Sodium Carbonate → 1,3-Difluoro-2,4-dimethoxybenzene

HRID 355400ノート

反応式

HRID 355400 の反応式
N[C:2]1[CH:7]=[C:6]([F:8])[C:5]([O:9][CH3:10])=[C:4]([F:11])[C:3]=1[O:12][CH3:13].N([O-])=O.[Na+].[PH2](O)=O.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>Cl.O>[F:11][C:4]1[C:5]([O:9][CH3:10])=[C:6]([F:8])[CH:7]=[CH:2][C:3]=1[O:12][CH3:13]

参加物

8

反応物 5

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 4124402Phosphinic AcidHCID 106791923,5-Difluoro-2,4-dimethoxybenzenamineHCID 23668193Sodium Nitrite

生成物 1

HCID 105833621,3-Difluoro-2,4-dimethoxybenzene収率 73%

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 962Water溶媒2 回

実験手順

A 0.3M solution of Compound 2 (0.566 g, 2.99 mmol) in 4M HCl is chilled in an ice bath, and treated with a cold solution of sodium nitrite (1.05 equivalents) in water. The resulting diazonium salt solution is stirred for 15 minutes, and then hypophosphorous acid (50% aqueous solution, Aldrich, 20 equivalents) is added over 5 minutes. The resulting mixture is stirred at room temperature for two hours, then diluted with water. The resulting mixture is neutralized with aqueous sodium carbonate or sodium hydroxide, and extracted twice with ether. The organic extract is washed once with water, once with brine, and dried over anhydrous sodium sulfate. The solution is concentrated in vacuo and the resulting residue is purified by flash chromatography to give 0.38 g (73%) of Compound 3 as a clear, colorless liquid: 1H NMR (CDCl3) 6.80 (td, 1H), 6.58 (m, 1H), 4.00 (s, 3H), 3.87 (s, 3H); 19F NMR (CDCl3) 138.8 (d, 1F), 150.1 (d, 1F). Anal. calc. for C8H8O2F2 : C, 55.19; H, 4.63. Found: C, 54.76; H, 4.63.

後処理

  1. extractionextracted twice with ether
  2. extractionThe organic extract
  3. washis washed once with water, once with brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationThe solution is concentrated in vacuo
  6. customthe resulting residue is purified by flash chromatography

出典と根拠

ORDレコード
ord-cd18a47b02674272af664d50e6eec2d7
出典データセット
uspto-grants-1998_11
特許番号
US05830912

反応ノート

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