p-Toluenesulfonic acid → HCID 60167285, compound

HRID 2281866Notes

Reaction equation

HRID 2281866 reaction equation
[C:1]([O:5][C:6](=[O:27])[NH:7][C:8]1[CH:17]=[C:16]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][C:14]=2[Br:26])[CH:9]=1)([CH3:4])([CH3:3])[CH3:2].CC1C=CC(S(O)(=O)=O)=CC=1.[I:39]NC(=O)CCC(N)=O>C1COCC1>[C:1]([O:5][C:6](=[O:27])[NH:7][C:8]1[CH:17]=[C:16]([O:18][CH2:19][C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][C:14]=2[Br:26])[C:9]=1[I:39])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 21864724N-IodosuccinamideHCID 60167284HCID 60167284, compound

Product 1

HCID 60167285HCID 60167285, compoundYield 94.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

Carbamate 10 (1.20 g, 2.80 mmol) was dissolved in freshly distilled THF (0.17 M) under Ar and in the absence of light, and TsOH□H2O (53 mg, 0.28 mmol) and N-iodosuccinamide (753 mg, 3.30 mmol) were added. The reaction mixture was allowed to stir at 25° C. for 2 h. After 2 h, the reaction was quenched with the addition saturated aqueous NaHCO3 and diluted with ethyl acetate. The organic layer was washed with saturated aqueous NaCl, dried over Na2SO4, and concentrated under reduced pressure. Flash chromatography (SiO2, 5×16 cm, 5% EtOAc/hexanes elution) provided 11 (1.47 g, 94%) as an orange solid. 1H NMR (CDCl3, 500 MHz) δ 8.16 (s, 1H), 8.09 (d, J=8.0 Hz, 1H), 7.70 (d, J=7.5 Hz, 1H), 7.62 (d, J=7.0 Hz, 2H), 7.39 (t, J=7.2 Hz, 2H), 7.34 (d, J=7.0 Hz, 1H), 7.32 (s, 1H), 7.25-7.22 (m, 2H), 5.28 (s, 2H), 1.58 (s, 9H). 13C NMR (CDCl3, 125 MHz) δ 155.8, 152.4, 139.0, 136.7, 135.9, 132.2, 131.9, 130.0, 128.5, 128.3, 128.0, 127.9, 121.4, 120.2, 120.1, 117.0, 101.9, 81.3, 71.3, 28.3. IR (film) νmax 3378, 2978, 1730, 1225, 1145 cm−1. ESI-TOF HRMS m/z 553.9820 (M+H+, C22H21BrINO3 requires 553.9822).

Workup

  1. additionwere added
  2. waitAfter 2 h
  3. customthe reaction was quenched with the addition saturated aqueous NaHCO3
  4. additiondiluted with ethyl acetate
  5. washThe organic layer was washed with saturated aqueous NaCl
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. washFlash chromatography (SiO2, 5×16 cm, 5% EtOAc/hexanes elution)

Sources & evidence

ORD record
ord-9ee0127c467c4a83b01bfff75e1573a6
Source dataset
uspto-grants-2015_09
Patent number
US09139596B2

Reaction notes

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