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

HRID 2236338노트

반응식

HRID 2236338 반응식
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

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 184547821,3-BIS(2,6-DIISOPROPYLPHENYL)imidazoLIDINIUM-CHLORIDE촉매HCID 8857Ethyl Acetate용매

반응 조건

온도
120 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-38990501b54e4cebb7237d9938a9e17a
출처 데이터셋
uspto-grants-2010_05
특허 번호
US07714161B2

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