Acetic Acid → N-{4-chloro-2-[(4-chlorophenoxyimino)phenylmethyl]phenyl}trifluoromethanesulfonamide

HRID 970874Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 970874
CN(C)CCN.Cl.[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][NH2:16])=[CH:11][CH:10]=1.C(O)(=O)C.[C:21]([C:29]1[CH:34]=[C:33]([Cl:35])[CH:32]=[CH:31][C:30]=1[NH:36][S:37]([C:40]([F:43])([F:42])[F:41])(=[O:39])=[O:38])(=O)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>CCO>[Cl:35][C:33]1[CH:32]=[CH:31][C:30]([NH:36][S:37]([C:40]([F:43])([F:41])[F:42])(=[O:39])=[O:38])=[C:29]([C:21](=[N:16][O:15][C:12]2[CH:13]=[CH:14][C:9]([Cl:8])=[CH:10][CH:11]=2)[C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)[CH:34]=1

Komponenten

6

Edukt 4

HCID 176Acetic AcidHCID 66053N,N-DimethylethylenediamineHCID 20445467O-(4-chlorophenyl)hydroxylamine hydrochlorideHCID 67271057N-(2-benzoyl-4-chlorophenyl)trifluoromethanesulfonamide

Produkt 1

HCID 72491662N-{4-chloro-2-[(4-chlorophenoxyimino)phenylmethyl]phenyl}trifluoromethanesulfonamideAusbeute 61 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel2×

Versuchsvorschrift

N,N-Dimethylethylenediamine (82 μL, 0.75 mmol) was added to a suspension of O-(4-chlorophenyl)hydroxylamine hydrochloride (141 mg, 0.51 mmol) in EtOH (15 mL), and the reaction allowed to stir at RT for 15 hours. Glacial acetic acid (3 mL) was then added to adjust the mixture to ca. pH 4 followed by a solution of N-(2-benzoyl-4-chlorophenyl)trifluoromethanesulfonamide 25 (170 mg, 0.47 mmol) in EtOH (5 mL), and the reaction stirred for 63 hours at RT. The reaction mixture was concentrated under vacuum, and the residue dissolved in CH2Cl2 (50 mL), washed with water (twice), brine, dried over MgSO4 and the solvent evaporated under reduced pressure. The residue was filtered through a pad of silica (eluting with CH2Cl2/PE, 3:7) and purified by radial thin layer chromatography (eluting with CH2Cl2/PE, 1:19 to 1:4) to afford N-{4-chloro-2-[(4-chlorophenoxyimino)phenylmethyl]phenyl}trifluoromethanesulfonamide 164 (140 mg, 61%), as a orange-brown solid. M.p. 86-87° C. 1H n.m.r. (200 MHz, CDCl3) δ 10.99, br s, 1H; 7.73, d, J=8.8 Hz, 1H; 7.54, m, 3H; 7.43-7.27, m, 5H; 7.07, m, 1H; 7.01, m, 2H. O-(4-Chlorophenyl)hydroxylamine hydrochloride was prepared by the procedure described in Example 2C.

Aufarbeitung

  1. stirringthe reaction stirred for 63 hours at RT
  2. concentrationThe reaction mixture was concentrated under vacuum
  3. dissolutionthe residue dissolved in CH2Cl2 (50 mL)
  4. washwashed with water (twice), brine
  5. dry with materialdried over MgSO4
  6. customthe solvent evaporated under reduced pressure
  7. filtrationThe residue was filtered through a pad of silica (eluting with CH2Cl2/PE, 3:7)
  8. custompurified by radial thin layer chromatography (eluting with CH2Cl2/PE, 1:19 to 1:4)

Quellen und Nachweise

ORD-Eintrag
ord-c22cb3121a764e9f845e099d72fb193a
Quelldatensatz
uspto-grants-2007_12
Patentnummer
US07312248B2

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