Cesium carbonate → 4-Bromo-1-chloro-2-(4-(2-cyclopropoxyethoxy)benzyl)benzene

HRID 1175288ノート

反応式

HRID 1175288 の反応式
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:16])=[C:6]([CH:15]=1)[CH2:7][C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1.C([O-])([O-])=O.[Cs+].[Cs+].CC1C=CC(S(O[CH2:34][CH2:35][O:36][CH:37]2[CH2:39][CH2:38]2)(=O)=O)=CC=1>CN(C=O)C.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:16])=[C:6]([CH2:7][C:8]2[CH:13]=[CH:12][C:11]([O:14][CH2:34][CH2:35][O:36][CH:37]3[CH2:39][CH2:38]3)=[CH:10][CH:9]=2)[CH:15]=1

参加物

6

反応物 3

HCID 10796Cesium carbonateHCID 574237514-((5-Bromo-2-chlorophenyl)methyl)phenolHCID 59557773Toluene-4-sulfonic acid 2-cyclopropoxy-ethyl ester

生成物 1

HCID 595577554-Bromo-1-chloro-2-(4-(2-cyclopropoxyethoxy)benzyl)benzene収率 64%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

実験手順

A mixture of 4-(5-bromo-2-chlorobenzyl)phenol (56.7 g, 210 mmol) and Cs2CO3 (135 g, 420 mmol) in DMF (350 mL) was stirred at room temperature for 30 min, and then 2-cyclopropoxyethyl 4-methylbenzenesulfonate (crude intermediate BP from the second preceeding step above) (53.3 g, 210 mmol) was added. The reaction mixture was stirred at room temperature overnight, and then diluted with water (3 L) and extracted with EtOAc. The organic layer was washed with water, then with brine, and dried over Na2SO4. The residue was concentrated and then purified by flash column chromatography on silica gel (eluent PE:EA=10:1) to give intermediate DK as a liquid (51 g, yield 64%). 1H NMR (CDCl3, 400 MHz): δ 7.22˜7.29 (m, 3H), 7.08 (d, J=8.8 Hz, 2H), 6.88 (d, J=8.8 Hz, 2H), 4.10 (t, J=4.8 Hz, 2H), 3.86 (t, J=4.8 Hz, 2H), 3.38˜3.32 (m, 1H), 0.62˜0.66 (m, 2H), 0.49-0.52 (m, 2H).

後処理

  1. additionwas added
  2. stirringThe reaction mixture was stirred at room temperature overnight
  3. extractionextracted with EtOAc
  4. washThe organic layer was washed with water
  5. dry with materialwith brine, and dried over Na2SO4
  6. concentrationThe residue was concentrated
  7. custompurified by flash column chromatography on silica gel (eluent PE:EA=10:1)

出典と根拠

ORDレコード
ord-b418a76bf2d7496eb3c5aa5975651cea
出典データセット
uspto-grants-2010_11
特許番号
US07838499B2

反応ノート

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