Benzohydroxamic acid → N-((4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)benzamide

HRID 336118Notes

Reaction equation

HRID 336118 reaction equation
[OH:1][NH:2][C:3](=[O:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.Br[CH2:12][C:13]1[CH:18]=[CH:17][C:16]([B:19]2[O:27][C:24]([CH3:26])([CH3:25])[C:21]([CH3:23])([CH3:22])[O:20]2)=[CH:15][CH:14]=1.[OH-].[Na+]>CO>[CH3:25][C:24]1([CH3:26])[C:21]([CH3:22])([CH3:23])[O:20][B:19]([C:16]2[CH:15]=[CH:14][C:13]([CH2:12][O:1][NH:2][C:3](=[O:10])[C:4]3[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=3)=[CH:18][CH:17]=2)[O:27]1

Participants

5

Reactant 3

HCID 10313Benzohydroxamic acidHCID 14798Sodium HydroxideHCID 37345062-(4-(Bromomethyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Product 1

HCID 58560766N-((4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)benzamideYield 6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

N-hydroxybenzamide (0.17 g, 1.2 mmol) was dissolved in 8 mL of MeOH followed by the addition of 4-bromomethylphenyl boronic acid pinacol ester (0.40 g, 1.30 mmol). A 40% aqueous solution of NaOH (2 mL) was then added dropwise and the reaction was left to stir at reflux overnight. After cooling to room temperature and concentrated, concentrated HCl was added until a pH of 1 was observed. The resulting solution was then extracted with EtOAc and washed with brine. The organic layer was collected and dried over MgSO4 then purified via silica gel chromatography affording B16 in 6% yield (0.03 g, 0.07 mmol). 1HNMR (400 MHz, CDCl3) δ=8.61 (br, 1H, NH), 7.83 (d, J=8 Hz, 2H), 7.64 (d, J=7.6 Hz, 2H), 7.51-7.37 (m, 5H), 5.04 (s, 2H), 1.35 (s, 12H). 13C NMR (100 MHz, CDCl3) δ=166.67, 138.45, 135.32, 132.35, 132.10, 128.95, 128.72, 127.25, 84.18, 78.45, 25.10. ESI-MS(+): m/z 354.10 [M+H]+, 376.10 [M+Na]+.

Workup

  1. waitthe reaction was left
  2. temperatureat reflux overnight
  3. concentrationconcentrated
  4. additionconcentrated HCl was added until a pH of 1
  5. extractionThe resulting solution was then extracted with EtOAc
  6. washwashed with brine
  7. customThe organic layer was collected
  8. dry with materialdried over MgSO4
  9. customthen purified via silica gel chromatography
  10. customaffording B16 in 6% yield (0.03 g, 0.07 mmol)

Sources & evidence

ORD record
ord-8b80ef4429024192b6b16197f8bf49ca
Source dataset
uspto-grants-2014_11
Patent number
US08889638B2

Reaction notes

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