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Citric Acid → [4-(3-Bromo-5-cyclopropylmethoxy-phenylsulfanyl)-2-methyl-phenoxy]-acetic Acid ethyl ester

HRID 1513118
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1513118
Br[C:2]1[CH:7]=[C:6]([O:8][CH2:9][CH:10]2[CH2:12][CH2:11]2)[CH:5]=[C:4]([Br:13])[CH:3]=1.[CH2:14]([O:16][C:17](=[O:28])[CH2:18][O:19][C:20]1[CH:25]=[CH:24][C:23]([SH:26])=[CH:22][C:21]=1[CH3:27])[CH3:15].C(N(CC)CC)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CN1C(=O)CCC1>[CH2:14]([O:16][C:17](=[O:28])[CH2:18][O:19][C:20]1[CH:25]=[CH:24][C:23]([S:26][C:2]2[CH:7]=[C:6]([O:8][CH2:9][CH:10]3[CH2:12][CH2:11]3)[CH:5]=[C:4]([Br:13])[CH:3]=2)=[CH:22][C:21]=1[CH3:27])[CH3:15]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 4

HCID 311Citric AcidHCID 8471TriethylamineHCID 16641178Ethyl (4-mercapto-2-methylphenoxy)acetateHCID 670243041,3-Dibromo-5-(cyclopropylmethoxy)benzene

Produkt 1

HCID 58368330[4-(3-Bromo-5-cyclopropylmethoxy-phenylsulfanyl)-2-methyl-phenoxy]-acetic Acid ethyl ester

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564
Bis(dibenzylideneacetone)palladium
Katalysator
HCID 13387N-methyl-2-pyrrolidoneLösungsmittel

Reaktionsbedingungen

Temperatur
140 °C

Versuchsvorschrift

1,3-Dibromo-5-cyclopropylmethoxy-benzene (5.27 g; 17.23 mmol), (4-Mercapto-2-methyl-phenoxy)-acetic acid ethyl ester (3 g; 13.26 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.36 g; 0.40 mmol), and 1,1′-bis-(diphenylphosphineo)ferrocene (0.44 g; 0.80 mmol) was added to a dry reaction flask under an atmosphere of nitrogen. Triethylamine (7.45 mL) and NMP (8 mL) was added, and the reaction mixture was stirred in a microwave oven for 1 h at 140° C. A 5% aqueous citric acid solution (150 mL) was added to the reaction mixture, which was extracted with ethyl acetate (4×100 mL). The pooled organic phases were dried and evaporated in vacuo. The crude reaction product was purified by flash chromatography (heptane: ethyl acetate (20:1→7:3). Yield 2.8 g; 47%). HPLC-MS: m/z: 451.0 (M+); Rt: 2.85 min

Aufarbeitung

  1. extractionwas extracted with ethyl acetate (4×100 mL)
  2. customThe pooled organic phases were dried
  3. customevaporated in vacuo
  4. customThe crude reaction product
  5. customwas purified by flash chromatography (heptane: ethyl acetate (20:1→7:3). Yield 2.8 g; 47%)

Quellen und Nachweise

ORD-Eintrag
ord-2407b02b5e144b6b860f0ae450a79b93
Quelldatensatz
uspto-grants-2012_07
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08217086B2

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