Cesium carbonate → Benzyl 2-(3-fluoro-4-((2-methoxyethoxy)methyl)phenyl)acrylate

HRID 1842922노트

반응식

HRID 1842922 반응식
[F:1][C:2]1[CH:3]=[C:4](B2OC(C)(C)C(C)(C)O2)[CH:5]=[CH:6][C:7]=1[CH2:8][O:9][CH2:10][CH2:11][O:12][CH3:13].C([O-])([O-])=O.[Cs+].[Cs+].Br[C:30](=[CH2:41])[C:31]([O:33][CH2:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:32]>CN(C=O)C.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[F:1][C:2]1[CH:3]=[C:4]([C:30](=[CH2:41])[C:31]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)=[O:32])[CH:5]=[CH:6][C:7]=1[CH2:8][O:9][CH2:10][CH2:11][O:12][CH3:13]

참가 물질

7

반응물 3

HCID 10796Cesium carbonateHCID 13443472Benzyl 2-bromoprop-2-enoateHCID 596373292-{3-Fluoro-4-[(2-methoxyethoxy)methyl]phenyl}-4,4,5,5-tetramethyl-1,3,2-dioxaborolane2회

생성물 1

HCID 59637287Benzyl 2-(3-fluoro-4-((2-methoxyethoxy)methyl)phenyl)acrylate수율 25.2%

시약·촉매·용매 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 6228Dimethylformamide용매HCID 8857Ethyl Acetate용매

실험 절차

A suspension of 2-(3-fluoro-4-((2-methoxyethoxy)methyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5 g, 16.129 mmol), Cs2CO3 (15.7 g, 48.38 mmol) in DMF (50 mL) was deoxygenated by purging Argon for 30 min at RT. Pd(dppf)Cl2 (657 mg, 0.806 mmol) was added and purging was continued. After 10 min, benzyl 2-bromoacrylate (4.6 g, 19.35 mmol) was added and stirred at 100° C. for 1 h until complete consumption of 2-(3-fluoro-4-((2-methoxyethoxy)methyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, as evidenced by TLC analysis. The reaction mixture was diluted with ethyl acetate (200 mL), filtered through a celite pad, washed with ethyl acetate (2×25 mL). The filtrate was washed with water (2×100 mL), brine (50 mL), dried over anhydrous NaSO4, filtered and concentrated. The obtained crude compound was purified by CC using 10% ethyl acetate in PE as eluent to afford benzyl 2-(3-fluoro-4-((2-methoxyethoxy)methyl)phenyl)acrylate (1.4 g, 25%) as pale brown oil (TLC solvent system: 30% EtOAc-PE; Rf: 0.4).

후처리

  1. customwas deoxygenated
  2. customby purging Argon for 30 min at RT
  3. custompurging
  4. filtrationfiltered through a celite pad
  5. washwashed with ethyl acetate (2×25 mL)
  6. washThe filtrate was washed with water (2×100 mL), brine (50 mL)
  7. dry with materialdried over anhydrous NaSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe obtained crude compound
  11. customwas purified by CC

출처 및 근거

ORD 기록
ord-f060a4c9a84b42cc8cbbcd6040d4042a
출처 데이터셋
uspto-grants-2015_02
특허 번호
US08946204B2

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