1-Bromo-4-fluorobenzene → {3-Cyano-6-[(4-fluorophenyl)carbonyl]phenyl}methyl 2,2-dimethylpropanoate

HRID 413484

反応式

HRID 413484 の反応式
[F:1][C:2]1[CH:7]=[CH:6][C:5]([Mg]Br)=[CH:4][CH:3]=1.FC1C=CC(Br)=CC=1.[Mg].[C:19]([C:21]1[CH:22]=[C:23]2[C:28](=[CH:29][CH:30]=1)[C:26](=[O:27])[O:25][CH2:24]2)#[N:20].[C:31](Cl)(=[O:36])[C:32]([CH3:35])([CH3:34])[CH3:33].[NH4+].[Cl-]>C1COCC1.CCOC(C)=O.CCCCCCC.C(OCC)C>[C:19]([C:21]1[CH:30]=[CH:29][C:28]([C:26]([C:5]2[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=2)=[O:27])=[C:23]([CH:22]=1)[CH2:24][O:25][C:31](=[O:36])[C:32]([CH3:35])([CH3:34])[CH3:33])#[N:20]

参加物

10

反応物 6

HCID 99931-Bromo-4-fluorobenzeneHCID 25517Ammonium ChlorideHCID 62493Pivaloyl chlorideHCID 8212181,3-Dihydro-1-oxoisobenzofuran-5-carbonitrileHCID 5462224MagnesiumHCID 178418676HCID 178418676、化合物

生成物 1

HCID 11302208{3-Cyano-6-[(4-fluorophenyl)carbonyl]phenyl}methyl 2,2-dimethylpropanoate

試薬・触媒・溶媒 3

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 21899848Ethylacetate heptane溶媒

実験手順

A solution of 4-fluorophenylmagnesium bromide, prepared from 4-fluorobromobenzene (19.2 g, 0.11 mol) and magnesium turnings (3.2 g, 0.13 mol) in dry THF (100 mL), was added dropwise to a suspension of 5-cyanophthalid (15.9 g, 0.1 mol) in dry THF (150 mL). The temperature was kept below 5° C. After the addition was complete, the reaction mixture was stirred overnight at room temperature. Pivaloylchloride (13.3 g, 0.11 mol) was added to the reaction mixture and the temperature was raised to 60° C. for 2 hours. The resulting solution was added to a saturated solution of NH4Cl (100 mL, aq) and ice (50 g). Diethylether (100 mL) was added and the phases were separated. The organic phase was washed with 0.1 N NaOH (2×100 mL) and water (100 mL) and the organic phase was dried with MgSO4 (20 g). Evaporation of the solvents gave a crude title compound (29.8 g, 88%) as an oil which was deemed sufficiently pure for further reaction. A pure sample is obtained by crystallisation from EtOAc/n-Heptane (1:9). The title compound is obtained as off white crystals.

後処理

  1. customwas kept below 5° C
  2. additionAfter the addition
  3. temperaturethe temperature was raised to 60° C. for 2 hours
  4. customthe phases were separated
  5. washThe organic phase was washed with 0.1 N NaOH (2×100 mL) and water (100 mL)
  6. dry with materialthe organic phase was dried with MgSO4 (20 g)
  7. customEvaporation of the solvents
  8. customgave a crude title compound (29.8 g, 88%) as an oil which
  9. customwas deemed sufficiently pure for further reaction

出典と根拠

ORDレコード
ord-31b13e3aa43348d48dce776b96465c28
出典データセット
uspto-grants-2003_05
特許番号
US06566540B2

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