Morpholine → 2,6-Dimethyl-4-morpholin-4-yl-phenylamine

HRID 905563

反応式

HRID 905563 の反応式
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.CC(C)([O-])C.[K+].[NH:53]1[CH2:58][CH2:57][O:56][CH2:55][CH2:54]1.Br[C:60]1[CH:66]=[C:65]([CH3:67])[C:63]([NH2:64])=[C:62]([CH3:68])[CH:61]=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].C1(C)C=CC=CC=1>[CH3:68][C:62]1[CH:61]=[C:60]([N:53]2[CH2:58][CH2:57][O:56][CH2:55][CH2:54]2)[CH:66]=[C:65]([CH3:67])[C:63]=1[NH2:64]

参加物

7

反応物 4

HCID 8083MorpholineHCID 905494-Bromo-2,6-xylidineHCID 634876Binap, (A+-)-HCID 23665647Potassium tert-butoxide

生成物 1

HCID 230094142,6-Dimethyl-4-morpholin-4-yl-phenylamine収率 41%

試薬・触媒・溶媒 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium触媒HCID 1140Toluene溶媒

実験手順

Bis(dibenzylideneacetone)palladium (2.88 g) and (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (4.69 g) were added to dry toluene (175 mL purged with argon) and stirred for 15 minutes under argon. Potassium tert-butoxide (7.06 g), morpholine (8.7 mL) and 4-bromo-2,6-dimethylaniline (10.03 g) were added subsequently. The reaction mixture was heated to reflux for 16 hours under argon, cooled and filtered through silica (200 g). Brine (250 mL) was added and the mixture was extracted with ethyl acetate (3×200 mL). The combined organic phases were dried over magnesium sulfate and concentrated in vacuo. The crude product was dissolved in diethyl ether (250 mL), filtered through silica (200 g) and concentrated in vacuo to furnish 8.5 g (41% yield) of the title compound as a dark oil. The product was used without further purification. GC-MS (m/z) 206 (M+); tR=6.90. 1H NMR (500 MHz, CDCl3): 2.18 (s, 6H), 3.02 (m, 4H), 3.85 (m, 4H), 6.62 (b, 2H).

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 16 hours under argon
  3. temperaturecooled
  4. filtrationfiltered through silica (200 g)
  5. additionBrine (250 mL) was added
  6. extractionthe mixture was extracted with ethyl acetate (3×200 mL)
  7. dry with materialThe combined organic phases were dried over magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. dissolutionThe crude product was dissolved in diethyl ether (250 mL)
  10. filtrationfiltered through silica (200 g)
  11. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-361715309f144525a3e8acc9f26de1a8
出典データセット
uspto-grants-2011_09
特許番号
US08012962B2

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