Formic Acid → HCID 15937755, compound

HRID 327453Notes

Reaction equation

HRID 327453 reaction equation
[N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[C:3]([NH:11][CH:12]=[O:13])[CH:2]=1.[CH:14](OC(=O)C)=[O:15].C(O)=O.C(OC(=O)C)(=O)C>C1COCC1.[Pt]=O.CO.C(O)(=O)C>[CH:14]([N:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH:3]([NH:11][CH:12]=[O:13])[CH2:2]1)=[O:15]

Participants

9

Reactant 4

HCID 284Formic AcidHCID 7918Acetic AnhydrideHCID 75269Acetic-formic anhydrideHCID 10899138HCID 10899138, compound

Product 1

HCID 15937755HCID 15937755, compoundYield 69%

Reagents, catalysts & solvents 4

HCID 82844Platinum oxide (PtO)CatalystHCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of N-(3-quinolyl)formamide (30.0 g, 0.175 mol), platinum oxide (2.0 g) and acetic acid (300 mL) was hydrogenated (50 lb. initial H2 pressure) until 2 equivalents of H2 were consumed (reaction time 3 hours). The mixture was filtered through celite and the acetic acid removed under pressure. It was dissolved in ethyl acetate and washed with NaOH solution and water. Evaporation of the ethyl acetate gave 29.4 g of crude material. This was dissolved in 200 mL THF and acetic formic anhydride (prepared from formic acid (27.2 g, 0.59 mol) and acetic anhydride (53.5 g, 0.52 mol) was added at 0° C. After 15 minutes, the solution was allowed to warm to room temperature, and after an additional 15 minutes, methanol (60 mL) was added. The solution was evaporated and the resulting oil was partitioned between ethyl acetate and 4N sodium hydroxide solution. The sodium hydroxide solution was repeatedly extracted with ethyl acetate. The combined ethyl acetate was evaporated, and the crude product was purified by chromatography on silica gel using 2.5% methanol:chloroform as eluant to give 22.55 g (69%) of product. An analytical sample was crystallized from methanol:ether (1:3); mp 125°-128° C. Anal. Calcd. for C11H12N2O2 : C, 64.69; H, 5.92; N, 13.72. Found: C, 64.60; H, 5.97; N, 13.66.

Workup

  1. customwere consumed
  2. custom(reaction time 3 hours)
  3. filtrationThe mixture was filtered through celite
  4. customthe acetic acid removed under pressure
  5. dissolutionIt was dissolved in ethyl acetate
  6. washwashed with NaOH solution and water
  7. customEvaporation of the ethyl acetate
  8. customgave 29.4 g of crude material
  9. additionwas added at 0° C
  10. waitafter an additional 15 minutes
  11. customThe solution was evaporated
  12. customthe resulting oil was partitioned between ethyl acetate and 4N sodium hydroxide solution
  13. extractionThe sodium hydroxide solution was repeatedly extracted with ethyl acetate
  14. customThe combined ethyl acetate was evaporated
  15. customthe crude product was purified by chromatography on silica gel using 2.5% methanol

Sources & evidence

ORD record
ord-702e892fca34429c88a04077b0d3918c
Source dataset
uspto-grants-1993_12
Patent number
US05273975

Reaction notes

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