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

HRID 716002

Reaktionsgleichung

Reaktionsgleichung von HRID 716002
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]

Komponenten

9

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-43d92552c94b4738bd539b682608c777
Quelldatensatz
uspto-grants-2015_11
Patentnummer
US09187483B2

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