(4-Chlorophenyl){2-[(3-nitropyridin-2-yl)amino]phenyl}methanone → {2-[(3-Aminopyridin-2-yl)amino]phenyl}(4-chlorophenyl)methanone

HRID 1633367Notes

Reaction equation

HRID 1633367 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[NH:16][C:17]2[C:22]([N+:23]([O-])=O)=[CH:21][CH:20]=[CH:19][N:18]=2)=[O:9])=[CH:4][CH:3]=1.C(OCC)(=O)C.CO.C(O)(=O)C.O>O.[Cl-].[Cl-].[Cl-].[Ti+3]>[NH2:23][C:22]1[C:17]([NH:16][C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=2[C:8]([C:5]2[CH:4]=[CH:3][C:2]([Cl:1])=[CH:7][CH:6]=2)=[O:9])=[N:18][CH:19]=[CH:20][CH:21]=1

Participants

6

Reactant 3

HCID 13388387(4-Chlorophenyl){2-[(3-nitropyridin-2-yl)amino]phenyl}methanoneHCID 21584119Ethylacetate methanolHCID 21899381Acetic acid--water (1/1)

Product 1

HCID 13388390{2-[(3-Aminopyridin-2-yl)amino]phenyl}(4-chlorophenyl)methanoneYield 59.4%

Reagents, catalysts & solvents 2

HCID 10313229titanium(III) trichlorideCatalyst2×HCID 962WaterSolvent2×

Procedure

Under an atmosphere of nitrogen, 29 g (0.187 mole) of titanium trichloride was added portionwise (cautiously; in hood) to 200 g of ice and the resulting solution was diluted to 250 ml volume with water. This was added, all at once, at 30° C. to a stirred solution of 11.0 g (0.0312 mole) of (4-chlorophenyl)[2-[(3-nitro-2-pyridinyl)amino]phenyl]methanone, 300 ml of ethyl acetate: methanol (1:1), 100 ml of acetic acid: water (1:1) and 20 ml more solution of titanium trichloride. The reaction mixture was stirred for 20 min then diluted with one liter of water and filtered. The filter cake was washed with water and then partitioned between 200 ml of methylene chloride and 75 ml of 10% aqueous sodium hydroxide solution. The methylene chloride layer was washed with 75 ml of water, dried over sodium sulfate and concentrated in vacuo. The residue (7 g) was recrystallized from ethyl acetate-isopropyl ether to give 6.0 g of gold solid, m.p. 145°-146° C.

Workup

  1. additionThis was added
  2. customat 30° C.
  3. filtrationfiltered
  4. washThe filter cake was washed with water
  5. custompartitioned between 200 ml of methylene chloride and 75 ml of 10% aqueous sodium hydroxide solution
  6. washThe methylene chloride layer was washed with 75 ml of water
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue (7 g) was recrystallized from ethyl acetate-isopropyl ether

Sources & evidence

ORD record
ord-f373c202c98646ce95cb35c3fd769ce8
Source dataset
uspto-grants-1984_10
Patent number
US04480100

Reaction notes

Loading…