P-Xylene → 1,3-Difluoro-5-[2-(4-fluorophenyl)ethenyl]benzene

HRID 78877

反応式

HRID 78877 の反応式
CC1C=CC(C)=CC=1.[F:9][C:10]1[CH:11]=[C:12]([CH:16]=[C:17]([F:19])[CH:18]=1)[C:13](Cl)=O.[F:20][C:21]1[CH:28]=[CH:27][C:24]([CH:25]=C)=[CH:23][CH:22]=1.CN1CCOCC1>CC([O-])=O.CC([O-])=O.[Pd+2].[Cl-].C(C1C=CC=C(C(C)C)C=1[NH+]1CCN(C2C(C(C)C)=CC=CC=2C(C)C)C1)(C)C.CCOC(C)=O>[F:9][C:10]1[CH:11]=[C:12]([CH:13]=[CH:25][C:24]2[CH:27]=[CH:28][C:21]([F:20])=[CH:22][CH:23]=2)[CH:16]=[C:17]([F:19])[CH:18]=1

参加物

8

反応物 4

HCID 7809P-XyleneHCID 79724-MethylmorpholineHCID 678834-FluorostyreneHCID 1456003,5-Difluorobenzoyl chloride

生成物 1

HCID 687399331,3-Difluoro-5-[2-(4-fluorophenyl)ethenyl]benzene収率 80.3%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 184547821,3-BIS(2,6-DIISOPROPYLPHENYL)imidazoLIDINIUM-CHLORIDE触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
120 °C

実験手順

A 25 mL round bottom flask was charged with p-xylene (10 mL), Pd(OAc)2 (11.3 mg, 0.05 mmol), 1,3-bis-(2,6-diisopropylphenyl)imidazolinium chloride (21.4 mg, 0.05 mmol), 3,5-difluorobenzoyl chloride (0.89 g, 5 mmol), 4-fluorostyrene (0.74 g, 6 mmol), and N-methyl morpholine (0.69 g, 6 mmol). The mixture was stirred at 120° C. for 3.5 h under nitrogen atmosphere. Then it was cooled to room temperature and EtOAc was added and filtered. The filtrate was washed with brine and dried over Na2SO4. Then it was filtered and purified via flash chromatography and gave the product (0.94 g, 80%) as white solid. Data are: 1H NMR (CDCl3, 300 MHz) δ 7.47 (m, 2H), 7.08-6.88 (m, 6H), 6.70 (tt, 1H); 13C NMR (CDCl3, 75 MHz) δ 163.52 (dd), 162.98 (d), 140.82 (t), 132.77, 130.26, 128.58 (d), 126.53, 116.03 (d), 109.20 (q), 102.98 (t); 19F NMR (CDCl3, 282 MHz) δ −31207.2 (q, 2F), −31965.6 (q, 1F); HRMS (EI+) found 234.0645 M+, calcd 234.0656 for C14H9F3.

後処理

  1. temperatureThen it was cooled to room temperature
  2. filtrationfiltered
  3. washThe filtrate was washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationThen it was filtered
  6. custompurified via flash chromatography

出典と根拠

ORDレコード
ord-d65cb79ebeeb483aa774de122614010f
出典データセット
uspto-grants-2014_09
特許番号
US08841477B2

関連ノート

読み込み中…