Dimethyl Sulfoxide → HCID 66605156, compound

HRID 2410661Notes

Reaction equation

HRID 2410661 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5](F)=[C:6]([CH:9]=1)[C:7]#[N:8].[NH2:11][C:12]1[CH:22]=[CH:21][C:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:14][CH:13]=1.CC([O-])(C)C.[K+].CS(C)=O>C(OCC)(=O)C.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([NH:11][C:12]2[CH:13]=[CH:14][C:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:21][CH:22]=2)=[C:6]([C:7]#[N:8])[CH:9]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 2337BenzocaineHCID 27249005-Bromo-2-fluorobenzonitrileHCID 23665647Potassium tert-butoxide

Product 1

HCID 66605156HCID 66605156, compoundYield 82.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A flask was charged with 5-bromo-2-fluorobenzonitrile (5 g, 25.00 mmol), ethyl 4-aminobenzoate (4.54 g, 27.5 mmol), and KOtBu (5.11 g, 45.5 mmol). To this was added DMSO (100 mL). After stirring at room temperature for 20 min, the reaction mixture was diluted with ethyl acetate and water. The aqueous was extracted with ethyl acetate, the combined organic was washed with water (3×), brine, dried over MgSO4 and filtered. The filtrate was concentrated. The residue was suspended in ethyl acetate, collected the solid by filtration. Repeated above procedure for several times (each collected solid was checked by LCMS) until the collected solid is pure. The mixture residue was further purified via silica gel chromatography (0-30% ethyl acetate in hexanes) to give total 7.15 g of ethyl 4-(4-bromo-2-cyanophenylamino)benzoate. MS (ESI) m/z 345.2 (M+H). 1H NMR (CDCl3) δ ppm 8.02 (2H, d, J=8.55 Hz), 7.65 (1H, d, J=2.44 Hz), 7.53 (1H, dd, J=9.00, 2.29 Hz), 7.25 (1H, d, J=9 Hz), 7.14 (2H, d, Hz), 6.47 (1H, s), 4.36 (2H, q, J=7.22 Hz), 1.38 (3H, t, J=7.17 Hz).

Workup

  1. extractionThe aqueous was extracted with ethyl acetate
  2. washthe combined organic was washed with water (3×), brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated
  6. customcollected the solid
  7. filtrationby filtration
  8. customThe mixture residue was further purified via silica gel chromatography (0-30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-c905e9a13d7e419885c1cae48fa49e15
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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