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

HRID 602615Notes

Reaction equation

HRID 602615 reaction equation
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

Participants

6

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

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, 119 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.

Workup

  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, 119 to 1:4)

Sources & evidence

ORD record
ord-6bf0b01cdd9c49b0a62125bb69791566
Source dataset
uspto-grants-2011_03
Patent number
US07906538B2

Reaction notes

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