Ethyl Acetate → HCID 21980758, compound

HRID 11132Notes

Reaction equation

HRID 11132 reaction equation
FC(F)(F)S(O[C:7]1[C:8]([O:32][CH3:33])=[CH:9][C:10]2[C:11]3[C:12]4[C:29](=[O:30])[NH:28][C:27](=[O:31])[C:13]=4[C:14]([C:20]4[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=4[Cl:26])=[CH:15][C:16]=3[NH:17][C:18]=2[CH:19]=1)(=O)=O.C([Sn](CCCC)(CCCC)/[CH:41]=[CH:42]/[CH2:43][CH2:44][OH:45])CCC.[Cl-].[Li+].C(OCC)(=O)C>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:26][C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][C:20]=1[C:14]1[C:13]2[C:27](=[O:31])[NH:28][C:29](=[O:30])[C:12]=2[C:11]2[C:10]3[CH:9]=[C:8]([O:32][CH3:33])[C:7](/[CH:41]=[CH:42]/[CH2:43][CH2:44][OH:45])=[CH:19][C:18]=3[NH:17][C:16]=2[CH:15]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 433294Lithium ChlorideHCID 110684124-(Tributylstannyl)but-3-en-1-olHCID 219804794-(2-Chlorophenyl)-9-methoxy-1,3-dioxo-1,2,3,6-tetrahydropyrrolo[3,4-c]carbazol-8-yl trifluoromethanesulfonate

Product 1

HCID 21980758HCID 21980758, compoundYield 95.9%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of the triflate (169) (0.20 g, 0.35 mmol) prepared as described in example 308, (3E)-4-(tributylstannyl)-3-buten-1-ol (0.19 g, 0.53 mmol) and lithium chloride (29 mg, 0.70 mmol) in DMF (10 mL) was purged by bubbling nitrogen through the liquid for 10 min. Bis(triphenylphosphine)palladium dichloride (12 mg, 0.017 mmol) was added last and the solution was flushed with nitrogen for 2 min more, then warmed under an atmosphere of nitrogen for 3 h. The mixture was diluted with brine, extracted with ethyl acetate and worked up to give an oil which was chromatographed on silica. Elution with ethyl acetate/petroleum ether (1:5) gave foreruns, while ethyl acetate/petroleum ether (1:1) increasing to pure ethyl acetate gave (170) as a yellow solid (0.15 g, 95%), mp 271–275° C. 1H NMR δ [(CD3)2SO] 11.86 (br s, 1H), 11.07 (br s, 1H), 8.45 (s, 1H), 7.70 (s, 1H), 7.58 (dd, J=8.1, 2.2 Hz, 1H), 7.55 (s, 1H), 7.51–7.41 (m, 3H), 6.87 (d, J=16.0 Hz, 1H), 6.44 (dt, J=16.0, 7.1 Hz, 1H), 4.62 (t, J=5.3 Hz, 1H), 3.94 (s, 3H), 3.58 (m, 2H), 2.42 (m, 2H). Found: C, 67.09; H, 4.36; N, 5.98. C25H19ClN2O4 requires C, 67.19; H, 4.28; N, 6.27.

Workup

  1. customwas purged
  2. customby bubbling nitrogen through the liquid for 10 min
  3. customthe solution was flushed with nitrogen for 2 min more
  4. temperaturewarmed under an atmosphere of nitrogen for 3 h
  5. additionThe mixture was diluted with brine
  6. extractionextracted with ethyl acetate
  7. customto give an oil which
  8. customwas chromatographed on silica
  9. washElution with ethyl acetate/petroleum ether (1:5)
  10. customgave foreruns

Sources & evidence

ORD record
ord-8fb542c851a94841addcbc8f675fb840
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

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