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Trimethylsilylacetylene → HCID 22630274, 화합물

HRID 2416355
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HRID 2416355 반응식
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]
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참가 물질

7

반응물 2

HCID 66111TrimethylsilylacetyleneHCID 22630272HCID 22630272, 화합물

생성물 1

HCID 22630274HCID 22630274, 화합물수율 51.5%

시약·촉매·용매 4

HCID 11776Triphenylphosphine촉매HCID 83717Copper iodide촉매HCID 178418476
HCID 178418476, 화합물
촉매
HCID 8471Triethylamine용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-0a977fdcd1ee425f8359479e2f8b9121
출처 데이터셋
uspto-grants-2004_11
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06824709B2

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