N,N,N',N'-Tetramethylethylenediamine → 5-Methyl-1,2,3,4-tetramethoxy-6-(1-hydroxytridec-12-yn-1-yl)benzene

HRID 1723963Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1723963
[CH3:1][C:2]1[C:3]([O:14][CH3:15])=[C:4]([O:12][CH3:13])[C:5]([O:10][CH3:11])=[C:6]([O:8][CH3:9])[CH:7]=1.CN(C)CCN(C)C.C([Li])CCC.[CH:29](=[O:42])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][C:40]#[CH:41]>C1COCC1>[CH3:1][C:2]1[C:3]([O:14][CH3:15])=[C:4]([O:12][CH3:13])[C:5]([O:10][CH3:11])=[C:6]([O:8][CH3:9])[C:7]=1[CH:29]([OH:42])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][C:40]#[CH:41]

Komponenten

6

Edukt 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 98777642,3,4,5-TetramethoxytolueneHCID 1101974612-TridecynalHCID 178418339Butyllithium

Produkt 1

HCID 574368525-Methyl-1,2,3,4-tetramethoxy-6-(1-hydroxytridec-12-yn-1-yl)benzene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

A solution of 5-methyl-1,2,3,4-tetramethoxybenzene (2.12 g, 10 mmol, Hansen, C. A.; Dean, A. B.; Draths, K. M.; Frost, J. W. J. Am. Chem. Soc. 1999, 121(15), 3799-3800.) and tetramethylethylenediamine (TMEDA, 2.96 mL, 20 mmol) in hexanes (25 mL) is cooled at 0° C. in an ice bath while a solution of n-butyllithium (2.0M in hexanes, 5 mL) is added dropwise. The yellow reaction mixture is stirred for thirty minutes and is then diluted with THF (20 mL). A solution of 12-tridecynal (4.27 g, 22 mmol, J. Org. Chem. 2001, 66(14), 4766-4770) in THF (10 mL) is added, and the mixture stirred for two hours. The reaction is quenched by the addition of saturated aqueous NH4Cl (20 mL). Water (30 mL) is added and the aqueous phase is separated and extracted with ethyl acetate (2×50 mL). The combined organic fractions are washed (1× water), dried (saturated aqueous NaCl, sodium sulfate), filtered, and concentrated. Chromatography (hexane-2:1 hexane:ethyl acetate gradient over silica gel 230-400 mesh) provides the desired product.

Aufarbeitung

  1. additionis added dropwise
  2. stirringthe mixture stirred for two hours
  3. customThe reaction is quenched by the addition of saturated aqueous NH4Cl (20 mL)
  4. additionWater (30 mL) is added
  5. customthe aqueous phase is separated
  6. extractionextracted with ethyl acetate (2×50 mL)
  7. washThe combined organic fractions are washed (1× water)
  8. dry with materialdried (saturated aqueous NaCl, sodium sulfate)
  9. filtrationfiltered
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-5958fd20681046038a8215541b661800
Quelldatensatz
uspto-grants-2009_02
Patentnummer
US07485283B2

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