Acetonitrile → (E)-3-{4-[6-Hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophene-3-carbonyl]phenyl}-N,N-dimethylacrylamide

HRID 400199Notes

Reaction equation

HRID 400199 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[C:11]3[CH:25]=[CH:24][C:23]([OH:26])=[CH:22][C:12]=3[S:13][C:14]=2[C:15]2[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=2)=[O:9])=[CH:4][CH:3]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[CH3:49][N:50]([CH3:55])[C:51](=[O:54])[CH:52]=[CH2:53].C(#N)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(N(CC)CC)C>[OH:26][C:23]1[CH:24]=[CH:25][C:11]2[C:10]([C:8]([C:5]3[CH:6]=[CH:7][C:2](/[CH:53]=[CH:52]/[C:51]([N:50]([CH3:55])[CH3:49])=[O:54])=[CH:3][CH:4]=3)=[O:9])=[C:14]([C:15]3[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=3)[S:13][C:12]=2[CH:22]=1

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 17587N,N-DimethylacrylamideHCID 80271Tri-o-tolylphosphineHCID 189443264-Bromophenyl-[6-Hydroxy-2-(4-hydroxyphenyl)benzo[b]thien-3-yl]methanone

Product 1

HCID 18944330(E)-3-{4-[6-Hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophene-3-carbonyl]phenyl}-N,N-dimethylacrylamideYield 71%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
85 °C

Procedure

To a screw cap seal tube is added 0.84 g (2.0 mmol) of the product from Example 2, 0.20 g (0.66 mmol) of tri-o-tolylphosphine, 0.21 g (2.1 mmol) of N,N-dimethyl acrylamide, 0.040 g (0.2 mmol) of palladium acetate, 40 mL of acetonitrile and 4 mL of triethylamine. The solution was purged with nitrogen then capped and heated to 85° C. for 3 hours. At the end of this time, the solution was concentrated, then taken up in 100 mL of water:ethyl acetate (1:2). The organic layer was separated and the water layer extracted once with ethyl acetate. The ethyl acetate layers were combined, dried (MgSO4) and concentrated an the residue subjected to column chromatography on silica. Elution with 50% ethyl acetate:hexane then ethyl acetate:hexane:isopropanol (60:35:5) yielded 0.63 g of product which was crystallized from chloroform:acetone:hexane to yield 0.47 g of product as a yellow solid, m.p. 208°-211° C.

Workup

  1. customTo a screw cap
  2. customseal tube
  3. customThe solution was purged with nitrogen
  4. customthen capped
  5. concentrationAt the end of this time, the solution was concentrated
  6. customThe organic layer was separated
  7. extractionthe water layer extracted once with ethyl acetate
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated an the residue
  10. washElution with 50% ethyl acetate

Sources & evidence

ORD record
ord-2434be40000f4e61ab960d5e3d29f43e
Source dataset
uspto-grants-1998_10
Patent number
US05827876

Reaction notes

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