Trimethylsilylacetylene → 1-Ethynyl-3-methoxymethoxymethyl-benzene

HRID 78264

Reaktionsgleichung

Reaktionsgleichung von HRID 78264
BrC1C=CC=C(COCOC)C=1.C[Si](C#C)(C)C.C(N(CC)C(C)C)(C)C.[CH3:28][O:29][CH2:30][O:31][CH2:32][C:33]1[CH:34]=[C:35]([C:39]#[C:40][Si](C)(C)C)[CH:36]=[CH:37][CH:38]=1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O1CCCC1.CN1CCCC1=O>[C:39]([C:35]1[CH:36]=[CH:37][CH:38]=[C:33]([CH2:32][O:31][CH2:30][O:29][CH3:28])[CH:34]=1)#[CH:40]

Komponenten

10

Edukt 5

HCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 2724141Tetrabutylammonium FluorideHCID 114475781-Bromo-3-[(methoxymethoxy)methyl]benzene2×HCID 66707789(3-Methoxymethoxymethyl-phenylethynyl)-trimethyl-silane

Produkt 1

HCID 144816921-Ethynyl-3-methoxymethoxymethyl-benzene

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittelHCID 13387N-methyl-2-pyrrolidoneLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

To a mixture of 1-bromo-3-methoxymethoxymethyl-benzene (3.0 g, 13 mmol) described in Manufacturing Example 214-1-1, trimethylsilylacetylene (2.6 g, 26 mmol), N,N-diisopropylethylamine (3.4 g, 26 mmol), copper (I) iodide (500 mg, 2.6 mmol), and 1-methyl-2-pyrrolidone (30 mL) was added tetrakis(triphenylphosphine)palladium (0) (1.5 g, 1.3 mmol), which was stirred for 15 minutes at 60° C. This mixture was partitioned into ethyl acetate and water. The organic layer was separated and concentrated under a reduced pressure. The residue was purified by silica gel column chromatography (heptane:ethyl acetate=8:1) to obtain a mixture of (3-methoxymethoxymethyl-phenylethynyl)-trimethyl-silane and 1-bromo-3-methoxymethoxymethyl-benzene (3.0 g of mixture, including approximately 30% (3-methoxymethoxymethyl-phenylethynyl)-trimethyl-silane). Tetrabutylammonium fluoride (2 mL, 1 M tetrahydrofuran solution) was added to a tetrahydrofuran (20 mL) solution of this mixture, which was stirred for 15 minutes at room temperature. The reaction solution was partitioned into ethyl acetate and water. The organic layer was separated and concentrated under a reduced pressure. The residue was purified by silica gel column chromatography (heptane:ethyl acetate=20:1) to obtain 1-ethynyl-3-methoxymethoxymethyl-benzene (470 mg). To a methanol (10 mL) solution of this 1-ethynyl-3-methoxymethoxymethyl-benzene (470 mg, 2.6 mmol) was added 5 N hydrochloric acid, which was stirred for 25 minutes at 70° C. The reaction solution was partitioned into ethyl acetate and water. The organic layer was separated and concentrated under a reduced pressure to obtain the title compound (350 mg, 20%).

Aufarbeitung

  1. customThis mixture was partitioned into ethyl acetate and water
  2. customThe organic layer was separated
  3. concentrationconcentrated under a reduced pressure
  4. customThe residue was purified by silica gel column chromatography (heptane:ethyl acetate=8:1)
  5. customto obtain
  6. stirringwas stirred for 15 minutes at room temperature
  7. customThe reaction solution was partitioned into ethyl acetate and water
  8. customThe organic layer was separated
  9. concentrationconcentrated under a reduced pressure
  10. customThe residue was purified by silica gel column chromatography (heptane:ethyl acetate=20:1)

Quellen und Nachweise

ORD-Eintrag
ord-64d57b9ab8a04ac0af5307b420563e63
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08841327B2

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