Water → ethyl 6-chloro-5-azido-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 855145ノート

反応式

HRID 855145 の反応式
[Cl:1][C:2]1[C:3](F)=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][CH:7]([C:12]([F:15])([F:14])[F:13])[C:6]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:5]2.[N-:22]=[N+:23]=[N-:24].[Na+].O.C(OCC)(=O)C>CS(C)=O>[Cl:1][C:2]1[C:3]([N:22]=[N+:23]=[N-:24])=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][CH:7]([C:12]([F:15])([F:14])[F:13])[C:6]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:5]2

参加物

6

反応物 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 33557Sodium AzideHCID 58934464ethyl 6-chloro-5-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate

生成物 1

HCID 58934903ethyl 6-chloro-5-azido-2-(trifluoromethyl)-2H-chromene-3-carboxylate収率 74.2%

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
85 °C

実験手順

To the solution of ethyl 6-chloro-5-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate (1.0 g, 3.1 mmol) in 20 mL of DMSO was added a solution of sodium azide (1.0 g, 5 mmol) in minimum amount of water. The reaction was then heated to 85° C. for 15 hrs. After cooling to room temperature, to the reaction was added 200 mL of ethyl acetate. The resulting suspension was then washed with brine, and dried over anhydrous magnesium sulfate. After removing the solvents, the residue was purified on silica gel column with ethyl acetate/hexane, it gave 0.8 g of a yellow oil. Part of the product was purified on reverse phase HPLC for further analytical characterization. It gave a pink solid. LC-MS(ES+) 348.3(M+1, 70), 320.2(M−27, 100). 1H NMR(CDCl3/400 MHz) 7.99(s, 1H), 7.24(d, J=8.8 Hz, 1H), 6.75(d, J=8.8 Hz, 1H), 5.67(q, J=6.8 Hz, 1H), 4.32(m, 2H), 1.35(t, J=7.2 Hz, 3H). 19F NMR(CDCl3/400 Hz) −78.71(d, J=6.8 Hz). 13C NMR(CDCl3/400 Hz) 163.7, 152.7, 134.4, 133.9, 131.9,123.3(q, J=287.3 Hz), 122.6, 117.7, 114.6, 114.2, 70.6(q, J=33.3 Hz), 61.9, 14.4. HRSM(EI+) m/e calc. for (C13H9ClF3N3O3) 347.0285(M+), found: 347.0294(M+).

後処理

  1. temperatureAfter cooling to room temperature, to the reaction
  2. washThe resulting suspension was then washed with brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customAfter removing the solvents
  5. customthe residue was purified on silica gel column with ethyl acetate/hexane, it

出典と根拠

ORDレコード
ord-c883b330260a4918a515d110219af48e
出典データセット
uspto-grants-2007_08
特許番号
US07259266B2

反応ノート

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