Hydrochloric Acid → Methyl 5-(2,6-dimethoxyphenyl)-3-methyl-5-oxopentanoate

HRID 594371ノート

反応式

HRID 594371 の反応式
I[C:2]1[C:7]([O:8][CH3:9])=[CH:6][CH:5]=[CH:4][C:3]=1[O:10][CH3:11].[CH:12]([Mg]Cl)(C)C.[CH3:17][CH:18]1[CH2:23][C:22](=[O:24])[O:21][C:20](=[O:25])[CH2:19]1.Cl.[NH4+].[Cl-].C([O-])([O-])=O.[Cs+].[Cs+].IC>C1COCC1.[Cu]I.O.CCOC(C)=O.CN(C=O)C.CCOCC>[CH3:11][O:10][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([O:8][CH3:9])[C:2]=1[C:22](=[O:24])[CH2:23][CH:18]([CH3:17])[CH2:19][C:20]([O:21][CH3:12])=[O:25]

参加物

14

反応物 7

HCID 313Hydrochloric AcidHCID 6328Methyl iodideHCID 10796Cesium carbonateHCID 25517Ammonium ChlorideHCID 778283-Methylglutaric anhydrideHCID 113914072-Iodo-1,3-dimethoxybenzeneHCID 178418918HCID 178418918、化合物

生成物 1

HCID 69085219Methyl 5-(2,6-dimethoxyphenyl)-3-methyl-5-oxopentanoate

試薬・触媒・溶媒 6

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒3 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
-10 °C

実験手順

A cooled (−10° C.) solution of commercially available 2-iodo-1,3-dimethoxybenzene (2.000 g; 7.57 mmol) in anh. THF (30 ml) was treated dropwise with a solution of 2 M isopropylmagnesium chloride in THF (5.10 ml; 10.20 mmol), and the mixture was further stirred at −10° C., under nitrogen, for 15 min. This mixture was then added dropwise to a cooled (−40° C.) solution of commercially available 4-methyldihydro-2H-pyran-2,6(3H)-dione (970 mg; 7.57 mmol) and CuI (360 mg; 1.89 mmol) in anh. THF (20 ml). Stirring was continued at −40° C. for 20 min., and 2 M aq. HCl (11.5 ml) was then added dropwise. Et2O (100 ml), and aq. sat. NH4Cl (30 ml) were added, and the separated organic layer was dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Anh. DMF (20 ml), and Cs2CO3 (3.165 g; 9.71 mmol) were successively added, and stirring at rt was continued for 15 min. After cooling to 0° C., iodomethane (1.655 g; 11.66 mmol) was added dropwise, and the resulting mixture was further stirred at 0° C. for 10 min., and then at rt for 1.5 h. AcOEt (100 ml) and water (100 ml) were added, and the separated organic layer was further washed with brine (25 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=20/1) afforded methyl 5-(2,6-dimethoxyphenyl)-3-methyl-5-oxopentanoate as a yellow oil. LC-MS (conditions D): tR=0.97 min.; [M+H]+: 281.29 g/mol.

後処理

  1. additionThis mixture was then added dropwise to
  2. stirringStirring
  3. waitwas continued at −40° C. for 20 min.
  4. dry with materialthe separated organic layer was dried over anh. MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure
  7. stirringstirring at rt
  8. waitwas continued for 15 min
  9. temperatureAfter cooling to 0° C.
  10. stirringthe resulting mixture was further stirred at 0° C. for 10 min.
  11. waitat rt for 1.5 h
  12. washthe separated organic layer was further washed with brine (25 ml)
  13. dry with materialdried over anh. MgSO4
  14. filtrationfiltered
  15. concentrationconcentrated to dryness under reduced pressure
  16. customPurification by FC (DCM/MeOH=20/1)

出典と根拠

ORDレコード
ord-c13e69d5abf34440996bc9c07c07acee
出典データセット
uspto-grants-2016_01
特許番号
US09242970B2

反応ノート

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