Ethyl 3-bromo-4-chlorobenzoate → 4-Chloro-3-(3,3-dimethylbutyl)benzoic acid ethyl ester

HRID 499943ノート

反応式

HRID 499943 の反応式
[CH3:1][C:2]([CH3:8])([CH3:7])[CH2:3][CH2:4][Mg]Cl.[CH2:9]([O:11][C:12](=[O:21])[C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15](Br)[CH:14]=1)[CH3:10]>O1CCOCC1.C(OCC)C.[Cl-].[Cl-].[Zn+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:9]([O:11][C:12](=[O:21])[C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15]([CH2:4][CH2:3][C:2]([CH3:8])([CH3:7])[CH3:1])[CH:14]=1)[CH3:10]

参加物

7

反応物 2

HCID 12594300Ethyl 3-bromo-4-chlorobenzoateHCID 178444610HCID 178444610、化合物

生成物 1

HCID 685074754-Chloro-3-(3,3-dimethylbutyl)benzoic acid ethyl ester

試薬・触媒・溶媒 4

HCID 3007855Zincchloride触媒HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 3283Diethyl Ether溶媒HCID 312751,4-Dioxane溶媒

実験手順

3,3-dimethyl-1-butylmagnesium chloride (8.00 mmol, 0.5 M THF, Platte Valley Scientific) was added dropwise to a solution of ZnCl2 (4.00 mmol, IM diethyl ether, Aldrich) in 1,4-dioxane (15 mL) at ambient temperature. The mixture was stirred 30 minutes followed by addition of 3-bromo-4-chlorobenzoic acid ethyl ester (1.05 g, 3.99 mmol) and Pd(dppf)2Cl2 (131 mg, 0.160 mmol). The mixture was heated to reflux for 30 minutes, cooled to ambient temperature, diluted with diethyl ether and quenched with H2O. The mixture was filtered through celite and the filtrate was washed with brine, dried (Na2SO4), filtered and concentrated under reduced pressure. Flash chromatography eluting with 5% to 15% ethyl acetate/hexanes provided the title compound. 1H NMR (DMSO-d6) δ 7.89 (d, 1H), 7.78 (dd, 1H), 7.56 (d, 1H), 4.32 (q, 2H), 2.73 (m, 2H), 1.41 (m, 2H), 1.32 (t, 3H), 0.97 (s, 9H); MS (DCI+) m/z 286 (M+NH4)+, 269 (M+H)+.

後処理

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 30 minutes
  3. customquenched with H2O
  4. filtrationThe mixture was filtered through celite
  5. washthe filtrate was washed with brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. washFlash chromatography eluting with 5% to 15% ethyl acetate/hexanes

出典と根拠

ORDレコード
ord-3336679174de47a39da913e9c74ad409
出典データセット
uspto-grants-2010_08
特許番号
US07767705B2

反応ノート

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