Iodine → 3-((6-(4-Bromophenyl)hexyloxy)methyl)-3-ethyloxetane

HRID 2242780Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2242780
II.Br[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][CH2:11][C:12]1([CH2:16][CH3:17])[CH2:15][O:14][CH2:13]1.[Br:18][C:19]1[CH:24]=[CH:23][C:22](I)=[CH:21][CH:20]=1.[NH4+].[Cl-]>CC(N(C)C)=O.[Zn].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C1COCC1>[Br:18][C:19]1[CH:24]=[CH:23][C:22]([CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][CH2:11][C:12]2([CH2:16][CH3:17])[CH2:15][O:14][CH2:13]2)=[CH:21][CH:20]=1

Komponenten

9

Edukt 4

HCID 807Iodine2×HCID 115221-Bromo-4-iodobenzeneHCID 25517Ammonium ChlorideHCID 592073103-{[(6-Bromohexyl)oxy]methyl}-3-ethyloxetane

Produkt 1

HCID 592073013-((6-(4-Bromophenyl)hexyloxy)methyl)-3-ethyloxetaneAusbeute 41 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 23994ZincKatalysator2×HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 8028TetrahydrofuranLösungsmittelHCID 31374DimethylacetamideLösungsmittel

Versuchsvorschrift

To a mixture of zinc powder (1.80 g, 27.5 mmol) in anhydrous DMA (20 ml) is added iodine (0.5 g, 1.97 mmol). This mixture is stirred until the red color of iodine disappeared (ca. 2 min), followed by the addition of 3-(6-bromohexyloxymethyl)-3-ethyloxetane (5.0 g, 17.9 mmol) and the resultant mixture is stirred at 85° C. for 4.5 h, then cooled to room temperature. In another flask charged with anhydrous THF (30 ml) is added 1-bromo-4-iodobenzene (7.0 g, 24.74 mmol) and Pd(dppf)Cl2 (0.5 g, 0.61 mmol). This mixture is stirred for 10 min, then the organic zinc reagent above is introduced. The reaction mixture is stirred overnight (˜16 h) at room temperature. Sat. aq. NH4Cl solution is added and the mixture is extracted with ethyl acetate (3×70 ml). The extracts are dried (Na2SO4) and evaporated under reduced pressure. The residue is purified by column chromatography on silica, eluting with petrol/ethyl acetate (10:0 to 4:1), to give a brown oil (2.6 g, 41%). 1H NMR (300 MHz, CDCl3): δ(ppm) 7.35 (d, J=8.4 Hz, 2H, Ar—H), 7.01 (d, J=8.4 Hz, 2H, Ar—H), 4.43 (d, J=5.7 Hz, 2H, OCH2), 4.34 (d, J=5.7 Hz, 2H, OCH2), 3.48 (s, 2H, OCH2), 3.41 (t, J=6.4 Hz, 2H, OCH2), 2.53 (t, J=7.9 Hz, 2H, ArCH2), 1.72 (q, J=7.6 Hz, 2H, CH2), 1.56 (m, 4H, CH2), 1.34 (m, 4H, CH2); 0.86 (t, J=7.6 Hz 3H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 141.6 (quat.), 131.2 (CH), 130.2 (CH), 119.3 (quat.), 78.4 (OCH2), 73.4 (OCH2), 71.4 (OCH2), 43.4 (quat.), 35.3 (CH2), 31.3 (CH2), 29.5 (CH2), 29.0 (CH2), 26.8 (CH2), 26.0 (CH2), 8.2 (CH3).

Aufarbeitung

  1. custom(ca. 2 min)
  2. stirringThe reaction mixture is stirred overnight (˜16 h) at room temperature
  3. extractionthe mixture is extracted with ethyl acetate (3×70 ml)
  4. dry with materialThe extracts are dried (Na2SO4)
  5. customevaporated under reduced pressure
  6. customThe residue is purified by column chromatography on silica
  7. washeluting with petrol/ethyl acetate (10:0 to 4:1)

Quellen und Nachweise

ORD-Eintrag
ord-2a1630fbe7284a9a981742b333d01e9e
Quelldatensatz
uspto-grants-2010_03
Patentnummer
US07674397B2

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