Tetrahydrofuran → 3-(2-Chloro-4-nitrobenzoyl)-4-methylbenzoic acid methyl ester

HRID 1012596

Reaktionsgleichung

Reaktionsgleichung von HRID 1012596
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[C:6](I)[CH:5]=1.C([Mg]Cl)(C)C.C1COCC1.[Cl:23][C:24]1[CH:32]=[C:31]([N+:33]([O-:35])=[O:34])[CH:30]=[CH:29][C:25]=1[C:26](Cl)=[O:27]>[Cl-].[Cl-].[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1.CCOC(C)=O.O>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[C:6]([C:26](=[O:27])[C:25]2[CH:29]=[CH:30][C:31]([N+:33]([O-:35])=[O:34])=[CH:32][C:24]=2[Cl:23])[CH:5]=1

Komponenten

8

Edukt 4

HCID 8028TetrahydrofuranHCID 81522Benzoyl chloride, 2-chloro-4-nitro-HCID 13614033Methyl 3-iodo-4-methylbenzoateHCID 178418918HCID 178418918, Verbindung

Produkt 1

HCID 673131903-(2-Chloro-4-nitrobenzoyl)-4-methylbenzoic acid methyl ester

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3007855ZincchlorideKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 86606854HCID 86606854, VerbindungLösungsmittel

Reaktionsbedingungen

Temperatur
-50 °C

Versuchsvorschrift

A dry flask was charged with 3-iodo-4-methylbenzoic acid methyl ester (21.6 g, 78.2 mmol) and the flask was evaporated and then filled with argon and this process repeated twice. Dry THF (140 mL) was added, and the solution cooled to −50° C.; then isopropylmagnesium chloride (41 mL, 2.0 M in diethyl ether, 82 mmol) was added slowly over 15 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 (10.78 g, 79.1 mmol, 0.8 M) was added dropwise over 20 min. The reaction mixture was stirred at 0° C. for 65 min; then 2-chloro-4-nitro-benzoyl chloride (17.2 g, 78.2 mmol) and tetrakis(triphenylphosphine)palladium(0) (4.03 g, 3.49 mmol) were added and the reaction mixture was allowed to warm to room temperature. After 4 h the reaction mixture was poured into a mixture of toluene/EtOAc/water, then shaken and separated. The aqueous phase was extracted with two more portions of EtOAc. The organic phases were combined, dried (MgSO4), filtered, and concentrated in vacuo to afford the crude product. Crystallization from mixtures of EtOAc/petroleum ether (40-60) gave the title compound as yellow solid. The mother liquid was concentrated in vacuo and purified by chromatography using DCM as the eluent to give a second crop of the title compound.

Aufarbeitung

  1. customthe flask was evaporated
  2. additionfilled with argon
  3. additionDry THF (140 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 65 min
  7. temperatureto warm to room temperature
  8. stirringshaken
  9. customseparated
  10. extractionThe aqueous phase was extracted with two more portions of EtOAc
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. customto afford the crude product
  15. customCrystallization from mixtures of EtOAc/petroleum ether (40-60)

Quellen und Nachweise

ORD-Eintrag
ord-1b67e7fcb93d44c4ac3e697ef3a8f4b7
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07977387B2

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