Diisopropylamine → 5-[2-(2,4-Difluorophenyl)ethenyl]-2,2-dimethyl-3(2H)-furanone

HRID 359358노트

반응식

HRID 359358 반응식
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][C:14]1([CH3:21])[C:18](=[O:19])[CH:17]=[C:16]([CH3:20])[O:15]1.[F:22][C:23]1[CH:30]=[C:29]([F:31])[CH:28]=[CH:27][C:24]=1[CH:25]=O.FC(F)(F)C(OC(=O)C(F)(F)F)=O>O1CCCC1.CCCCCC.C(N(CC)CC)C.CN(C)P(N(C)C)(N(C)C)=O>[F:22][C:23]1[CH:30]=[C:29]([F:31])[CH:28]=[CH:27][C:24]=1[CH:25]=[CH:20][C:16]1[O:15][C:14]([CH3:21])([CH3:13])[C:18](=[O:19])[CH:17]=1

참가 물질

10

반응물 5

HCID 7912DiisopropylamineHCID 9845Trifluoroacetic anhydrideHCID 737702,4-DifluorobenzaldehydeHCID 1370803(2H)-Furanone, 2,2,5-trimethyl-HCID 178418339Butyllithium

생성물 1

HCID 539726665-[2-(2,4-Difluorophenyl)ethenyl]-2,2-dimethyl-3(2H)-furanone수율 65%

시약·촉매·용매 4

HCID 8028Tetrahydrofuran용매3회HCID 8058Hexane용매HCID 8471Triethylamine용매HCID 12679Hexamethylphosphoramide용매

실험 절차

To a solution of dry diisopropylamine (3.3 mL, 24 mM) in dry tetrahydrofuran (25 mL) at -78° C., was added dropwise 2.3N solution of n-butyllithium in hexane (10.4 mL,24mM). After the reaction solution was stirred 15 minutes, a solution of 2,2,5-trimethyl-3(2H)-furanone (2.0 g, 16 mm) in tetrahydrofuran (10 mL) was added dropwise. Hexamethylphosphoramide (4.4 mL, 24 mM) was then added dropwise after 30 minutes. Finally, 2,4-difluorobenzaldehyde (3.5 mL, 31.8 mM) in tetrahydrofuran (10 mL) was added in one portion. The reaction solution was stirred 10 minutes when trifluoroacetic anhydride (11.87 g, 55.7 mM) was added in one portion. Again, the reaction solution was stirred 15, minutes when triethylamine (5.6 g, 55.7 mM) was added and was allowed to warm to room temperature. The reaction solution was partitioned between saturated aqueous sodium chloride (50 mL) and diethyl ether (50 mL). The layers were separated. The organic layers were then washed with saturated aqueous sodium chloride (2×25 mL), dried over MgSO4, filtered and concentrated under reduced pressure to give an orange liquid. The crude product was purified by chromatography (silica gel, pet. ether-ethyl acetate) to afford a yellow crystalline solid (2.6 g, 65% yield), m.p. 98.5°-100° C.

후처리

  1. additionwas added in one portion
  2. additionwas added
  3. customThe reaction solution was partitioned between saturated aqueous sodium chloride (50 mL) and diethyl ether (50 mL)
  4. customThe layers were separated
  5. washThe organic layers were then washed with saturated aqueous sodium chloride (2×25 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto give an orange liquid
  10. customThe crude product was purified by chromatography (silica gel, pet. ether-ethyl acetate)

출처 및 근거

ORD 기록
ord-d7b5719dccfd49bca7dbd25ecdbb694c
출처 데이터셋
uspto-grants-1991_03
특허 번호
US05001126

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