Chlorosulfonyl isocyanate → ethyl 5-carbamoyl-4-(4-nitrophenyl)-1H-pyrrole-3-carboxylate

HRID 227671Notes

Reaction equation

HRID 227671 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[C:11]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:12][NH:13][CH:14]=2)=[CH:6][CH:5]=1)([O-:3])=[O:2].ClS([N:24]=[C:25]=[O:26])(=O)=O>ClCCl>[C:25]([C:14]1[NH:13][CH:12]=[C:11]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:10]=1[C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)(=[O:26])[NH2:24]

Participants

4

Reactant 2

HCID 70918Chlorosulfonyl isocyanateHCID 53440113ethyl 4-(4-nitrophenyl)-1H-pyrrole-3-carboxylate

Product 1

HCID 57756867ethyl 5-carbamoyl-4-(4-nitrophenyl)-1H-pyrrole-3-carboxylateYield 73.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-24 °C

Procedure

To 18 g (69.16 mmol) of ethyl 4-(4-nitrophenyl)-1H-pyrrole-3-carboxylate suspended in 300 cm3 of dichloromethane are added, at a temperature in the region of −24° C. under an argon atmosphere, 8.1 cm3 (91.29 mmol) of chlorosulfonyl isocyanate dissolved in 100 cm3 of dichloromethane. After stirring for 30 minutes at a temperature in the region of −24° C., the reaction medium is allowed to warm to a temperature in the region of 20° C. over 2 hours. After initiating the crystallization using a glass rod, the reaction mixture is stirred at a temperature in the region of 20° C. for 30 minutes. The reaction mixture is then cooled to a temperature in the region of 5° C. and then filtered through a No 3 sinter funnel. The solid is washed with three times 40 cm3 of dichloromethane and then dried under reduced pressure (2.7 kPa) at a temperature in the region of 40° C. for 3 hours. The solid is then suspended in 500 cm3 of water; the resulting mixture is then heated at a temperature in the region of 40° C. for 3 hours and then cooled at a temperature in the region of 5° C. for 1 hour before filtering through a No 3 sinter funnel. The solid is successively washed with twice 50 cm3 of water and twice 30 cm3 of petroleum ether and then dried under reduced pressure (2.7 kPa) at a temperature in the region of 40° C. for 16 hours to give 15.4 g of ethyl 5-carbamoyl-4-(4-nitrophenyl)-1H-pyrrole-3-carboxylate in the form of a beige-coloured solid; EI: m/z=303: M+; m/z=274 [M-CH2CH3]+; m/z=258 [M-OCH2CH3]+; m/z=241 [258-OH]+ base peak.

Workup

  1. additionare added, at a temperature in the region of −24° C. under an argon atmosphere
  2. temperatureto warm to a temperature in the region of 20° C. over 2 hours
  3. customthe crystallization
  4. stirringthe reaction mixture is stirred at a temperature in the region of 20° C. for 30 minutes
  5. temperatureThe reaction mixture is then cooled to a temperature in the region of 5° C.
  6. filtrationfiltered through a No 3 sinter funnel
  7. washThe solid is washed with three times 40 cm3 of dichloromethane
  8. customdried under reduced pressure (2.7 kPa) at a temperature in the region of 40° C. for 3 hours
  9. temperaturethe resulting mixture is then heated at a temperature in the region of 40° C. for 3 hours
  10. temperaturecooled at a temperature in the region of 5° C. for 1 hour
  11. filtrationbefore filtering through a No 3 sinter funnel
  12. washThe solid is successively washed with twice 50 cm3 of water and twice 30 cm3 of petroleum ether
  13. customdried under reduced pressure (2.7 kPa) at a temperature in the region of 40° C. for 16 hours

Sources & evidence

ORD record
ord-46051ad5240e424fa856523b51a10160
Source dataset
uspto-grants-2009_07
Patent number
US07560571B2

Reaction notes

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