Benzophenone imine → N-(2-Chloro-5-(diphenylmethyleneamino)pyridin-3-YL)-4-fluorobenzenesulfonamide

HRID 1621784Notes

Reaction equation

HRID 1621784 reaction equation
Br[C:2]1[CH:3]=[C:4]([NH:9][S:10]([C:13]2[CH:18]=[CH:17][C:16]([F:19])=[CH:15][CH:14]=2)(=[O:12])=[O:11])[C:5]([Cl:8])=[N:6][CH:7]=1.C1(P(C2C3CC4C(=CC=CC=4)OC=3C=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+].[C:53](=[NH:66])([C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)[C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1>[Cl:8][C:5]1[C:4]([NH:9][S:10]([C:13]2[CH:18]=[CH:17][C:16]([F:19])=[CH:15][CH:14]=2)(=[O:12])=[O:11])=[CH:3][C:2]([N:66]=[C:53]([C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)[C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)=[CH:7][N:6]=1

Participants

7

Reactant 4

HCID 136809Benzophenone imineHCID 22240502(Diphenylphosphino)xantheneHCID 23676156Sodium t-butoxideHCID 53363354N-(5-bromo-2-chloropyridin-3-yl)-4-fluorobenzenesulfonamide

Product 1

HCID 86647061N-(2-Chloro-5-(diphenylmethyleneamino)pyridin-3-YL)-4-fluorobenzenesulfonamideYield 40.7%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of N-(5-bromo-2-chloropyridin-3-yl)-4-fluorobenzenesulfonamide (Inogent, Inc.) (1.000 g, 2.74 mmol), palladium (II) acetate (Aldrich) (0.035 g, 0.156 mmol), (diphenylphosphino)xanthene (Acros) (0.176 g, 0.304 mmol), sodium tert-butoxide (Fluka) (0.620 g, 6.45 mmol), toluene (10 mL), and benzophenone imine (Aldrich) (0.459 mL, 2.74 mmol) was heated at 100° C. in a sealed tube for 6 h. The reaction mixture was partitioned between EtOAc and Tris HCl (1 M, pH 7). The aqueous layer was extracted with EtOAc (2×10 mL). The combined organic layers were dried over MgSO4 and concentrated. The crude product was purified by column chromatography (120 g, 10% to 20% acetone in hexanes) to give the product as a yellow solid (0.520 g). m/z (ESI, +ve ion) 466.0 (M+H)+. 1H NMR (300 MHz, CDCl3) δ 7.75 (d, J=7.45 Hz, 2H); 7.61 (d, J=2.05 Hz, 1H); 7.50-7.59 (m, 3H); 7.40-7.49 (m, 3H); 7.35 (br. s., 3H); 7.03-7.17 (m, 4H); 6.73 (br. s., 1H).

Workup

  1. customThe reaction mixture was partitioned between EtOAc and Tris HCl (1 M, pH 7)
  2. extractionThe aqueous layer was extracted with EtOAc (2×10 mL)
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. concentrationconcentrated
  5. customThe crude product was purified by column chromatography (120 g, 10% to 20% acetone in hexanes)

Sources & evidence

ORD record
ord-a84ef6d1ab3d4560b5570742f7ad4e70
Source dataset
uspto-grants-2014_07
Patent number
US08772480B2

Reaction notes

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