Dimethylformamide → 2,4-Difluoro-3-formylbenzoic acid

HRID 79025

반응식

HRID 79025 반응식
CN(CCN(C)C)C.C([Li])(CC)C.[F:14][C:15]1[CH:23]=[C:22]([F:24])[CH:21]=[CH:20][C:16]=1[C:17]([OH:19])=[O:18].CN([CH:28]=[O:29])C>C1COCC1>[F:14][C:15]1[C:23]([CH:28]=[O:29])=[C:22]([F:24])[CH:21]=[CH:20][C:16]=1[C:17]([OH:19])=[O:18]

참가 물질

6

반응물 4

HCID 6228DimethylformamideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 741022,4-Difluorobenzoic acidHCID 178418400CID 53628100

생성물 1

HCID 583743952,4-Difluoro-3-formylbenzoic acid수율 11%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-75 °C

실험 절차

A solution of TMEDA (10.5 mL, 70 mmol) in THF (50 mL) was cooled to <−80° C. and treated with sec-butyllithium (50 mL, 70 mmol). A solution of 2,4-difluorobenzoic acid (5.0 g, 31.6 mmol) in THF was added dropwise maintaining the temperature below −80° C. The reaction mixture was allowed to warm to −75° C. and treated with DMF (15 mL), the mixture then allowed to warm to 0° C. before quenching the reaction with water. The aqueous layer was separated, acidified to pH ˜2 (concentrated HCl) and extracted twice with diethyl ether. The combined organic extracts were dried (Na2SO4), filtered and concentrated in vacuo to give a yellow oil. The crude product was crystallized from cyclohexane/diethyl ether to give the title compound as a yellow solid (670 mg, 11%). 1H NMR (CDCl3, 400 MHz) 10.40 (1 H, s), 8.31 (1 H, ddd, J=8.96, 8.02, 6.08 Hz), 7.12 (1 H, td, J=9.09, 1.42 Hz).

후처리

  1. temperaturemaintaining the temperature below −80° C
  2. temperatureto warm to 0° C.
  3. custombefore quenching
  4. customthe reaction with water
  5. customThe aqueous layer was separated
  6. extractionextracted twice with diethyl ether
  7. dry with materialThe combined organic extracts were dried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give a yellow oil
  11. customThe crude product was crystallized from cyclohexane/diethyl ether

출처 및 근거

ORD 기록
ord-a47cc2a286804b1e87ac2eff419cddd0
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08841462B2

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