Acetonitrile → 5-(6,7-Dihydropyrido[3,2-b]thieno[2,3-d]oxepin-9-yl)pyridin-2-amine

HRID 84448

Reaktionsgleichung

Reaktionsgleichung von HRID 84448
Br[C:2]1[S:15][C:5]2[C:6]3[N:14]=[CH:13][CH:12]=[CH:11][C:7]=3[O:8][CH2:9][CH2:10][C:4]=2[CH:3]=1.[NH2:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][N:18]=1.C(#N)C>C(=O)([O-])[O-].[Na+].[Na+].O.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>[N:14]1[C:6]2[C:5]3[S:15][C:2]([C:20]4[CH:21]=[CH:22][C:17]([NH2:16])=[N:18][CH:19]=4)=[CH:3][C:4]=3[CH2:10][CH2:9][O:8][C:7]=2[CH:11]=[CH:12][CH:13]=1

Komponenten

7

Edukt 3

HCID 6342AcetonitrileHCID 22396308(6-Aminopyridin-3-yl)boronic acidHCID 579004919-Bromo-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine

Produkt 1

HCID 442423665-(6,7-Dihydropyrido[3,2-b]thieno[2,3-d]oxepin-9-yl)pyridin-2-amineAusbeute 36 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418476HCID 178418476, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 10340Sodium CarbonateLösungsmittel

Versuchsvorschrift

A mixture of 9-bromo-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine (113 mg, 0.400 mmol), 2-aminopyridine-5-boronic acid, pinacol ester (96.8 mg, 0.440 mmol) and bis(triphenylphosphine)palladium(II) chloride (14.0 mg, 0.0200 mmol) in 1.0 M of sodium carbonate in water (0.500 mL) and acetonitrile (3 mL, 60 mmol) was degassed and microwaved on 300 watts at 140° C. for 20 minutes. The reaction mixture was partitioned between ethyl acetate and water and filtered from inorganic salts. The organic layer was washed with water, brine, dried over MgSO4 and evaporated to dryness. The crude residue was purified on silicagel column, eluting with 50% of ethyl acetate in methylene chloride to give 142 (yield 43 mg, 36%). 1H NMR (400 MHz, DMSO-d6) δ 8.27 (d, J=2.3, 1H), 8.21 (dd, J=1.4, 4.5, 1H), 7.68 (dd, J=2.5, 8.6, 1H), 7.38 (dd, J=1.4, 8.1, 1H), 7.21 (s, 1H), 7.17 (dd, J=4.5, 8.1, 1H), 6.50 (d, J=8.7, 1H), 6.21 (s, 2H), 4.32 (t, J=4.8, 2H), 3.19 (t, J=4.8, 2H). MS: (ESI+) 296.1

Aufarbeitung

  1. custommicrowaved on 300 watts at 140° C. for 20 minutes
  2. customThe reaction mixture was partitioned between ethyl acetate and water
  3. filtrationfiltered from inorganic salts
  4. washThe organic layer was washed with water, brine
  5. dry with materialdried over MgSO4
  6. customevaporated to dryness
  7. customThe crude residue was purified on silicagel column
  8. washeluting with 50% of ethyl acetate in methylene chloride

Quellen und Nachweise

ORD-Eintrag
ord-533d94fac4454b6d995c4e31ed3a856a
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08846762B2

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