4-Toluenesulfonyl chloride → HCID 22272441, compound

HRID 346723Notes

Reaction equation

HRID 346723 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:9]=[CH:10][C:11]([N+:19]([O-])=O)=[C:12]([NH:14][S:15]([CH3:18])(=[O:17])=[O:16])[CH:13]=2)[CH2:4][CH2:3]1.O.NN.[C:25]1([CH3:35])[CH:30]=[CH:29][C:28]([S:31]([Cl:34])(=[O:33])=[O:32])=[CH:27][CH:26]=1.C(Cl)Cl.CO>C1COCC1.[Ni]>[ClH:34].[CH3:35][C:25]1[CH:30]=[CH:29][C:28]([S:31]([NH:19][C:11]2[CH:10]=[CH:9][C:8]([N:5]3[CH2:6][CH2:7][N:2]([CH3:1])[CH2:3][CH2:4]3)=[CH:13][C:12]=2[NH:14][S:15]([CH3:18])(=[O:17])=[O:16])(=[O:33])=[O:32])=[CH:27][CH:26]=1

Participants

7

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 24654Hydrazine hydrate (1:1)2×HCID 21226129Dichloromethane methanolHCID 22272564HCID 22272564, compound

Product 1

HCID 22272441HCID 22272441, compoundYield 28%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 8028TetrahydrofuranSolvent

Procedure

N-[5-(4-methyl-1-piperazinyl)-2-nitrophenyl]-methanesulfonamide (0.45 g, 1.43 mmol) was dissolved in THF (10 mL) followed by the addition of Raney-Ni (0.15 g in ethanol) and hydrazine hydrate (78 mg, 1.56 mmol). The reaction was stirred for 1 h. Another aliquot of hydrazine hydrate (20 μL) was added and the reaction stirred for another hour, filtered through Celite and concentrated to give 0.42 g that was used to the next step without further purification. The material was dissolved in DMF (10 mL) and divided into 3 equal parts. To one part was added p-toluene sulfonyl chloride (0.095 g, 0.5 mmol) and the reaction was stirred for 1 h and poured into a mixture of petroleum ether/acetone (30 mL/10 mL) to give a precipitate. Additional product was found in the solution and added to the precipitate. The product was isolated by chromatography (SiO2, CH2Cl2/MeOH 9:1) to give 0.063 g, (28% yield). MS (posES-FIA) m/z=found: 38.1393; Calcd: 438.1395.

Workup

  1. stirringthe reaction stirred for another hour
  2. filtrationfiltered through Celite
  3. concentrationconcentrated
  4. customto give 0.42 g that
  5. customwas used to the next step without further purification
  6. dissolutionThe material was dissolved in DMF (10 mL)
  7. stirringthe reaction was stirred for 1 h
  8. customto give a precipitate
  9. additionadded to the precipitate
  10. customto give 0.063 g, (28% yield)

Sources & evidence

ORD record
ord-d4d414a033e94a1d93c1968677beea36
Source dataset
uspto-grants-2007_02
Patent number
US07173035B2

Reaction notes

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