Pyridine → HCID 66801527, compound

HRID 2366296Notes

Reaction equation

HRID 2366296 reaction equation
[F:1][C:2]1[CH:18]=[CH:17][CH:16]=[C:15]([N+:19]([O-:21])=[O:20])[C:3]=1[C:4](Cl)=[N:5][C:6]1[C:11]([F:12])=[CH:10][N:9]=[CH:8][C:7]=1F.NC(N)=[S:24].N1C=CC=CC=1.CCN(CC)CC>C(O)(C)C>[F:1][C:2]1[CH:18]=[CH:17][CH:16]=[C:15]([N+:19]([O-:21])=[O:20])[C:3]=1[C:4]1[S:24][C:7]2[CH:8]=[N:9][CH:10]=[C:11]([F:12])[C:6]=2[N:5]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 8471TriethylamineHCID 2723790ThioureaHCID 86669022HCID 86669022, compound

Product 1

HCID 66801527HCID 66801527, compoundYield 41%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

A suspension of 2-fluoro-N-(3,5-difluoropyridin-4-yl)-6-nitrobenzimidoyl chloride (12.05 g, 36.4 mmol), thiourea (12.05 g, 159 mmol) and pyridine (16 mL, 200 mmol) in isopropanol (200 mL) under a nitrogen atmosphere was heated under reflux for 4 hours. Et3N (33.2 mL, 239 mmol) was added over 5 minutes and the reaction mixture was heated under reflux for 18 hours. After cooling to room temperature, the volatiles were removed under reduced pressure and the resultant residue was partitioned between water and EtOAc. The aqueous phase was further extracted with EtOAc (×5) and the combined organic layers were dried (Na2SO4) and concentrated to dryness. The resultant residue was purified by column chromatography on silica gel eluting with 0-50% EtOAc in cyclohexane to afford the title compound as a yellow solid (4.33 g, 41% yield). LCMS (Method D): RT=3.21 min, m/z: 294 [M+H+].

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 4 hours
  3. temperaturethe reaction mixture was heated
  4. temperatureunder reflux for 18 hours
  5. customthe volatiles were removed under reduced pressure
  6. customthe resultant residue was partitioned between water and EtOAc
  7. extractionThe aqueous phase was further extracted with EtOAc (×5)
  8. dry with materialthe combined organic layers were dried (Na2SO4)
  9. concentrationconcentrated to dryness
  10. customThe resultant residue was purified by column chromatography on silica gel eluting with 0-50% EtOAc in cyclohexane

Sources & evidence

ORD record
ord-20a06f19cc2e4c068c2e6eddefc775e0
Source dataset
uspto-grants-2014_04
Patent number
US08697708B2

Reaction notes

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