Hydrochloric Acid → 4-Acetyl-2-fluorobenzonitrile

HRID 844019

反応式

HRID 844019 の反応式
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([F:10])[CH:3]=1.[CH:11]([O:13]CCCC)=[CH2:12].C(N(CC)CC)C.C([O-])(=O)C.[Tl+].Cl>CN(C)C=O.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[C:11]([C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([F:10])[CH:3]=1)(=[O:13])[CH3:12]

参加物

10

反応物 5

HCID 313Hydrochloric AcidHCID 8108Butyl vinyl etherHCID 8471TriethylamineHCID 11247thallium(I) acetateHCID 7360294-Bromo-2-fluorobenzonitrile

生成物 1

HCID 224816534-Acetyl-2-fluorobenzonitrile収率 76.6%

試薬・触媒・溶媒 4

HCID 812191,3-Bis(diphenylphosphino)propane触媒HCID 167845palladium(II) acetate触媒2 回HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
90 °C

実験手順

A mixture of 4-Bromo-2-fluoro-benzonitrile (5.0 grams, 20.0 mmole), butyl vinyl ether (12.5 grams, 124.0 mmole), triethylamine (4.0 grams, 40.0 mmole), dppp (0.453 grams, 1.1 mmole), Thallium acetate (5.8 grams, 22.0 mmole) and Pd(OAc)2 (0.224 grams, 1.0 mmole) in dimethylformamide (50 ml) under N2 was heated to 90° C. for 3 hours. An additional 0.453 g dpp and 0.244 g Pd(OAc)2 was added and the mixture was heated to 90° C. for 4 hours. The mixture was cooled to room temperature, 25 ml 2 N hydrochloric acid was added and the mixture was stirred at room temperature for 30 hours. The mixture was poured into 300 ml water and extracted with diethyl ether. The combined extracts were washed with water and brine, dried over magnesium sulfate and concentrated to give an oil which was purified via flash chromatography on silica using 30% ethyl acetate/hexane as eluent to give an oil (2.5 g). 1H-NMR (CDCl3): δ2.63 (s, 3H), 7.73 (m, 2H), 7.81 (m, 1H).

後処理

  1. temperaturethe mixture was heated to 90° C. for 4 hours
  2. temperatureThe mixture was cooled to room temperature
  3. extractionextracted with diethyl ether
  4. washThe combined extracts were washed with water and brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. customto give an oil which
  8. customwas purified via flash chromatography on silica using 30% ethyl acetate/hexane as eluent

出典と根拠

ORDレコード
ord-7471ca216a7e4abfbaca5ffb44d3da7c
出典データセット
uspto-grants-2002_04
特許番号
US06380218B1

関連ノート

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