Stannous Chloride → HCID 86673523, compound

HRID 1424553Notes

Reaction equation

HRID 1424553 reaction equation
Cl[Sn]Cl.[F:4][C:5]1[C:10]([F:11])=[C:9]([C:12]#[C:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[N+:20]([O-])=O)[C:8]([F:23])=[C:7]([F:24])[N:6]=1>CCO>[F:4][C:5]1[C:10]([F:11])=[C:9]([C:12]#[C:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[NH2:20])[C:8]([F:23])=[C:7]([F:24])[N:6]=1

Participants

4

Reactant 2

HCID 24479Stannous ChlorideHCID 70974574HCID 70974574, compound2×

Product 1

HCID 86673523HCID 86673523, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

SnCl2 (3.26 g, 17.2 mmol) was added to the solution of 2,3,5,6-tetrafluoro-4-((2-nitrophenyl)ethynyl) pyridine, (12c) (1.02 g, 3.44 mmol) in EtOH (100 mL). The reaction mixture was refluxed for 1.5 hours. After basification till pH>9 with NaOH (1.0 N solution), the product was extracted with dichloromethane. Solvent was evaporated and 0.22 g (24%) of the product aniline was purified by recrystallization with benzene. The residue was purified by column chromatography on silica gel using EtOAc:Hexane=1:10 as the eluent to yield the product (0.53 g, 68%): 1H-NMR (300 MHz, acetone-d6) δ 7.39 (d, J=7.5 Hz, 1H), 7.26 (ddd, J=8.4, 6.9, 1.5 Hz, 1H), 6.89 (d, J=8.4 Hz, 1H), 6.69 (ddd, J=7.5, 7.5, 1.2 Hz, 1H), 5.35 (s, 2H); 13C-NMR (150 MHz, CDCl3) δ 149.3, 143.7 (dm, J=245.3 Hz), 141.4 (dm, J=260.9 Hz), 133.0, 132.6, 118.3, 117.8 (m), 114.8, 104.7, 104.6 (t, J=3.5 Hz), 79.4 (t, J=4.3 Hz); HRMS (ESI+): calcd for C13H7F4N2 [M +H]+ 267.05454, found 267.05454; m.p. 133-134° C.

Workup

  1. temperatureThe reaction mixture was refluxed for 1.5 hours
  2. extractionAfter basification till pH>9 with NaOH (1.0 N solution), the product was extracted with dichloromethane
  3. customSolvent was evaporated
  4. custom0.22 g (24%) of the product aniline was purified by recrystallization with benzene
  5. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-3ee6c1e793054aaf9ba06cedb08a12a0
Source dataset
uspto-grants-2015_01
Patent number
US08927728B2

Reaction notes

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