Hydrochloric Acid → 4-Acetyl-2-fluorobenzonitrile

HRID 844019

반응식

HRID 844019 반응식
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]

참가 물질

10

반응물 5

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

생성물 1

HCID 224816534-Acetyl-2-fluorobenzonitrile수율 76.6%

시약·촉매·용매 4

HCID 812191,3-Bis(diphenylphosphino)propane촉매HCID 167845palladium(II) acetate촉매2회HCID 962Water용매HCID 6228Dimethylformamide용매

반응 조건

온도
90 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-7471ca216a7e4abfbaca5ffb44d3da7c
출처 데이터셋
uspto-grants-2002_04
특허 번호
US06380218B1

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