Ethanol → HCID 86614352, compound

HRID 2265139Notes

Reaction equation

HRID 2265139 reaction equation
C([O:4][CH:5]1[C:14]2[N:13]=[CH:12][CH:11]=[CH:10][C:9]=2[CH2:8][CH:7]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:6]1)(=O)C.C(O)C.[Na].[Cl-].[NH4+]>C(OC(=O)C)(=O)C.O1CCCC1>[OH:4][CH:5]1[C:14]2[N:13]=[CH:12][CH:11]=[CH:10][C:9]=2[CH2:8][CH:7]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:6]1

Participants

7

Reactant 4

HCID 702EthanolHCID 25517Ammonium ChlorideHCID 5360545SodiumHCID 42611478HCID 42611478, compound2×

Product 1

HCID 86614352HCID 86614352, compound

Reagents, catalysts & solvents 2

HCID 7918Acetic AnhydrideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
130 °C

Procedure

At 0° C. 1.04 kg of metachloroperbenzoic acid was added to chloroform (6 L) solution of 689 g of the compound obtained in the above, and stirred at room temperature for 3 hours. 1:1 mixed solution of aqueous saturated sodium hydrogencarbonate solution and aqueous saturated sodium sulfite solution was added to the reaction liquid, and extracted with chloroform. The organic layer was washed with aqueous saturated sodium hydrogencarbonate solution and aqueous saturated sodium chloride solution, and dried with anhydrous sodium sulfate, and the solvent was evaporated off under reduced pressure to obtain ethyl 5,6,7,8-tetrahydroquinoline-6-carboxylate 1-oxide. The obtained compound was dissolved in 2 L of acetic anhydride, and stirred at 130° C. for 1 hour. The reaction liquid was distilled under reduced pressure, and diluted with aqueous saturated sodium hydrogencarbonate solution, and extracted with chloroform. The solvent was evaporated off under reduced pressure to obtain a mixture of ethyl (6RS,8SR)-8-acetoxy-5,6,7,8-tetrahydroquinoline-6-carboxylate and ethyl (6RS,8RS)-8-acetoxy-5,6,7,8-tetrahydroquinoline-6-carboxylate. At 0° C., ethanol (3.36 L) solution of 77.2 g of sodium was added to tetrahydrofuran (3 L) solution of the resulting mixture, and stirred at 0° C. for 1 hour. Aqueous saturated ammonium chloride solution was added to the reaction liquid, then extracted with chloroform, and the organic layer was dried with anhydrous sodium sulfate. The solvent was evaporated off under reduced pressure, and the residue was separated and purified through silica gel column chromatography (hexane/ethyl acetate=2/1) to obtain 336 g of ethyl (6RS,8SR)-8-hydroxy-5,6,7,8-tetrahydroquinoline-6-carboxylate as a brown oily substance. This compound contained impurities.

Workup

  1. customThe reaction liquid
  2. distillationwas distilled under reduced pressure
  3. additiondiluted with aqueous saturated sodium hydrogencarbonate solution
  4. extractionextracted with chloroform
  5. customThe solvent was evaporated off under reduced pressure
  6. customto obtain
  7. stirringstirred at 0° C. for 1 hour
  8. extractionextracted with chloroform
  9. dry with materialthe organic layer was dried with anhydrous sodium sulfate
  10. customThe solvent was evaporated off under reduced pressure
  11. customthe residue was separated
  12. custompurified through silica gel column chromatography (hexane/ethyl acetate=2/1)

Sources & evidence

ORD record
ord-f69b3cce4d0740beacf90707a7f96af2
Source dataset
uspto-grants-2010_12
Patent number
US07855294B2

Reaction notes

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