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

HRID 1429321Notes

Reaction equation

HRID 1429321 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.[CH2:27]([Li])[CH2:28][CH2:29][CH3:30].[B:32](OC(C)C)([O:37]C(C)C)[O:33]C(C)C.Cl.[CH3:46][CH2:47][CH2:48][CH2:49][CH2:50][CH3:51]>ClCCl.C1COCC1>[CH3:26][C:15]1([CH3:25])[C:14]2[CH:13]=[C:12]([C:28]3[CH:29]=[C:30]4[C:50](=[CH:51][CH:27]=3)[CH:49]=[C:48]([B:32]([OH:37])[OH:33])[CH:47]=[CH:46]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

In argon atmosphere, a liquid mixture of 12.00 g (30.1 mmol) of 2-(6-bromonaphthalene-2-yl)-9,9-dimethyl-9H-fluorene and 120 ml of dry THF was cooled to −70° C., and 23.3 ml (36.0 mmol) of a 1.55 M hexane solution of n-butyllithium was added dropwise while stirring. Then, the reaction mixture was stirred at −70° C. for 2 h. The reaction solution was cooled again to −70° C., and 17.0 g (90.2 mol) of triisopropyl borate was added dropwise. The reaction mixture was heated up to room temperature, stirred for one hour, and left standing overnight. The reaction mixture was cooled on an ice bath, added with a 6 N hydrochloric acid, and stirred at room temperature for one hour. The reaction mixture was added with dichloromethane and allowed to stand for separation of liquid phases. The organic phase was washed with water and dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified 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. stirringThen, the reaction mixture was stirred at −70° C. for 2 h
  2. temperatureThe reaction solution was cooled again to −70° C.
  3. temperatureThe reaction mixture was heated up to room temperature
  4. stirringstirred for one hour
  5. waitleft
  6. temperatureThe reaction mixture was cooled on an ice bath
  7. stirringstirred at room temperature for one hour
  8. customto stand for separation of liquid phases
  9. washThe organic phase was washed with water
  10. dry with materialdried over sodium sulfate
  11. distillationThe solvent was distilled off under reduced pressure
  12. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-ace24bfe574845159aef23be6aa1625e
Source dataset
uspto-grants-2015_01
Patent number
US08940412B2

Reaction notes

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