Hydrochloric Acid → 4-Fluoro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde

HRID 1037138Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1037138
[F:1][C:2]1[C:10]2[C:9]([CH3:12])([CH3:11])[O:8][B:7]([OH:13])[C:6]=2[CH:5]=[C:4]([CH3:14])[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>[F:1][C:2]1[C:10]2[C:9]([CH3:11])([CH3:12])[O:8][B:7]([OH:13])[C:6]=2[CH:5]=[C:4]([CH:14]=[O:22])[CH:3]=1

Komponenten

7

Edukt 5

HCID 313Hydrochloric AcidHCID 7187Benzoyl PeroxideHCID 10340Sodium CarbonateHCID 67184N-bromobutanimideHCID 866855004-fluoro-3,3,6-trimethylbenzo[c][1,2]oxaborol-1(3H)-ol

Produkt 1

HCID 866855024-Fluoro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehydeAusbeute 894,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 5943Carbon TetrachlorideLösungsmittel

Versuchsvorschrift

To a solution of 4-fluoro-3,3,6-trimethylbenzo[c][1,2]oxaborol-1(3H)-ol (1.94 g, 10 mmol) in CCl4 (19.4 mL) at rt was added benzoyl peroxide (0.24 g, 1.0 mmol) and NBS (3.56 g, 20 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 over silica gel eluted with PE-EA (2:1) to give 4-fluoro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde (1.86 g, 89.4% yield) as a brown solid. 1H NMR (400 MHz, DMSO-d6) δ 10.04 (d, J=1.6 Hz, 1H), 9.53 (s, 1H), 8.09 (s, 1H), 7.77 (m, 1H), 1.55 (d, J=5.6 Hz, 6H) ppm.

Aufarbeitung

  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 over silica gel
  8. washeluted with PE-EA (2:1)

Quellen und Nachweise

ORD-Eintrag
ord-ffa63e0818e443439ef4f988bbb888de
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08546357B2

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