Ethynyltributyltin → ethyl 8-chloro-6-ethynyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 854991

反応式

HRID 854991 の反応式
[Cl:1][C:2]1[CH:3]=[C:4](I)[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:15])([F:14])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2.[CH2:22]([Sn](CCCC)(CCCC)C#C)[CH2:23]CC>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]([C:22]#[CH:23])[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:15])([F:14])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2

参加物

5

反応物 2

HCID 621176EthynyltributyltinHCID 58934641ethyl 8-chloro-6-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate

生成物 1

HCID 86599477ethyl 8-chloro-6-ethynyl-2-(trifluoromethyl)-2H-chromene-3-carboxylate収率 75.6%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 1140Toluene溶媒

実験手順

To 0.86 g (2.0 mmole) of ethyl 8-chloro-6-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate was added 46 mg (0.040 mmole) tetrakis(triphenylphosphine)palladium(0), 6 mLs degassed toluene and 0.64 mL (0.69 g, 2.2 mmole) tributyl(ethynyl)tin. The stirred mixture was heated to reflux for 3 h. After allowing the reaction to cool, the mixture was washed with 20% aq. ammonium fluoride and the aqueous layer extracted three times with diethyl ether. The combined extracts were filtered through silica, the silica washed with diethyl ether and the organic fractions concd in vacuo. Chromatographic purification (70 g silica, 5% ethyl acetate/hexanes) afforded a solid which was triturated with hexanes to give 0.50 g (75.6%) of a crystalline solid: 1H NMR (d6-acetone/400 MHz) 1.32 (t, 3H, J=7.1 Hz), 3.73 (s,1H), 4.32 (m, 2H), 6.04 (q, 1H, J=6.9 Hz), 7.60 (m, 2H), 7.90 (s, 1H); 19F NMR (d6-acetone/400 MHz) −79.6 (d, 3F, J=6.8 Hz); MS(ESI+) 331 (M+1, 100, one Cl pattern).

後処理

  1. temperatureThe stirred mixture was heated
  2. temperatureto reflux for 3 h
  3. customthe reaction
  4. temperatureto cool
  5. washthe mixture was washed with 20% aq. ammonium fluoride
  6. extractionthe aqueous layer extracted three times with diethyl ether
  7. filtrationThe combined extracts were filtered through silica
  8. washthe silica washed with diethyl ether
  9. customChromatographic purification (70 g silica, 5% ethyl acetate/hexanes)
  10. customafforded a solid which
  11. customwas triturated with hexanes

出典と根拠

ORDレコード
ord-d7d523f59f574524b6429c23318514cc
出典データセット
uspto-grants-2007_08
特許番号
US07259266B2

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