Acetic Acid → HCID 19783238, Verbindung

HRID 257556Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 257556
C([NH:5][S:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:15]1[CH:20]=[CH:19][C:18]([CH2:21][CH:22]([C:32](=O)[CH2:33][CH2:34][CH2:35][CH3:36])[C:23](=NOC)[C:24]([O:26][CH2:27][CH3:28])=[O:25])=[CH:17][CH:16]=1)(=[O:8])=[O:7])(C)(C)C.Cl.[Cl:39][C:40]1[CH:45]=[CH:44][C:43]([N+:46]([O-:48])=[O:47])=[CH:42][C:41]=1[NH:49][NH2:50].C(O)(=O)C>COCCO>[CH2:33]([C:32]1[C:22]([CH2:21][C:18]2[CH:19]=[CH:20][C:15]([C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=3[S:6](=[O:8])(=[O:7])[NH2:5])=[CH:16][CH:17]=2)=[C:23]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[N:49]([C:41]2[CH:42]=[C:43]([N+:46]([O-:48])=[O:47])[CH:44]=[CH:45][C:40]=2[Cl:39])[N:50]=1)[CH2:34][CH2:35][CH3:36]

Komponenten

5

Edukt 3

HCID 176Acetic AcidHCID 53747773HCID 53747773, VerbindungHCID 67885116HCID 67885116, Verbindung

Produkt 1

HCID 19783238HCID 19783238, VerbindungAusbeute 49,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 80192-MethoxyethanolLösungsmittel

Reaktionsbedingungen

Temperatur
105 °C

Versuchsvorschrift

A mixture of 3.07 g (5.79 mmol) of ethyl 3-[[2'-(N-t-butylsulfamoyl)biphenyl-4-yl]methyl]-2-methoxyimino-4-oxooctanoate (from Step F), 5.00 g (22.3 mmol) of 2-chloro-5-nitrophenylhydrazine hydrochloride [prepared from 2-chloro-5-nitroaniline according to H. Stroh and G. Westphal, Chem. Ber., 96, 184 (1963)], 55 mL of glacial acetic acid, and 25 mL of 2-methoxyethanol was stirred under N2 at 105° C. for 20 hours. The cooled mixture was concentrated in vacuo and the residue was partitioned between 200 mL of 0.2N HCl and 200 mL of ethyl acetate. The organic layer was washed with H2O (200 mL), dried over Na2SO4, filtered, and concentrated. Flash chromatography of the residue twice on silica gel (first column eluted with 2% MeOH in CH2Cl2, second column eluted with 1% MeOH in CH2Cl2) to provide 1.71 g (47%) of the title compound as a viscous, orange oil; homogeneous by TLC in 98:2 CH2Cl2 --MeOH; mass spectrum (FAB) m/e 598 (M+1)+. 400 MHz 1H NMR (CDCl3) δ0.87 (t, J=7.3 Hz, 3H), 1.06 (t, J=7.1 Hz, 3H), 1.34 (m, 2H), 1.59 (m, 2H, partially obscured by H2O peak), 2.62 (t, J=7.8 Hz, 2H), 4.10 (s, 2H), overlapping 4.14 (q, J=7.0 Hz, 2H), 4.24 (s, 2H), 7.26 (d, J=8.2 Hz, 2H), 7.32 (dd, J=7.5, 1.3 Hz, 1H), 7.41 (d, J=8.2 Hz, 2H), 7.49 (m, 1H), 7.58 (m, 1H), 7.66 (d, J=8.8 Hz, 1 H), 8.14 (dd, J=7.9, 1.3 Hz, 1H), 8.26 (dd, J=8.8, 2.7 Hz, 1H), 8.36 (d, J=2.6 Hz, 1H).

Aufarbeitung

  1. concentrationThe cooled mixture was concentrated in vacuo
  2. customthe residue was partitioned between 200 mL of 0.2N HCl and 200 mL of ethyl acetate
  3. washThe organic layer was washed with H2O (200 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-4b80509caa9e430fbeedf2214468b12e
Quelldatensatz
uspto-grants-1993_11
Patentnummer
US05262412

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