Potassium Iodide → HCID 117737273, compound

HRID 1504548Notes

Reaction equation

HRID 1504548 reaction equation
N[C:2]1[CH:7]=[CH:6][C:5]([S:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:4][C:3]=1/[CH:16]=[CH:17]/[C:18]([O:20][CH2:21][CH3:22])=[O:19].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.N([O-])=O.[Na+].[I-:39].[K+]>C(#N)C.O.C(OCC)(=O)C>[CH2:21]([O:20][C:18](=[O:19])[CH:17]=[CH:16][C:3]1[CH:4]=[C:5]([S:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:6]=[CH:7][C:2]=1[I:39])[CH3:22]

Participants

8

Reactant 4

HCID 4875Potassium IodideHCID 521998p-Toluenesulfonic acid monohydrateHCID 23668193Sodium NitriteHCID 117740420(E)-Ethyl 3-(2-amino-5-(benzylthio)phenyl)acrylate

Product 1

HCID 117737273HCID 117737273, compoundYield 64%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (E)-ethyl 3-(2-amino-5-(benzylthio)phenyl)acrylate (150 g, 479 mmol, 1.0 equiv) in acetonitrile (2.0 L) was added para-toluenesulfonic acid monohydrate (273.16 g, 1437 mmol, 3.0 equiv, Spectrochem). The reaction mixture was cooled to 0° C. and a solution of sodium nitrite (66.03 g, 958 mmol, 2.0 equiv, Spectrochem) and potassium iodide (185.7 g, 1198 mmol, 2.5 equiv, Spectrochem) in water (450 mL) was added drop wise keeping temperature below 5° C. The reaction mixture was stirred at 0° C. for 5 h. The mixture was then diluted with ethyl acetate (5.0 L) and quenched with 2M aqueous sodium hyposulfite solution (5.0 L). The layers were separated and the organic layer was washed with saturated aqueous sodium bicarbonate solution (3.0 L). The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to obtain the crude material which was purified by column chromatography (silica gel; mesh size 60-120, elution 0-5% ethyl acetate in hexane) to yield ethyl-3-(5-(benzylthio)-2-iodophenyl)acrylate (130 g, 64%) as light brown solid. TLC solvent system: 20% ethyl acetate in hexane. Product's Rf: 0.6. MS (ESI, positive ion) m/z; 425.0 (M+1)

Workup

  1. customtemperature below 5° C
  2. customquenched with 2M aqueous sodium hyposulfite solution (5.0 L)
  3. customThe layers were separated
  4. washthe organic layer was washed with saturated aqueous sodium bicarbonate solution (3.0 L)
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto obtain the crude material which
  9. customwas purified by column chromatography (silica gel; mesh size 60-120, elution 0-5% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-94ab5991e75347db92e8dce16297750e
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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