Diisopropylamine → 1-(5-Bromo-2-fluorophenyl)ethanone

HRID 81542

반응식

HRID 81542 반응식
C(NC(C)C)(C)C.[Li]CCCC.[Br:13][C:14]1[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=1.[CH3:21][CH2:22][O:23]C(C(F)F)=O>C1COCC1>[Br:13][C:14]1[CH:19]=[CH:18][C:17]([F:20])=[C:16]([C:22](=[O:23])[CH3:21])[CH:15]=1

참가 물질

6

반응물 4

HCID 7912DiisopropylamineHCID 9961Ethyl difluoroacetateHCID 99931-Bromo-4-fluorobenzeneHCID 178418339Butyllithium

생성물 1

HCID 226074761-(5-Bromo-2-fluorophenyl)ethanone

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
-70 °C

실험 절차

A solution of 17.78 ml (126 mmol) diisopropyl amine in 375 ml THF was cooled to −78° C. A 1.6 M solution of BuLi in hexanes (79 ml, 126 mmol) was added drop wise. After 15 minutes 20 g of 4-bromo-1-fluoro benzene (114 mmol) was added dropwise while keeping the temperature below −60° C. After stirring for 2.5 h at −70° C. 13.22 ml ethyl difluoro acetate were added. The mixture was warmed to −40° C. and then quenched by pouring the mixture onto 1M HCl. The mixture was extracted with ligroine, dried with MgSO4.H2O, concentrated and purified by column chromatography (silica gel; hexane/5-15% TBME) to give the desired product as a yellow liquid. 1H-NMR (CDCl3, 360 MHz): 8.09 (dd, 1H), 7.82-7.77 (m, 1H), 7.17 (t, 1H), 6.45 (t, 1H, CHF2)

후처리

  1. customthe temperature below −60° C
  2. temperatureThe mixture was warmed to −40° C.
  3. customquenched
  4. additionby pouring the mixture onto 1M HCl
  5. extractionThe mixture was extracted with ligroine
  6. dry with materialdried with MgSO4.H2O
  7. concentrationconcentrated
  8. custompurified by column chromatography (silica gel; hexane/5-15% TBME)

출처 및 근거

ORD 기록
ord-7b551148282c46dabae0aa0aae5dc79b
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08846658B2

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