Water → 8-[3-(Methyloxy)-4-nitrophenyl]-1,4-dioxaspiro[4.5]dec-7-ene

HRID 419403

反応式

HRID 419403 の反応式
CC1(C)C(C)(C)OB([C:9]2[CH2:18][CH2:17][C:12]3([O:16][CH2:15][CH2:14][O:13]3)[CH2:11][CH:10]=2)O1.Cl[C:21]1[CH:22]=[CH:23][C:24]([N+:29]([O-:31])=[O:30])=[C:25]([O:27][CH3:28])[CH:26]=1.C([O-])([O-])=O.[Na+].[Na+].O>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:28][O:27][C:25]1[CH:26]=[C:21]([C:9]2[CH2:18][CH2:17][C:12]3([O:13][CH2:14][CH2:15][O:16]3)[CH2:11][CH:10]=2)[CH:22]=[CH:23][C:24]=1[N+:29]([O-:31])=[O:30]

参加物

7

反応物 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 811105-Chloro-2-nitroanisoleHCID 36970768-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-dioxaspiro(4.5)dec-7-ene

生成物 1

HCID 594525898-[3-(Methyloxy)-4-nitrophenyl]-1,4-dioxaspiro[4.5]dec-7-ene収率 91%

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

To a stirred solution of 8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-dioxaspiro[4.5]dec-7-ene (1.09 g, 4.13 mmol) in dioxane (17 mL) was added 5-chloro-2-nitroanisole (0.64 g, 3.44 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.12 g, 0.17 mmol) and 1.0 M Na2CO3 in H2O (10.32 mL, 10.32 mmol). The mixture was degassed by purging the reaction flask with vacuum/then N2 back-fill (5×). Under N2 the reaction was then heated to 80° C. and stirred overnight (approximately 16 h). The reaction was cooled to rt and diluted with EtOAc, then filtered through Celite, washing with EtOAc. The filtrate was concentrated under vacuum. The residue was taken up in EtOAc and H2O. The H2O layer was separated and extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, filtered, then concentrated and purified by silica gel chromatography to give the title compound of step C (911 mg, 3.13 mmol, 91%) as an amber oil. MS (ESI): 292 [M+H]+.

後処理

  1. customThe mixture was degassed
  2. customby purging the reaction flask with vacuum/then N2 back-fill (5×)
  3. temperatureThe reaction was cooled to rt
  4. additiondiluted with EtOAc
  5. filtrationfiltered through Celite
  6. washwashing with EtOAc
  7. concentrationThe filtrate was concentrated under vacuum
  8. customThe H2O layer was separated
  9. extractionextracted with EtOAc
  10. washThe combined organic layers were washed with brine
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated
  14. custompurified by silica gel chromatography

出典と根拠

ORDレコード
ord-d47a307b0812490cbbcc81284648414d
出典データセット
uspto-grants-2012_01
特許番号
US08093239B2

関連ノート

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