Propargyl bromide → 1,2,4-Trichlorophenyl-3-(2-propynyloxy) benzene

HRID 1858120

Reaktionsgleichung

Reaktionsgleichung von HRID 1858120
C1C2C(COC([C:18]3[C:31](OC)=[CH:30][C:21]([O:22][CH2:23][CH2:24][CH2:25]CC(O)=O)=[C:20](CN)[C:19]=3OC)=O)C3C(=CC=CC=3)C=2C=CC=1.[Cl:38][C:39]1[C:44]([Cl:45])=[CH:43][CH:42]=[C:41]([Cl:46])[C:40]=1O.C1OC2C(=C(O)C=CC=2)O1.CC(C)([O-])C.[K+].C(Br)C#C>CN(C=O)C>[Cl:45][C:44]1([C:19]2[CH:18]=[CH:31][CH:30]=[C:21]([O:22][CH2:23][C:24]#[CH:25])[CH:20]=2)[CH:43]=[CH:42][C:41]([Cl:46])=[CH:40][CH:39]1[Cl:38]

Komponenten

7

Edukt 5

HCID 7842Propargyl bromideHCID 136182,3,6-TrichlorophenolHCID 5867271,3-Benzodioxol-4-olHCID 23665647Potassium tert-butoxideHCID 867560505-(4-Fmoc-aminomethyl-3,5-dimethoxyphenoxy)valeric acid

Produkt 1

HCID 867560491,2,4-Trichlorophenyl-3-(2-propynyloxy) benzene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

1,2,4-trichlorophenyl-3-(2-propynyloxy) benzene (TCPB) and 1-(2-propynyloxy)methylenedioxyphenyl ether (MDPPE) were synthesized by the method of F. Albericio et al., "Preparation and Application of the 5-(4-(9-Fluorenylmethyloxy carbonyl)-Aminomethyl-3,5-Dimethoxyphenoxy)-Valeric Acid Handle for the Solid Phase Synthesis of C-Terminal Peptide Amides under Mild Conditions," J. Org. Chem. vol. 55, pp. 3730-3743 (1990) (FIG. 2). A mixture of 2,3,6-trichlorophenol or methylenedioxyphenol (0.05 mole), potassium tert-butoxide (6.16 g, 0.055 mole), propargyl bromide (6.6 g, 0.055 mole) in dry DMF (60 mL) was heated and stirred at 110° C. for 5 h, after which the solvent was removed under high vacuum. Ethyl acetate was added, the inorganic salts were removed by filtration, and the organic extract was washed sequentially with water, 2 M NaOH, and saturated aqueous NaCl. The organic phase was dried overnight (Na2SO4) to give a crude product. MDPPE, a liquid product, was purified by silica gel chromatography using hexane-ethyl acetate (7:3) as the eluting solvent. Yield: 6.5 g (74%). 1H NMR (CDCl3): d 2.54 (t, 1H, CH), 4.61 (d, 2H, --OCH2 --), 5.92 (s, 2H, --OCH2O--), 6.38-6.73 (m, 3H, aromatics). GC-MS (m/z): M+· =176.

Aufarbeitung

  1. temperaturewas heated
  2. customafter which the solvent was removed under high vacuum
  3. additionEthyl acetate was added
  4. customthe inorganic salts were removed by filtration
  5. extractionthe organic extract
  6. washwas washed sequentially with water, 2 M NaOH, and saturated aqueous NaCl
  7. dry with materialThe organic phase was dried overnight (Na2SO4)

Quellen und Nachweise

ORD-Eintrag
ord-0cd46401290842c781b8e09766f3081f
Quelldatensatz
uspto-grants-2000_11
Patentnummer
US06150404

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