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

HRID 1671631

반응식

HRID 1671631 반응식
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

참가 물질

10

반응물 5

HCID 313Hydrochloric AcidHCID 807Iodine2회HCID 6577Chloroacetyl chlorideHCID 76093,4-Dichlorobenzyl chlorideHCID 5872542-(4-Chlorophenyl)-2-oxoethyl acetate

생성물 1

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

시약·촉매·용매 4

HCID 23994Zinc촉매HCID 178418397HCID 178418397, 화합물촉매HCID 8857Ethyl Acetate용매HCID 31374Dimethylacetamide용매

반응 조건

온도
80 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-ea153a608bf54ff583984d08a8a8e90d
출처 데이터셋
uspto-grants-2011_08
특허 번호
US07994333B2

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