Benzoic Acid → 5-(4-carboxybenzylidene)-3-[(1-{3,4-dimethylphenyl}-4-hydroxy-3-methyl-1H-pyrazol-4-ylmethylene)amino]-2-thioxothiazolidin-4-one

HRID 2085360Notes

Reaction equation

HRID 2085360 reaction equation
[NH2:1][N:2]1[C:6](=[O:7])[CH2:5][S:4][C:3]1=[S:8].[CH3:9][C:10]1[CH:11]=[C:12]([N:17]2[C:21](O)=[C:20]([CH:23]=O)[C:19]([CH3:25])=[N:18]2)[CH:13]=[CH:14][C:15]=1[CH3:16].N1CCCCC1.[CH:32]([C:34]1[CH:42]=[CH:41][C:37]([C:38]([OH:40])=[O:39])=[CH:36][CH:35]=1)=O.C(O)(=[O:50])C1C=CC=CC=1>C1(C)C=CC=CC=1.C(O)C>[C:38]([C:37]1[CH:41]=[CH:42][C:34]([CH:32]=[C:5]2[S:4][C:3](=[S:8])[N:2]([N:1]=[CH:23][C:20]3([OH:50])[CH2:21][N:17]([C:12]4[CH:13]=[CH:14][C:15]([CH3:16])=[C:10]([CH3:9])[CH:11]=4)[N:18]=[C:19]3[CH3:25])[C:6]2=[O:7])=[CH:35][CH:36]=1)([OH:40])=[O:39]

Participants

8

Reactant 5

HCID 243Benzoic AcidHCID 8082PiperidineHCID 120884-Formylbenzoic acidHCID 740333-AminorhodanineHCID 178426271HCID 178426271, compound

Product 1

HCID 867594175-(4-carboxybenzylidene)-3-[(1-{3,4-dimethylphenyl}-4-hydroxy-3-methyl-1H-pyrazol-4-ylmethylene)amino]-2-thioxothiazolidin-4-oneYield 165.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

A mixture of 3-aminorhodanine (148 mg, 1.00 mmol), 1-(3,4-dimethylphenyl)-5-hydroxy-3-methyl-1H-pyrazole-4-carbaldehyde (230 mg, 1.00 mmol) and ethanol (10 mL) was stirred 96 h. The solid was filtered, washed with ethanol and ether and dried. A mixture of the resulting crude imine (80 mg, 0.222 mmol), piperidine (2 mg, 0.022 mmol), 4-formylbenzoic acid (33 mg, 0.222 mmol), benzoic acid (3 mg, 0.022 mmol) and toluene (10 mL) was heated under reflux for 6 h in an apparatus fitted with a Dean and Stark separator to remove water. After cooling, the solid was filtered off, washed with toluene and ether, and purified by reverse phase HPLC (CombiPrep ODS-A, 10-90% acetonitrile/water+0.1% trifluoroacetic acid) to give the title compound (18 mg, 16%) as a solid. LCMS, m/e 493 [M+H]+.

Workup

  1. filtrationThe solid was filtered
  2. washwashed with ethanol and ether
  3. customdried
  4. temperaturewas heated
  5. temperatureunder reflux for 6 h in an apparatus
  6. customfitted with a Dean and Stark separator
  7. customto remove water
  8. temperatureAfter cooling
  9. filtrationthe solid was filtered off
  10. washwashed with toluene and ether
  11. custompurified by reverse phase HPLC (CombiPrep ODS-A, 10-90% acetonitrile/water+0.1% trifluoroacetic acid)

Sources & evidence

ORD record
ord-0eb958c6308d4de1802bc800fc4a2af2
Source dataset
uspto-grants-2004_04
Patent number
US06720345B1

Reaction notes

Loading…