Tetrahydrofuran → 3-(2-Chloro-4-nitro-benzoyl)-4-methoxy-benzoic acid methyl ester

HRID 1012600노트

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HRID 1012600 반응식
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[C:6](I)[CH:5]=1.C([Mg]Cl)(C)C.C1COCC1.[Cl:24][C:25]1[CH:33]=[C:32]([N+:34]([O-:36])=[O:35])[CH:31]=[CH:30][C:26]=1[C:27](Cl)=[O:28]>[Cl-].[Cl-].[Zn+2].CC([O-])=O.CC([O-])=O.[Cu+2].CCOC(C)=O.O>[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[C:6]([C:27](=[O:28])[C:26]2[CH:30]=[CH:31][C:32]([N+:34]([O-:36])=[O:35])=[CH:33][C:25]=2[Cl:24])[CH:5]=1

참가 물질

8

반응물 4

HCID 8028TetrahydrofuranHCID 81522Benzoyl chloride, 2-chloro-4-nitro-HCID 316980Methyl 3-iodo-4-methoxybenzoateHCID 178418918HCID 178418918, 화합물

생성물 1

HCID 673140343-(2-Chloro-4-nitro-benzoyl)-4-methoxy-benzoic acid methyl ester

시약·촉매·용매 3

HCID 8895Cupric acetate촉매HCID 3007855Zincchloride촉매HCID 22728543Water ethylacetate용매

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온도
-50 °C

실험 절차

A dry flask was charged with 3-iodo-4-methoxy-benzoic acid methyl ester (8.9 g, 30.5 mmol) and the flask was evaporated and then filled with argon and this process repeated twice. Dry THF (50 mL) was added, and the solution cooled to −50° C.; then isopropylmagnesium chloride (15.2 mL, 2.0 M in diethyl ether, 30.5 mmol) was added slowly over 20 min keeping the temperature below −40° C. On completion of the addition the reaction mixture was stirred at −40° C. for 45 min. A THF solution of ZnCl2 (5.19 g, 38.1 mmol, 1.0 M) was added dropwise over 20 min. The reaction mixture was stirred at 0° C. for 20 min; then 2-chloro-4-nitro-benzoyl chloride (7.04 g, 32.0 mmol) and Cu(OAc)2 (122 mg, 0.61 mmol) were added and the reaction mixture was allowed to warm to room temperature. After 16 h the reaction mixture was poured into a mixture of EtOAc/water, then shaken and separated. The aqueous phase was extracted with more EtOAc. The organic phases were combined, dried (MgSO4), filtered, and concentrated in vacuo to afford the crude product. The crude product was purified by flash chromatography using EtOAc/petroleum ether (40-60) 1:6 followed by 1:3 as the eluent to give the title compound as yellow solid.

후처리

  1. customthe flask was evaporated
  2. additionfilled with argon
  3. additionDry THF (50 mL) was added
  4. customthe temperature below −40° C
  5. additionOn completion of the addition the reaction mixture
  6. stirringThe reaction mixture was stirred at 0° C. for 20 min
  7. temperatureto warm to room temperature
  8. stirringshaken
  9. customseparated
  10. extractionThe aqueous phase was extracted with more EtOAc
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. customto afford the crude product
  15. customThe crude product was purified by flash chromatography

출처 및 근거

ORD 기록
ord-cccbafb37eb34f29bb7a0b723d965910
출처 데이터셋
uspto-grants-2011_07
특허 번호
US07977387B2

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