Cyclopentanone → 5-Cyclopentylidenemethylthiophene-2-carbonitrile

HRID 35926

反応式

HRID 35926 の反応式
Br[CH2:2][C:3]1[S:7][C:6]([C:8]#[N:9])=[CH:5][CH:4]=1.P(OCC)(OCC)OCC.[C:20]1(=O)[CH2:24][CH2:23][CH2:22][CH2:21]1.[H-].[Na+]>O1CCCC1.C1OCCOCCOCCOCCOC1>[C:20]1(=[CH:2][C:3]2[S:7][C:6]([C:8]#[N:9])=[CH:5][CH:4]=2)[CH2:24][CH2:23][CH2:22][CH2:21]1

参加物

7

反応物 4

HCID 8452CyclopentanoneHCID 24758Sodium hydrideHCID 31215Triethyl phosphiteHCID 105600165-(Bromomethyl)thiophene-2-carbonitrile

生成物 1

HCID 199395365-Cyclopentylidenemethylthiophene-2-carbonitrile

試薬・触媒・溶媒 2

HCID 3633615-Crown-5触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

In a second process, 20 g of 5-bromomethylthiophene-2-carbonitrile is heated with 200 ml of triethyl phosphite for 4 hours to 150°. Then triethyl phosphite is removed at 40°-60°/0.06 mbar, and the residue is distilled on a bulb tube at 130°-150°/0.004 mbar, resulting in 24 g of (5-cyano-2-thienyl)methylphosphonic acid diethyl ester. Of this product, 5 g is added dropwise, with 1.5 ml of cyclopentanone in 5 ml of tetrahydrofuran, to a suspension of 581 mg of sodium hydride/oil (80% strength) and 116 mg of 15-crown-5 in 5 ml of tetrahydrofuran. After 2 hours of agitation at room temperature, the mixture is poured on water and extracted with ethyl acetate. The ethyl acetate phase is dried and evaporated, and the residue is recrystallized from isopropanol, thus obtaining 3.0 g of 5-cyclopentylidenemethylthiophene-2-carbonitrile, identical to the product described above.

後処理

  1. customThen triethyl phosphite is removed at 40°-60°/0.06 mbar
  2. distillationthe residue is distilled on a bulb tube at 130°-150°/0.004 mbar
  3. customresulting in 24 g of (5-cyano-2-thienyl)methylphosphonic acid diethyl ester
  4. additionthe mixture is poured on water
  5. extractionextracted with ethyl acetate
  6. dry with materialThe ethyl acetate phase is dried
  7. customevaporated
  8. customthe residue is recrystallized from isopropanol

出典と根拠

ORDレコード
ord-05be005f6337417b880409a441dae2b1
出典データセット
uspto-grants-1995_05
特許番号
US05411982

関連ノート

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