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Trimethylsilylacetylene → HCID 22630274、化合物

HRID 2416355
ノート
印刷プレビュー

反応式

HRID 2416355 の反応式
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([O:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])=[CH:9][CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.[CH3:21][Si:22]([C:25]#[CH:26])([CH3:24])[CH3:23]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>[CH2:16]([O:15][C:8]1[CH:9]=[CH:10][C:11]2[C:12]3[C:4](=[CH:3][C:2]([C:26]#[C:25][Si:22]([CH3:24])([CH3:23])[CH3:21])=[CH:14][CH:13]=3)[CH2:5][C:6]=2[CH:7]=1)[CH2:17][CH2:18][CH2:19][CH3:20]
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 2

HCID 66111TrimethylsilylacetyleneHCID 22630272HCID 22630272、化合物

生成物 1

HCID 22630274HCID 22630274、化合物収率 51.5%

試薬・触媒・溶媒 4

HCID 11776Triphenylphosphine触媒HCID 83717Copper iodide触媒HCID 178418476
HCID 178418476、化合物
触媒
HCID 8471Triethylamine溶媒

実験手順

A mixture of 2-bromo-7-pentyloxyfluorene (12 g), trimethylsilylacetylene (7.1 g), dichlorobis(triphenylphosphine)palladium (0.3 g), copper iodide (0.08 g), triphenylphosphine (0.2 g) and triethylamine (200 mL) was heated for 3 hours while refluxing. Insoluble matters were removed from the reaction mixture by filtration, and triethylamine was distilled off under reduced pressure. The residue was purified by means of column chromatography (silica gel, eluting solvent: toluene) to obtain 6.5 g of 2-pentyloxy-7-trimethylsilylethynylfluorene. This was dissolved in tetrahydrofuran (100 mL) and cooled down to −60° C. on a dry ice-acetone bath. A 1M solution (46 mL) of tetraethylammonium fluoride was added thereto, and then the dry ice-acetone bath was removed, followed by stirring the solution until the temperature came up to −10° C. At a point of time when −10° C. was reached, water (30 mL) was added and stirred until the temperature came up to a room temperature, and then water was further added to terminate the reaction. The product was extracted with toluene, and the toluene layer was dried on anhydrous magnesium sulfate. A residue obtained by distilling the solvent off was purified by means of column chromatography (silica gel, eluting solvent: toluene). Then, it was recrystallized from ethanol to obtain 2-pentyloxy-7-ethynylfluorene (5 g) of colorless needle crystal. The melting point of this compound was 108° C.

後処理

  1. temperaturewas heated for 3 hours
  2. temperaturewhile refluxing
  3. customInsoluble matters were removed from the reaction mixture by filtration, and triethylamine
  4. distillationwas distilled off under reduced pressure
  5. customThe residue was purified by means of column chromatography (silica gel, eluting solvent: toluene)

出典と根拠

ORDレコード
ord-0a977fdcd1ee425f8359479e2f8b9121
出典データセット
uspto-grants-2004_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06824709B2

反応ノート

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