Hydrochloric Acid → 1-Chloro-3-(3,4-dichlorophenyl)propan-2-one

HRID 1671631

Reaktionsgleichung

Reaktionsgleichung von HRID 1671631
C(OCC(C1C=CC(Cl)=CC=1)=O)(=O)C.II.[Cl:17][C:18]1[CH:19]=[C:20]([CH:23]=[CH:24][C:25]=1[Cl:26])[CH2:21]Cl.[Cl:27][CH2:28][C:29](Cl)=[O:30].Cl>CN(C)C(=O)C.[Zn].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.C(OCC)(=O)C>[Cl:27][CH2:28][C:29](=[O:30])[CH2:21][C:20]1[CH:23]=[CH:24][C:25]([Cl:26])=[C:18]([Cl:17])[CH:19]=1

Komponenten

10

Edukt 5

HCID 313Hydrochloric AcidHCID 807Iodine2×HCID 6577Chloroacetyl chlorideHCID 76093,4-Dichlorobenzyl chlorideHCID 5872542-(4-Chlorophenyl)-2-oxoethyl acetate

Produkt 1

HCID 161001771-Chloro-3-(3,4-dichlorophenyl)propan-2-oneAusbeute 45 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 23994ZincKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 8857Ethyl AcetateLösungsmittelHCID 31374DimethylacetamideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

The organozinc species was generated as described by S. Huo (Organic Letters 2003, 5 (4), 423-5). In a flame-dried 25 mL 2-necked round-bottomed flask, under an inert atmosphere, iodine (65 mg, 0.26 mmol) was taken up in 6 mL anhydrous N,N-dimethylacetamide. Zinc dust (0.502 g, 7.67 mmol) was added, and the suspension stirred until the red color of the iodine disappeared. Then, 3,4-dichlorobenzyl chloride (0.71 mL, 1.0 g, 5.1 mmol) was added via syringe, and the mixture heated at 80° C. until the t.l.c. of a hydrolyzed aliquot (5% ethyl acetate in hexanes, visualized by cerium molybdate staining) showed that the starting material had been consumed. The reaction vessel was placed in a water bath to cool it, and Pd(PPh3)4 (0.118 g, 0.102 mmol) was added, followed by dropwise addition, via syringe, of chloroacetyl chloride (0.61 mL, 0.87 g, 7.7 mmol). The brown suspension was allowed to stir overnight at room temperature. To work up the reaction, 12 mL 1 M HCl was added, and the mixture extracted into ethyl acetate (4×12 mL). The combined organic layers were washed with brine, dried over anhydrous MgSO4, filtered, and evaporated. The crude product was purified by flash chromatography over silica gel (1-30% ethyl acetate in hexanes), to give material of sufficient purity to be used in the next step (0.545 g, 45% yield): 1H NMR (400 MHz, CDCl3) δ 3.89 (s, 2H) 4.13 (s, 2H) 7.06 (dd, J=8.2, 2.6 Hz, 1H) 7.33 (d, J=2.0 Hz, 1H) 7.42 (d, J=8.3 Hz, 1H).

Aufarbeitung

  1. customhad been consumed
  2. customThe reaction vessel was placed in a water bath
  3. additionwas added
  4. additionwas added
  5. extractionthe mixture extracted into ethyl acetate (4×12 mL)
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationfiltered
  9. customevaporated
  10. customThe crude product was purified by flash chromatography over silica gel (1-30% ethyl acetate in hexanes)
  11. customto give material of sufficient purity

Quellen und Nachweise

ORD-Eintrag
ord-ea153a608bf54ff583984d08a8a8e90d
Quelldatensatz
uspto-grants-2011_08
Patentnummer
US07994333B2

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