Triethylsilane → ethyl 2-ethyl-5-(tetrahydro-2H-pyran-4-yl)thiophene-3-carboxylate

HRID 1877208

反応式

HRID 1877208 の反応式
Br[C:2]1[S:6][C:5]([CH2:7][CH3:8])=[C:4]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:3]=1.C([Mg]Br)(C)C.O1CCCC1.[O:24]1[CH2:29][CH2:28][C:27](=O)[CH2:26][CH2:25]1.[Cl-].[NH4+].C([SiH](CC)CC)C>O1CCCC1.FC(F)(F)C(O)=O>[CH2:7]([C:5]1[S:6][C:2]([CH:27]2[CH2:28][CH2:29][O:24][CH2:25][CH2:26]2)=[CH:3][C:4]=1[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH3:8]

参加物

8

反応物 5

HCID 12052TriethylsilaneHCID 25517Ammonium ChlorideHCID 121599Tetrahydro-4H-pyran-4-oneHCID 68515411Ethyl 5-bromo-2-ethylthiophene-3-carboxylateHCID 178420663HCID 178420663、化合物

生成物 1

HCID 68514211ethyl 2-ethyl-5-(tetrahydro-2H-pyran-4-yl)thiophene-3-carboxylate収率 26%

試薬・触媒・溶媒 2

HCID 6422Trifluoroacetic acid溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of ethyl 5-bromo-2-ethylthiophene-3-carboxylate (5.00 g) synthesized in Example 69 (4) in tetrahydrofuran (50 mL) was added dropwise 1.0M isopropylmagnesium bromide-tetrahydrofuran solution (22.8 mL) at −45° C., and the mixture was stirred for 1 hr under an argon atmosphere. Tetrahydro-4H-pyran-4-one (5.26 mL) was added dropwise, and the mixture was stirred at −45° C. for 1 hr, and then at room temperature for 2 hr. Saturated aqueous ammonium chloride solution was added to quench the reaction, tetrahydrofuran was evaporated using evaporator, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=2:3, volume ratio) to give a colorless oil. To a solution of the obtained oil in trifluoroacetic acid (25 mL) was added triethylsilane (2.86 mL), and the mixture was stirred at room temperature for 1.5 hr, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=3:17, volume ratio) to give the title compound (1.35 g, 26%) as a colorless oil.

後処理

  1. stirringthe mixture was stirred at −45° C. for 1 hr
  2. waitat room temperature for 2 hr
  3. customto quench
  4. customthe reaction, tetrahydrofuran
  5. customwas evaporated
  6. customevaporator
  7. extractionthe mixture was extracted with ethyl acetate
  8. washThe extract was washed with saturated brine
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by silica gel column chromatography (ethyl acetate:hexane=2:3, volume ratio)
  12. customto give a colorless oil
  13. stirringthe mixture was stirred at room temperature for 1.5 hr
  14. concentrationconcentrated under reduced pressure
  15. customThe residue was purified by silica gel column chromatography (ethyl acetate:hexane=3:17, volume ratio)

出典と根拠

ORDレコード
ord-9a04b18210df4113b31ca62bfca9ab5f
出典データセット
uspto-grants-2012_11
特許番号
US08309580B2

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