Acetic Acid → HCID 10759629, compound

HRID 1586191Notes

Reaction equation

HRID 1586191 reaction equation
[OH-].[Na+].[C:3]1([CH3:13])[CH:8]=[CH:7][C:6]([S:9]([NH2:12])(=[O:11])=[O:10])=[CH:5][CH:4]=1.[Cl:14][C:15]1[CH:20]=[CH:19][C:18]([N:21]=[C:22]=[S:23])=[CH:17][CH:16]=1.C(O)(=O)C>CC(C)=O.O>[CH3:13][C:3]1[CH:4]=[CH:5][C:6]([S:9]([NH:12][C:22]([NH:21][C:18]2[CH:19]=[CH:20][C:15]([Cl:14])=[CH:16][CH:17]=2)=[S:23])(=[O:10])=[O:11])=[CH:7][CH:8]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 6269P-ToluenesulfonamideHCID 14798Sodium HydroxideHCID 164804-Chlorophenyl isothiocyanate

Product 1

HCID 10759629HCID 10759629, compoundYield 132%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

1N sodium hydroxide solution (6 mL, 6 mmol) was added to a solution containing the 4-toluenesulfonamide (1 g, 5.85 mmol) in acetone (25 mL). After stirring at room temperature for 30 min, the 4-chlorophenyl isothiocyanate (1.0 mmol) was added. After refluxing for 4 h, the mixture was cooled to room temperature and neutralized with 1N acetic acid solution to pH 5. The mixture was allowed to stir at room temperature for 30 min before adding water (45 mL) to produce a white precipitate which was collected by filtration. After the solid was dried in the oven, it was recrystallized to give 0.45 g (22.6%) of N-[(4-methylphenyl)sulfonyl]-N'-(4-chlorophenyl)thiourea. To an aqueous solution (50 mL) of sulfonylthiourea (1.2 g, 3.67 mmol), 1N sodium hydroxide solution (4 mL) was added and stirred for 2 minutes, followed by addition of methyl iodide (4.04 mmol). The reaction mixture was stirred at room temperature for 20 minutes, and neutralized with 1N acetic acid (4 mL). The resulting mixture was extracted with chloroform to give 1.06 g (85%) of N-[(4-methylphenyl)sulfonyl]-N'-(4-chlorophenyl)-S-methylpseudothiourea. The S-methyl pseudourea (0.99 g, 2.8 mmol) was added to a stirred solution of hydroxylamine hydrochloride (8.4 mmol) and triethylamine (1.2 mL, 8.4 mmol) in chloroform (50 mL). The solution was refluxed for 48 h and the solvent was removed by evaporation to produce a solid residue. Ether (20 mL) was added to the residue and the white precipitate was collected by filtration. The solid was then heated with toluene and the undissolved solid was removed by filtration. The filtrate was again evaporated to obtain a solid which was subsequently recrystallized from methanol to yield the target compound (0.12 g, 12.7%); mp: 201-203° C.; MS m/z 294 (M+ -32); 1H NMR (300 MHz, DMSO-d6) d 2.36 (s, 3H, CH3), 7.31-7.36 (m, 4H, ArH), 7.45 (d, J=8.8 Hz, 2H, ArH), 7.71 (d, J=8.1 Hz, 2H, ArH), 9.40 (s, 1H, NH), 9.69 (br s, 2H, NH & OH); 13C NMR (100 MHz, DMSO-d6) d 20.9, 124.7, 125.9, 128.2, 128.3, 129.1, 136.2, 140.6, 141.6, 154.0. Analysis for C14H14ClN3O3S (339.8): theory: C, 49.49; H, 4.15; N, 12.37. Found: C, 49.67; H, 4.16; N, 12.47.

Workup

  1. temperatureAfter refluxing for 4 h
  2. stirringto stir at room temperature for 30 min
  3. customto produce a white precipitate which
  4. filtrationwas collected by filtration
  5. customAfter the solid was dried in the oven, it
  6. customwas recrystallized

Sources & evidence

ORD record
ord-48c9b634ef964267bbb63e8ad4fa3b3c
Source dataset
uspto-grants-1999_08
Patent number
US05942546

Reaction notes

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