Water → HCID 10808872, Verbindung

HRID 865033Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 865033
[F:1][C:2]([F:10])([F:9])[C:3]([OH:8])([CH3:7])[C:4](O)=[O:5].S(Cl)(Cl)=O.[NH2:15][C:16]1[CH:21]=[CH:20][C:19]([S:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[C:18]([C:29]#[N:30])[CH:17]=1.O>CN(C)C(=O)C>[C:23]1([S:22][C:19]2[CH:20]=[CH:21][C:16]([NH:15][C:4](=[O:5])[C:3]([OH:8])([CH3:7])[C:2]([F:10])([F:9])[F:1])=[CH:17][C:18]=2[C:29]#[N:30])[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Komponenten

6

Edukt 4

HCID 962WaterHCID 24386Thionyl ChlorideHCID 1471779HCID 1471779, VerbindungHCID 27751253,3,3-Trifluoro-2-hydroxy-2-methylpropanoic acid

Produkt 1

HCID 10808872HCID 10808872, VerbindungAusbeute 158,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 31374DimethylacetamideLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

To a stirred, cooled (-20° C.) solution of 3,3,3-trifluoro-2-hydroxy-2-methylpropanoic acid (2.16 g 13.7 mmol) in N,N-dimethylacetamide (20 mL) was rapidly added thionyl chloride (1.73 g, 14.5 mmol) and the mixture (a precipitate formed after a few minutes) stirred at -20° C. to -10° C. for 1 hour. (4-Amino-2-cyanophenyl)phenyl sulfide (2.08 g, 9.2 mmol) was then added in one portion and the mixture allowed to stir at room temperature overnight. The solution was poured into 500 mL of water and extracted with two 100 mL portions of ethyl ether. The oil obtained in removal of the ethyl ether was chromatographed on 325 g of silica gel using an ethyl ether (0%, 5%, 10% and 20%) in methylene chloride gradient. The proper fractions were combined, the solvent removed in vacuo and the residue heated overnight at 60° C./0.1 mm to yield 5.35 g (93%) of N-(4-phenylthio-3-cyanophenyl)-3,3,3,-trifluoro-2-hydroxy-2-methylpropanamide, mp 124°-126° C. 1H-NMR (300 MHz, d6 -DMSO): 1.59 (s, 3H, CH3), 7.32-7.47 (m, 6H, aromatic), 7.59 (s, 1H, OH), 8.07 (dd 1H, J=8.8, 2.3 Hz, aromatic), 8.33 (d, 1H, J=2.3 Hz, aromatic), 10.48 (s, 1H, NH). MS (CI, CH4): 367(M+1).

Aufarbeitung

  1. customthe mixture (a precipitate formed after a few minutes)
  2. stirringto stir at room temperature overnight
  3. extractionextracted with two 100 mL portions of ethyl ether
  4. customThe oil obtained in removal of the ethyl ether
  5. customwas chromatographed on 325 g of silica gel using an ethyl ether (0%, 5%, 10% and 20%) in methylene chloride gradient
  6. customthe solvent removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-2f1e5da09c574ed2aca2033cedcc6d13
Quelldatensatz
uspto-grants-1996_10
Patentnummer
US05565465

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