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Trimethyl borate → 5-Bromo-2-chlorophenylboronic acid

HRID 1191568
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HRID 1191568 반응식
[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
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참가 물질

5

반응물 3

HCID 8470Trimethyl borateHCID 510000714-Bromo-1-chloro-2-iodobenzeneHCID 178418918HCID 178418918, 화합물

생성물 1

HCID 467368165-Bromo-2-chlorophenylboronic acid수율 79.3%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

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온도
-75 °C

실험 절차

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 stirred at room temperature for 1.5 hours. 2M Aqueous hydrochloric acid (30 ml) is added, and the crude product is then 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.

후처리

  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 stirred at room temperature for 1.5 hours
  9. addition2M Aqueous hydrochloric acid (30 ml) is added
  10. extractionthe crude product is then 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

출처 및 근거

ORD 기록
ord-bc9233a8cfa0455a9258bbfab2c5ab0b
출처 데이터셋
uspto-grants-2014_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08680012B2

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