Hydrochloric Acid → (3-(Phenanthren-9-yl)phenyl)boronic acid

HRID 1429323Notes

Reaction equation

HRID 1429323 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2[C:9]3[C:14]([C:15]4C=CC=C[C:20]=4[CH:21]=2)=[CH:13][CH:12]=[CH:11][CH:10]=3)[CH:5]=[CH:6][CH:7]=1.[CH2:22]([Li])[CH2:23][CH2:24][CH3:25].[B:27](OC(C)C)([O:32]C(C)C)[O:28]C(C)C.Cl>ClCCl.CCCCCC.C1COCC1>[CH:22]1[C:20]2[CH:21]=[C:8]([C:4]3[CH:3]=[C:2]([B:27]([OH:32])[OH:28])[CH:7]=[CH:6][CH:5]=3)[C:9]3[C:14](=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:15]=2[CH:25]=[CH:24][CH:23]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 21531Triisopropyl borateHCID 221380359-(3-Bromophenyl)phenanthreneHCID 178418339Butyllithium

Product 1

HCID 57539958(3-(Phenanthren-9-yl)phenyl)boronic acidYield 67%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-60 °C

Procedure

In argon atmosphere, a liquid mixture of 15.45 g (46.4 mmol) of 9-(3-bromophenyl)phenanthrene and 150 ml of dry THF was cooled to −60° C., and 35.9 ml (55.6 mmol) of a 1.55 M hexane solution of n-butyllithium was added dropwise under stirring. Then, the reaction mixture was stirred at −60° C. for 2 h. The reaction solution was cooled again to −60° C., and 26.2 g (139 mol) of triisopropyl borate was added dropwise. The reaction mixture was heated up to room temperature, stirred for one hour, and left standing overnight. The solvent was removed by distillation under reduced pressure to concentrate the reaction mixture. The concentrated reaction mixture was cooled to 0° C., added with hydrochloric acid, and stirred at room temperature for one hour. After the reaction, dichloromethane was added to the reaction mixture, and the aqueous phase was removed. The organic phase was dried over sodium sulfate, and then the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel chromatography to obtain 13.4 g (yield: 67%) of 3-(9-phenanthrenyl)phenylboronic acid.

Workup

  1. stirringThen, the reaction mixture was stirred at −60° C. for 2 h
  2. temperatureThe reaction solution was cooled again to −60° C.
  3. temperatureThe reaction mixture was heated up to room temperature
  4. stirringstirred for one hour
  5. waitleft
  6. customThe solvent was removed by distillation under reduced pressure
  7. concentrationto concentrate the reaction mixture
  8. customThe concentrated reaction mixture
  9. temperaturewas cooled to 0° C.
  10. stirringstirred at room temperature for one hour
  11. additionwas added to the reaction mixture
  12. customthe aqueous phase was removed
  13. dry with materialThe organic phase was dried over sodium sulfate
  14. customthe solvent was removed by distillation under reduced pressure
  15. customThe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-2f85134bd655419fb1f425ddde0dbf67
Source dataset
uspto-grants-2015_01
Patent number
US08940412B2

Reaction notes

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