Hydrochloric Acid → 2-(9-Phenanthrenyl)naphthalene-7-boronic acid

HRID 1429329Notes

Reaction equation

HRID 1429329 reaction equation
BrC1C=C2C(C=CC([C:12]3[C:13]4[C:18]([C:19]5[CH:20]=[CH:21][CH:22]=[CH:23][C:24]=5[CH:25]=3)=[CH:17][CH:16]=[CH:15][CH:14]=4)=C2)=CC=1.[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.[CH3:45][CH2:46][CH2:47][CH2:48][CH2:49][CH3:50]>ClCCl.C1COCC1>[CH:23]1[C:24]2[CH:25]=[C:12]([C:47]3[CH:46]=[CH:45][C:29]4[C:49](=[CH:50][C:26]([B:31]([OH:36])[OH:32])=[CH:27][CH:28]=4)[CH:48]=3)[C:13]3[C:18](=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:19]=2[CH:20]=[CH:21][CH:22]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 21531Triisopropyl borateHCID 575400157-Bromo-2-(9-phenanthrenyl)naphthaleneHCID 178418339Butyllithium

Product 1

HCID 585446282-(9-Phenanthrenyl)naphthalene-7-boronic acidYield 85%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

In argon atmosphere, a liquid mixture of 12.27 (32.01 mmol) of 7-bromo-2-(9-phenanthrenyl)naphthalene and 130 ml of dry THF was cooled to −70° C., and 24.8 ml (38.4 mmol) of a 1.56 M hexane solution of n-butyllithium was added dropwise under stirring. Further, the reaction mixture was stirred at −70° C. for 4 h. The reaction mixture was added dropwise with 18.06 g (96.04 mmol) of triisopropyl borate while maintaining the temperature at −60° C. or lower and then stirred for one hour. The reaction mixture was heated, stirred at room temperature for 3 h, and then allowed to stand overnight. The reaction mixture was added with 100 ml of a 6 N hydrochloric acid while maintaining the temperature at 20° C. or lower by cooling on an ice bath. The reaction mixture was stirred at room temperature for 30 min, added with dichloromethane, and then allowed to separate into liquid phases. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was removed by distillation to obtain 9.50 g (yield: 85%) of 2-(9-phenanthrenyl)naphthalene-7-boronic acid.

Workup

  1. stirringFurther, the reaction mixture was stirred at −70° C. for 4 h
  2. temperaturewhile maintaining the temperature at −60° C.
  3. stirringlower and then stirred for one hour
  4. temperatureThe reaction mixture was heated
  5. stirringstirred at room temperature for 3 h
  6. temperaturewhile maintaining the temperature at 20° C.
  7. temperaturelower by cooling on an ice bath
  8. stirringThe reaction mixture was stirred at room temperature for 30 min
  9. customto separate into liquid phases
  10. washThe organic phase was washed with water
  11. dry with materialdried over anhydrous sodium sulfate
  12. customThe solvent was removed by distillation

Sources & evidence

ORD record
ord-a6c504ab49ab46a6a2271d216e185e51
Source dataset
uspto-grants-2015_01
Patent number
US08940412B2

Reaction notes

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