Ethanol → HCID 58335365, compound

HRID 1891418Notes

Reaction equation

HRID 1891418 reaction equation
[Cl:1][C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([OH:11])[C:5]([O:12][CH2:13][CH2:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[C:4]([O:22][CH2:23][CH2:24][Cl:25])[C:3]=1[C:26](=[O:28])[CH3:27].O.O.Cl[Sn]Cl.[CH3:34][CH2:35]O>>[C:26]([C:3]1[C:4]([O:22][CH2:23][CH2:24][Cl:25])=[C:5]([O:12][CH2:13][CH2:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:6]2[O:11][C:34]([CH3:35])=[N:8][C:7]=2[C:2]=1[Cl:1])(=[O:28])[CH3:27]

Participants

4

Reactant 3

HCID 702EthanolHCID 61436Stannous chloride dihydrateHCID 58335324HCID 58335324, compound

Product 1

HCID 58335365HCID 58335365, compoundYield 64%

Conditions

Temperature
50 °C

Procedure

To a stirred solution 37h) (46 mg, 0.11 mmol) in dry EtOH (5 mL) under nitrogen was added SnCl2.2H2O (241 mg, 1.07 mmol). The solution was heated to reflux for 4 h. The solution was concentrated in vacuo and the residue was dissolved in EtOAc (5 mL) and treated with sodium potassium tartrate (1M, 5 mL). The mixture was warmed to 50° C. heated at this temperature until the layers visibly separated. The organic layer was separated and the aqueous further extracted with EtOAc (2×5 mL). The organics were pooled, dried over Na2SO4, filtered and concentrated in vacuo. The crude material was taken up in dry DMF (3 mL) and to this solution triethyl orthoacetate (3 mL, excess) was added. The solution was stirred at reflux for 1 h. The solution was concentrated in vacuo and the residue was taken in CH2Cl2 (5 mL) and washed with water. The organic layer was dried over Na2SO4 and concentrated in vacuo. The crude product was purified by flash chromatography (silica gel, ethyl acetate/petroleum spirit 3:18) to give the title compound (30 mg, 64%). 1H NMR (300 MHz, CDCl3) δ 7.33-7.21 (m, 5H), 4.45-4.40 (t, J=6.6 Hz, 2H), 4.29-4.25 (m, 2H), 3.75-3.72 (t, J=5.7 Hz, 2H), 2.89-2.84 (t, J=7.2 Hz, 2H), 2.65 (s, 3H), 2.59 (s, 3H), 2.19-2.09 (m, 2H), ESIMS m/z [M+H]+ 422.2.

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 4 h
  3. concentrationThe solution was concentrated in vacuo
  4. dissolutionthe residue was dissolved in EtOAc (5 mL)
  5. additiontreated with sodium potassium tartrate (1M, 5 mL)
  6. temperatureheated at this temperature until the layers
  7. customvisibly separated
  8. customThe organic layer was separated
  9. extractionthe aqueous further extracted with EtOAc (2×5 mL)
  10. dry with materialdried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. additionwas added
  14. temperatureat reflux for 1 h
  15. concentrationThe solution was concentrated in vacuo
  16. washwashed with water
  17. dry with materialThe organic layer was dried over Na2SO4
  18. concentrationconcentrated in vacuo
  19. customThe crude product was purified by flash chromatography (silica gel, ethyl acetate/petroleum spirit 3:18)

Sources & evidence

ORD record
ord-4e5139d8c2574ef0bae999039a2fc1ea
Source dataset
uspto-grants-2013_08
Patent number
US08507539B2

Reaction notes

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