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

HRID 1643540노트

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HRID 1643540 반응식
[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

참가 물질

8

반응물 3

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

생성물 1

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

시약·촉매·용매 4

HCID 24290Palladium Chloride촉매HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 83681Tris(1,1-dimethylethyl)phosphine촉매HCID 6228Dimethylformamide용매

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온도
45 °C

실험 절차

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)+.

후처리

  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

출처 및 근거

ORD 기록
ord-b648139b108f4e518df8e479b66ff052
출처 데이터셋
uspto-grants-2012_02
특허 번호
US08119624B2

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