Cesium fluoride → Methyl 3,5-bis(methoxymethoxy)-4-(2-methylallyl)benzoate

HRID 1643540ノート

反応式

HRID 1643540 の反応式
[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([O:10][CH2:11][O:12][CH3:13])[C:7](Br)=[C:6]([O:15][CH2:16][O:17][CH3:18])[CH:5]=1.[F-].[Cs+].[CH3:22][C:23](=[CH2:38])[CH2:24][Sn](CCCC)(CCCC)CCCC>CN(C=O)C.[Cu]I.Cl[Pd]Cl.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C>[CH3:1][O:2][C:3](=[O:19])[C:4]1[CH:9]=[C:8]([O:10][CH2:11][O:12][CH3:13])[C:7]([CH2:24][C:23]([CH3:38])=[CH2:22])=[C:6]([O:15][CH2:16][O:17][CH3:18])[CH:5]=1

参加物

8

反応物 3

HCID 25953Cesium fluorideHCID 11013379Methallyltri-n-butyltinHCID 59560261Methyl 4-bromo-3,5-bis(methoxymethoxy)benzoate

生成物 1

HCID 59560052Methyl 3,5-bis(methoxymethoxy)-4-(2-methylallyl)benzoate収率 125.4%

試薬・触媒・溶媒 4

HCID 24290Palladium Chloride触媒HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 83681Tris(1,1-dimethylethyl)phosphine触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
45 °C

実験手順

To a solution of 4-bromo-3,5-bis-methoxymethoxy-benzoic acid methyl ester (3 h) (3.10 g, 9.25 mmol) in DMF (20 mL) was added CsF (2.80 g, 18.4 mmol), CuI (200 mg, 1.05 mmol), PdCl2 (200 mg, 1.12 mmol), 2-methylallyltributyltin (3.80, 11.0 mmol) and PtBu3 (220 mg, 1.09 mmol). The reaction mixture was degassed and heated to 45° C. overnight. The mixture was filtered through Celite, quenched with H2O (100 mL), extracted with EtOAc (2×100 mL). The organic layers were dried over MgSO4 and concentrated. The residue was purified by flash column chromatography eluting with 5% EtOAc in hexanes to give the desired product as brown oil (3.6 g) which contained tin impurities. 1H NMR (400 MHz, CDCl3) δ 7.44-7.46 (m, 2 H) 5.22 (s, 4 H) 4.61-4.76 (m, 1 H) 4.38-4.55 (m, 1 H) 3.90 (s, 3 H) 3.47 (s, 6 H) 3.42-3.45 (m, 2 H) 1.80 (s, 3 H); LCMS for C16H22O6 m/z 311.10 (M+H)+.

後処理

  1. customThe reaction mixture was degassed
  2. filtrationThe mixture was filtered through Celite
  3. customquenched with H2O (100 mL)
  4. extractionextracted with EtOAc (2×100 mL)
  5. dry with materialThe organic layers were dried over MgSO4
  6. concentrationconcentrated
  7. customThe residue was purified by flash column chromatography
  8. washeluting with 5% EtOAc in hexanes

出典と根拠

ORDレコード
ord-b648139b108f4e518df8e479b66ff052
出典データセット
uspto-grants-2012_02
特許番号
US08119624B2

反応ノート

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