Azobisisobutyronitrile → Methyl 3-(bromomethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate

HRID 79858Notes

Reaction equation

HRID 79858 reaction equation
[CH3:1][O:2][C:3](=[O:20])[C:4]1[CH:9]=[CH:8][C:7]([B:10]2[O:14][C:13]([CH3:16])([CH3:15])[C:12]([CH3:18])([CH3:17])[O:11]2)=[C:6]([CH3:19])[CH:5]=1.C1C(=O)N([Br:28])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3](=[O:20])[C:4]1[CH:9]=[CH:8][C:7]([B:10]2[O:11][C:12]([CH3:18])([CH3:17])[C:13]([CH3:15])([CH3:16])[O:14]2)=[C:6]([CH2:19][Br:28])[CH:5]=1

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 110870242-Methyl-4-methoxycarbonylphenylboronic acid, pinacol ester

Product 1

HCID 59610334Methyl 3-(bromomethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoateYield 103%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
25 °C

Procedure

The solution of 3-Methyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid methyl ester (3.71 g, 13.4 mmol), NBS (2.39 g, 13.4 mmol), and AIBN (235 mg) in CCl4 (20 ml) was heated at 80° C. for 14 hours. The mixture was cooled to 25° C., and was filtered and washed with CCl4. The solution was concentrated under reduced pressure, and was diluted with EtOAc. The solution was washed with water and brine and was dried with Na2SO4. Concentration gave 3-Bromomethyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid methyl ester (4.9 g).

Workup

  1. filtrationwas filtered
  2. washwashed with CCl4
  3. concentrationThe solution was concentrated under reduced pressure
  4. additionwas diluted with EtOAc
  5. washThe solution was washed with water and brine
  6. dry with materialwas dried with Na2SO4
  7. concentrationConcentration

Sources & evidence

ORD record
ord-cac2eaa4e10946829a3c34a600fab174
Source dataset
uspto-grants-2014_09
Patent number
US08841278B2

Reaction notes

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