Pyridine → HCID 59457990, compound

HRID 547518Notes

Reaction equation

HRID 547518 reaction equation
[N+:1]([C:4]1[CH:12]=[CH:11][C:7](C(O)=O)=[CH:6][CH:5]=1)([O-:3])=[O:2].[N:13]1[CH:18]=[CH:17][C:16]([NH:19][C:20]2[CH:25]=[CH:24][CH:23]=[C:22](N)[CH:21]=2)=[CH:15][CH:14]=1.[N:27]1[CH:32]=CC=CC=1.[O:33]=S(Cl)Cl>CN(C=O)C.O1CCOCC1>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([NH:27][C:32](=[O:33])[C:22]2[CH:23]=[CH:24][CH:25]=[C:20]([NH:19][C:16]3[CH:17]=[CH:18][N:13]=[CH:14][CH:15]=3)[CH:21]=2)=[CH:11][CH:12]=1)([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 1049PyridineHCID 61084-Nitrobenzoic AcidHCID 24386Thionyl ChlorideHCID 14855138HCID 14855138, compound

Product 1

HCID 59457990HCID 59457990, compoundYield 79%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 312751,4-DioxaneSolvent

Procedure

4-Nitrobenzoic acid (4.3 g, 16.36 mmol) was suspended in SOCl2 (30 mL), 2 drops of DMF were added, and the mixture was refluxed for 1 h (until a clear solution was obtained). The reaction mixture was cooled to room temperature and excess SOCl2 was removed under vacuum. The resulting residue was dissolved in 1,4-dioxane and added to a suspension of A4 (3.0 g, 16.20 mmol) in 1,4-dioxane (300 mL) containing pyridine (8 mL). The reaction mixture was stirred 16 h at 50° C., and the solvent was then evaporated. The residue was stirred in dilute aqueous ammonia, and the resulting precipitate was filtered and crystallized from MeOH to give A5 (5.3 g, 79%): mp (MeOH) 219-222° C.; 1H NMR [(CD3)2SO] δ10.63 (s, 1 H, NH), 9.04 (s, 1 H, NH), 8.37 (d, J=8.9 Hz, 2 H, ArH), 8.24-8.18 (m, 4 H, ArH), 7.81 (bs, 1 H, ArH), 7.45 (d, J=8.5 Hz, 1 H, ArH), 7.34 (t, J=8.0 Hz, 1 H, ArH), 6.99-6.95 (m, 3 H, ArH), 13C NMR [(CD3)2SO] δ 166.9, 164.0, 150.3, 149.4 (2×C), 149.1, 140.5, 139.6, 129.5 (2×C), 129.2, 123.5 (2×C), 123.4, 115.8, 114.6, 111.6, 109; HRMS (FAB+) calc. for Cs8H15N4O3 (M+1) m/z 335.1144, found 335.1154.

Workup

  1. temperaturethe mixture was refluxed for 1 h (until a clear solution
  2. customwas obtained)
  3. customexcess SOCl2 was removed under vacuum
  4. dissolutionThe resulting residue was dissolved in 1,4-dioxane
  5. customthe solvent was then evaporated
  6. stirringThe residue was stirred in dilute aqueous ammonia
  7. filtrationthe resulting precipitate was filtered
  8. customcrystallized from MeOH

Sources & evidence

ORD record
ord-478cba23b6214274ac5e6a39156057a4
Source dataset
uspto-grants-2011_05
Patent number
US07939546B2

Reaction notes

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