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Trimethyl borate → 5-Bromo-2-chlorophenylboronic acid

HRID 72271
ノート
印刷プレビュー

反応式

HRID 72271 の反応式
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[C:4](I)[CH:3]=1.C([Mg]Cl)(C)C.[B:15](OC)([O:18]C)[O:16]C>O1CCCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[C:4]([B:15]([OH:18])[OH:16])[CH:3]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 8470Trimethyl borateHCID 510000714-Bromo-1-chloro-2-iodobenzeneHCID 178418918HCID 178418918、化合物

生成物 1

HCID 467368165-Bromo-2-chlorophenylboronic acid収率 79.3%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-75 °C

実験手順

4-Bromo-1-chloro-2-iodobenzene (10.35 g, 33 mmol) is dissolved in anhydrous tetrahydrofuran (60 ml) and the solution is cooled to −75° C. under an atmosphere of argon. Isopropylmagnesium chloride (17.1 ml, 34 mmol, 2M solution in tetrahydrofuran) is added dropwise over 30 minutes, maintaining the internal temperature below −70° C. by external cooling. Once the addition is complete, the reaction mixture is stirred at approximately −70° C. for 30 minutes and then allowed to warm to room temperature and stirred for 1 hour. The reaction mixture is then cooled to −78° C. and trimethyl borate (7.3 ml, 65 mmol) is added dropwise. The mixture is stirred at −78° C. for 30 minutes and then the cooling bath is removed and the mixture is stirred at room temperature for 1.5 hours. 2M Aqueous hydrochloric acid (30 ml) is added, and the crude product is extracted with ethyl acetate. The organic phase is washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. Trituration with hexane gives 5-bromo-2-chlorophenylboronic acid (6.16 g) as an off-white solid.

後処理

  1. temperaturemaintaining the internal temperature below −70° C. by external cooling
  2. additionOnce the addition
  3. temperatureto warm to room temperature
  4. stirringstirred for 1 hour
  5. temperatureThe reaction mixture is then cooled to −78° C.
  6. stirringThe mixture is stirred at −78° C. for 30 minutes
  7. customthe cooling bath is removed
  8. stirringthe mixture is stirred at room temperature for 1.5 hours
  9. addition2M Aqueous hydrochloric acid (30 ml) is added
  10. extractionthe crude product is extracted with ethyl acetate
  11. washThe organic phase is washed with water and brine
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. customthe filtrate evaporated in vacuo

出典と根拠

ORDレコード
ord-32389e2238464edc91c2cbfc2098ed62
出典データセット
uspto-grants-2014_09
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08828908B2

反応ノート

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