Triphenylphosphine → Methyl 5-fluoro-2-(pent-4-en-2-yloxy)benzoate

HRID 921109

반응식

HRID 921109 반응식
[F:1][C:2]1[CH:3]=[CH:4][C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[CH3:13][C@@H:14](O)[CH2:15][CH:16]=[CH2:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.CCOCC>[F:1][C:2]1[CH:3]=[CH:4][C:5]([O:12][CH:16]([CH2:15][CH:14]=[CH2:13])[CH3:17])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

참가 물질

7

반응물 4

HCID 11776TriphenylphosphineHCID 2783186Methyl 5-fluoro-2-hydroxybenzoateHCID 5363146Diisopropyl azodicarboxylateHCID 6999724(2R)-pent-4-en-2-ol

생성물 1

HCID 118307052Methyl 5-fluoro-2-(pent-4-en-2-yloxy)benzoate수율 81%

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매

실험 절차

To a solution of methyl 5-fluoro-2-hydroxybenzoate (1.0 g, 5.88 mmol), (R)-(−)-pent-4-en-2-ol (1.210 ml, 11.76 mmol) and triphenylphosphine (2.004 g, 7.64 mmol) in THF (14 ml) was added dropwise DIAD (1.486 ml, 7.64 mmol) and the resulting solution was stirred at rt. After 20 h, the reaction was diluted with Et2O and washed with 1N NaOH, water (3×'s) and brine. The organic phase was dried (Na2SO4), filtered and concentrated. The residue was purified by flash chromatography (Biotage; 0%-40% EtOAc/hexane; 20 CV) to give methyl 5-fluoro-2-(pent-4-en-2-yloxy)benzoate (1.1331 g, 4.76 mmol, 81% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.49 (dd, J=8.7, 3.3 Hz, 1H), 7.15 (ddd, J=8.9, 7.7, 3.4 Hz, 1H), 6.96 (dd, J=9.0, 4.2 Hz, 1H), 6.02-5.79 (m, 1H), 5.20-5.06 (m, 2H), 4.50-4.34 (m, 1H), 3.90 (s, 3H), 2.60-2.32 (m, 2H), 1.34 (d, J=6.1 Hz, 3H).

후처리

  1. washwashed with 1N NaOH, water (3×'s) and brine
  2. dry with materialThe organic phase was dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was purified by flash chromatography (Biotage; 0%-40% EtOAc/hexane; 20 CV)

출처 및 근거

ORD 기록
ord-ea84e7e8c279414b964ae8ccbd240ced
출처 데이터셋
uspto-grants-2016_03
특허 번호
US09273067B2

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