Ethanol → HCID 58335370, compound

HRID 1891419Notes

Reaction equation

HRID 1891419 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][CH:15]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)[CH3:16])=[C:4]([O:24][CH2:25][CH2:26][Cl:27])[C:3]=1[C:28](=[O:30])[CH3:29].O.O.Cl[Sn]Cl.[CH3:36][CH2:37]O>>[C:28]([C:3]1[C:4]([O:24][CH2:25][CH2:26][Cl:27])=[C:5]([O:12][CH2:13][CH2:14][CH:15]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)[CH3:16])[C:6]2[O:11][C:36]([CH3:37])=[N:8][C:7]=2[C:2]=1[Cl:1])(=[O:30])[CH3:29]

Participants

4

Reactant 3

HCID 702EthanolHCID 61436Stannous chloride dihydrateHCID 58335364HCID 58335364, compound

Product 1

HCID 58335370HCID 58335370, compoundYield 64%

Conditions

Temperature
50 °C

Procedure

To a stirred solution 38f) (242 mg, 0.52 mmol) in dry EtOH (10 mL) under nitrogen was added SnCl2.2H2O (1.11 g, 4.92 mmol). The solution was heated at reflux for 4 h. The solution was concentrated in vacuo and the residue was dissolved in EtOAc (10 mL) and treated with sodium potassium tartrate (1M, 10 mL). The mixture was warmed at 50° C. 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 (5 mL) and to this was added triethyl orthoacetate (5 mL, excess). 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 2:8) to give the title compound (151 mg, 64%). 1H NMR (300 MHz, CDCl3) δ 7.21-7.16 (m, 2H), 7.02-6.96 (m, 2H), 4.36-4.19 (m, 4H), 3.74-3.71 (m, 2H), 3.30-3.11 (m, 1H), 2.62 (s, 3H), 2.58 (s, 3H) 2.16-1.97 (m, 2H), 1.34-1.31 (d, J=7.0 Hz, 3H), ESIMS m/z [M+H]+ 454.2.

Workup

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

Sources & evidence

ORD record
ord-412bb939629d4e718ede23da58e86617
Source dataset
uspto-grants-2013_08
Patent number
US08507539B2

Reaction notes

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