Hydrochloric Acid → 3,3-Diethyl-1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbaldehyde

HRID 1750838Notes

Reaction equation

HRID 1750838 reaction equation
[CH2:1]([C:3]1([CH2:14][CH3:15])[O:7][B:6]([OH:8])[C:5]2[CH:9]=[CH:10][C:11]([CH3:13])=[CH:12][C:4]1=2)[CH3:2].C(OOC(=O)C1C=CC=CC=1)(=[O:23])C1C=CC=CC=1.C1C(=O)N(Br)C(=O)C1.C([O-])([O-])=O.[Na+].[Na+].Cl>C(Cl)(Cl)(Cl)Cl>[CH2:14]([C:3]1([CH2:1][CH3:2])[O:7][B:6]([OH:8])[C:5]2[CH:9]=[CH:10][C:11]([CH:13]=[O:23])=[CH:12][C:4]1=2)[CH3:15]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7187Benzoyl PeroxideHCID 10340Sodium CarbonateHCID 67184N-bromobutanimideHCID 866850833,3-diethyl-5-methylbenzo[c][1,2]oxaborol-1(3H)-ol

Product 1

HCID 866850843,3-Diethyl-1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbaldehydeYield 561.5%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 3,3-diethyl-5-methylbenzo[c][1,2]oxaborol-1(3H)-ol (2.0 g, 9.8 mmol) in CCl4 (25 ml) at rt was added benzoyl peroxide (237 mg, 0.98 mmol) followed by NBS (3.489 g, 19.6 mmol). The reaction mixture was refluxed for 16 h, cooled to rt and treated with aqueous Na2CO3. The aqueous layer was acidified with 3N HCl to pH=3 and extracted with EA (50 ml×3). The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure to give the desired product (1.2 g, yield 56%) as white solid. 1H NMR (300 MHz, DMSO-d6): δ 10.06 (s, 1H), 9.30 (s, 1H), 7.85 (m, 3H), 1.86 (m, 4H), 0.55 (m, 6H). MS: m/z=219 [M+1]+.

Workup

  1. temperatureThe reaction mixture was refluxed for 16 h
  2. extractionextracted with EA (50 ml×3)
  3. washThe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b0822cd84a0c435ea5f2eae4747e72bc
Source dataset
uspto-grants-2015_10
Patent number
US09156860B2

Reaction notes

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