Hydrochloric Acid → 6-(9,9-dimethyl-9H-fluorene-2-yl)naphthalene-2-ylboronic acid

HRID 1431035Notes

Reaction equation

HRID 1431035 reaction equation
BrC1C=C2C(=CC=1)C=C([C:12]1[CH:24]=[CH:23][C:22]3[C:21]4[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=4)[C:15]([CH3:26])([CH3:25])[C:14]=3[CH:13]=1)C=C2.[CH3:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32].[CH2:33]([Li])[CH2:34][CH2:35][CH3:36].[B:38](OC(C)C)([O:43]C(C)C)[O:39]C(C)C.Cl>ClCCl.C1COCC1>[CH3:26][C:15]1([CH3:25])[C:14]2[CH:13]=[C:12]([C:29]3[CH:28]=[C:27]4[C:32](=[CH:31][CH:30]=3)[CH:36]=[C:35]([B:38]([OH:43])[OH:39])[CH:34]=[CH:33]4)[CH:24]=[CH:23][C:22]=2[C:21]2[C:16]1=[CH:17][CH:18]=[CH:19][CH:20]=2

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 21531Triisopropyl borateHCID 576484592-(6-bromonaphthalene-2-yl)-9,9-dimethyl-9H-fluoreneHCID 178418339Butyllithium

Product 1

HCID 666536326-(9,9-dimethyl-9H-fluorene-2-yl)naphthalene-2-ylboronic acidYield 57%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

A mixed solution of 12.00 g (30.1 mmol) of 2-(6-bromonaphthalene-2-yl)-9,9-dimethyl-9H-fluorene and 120 ml of dehydrated THF was cooled to −70° C. under argon atmosphere, and 23.3 ml (36.0 mmol) of a hexane solution of 1.55M n-butyllithium was added dropwise thereto with stirring. The reaction mixture was stirred at −70° C. for 2 hours. The reaction solution was cooled again to −70° C., and 17.0 g (90.2 mol) of triisopropyl borate was added dropwise thereto. The reaction mixture was heated to room temperature and stirred for one hour, then it was left standing overnight. The reaction mixture was cooled on an ice bath, and a 6N hydrochloric acid aqueous solution was added thereto and stirred at room temperature for one hour. Dichloromethane was added to the reaction mixture to separate the liquid, and the organic phase was washed with water and dried on sodium sulfate. The solvent was removed by distillation under reduced pressure, and the residue was refined by silica gel chromatography to obtain 6.25 g (yield: 57%) of 6-(9,9-dimethyl-9H-fluorene-2-yl)naphthalene-2-ylboronic acid.

Workup

  1. stirringThe reaction mixture was stirred at −70° C. for 2 hours
  2. temperatureThe reaction mixture was heated to room temperature
  3. stirringstirred for one hour
  4. waitit was left
  5. temperatureThe reaction mixture was cooled on an ice bath
  6. stirringstirred at room temperature for one hour
  7. customto separate the liquid
  8. washthe organic phase was washed with water
  9. customdried on sodium sulfate
  10. customThe solvent was removed by distillation under reduced pressure

Sources & evidence

ORD record
ord-ac8e5dc5c7884fa58673b0900ed333cc
Source dataset
uspto-grants-2015_01
Patent number
US08941099B2

Reaction notes

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