3-Methoxypropyne → 4-Chloro-3-(3-methoxyprop-1-yn-1-yl)benzoic acid

HRID 219835Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 219835
[CH2:1]([O:4][CH3:5])[C:2]#[CH:3].[Cl:6][C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1I>C1COCC1.C(N(CC)CC)C.CCOC(C)=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:6][C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1[C:3]#[C:2][CH2:1][O:4][CH3:5]

Komponenten

7

Edukt 2

HCID 693933-MethoxypropyneHCID 27576164-Chloro-3-iodobenzoic acid

Produkt 1

HCID 675293394-Chloro-3-(3-methoxyprop-1-yn-1-yl)benzoic acid

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittelHCID 8471TriethylamineLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

Methyl propargyl ether (Fluka; 68898; 1.27 mL; 15 mmol; 1.50 eq.) was added dropwise to a suspension of 4-chloro-3-iodobenzoic acid (ABCR; TWC2211-D1; 2 824.60 mg; 10 mmol; 1 eq.), dichlorobis(triphenylphosphine)palladium(II) (701.91 mg; 1 mmol; 0.10 eq.) and cuprous iodide (190.45 mg; 1 mmol; 0.10 eq.) in a mixture of THF (20 mL) and triethylamine (10 mL). The reaction was stirred at RT for 2 h. The reaction mixture was quenched with saturated aqueous NH4Cl, and extracted twice with EtOAc. The combined extract were evaporated under vacuo to afford an orange solid. The latter was dissolved in EtOAc and extracted 4 times with NaOH 0.1M. Then the aqueous layer was filtered, acidified to pH=3-4 with HCl 1M, and extracted with EtOAc. The combined organic layers were dried over magnesium sulfate, filtered and concentrated to afford the title compound as a slightly orange powder. 1H NMR (DMSO-d6, 300 MHz) δ 13.42 (br. s., 1H), 8.03 (d, J=2.07 Hz, 1H), 7.92 (dd, J=2.17, 8.38 Hz, 1H), 7.71 (d, J=8.48 Hz, 1H), 4.41 (s, 2H), 3.19-3.37 (m, 3H). LC/MS (Method B): 223.0 (M−H)−. HPLC (Method A) Rt 3.51 min (Purity: 98.8%).

Aufarbeitung

  1. customThe reaction mixture was quenched with saturated aqueous NH4Cl
  2. extractionextracted twice with EtOAc
  3. extractionThe combined extract
  4. customwere evaporated under vacuo
  5. customto afford an orange solid
  6. extractionextracted 4 times with NaOH 0.1M
  7. filtrationThen the aqueous layer was filtered
  8. extractionextracted with EtOAc
  9. dry with materialThe combined organic layers were dried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-5e96189b418040f68b766b12f9391724
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08202865B2

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