Sodium Carbonate → 3-Pyridinecarboxylic acid, 1,1-dimethylethyl ester

HRID 420153

반응식

HRID 420153 반응식
C(OC(N1CCC2(CC(=O)C3C(=CC=C(Br)C=3)O2)CC1)=O)(C)(C)C.C(O[K])(C)=O.[C:30]([O:34][C:35](=[O:43])[C:36]1[CH:41]=[C:40](Br)[CH:39]=[N:38][CH:37]=1)([CH3:33])([CH3:32])[CH3:31].C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.CCOC(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].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>[C:30]([O:34][C:35](=[O:43])[C:36]1[CH:41]=[CH:40][CH:39]=[N:38][CH:37]=1)([CH3:33])([CH3:31])[CH3:32]

참가 물질

11

반응물 4

HCID 10340Sodium CarbonateHCID 2794759tert-Butyl 6-bromo-4-oxospiro[chroman-2,4'-piperidine]-1'-carboxylateHCID 18422124tert-Butyl 5-bromonicotinateHCID 178476685HCID 178476685, 화합물

생성물 1

HCID 1824843-Pyridinecarboxylic acid, 1,1-dimethylethyl ester

시약·촉매·용매 6

HCID 167845palladium(II) acetate촉매HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)촉매HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

반응 조건

온도
100 °C

실험 절차

tert-butyl-6-bromo-4-oxospiro[chroman-2,4′-piperidine]-1′-carboxylate (19.8 g, 50.0 mmol), bis(pinacolato)diboran (14.0 g, 55.0 mmol), Pd(OAc)2 (560 mg, 2.50 mmol), DPPF (2.77 g, 5.00 mmol), and AcOK (5.82 g, 60.0 mmol) were suspended in dioxane (250 mL) and heated at 100° C. for 10 hours. After cooling down to room temperature, 5-bromo-nicotinic acid tert-butyl ester (14.2 g, 55.0 mmol), Pd(PPh3)4 (5.78 g, 5.00 mmol) and 2M Na2CO3 aq. (125 mL, 250 mmol) were added to the reaction mixture; and then heated at 100° C. for 15 hours. The reaction mixture was diluted with EtOAc and H2O, organic layer was washed with brine and dried over MgSO4. After filtration, the solvents were removed in vacuo and the residue was purified by silica gel column chromatography (hexane/EtOAc=10/0 to 6/4) and the obtained brown solid was crystallized from EtOAc/hexane (1/1) to afford 5-{1′-tert-butoxycarbonyl]-4-oxospiro[chroman-2,4′-piperidin]-6-yl}nicotinic acid tert-butyl ester as a pale yellow solid.

후처리

  1. temperatureAfter cooling down to room temperature
  2. temperatureand then heated at 100° C. for 15 hours
  3. washwas washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationAfter filtration
  6. customthe solvents were removed in vacuo
  7. customthe residue was purified by silica gel column chromatography (hexane/EtOAc=10/0 to 6/4)
  8. customthe obtained brown solid was crystallized from EtOAc/hexane (1/1)

출처 및 근거

ORD 기록
ord-7d3fb9ad22a1491aab38b03b5b47e941
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08093389B2

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