bicarbonate, water and brine
  4. dry with materialdried of magnesium sulfate
  5. filtrationfiltered
  6. customrotary evaporated
  7. customto remove the solvent
  8. customThe product was isolated by flash column chromatography in methylene chloride

Sources & evidence

ORD record
ord-c4ff997672184e2085202e184ed8988d
Source dataset
uspto-grants-2003_09
Patent number
US06627111B2

Reaction notes

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