Hydrochloric Acid → Benzo[c]phenanthren-5-ylboronic acid

HRID 2274125Notes

Reaction equation

HRID 2274125 reaction equation
Br[C:2]1[C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=2[C:13]2[C:12]3[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=3[CH:6]=[CH:5][C:4]=2[CH:3]=1.C([Li])CCC.[B:25](OC(C)C)([O:30]C(C)C)[O:26]C(C)C.Cl>CCCCCC.CCOCC>[CH:19]1[C:14]2[C:13]3[C:12]4[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=4[CH:6]=[CH:5][C:4]=3[CH:3]=[C:2]([B:25]([OH:30])[OH:26])[C:15]=2[CH:16]=[CH:17][CH:18]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 21531Triisopropyl borateHCID 106624825-Bromobenzo[c]phenanthreneHCID 178418339Butyllithium

Product 1

HCID 59622711Benzo[c]phenanthren-5-ylboronic acidYield 60%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent2×

Conditions

Temperature
-40 °C

Procedure

Under the atmosphere of argon, 10.1 g of 5-bromobenzo[c]phenanthrene was placed in a flask, and 400 mL of dehydrated ether was added. The reaction solution was cooled to −40° C., and 22 mL of a hexane solution of 1.6 M n-butyl lithium was added. The resultant was heated to 0° C., and stirred for 1 hour. The reaction solution was cooled to −60° C., and 10 mL of a dehydrated ether solution of 14.4 g of triisopropyl borate was added dropwise. While heating the reaction solution to room temperature, stirring was continued for 5 hours. 10 mL of a 10% aqueous hydrochloric acid solution was added, followed by stirring for 1 hour. An aqueous phase was removed, and an organic phase was washed with water and saturated saline, and dried with magnesium sulfate. After filtering off magnesium sulfate, the organic phase was concentrated. The resulting solids were washed with hexane, whereby 5.37 g (yield 60%) of benzo[c]phenanthrene-5-boronic acid as an intended product was obtained.

Workup

  1. temperatureThe resultant was heated to 0° C.
  2. temperatureThe reaction solution was cooled to −60° C.
  3. temperatureWhile heating the reaction solution to room temperature
  4. stirringstirring
  5. waitwas continued for 5 hours
  6. stirringby stirring for 1 hour
  7. customAn aqueous phase was removed
  8. washan organic phase was washed with water and saturated saline
  9. dry with materialdried with magnesium sulfate
  10. filtrationAfter filtering off magnesium sulfate
  11. concentrationthe organic phase was concentrated

Sources & evidence

ORD record
ord-6c9d4a7992234e29aacd9655ff030bf1
Source dataset
uspto-grants-2015_09
Patent number
US09126943B2

Reaction notes

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