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Cesium carbonate → Tert-butyl 2-[4-[4-(trifluoromethylsulfonyl)anilino]cyclohexoxy]acetate

HRID 1772290
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1772290
[NH2:1][CH:2]1[CH2:7][CH2:6][CH:5]([O:8][CH2:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:4][CH2:3]1.Br[C:18]1[CH:23]=[CH:22][C:21]([S:24]([C:27]([F:30])([F:29])[F:28])(=[O:26])=[O:25])=[CH:20][CH:19]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[F:29][C:27]([F:28])([F:30])[S:24]([C:21]1[CH:22]=[CH:23][C:18]([NH:1][CH:2]2[CH2:7][CH2:6][CH:5]([O:8][CH2:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:4][CH2:3]2)=[CH:19][CH:20]=1)(=[O:25])=[O:26]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 3

HCID 10796Cesium carbonateHCID 3001141-Bromo-4-trifluoromethanesulfonylbenzeneHCID 10680931Tert-butyl 2-(4-aminocyclohexoxy)acetate

Produkt 1

HCID 86719526Tert-butyl 2-[4-[4-(trifluoromethylsulfonyl)anilino]cyclohexoxy]acetateAusbeute 98,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845
palladium(II) acetate
Katalysator
HCID 634876Binap, (A+-)-Katalysator
HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A suspension of tert-butyl 2-(4-aminocyclohexoxy)acetate (0.5 g, 1.7 mmol, 1 eq.), 1-bromo-4-(trifluoromethylsulfonyl)benzene (0.4 g, 1.7 mmol, 1 eq.), cesium carbonate (1.4 g, 4.3 mmol, 2.5 eq.), and BINAP (54 mg, 0.08 mmol, 0.05 eq.), in toluene (15 mL), was bubbled with nitrogen for 10 minutes before the addition of Pd(OAc)2 (19 mg, 0.08 mmol, 0.05 eq.) to the reaction mixture. Nitrogen gas was bubbled through the reaction mixture for another 10 minutes and the contents were heated at 100° C. under nitrogen atmosphere for 3 hours. The contents were cooled to room temperature, diluted with ethyl acetate, filtered through Celite®, and concentrated. The crude material was purified by silica gel column chromatography using ethyl acetate/heptanes to elute. The product containing fractions were combined and concentrated to obtain tert-butyl 2-[4-[4-(trifluoromethylsulfonyl)anilino]cyclohexoxy]acetate (0.73 g, 77%); (CI, m/z): [M+H]+ 438; 1H NMR (400 MHz, CDCl3): δ 7.74 (d, J=8.9 Hz, 2H), 6.56-6.70 (m, 2H), 4.44 (d, J=7.4 Hz, 1H), 4.02 (s, 2H), 3.32-3.49 (m, 2H), 2.07-2.25 (m, 4H), 1.44-1.55 (m, 11H), 1.21-1.35 (m, 2H).

Aufarbeitung

  1. customNitrogen gas was bubbled through the reaction mixture for another 10 minutes
  2. temperatureThe contents were cooled to room temperature
  3. additiondiluted with ethyl acetate
  4. filtrationfiltered through Celite®
  5. concentrationconcentrated
  6. customThe crude material was purified by silica gel column chromatography
  7. washto elute
  8. additionThe product containing fractions
  9. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-20714f17df9d4fc2a4b2a7d3457beb87
Quelldatensatz
uspto-grants-2016_02
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09249102B2

Notizen zur Reaktion

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