Thionyl Chloride → 5-(1-Methyl-1-phenyl-ethylcarbamoyl)-3-(2-nitro-benzoylamino)-thieno[2,3-c]pyrazole-1-carboxylic Acid ethyl Ester

HRID 549436Notes

Reaction equation

HRID 549436 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[C:10]2[S:11][C:12]([C:14](O)=[O:15])=[CH:13][C:9]=2[C:8]([NH:17][C:18](=[O:28])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=2[N+:25]([O-:27])=[O:26])=[N:7]1)=[O:5])[CH3:2].O=S(Cl)Cl.[C:33]([NH2:42])([C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)([CH3:35])[CH3:34].CCN(C(C)C)C(C)C>C1(C)C=CC=CC=1.ClCCl>[CH2:1]([O:3][C:4]([N:6]1[C:10]2[S:11][C:12]([C:14](=[O:15])[NH:42][C:33]([CH3:35])([C:36]3[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=3)[CH3:34])=[CH:13][C:9]=2[C:8]([NH:17][C:18](=[O:28])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=2[N+:25]([O-:27])=[O:26])=[N:7]1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 24386Thionyl ChlorideHCID 68509CumylamineHCID 81531DiisopropylethylamineHCID 577372633-(2-Nitro-benzoylamino)-thieno[2,3-c]pyrazole-1,5-dicarboxylic Acid 1-ethyl Ester

Product 1

HCID 577372605-(1-Methyl-1-phenyl-ethylcarbamoyl)-3-(2-nitro-benzoylamino)-thieno[2,3-c]pyrazole-1-carboxylic Acid ethyl Ester

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 1.995 g (4.93 mmol) of 3-(2-Nitro-benzoylamino)-thieno[2,3-c]pyrazole-1,5-dicarboxylic acid 1-ethyl ester in toluene (35 mL) a total volume of 7.5 ml of SOCl2 was added in a step-wise manner. The suspension so obtained was heated at 80° C. for 7 hours and then evaporated to dryness. The solid was taken up with toluene and dried up twice. Next the solid was dissolved in dichloromethane (30 mL) and added drop-wise to a solution of 1.334 g (9.86 mmol) of cumylamine and DIEA (3.37 mL, 19.73 mmol) in dichloromethane (50 mL) at 0° C. The mixture was stirred and allowed to reach room temperature overnight, washed with 1 N HCl, brine, water, dried up with Na2SO4 and evaporated to dryness. The crude was then purified by silica gel chromatography (flash chromatography column) eluting with dichloromethane-methanol 99:1. The titled compound was so isolated as a colourless solid (1.80 g 70%).

Workup

  1. customThe suspension so obtained
  2. customevaporated to dryness
  3. customdried up twice
  4. dissolutionNext the solid was dissolved in dichloromethane (30 mL)
  5. washwashed with 1 N HCl, brine, water
  6. dry with materialdried up with Na2SO4
  7. customevaporated to dryness
  8. customThe crude was then purified by silica gel chromatography (flash chromatography column)
  9. washeluting with dichloromethane-methanol 99:1

Sources & evidence

ORD record
ord-29776d623c014021aa8a4fc2ab46e1d3
Source dataset
uspto-grants-2011_05
Patent number
US07943654B2

Reaction notes

Loading…