Acetic Acid → 2-[1-(2,5-Bistrifluoromethylbenzyloxyimino)ethyl]-4-chlorophenyltrifluoromethanesulfonamide

HRID 602594Notes

Reaction equation

HRID 602594 reaction equation
[C:1]([C:4]1[CH:9]=[C:8]([Cl:10])[CH:7]=[CH:6][C:5]=1[NH:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])(=O)[CH3:2].Cl.[F:20][C:21]([F:36])([F:35])[C:22]1[CH:30]=[CH:29][C:28]([C:31]([F:34])([F:33])[F:32])=[CH:27][C:23]=1[CH2:24][O:25][NH2:26].CC([O-])=O.[Na+].CC(O)=O>CO.O>[F:20][C:21]([F:35])([F:36])[C:22]1[CH:30]=[CH:29][C:28]([C:31]([F:34])([F:32])[F:33])=[CH:27][C:23]=1[CH2:24][O:25][N:26]=[C:1]([C:4]1[CH:9]=[C:8]([Cl:10])[CH:7]=[CH:6][C:5]=1[NH:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])[CH3:2]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 517045Sodium AcetateHCID 67271047N-(2-acetyl-4-chlorophenyl)trifluoromethanesulfonamideHCID 86230469O-(2,5-bistrifluoromethylbenzyl)hydroxylamine hydrochloride

Product 1

HCID 866039952-[1-(2,5-Bistrifluoromethylbenzyloxyimino)ethyl]-4-chlorophenyltrifluoromethanesulfonamideYield 19%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A solution of N-(2-acetyl-4-chlorophenyl)trifluoromethanesulfonamide 19 (300 mg, 0.99 mmol), O-(2,5-bistrifluoromethylbenzyl)hydroxylamine hydrochloride (296 mg, 1.0 mmol) and anhydrous NaOAc (53 mg, 0.65 mmol) in MeOH (5 mL) and H2O (15 mL) was adjusted to pH 4.5 with AcOH and heated for 15 h at reflux. The reaction mixture was concentrated under vacuum and the residue filtered through a pad of silica (eluting with CH2Cl2). Purification by radial thin layer chromatography (eluting with CH2Cl2/PE, 1:19 to 1:9) afforded N-{2-[1-(2,5-bistrifluoromethylbenzyloxyimino)ethyl]-4-chlorophenyl}trifluoromethanesulfonamide 120 (100 mg, 19%), as a pale yellow solid. M.p. 73-75° C. 1H n.m.r. (200 MHz, CDCl3) δ 10.94, br s, 1H; 7.88-7.71, m, 3H, 7.60, d, J=8.8 Hz, 1H, 7.50, d, J=2.4 Hz, 1H, 7.33, dd, J=2.4 and 8.8 Hz, 1H, 5.46, s, 2H, 2.41, s, 3H.

Workup

  1. temperatureheated for 15 h
  2. temperatureat reflux
  3. concentrationThe reaction mixture was concentrated under vacuum
  4. filtrationthe residue filtered through a pad of silica (eluting with CH2Cl2)
  5. customPurification
  6. washby radial thin layer chromatography (eluting with CH2Cl2/PE, 1:19 to 1:9)

Sources & evidence

ORD record
ord-86509a61518a46e78880cec289515a0b
Source dataset
uspto-grants-2011_03
Patent number
US07906538B2

Reaction notes

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