Hydrochloric Acid → 2-(9-Phenanthrenyl)naphthalene-6-boronic acid

HRID 1429327Notes

Reaction equation

HRID 1429327 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([C:12]1[C:13]3[C:18]([C:19]4C=CC=C[C:24]=4[CH:25]=1)=[CH:17][CH:16]=[CH:15][CH:14]=3)[CH:6]=[CH:5]2.[CH2:26]([Li])[CH2:27][CH2:28][CH3:29].[B:31](OC(C)C)([O:36]C(C)C)[O:32]C(C)C.Cl>CCCCCC.C(OCC)C.C1(C)C=CC=CC=1>[CH:26]1[C:24]2[CH:25]=[C:12]([C:7]3[CH:6]=[CH:5][C:4]4[C:9](=[CH:10][CH:11]=[C:2]([B:31]([OH:36])[OH:32])[CH:3]=4)[CH:8]=3)[C:13]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[C:19]=2[CH:29]=[CH:28][CH:27]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 21531Triisopropyl borateHCID 575398276-Bromo-2-(9-phenanthrenyl)naphthaleneHCID 178418339Butyllithium

Product 1

HCID 575398092-(9-Phenanthrenyl)naphthalene-6-boronic acidYield 58%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent2×

Conditions

Temperature
-10 °C

Procedure

In argon atmosphere, a liquid mixture of 9.80 (25.6 mmol) of 6-bromo-2-(9-phenanthrenyl)naphthalene, 100 ml of dry toluene, and 100 ml of dry diethyl ether was cooled to −10° C. and 19.7 ml (30.7 mmol) of a 1.56 M hexane solution of n-butyllithium was added dropwise under stirring. Further, the reaction mixture was stirred at −10° C. for 4 h. The reaction solution was cooled to −60° C., and 14.4 g (76.7 mmol) of triisopropyl borate was added dropwise. The reaction mixture was heated and stirred at room temperature for 16 h. The reaction mixture was added with hydrochloric acid and stirred at room temperature overnight. After the reaction, the reaction mixture was separated into liquid phases, and the organic phase was washed with water. The solvent was removed by distillation under reduced pressure until the mixture was turned to slurry. After adding hexane to the residue, the solid matter was collected by filtration and recrystallized from THF and then from hexane to obtain 5.20 g (yield: 58%) of 2-(9-phenanthrenyl)naphthalene-6-boronic acid.

Workup

  1. stirringFurther, the reaction mixture was stirred at −10° C. for 4 h
  2. temperatureThe reaction solution was cooled to −60° C.
  3. temperatureThe reaction mixture was heated
  4. stirringstirred at room temperature for 16 h
  5. stirringstirred at room temperature overnight
  6. customAfter the reaction
  7. customthe reaction mixture was separated into liquid phases
  8. washthe organic phase was washed with water
  9. customThe solvent was removed by distillation under reduced pressure until the mixture
  10. additionAfter adding hexane to the residue
  11. filtrationthe solid matter was collected by filtration
  12. customrecrystallized from THF

Sources & evidence

ORD record
ord-93ef9fa87b4140929eabc64321febf6e
Source dataset
uspto-grants-2015_01
Patent number
US08940412B2

Reaction notes

Loading…