3-(Methoxycarbonyl)benzoic acid → HCID 69222561, compound

HRID 2113903Notes

Reaction equation

HRID 2113903 reaction equation
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:12]=[CH:11][CH:10]=[C:6]([C:7]([OH:9])=O)[CH:5]=1.C(C1NC=CN=1)(C1NC=CN=1)=O.[CH3:26][N:27]([CH3:38])[C:28]1[CH:37]=[CH:36][C:31]([C:32]([NH:34]O)=[NH:33])=[CH:30][N:29]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>>[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:12]=[CH:11][CH:10]=[C:6]([C:7]2[O:9][N:33]=[C:32]([C:31]3[CH:30]=[N:29][C:28]([N:27]([CH3:38])[CH3:26])=[CH:37][CH:36]=3)[N:34]=2)[CH:5]=1

Participants

5

Reactant 4

HCID 6018803-(Methoxycarbonyl)benzoic acidHCID 2724141Tetrabutylammonium FluorideHCID 5250894Bis-(1H-imidazol-2-YL)-methanoneHCID 178482802HCID 178482802, compound

Product 1

HCID 69222561HCID 69222561, compound

Procedure

In a 50 ml round flask, a mixture of 5.6 (31.1 mmol) of isophtalic acid monomethyl ester and 6.71 g (34.2 mmol, 1.1 eq.) of carbonyl-diimidazole is stirred for 1 h at rt. Then, 5.60 g (31.1 mmol) of 6-dimethylamino-N-hydroxy-nicotinamidine is added and the resulting mixture stirred for another 3 h. After completion of the reaction, the solvent is removed. The resulting residue is suspended in water, vigorously stirred and then filtered. The obtained solid is washed two times with diethyl-ether and dried. This yields 10.0 g (94%) of a light yellow solid. Mass spectrum: m/z (M+H)+: 343.1The crude intermediate (9.8 g (28.7 mmol) is then redissolved in 200 ml of THF and 1.81 g (5.7 mmol, 0.2 eq.) of tetrabutyl-ammonium fluoride tri-hydrate TBAF) is added. After 1.5 h, another 0.2 eq. of TBAF is and the mixture stirred at rt for 20 h. Then, solvent is removed under vacuo, and the residue taken up in 200 ml of dichloro-methane and washed twice with NaHCO3 (5%). The combined aqueous phases are extracted three times with dichloro-methane, the combined organic phases dried (Na2SO4) and concentrated. This yields the title compound as light yellow solid, which is used for the next step without purification. Mass spectrum: m/z (M+H)+: 325.2

Workup

  1. stirringthe resulting mixture stirred for another 3 h
  2. customAfter completion of the reaction
  3. customthe solvent is removed
  4. stirringvigorously stirred
  5. filtrationfiltered
  6. washThe obtained solid is washed two times with diethyl-ether
  7. customdried
  8. dissolutionMass spectrum: m/z (M+H)+: 343.1The crude intermediate (9.8 g (28.7 mmol) is then redissolved in 200 ml of THF
  9. waitAfter 1.5 h
  10. stirringthe mixture stirred at rt for 20 h
  11. customThen, solvent is removed under vacuo
  12. washwashed twice with NaHCO3 (5%)
  13. extractionThe combined aqueous phases are extracted three times with dichloro-methane
  14. dry with materialthe combined organic phases dried (Na2SO4)
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-3e7e5c097bcd4e00b414ab2326ea9673
Source dataset
uspto-grants-2008_10
Patent number
US07432293B2

Reaction notes

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