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

HRID 84944

반응식

HRID 84944 반응식
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]

참가 물질

9

반응물 4

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

생성물 1

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

시약·촉매·용매 4

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

반응 조건

온도
50 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-fad7574bf7b346bd8d9f520537762d70
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08846951B2

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