Ethylene Glycol → 4a-Methyl-6-(phenylsulfanyl)-1,2,3,4,4a,9-hexahydro[1]benzofuro[2,3-c]pyridine-2-carboxylic acid tert-butyl ester

HRID 1616873ノート

反応式

HRID 1616873 の反応式
I[C:2]1[CH:3]=[CH:4][C:5]2[O:21][CH:9]3[CH2:10][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:12][CH2:13][C:8]3([CH3:22])[C:6]=2[CH:7]=1.CC(C)([O-])C.[Na+].C(O)CO.CN(C)C=O.[C:38]1([SH:44])[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1>[Cu]I>[C:17]([O:16][C:14]([N:11]1[CH2:12][CH2:13][C:8]2([CH3:22])[C:6]3[CH:7]=[C:2]([S:44][C:38]4[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=4)[CH:3]=[CH:4][C:5]=3[O:21][CH:9]2[CH2:10]1)=[O:15])([CH3:20])([CH3:19])[CH3:18]

参加物

7

反応物 5

HCID 174Ethylene GlycolHCID 6228DimethylformamideHCID 7969ThiophenolHCID 23676156Sodium t-butoxideHCID 68304820tert-butyl 6-iodo-4a-methyl-3,4,4a,9a-tetrahydro[1]benzofuro[2,3-c]pyridine-2(1H)-carboxylate

生成物 1

HCID 673240934a-Methyl-6-(phenylsulfanyl)-1,2,3,4,4a,9-hexahydro[1]benzofuro[2,3-c]pyridine-2-carboxylic acid tert-butyl ester

試薬・触媒・溶媒 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒

反応条件

温度
120 °C

実験手順

Into a sealed tube was added tert-butyl 6-iodo-4a-methyl-3,4,4a,9a-tetrahydro[1]benzofuro[2,3-c]pyridine-2(1H)-carboxylate P24 (0.491 g, 1.18 mmol), sodium tert-butoxide (341 mg, 3.55 mmol), copper (I) iodide (20 mg, 0.08 mmol), 1,2-ethanediol (132 μL, 2.38 mmol), N,N-dimethylformamide (17 mL, 210 mmol), and benzenethiol (123 μL, 1.19 mmol). The reaction was heated at 120° C. overnight. The reaction was concentrated and partitioned between DCM and water. The DCM layer was washed with brine, dried, filtered and concentrated under vacuum. The crude product was dissolved in DCM and purified on a 12 g silica gel column eluting with hexanes to 2:1 hexanes:ethyl acetate to give the product which was taken directly into the next step.

後処理

  1. concentrationThe reaction was concentrated
  2. custompartitioned between DCM and water
  3. washThe DCM layer was washed with brine
  4. customdried
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. dissolutionThe crude product was dissolved in DCM
  8. custompurified on a 12 g silica gel column
  9. washeluting with hexanes to 2:1 hexanes
  10. customethyl acetate to give the product which

出典と根拠

ORDレコード
ord-452927a345a74663b64cdacc493db5b3
出典データセット
uspto-grants-2014_07
特許番号
US08765779B2

反応ノート

読み込み中…