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

HRID 1037138노트

반응식

HRID 1037138 반응식
[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

참가 물질

7

반응물 5

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

생성물 1

HCID 866855024-Fluoro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde수율 894.3%

시약·촉매·용매 1

HCID 5943Carbon Tetrachloride용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-ffa63e0818e443439ef4f988bbb888de
출처 데이터셋
uspto-grants-2013_10
특허 번호
US08546357B2

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