Formic Acid → HCID 25191984, compound

HRID 1639674Notes

Reaction equation

HRID 1639674 reaction equation
C(O)=O.[N:4]1[O:5][N:6]=[C:7]2[CH:12]=[C:11]([C:13](Cl)=[O:14])[CH:10]=[CH:9][C:8]=12.O.OS(O)(=O)=O.[CH2:22]1[CH2:26]O[CH2:24][CH2:23]1>CO.C(Cl)(Cl)Cl>[CH:22]12[N:4]([C:13]([C:11]3[CH:10]=[CH:9][C:8]4=[N:4][O:5][N:6]=[C:7]4[CH:12]=3)=[O:14])[CH:8]([CH2:9][CH2:26]1)[CH2:7][CH2:24][CH2:23]2

Participants

8

Reactant 5

HCID 284Formic AcidHCID 962WaterHCID 1118Sulfuric AcidHCID 8028TetrahydrofuranHCID 27354532,1,3-Benzoxadiazole-5-carbonyl chloride

Product 1

HCID 25191984HCID 25191984, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6212ChloroformSolvent

Procedure

The preceding product (3.3 g) was dissolved in THF (50 ml) and methanol (50 ml), and freshly prepared Zn/Cu (15 g) was added followed by formic acid (5 ml). The mixture was stirred at room temperature for 20 minutes before filtering the solids and evaporating the solvent until ˜10 ml remained. Concentrated sodium hydroxide solution was added until pH 10 was reached and the mixture extracted with chloroform (100 ml) and the organic phase dried over sodium sulfate. Triethylamine (2 ml) was added followed by a solution of [2,1,3]-benzoxadiazole-5-carbonylchloride (0.5 g, 2.73 mmol) in chloroform (20 ml), slowly. After stirring the mixture for 20 minutes, water (100 ml) and H2SO4 (→pH2) were added and the aqueous phase extracted with chloroform (100 ml), dried over magnesium sulfate, and concentrated under vacuum to give an oil. The material was purified by silica gel chromatography eluting with hexane/ethyl acetate (3:2), to give after crystallization from dichloromethane/MTBE 133 mg of a white solid: mp=128-130° C., LC-MS, MH+=258; 1H NMR (300 MHz, CDCl3) δ 7.92 (s, 1H); 7.90 (d, 1H, J=6.3 Hz); 7.52 (d, 1H, J=6.3 Hz); 4.84 (s, 1H); 4.06 (s, 1H); 2.06-1.50 ppm (m, 10H).

Workup

  1. filtrationbefore filtering the solids
  2. customevaporating the solvent until ˜10 ml
  3. additionConcentrated sodium hydroxide solution was added until pH 10
  4. extractionthe mixture extracted with chloroform (100 ml)
  5. dry with materialthe organic phase dried over sodium sulfate
  6. additionTriethylamine (2 ml) was added
  7. stirringAfter stirring the mixture for 20 minutes
  8. extractionthe aqueous phase extracted with chloroform (100 ml)
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated under vacuum
  11. customto give an oil
  12. customThe material was purified by silica gel chromatography
  13. washeluting with hexane/ethyl acetate (3:2)
  14. customto give
  15. customafter crystallization from dichloromethane/MTBE 133 mg of a white solid

Sources & evidence

ORD record
ord-0c34d1db452d4c3590b96e769974c7c7
Source dataset
uspto-grants-2012_02
Patent number
US08110584B2

Reaction notes

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