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

HRID 905563

반응식

HRID 905563 반응식
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]

참가 물질

7

반응물 4

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

생성물 1

HCID 230094142,6-Dimethyl-4-morpholin-4-yl-phenylamine수율 41%

시약·촉매·용매 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladium촉매HCID 1140Toluene용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-361715309f144525a3e8acc9f26de1a8
출처 데이터셋
uspto-grants-2011_09
특허 번호
US08012962B2

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