Ammonium Chloride → 3-(4-Fluorophenyl)-3-methylbutyraldehyde

HRID 54256

반응식

HRID 54256 반응식
[F:1][C:2]1[CH:7]=[CH:6][C:5]([Mg]Br)=[CH:4][CH:3]=1.[CH3:10][C:11]([CH3:15])=[CH:12][CH:13]=[O:14].[Cl-].[NH4+]>O1CCCC1.[Cu]Br>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:11]([CH3:15])([CH3:10])[CH2:12][CH:13]=[O:14])=[CH:4][CH:3]=1

참가 물질

6

반응물 3

HCID 25517Ammonium ChlorideHCID 610203-Methyl-2-butenalHCID 178418676HCID 178418676, 화합물

생성물 1

HCID 214680123-(4-Fluorophenyl)-3-methylbutyraldehyde수율 43%

시약·촉매·용매 2

HCID 24593copper(I) bromide촉매HCID 8028Tetrahydrofuran용매

반응 조건

온도
5 °C

실험 절차

Under a nitrogen atmosphere, a stirring solution of 66.6 grams (0.334 mole) of 4-fluorophenylmagnesium bromide (1M in diethyl ether) is cooled to -10° C., and 2.2 grams (0.015 mole) of copper(I) bromide is added in one portion. Upon completion of addition, a solution of 25.0 grams (0.297 mole) of 3-methyl-2-butenal in 20 mL of tetrahydrofuran is added dropwise at a rate to maintain the reaction mixture temperature at about 5° C. The complete addition requires about one hour. Upon completion of addition, the reaction mixture is stirred for one additional hour and then is stored in a refrigerator for about 18 hours. After this time the reaction mixture is poured into 500 mL of aqueous ammonium chloride and extracted with four portions of diethyl ether. The combined extracts are concentrated under reduced pressure to a residue. The residue is subjected to column chromatography on silica gel, using methylene chloride as the eluant. The product-containing fractions are combined and concentrated under reduced pressure to a residue. The residue is subjected to a second column chromatography on silica gel, using 100% petroleum ether and combinations of methylene chloride in petroleum ether. The product-containing fractions are combined and concentrated under reduced pressure, yielding about 23.0 grams of 3-(4-fluorophenyl)-3-methylbutyraldehyde. The NMR spectrum is consistent with the proposed structure.

후처리

  1. additionUpon completion of addition
  2. additionThe complete addition
  3. additionUpon completion of addition
  4. waitis stored in a refrigerator for about 18 hours
  5. extractionextracted with four portions of diethyl ether
  6. concentrationThe combined extracts are concentrated under reduced pressure to a residue
  7. concentrationconcentrated under reduced pressure to a residue
  8. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-74247e5a08c9439fb977ff6250e38b1e
출처 데이터셋
uspto-grants-1997_04
특허 번호
US05622954

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