Hydrochloric Acid → ethyl 2-(1-(1,3-diethoxy-2-propoxycarbonyloxy)-2-methylpropyl)-5-(5-isopropoxy-4-methoxy-2-nitrobenzoyl)-2H-1,2,3-triazole-4-carboxylate

HRID 1794700Notes

Reaction equation

HRID 1794700 reaction equation
O.[C:2]1([CH3:12])[CH:7]=CC(S(O)(=O)=O)=C[CH:3]=1.[CH:13]([O:16][C:17]1[C:18]([O:38][CH3:39])=[CH:19][C:20]([N+:35]([O-:37])=[O:36])=[C:21]([CH:34]=1)[C:22]([C:24]1[NH:28][N:27]=[N:26][C:25]=1[C:29]([O:31][CH2:32][CH3:33])=[O:30])=[O:23])([CH3:15])[CH3:14].C(N1C=CN=C1)(N1C=CN=C1)=O.[CH2:52]([O:54][CH2:55][CH:56]([OH:61])[CH2:57][O:58][CH2:59][CH3:60])[CH3:53].FC(F)(F)[C:64]([OH:66])=[O:65].Cl>C(Cl)Cl>[CH2:52]([O:54][CH2:55][CH:56]([O:61][C:64]([O:66][CH:7]([N:27]1[N:26]=[C:25]([C:29]([O:31][CH2:32][CH3:33])=[O:30])[C:24]([C:22](=[O:23])[C:21]2[CH:34]=[C:17]([O:16][CH:13]([CH3:15])[CH3:14])[C:18]([O:38][CH3:39])=[CH:19][C:20]=2[N+:35]([O-:37])=[O:36])=[N:28]1)[CH:2]([CH3:3])[CH3:12])=[O:65])[CH2:57][O:58][CH2:59][CH3:60])[CH3:53]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 6422Trifluoroacetic acidHCID 682631,1'-CarbonyldiimidazoleHCID 776641,3-Diethoxy-2-propanolHCID 521998p-Toluenesulfonic acid monohydrateHCID 178470513HCID 178470513, compound

Product 1

HCID 69470612ethyl 2-(1-(1,3-diethoxy-2-propoxycarbonyloxy)-2-methylpropyl)-5-(5-isopropoxy-4-methoxy-2-nitrobenzoyl)-2H-1,2,3-triazole-4-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-30 °C

Procedure

p-Toluenesulfonic acid monohydrate (57 mg) and isobutyl aldehyde (0.41 ml) were added to a solution of ethyl 5-(5-isopropoxy-4-methoxy-2-nitrobenzoyl)-1H-1,2,3-triazole-4-carboxylate (1.14 g), prepared in step (32a), in methylene chloride solution (17 ml) at −20° C. The mixture was stirred at that temperature for one hr. 1,1′-Carbonyldiimidazole (732 mg) was added to the reaction solution. Further, one hr after that, 1,3-diethoxy-2-propanol (4.70 ml) was added thereto. The reaction solution was cooled to −30° C. Trifluoroacetic acid (0.70 ml) was added thereto. The temperature was raised to room temperature, followed by stirring for 25 hr. 0.5 M hydrochloric acid was added to the reaction solution under ice cooling to stop the reaction, and separation was then carried out. The organic layer was washed five times with a 7% aqueous sodium hydrogencarbonate solution. The solvent was evaporated under reduced pressure. Diethyl ether and water were added to the residue. The organic layer after the separation was successively washed twice with water, with 0.5 M hydrochloric acid, twice with water, and then with 20% saline. The solvent was evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (ethyl acetate/hexane) to give a crude product of ethyl 2-(1-(1,3-diethoxy-2-propoxycarbonyloxy)-2-methylpropyl)-5-(5-isopropoxy-4-methoxy-2-nitrobenzoyl)-2H-1,2,3-triazole-4-carboxylate (1.15 g).

Workup

  1. temperatureThe temperature was raised to room temperature
  2. stirringby stirring for 25 hr
  3. customthe reaction, and separation
  4. washThe organic layer was washed five times with a 7% aqueous sodium hydrogencarbonate solution
  5. customThe solvent was evaporated under reduced pressure
  6. additionDiethyl ether and water were added to the residue
  7. customThe organic layer after the separation
  8. washwas successively washed twice with water, with 0.5 M hydrochloric acid, twice with water
  9. customThe solvent was evaporated under reduced pressure
  10. customThe residue was purified by column chromatography on silica gel (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-8af3fa9f1b3c42eeb0f87bceed722962
Source dataset
uspto-grants-2006_04
Patent number
US07022860B2

Reaction notes

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