Nitrogen → 4-Fluoro-1-naphthaleneboronic Acid (contains varying amounts of Anhydride)

HRID 842050노트

반응식

HRID 842050 반응식
N#N.Br[C:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7]([F:14])=[CH:6][CH:5]=1.C([Li])CCC.[B:20](OCC)([O:24]CC)[O:21]CC>CCCCCC.O1CCCC1>[F:14][C:7]1[C:8]2[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:4]([B:20]([OH:24])[OH:21])=[CH:5][CH:6]=1

참가 물질

7

반응물 4

HCID 947NitrogenHCID 9009Triethyl borateHCID 676471-Bromo 4-fluoronaphthaleneHCID 178418339Butyllithium

생성물 1

HCID 27826754-Fluoro-1-naphthaleneboronic Acid (contains varying amounts of Anhydride)

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매

반응 조건

온도
-70 °C

실험 절차

To a 250 mL three-necked round-bottomed flask equipped with septum and N2 (nitrogen) inlet were added 4.62 g (20.53 mmol) 4-bromo-1-fluoronaphthalene and 100 mL dry tetrahydrofuran. The solution was cooled to −70° C., and 15.4 mL (24.64 mmol) of a 1.6 M solution of butyl lithium in hexane was added dropwise over 5 min. The reaction was stirred at −70° C. for 10 min, then 4.2 mL (3.59 g, 24.64 mmol) triethyl borate was added, and the reaction stirred at −70° C. for 20 min and warmed to room temperature. After stirring overnight at room temperature, the reaction was quenched with saturated aqueous ammonium chloride solution, acidified with 1 N hydrochloric acid, and extracted into ethyl acetate (twice). The combined organic layer was washed with brine, dried over sodium sulfate, and evaporated. The residue was triturated with hexane to give an off-white powder, 1.97 g (51%), as a mixture of monoaryl and diaryl boronic acids. 1H-NMR (δ, CDCl3): 7.2-7.4 (m, 1H), 7.5-7.7 (m, 3H), 8.0-8.5 (m, 1H), 8.5 and 9.2 (m, 1H); APCI (−) (%): 189 (parent−1, 60).

후처리

  1. stirringthe reaction stirred at −70° C. for 20 min
  2. temperaturewarmed to room temperature
  3. stirringAfter stirring overnight at room temperature
  4. customthe reaction was quenched with saturated aqueous ammonium chloride solution
  5. extractionextracted into ethyl acetate (twice)
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. customThe residue was triturated with hexane
  10. customto give an off-white powder, 1.97 g (51%)

출처 및 근거

ORD 기록
ord-61c0b2fc45a44e5bb1834ac1559e11b8
출처 데이터셋
uspto-grants-2002_04
특허 번호
US06372768B1

반응 노트

불러오는 중…