Acetic Acid → HCID 117736931, compound

HRID 1504483Notes

Reaction equation

HRID 1504483 reaction equation
[CH2:1]([S:8][C:9]1[CH:10]=[CH:11][C:12]([NH:22][C:23]2[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][C:24]=2[Br:30])=[C:13](/[CH:15]=[CH:16]/[C:17](OCC)=[O:18])[CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CO.C[O-].[Na+].C(O)(=O)C>CCCCCCC>[CH2:1]([S:8][C:9]1[CH:14]=[C:13]2[C:12](=[CH:11][CH:10]=1)[N:22]([C:23]1[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][C:24]=1[Br:30])[C:17](=[O:18])[CH:16]=[CH:15]2)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 887MethanolHCID 10942334Sodium MethoxideHCID 117746874(E)-ethyl 3-(5-(benzylthio)-2-((2-bromo-4-chlorophenyl)amino)phenyl)acrylate

Product 1

HCID 117736931HCID 117736931, compoundYield 61.6%

Reagents, catalysts & solvents 1

HCID 8900HeptaneSolvent

Conditions

Temperature
80 °C

Procedure

A 250-mL RBF was charged with (E)-ethyl 3-(5-(benzylthio)-2-((2-bromo-4-chlorophenyl)amino)phenyl)acrylate (10.4 g, 20.68 mmol) and MeOH (103 ml) to give a thick, yellow suspension. Sodium methoxide (25 wt % in MeOH) (0.894 ml, 4.14 mmol) was added. A reflux condenser was attached, and the flask was heated to 80° C. overnight. The mixture was cooled to room temperature. Acetic acid (1.776 ml, 31.0 mmol) was added, and the mixture was concentrated. The residue was taken up in 2-PrOH and heated to boiling to give a brown solution. The mixture was cooled to room temperature with stirring then was concentrated. The residue was taken up in DCM and loaded onto a 25-g silica gel loading column. The column was eluted directly onto a pre-equilibrated 120-g Redi-Sep silica gel column with 0-50% EtOAc/Heptane to give a solid. The solid was taken up in heptane and filtered. The filtered solid was washed with heptane and dried under a stream of N2 (g) to give 6-(benzylthio)-1-(2-bromo-4-chlorophenyl)quinolin-2(1 H)-one (5.816 g, 12.73 mmol, 61.6% yield) as a tan solid. 1 H NMR (400 MHz, DMSO-d6)□=8.09 (d, J=2.3 Hz, 1 H), 8.01 (d, J=9.5 Hz, 1 H), 7.83 (d, J=2.2 Hz, 1 H), 7.72 (dd, J=2.3, 8.4 Hz, 1 H), 7.56 (d, J=8.4 Hz, 1 H), 7.41 (dd, J=2.2, 8.8 Hz, 1 H), 7.37-7.17 (m, 5 H), 6.71 (d, J=9.6 Hz, 1 H), 6.41 (d, J=8.8 Hz, 1 H), 4.25 (s, 2 H), 3.32 (s, 3 H). m/z (ESI) 456.0 (M+H)+.

Workup

  1. customto give a thick, yellow suspension
  2. customA reflux condenser was attached
  3. temperatureThe mixture was cooled to room temperature
  4. concentrationthe mixture was concentrated
  5. temperatureheated
  6. customto give a brown solution
  7. temperatureThe mixture was cooled to room temperature
  8. concentrationthen was concentrated
  9. washThe column was eluted directly onto a pre-equilibrated 120-g Redi-Sep silica gel column with 0-50% EtOAc/Heptane
  10. customto give a solid
  11. filtrationfiltered
  12. washThe filtered solid was washed with heptane
  13. dry with materialdried under a stream of N2 (g)

Sources & evidence

ORD record
ord-b781f6ea4cef4ce79cf1aff45816a348
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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