4-Toluenesulfonyl chloride → HCID 69652090, compound

HRID 2213541Notes

Reaction equation

HRID 2213541 reaction equation
C([N:3]([CH2:6][CH3:7])CC)C.Cl.[Cl:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([Cl:16])[C:11]=1[NH:17][NH2:18].N12CCCN=[C:25]1[CH2:24][CH2:23][CH2:22][CH2:21][CH2:20]2.C1(C)C=CC(S(Cl)(=O)=[O:37])=CC=1.[C:41]([O:44][CH2:45][CH3:46])(=[O:43])[CH3:42]>C(O)C>[CH2:45]([O:44][C:41]([C:42]1[C:6]([CH2:7][O:37][C:25]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[N:3][N:17]([C:11]2[C:10]([Cl:9])=[CH:15][CH:14]=[CH:13][C:12]=2[Cl:16])[N:18]=1)=[O:43])[CH3:46]

Participants

7

Reactant 5

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene2×HCID 2723909(2,6-Dichlorophenyl)hydrazine monohydrochloride

Product 1

HCID 69652090HCID 69652090, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Triethylamine (2.09 mL, 15.0 mmol) was added to a stirred suspension of the product from step a (10.0 mmol) and 2,6-dichlorophenylhydrazine-hydrochloride (3.20 g, 10.0 mmol) in ethanol (30 mL). The resultant solution was stirred at room temperature for 18 hours. The reaction mixture was diluted with ethyl acetate and was washed sequentially with 2M HCl and brine. The organic phase was dried (MgSO4) and the filtrate was evaporated at reduced pressure. The residue was dissolved in DCM (100 mL) and the solution was cooled in ice/water. 1,8-Diazabicyclo[5.4.0]undec-7-ene (1.84 mL, 12.3 mmol) and p-toluenesulfonyl chloride (2.14 g, 11.2 mmol) were added sequentially, the coolant removed and the reaction mixture was stirred at room temperature for 40 minutes. The reaction mixture was re-cooled in ice/water and further 1,8-diazabicyclo[5.4.0]undec-7-ene (1.84 mL, 12.3 mmol) was added. The coolant was removed and the reaction mixture was stirred at room temperature for 18 h. The reaction mixture was washed sequentially with 2M HCl, saturated aqueous sodium hydrogen carbonate and brine. The organic phase was dried (MgSO4) and the filtrate evaporated at reduced pressure. The residue was purified by flash column chromatography (2:1 hexane:ethyl acetate) to recover the title compound (1.44 g, 37%). 1H NMR (CDCl3) 7.48-7.44 (3H, m), 7.32-7.27 (2H, m), 7.08-6.98 (3H, m), 5.52 (2H, s), 4.49 (2H, q, J=7.2 Hz), 1.41 (3H, t, J=7.2 Hz).

Workup

  1. washwas washed sequentially with 2M HCl and brine
  2. dry with materialThe organic phase was dried (MgSO4)
  3. customthe filtrate was evaporated at reduced pressure
  4. dissolutionThe residue was dissolved in DCM (100 mL)
  5. temperaturethe solution was cooled in ice/water
  6. customthe coolant removed
  7. temperatureThe reaction mixture was re-cooled in ice/water
  8. customThe coolant was removed
  9. stirringthe reaction mixture was stirred at room temperature for 18 h
  10. washThe reaction mixture was washed sequentially with 2M HCl, saturated aqueous sodium hydrogen carbonate and brine
  11. dry with materialThe organic phase was dried (MgSO4)
  12. customthe filtrate evaporated at reduced pressure
  13. customThe residue was purified by flash column chromatography (2:1 hexane:ethyl acetate)
  14. customto recover the title compound (1.44 g, 37%)

Sources & evidence

ORD record
ord-11ceff5337334aa4a5a0719023595040
Source dataset
uspto-grants-2006_09
Patent number
US07105558B2

Reaction notes

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