Hydrochloric Acid → 2,2,2-Trifluoro-N-phenylacetamide

HRID 2081692ノート

反応式

HRID 2081692 の反応式
Br[C:2]1[CH:14]=[CH:13][CH:12]=[CH:11][C:3]=1[NH:4][C:5](=[O:10])[C:6]([F:9])([F:8])[F:7].C[Li].C([Li])(C)(C)C.ClC1CC2C(=CC=CC=2)C1=O.[OH-].[K+].Cl>O1CCCC1.C(OCC)C.CCCCC.CO>[F:7][C:6]([F:8])([F:9])[C:5]([NH:4][C:3]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:2]=1)=[O:10]

参加物

11

反応物 6

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 526932-Chloro-2,3-dihydro-1H-inden-1-oneHCID 4263215N-(2-Bromophenyl)-2,2,2-trifluoroacetamideHCID 178418306HCID 178418306、化合物HCID 178418348HCID 178418348、化合物

生成物 1

HCID 678812,2,2-Trifluoro-N-phenylacetamide収率 21.8%

試薬・触媒・溶媒 4

HCID 887Methanol溶媒HCID 3283Diethyl Ether溶媒HCID 8003Pentane溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

A solution of o-bromotrifluoroacetanilide (325 mg, 1.2 mM) in tetrahydrofuran (THF)(20 cm3) was cooled to -78° C. and to this was added methyl lithium (1 molar equivalent of a 1.4 M solution in diethyl ether). This addition was followed 10 minutes later by the introduction of tert-butyllithium (2 molar equivalent of a 1.7 M solution in pentane). The reaction mixture was stirred for 1 hour at -78° C., and then a solution of the chloroindanone (272 mg. 1.2 mM) in THF (3 cm3) added dropwise via a cannula. The solution was allowed to warm slowly to room temperature, and stirred for one hour, then a 10% solution potassium hydroxide in methanol (3 cm3) was introduced. After stirring for 30 minutes, the reaction mixture was poured into 2 M HCl, and extracted with dichloromethane (3 ×10 cm3). The combined organic extracts were dried (Na2SO4 ) and evaporated in vacuo to afford a solid residue which was chromatographed on silica, eluting with 10% ethyl acetate/petroleum ether (60°-80° C.) to yield trifluoroacetanilide (RF 0.4)(50 mg), and the 2-chloro-1-hydroxy-5-methoxy-4,6-dimethyl-1-(2'-trifluoroacetamidophenyl)indane (RF 0.3) (220 mg, 44%). The latter compound is a colourless solid. M.p. 182° C. 1H NMR (CDCl3)δ: 10.7 (1H, br), 8.25 (1H, dd), 7.36 (1H, ddd), 7.06 (1H, s), 6.98 (1H, ddd), 6.39 (1H, dd), 4.76 (1H, dd, J=4.8, 2.7Hz), 3.78 (3H, s), 3.63 (1H, s, exchanges with D2O), 3.11 (2H, 2 ×2nd order multiplets), 2.33 (3H, s), 2.23 (3H, s).

後処理

  1. additionThis addition
  2. temperatureto warm slowly to room temperature
  3. stirringstirred for one hour
  4. stirringAfter stirring for 30 minutes
  5. extractionextracted with dichloromethane (3 ×10 cm3)
  6. dry with materialThe combined organic extracts were dried (Na2SO4 )
  7. customevaporated in vacuo
  8. customto afford a solid residue which
  9. customwas chromatographed on silica
  10. washeluting with 10% ethyl acetate/petroleum ether (60°-80° C.)

出典と根拠

ORDレコード
ord-1e9894d32c674c8e8d6f6189511c54a3
出典データセット
uspto-grants-1993_02
特許番号
US05185360

反応ノート

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