Trimethylsilylacetylene → 1-Ethynyl-3-methoxymethoxymethyl-benzene

HRID 78264

反応式

HRID 78264 の反応式
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]

参加物

10

反応物 5

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

生成物 1

HCID 144816921-Ethynyl-3-methoxymethoxymethyl-benzene

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 8028Tetrahydrofuran溶媒HCID 13387N-methyl-2-pyrrolidone溶媒

反応条件

温度
60 °C

実験手順

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%).

後処理

  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)

出典と根拠

ORDレコード
ord-64d57b9ab8a04ac0af5307b420563e63
出典データセット
uspto-grants-2014_09
特許番号
US08841327B2

関連ノート

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