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

HRID 855145노트

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HRID 855145 반응식
[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

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 679Dimethyl Sulfoxide용매

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온도
85 °C

실험 절차

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+).

후처리

  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

출처 및 근거

ORD 기록
ord-c883b330260a4918a515d110219af48e
출처 데이터셋
uspto-grants-2007_08
특허 번호
US07259266B2

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