Hydrochloric Acid → HCID 69269859, compound

HRID 751525Notes

Reaction equation

HRID 751525 reaction equation
[Cl-].[CH3:2][O:3][CH2:4][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C[C:25]([O-:28])(C)C.[K+].[Cl:30][C:31]1[CH:32]=[CH:33][C:34]([N+:39]([O-:41])=[O:40])=[C:35]([CH:38]=1)[CH:36]=O.Cl>O1CCCC1.CO.O1CCOCC1>[Cl:30][C:31]1[CH:32]=[CH:33][C:34]([N+:39]([O-:41])=[O:40])=[C:35]([CH2:36][CH:4]([O:28][CH3:25])[O:3][CH3:2])[CH:38]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 811235-Chloro-2-nitrobenzaldehydeHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 23665647Potassium tert-butoxide

Product 1

HCID 69269859HCID 69269859, compoundYield 19.3%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent3×HCID 312751,4-DioxaneSolvent

Procedure

Slurry (methoxymethyl)triphenylphosphonium chloride (32.3 g, 93.7 mmol) in tetrahydrofuran (350 ml) and cool in an ice-water bath. Add 1.0M KOtBu (94 ml, 94 mmol) in tetrahydrofuran solution to the reaction dropwise via an addition funnel. Stir reaction for one hour, then add 5-chloro-2-nitrobenzaldehyde (14.5 g, 78.1 mmol) dropwise as a solution in 100 ml tetrahydrofuran. Continue to stir in the ice bath for 20 minutes, then let warm to ambient temperature. Quench with 0.1 N HCl, extract with ethyl acetate, wash organics with water and brine. Dry with sodium sulfate, filter, concentrate to a brown oil. Purify by flash chromatography (1% EtOAc:Hexanes) to give a crude mix of three spots. Dissolve the crude oil in methanol (200 ml), cool in an ice bath, add 4N HCl in dioxane (30 ml), stir overnight, warming to ambient temperature. Concentrate to brown oil. Purify by flash chromatography, elute with hexanes to 3% EtOAc:hexanes gradient. Yields the title compound (3.7 g, 15.1 mmol, 19%).

Workup

  1. customto the reaction dropwise via an addition funnel
  2. customreaction for one hour
  3. customQuench with 0.1 N HCl
  4. extractionextract with ethyl acetate
  5. washwash organics with water and brine
  6. dry with materialDry with sodium sulfate
  7. filtrationfilter
  8. concentrationconcentrate to a brown oil
  9. customPurify by flash chromatography (1% EtOAc:Hexanes)
  10. customto give a crude
  11. additionmix of three spots
  12. temperaturecool in an ice bath
  13. stirringstir overnight
  14. temperaturewarming to ambient temperature
  15. concentrationConcentrate to brown oil
  16. customPurify by flash chromatography
  17. washelute with hexanes to 3% EtOAc

Sources & evidence

ORD record
ord-39d47796d702470ab6356fc3e527643a
Source dataset
uspto-grants-2008_07
Patent number
US07405305B2

Reaction notes

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