Phenol → ethyl 6-chloro-5-phenoxy-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 855034ノート

反応式

HRID 855034 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.[C:22]1([OH:28])[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C(=O)([O-])[O-].[K+].[K+].CC#N>CN(C=O)C.O>[Cl:1][C:2]1[C:3]([O:28][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[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

7

反応物 4

HCID 996PhenolHCID 6342AcetonitrileHCID 11430Potassium CarbonateHCID 58934464ethyl 6-chloro-5-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate

生成物 1

HCID 58934759ethyl 6-chloro-5-phenoxy-2-(trifluoromethyl)-2H-chromene-3-carboxylate

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
110 °C

実験手順

To 162.3 g (0.5 mmole) of ethyl 6-chloro-5-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate was added 75 mg (0.80 mmole) of phenol and 120 mg (0.87 mmole) of potassium carbonate in 1.5 mL DMF. The mixture was heated to 110° C. and allowed to stir overnight. After cooling, the mixture was diluted with water and extracted three times with diethyl ether. The combined organic fractions were washed with water, dried and concd to give a crude oil. Preparative reverse phase chromatography (C 18, 4.0 cm×25 cm column, gradient 50%-100% CH3CN) afforded 50 mg (25.1%) of a clear, colorless oil: 1H NMR (CDCl3/400 MHz) 1.28 (t, 3H, J=7.1 Hz), 4.26 (m, 2H), 5.70 (q, 1H, J=6.7 Hz), 6.82 (d, 2H, J=7.9 Hz), 6.87 (d, 1H, J=8.7 Hz), 7.06 (t, 1H, J=7.4 Hz), 7.31 (t, 2H, J=8.1 Hz), 7.38 (d, 1H, J=8.9 Hz), 7.79 (s, 1H); 19F NMR (CDCl3/400 MHz) −78.7 (d, 3F, 6.8 Hz); MS (ESI+) 399 (M+1, 100); MS (EI) 398 (M+, 50), 329 (100), 283 (79), 231 (32); HRMS (EI) m/z calcd for (C19H14O4ClF3) 398.0533, found 398.0538.

後処理

  1. temperatureAfter cooling
  2. extractionextracted three times with diethyl ether
  3. washThe combined organic fractions were washed with water
  4. customdried
  5. customto give a crude oil

出典と根拠

ORDレコード
ord-6b3bdeae1c3941afb67e456e5ed89848
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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