Acetic Acid → HCID 14372169, compound

HRID 1383015Notes

Reaction equation

HRID 1383015 reaction equation
[O:1]1[C:5]2=[N:6][CH:7]=[C:8]([C:10]([OH:12])=[O:11])[CH:9]=[C:4]2[CH:3]=[CH:2]1.C([NH:16]C(C)C)(C)C.C([Li])CCC.CCCCCC.C(O)(=O)C.O.O.O.C([O-])(=O)C.[Na+].N[O:44][S:45]([OH:48])(=O)=O>O1CCCC1.C(OCC)C>[S:45]([C:2]1[O:1][C:5]2=[N:6][CH:7]=[C:8]([C:10]([OH:12])=[O:11])[CH:9]=[C:4]2[CH:3]=1)(=[O:48])(=[O:44])[NH2:16]

Participants

10

Reactant 7

HCID 176Acetic AcidHCID 7912DiisopropylamineHCID 8058HexaneHCID 76284hydroxylamine-O-sulfonic acidHCID 14372168Furo[2,3-b]pyridine-5-carboxylic acidHCID 23665404Sodium Acetate TrihydrateHCID 178418339Butyllithium

Product 1

HCID 14372169HCID 14372169, compoundYield 57%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

To a suspension of furo[2,3-b]pyridine-5-carboxylic acid (1.8 g, 11 mmol) in dry tetrahydrofuran (45 mL), under a nitrogen atmosphere and cooled to -70° C., was added diisopropylamine (1.54 mL, 11 mmol) to give a partial solution. Then 1.6M butyl lithium in hexane (19.7 mL, 31.5 mmol) was added dropwise to give a yellow precipitate. This suspension was stirred for 2.5 hours and then sulfur dioxide gas was bubbled over the reaction surface to give a very thick precipitate. After warming to room temperature, the reaction mixture was diluted with diethyl ether (50 mL) and glacial acetic acid (0.63 mL, 11 mmol) was added. This precipitate was collected by filtration and rinsed with diethyl ether. The hydroscopic sulfinate salt was dissolved in water (43 mL) and sodium acetate trihydrate (12.4 g, 92 mmol) and hydroxylamine-o-sulfonic acid (3.46 g, 30.6 mmol) were added. After stirring for 12-20 hours, the partial suspension was acidified with conc. hydrochloric and after stirring for several hours, the precipitated product was collected by filtration. This crude product (2.2 g) was recrystallized twice from ethanol/methanol (1:1) to give pure product (1.51 g, 57% yield), mp: 307°-308° (decomposition).

Workup

  1. customto give a partial solution
  2. customto give a yellow precipitate
  3. customsulfur dioxide gas was bubbled over the reaction surface
  4. customto give a very thick precipitate
  5. temperatureAfter warming to room temperature
  6. additionwas added
  7. filtrationThis precipitate was collected by filtration
  8. washrinsed with diethyl ether
  9. dissolutionThe hydroscopic sulfinate salt was dissolved in water (43 mL)
  10. stirringAfter stirring for 12-20 hours
  11. stirringafter stirring for several hours
  12. filtrationthe precipitated product was collected by filtration
  13. customThis crude product (2.2 g) was recrystallized twice from ethanol/methanol (1:1)

Sources & evidence

ORD record
ord-741e83548ea54bbd817be9e0fc039d0e
Source dataset
uspto-grants-1989_02
Patent number
US04808595

Reaction notes

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