Triphenylphosphine → 2-Methyl-5-trimethylsilanylethynyl-thiazole-4-carbonitrile

HRID 1443110ノート

反応式

HRID 1443110 の反応式
Br[C:2]1[S:6][C:5]([CH3:7])=[N:4][C:3]=1[C:8]#[N:9].[CH3:10][Si:11]([C:14]#[CH:15])([CH3:13])[CH3:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[CH3:7][C:5]1[S:6][C:2]([C:15]#[C:14][Si:11]([CH3:13])([CH3:12])[CH3:10])=[C:3]([C:8]#[N:9])[N:4]=1

参加物

8

反応物 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 8493835-Bromo-2-methylthiazole-4-carbonitrile

生成物 1

HCID 685385072-Methyl-5-trimethylsilanylethynyl-thiazole-4-carbonitrile

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒HCID 962Water溶媒HCID 8471Triethylamine溶媒

反応条件

温度
70 °C

実験手順

5-Bromo-2-methyl-thiazole-4-carbonitrile (4.8 g, 23.6 mmol) was suspended in 50 ml triethyl amine. Trimethylsilylacetylene (4.64 g, 47.3 mmol), triphenylphosphine (186 mg, 0.7 mmol) and bis(triphenylphosphine)palladium(II)chloride (0.83 g, 1.18 mmol) were added and this mixture was evacuated and purged with argon several times to remove oxygen from the solution. Copper(I)iodide (45 mg, 0.24 mmol) was added and the reaction mixture was stirred at 70° C. for 5 hrs. The residue was taken up in water, extracted three times with ethyl acetate and several times with water. The combined organic extracts were dried with sodium sulfate, filtered and evaporated. The crude product was purified by chromatography on silica gel (heptane/ethyl acetate 90:10->1:1 gradient). The desired product was obtained as a black solid (4.1 g, 79%).

後処理

  1. customthis mixture was evacuated
  2. custompurged with argon several times
  3. customto remove oxygen from the solution
  4. extractionextracted three times with ethyl acetate and several times with water
  5. dry with materialThe combined organic extracts were dried with sodium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude product was purified by chromatography on silica gel (heptane/ethyl acetate 90:10->1:1 gradient)

出典と根拠

ORDレコード
ord-7d3bfd896b1a405289e86edc6d6d7c1d
出典データセット
uspto-grants-2010_02
特許番号
US07659401B2

反応ノート

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