Hydrochloric Acid → (4-(Phenanthren-9-yl)phenyl)boronic acid

HRID 1429325Notes

Reaction equation

HRID 1429325 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]3[C:14]([C:15]4[CH:16]=[CH:17][CH:18]=[CH:19][C:20]=4[CH:21]=2)=[CH:13][CH:12]=[CH:11][CH:10]=3)=[CH:4][CH:3]=1.C([Li])CCC.[B:27](OC(C)C)([O:32]C(C)C)[O:28]C(C)C.Cl>CCCCCC.C1(C)C=CC=CC=1.C1COCC1>[CH:19]1[C:20]2[CH:21]=[C:8]([C:5]3[CH:6]=[CH:7][C:2]([B:27]([OH:32])[OH:28])=[CH:3][CH:4]=3)[C:9]3[C:14](=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:15]=2[CH:16]=[CH:17][CH:18]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 21531Triisopropyl borateHCID 231486109-(4-Bromophenyl)phenanthreneHCID 178418339Butyllithium

Product 1

HCID 57572957(4-(Phenanthren-9-yl)phenyl)boronic acidYield 72%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Conditions

Temperature
-60 °C

Procedure

In argon atmosphere, a liquid mixture of 21.3 (63.9 mmol) of 9-(4-bromophenyl)phenanthrene and 200 ml of dry THF was cooled to −60° C. under argon atmosphere, and 49.2 ml (76.7 mmol) of a 1.55 M hexane solution of n-butyllithium was added dropwise under stirring. Further, the reaction mixture was stirred at −60° C. for 2 h. The reaction solution was cooled again to −60° C., and 36.1 g (192 mol) of triisopropyl borate was added dropwise. The reaction mixture was heated up to room temperature and stirred for 17 h. The reaction mixture was cooled to 0° C., added with hydrochloric acid, and stirred at room temperature for one hour. After the reaction, toluene was added to the reaction mixture and the aqueous phase was removed. The organic phase was dried over magnesium sulfate, and then the solvent was removed by distillation under reduced pressure. The residue was recrystallized from toluene and then from hexane to obtain 13.8 g (yield: 72%) of 4-(9-phenanthrenyl)phenylboronic acid.

Workup

  1. stirringFurther, 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 17 h
  5. temperatureThe reaction mixture was cooled to 0° C.
  6. stirringstirred at room temperature for one hour
  7. additionwas added to the reaction mixture
  8. customthe aqueous phase was removed
  9. dry with materialThe organic phase was dried over magnesium sulfate
  10. customthe solvent was removed by distillation under reduced pressure
  11. customThe residue was recrystallized from toluene

Sources & evidence

ORD record
ord-799403b117a344c19af69e39965f90ae
Source dataset
uspto-grants-2015_01
Patent number
US08940412B2

Reaction notes

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