Ethanol → HCID 59674890, compound

HRID 1391505Notes

Reaction equation

HRID 1391505 reaction equation
FC(F)(F)S(O[C:7]1[CH2:8][CH2:9][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:11][CH:12]=1)(=O)=O.CC1(C)C(C)(C)OB([C:30]2[CH:31]=[C:32]([OH:36])[CH:33]=[CH:34][CH:35]=2)O1.C(O)C.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.ClCCl.CCCCCC.C(OCC)(=O)C>[OH:36][C:32]1[CH:31]=[C:30]([C:7]2[CH2:8][CH2:9][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:11][CH:12]=2)[CH:35]=[CH:34][CH:33]=1

Participants

9

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 27346233-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenolHCID 10991161Tert-butyl 4-(trifluoromethanesulfonyloxy)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 59674890HCID 59674890, compoundYield 208%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolventHCID 21226440Methylenechloride HexaneSolvent

Procedure

The tert-butyl 4-{[(trifluoromethyl)sulfonyl]oxy}-3,6-dihydropyridine-1(2H)-carboxylate (6.42 g, 9.23 mmol), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 4.69 g, 21.3 mmol, and tetrakis(triphenylphosphine)palladium(0) (200 mg, 0.17 mmol) were mixed in dioxane (20 mL), ethanol (10 mL) and 2 M aqueous sodium carbonate (5.0 mL). The solution was refluxed for 4 hours, cooled to room temperature, and poured into ethyl acetate (150 mL). The solution was extracted with 1N aqueous hydrochloric acid (2×100 mL), filtered through celite, extracted with saturated aqueous sodium bicarbonate (2×100 mL), and extracted with saturated with saturated aqueous ammonium chloride (2×100 mL). The solution was dried over sodium sulfate, vacuum filtered through a bed of silica gel and solvent removed at reduced pressure to afford a red oil. The tert-butyl 4-(3-hydroxyphenyl)-3,6-dihydropyridine-1(2H)-carboxylate (5.3 g, 19.2 mmol) was obtained as a combination of two crystallization crops from dichloromethane/hexane crystallization solvents. HRMS m/z 276.1614 (calcd for M+H 276.1594.)

Workup

  1. temperatureThe solution was refluxed for 4 hours
  2. extractionThe solution was extracted with 1N aqueous hydrochloric acid (2×100 mL)
  3. filtrationfiltered through celite
  4. extractionextracted with saturated aqueous sodium bicarbonate (2×100 mL)
  5. extractionextracted with saturated with saturated aqueous ammonium chloride (2×100 mL)
  6. dry with materialThe solution was dried over sodium sulfate, vacuum
  7. filtrationfiltered through a bed of silica gel and solvent
  8. customremoved at reduced pressure
  9. customto afford a red oil

Sources & evidence

ORD record
ord-471de0d5e2384270aaddb0e9a2a9a095
Source dataset
uspto-grants-2008_03
Patent number
US07338965B2

Reaction notes

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