Azobisisobutyronitrile → 2-[2-(Bromomethyl)-5-fluorophenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

HRID 1097184Notes

Reaction equation

HRID 1097184 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([B:9]2[O:17][C:14]([CH3:16])([CH3:15])[C:11]([CH3:13])([CH3:12])[O:10]2)[C:5]([CH3:8])=[CH:6][CH:7]=1.C1C(=O)N([Br:25])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C.C1(=O)NC(=O)CC1>C(Cl)(Cl)(Cl)Cl>[Br:25][CH2:8][C:5]1[C:4]([B:9]2[O:17][C:14]([CH3:16])([CH3:15])[C:11]([CH3:13])([CH3:12])[O:10]2)=[CH:3][C:2]([F:1])=[CH:7][CH:6]=1

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 11439SuccinimideHCID 67184N-bromobutanimideHCID 790162605-Fluoro-2-Methylbenzeneboronic acid pinacol ester, 97%

Product 1

HCID 532171032-[2-(Bromomethyl)-5-fluorophenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneYield 84%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

3-Fluoro-6-methylphenylboronic acid pinacol ester (29a, 5.01 g, 21.2 mmol) and 140 ml CCl4 were placed in 500 ml round-bottom flask. NBS (3.97 g, 22.3 mmol, 1.05 eq) and AIBN (0.054 g, 0.33 mmol, 0.016 eq) were added and the reaction mixture was refluxed for 3.5 h in the presence of 75 W incandescent bulb. After 3.5 h the solution was cooled down to room temperature allowing the succinimide to precipitate out. The solid was filtered off. The solvent was removed and oily product was collected. Purification with column chromatography (95/5 Hexanes/Ethyl acetate) resulted in pure product (30a, 5.59 g, 84% yield).

Workup

  1. temperaturethe reaction mixture was refluxed for 3.5 h in the presence of 75 W incandescent bulb
  2. customto precipitate out
  3. filtrationThe solid was filtered off
  4. customThe solvent was removed
  5. customoily product was collected
  6. customPurification with column chromatography (95/5 Hexanes/Ethyl acetate)

Sources & evidence

ORD record
ord-ce89ff158d77471692c6d8b2de96ecc9
Source dataset
uspto-grants-2012_03
Patent number
US08143068B2

Reaction notes

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