Morpholine → HCID 86699753, Verbindung

HRID 515186Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 515186
Br[C:2]1[CH:9]=[C:8]([CH3:10])[C:5]([C:6]#[N:7])=[C:4]([O:11][CH3:12])[CH:3]=1.[NH:13]1[CH2:18][CH2:17][O:16][CH2:15][CH2:14]1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[CH3:12][O:11][C:4]1[CH:3]=[C:2]([N:13]2[CH2:18][CH2:17][O:16][CH2:15][CH2:14]2)[CH:9]=[C:8]([CH3:10])[C:5]=1[C:6]#[N:7]

Komponenten

8

Edukt 4

HCID 8083MorpholineHCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 454803844-bromo-2-methoxy-6-methylbenzonitrile

Produkt 1

HCID 86699753HCID 86699753, VerbindungAusbeute 29 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

A solution of 4-bromo-2-methoxy-6-methyl-benzonitrile (synthesized according to the methods described in sections a) and b) of example 10) (2.0 g, 8.85 mmol), morpholine (1.2 ml, 12.8 mmol) and caesium carbonate (3.9 g, 12.0 mmol) in toluene (75 ml) is degassed and flushed with argon for 30 min and the mixture is heated to 40° C. followed by the addition of tris(dibenzylideneacetone)-dipalladium(0) (0.37 g, 0.39 mmol) and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.55 g, 0.88 mmol). The resulting mixture is stirred at 110° C. for 16 h. After completion of the reaction (monitored by TLC), the mixture is poured into water (60 ml) and extracted with ethyl acetate (3×50 ml).The combined organic layers are washed with water (2×50 ml), brine (2×30 ml), dried over sodium sulfate and concentrated in vacuo. The crude product is purified by flash column chromatography (silica gel, 25% ethyl acetate/hexane) affording 2-methoxy-6-methyl-4-morpholin-4-yl-benzonitrile (0.6 g, 2.58 mmol, 29%).

Aufarbeitung

  1. customis degassed
  2. customflushed with argon for 30 min
  3. customAfter completion of the reaction (monitored by TLC)
  4. extractionextracted with ethyl acetate (3×50 ml).The combined organic layers
  5. washare washed with water (2×50 ml), brine (2×30 ml)
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe crude product is purified by flash column chromatography (silica gel, 25% ethyl acetate/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-b9f1362256f24bbab7defc92f686036e
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09108936B2

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