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

HRID 1662911Notes

Reaction equation

HRID 1662911 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.CCCCCC.[CH2:32]([Li])[CH2:33][CH2:34][CH3:35].[B:37](OC(C)C)([O:42]C(C)C)[O:38]C(C)C.Cl>C(OCC)C.C1(C)C=CC=CC=1>[CH:32]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:37]([OH:42])[OH:38])[CH:3]=4)[CH:8]=3)[C:13]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[C:19]=2[CH:35]=[CH:34][CH:33]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 21531Triisopropyl borateHCID 575398276-Bromo-2-(9-phenanthrenyl)naphthaleneHCID 178418339Butyllithium

Product 1

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

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-10 °C

Procedure

Under an argon gas atmosphere, a mixture of 9.80 g (25.6 mmol) of 6-bromo-2-(9-phenanthrenyl)naphthalene, 100 mL of dehydrated toluene and 100 mL of dehydrated diethylether was cooled down to −10 degrees C., and added with 19.7 mL (30.7 mmol) of hexane solution of 1.56M n-butyllithium in drops while being stirred. Then, the reaction mixture was stirred for four hours at −10 degree C. The reaction mixture was further cooled down to −60 degrees C., and added with 14.4 g (76.7 mmol) of triisopropyl borate in drops. The reaction mixture was subsequently warmed up to room temperature, and stirred for 16 hours at room temperature. The reaction mixture was further added with solution of hydrochloric acid to be stirred for one night at room temperature. After the reaction, the reaction mixture experienced liquid separation, organic phase thereof was cleansed with water, and the solvent was distilled away under reduced pressure until the reaction mixture became slurry. By adding residue thereof with hexane, filtering the solid and recrystallizing the residue by THF and hexane, 5.20 g of 2-(9-phenanthrenyl)naphthalene-6-boronic acid was obtained at an yield of 58%.

Workup

  1. stirringThen, the reaction mixture was stirred for four hours at −10 degree C
  2. temperatureThe reaction mixture was further cooled down to −60 degrees C
  3. temperatureThe reaction mixture was subsequently warmed up to room temperature
  4. stirringstirred for 16 hours at room temperature
  5. stirringto be stirred for one night at room temperature
  6. customAfter the reaction
  7. customliquid separation, organic phase
  8. distillationthe solvent was distilled away under reduced pressure until the reaction mixture
  9. additionBy adding residue
  10. filtrationwith hexane, filtering the solid
  11. customrecrystallizing the residue by THF and hexane

Sources & evidence

ORD record
ord-c5d9b747bcbc44138bcb20e6188205b6
Source dataset
uspto-grants-2011_10
Patent number
US08034256B2

Reaction notes

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