Allyltributylstannane → HCID 18979997, compound

HRID 2256991Notes

Reaction equation

HRID 2256991 reaction equation
O1C=[CH:4][CH:3]=[C:2]1P(C1OC=CC=1)C1OC=CC=1.[Cl:17][C:18]1[CH:19]=[CH:20][C:21]2[C:27](=[O:28])[C:26](I)=[C:25]([O:30][CH3:31])[C:24](=[O:32])[NH:23][C:22]=2[CH:33]=1.C([Sn](CCCC)(CCCC)CCCC)C=C>C1(C)C=CC=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]>[CH2:4]([C:26]1[C:27](=[O:28])[C:21]2[CH:20]=[CH:19][C:18]([Cl:17])=[CH:33][C:22]=2[NH:23][C:24](=[O:32])[C:25]=1[O:30][CH3:31])[CH:3]=[CH2:2]

Participants

6

Reactant 3

HCID 90628AllyltributylstannaneHCID 521585Tris(furan-2-yl)phosphaneHCID 18980002HCID 18980002, compound

Product 1

HCID 18979997HCID 18979997, compoundYield 831.6%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent

Procedure

A solution of tri(2-furyl)phosphine (0.019 g) and tris-(dibenzylideneacetone)dipalladium(O) (0.020 g) in toluene (25 mL) was allowed to stir for 10 minutes. To this solution was added 8-chloro-4-iodo-3-methoxy-2,5-dioxo-2,5-dihydro-1H-benz[b]azepine (0.750 g), followed by allyltributyltin (0.83 g). The reaction mixture was heated to reflux for 16 hours, was allowed to cool, and the toluene was evaporated. The residue was dissolved in ethyl acetate, and the resulting solution was filtered through silica gel and stirred over an equal volume of 1 molar aqueous potassium fluoride for 0.5 hour. The organic portion was separated, washed (water, brine), dried, filtered through diatomaceous earth and evaporated. The resulting orange solid was triturated with hexanes and subsequently chromatographed, with ethyl acetate:hexanes (5:1) as the eluent, to afford the title compound (0.189 g); mp 135°-136° C.; NMR: 11.43 (broad s,1), 7.63 (d,1, J=8.5), 7.36 (d,1, J=2.0), 7.29 (dd,1, J=8.6, 1.9), 5.85-5.72 (m,1), 5.00-4.96 (m,1), 4.94 (m,1), 3.80 (s,3), 3.28 (m,2). Analysis for C14H12ClNO3 0.25 H2O.: Calculated: C, 59.58; H, 4.46; N, 4.96; N, 4.96; Found C, 59,74; H, 4.39; N, 4.93.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 16 hours
  3. temperatureto cool
  4. customthe toluene was evaporated
  5. dissolutionThe residue was dissolved in ethyl acetate
  6. filtrationthe resulting solution was filtered through silica gel
  7. stirringstirred over an equal volume of 1 molar aqueous potassium fluoride for 0.5 hour
  8. customThe organic portion was separated
  9. washwashed (water, brine)
  10. customdried
  11. filtrationfiltered through diatomaceous earth
  12. customevaporated
  13. customThe resulting orange solid was triturated with hexanes
  14. customsubsequently chromatographed, with ethyl acetate:hexanes (5:1) as the eluent

Sources & evidence

ORD record
ord-b1a7ab27941e4f9e85fe283c7a1a7cc2
Source dataset
uspto-grants-1997_08
Patent number
US05656626

Reaction notes

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