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

HRID 84944

Reaction equation

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]

Participants

Conditions

Temperature: 50 °C

Procedure

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).

Workup

customIn a flask under nitrogen was placed
temperaturecooled
stirringstirred for 15 minutes
filtrationThe mixture was filtered
washthe precipitate washed with 25 mL of ethyl acetate
concentrationThe filtrate was concentrated

Sources & evidence

ORD record: ord-fad7574bf7b346bd8d9f520537762d70
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08846951B2

Linked notes

Loading…