Picolinic acid → N,N'-bis(picolinoyl)-4,4'-diaminobenzophenone

HRID 636287Notes

Reaction equation

HRID 636287 reaction equation
[NH2:1][C:2]1[CH:16]=[CH:15][C:5]([C:6]([C:8]2[CH:13]=[CH:12][C:11]([NH2:14])=[CH:10][CH:9]=2)=[O:7])=[CH:4][CH:3]=1.[CH:17]1[CH:18]=[CH:19][C:20]2N(O)N=[N:23][C:21]=2[CH:22]=1.[N:27]1[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=1[C:33](O)=[O:34].CN([P+]([O:46]N1N=NC2C=CC=CC1=2)(N(C)C)N(C)C)C.F[P-](F)(F)(F)(F)F>CN(C=O)C>[N:27]1[CH:32]=[CH:31][CH:30]=[CH:29][C:28]=1[C:33]([NH:1][C:2]1[CH:16]=[CH:15][C:5]([C:6]([C:8]2[CH:13]=[CH:12][C:11]([NH:14][C:22](=[O:46])[C:21]3[CH:20]=[CH:19][CH:18]=[CH:17][N:23]=3)=[CH:10][CH:9]=2)=[O:7])=[CH:4][CH:3]=1)=[O:34]

Participants

6

Reactant 4

HCID 1018Picolinic acidHCID 691494,4'-DiaminobenzophenoneHCID 757711-HydroxybenzotriazoleHCID 151348Benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate

Product 1

HCID 21256689N,N'-bis(picolinoyl)-4,4'-diaminobenzophenoneYield 24%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of 4,4′-diaminobenzophenone (637 mg, 3.00 mmol) in DMF (30 mL) was added sequentially IPr2NEt (5.30 mL, 30.4 mmol), HOBt (1.23 g, 9.10 mmol), picolinic acid (1.14 g, 9.00 mmol) and BOP reagent (3.98 g, 9.0 mmol). After 17 h at room temperature, the reaction mixture was concentrated in vacuo to ca. 20 mL and added to a rapidly-stirred mixture of EtOAc (100 mL), H2O (100 mL), and sat'd NaCl (100 mL). After stirring for ca 1 h, the phases were separated and the aqueous layer was extracted with EtOAc (2×100 mL). The combined organic layers were washed with H2O (100 mL), dried over MgSO4, filtered, and concentrated in vacuo to a brown solid. Purification by flash chromatography (silica gel, 1% MeOH/CHCl3) afforded 303 mg (24%) of the desired product as a yellow solid. MS (ES+) m/z [M+H]+.

Workup

  1. concentrationthe reaction mixture was concentrated in vacuo to ca. 20 mL
  2. additionadded to a rapidly-stirred mixture of EtOAc (100 mL), H2O (100 mL), and sat'd NaCl (100 mL)
  3. customthe phases were separated
  4. extractionthe aqueous layer was extracted with EtOAc (2×100 mL)
  5. washThe combined organic layers were washed with H2O (100 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo to a brown solid
  9. customPurification by flash chromatography (silica gel, 1% MeOH/CHCl3)

Sources & evidence

ORD record
ord-17fa5d174ae349ab833e76bba5bbede3
Source dataset
uspto-grants-2001_02
Patent number
US06191146B1

Reaction notes

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