Hydroxyamine hydrochloride → (NE)-N-[(4-fluoro-1-hydroxy-3,3-dimethyl-2,1-benzoxaborol-6-yl)methylidene]hydroxylamine

HRID 1037139ノート

反応式

HRID 1037139 の反応式
[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]([CH:14]=O)[CH:3]=1.[NH2:16][OH:17].Cl.CC([O-])=O.[Na+]>C1COCC1.O>[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](/[CH:14]=[N:16]/[OH:17])[CH:3]=1

参加物

6

反応物 3

HCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 866855024-Fluoro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde

生成物 1

HCID 89573609(NE)-N-[(4-fluoro-1-hydroxy-3,3-dimethyl-2,1-benzoxaborol-6-yl)methylidene]hydroxylamine収率 95.8%

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of 4-fluoro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde (1.86 g, 8.94 mmol) and NH2OH.HCl (0.69 g, 9.84 mmol) in THF (16 mL) and H2O (4 mL) at rt was added NaOAc (0.92 g, 11.18 mmol). The reaction mixture was stirred for 3 h and diluted with H2O. The mixture was extracted with EA and the organic layer was separated. The organic solution 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 (5:1 to 2:1) to give (E)-4-fluoro-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-6-carbaldehyde oxime (1.8 g, 95.8% yield) as a light yellow solid. 1H NMR (500 MHz, DMSO-d6) δ 11.38 (s, 1H), 9.34 (s, 1H), 8.19 (s, 1H), 7.74 (s, 1H), 7.46 (dd, J=1.2 Hz, J=11.2 Hz, 1H), 1.524 (s, 6H) ppm.

後処理

  1. extractionThe mixture was extracted with EA
  2. customthe organic layer was separated
  3. washThe organic solution 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 (5:1 to 2:1)

出典と根拠

ORDレコード
ord-a3f59dd8b0644f6db1ce84d60db103bc
出典データセット
uspto-grants-2013_10
特許番号
US08546357B2

反応ノート

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