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Tri-o-tolylphosphine → (E)-3-(3,3-Dimethyl-2-oxo-2,3,4,5-tetrahydro-1H-pyrido[2,3-e][1,4]diazepin-7-yl)-N-(3-isopropyl-2-propoxybenzyl)-N-methylacrylamide

HRID 2097037
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2097037
[CH:1]([C:4]1[C:5]([O:17][CH2:18][CH2:19][CH3:20])=[C:6]([CH:14]=[CH:15][CH:16]=1)[CH2:7][N:8]([CH3:13])[C:9](=[O:12])[CH:10]=[CH2:11])([CH3:3])[CH3:2].C(N(C(C)C)CC)(C)C.Br[C:31]1[CH:44]=[N:43][C:34]2[NH:35][C:36](=[O:42])[C:37]([CH3:41])([CH3:40])[NH:38][CH2:39][C:33]=2[CH:32]=1.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)CC.CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:40][C:37]1([CH3:41])[C:36](=[O:42])[NH:35][C:34]2[N:43]=[CH:44][C:31](/[CH:11]=[CH:10]/[C:9]([N:8]([CH2:7][C:6]3[CH:14]=[CH:15][CH:16]=[C:4]([CH:1]([CH3:3])[CH3:2])[C:5]=3[O:17][CH2:18][CH2:19][CH3:20])[CH3:13])=[O:12])=[CH:32][C:33]=2[CH2:39][NH:38]1
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Komponenten

8

Edukt 4

HCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 59277555N-(3-Isopropyl-2-propoxybenzyl)-N-methylacrylamideHCID 594569147-Bromo-3,3-dimethyl-1,3,4,5-tetrahydropyrido[2,3-e][1,4]diazepin-2-one

Produkt 1

HCID 16659657(E)-3-(3,3-Dimethyl-2-oxo-2,3,4,5-tetrahydro-1H-pyrido[2,3-e][1,4]diazepin-7-yl)-N-(3-isopropyl-2-propoxybenzyl)-N-methylacrylamide
Ausbeute 31 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 7854PropionitrileLösungsmittel

Versuchsvorschrift

A solution of N-(3-isopropyl-2-propoxybenzyl)-N-methylacrylamide (0.397 g, 1.47 mmol) in propionitrile (5 mL) and DMF (1 mL) was deoxygenated with Ar for 20 min. The solution was treated with diisopropylethylamine (0.40 mL, 2.33 mmol) and 7-bromo-3,3-dimethyl-1,3,4,5-tetrahydro-pyrido[2,3-e][1,4]diazepin-2-one (0.300 g, 1.11 mmol). The solution was deoxygenated with Ar for 20 min. Pd(OAc)2 (0.024 g, 0.111 mmol) and P(o-tol)3 (0.067 g, 0.222 mmol) were then added and the mixture deoxygenated with Ar for 20 min. The mixture was heated to reflux for 18 h, then allowed to cool. The solution was diluted with EtOAc (30 mL) and H2O (50 mL). The aqueous layer was extracted with EtOAc (3×50 mL). The combined organics were washed with brine (2×100 mL), dried over Na2SO4, filtered and concentrated to an orange oil. Purification by column chromatography (silica gel, CH2Cl2/MeOH, 100 to 95:5) gave the title compound (0.16 g, 31%) as an off-white solid and as a mixture of amide rotamers: 1H NMR (300 MHz, DMSO-d6) δ 9.80-9.77 (m, 1H), 8.40-8.35 (m, 1H), 8.01-7.91 (m, 1H), 7.55-7.48 (m, 1H), 7.31-7.20 (m, 2H), 7.10-7.03 (m, 1H), 6.88-6.85 (m, 1H), 4.81-4.66 (m, 2H), 3.90-3.83 (m, 2H), 3.77-3.69 (m, 2H), 3.32-3.25 (m, 1H), 3.12-2.90 (m, 4H), 1.81-1.77 (m, 2H), 1.31-1.28 (m, 6H), 1.19-1.17 (m, 6H), 1.06-1.01 (3H).

Aufarbeitung

  1. customThe solution was deoxygenated with Ar for 20 min
  2. customthe mixture deoxygenated with Ar for 20 min
  3. temperatureThe mixture was heated
  4. temperatureto reflux for 18 h
  5. temperatureto cool
  6. additionThe solution was diluted with EtOAc (30 mL) and H2O (50 mL)
  7. extractionThe aqueous layer was extracted with EtOAc (3×50 mL)
  8. washThe combined organics were washed with brine (2×100 mL)
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated to an orange oil
  12. customPurification by column chromatography (silica gel, CH2Cl2/MeOH, 100 to 95:5)

Quellen und Nachweise

ORD-Eintrag
ord-83834114baf549f98ea9d9880d4f9ed5
Quelldatensatz
uspto-grants-2013_05
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08450307B2

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