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

HRID 545205ノート

反応式

HRID 545205 の反応式
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]

参加物

11

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 6

HCID 167845palladium(II) acetate触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

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-nicotinicacid 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.

後処理

  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)

出典と根拠

ORDレコード
ord-6f158bd9646b4328bd380fd459307850
出典データセット
uspto-grants-2011_05
特許番号
US07935712B2

反応ノート

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