Acrylonitrile → (E)-Methyl 3-(2-cyanovinyl)benzo[b]thiophene-2-carboxylate

HRID 716002

反応式

HRID 716002 の反応式
Br[C:2]1[C:3]2[CH:14]=[CH:13][CH:12]=[CH:11][C:4]=2[S:5][C:6]=1[C:7]([O:9][CH3:10])=[O:8].C[N:16](C1CCCCC1)[CH:17]1CCC[CH2:19][CH2:18]1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C(#N)C=C>O1CCOCC1.C1(C)C=CC=CC=1.C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:17](/[CH:18]=[CH:19]/[C:2]1[C:3]2[CH:14]=[CH:13][CH:12]=[CH:11][C:4]=2[S:5][C:6]=1[C:7]([O:9][CH3:10])=[O:8])#[N:16]

参加物

9

反応物 4

HCID 7855AcrylonitrileHCID 24210N-Methyl dicyclohexylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 12238750Methyl 3-bromobenzo[b]thiophene-2-carboxylate

生成物 1

HCID 86647799(E)-Methyl 3-(2-cyanovinyl)benzo[b]thiophene-2-carboxylate

試薬・触媒・溶媒 4

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
50 °C

実験手順

In a flask under nitrogen was placed tris(dibenzylideneacetone)dipalladium(0) (313 mg, 0.34 mmol) in 25 mL of 1,4-dioxane followed by the product obtained from Example 97A (4.5 g, 16.7 mmol), N-methyldicyclohexylamine (3.91 g, 20.0 mmol), tri-tert-butylphosphine (0.68 mL of a 1.0 M solution in toluene, 0.68 mmol) and acrylonitrile (1.06 g, 20.0 mmol). The mixture was stirred and heated at 50° C. under nitrogen for 90 minutes and then cooled and diluted with 100 mL of ethyl acetate and stirred for 15 minutes. The mixture was filtered and the precipitate washed with 25 mL of ethyl acetate. The filtrate was concentrated and worked up as described in Example 55B to afford the title compound. 1H NMR (300 MHz, DMSO-d6) δ ppm 3.92 (s, 3H) 6.55 (d, J=17.29 Hz, 1H) 7.54-7.66 (m, 2H) 8.13-8.25 (m, 3H).

後処理

  1. customIn a flask under nitrogen was placed
  2. temperaturecooled
  3. stirringstirred for 15 minutes
  4. filtrationThe mixture was filtered
  5. washthe precipitate washed with 25 mL of ethyl acetate
  6. concentrationThe filtrate was concentrated

出典と根拠

ORDレコード
ord-43d92552c94b4738bd539b682608c777
出典データセット
uspto-grants-2015_11
特許番号
US09187483B2

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