Hydrochloric Acid → HCID 86685509, compound

HRID 1037145Notes

Reaction equation

HRID 1037145 reaction equation
[Cl:1][C:2]1[C:13]([CH3:14])=[CH:12][C:5]2[B:6]([OH:11])[O:7][C:8]([CH3:10])([CH3:9])[C:4]=2[CH:3]=1.C(OOC(=O)C1C=CC=CC=1)(=[O:22])C1C=CC=CC=1.C1C(=O)N(Br)C(=O)C1.C([O-])([O-])=O.[Na+].[Na+].Cl>C(Cl)(Cl)(Cl)Cl>[Cl:1][C:2]1[C:13]([CH:14]=[O:22])=[CH:12][C:5]2[B:6]([OH:11])[O:7][C:8]([CH3:10])([CH3:9])[C:4]=2[CH:3]=1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7187Benzoyl PeroxideHCID 10340Sodium CarbonateHCID 67184N-bromobutanimideHCID 86685507HCID 86685507, compound

Product 1

HCID 86685509HCID 86685509, compoundYield 531.2%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 5-chloro-3,3,6-trimethylbenzo[c][1,2]oxaborol-1(3H)-ol (540 mg, 2.57 mmol) in CCl4 (30 mL) at rt was added benzoyl peroxide (62 mg, 0.26 mmol) followed by NBS (915 mg, 5.14 mmol). The reaction mixture was refluxed for 16 h, cooled to rt and treated with Na2CO3. The aqueous layer was acidified with 3 N HCl to pH of 3 and extracted with EA. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel eluted with DCM-MeOH (20:1) to give 5-chloro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde (310 mg; yield 53.8%) as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 10.38 (s, 1H), 9.41 (s, 1H), 8.22 (s, 1H), 7.82 (s, 1H), 1.50 (s, 6H) ppm; MS: m/z=224.9 (M+1, ESI+).

Workup

  1. temperatureThe reaction mixture was refluxed for 16 h
  2. extractionextracted with EA
  3. washThe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography on silica gel
  8. washeluted with DCM-MeOH (20:1)

Sources & evidence

ORD record
ord-ff7ab21f56634db496980994754aea9d
Source dataset
uspto-grants-2013_10
Patent number
US08546357B2

Reaction notes

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